The cobalt(II) and nickel(II) cupferronato (
N-nitroso-
N-phenylhydroxylaminato) mixed-ligand complexes of 2-aminopyridine (2-NH
2py) [Co(PhN
2O
2)
2(2-NH
2py)
2] (1), [Ni(PhN
2O
2)
2(2-NH
2py)
2] (2) and 2,6-diamino-4-phenyl-1,3,5-triazine (dpt) [Co(PhN
2O
2)
2(dpt)
2]·[Co(PhN
2O
2)
2(EtOH)
2] (3) have been synthesized and characterized by X-ray diffraction analysis. The cobalt (1) and nickel (2) complexes are isostructural. The crystal lattice of (3) contains different neutral cobalt(II) complexes [Co(PhN
2O
2)
2(dpt)
2] (3
a) and [Co(PhN
2O
2)
2(EtOH)
2] (3
b). Molecules of (1)–(3) contain octahedral metal centres with all-
cis-(1) and -(2) and all-
trans-(3) disposal of the ligands. Intramolecular N—H
O hydrogen bonding between the NH
2 groups and the O atom of the cupferronato anion can be observed in (1)–(3). Intermolecular N—H
O and N—H
N interactions between symmetry-related molecules of (1) and (2) led to hexameric aggregates which connect through common edges into a two-dimensional supramolecular network of hexagonal-grid type. In complex (3) the self-complementary dpt units of the (3
a) molecules are maintained by intermolecular N—H
N hydrogen bonds, generating infinite chains. These (3
a) chains are crosslinked by the (3
b) subunits
via N—H
O and O—H
N hydrogen bonds, thus completing the parallel two-dimensional supramolecular network consisting of pseudo-hexagonal-grid sheets. In each crystal structure the two-dimensional supramolecular networks are controlled by both hydrogen bonds and π
π stacking interactions.
Supporting information
CCDC references: 143826; 143827; 166495
C1D is disordered over two sites
For all compounds, data collection: CAD-4 EXPRESS; cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
(coapir) 'di(2-aminopyridine)-bis(
N-nitroso-
N-phenylhydroxylaminato)-cobalt(II)'
top
Crystal data top
C22H22CoN8O4 | F(000) = 1076 |
Mr = 521.41 | Dx = 1.446 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.270 (1) Å | Cell parameters from 25 reflections |
b = 11.579 (2) Å | θ = 15.0–16.5° |
c = 25.019 (4) Å | µ = 0.76 mm−1 |
β = 91.42 (2)° | T = 293 K |
V = 2395.0 (6) Å3 | Prism, red |
Z = 4 | 0.45 × 0.40 × 0.40 mm |
Data collection top
Enraf-Nonius CAD4 diffractometer | 3093 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.015 |
Graphite monochromator | θmax = 28.0°, θmin = 2.6° |
ω–2θ scans | h = −10→0 |
Absorption correction: ψ scan MolEN, Structure Determination System. Enraf-Nonius, 1990) | k = −15→0 |
Tmin = 0.945, Tmax = 1 | l = −33→33 |
6214 measured reflections | 3 standard reflections every 60 min |
5671 independent reflections | intensity decay: 2% |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.041 | w = 1/[σ2(Fo2) + (0.0635P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.113 | (Δ/σ)max = 0.002 |
S = 0.96 | Δρmax = 0.32 e Å−3 |
5671 reflections | Δρmin = −0.28 e Å−3 |
316 parameters | |
Crystal data top
C22H22CoN8O4 | V = 2395.0 (6) Å3 |
Mr = 521.41 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.270 (1) Å | µ = 0.76 mm−1 |
b = 11.579 (2) Å | T = 293 K |
c = 25.019 (4) Å | 0.45 × 0.40 × 0.40 mm |
β = 91.42 (2)° | |
Data collection top
Enraf-Nonius CAD4 diffractometer | 3093 reflections with I > 2σ(I) |
Absorption correction: ψ scan MolEN, Structure Determination System. Enraf-Nonius, 1990) | Rint = 0.015 |
Tmin = 0.945, Tmax = 1 | 3 standard reflections every 60 min |
6214 measured reflections | intensity decay: 2% |
5671 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | Δρmax = 0.32 e Å−3 |
5671 reflections | Δρmin = −0.28 e Å−3 |
316 parameters | |
Special details top
Experimental. this compound is isostructural with the analogous Ni(II) complex |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Co1 | 0.66666 (4) | 0.41944 (3) | 0.872180 (12) | 0.05022 (12) | |
O1A | 0.4982 (2) | 0.35131 (16) | 0.81839 (7) | 0.0627 (5) | |
O2A | 0.4501 (2) | 0.50908 (16) | 0.88450 (7) | 0.0646 (5) | |
N1A | 0.3784 (2) | 0.42418 (17) | 0.81123 (8) | 0.0507 (5) | |
N2A | 0.3473 (3) | 0.50499 (19) | 0.84483 (8) | 0.0607 (5) | |
C1A | 0.2742 (3) | 0.4112 (2) | 0.76493 (9) | 0.0529 (6) | |
C2A | 0.1309 (3) | 0.4716 (3) | 0.76034 (12) | 0.0727 (8) | |
H2A | 0.1006 | 0.5225 | 0.7870 | 0.095* | |
C3A | 0.0341 (4) | 0.4552 (3) | 0.71583 (15) | 0.0924 (11) | |
H3A | −0.0638 | 0.4944 | 0.7128 | 0.120* | |
C4A | 0.0781 (4) | 0.3827 (4) | 0.67607 (14) | 0.0926 (11) | |
H4A | 0.0122 | 0.3740 | 0.6457 | 0.120* | |
C5A | 0.2211 (4) | 0.3221 (4) | 0.68109 (12) | 0.0924 (11) | |
H5A | 0.2506 | 0.2708 | 0.6544 | 0.120* | |
C6A | 0.3197 (3) | 0.3373 (3) | 0.72513 (11) | 0.0717 (8) | |
H6A | 0.4173 | 0.2977 | 0.7282 | 0.093* | |
O1B | 0.8002 (2) | 0.54463 (14) | 0.91259 (6) | 0.0579 (4) | |
O2B | 0.7268 (3) | 0.5372 (2) | 0.81340 (7) | 0.0773 (6) | |
N1B | 0.8244 (3) | 0.63231 (19) | 0.88088 (8) | 0.0555 (5) | |
N2B | 0.7912 (3) | 0.6303 (2) | 0.83034 (10) | 0.0724 (6) | |
C1B | 0.8944 (3) | 0.7368 (2) | 0.90277 (11) | 0.0569 (6) | |
C2B | 0.8649 (4) | 0.8405 (3) | 0.87728 (14) | 0.0790 (9) | |
H2B | 0.7978 | 0.8439 | 0.8469 | 0.103* | |
C3B | 0.9361 (5) | 0.9380 (3) | 0.89754 (19) | 0.0992 (12) | |
H3B | 0.9159 | 1.0090 | 0.8813 | 0.129* | |
C4B | 1.0381 (5) | 0.9317 (3) | 0.9420 (2) | 0.1010 (12) | |
H4B | 1.0901 | 0.9978 | 0.9547 | 0.131* | |
C5B | 1.0624 (4) | 0.8303 (3) | 0.96702 (15) | 0.0909 (10) | |
H5B | 1.1297 | 0.8272 | 0.9973 | 0.118* | |
C6B | 0.9885 (4) | 0.7299 (3) | 0.94818 (13) | 0.0740 (8) | |
H6B | 1.0028 | 0.6601 | 0.9660 | 0.096* | |
N1C | 0.6148 (2) | 0.30970 (17) | 0.93901 (7) | 0.0497 (5) | |
N2C | 0.6729 (3) | 0.43834 (18) | 1.00703 (8) | 0.0613 (6) | |
H2C1 | 0.7255 | 0.4801 | 0.9850 | 0.074* | |
H2C2 | 0.6659 | 0.4595 | 1.0398 | 0.074* | |
C1C | 0.6021 (3) | 0.3408 (2) | 0.99038 (9) | 0.0503 (6) | |
C2C | 0.5168 (4) | 0.2710 (2) | 1.02627 (11) | 0.0659 (7) | |
H2C | 0.5042 | 0.2952 | 1.0614 | 0.086* | |
C3C | 0.4538 (4) | 0.1699 (3) | 1.01003 (12) | 0.0725 (8) | |
H3C | 0.3952 | 0.1247 | 1.0334 | 0.094* | |
C4C | 0.4768 (4) | 0.1332 (2) | 0.95787 (13) | 0.0723 (8) | |
H4C | 0.4397 | 0.0614 | 0.9463 | 0.094* | |
C5C | 0.5549 (3) | 0.2053 (2) | 0.92439 (12) | 0.0637 (7) | |
H5C | 0.5681 | 0.1815 | 0.8893 | 0.083* | |
N1D | 0.8671 (2) | 0.30835 (19) | 0.85570 (8) | 0.0575 (5) | |
N2D | 0.7621 (4) | 0.2262 (3) | 0.77968 (11) | 0.1106 (11) | |
H2D1 | 0.6737 | 0.2637 | 0.7841 | 0.133* | |
H2D2 | 0.7711 | 0.1809 | 0.7527 | 0.133* | |
C1D | 0.8847 (4) | 0.2381 (2) | 0.81455 (11) | 0.0658 (7) | |
C2D | 1.0316 (4) | 0.1760 (3) | 0.80775 (15) | 0.0828 (10) | |
H2D | 1.0441 | 0.1277 | 0.7785 | 0.108* | |
C3D | 1.1514 (4) | 0.1886 (3) | 0.84437 (18) | 0.0861 (10) | |
H3D | 1.2480 | 0.1488 | 0.8405 | 0.112* | |
C4D | 1.1322 (4) | 0.2594 (3) | 0.88706 (15) | 0.0838 (9) | |
H4D | 1.2145 | 0.2680 | 0.9128 | 0.109* | |
C5D | 0.9913 (4) | 0.3169 (3) | 0.89134 (12) | 0.0700 (7) | |
H5D | 0.9792 | 0.3654 | 0.9206 | 0.091* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0553 (2) | 0.0607 (2) | 0.03462 (16) | 0.00110 (17) | −0.00042 (12) | −0.00401 (15) |
O1A | 0.0603 (11) | 0.0723 (12) | 0.0549 (10) | 0.0137 (10) | −0.0087 (8) | −0.0146 (9) |
O2A | 0.0703 (11) | 0.0751 (12) | 0.0481 (10) | 0.0145 (10) | −0.0075 (9) | −0.0136 (9) |
N1A | 0.0515 (11) | 0.0563 (12) | 0.0441 (11) | 0.0002 (10) | 0.0009 (8) | −0.0026 (10) |
N2A | 0.0658 (14) | 0.0675 (14) | 0.0486 (12) | 0.0072 (11) | −0.0022 (10) | −0.0033 (11) |
C1A | 0.0507 (14) | 0.0620 (15) | 0.0458 (13) | −0.0149 (12) | −0.0003 (10) | 0.0049 (12) |
C2A | 0.0573 (17) | 0.089 (2) | 0.0710 (19) | 0.0004 (16) | −0.0067 (14) | −0.0036 (16) |
C3A | 0.0582 (19) | 0.125 (3) | 0.093 (3) | 0.0050 (19) | −0.0167 (17) | 0.000 (2) |
C4A | 0.067 (2) | 0.144 (3) | 0.065 (2) | −0.016 (2) | −0.0161 (16) | 0.000 (2) |
C5A | 0.078 (2) | 0.142 (3) | 0.0576 (19) | −0.008 (2) | −0.0056 (16) | −0.023 (2) |
C6A | 0.0611 (16) | 0.101 (2) | 0.0527 (16) | −0.0007 (16) | −0.0017 (13) | −0.0125 (16) |
O1B | 0.0753 (11) | 0.0562 (10) | 0.0421 (9) | −0.0107 (9) | −0.0036 (8) | 0.0095 (7) |
O2B | 0.0961 (15) | 0.0901 (14) | 0.0455 (11) | −0.0072 (13) | −0.0019 (10) | 0.0072 (10) |
N1B | 0.0582 (12) | 0.0605 (12) | 0.0477 (12) | −0.0001 (10) | 0.0025 (9) | 0.0131 (10) |
N2B | 0.0796 (16) | 0.0843 (17) | 0.0532 (14) | −0.0015 (14) | 0.0014 (12) | 0.0165 (13) |
C1B | 0.0529 (14) | 0.0550 (15) | 0.0632 (17) | −0.0002 (12) | 0.0091 (12) | 0.0098 (12) |
C2B | 0.080 (2) | 0.070 (2) | 0.088 (2) | −0.0002 (16) | 0.0179 (17) | 0.0262 (17) |
C3B | 0.110 (3) | 0.065 (2) | 0.124 (3) | −0.007 (2) | 0.027 (3) | 0.026 (2) |
C4B | 0.097 (3) | 0.069 (2) | 0.138 (4) | −0.024 (2) | 0.026 (3) | −0.006 (2) |
C5B | 0.080 (2) | 0.088 (3) | 0.104 (3) | −0.0048 (19) | −0.0131 (19) | −0.017 (2) |
C6B | 0.078 (2) | 0.0630 (18) | 0.080 (2) | 0.0045 (15) | −0.0087 (16) | −0.0003 (15) |
N1C | 0.0546 (11) | 0.0516 (11) | 0.0432 (11) | 0.0077 (10) | 0.0040 (9) | −0.0008 (9) |
N2C | 0.0823 (15) | 0.0644 (14) | 0.0375 (11) | 0.0049 (12) | 0.0076 (10) | −0.0009 (9) |
C1C | 0.0518 (13) | 0.0537 (15) | 0.0458 (13) | 0.0177 (12) | 0.0065 (10) | 0.0067 (11) |
C2C | 0.0763 (18) | 0.0622 (17) | 0.0600 (17) | 0.0148 (15) | 0.0184 (14) | 0.0127 (13) |
C3C | 0.076 (2) | 0.071 (2) | 0.071 (2) | 0.0120 (16) | 0.0181 (15) | 0.0180 (16) |
C4C | 0.0746 (19) | 0.0521 (16) | 0.090 (2) | 0.0007 (15) | 0.0000 (17) | 0.0120 (15) |
C5C | 0.0654 (17) | 0.0604 (17) | 0.0652 (17) | 0.0091 (14) | 0.0010 (13) | −0.0031 (13) |
N1D | 0.0571 (12) | 0.0664 (14) | 0.0494 (13) | 0.0023 (10) | 0.0073 (10) | −0.0040 (10) |
N2D | 0.090 (2) | 0.159 (3) | 0.083 (2) | 0.007 (2) | 0.0104 (16) | −0.069 (2) |
C1D | 0.0734 (18) | 0.0716 (18) | 0.0533 (16) | −0.0072 (15) | 0.0222 (14) | −0.0103 (13) |
C2D | 0.089 (2) | 0.0636 (18) | 0.098 (2) | −0.0018 (17) | 0.051 (2) | −0.0080 (17) |
C3D | 0.0608 (19) | 0.073 (2) | 0.125 (3) | 0.0054 (16) | 0.027 (2) | 0.019 (2) |
C4D | 0.0611 (18) | 0.087 (2) | 0.103 (3) | 0.0153 (17) | 0.0020 (17) | 0.010 (2) |
C5D | 0.0647 (17) | 0.0790 (19) | 0.0659 (18) | 0.0073 (15) | −0.0051 (14) | −0.0002 (15) |
Geometric parameters (Å, º) top
Co1—O1A | 2.0690 (17) | C1B—C6B | 1.363 (4) |
Co1—O1B | 2.0708 (17) | C1B—C2B | 1.378 (4) |
Co1—O2B | 2.075 (2) | C2B—C3B | 1.365 (5) |
Co1—O2A | 2.0992 (18) | C3B—C4B | 1.382 (5) |
Co1—N1D | 2.146 (2) | C4B—C5B | 1.342 (5) |
Co1—N1C | 2.152 (2) | C5B—C6B | 1.390 (4) |
O1A—N1A | 1.310 (2) | N1C—C1C | 1.341 (3) |
O2A—N2A | 1.292 (3) | N1C—C5C | 1.353 (3) |
N1A—N2A | 1.288 (3) | N2C—C1C | 1.333 (3) |
N1A—C1A | 1.435 (3) | C1C—C2C | 1.411 (3) |
C1A—C6A | 1.372 (4) | C2C—C3C | 1.340 (4) |
C1A—C2A | 1.378 (4) | C3C—C4C | 1.390 (4) |
C2A—C3A | 1.369 (4) | C4C—C5C | 1.358 (4) |
C3A—C4A | 1.358 (5) | N1D—C1D | 1.323 (3) |
C4A—C5A | 1.378 (5) | N1D—C5D | 1.347 (3) |
C5A—C6A | 1.366 (4) | N2D—C1D | 1.328 (4) |
O1B—N1B | 1.307 (2) | C1D—C2D | 1.425 (4) |
O2B—N2B | 1.271 (3) | C2D—C3D | 1.341 (5) |
N1B—N2B | 1.287 (3) | C3D—C4D | 1.358 (5) |
N1B—C1B | 1.443 (3) | C4D—C5D | 1.349 (4) |
| | | |
O1A—Co1—O1B | 157.94 (7) | N2B—N1B—C1B | 117.5 (2) |
O1A—Co1—O2B | 87.63 (8) | O1B—N1B—C1B | 119.1 (2) |
O1B—Co1—O2B | 75.63 (8) | O2B—N2B—N1B | 114.8 (2) |
O1A—Co1—O2A | 73.80 (7) | C6B—C1B—C2B | 121.8 (3) |
O1B—Co1—O2A | 91.65 (7) | C6B—C1B—N1B | 118.9 (2) |
O2B—Co1—O2A | 89.96 (8) | C2B—C1B—N1B | 119.3 (3) |
O1A—Co1—N1D | 99.04 (8) | C3B—C2B—C1B | 118.6 (3) |
O1B—Co1—N1D | 96.21 (8) | C2B—C3B—C4B | 120.3 (3) |
O2B—Co1—N1D | 93.32 (9) | C5B—C4B—C3B | 120.2 (3) |
O2A—Co1—N1D | 172.01 (8) | C4B—C5B—C6B | 120.9 (4) |
O1A—Co1—N1C | 97.84 (8) | C1B—C6B—C5B | 118.1 (3) |
O1B—Co1—N1C | 98.52 (7) | C1C—N1C—C5C | 117.6 (2) |
O2B—Co1—N1C | 174.11 (8) | C1C—N1C—Co1 | 127.42 (16) |
O2A—Co1—N1C | 89.46 (7) | C5C—N1C—Co1 | 113.33 (17) |
N1D—Co1—N1C | 88.01 (8) | N2C—C1C—N1C | 118.9 (2) |
N1A—O1A—Co1 | 109.75 (13) | N2C—C1C—C2C | 120.6 (2) |
N2A—O2A—Co1 | 114.62 (14) | N1C—C1C—C2C | 120.5 (3) |
N2A—N1A—O1A | 122.8 (2) | C3C—C2C—C1C | 120.3 (3) |
N2A—N1A—C1A | 118.5 (2) | C2C—C3C—C4C | 119.4 (3) |
O1A—N1A—C1A | 118.70 (19) | C5C—C4C—C3C | 118.0 (3) |
N1A—N2A—O2A | 112.9 (2) | N1C—C5C—C4C | 124.0 (3) |
C6A—C1A—C2A | 120.4 (2) | C1D—N1D—C5D | 117.6 (2) |
C6A—C1A—N1A | 118.7 (2) | C1D—N1D—Co1 | 128.21 (19) |
C2A—C1A—N1A | 120.8 (2) | C5D—N1D—Co1 | 114.11 (18) |
C3A—C2A—C1A | 118.8 (3) | N1D—C1D—N2D | 118.6 (3) |
C4A—C3A—C2A | 121.3 (3) | N1D—C1D—C2D | 120.9 (3) |
C3A—C4A—C5A | 119.5 (3) | N2D—C1D—C2D | 120.6 (3) |
C6A—C5A—C4A | 120.1 (3) | C3D—C2D—C1D | 118.8 (3) |
C5A—C6A—C1A | 119.8 (3) | C2D—C3D—C4D | 120.3 (3) |
N1B—O1B—Co1 | 109.59 (14) | C5D—C4D—C3D | 118.6 (3) |
N2B—O2B—Co1 | 115.27 (16) | N1D—C5D—C4D | 123.9 (3) |
N2B—N1B—O1B | 123.4 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2C—H2C1···O1B | 0.86 | 2.07 | 2.886 (3) | 159 |
N2D—H2D1···O1A | 0.86 | 1.98 | 2.812 (3) | 161 |
N2C—H2C2···O2Ai | 0.86 | 2.17 | 2.984 (3) | 157 |
N2D—H2D2···O2Bii | 0.86 | 2.35 | 3.198 (3) | 171 |
N2D—H2D2···N2Bii | 0.86 | 2.21 | 2.990 (3) | 152 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+3/2, y−1/2, −z+3/2. |
(niapir) 'di(2-aminopyridine)-bis(
N-nitroso-
N-phenylhydroxylaminato)-nickel(II)'
top
Crystal data top
C22H22N8NiO4 | F(000) = 1080 |
Mr = 521.19 | Dx = 1.452 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.321 (1) Å | Cell parameters from 25 reflections |
b = 11.535 (2) Å | θ = 14.3–18.4° |
c = 24.852 (2) Å | µ = 0.86 mm−1 |
β = 91.55 (1)° | T = 293 K |
V = 2384.5 (5) Å3 | Prism, green |
Z = 4 | 0.65 × 0.40 × 0.30 mm |
Data collection top
Enraf-Nonius CAd4 diffractometer | 3620 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.017 |
Graphite monochromator | θmax = 30.0°, θmin = 2.4° |
ω–2θ scans | h = 0→11 |
Absorption correction: ψ scan MolEN, Structure Determination System. Enraf-Nonius, 1990) | k = 0→16 |
Tmin = 0.876, Tmax = 1 | l = −34→34 |
7525 measured reflections | 3 standard reflections every 60 min |
6888 independent reflections | intensity decay: 4% |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.036 | w = 1/[σ2(Fo2) + (0.0484P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.095 | (Δ/σ)max = 0.001 |
S = 0.93 | Δρmax = 0.33 e Å−3 |
6888 reflections | Δρmin = −0.27 e Å−3 |
316 parameters | |
Crystal data top
C22H22N8NiO4 | V = 2384.5 (5) Å3 |
Mr = 521.19 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.321 (1) Å | µ = 0.86 mm−1 |
b = 11.535 (2) Å | T = 293 K |
c = 24.852 (2) Å | 0.65 × 0.40 × 0.30 mm |
β = 91.55 (1)° | |
Data collection top
Enraf-Nonius CAd4 diffractometer | 3620 reflections with I > 2σ(I) |
Absorption correction: ψ scan MolEN, Structure Determination System. Enraf-Nonius, 1990) | Rint = 0.017 |
Tmin = 0.876, Tmax = 1 | 3 standard reflections every 60 min |
7525 measured reflections | intensity decay: 4% |
6888 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | Δρmax = 0.33 e Å−3 |
6888 reflections | Δρmin = −0.27 e Å−3 |
316 parameters | |
Special details top
Experimental. this compound is isostructural with the analogous Co(II) complex |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ni1 | 0.66627 (3) | 0.41821 (2) | 0.872731 (9) | 0.04894 (9) | |
O1A | 0.49723 (16) | 0.34994 (12) | 0.82018 (5) | 0.0579 (3) | |
O2A | 0.45975 (17) | 0.51374 (12) | 0.88548 (5) | 0.0624 (4) | |
N1A | 0.38060 (19) | 0.42625 (14) | 0.81286 (6) | 0.0509 (4) | |
N2A | 0.3562 (2) | 0.51052 (15) | 0.84567 (6) | 0.0591 (4) | |
C1A | 0.2762 (2) | 0.41478 (17) | 0.76617 (7) | 0.0526 (4) | |
C2A | 0.1348 (3) | 0.4765 (2) | 0.76241 (9) | 0.0704 (6) | |
H2A | 0.1062 | 0.5268 | 0.7898 | 0.091* | |
C3A | 0.0365 (3) | 0.4625 (3) | 0.71747 (12) | 0.0898 (8) | |
H3A | −0.0594 | 0.5037 | 0.7144 | 0.117* | |
C4A | 0.0791 (3) | 0.3879 (3) | 0.67689 (10) | 0.0904 (9) | |
H4A | 0.0121 | 0.3790 | 0.6466 | 0.118* | |
C5A | 0.2194 (3) | 0.3271 (3) | 0.68117 (10) | 0.0866 (8) | |
H5A | 0.2484 | 0.2773 | 0.6537 | 0.113* | |
C6A | 0.3187 (3) | 0.3394 (2) | 0.72632 (9) | 0.0686 (6) | |
H6A | 0.4135 | 0.2969 | 0.7296 | 0.089* | |
O1B | 0.80078 (16) | 0.54060 (11) | 0.91317 (5) | 0.0550 (3) | |
O2B | 0.7211 (2) | 0.53312 (14) | 0.81327 (5) | 0.0700 (4) | |
N1B | 0.8227 (2) | 0.62988 (14) | 0.88091 (6) | 0.0524 (4) | |
N2B | 0.7871 (2) | 0.62687 (18) | 0.82984 (7) | 0.0664 (5) | |
C1B | 0.8934 (2) | 0.73362 (17) | 0.90198 (8) | 0.0548 (5) | |
C2B | 0.8625 (3) | 0.8378 (2) | 0.87642 (10) | 0.0744 (6) | |
H2B | 0.7945 | 0.8410 | 0.8462 | 0.097* | |
C3B | 0.9344 (4) | 0.9369 (2) | 0.89653 (13) | 0.0914 (9) | |
H3B | 0.9139 | 1.0080 | 0.8801 | 0.119* | |
C4B | 1.0365 (4) | 0.9308 (2) | 0.94109 (15) | 0.0952 (9) | |
H4B | 1.0880 | 0.9974 | 0.9537 | 0.124* | |
C5B | 1.0627 (3) | 0.8277 (3) | 0.96690 (12) | 0.0877 (8) | |
H5B | 1.1292 | 0.8248 | 0.9976 | 0.114* | |
C6B | 0.9904 (3) | 0.7276 (2) | 0.94745 (10) | 0.0709 (6) | |
H6B | 1.0072 | 0.6572 | 0.9649 | 0.092* | |
N1C | 0.60937 (18) | 0.30755 (13) | 0.93652 (6) | 0.0497 (4) | |
N2C | 0.6679 (2) | 0.43514 (14) | 1.00605 (6) | 0.0605 (4) | |
H2C1 | 0.7208 | 0.4769 | 0.9840 | 0.073* | |
H2C2 | 0.6612 | 0.4560 | 1.0391 | 0.073* | |
C1C | 0.5960 (2) | 0.33741 (16) | 0.98887 (7) | 0.0504 (4) | |
C2C | 0.5112 (3) | 0.2669 (2) | 1.02438 (9) | 0.0667 (6) | |
H2C | 0.4978 | 0.2903 | 1.0598 | 0.087* | |
C3C | 0.4494 (3) | 0.1652 (2) | 1.00705 (10) | 0.0715 (6) | |
H3C | 0.3910 | 0.1191 | 1.0302 | 0.093* | |
C4C | 0.4732 (3) | 0.12964 (19) | 0.95435 (10) | 0.0696 (6) | |
H4C | 0.4370 | 0.0577 | 0.9422 | 0.090* | |
C5C | 0.5508 (3) | 0.20283 (18) | 0.92121 (9) | 0.0606 (5) | |
H5C | 0.5646 | 0.1797 | 0.8858 | 0.079* | |
N1D | 0.86621 (19) | 0.31411 (14) | 0.85667 (6) | 0.0537 (4) | |
N2D | 0.7608 (3) | 0.2348 (2) | 0.77907 (8) | 0.1065 (9) | |
H2D1 | 0.6737 | 0.2731 | 0.7840 | 0.128* | |
H2D2 | 0.7685 | 0.1905 | 0.7514 | 0.128* | |
C1D | 0.8838 (3) | 0.24414 (18) | 0.81426 (8) | 0.0618 (5) | |
C2D | 1.0278 (3) | 0.1816 (2) | 0.80765 (11) | 0.0778 (7) | |
H2D | 1.0395 | 0.1337 | 0.7779 | 0.101* | |
C3D | 1.1490 (3) | 0.1918 (2) | 0.84487 (12) | 0.0803 (7) | |
H3D | 1.2442 | 0.1509 | 0.8409 | 0.104* | |
C4D | 1.1303 (3) | 0.2626 (2) | 0.88831 (11) | 0.0809 (7) | |
H4D | 1.2121 | 0.2706 | 0.9143 | 0.105* | |
C5D | 0.9903 (3) | 0.3207 (2) | 0.89263 (9) | 0.0665 (6) | |
H5D | 0.9787 | 0.3686 | 0.9224 | 0.086* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.05824 (15) | 0.05740 (15) | 0.03106 (11) | 0.00112 (12) | −0.00096 (9) | −0.00355 (11) |
O1A | 0.0621 (8) | 0.0640 (8) | 0.0471 (7) | 0.0111 (7) | −0.0075 (6) | −0.0089 (6) |
O2A | 0.0748 (9) | 0.0689 (9) | 0.0432 (7) | 0.0124 (7) | −0.0047 (7) | −0.0099 (7) |
N1A | 0.0550 (9) | 0.0569 (9) | 0.0407 (8) | −0.0004 (8) | −0.0010 (7) | 0.0006 (7) |
N2A | 0.0695 (11) | 0.0638 (11) | 0.0439 (9) | 0.0082 (9) | −0.0010 (8) | −0.0013 (8) |
C1A | 0.0521 (11) | 0.0631 (12) | 0.0425 (9) | −0.0123 (10) | −0.0013 (8) | 0.0078 (9) |
C2A | 0.0633 (14) | 0.0800 (15) | 0.0672 (14) | 0.0025 (12) | −0.0071 (11) | −0.0014 (12) |
C3A | 0.0606 (15) | 0.120 (2) | 0.088 (2) | 0.0018 (15) | −0.0183 (13) | 0.0050 (17) |
C4A | 0.0687 (16) | 0.142 (3) | 0.0600 (15) | −0.0201 (17) | −0.0173 (12) | 0.0046 (16) |
C5A | 0.0777 (17) | 0.127 (2) | 0.0545 (14) | −0.0123 (16) | −0.0060 (12) | −0.0177 (14) |
C6A | 0.0636 (13) | 0.0926 (17) | 0.0492 (12) | −0.0007 (12) | −0.0032 (10) | −0.0093 (11) |
O1B | 0.0749 (9) | 0.0529 (7) | 0.0369 (6) | −0.0073 (7) | −0.0042 (6) | 0.0068 (6) |
O2B | 0.0919 (11) | 0.0817 (10) | 0.0362 (7) | −0.0063 (9) | −0.0034 (7) | 0.0053 (7) |
N1B | 0.0606 (10) | 0.0549 (9) | 0.0419 (8) | 0.0002 (8) | 0.0033 (7) | 0.0089 (7) |
N2B | 0.0793 (12) | 0.0761 (12) | 0.0439 (10) | −0.0004 (10) | 0.0014 (9) | 0.0138 (9) |
C1B | 0.0528 (11) | 0.0550 (12) | 0.0572 (12) | 0.0022 (9) | 0.0102 (9) | 0.0065 (9) |
C2B | 0.0817 (16) | 0.0646 (14) | 0.0775 (16) | −0.0009 (12) | 0.0129 (13) | 0.0216 (12) |
C3B | 0.108 (2) | 0.0680 (17) | 0.099 (2) | −0.0078 (15) | 0.0261 (18) | 0.0192 (15) |
C4B | 0.099 (2) | 0.0709 (18) | 0.117 (3) | −0.0250 (16) | 0.0278 (19) | −0.0092 (17) |
C5B | 0.0817 (17) | 0.0842 (19) | 0.096 (2) | −0.0043 (15) | −0.0113 (15) | −0.0188 (16) |
C6B | 0.0770 (15) | 0.0607 (13) | 0.0742 (15) | 0.0053 (12) | −0.0112 (12) | −0.0005 (11) |
N1C | 0.0565 (9) | 0.0524 (9) | 0.0404 (8) | 0.0065 (7) | 0.0030 (7) | −0.0003 (7) |
N2C | 0.0812 (12) | 0.0655 (11) | 0.0351 (8) | 0.0017 (9) | 0.0055 (8) | −0.0029 (7) |
C1C | 0.0590 (11) | 0.0533 (11) | 0.0390 (9) | 0.0169 (9) | 0.0037 (8) | 0.0058 (8) |
C2C | 0.0800 (15) | 0.0671 (14) | 0.0537 (12) | 0.0156 (12) | 0.0165 (11) | 0.0150 (10) |
C3C | 0.0773 (15) | 0.0633 (14) | 0.0746 (16) | 0.0091 (12) | 0.0159 (12) | 0.0198 (12) |
C4C | 0.0769 (15) | 0.0495 (12) | 0.0823 (17) | 0.0019 (11) | −0.0007 (13) | 0.0077 (11) |
C5C | 0.0679 (13) | 0.0563 (12) | 0.0573 (12) | 0.0062 (10) | −0.0004 (10) | −0.0009 (10) |
N1D | 0.0575 (10) | 0.0618 (10) | 0.0420 (9) | 0.0019 (8) | 0.0064 (7) | −0.0033 (7) |
N2D | 0.0875 (15) | 0.157 (2) | 0.0750 (14) | 0.0033 (15) | 0.0055 (12) | −0.0682 (15) |
C1D | 0.0679 (13) | 0.0660 (13) | 0.0525 (12) | −0.0087 (11) | 0.0185 (10) | −0.0109 (10) |
C2D | 0.0862 (17) | 0.0613 (14) | 0.0880 (18) | −0.0034 (13) | 0.0426 (15) | −0.0095 (13) |
C3D | 0.0685 (16) | 0.0656 (15) | 0.108 (2) | 0.0099 (12) | 0.0251 (15) | 0.0127 (15) |
C4D | 0.0657 (15) | 0.0867 (18) | 0.0903 (18) | 0.0129 (13) | 0.0005 (13) | 0.0078 (15) |
C5D | 0.0663 (14) | 0.0762 (15) | 0.0567 (13) | 0.0089 (12) | −0.0018 (10) | −0.0011 (11) |
Geometric parameters (Å, º) top
Ni1—O2B | 2.0458 (15) | C1B—C6B | 1.372 (3) |
Ni1—O1B | 2.0481 (13) | C1B—C2B | 1.380 (3) |
Ni1—O1A | 2.0506 (13) | C2B—C3B | 1.378 (4) |
Ni1—O2A | 2.0730 (14) | C3B—C4B | 1.380 (4) |
Ni1—N1D | 2.0988 (16) | C4B—C5B | 1.366 (4) |
Ni1—N1C | 2.0994 (15) | C5B—C6B | 1.384 (3) |
O1A—N1A | 1.3192 (19) | N1C—C5C | 1.353 (3) |
O2A—N2A | 1.295 (2) | N1C—C1C | 1.353 (2) |
N1A—N2A | 1.288 (2) | N2C—C1C | 1.341 (2) |
N1A—C1A | 1.436 (2) | C1C—C2C | 1.404 (3) |
C1A—C6A | 1.372 (3) | C2C—C3C | 1.346 (3) |
C1A—C2A | 1.376 (3) | C3C—C4C | 1.392 (3) |
C2A—C3A | 1.376 (3) | C4C—C5C | 1.355 (3) |
C3A—C4A | 1.379 (4) | N1D—C1D | 1.339 (2) |
C4A—C5A | 1.364 (4) | N1D—C5D | 1.350 (3) |
C5A—C6A | 1.383 (3) | N2D—C1D | 1.332 (3) |
O1B—N1B | 1.3207 (19) | C1D—C2D | 1.412 (3) |
O2B—N2B | 1.276 (2) | C2D—C3D | 1.355 (4) |
N1B—N2B | 1.296 (2) | C3D—C4D | 1.366 (4) |
N1B—C1B | 1.427 (3) | C4D—C5D | 1.351 (3) |
| | | |
O2B—Ni1—O1B | 77.19 (6) | N2B—N1B—C1B | 117.57 (16) |
O2B—Ni1—O1A | 87.21 (6) | O1B—N1B—C1B | 119.58 (15) |
O1B—Ni1—O1A | 159.00 (5) | O2B—N2B—N1B | 115.07 (16) |
O2B—Ni1—O2A | 88.17 (6) | C6B—C1B—C2B | 121.4 (2) |
O1B—Ni1—O2A | 90.16 (6) | C6B—C1B—N1B | 119.14 (18) |
O1A—Ni1—O2A | 75.19 (5) | C2B—C1B—N1B | 119.5 (2) |
O2B—Ni1—N1D | 92.28 (6) | C3B—C2B—C1B | 118.8 (2) |
O1B—Ni1—N1D | 93.57 (6) | C2B—C3B—C4B | 120.0 (2) |
O1A—Ni1—N1D | 101.12 (6) | C5B—C4B—C3B | 120.6 (2) |
O2A—Ni1—N1D | 176.25 (6) | C4B—C5B—C6B | 120.0 (3) |
O2B—Ni1—N1C | 177.04 (6) | C1B—C6B—C5B | 119.1 (2) |
O1B—Ni1—N1C | 100.37 (5) | C5C—N1C—C1C | 117.33 (17) |
O1A—Ni1—N1C | 94.74 (6) | C5C—N1C—Ni1 | 114.66 (13) |
O2A—Ni1—N1C | 90.17 (6) | C1C—N1C—Ni1 | 126.68 (13) |
N1D—Ni1—N1C | 89.53 (6) | N2C—C1C—N1C | 118.19 (17) |
N1A—O1A—Ni1 | 108.72 (10) | N2C—C1C—C2C | 120.97 (18) |
N2A—O2A—Ni1 | 113.91 (11) | N1C—C1C—C2C | 120.83 (19) |
N2A—N1A—O1A | 122.98 (15) | C3C—C2C—C1C | 119.8 (2) |
N2A—N1A—C1A | 118.58 (16) | C2C—C3C—C4C | 119.7 (2) |
O1A—N1A—C1A | 118.44 (15) | C5C—C4C—C3C | 118.1 (2) |
N1A—N2A—O2A | 113.07 (15) | N1C—C5C—C4C | 124.0 (2) |
C6A—C1A—C2A | 121.03 (19) | C1D—N1D—C5D | 117.23 (18) |
C6A—C1A—N1A | 118.66 (18) | C1D—N1D—Ni1 | 126.77 (14) |
C2A—C1A—N1A | 120.29 (19) | C5D—N1D—Ni1 | 115.99 (13) |
C3A—C2A—C1A | 118.9 (2) | N2D—C1D—N1D | 117.8 (2) |
C2A—C3A—C4A | 120.5 (2) | N2D—C1D—C2D | 121.5 (2) |
C5A—C4A—C3A | 120.0 (2) | N1D—C1D—C2D | 120.7 (2) |
C4A—C5A—C6A | 120.1 (2) | C3D—C2D—C1D | 119.6 (2) |
C1A—C6A—C5A | 119.4 (2) | C2D—C3D—C4D | 119.6 (2) |
N1B—O1B—Ni1 | 108.80 (10) | C5D—C4D—C3D | 118.4 (2) |
N2B—O2B—Ni1 | 114.72 (11) | N1D—C5D—C4D | 124.4 (2) |
N2B—N1B—O1B | 122.82 (17) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2C—H2C1···O1B | 0.86 | 2.04 | 2.858 (2) | 160 |
N2D—H2D1···O1A | 0.86 | 1.96 | 2.782 (3) | 161 |
N2C—H2C2···O2Ai | 0.86 | 2.18 | 2.983 (2) | 156 |
N2D—H2D2···O2Bii | 0.86 | 2.43 | 3.274 (2) | 168 |
N2D—H2D2···N2Bii | 0.86 | 2.19 | 2.996 (2) | 157 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+3/2, y−1/2, −z+3/2. |
(codpt) 'Di-(2,6-diamino-4-phenyl-1,3,5-triazine)-bis(
N-nitroso-N–
phenylhydroxylaminato)-cobalt(II) di-ethanol-bis(
N-nitroso-N–
phenylhydroxylaminato)-cobalt(II)'
top
Crystal data top
C23H25CoN9O5 | Z = 2 |
Mr = 566.45 | F(000) = 586 |
Triclinic, P1 | Dx = 1.479 Mg m−3 |
a = 10.225 (1) Å | Mo Kα radiation, λ = 0.71070 Å |
b = 10.214 (2) Å | Cell parameters from 25 reflections |
c = 14.163 (1) Å | θ = 14.0–14.9° |
α = 73.340 (9)° | µ = 0.73 mm−1 |
β = 68.180 (8)° | T = 293 K |
γ = 70.450 (13)° | Prism, dark-orange |
V = 1271.6 (3) Å3 | 0.50 × 0.25 × 0.25 mm |
Data collection top
Enraf-Nonius CAD4 diffractometer | 7753 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.013 |
Graphite monochromator | θmax = 35.0°, θmin = 2.2° |
ω–2θ scans | h = −16→16 |
Absorption correction: ψ scan MolEN, Structure Determination System. Enraf-Nonius, 1990) | k = −16→16 |
Tmin = 0.889, Tmax = 1 | l = −22→22 |
23705 measured reflections | 3 standard reflections every 60 min |
11074 independent reflections | intensity decay: 4% |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.036 | w = 1/[σ2(Fo2) + (0.0683P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.106 | (Δ/σ)max < 0.001 |
S = 0.98 | Δρmax = 0.64 e Å−3 |
11074 reflections | Δρmin = −0.46 e Å−3 |
360 parameters | |
Crystal data top
C23H25CoN9O5 | γ = 70.450 (13)° |
Mr = 566.45 | V = 1271.6 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.225 (1) Å | Mo Kα radiation |
b = 10.214 (2) Å | µ = 0.73 mm−1 |
c = 14.163 (1) Å | T = 293 K |
α = 73.340 (9)° | 0.50 × 0.25 × 0.25 mm |
β = 68.180 (8)° | |
Data collection top
Enraf-Nonius CAD4 diffractometer | 7753 reflections with I > 2σ(I) |
Absorption correction: ψ scan MolEN, Structure Determination System. Enraf-Nonius, 1990) | Rint = 0.013 |
Tmin = 0.889, Tmax = 1 | 3 standard reflections every 60 min |
23705 measured reflections | intensity decay: 4% |
11074 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.98 | Δρmax = 0.64 e Å−3 |
11074 reflections | Δρmin = −0.46 e Å−3 |
360 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Co1 | 0.5000 | 1.0000 | 0.5000 | 0.02564 (5) | |
N1A | 0.38326 (10) | 1.19585 (10) | 0.63098 (7) | 0.03233 (17) | |
N2A | 0.31499 (11) | 1.10040 (11) | 0.68729 (7) | 0.03554 (19) | |
O1A | 0.47578 (9) | 1.18812 (8) | 0.53713 (6) | 0.03358 (15) | |
O2A | 0.34867 (9) | 0.99251 (8) | 0.64424 (6) | 0.03227 (15) | |
C1A | 0.35251 (13) | 1.31944 (13) | 0.67309 (9) | 0.0379 (2) | |
C2A | 0.3185 (2) | 1.3104 (2) | 0.77839 (11) | 0.0611 (4) | |
H2A | 0.3155 | 1.2239 | 0.8232 | 0.079* | |
C3A | 0.2889 (2) | 1.4311 (2) | 0.81652 (13) | 0.0721 (5) | |
H3A | 0.2671 | 1.4254 | 0.8872 | 0.094* | |
C4A | 0.29137 (19) | 1.5593 (2) | 0.75083 (14) | 0.0652 (5) | |
H4A | 0.2694 | 1.6403 | 0.7772 | 0.085* | |
C5A | 0.3264 (2) | 1.56773 (17) | 0.64575 (15) | 0.0619 (4) | |
H5A | 0.3293 | 1.6544 | 0.6013 | 0.081* | |
C6A | 0.35757 (17) | 1.44727 (14) | 0.60573 (11) | 0.0489 (3) | |
H6A | 0.3814 | 1.4527 | 0.5349 | 0.064* | |
N1B | 0.67461 (9) | 0.89881 (9) | 0.57653 (6) | 0.02890 (16) | |
N3B | 0.72022 (10) | 0.78253 (10) | 0.73848 (7) | 0.03336 (18) | |
N5B | 0.86067 (10) | 0.93883 (10) | 0.62033 (7) | 0.03169 (17) | |
N2B | 0.57089 (12) | 0.71853 (11) | 0.68169 (8) | 0.0415 (2) | |
H2B1 | 0.5285 | 0.7281 | 0.6369 | 0.054* | |
H2B2 | 0.5576 | 0.6556 | 0.7372 | 0.054* | |
N6B | 0.82505 (10) | 1.03854 (11) | 0.46191 (7) | 0.03482 (19) | |
H6B1 | 0.7803 | 1.0527 | 0.4177 | 0.045* | |
H6B2 | 0.8954 | 1.0768 | 0.4464 | 0.045* | |
C7B | 0.88620 (12) | 0.84949 (12) | 0.79025 (8) | 0.0335 (2) | |
C8B | 0.89527 (14) | 0.73386 (14) | 0.87116 (10) | 0.0424 (3) | |
H8B | 0.8568 | 0.6599 | 0.8778 | 0.055* | |
C9B | 0.96179 (16) | 0.72961 (17) | 0.94150 (11) | 0.0510 (3) | |
H9B | 0.9683 | 0.6522 | 0.9951 | 0.066* | |
C10 | 1.01847 (18) | 0.83884 (18) | 0.93289 (11) | 0.0540 (3) | |
H10B | 1.0624 | 0.8351 | 0.9809 | 0.070* | |
C11B | 1.01017 (18) | 0.95429 (18) | 0.85288 (11) | 0.0536 (3) | |
H11B | 1.0491 | 1.0276 | 0.8468 | 0.070* | |
C12B | 0.94341 (15) | 0.96033 (14) | 0.78153 (9) | 0.0422 (3) | |
H12B | 0.9370 | 1.0381 | 0.7281 | 0.055* | |
C2B | 0.65685 (11) | 0.80099 (11) | 0.66506 (8) | 0.02988 (18) | |
C4B | 0.81714 (11) | 0.85785 (11) | 0.71232 (8) | 0.02985 (18) | |
C6B | 0.78537 (10) | 0.95738 (11) | 0.55442 (7) | 0.02777 (17) | |
Co2 | 0.5000 | 0.5000 | 1.0000 | 0.03589 (6) | |
N1C | 0.73154 (11) | 0.41686 (10) | 0.82994 (7) | 0.03597 (19) | |
O1C | 0.58834 (10) | 0.46681 (10) | 0.85274 (6) | 0.03897 (17) | |
N2C | 0.80358 (12) | 0.39799 (13) | 0.89313 (8) | 0.0444 (2) | |
O2C | 0.72266 (11) | 0.43358 (12) | 0.98057 (7) | 0.0495 (2) | |
C1C | 0.80906 (14) | 0.37803 (13) | 0.73042 (9) | 0.0409 (2) | |
C2C | 0.73077 (19) | 0.34609 (16) | 0.68257 (11) | 0.0532 (3) | |
H2C | 0.6326 | 0.3487 | 0.7146 | 0.069* | |
C3C | 0.8028 (2) | 0.31005 (19) | 0.58538 (14) | 0.0712 (5) | |
H3C | 0.7532 | 0.2859 | 0.5523 | 0.093* | |
C4C | 0.9474 (3) | 0.3099 (2) | 0.53759 (14) | 0.0816 (7) | |
H4C | 0.9937 | 0.2901 | 0.4711 | 0.106* | |
C5C | 1.0221 (2) | 0.3385 (2) | 0.58727 (14) | 0.0788 (6) | |
H5C | 1.1208 | 0.3337 | 0.5555 | 0.102* | |
C6C | 0.95473 (18) | 0.37501 (19) | 0.68483 (12) | 0.0588 (4) | |
H6C | 1.0060 | 0.3966 | 0.7180 | 0.077* | |
O1D | 0.52678 (15) | 0.70957 (11) | 0.94015 (9) | 0.0613 (3) | |
H1D | 0.589 (3) | 0.730 (3) | 0.885 (2) | 0.092* | |
C1DX | 0.4549 (5) | 0.8301 (3) | 0.9885 (3) | 0.0890 (15) | 0.738 (9) |
H1D1 | 0.5551 | 0.8323 | 0.9719 | 0.107* | 0.738 (9) |
H1D2 | 0.4126 | 0.7760 | 1.0552 | 0.107* | 0.738 (9) |
C1DY | 0.4112 (9) | 0.8499 (8) | 0.9295 (9) | 0.077 (3) | 0.262 (9) |
H1D3 | 0.4382 | 0.9230 | 0.8706 | 0.092* | 0.262 (9) |
H1D4 | 0.3111 | 0.8455 | 0.9487 | 0.092* | 0.262 (9) |
C2D | 0.3686 (5) | 0.9315 (5) | 0.9409 (6) | 0.231 (3) | |
H2D1 | 0.4187 | 1.0025 | 0.8981 | 0.347* | |
H2D2 | 0.2826 | 0.9732 | 0.9914 | 0.347* | |
H2D3 | 0.3415 | 0.8928 | 0.8987 | 0.347* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.02650 (9) | 0.02858 (9) | 0.02481 (8) | −0.01247 (6) | −0.00845 (6) | −0.00209 (6) |
N1A | 0.0341 (4) | 0.0376 (4) | 0.0291 (4) | −0.0147 (3) | −0.0081 (3) | −0.0074 (3) |
N2A | 0.0365 (4) | 0.0439 (5) | 0.0297 (4) | −0.0196 (4) | −0.0054 (3) | −0.0073 (3) |
O1A | 0.0386 (4) | 0.0358 (4) | 0.0280 (3) | −0.0174 (3) | −0.0044 (3) | −0.0066 (3) |
O2A | 0.0347 (4) | 0.0368 (4) | 0.0287 (3) | −0.0169 (3) | −0.0085 (3) | −0.0035 (3) |
C1A | 0.0369 (5) | 0.0443 (6) | 0.0386 (5) | −0.0163 (4) | −0.0069 (4) | −0.0161 (4) |
C2A | 0.0849 (11) | 0.0698 (10) | 0.0393 (6) | −0.0420 (9) | −0.0052 (7) | −0.0181 (6) |
C3A | 0.0843 (12) | 0.0939 (13) | 0.0514 (8) | −0.0485 (11) | 0.0075 (8) | −0.0405 (9) |
C4A | 0.0575 (9) | 0.0700 (10) | 0.0797 (11) | −0.0288 (8) | 0.0021 (8) | −0.0471 (9) |
C5A | 0.0719 (10) | 0.0453 (7) | 0.0795 (11) | −0.0175 (7) | −0.0250 (9) | −0.0222 (7) |
C6A | 0.0621 (8) | 0.0423 (6) | 0.0494 (7) | −0.0177 (6) | −0.0181 (6) | −0.0123 (5) |
N1B | 0.0276 (4) | 0.0329 (4) | 0.0299 (4) | −0.0158 (3) | −0.0125 (3) | 0.0031 (3) |
N3B | 0.0346 (4) | 0.0389 (4) | 0.0307 (4) | −0.0190 (3) | −0.0147 (3) | 0.0051 (3) |
N5B | 0.0304 (4) | 0.0424 (4) | 0.0280 (4) | −0.0188 (3) | −0.0118 (3) | 0.0001 (3) |
N2B | 0.0467 (5) | 0.0401 (5) | 0.0476 (5) | −0.0276 (4) | −0.0268 (4) | 0.0137 (4) |
N6B | 0.0340 (4) | 0.0479 (5) | 0.0285 (4) | −0.0248 (4) | −0.0124 (3) | 0.0049 (3) |
C7B | 0.0328 (5) | 0.0427 (5) | 0.0288 (4) | −0.0151 (4) | −0.0129 (4) | −0.0013 (4) |
C8B | 0.0463 (6) | 0.0467 (6) | 0.0400 (6) | −0.0199 (5) | −0.0221 (5) | 0.0047 (5) |
C9B | 0.0534 (7) | 0.0623 (8) | 0.0408 (6) | −0.0173 (6) | −0.0271 (6) | 0.0053 (6) |
C10 | 0.0583 (8) | 0.0743 (10) | 0.0433 (6) | −0.0226 (7) | −0.0288 (6) | −0.0068 (6) |
C11B | 0.0639 (9) | 0.0682 (9) | 0.0484 (7) | −0.0323 (7) | −0.0269 (7) | −0.0086 (6) |
C12B | 0.0517 (7) | 0.0507 (6) | 0.0350 (5) | −0.0254 (5) | −0.0191 (5) | −0.0015 (5) |
C2B | 0.0288 (4) | 0.0307 (4) | 0.0317 (4) | −0.0137 (3) | −0.0127 (3) | 0.0037 (3) |
C4B | 0.0288 (4) | 0.0355 (5) | 0.0281 (4) | −0.0133 (4) | −0.0111 (3) | −0.0010 (3) |
C6B | 0.0255 (4) | 0.0330 (4) | 0.0271 (4) | −0.0135 (3) | −0.0091 (3) | −0.0005 (3) |
Co2 | 0.03992 (11) | 0.03612 (11) | 0.02803 (9) | −0.01189 (8) | −0.00715 (8) | −0.00244 (7) |
N1C | 0.0382 (5) | 0.0366 (4) | 0.0315 (4) | −0.0093 (4) | −0.0108 (4) | −0.0041 (3) |
O1C | 0.0376 (4) | 0.0448 (4) | 0.0328 (4) | −0.0101 (3) | −0.0110 (3) | −0.0049 (3) |
N2C | 0.0438 (5) | 0.0508 (6) | 0.0398 (5) | −0.0102 (4) | −0.0158 (4) | −0.0085 (4) |
O2C | 0.0476 (5) | 0.0653 (6) | 0.0384 (4) | −0.0115 (4) | −0.0165 (4) | −0.0129 (4) |
C1C | 0.0466 (6) | 0.0368 (5) | 0.0337 (5) | −0.0030 (5) | −0.0119 (5) | −0.0078 (4) |
C2C | 0.0659 (9) | 0.0484 (7) | 0.0477 (7) | −0.0042 (6) | −0.0242 (7) | −0.0157 (6) |
C3C | 0.0976 (14) | 0.0601 (9) | 0.0555 (9) | 0.0102 (9) | −0.0368 (9) | −0.0280 (7) |
C4C | 0.0965 (15) | 0.0744 (12) | 0.0469 (8) | 0.0231 (10) | −0.0195 (9) | −0.0282 (8) |
C5C | 0.0633 (11) | 0.0896 (14) | 0.0513 (9) | 0.0054 (9) | 0.0005 (8) | −0.0193 (9) |
C6C | 0.0485 (8) | 0.0703 (10) | 0.0477 (7) | −0.0064 (7) | −0.0083 (6) | −0.0152 (7) |
O1D | 0.0760 (8) | 0.0387 (5) | 0.0507 (6) | −0.0212 (5) | 0.0046 (5) | −0.0055 (4) |
C1DX | 0.140 (3) | 0.0393 (12) | 0.0669 (19) | −0.0177 (15) | −0.014 (2) | −0.0084 (12) |
C1DY | 0.071 (5) | 0.043 (3) | 0.080 (7) | 0.013 (3) | −0.011 (4) | −0.007 (3) |
C2D | 0.138 (4) | 0.105 (3) | 0.451 (10) | 0.046 (3) | −0.118 (5) | −0.107 (5) |
Geometric parameters (Å, º) top
Co1—O1A | 2.0479 (8) | C7B—C12B | 1.3959 (16) |
Co1—O1Ai | 2.0479 (8) | C7B—C4B | 1.4863 (13) |
Co1—O2Ai | 2.0526 (8) | C8B—C9B | 1.3843 (17) |
Co1—O2A | 2.0526 (8) | C9B—C10 | 1.378 (2) |
Co1—N1B | 2.2342 (8) | C10—C11B | 1.386 (2) |
Co1—N1Bi | 2.2342 (8) | C11B—C12B | 1.3928 (16) |
N1A—N2A | 1.2921 (12) | Co2—O1Cii | 2.0200 (9) |
N1A—O1A | 1.3203 (11) | Co2—O1C | 2.0200 (9) |
N1A—C1A | 1.4404 (15) | Co2—O2C | 2.0801 (10) |
N2A—O2A | 1.2962 (13) | Co2—O2Cii | 2.0801 (10) |
C1A—C2A | 1.3821 (18) | Co2—O1Dii | 2.1342 (11) |
C1A—C6A | 1.3827 (19) | Co2—O1D | 2.1342 (11) |
C2A—C3A | 1.384 (2) | N1C—N2C | 1.2949 (14) |
C3A—C4A | 1.374 (3) | N1C—O1C | 1.3235 (14) |
C4A—C5A | 1.379 (3) | N1C—C1C | 1.4324 (15) |
C5A—C6A | 1.393 (2) | N2C—O2C | 1.2827 (15) |
N1B—C6B | 1.3495 (12) | C1C—C6C | 1.379 (2) |
N1B—C2B | 1.3554 (12) | C1C—C2C | 1.383 (2) |
N3B—C4B | 1.3360 (13) | C2C—C3C | 1.389 (2) |
N3B—C2B | 1.3577 (13) | C3C—C4C | 1.378 (3) |
N5B—C4B | 1.3330 (13) | C4C—C5C | 1.353 (3) |
N5B—C6B | 1.3548 (12) | C5C—C6C | 1.392 (2) |
N2B—C2B | 1.3287 (13) | O1D—C1DY | 1.533 (7) |
N6B—C6B | 1.3325 (12) | C1DX—C1DY | 1.028 (11) |
C7B—C8B | 1.3951 (16) | C1DX—C2D | 1.317 (7) |
| | | |
O1A—Co1—O1Ai | 180.000 (1) | N2B—C2B—N1B | 118.01 (9) |
O1A—Co1—O2Ai | 102.99 (3) | N2B—C2B—N3B | 117.74 (9) |
O1Ai—Co1—O2Ai | 77.01 (3) | N1B—C2B—N3B | 124.24 (9) |
O1A—Co1—O2A | 77.01 (3) | N5B—C4B—N3B | 125.43 (9) |
O1Ai—Co1—O2A | 102.99 (3) | N5B—C4B—C7B | 116.28 (9) |
O2Ai—Co1—O2A | 180.0 | N3B—C4B—C7B | 118.27 (9) |
O1A—Co1—N1B | 89.18 (3) | N6B—C6B—N1B | 118.69 (8) |
O1Ai—Co1—N1B | 90.82 (3) | N6B—C6B—N5B | 117.06 (8) |
O2Ai—Co1—N1B | 91.54 (3) | N1B—C6B—N5B | 124.25 (8) |
O2A—Co1—N1B | 88.46 (3) | O1Cii—Co2—O1C | 180.000 (1) |
O1A—Co1—N1Bi | 90.82 (3) | O1Cii—Co2—O2C | 103.38 (4) |
O1Ai—Co1—N1Bi | 89.18 (4) | O1C—Co2—O2C | 76.62 (4) |
O2Ai—Co1—N1Bi | 88.46 (3) | O1Cii—Co2—O2Cii | 76.62 (4) |
O2A—Co1—N1Bi | 91.54 (3) | O1C—Co2—O2Cii | 103.38 (4) |
N1B—Co1—N1Bi | 180.0 | O2C—Co2—O2Cii | 180.0 |
N2A—N1A—O1A | 124.04 (9) | O1Cii—Co2—O1Dii | 87.19 (4) |
N2A—N1A—C1A | 117.30 (9) | O1C—Co2—O1Dii | 92.81 (4) |
O1A—N1A—C1A | 118.64 (8) | O2C—Co2—O1Dii | 92.89 (5) |
N1A—N2A—O2A | 113.63 (9) | O2Cii—Co2—O1Dii | 87.11 (5) |
N1A—O1A—Co1 | 109.60 (6) | O1Cii—Co2—O1D | 92.81 (4) |
N2A—O2A—Co1 | 115.67 (6) | O1C—Co2—O1D | 87.19 (4) |
C2A—C1A—C6A | 120.85 (12) | O2C—Co2—O1D | 87.11 (5) |
C2A—C1A—N1A | 120.72 (12) | O2Cii—Co2—O1D | 92.89 (5) |
C6A—C1A—N1A | 118.43 (10) | O1Dii—Co2—O1D | 180.0 |
C1A—C2A—C3A | 119.35 (16) | N2C—N1C—O1C | 123.79 (10) |
C4A—C3A—C2A | 120.55 (15) | N2C—N1C—C1C | 118.89 (10) |
C3A—C4A—C5A | 119.91 (14) | O1C—N1C—C1C | 117.29 (9) |
C4A—C5A—C6A | 120.43 (16) | N1C—O1C—Co2 | 110.63 (7) |
C1A—C6A—C5A | 118.90 (14) | O2C—N2C—N1C | 113.43 (10) |
C6B—N1B—C2B | 114.46 (8) | N2C—O2C—Co2 | 115.37 (7) |
C6B—N1B—Co1 | 121.09 (6) | C6C—C1C—C2C | 122.18 (13) |
C2B—N1B—Co1 | 122.12 (6) | C6C—C1C—N1C | 120.83 (12) |
C4B—N3B—C2B | 114.74 (8) | C2C—C1C—N1C | 116.98 (12) |
C4B—N5B—C6B | 115.30 (8) | C1C—C2C—C3C | 118.14 (17) |
C8B—C7B—C12B | 119.60 (10) | C4C—C3C—C2C | 120.45 (18) |
C8B—C7B—C4B | 121.60 (10) | C5C—C4C—C3C | 120.07 (16) |
C12B—C7B—C4B | 118.80 (9) | C4C—C5C—C6C | 121.54 (19) |
C9B—C8B—C7B | 119.75 (12) | C1C—C6C—C5C | 117.55 (17) |
C10—C9B—C8B | 120.71 (12) | C1DY—O1D—Co2 | 129.3 (4) |
C9B—C10—C11B | 120.11 (12) | C1DY—C1DX—C2D | 39.2 (5) |
C10—C11B—C12B | 119.92 (13) | C1DX—C1DY—O1D | 64.0 (5) |
C11B—C12B—C7B | 119.92 (12) | | |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+1, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2B—H2B1···O1Ai | 0.86 | 2.38 | 3.1372 (13) | 147 |
N6B—H6B1···O2Ai | 0.86 | 2.05 | 2.8550 (12) | 155 |
N6B—H6B2···N5Biii | 0.86 | 2.28 | 3.0491 (13) | 149 |
N2B—H2B2···O1C | 0.86 | 2.16 | 2.9923 (13) | 163 |
O1D—H1D···N3B | 0.83 (3) | 2.04 (3) | 2.8622 (15) | 171 (2) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (iii) −x+2, −y+2, −z+1. |
Experimental details
| (coapir) | (niapir) | (codpt) |
Crystal data |
Chemical formula | C22H22CoN8O4 | C22H22N8NiO4 | C23H25CoN9O5 |
Mr | 521.41 | 521.19 | 566.45 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n | Triclinic, P1 |
Temperature (K) | 293 | 293 | 293 |
a, b, c (Å) | 8.270 (1), 11.579 (2), 25.019 (4) | 8.321 (1), 11.535 (2), 24.852 (2) | 10.225 (1), 10.214 (2), 14.163 (1) |
α, β, γ (°) | 90, 91.42 (2), 90 | 90, 91.55 (1), 90 | 73.340 (9), 68.180 (8), 70.450 (13) |
V (Å3) | 2395.0 (6) | 2384.5 (5) | 1271.6 (3) |
Z | 4 | 4 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.76 | 0.86 | 0.73 |
Crystal size (mm) | 0.45 × 0.40 × 0.40 | 0.65 × 0.40 × 0.30 | 0.50 × 0.25 × 0.25 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD4 diffractometer | Enraf-Nonius CAd4 diffractometer | Enraf-Nonius CAD4 diffractometer |
Absorption correction | ψ scan MolEN, Structure Determination System. Enraf-Nonius, 1990) | ψ scan MolEN, Structure Determination System. Enraf-Nonius, 1990) | ψ scan MolEN, Structure Determination System. Enraf-Nonius, 1990) |
Tmin, Tmax | 0.945, 1 | 0.876, 1 | 0.889, 1 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6214, 5671, 3093 | 7525, 6888, 3620 | 23705, 11074, 7753 |
Rint | 0.015 | 0.017 | 0.013 |
(sin θ/λ)max (Å−1) | 0.660 | 0.703 | 0.806 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.113, 0.96 | 0.036, 0.095, 0.93 | 0.036, 0.106, 0.98 |
No. of reflections | 5671 | 6888 | 11074 |
No. of parameters | 316 | 316 | 360 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.28 | 0.33, −0.27 | 0.64, −0.46 |
Hydrogen-bond geometry (Å, º) for (coapir) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2C—H2C1···O1B | 0.86 | 2.07 | 2.886 (3) | 158.8 |
N2D—H2D1···O1A | 0.86 | 1.98 | 2.812 (3) | 161.4 |
N2C—H2C2···O2Ai | 0.86 | 2.17 | 2.984 (3) | 157.0 |
N2D—H2D2···O2Bii | 0.86 | 2.35 | 3.198 (3) | 171.3 |
N2D—H2D2···N2Bii | 0.86 | 2.21 | 2.990 (3) | 151.5 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+3/2, y−1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) for (niapir) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2C—H2C1···O1B | 0.86 | 2.04 | 2.858 (2) | 159.8 |
N2D—H2D1···O1A | 0.86 | 1.96 | 2.782 (3) | 160.8 |
N2C—H2C2···O2Ai | 0.86 | 2.18 | 2.983 (2) | 155.6 |
N2D—H2D2···O2Bii | 0.86 | 2.43 | 3.274 (2) | 167.9 |
N2D—H2D2···N2Bii | 0.86 | 2.19 | 2.996 (2) | 156.8 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+3/2, y−1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) for (codpt) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2B—H2B1···O1Ai | 0.86 | 2.38 | 3.1372 (13) | 147.4 |
N6B—H6B1···O2Ai | 0.86 | 2.05 | 2.8550 (12) | 154.6 |
N6B—H6B2···N5Bii | 0.86 | 2.28 | 3.0491 (13) | 148.6 |
N2B—H2B2···O1C | 0.86 | 2.16 | 2.9923 (13) | 163.2 |
O1D—H1D···N3B | 0.83 (3) | 2.04 (3) | 2.8622 (15) | 171 (2) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+2, −y+2, −z+1. |