Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049999/pr2016sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049999/pr2016Isup2.hkl |
CCDC reference: 667170
To 4.0 g (20 mmol) of 1,5,8,12-tetraazadodecane in 15 ml of ethanol was added 6.0 g (40 mmol) of salicylaldehyde in 10 ml of ethanol drop-wise. The deep yellow solution was left to stir for half an hour and a crystalline product resulted (H~2~L). To 0.85 g of H~2~L dissolved in 10.0 ml of methanol was added 0.58 g of FeCl3.xH2O. The solution became violet and a red-purple solid precipitated. This was stirred overnight, the solid filtered, washed with methanol and dried. Crystallization was effected by slow evaporation of a DMF solution of the complex.
The H atoms were idealized with C—H distances of 0.93 (aromatic C—H), and 0.97 (CH~2~) \%A and Uĩso~(H) = 1.2U~eq~(C). The amine H atoms were refined isotropically.
Metal complexes of linear hexadentate ligands have fascinated inorganic chemists since their first report in 1947 (Dwyer & Lions, 1947). The first such report of a Fe complex of a linear FeN4O2 ligand derived from the Schiff base condensation of salicylaldehyde and triethylenetetraamine (Sal222, see Figure 1) was in 1955 (Das Sarma & Bailer, 1955). However, this interest lapsed for several years until the discovery that such complexes exhibited spin-crossover magnetic behavior (Sinn et al., 1978). Hexadentate linear FeN4O2 ligands derived from the Schiff base condensation of salicylaldehyde and linear tetramines can be characterized by the number of linking carbon atoms in the tetramine backbone (see Figure 1). The structures of Fe complexes of Sal222 (Sinn et al., 1978; Hayami et al., 1997; Floquet et al., 2004; Dorbes et al., 2005; Bera et al., 2005; Nishida et al., 1987; Salmon et al., 1999; McPartlin et al., 1978; Maeda et al., 1991; Boinnard et al., 1994), Sal232 (Hayami et al., 1997), Sal323 (Hayami et al., 1997; Ito et al., 1983), and Sal333 (Ito et al., 1983) have been reported. When chelating to Fe, as the number of carbon atoms in the tetramine backbone increases from 6 to 9, the conformation adopted by the ligand changes from a cis-FeN4O2 to a trans-FeN4O2 arrangement for the phenolic O donors. All structurally characterized Fe complexes with Sal222 have adopted the cis-FeN4O2 conformation while all those with either Sal323 or Sal333 have adopted the trans-FeN4O2 conformation. Further, it has been observed that the angles subtended at the Fe center reflect the magnetic properties of the compound (Hayami et al., 1997;Nishida et al., 1987) with low-spin compounds having such angles closer to 90° and 180°.
Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS (Bruker, 1997); data reduction: XSCANS (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).
[Fe(C22H28N4O2)]Cl | Dx = 1.461 Mg m−3 |
Mr = 471.78 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pccn | Cell parameters from 52 reflections |
a = 7.5156 (15) Å | θ = 2.5–27.6° |
b = 16.161 (3) Å | µ = 0.86 mm−1 |
c = 17.654 (4) Å | T = 293 K |
V = 2144.2 (7) Å3 | Prism, black |
Z = 4 | 0.47 × 0.35 × 0.27 mm |
F(000) = 988 |
Bruker P4 diffractometer | 1284 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 25.0°, θmin = 2.3° |
ω scans | h = 0→8 |
Absorption correction: ψ scans (North et al., 1968) | k = 0→19 |
Tmin = 0.576, Tmax = 0.731 | l = 0→20 |
1873 measured reflections | 3 standard reflections every 97 reflections |
1873 independent reflections | intensity decay: none |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0362P)2 + 2.7631P] where P = (Fo2 + 2Fc2)/3 |
1873 reflections | (Δ/σ)max < 0.001 |
154 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.44 e Å−3 |
[Fe(C22H28N4O2)]Cl | V = 2144.2 (7) Å3 |
Mr = 471.78 | Z = 4 |
Orthorhombic, Pccn | Mo Kα radiation |
a = 7.5156 (15) Å | µ = 0.86 mm−1 |
b = 16.161 (3) Å | T = 293 K |
c = 17.654 (4) Å | 0.47 × 0.35 × 0.27 mm |
Bruker P4 diffractometer | 1284 reflections with I > 2σ(I) |
Absorption correction: ψ scans (North et al., 1968) | Rint = 0.000 |
Tmin = 0.576, Tmax = 0.731 | 3 standard reflections every 97 reflections |
1873 measured reflections | intensity decay: none |
1873 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.39 e Å−3 |
1873 reflections | Δρmin = −0.44 e Å−3 |
154 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Fe | 0.2500 | 0.2500 | 0.45616 (4) | 0.0252 (2) | |
Cl | −0.2500 | 0.2500 | 0.64500 (8) | 0.0477 (4) | |
O1 | 0.1430 (3) | 0.35514 (14) | 0.46105 (14) | 0.0328 (6) | |
N1 | 0.0734 (4) | 0.21620 (19) | 0.38082 (17) | 0.0290 (7) | |
N2 | 0.0916 (4) | 0.2076 (2) | 0.53991 (19) | 0.0321 (8) | |
H2N | 0.018 (5) | 0.239 (3) | 0.543 (2) | 0.036 (12)* | |
C1 | 0.0179 (5) | 0.3553 (2) | 0.3355 (2) | 0.0306 (8) | |
C2 | 0.0830 (5) | 0.3955 (2) | 0.4010 (2) | 0.0304 (9) | |
C3 | 0.0817 (5) | 0.4824 (2) | 0.4026 (3) | 0.0387 (10) | |
H3A | 0.1254 | 0.5100 | 0.4450 | 0.027 (10)* | |
C4 | 0.0173 (6) | 0.5272 (3) | 0.3428 (3) | 0.0458 (11) | |
H4A | 0.0212 | 0.5847 | 0.3443 | 0.053 (13)* | |
C5 | −0.0538 (6) | 0.4877 (3) | 0.2800 (3) | 0.0500 (12) | |
H5A | −0.1004 | 0.5185 | 0.2402 | 0.073 (16)* | |
C6 | −0.0553 (6) | 0.4032 (3) | 0.2768 (2) | 0.0426 (10) | |
H6A | −0.1055 | 0.3769 | 0.2351 | 0.039 (11)* | |
C7 | −0.0010 (5) | 0.2664 (2) | 0.3343 (2) | 0.0314 (9) | |
H7A | −0.0729 | 0.2437 | 0.2968 | 0.032 (9)* | |
C8 | −0.0042 (5) | 0.1322 (2) | 0.3848 (2) | 0.0365 (10) | |
H8A | 0.0898 | 0.0912 | 0.3824 | 0.034 (11)* | |
H8B | −0.0833 | 0.1235 | 0.3422 | 0.034 (11)* | |
C9 | −0.1069 (5) | 0.1228 (2) | 0.4585 (2) | 0.0436 (11) | |
H9A | −0.1953 | 0.1664 | 0.4614 | 0.042 (11)* | |
H9B | −0.1697 | 0.0703 | 0.4575 | 0.051 (12)* | |
C10 | 0.0070 (6) | 0.1259 (2) | 0.5292 (2) | 0.0420 (10) | |
H10A | −0.0664 | 0.1135 | 0.5730 | 0.072 (16)* | |
H10B | 0.0987 | 0.0838 | 0.5259 | 0.048 (12)* | |
C11 | 0.1977 (5) | 0.2105 (3) | 0.6102 (2) | 0.0455 (11) | |
H11A | 0.2777 | 0.1634 | 0.6124 | 0.063 (14)* | |
H11B | 0.1199 | 0.2085 | 0.6540 | 0.057 (13)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe | 0.0230 (3) | 0.0250 (3) | 0.0277 (4) | 0.0014 (3) | 0.000 | 0.000 |
Cl | 0.0391 (7) | 0.0573 (9) | 0.0468 (8) | 0.0180 (8) | 0.000 | 0.000 |
O1 | 0.0354 (15) | 0.0276 (13) | 0.0353 (15) | 0.0095 (11) | −0.0071 (12) | −0.0031 (11) |
N1 | 0.0256 (17) | 0.0286 (15) | 0.0327 (17) | −0.0019 (13) | 0.0018 (14) | −0.0032 (13) |
N2 | 0.0294 (18) | 0.0321 (18) | 0.0349 (19) | 0.0075 (15) | 0.0068 (15) | 0.0045 (15) |
C1 | 0.025 (2) | 0.037 (2) | 0.030 (2) | 0.0020 (17) | 0.0002 (16) | 0.0018 (16) |
C2 | 0.022 (2) | 0.030 (2) | 0.039 (2) | 0.0037 (16) | 0.0028 (16) | −0.0007 (17) |
C3 | 0.035 (2) | 0.028 (2) | 0.053 (3) | 0.0043 (18) | 0.000 (2) | −0.0046 (19) |
C4 | 0.039 (2) | 0.034 (2) | 0.064 (3) | 0.0079 (19) | 0.007 (2) | 0.011 (2) |
C5 | 0.047 (3) | 0.050 (3) | 0.053 (3) | 0.008 (2) | 0.001 (2) | 0.023 (2) |
C6 | 0.036 (2) | 0.059 (3) | 0.033 (2) | 0.001 (2) | 0.0002 (19) | 0.005 (2) |
C7 | 0.0231 (17) | 0.044 (2) | 0.0272 (18) | 0.0008 (16) | −0.0020 (16) | −0.0080 (17) |
C8 | 0.028 (2) | 0.034 (2) | 0.047 (2) | −0.0030 (17) | −0.0037 (18) | −0.0104 (18) |
C9 | 0.032 (2) | 0.030 (2) | 0.069 (3) | −0.0091 (17) | 0.011 (2) | −0.005 (2) |
C10 | 0.045 (2) | 0.031 (2) | 0.049 (3) | 0.0005 (19) | 0.014 (2) | 0.0071 (19) |
C11 | 0.035 (2) | 0.075 (3) | 0.027 (2) | 0.011 (2) | 0.0061 (17) | 0.0108 (19) |
Fe—O1 | 1.882 (2) | C4—C5 | 1.387 (6) |
Fe—O1i | 1.882 (2) | C4—H4A | 0.9300 |
Fe—N1 | 1.957 (3) | C5—C6 | 1.367 (6) |
Fe—N1i | 1.957 (3) | C5—H5A | 0.9300 |
Fe—N2i | 2.018 (3) | C6—H6A | 0.9300 |
Fe—N2 | 2.018 (3) | C7—H7A | 0.9300 |
O1—C2 | 1.323 (4) | C8—C9 | 1.520 (5) |
N1—C7 | 1.283 (5) | C8—H8A | 0.9700 |
N1—C8 | 1.479 (5) | C8—H8B | 0.9700 |
N2—C11 | 1.476 (5) | C9—C10 | 1.515 (6) |
N2—C10 | 1.478 (5) | C9—H9A | 0.9700 |
N2—H2N | 0.75 (4) | C9—H9B | 0.9700 |
C1—C6 | 1.406 (5) | C10—H10A | 0.9700 |
C1—C2 | 1.414 (5) | C10—H10B | 0.9700 |
C1—C7 | 1.443 (5) | C11—C11i | 1.500 (9) |
C2—C3 | 1.406 (5) | C11—H11A | 0.9700 |
C3—C4 | 1.369 (6) | C11—H11B | 0.9700 |
C3—H3A | 0.9300 | ||
O1—Fe—O1i | 174.73 (15) | C3—C4—H4A | 119.7 |
O1—Fe—N1 | 89.62 (12) | C5—C4—H4A | 119.7 |
O1i—Fe—N1 | 93.97 (12) | C6—C5—C4 | 119.8 (4) |
O1—Fe—N1i | 93.97 (12) | C6—C5—H5A | 120.1 |
O1i—Fe—N1i | 89.62 (12) | C4—C5—H5A | 120.1 |
N1—Fe—N1i | 94.36 (17) | C5—C6—C1 | 121.1 (4) |
O1—Fe—N2i | 84.96 (12) | C5—C6—H6A | 119.5 |
O1i—Fe—N2i | 91.18 (12) | C1—C6—H6A | 119.5 |
N1—Fe—N2i | 173.15 (13) | N1—C7—C1 | 125.2 (3) |
N1i—Fe—N2i | 90.19 (13) | N1—C7—H7A | 117.4 |
O1—Fe—N2 | 91.18 (12) | C1—C7—H7A | 117.4 |
O1i—Fe—N2 | 84.96 (12) | N1—C8—C9 | 109.5 (3) |
N1—Fe—N2 | 90.19 (13) | N1—C8—H8A | 109.8 |
N1i—Fe—N2 | 173.15 (13) | C9—C8—H8A | 109.8 |
N2i—Fe—N2 | 85.8 (2) | N1—C8—H8B | 109.8 |
C2—O1—Fe | 123.6 (2) | C9—C8—H8B | 109.8 |
C7—N1—C8 | 116.1 (3) | H8A—C8—H8B | 108.2 |
C7—N1—Fe | 123.7 (3) | C10—C9—C8 | 114.5 (3) |
C8—N1—Fe | 119.4 (2) | C10—C9—H9A | 108.6 |
C11—N2—C10 | 111.6 (3) | C8—C9—H9A | 108.6 |
C11—N2—Fe | 106.7 (2) | C10—C9—H9B | 108.6 |
C10—N2—Fe | 117.6 (3) | C8—C9—H9B | 108.6 |
C11—N2—H2N | 108 (3) | H9A—C9—H9B | 107.6 |
C10—N2—H2N | 107 (3) | N2—C10—C9 | 112.2 (3) |
Fe—N2—H2N | 106 (3) | N2—C10—H10A | 109.2 |
C6—C1—C2 | 119.1 (4) | C9—C10—H10A | 109.2 |
C6—C1—C7 | 119.8 (4) | N2—C10—H10B | 109.2 |
C2—C1—C7 | 120.2 (3) | C9—C10—H10B | 109.2 |
O1—C2—C3 | 118.6 (3) | H10A—C10—H10B | 107.9 |
O1—C2—C1 | 123.1 (3) | N2—C11—C11i | 108.0 (3) |
C3—C2—C1 | 118.2 (4) | N2—C11—H11A | 110.1 |
C4—C3—C2 | 121.0 (4) | C11i—C11—H11A | 110.1 |
C4—C3—H3A | 119.5 | N2—C11—H11B | 110.1 |
C2—C3—H3A | 119.5 | C11i—C11—H11B | 110.1 |
C3—C4—C5 | 120.6 (4) | H11A—C11—H11B | 108.4 |
O1i—Fe—O1—C2 | −173.3 (3) | Fe—O1—C2—C3 | −151.3 (3) |
N1—Fe—O1—C2 | −40.4 (3) | Fe—O1—C2—C1 | 29.5 (5) |
N1i—Fe—O1—C2 | 53.9 (3) | C6—C1—C2—O1 | 175.3 (3) |
N2i—Fe—O1—C2 | 143.8 (3) | C7—C1—C2—O1 | 5.7 (5) |
N2—Fe—O1—C2 | −130.6 (3) | C6—C1—C2—C3 | −3.9 (5) |
O1—Fe—N1—C7 | 29.5 (3) | C7—C1—C2—C3 | −173.4 (4) |
O1i—Fe—N1—C7 | −154.4 (3) | O1—C2—C3—C4 | −178.4 (4) |
N1i—Fe—N1—C7 | −64.4 (3) | C1—C2—C3—C4 | 0.8 (6) |
N2i—Fe—N1—C7 | 67.0 (12) | C2—C3—C4—C5 | 2.1 (6) |
N2—Fe—N1—C7 | 120.7 (3) | C3—C4—C5—C6 | −1.8 (7) |
O1—Fe—N1—C8 | −139.4 (3) | C4—C5—C6—C1 | −1.4 (7) |
O1i—Fe—N1—C8 | 36.8 (3) | C2—C1—C6—C5 | 4.3 (6) |
N1i—Fe—N1—C8 | 126.7 (3) | C7—C1—C6—C5 | 173.9 (4) |
N2i—Fe—N1—C8 | −101.8 (11) | C8—N1—C7—C1 | 162.0 (4) |
N2—Fe—N1—C8 | −48.2 (3) | Fe—N1—C7—C1 | −7.2 (5) |
O1—Fe—N2—C11 | −99.5 (3) | C6—C1—C7—N1 | 173.4 (4) |
O1i—Fe—N2—C11 | 76.9 (3) | C2—C1—C7—N1 | −17.1 (6) |
N1—Fe—N2—C11 | 170.9 (3) | C7—N1—C8—C9 | −106.7 (4) |
N1i—Fe—N2—C11 | 39.2 (12) | Fe—N1—C8—C9 | 63.0 (4) |
N2i—Fe—N2—C11 | −14.7 (2) | N1—C8—C9—C10 | −65.7 (4) |
O1—Fe—N2—C10 | 134.3 (3) | C11—N2—C10—C9 | 178.3 (3) |
O1i—Fe—N2—C10 | −49.2 (3) | Fe—N2—C10—C9 | −58.0 (4) |
N1—Fe—N2—C10 | 44.7 (3) | C8—C9—C10—N2 | 65.0 (4) |
N1i—Fe—N2—C10 | −86.9 (12) | C10—N2—C11—C11i | 170.8 (4) |
N2i—Fe—N2—C10 | −140.8 (3) | Fe—N2—C11—C11i | 41.1 (4) |
Symmetry code: (i) −x+1/2, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···Cl | 0.75 (4) | 2.70 (4) | 3.241 (3) | 131 (4) |
Experimental details
Crystal data | |
Chemical formula | [Fe(C22H28N4O2)]Cl |
Mr | 471.78 |
Crystal system, space group | Orthorhombic, Pccn |
Temperature (K) | 293 |
a, b, c (Å) | 7.5156 (15), 16.161 (3), 17.654 (4) |
V (Å3) | 2144.2 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.86 |
Crystal size (mm) | 0.47 × 0.35 × 0.27 |
Data collection | |
Diffractometer | Bruker P4 |
Absorption correction | ψ scans (North et al., 1968) |
Tmin, Tmax | 0.576, 0.731 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1873, 1873, 1284 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.114, 1.05 |
No. of reflections | 1873 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.39, −0.44 |
Computer programs: XSCANS (Bruker, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000).
Fe—O1 | 1.882 (2) | Fe—N2 | 2.018 (3) |
Fe—N1 | 1.957 (3) | ||
O1—Fe—O1i | 174.73 (15) | N1—Fe—N2i | 173.15 (13) |
O1—Fe—N1 | 89.62 (12) | O1—Fe—N2 | 91.18 (12) |
O1i—Fe—N1 | 93.97 (12) | N1—Fe—N2 | 90.19 (13) |
N1—Fe—N1i | 94.36 (17) | N2i—Fe—N2 | 85.8 (2) |
O1—Fe—N2i | 84.96 (12) |
Symmetry code: (i) −x+1/2, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···Cl | 0.75 (4) | 2.70 (4) | 3.241 (3) | 131 (4) |
Metal complexes of linear hexadentate ligands have fascinated inorganic chemists since their first report in 1947 (Dwyer & Lions, 1947). The first such report of a Fe complex of a linear FeN4O2 ligand (i.e. a ligand in which all the N and O donor atoms are linked in a straight chain with no branching) derived from the Schiff base condensation of salicylaldehyde and triethylenetetraamine was in 1955 (Das Sarma & Bailar, 1955). However, this interest lapsed for several years until the discovery that such complexes exhibited spin-crossover magnetic behavior (Sinn et al., 1978). Hexadentate linear FeN4O2 ligands derived from the Schiff base condensation of salicylaldehyde and linear tetramines can be characterized by the number of linking carbon atoms in the tetramine backbone (see Scheme 1). The structures of Fe complexes of Sal222 (Sinn et al., 1978; Hayami et al., 1997; Floquet et al., 2004; Dorbes et al., 2005; Bera et al., 2005; Nishida et al., 1987; Salmon et al., 1999; McPartlin et al., 1978; Maeda et al., 1991; Boinnard et al., 1994), Sal232 (Hayami et al., 1997), Sal323 (Hayami et al., 1997; Ito et al., 1983), and Sal333 (Ito et al., 1983) have been reported. When chelating to Fe, as the number of carbon atoms in the tetramine backbone increases from 6 to 9, the conformation adopted by the ligand changes from a cis-FeN4O2 to a trans-FeN4O2 arrangement for the phenolic O donors. All structurally characterized Fe complexes with Sal222 have adopted the cis-FeN4O2 conformation while all those with either Sal323 or Sal333 have adopted the trans-FeN4O2 conformation. Further, it has been observed that the angles subtended at the Fe center reflect the magnetic properties of the compound (Hayami et al., 1997; Nishida et al., 1987) with low-spin compounds having angles closer to 90° and 180°. While several structures containing the 323 backbone have been structurally characterized, there is no report of a structure containing a chloride anion. There is a report of an isomorphous and isostructural Mn derivative (Zhu et al., 2002).
In the structure of I both the Fe of the cation and Cl anion lie on crystallographic 2 fold axes. The cation has adopted a conformation in which the phenolic O donors are trans to each other. The cis and trans bond angles subtended at the Fe center range from 84.96 (12) to 94.36 (17)° and 173.15 (13) to 174.73 (15)° respectively, indicating that the Fe is low spin. The Fe—O (1.882 (2) Å) and Fe—N bond lengths [1.957 (3)and 2.018 (3) Å] also reflect this.