Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805022762/wn6368sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805022762/wn6368Isup2.hkl |
CCDC reference: 195192
Data collection: CrystalClear (Rigaku, 1990); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
C20H26N22+·2Cl−·CH4O | F(000) = 424 |
Mr = 397.37 | Dx = 1.310 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: p 2yb | Cell parameters from 3734 reflections |
a = 11.7262 (13) Å | θ = 3.0–25.5° |
b = 7.6968 (7) Å | µ = 0.34 mm−1 |
c = 11.8788 (13) Å | T = 193 K |
β = 109.970 (5)° | Prism, colorless |
V = 1007.65 (18) Å3 | 0.70 × 0.50 × 0.50 mm |
Z = 2 |
Rigaku Mercury diffractometer | 2874 independent reflections |
Radiation source: fine-focus sealed tube | 2855 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
Detector resolution: 14.62 pixels mm-1 | θmax = 25.5°, θmin = 3.0° |
ω scans | h = −14→14 |
Absorption correction: multi-scan (Jacobson, 1998) | k = −9→8 |
Tmin = 0.799, Tmax = 0.850 | l = −13→14 |
6594 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.128 | w = 1/[σ2(Fo2) + (0.0733P)2 + 0.7886P] where P = (Fo2 + 2Fc2)/3 |
S = 1.13 | (Δ/σ)max < 0.001 |
2874 reflections | Δρmax = 0.60 e Å−3 |
236 parameters | Δρmin = −0.49 e Å−3 |
2 restraints | Absolute structure: Flack (1983), 855 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.02 (9) |
Experimental. Compound 3: pale yellow oil, yield 29%, [a\]D25 + 104 (c, 0.8, CH3OH). 1H NMR (400 MHz, CDCl3): d\ 2.49–2.57 (m, 2H, PhCH2), 2.65–2.75 (m, 4H, CHH), 2.89–2.96 (m, 6H, 2- and 5-CHH, 3- and 6-CH, PhCH X 2), 3.03–3.0 (m, 2H, 7-and 8-CHH), 7.17–7.29 (m, 10H, PhH); MS: m/z: 292.19 (M+, 73%), 250.16 (8), 201.13 (100), 160.11 (20), 146.16 (25), 117.07 (29), 91.05 (31). Compound 3 with 2HCl: white crystal, m.p.: 188–190°C. Anal. calcd for (%) C20H26N2Cl2: C 65.75, H 7.17, N 7.67. Found (%): C 65.48, H 7.42, N 7.63. IR ν: 3455, 3070, 2988, 2240, 1499 cm-1. Compound 4: pale yellow oil, yield 25%, [a\]D25 + 134 (c, 0.8, CH3OH). 1H NMR (400 MHz, CDCl3) d\: 2.69–2.78 (m, 10H), 2.89–3.00 (m, 4H), 7.20–7.33 (m, 10H, PhH). MS m/z (%): 292.19 (71, M+), 250.16 (9), 201.13 (100), 160.11 (21), 146.16 (25), 117.07 (32), 91.05 (35). Compound 4 with 2HCl: white crystal, m.p.: 136–138°C. IR (KBr) νmax: 3456, 3070, 2986, 2238, 1497 cm-1. Compound 4 with 2picrate: yellow crystal, m.p.: 158–160°C. Anal. calcd (%) for C32H30N8O14: C 51.20, H 4.03, N 14.93. Found (%): C 50.87, H 4.01, N 14.91. Scheme 2. Synthesis of the title compound |
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 | ||
Cl1 | 0.40910 (7) | 0.56743 (12) | 0.32834 (8) | 0.0320 (2) | |
Cl2 | 0.09437 (7) | 0.65047 (12) | 0.48121 (10) | 0.0385 (3) | |
O1 | 0.6239 (6) | 0.1698 (12) | 0.3596 (6) | 0.128 (2)* | |
H1 | 0.6978 | 0.1647 | 0.4014 | 0.193* | |
N1 | 0.2888 (2) | 0.2593 (4) | 0.3883 (3) | 0.0254 (6) | |
N2 | 0.1871 (2) | 0.0101 (4) | 0.4494 (3) | 0.0260 (6) | |
C1 | 0.1563 (3) | 0.2582 (5) | 0.3125 (3) | 0.0238 (7) | |
H1B | 0.1146 | 0.3536 | 0.3406 | 0.029* | |
C2 | 0.1036 (3) | 0.0827 (5) | 0.3340 (3) | 0.0260 (7) | |
H2A | 0.0216 | 0.0997 | 0.3384 | 0.031* | |
H2B | 0.0973 | 0.0016 | 0.2674 | 0.031* | |
C3 | 0.2144 (3) | 0.1487 (5) | 0.5453 (3) | 0.0241 (7) | |
H3 | 0.1370 | 0.2101 | 0.5380 | 0.029* | |
C4 | 0.3004 (3) | 0.2787 (5) | 0.5180 (3) | 0.0261 (7) | |
H4A | 0.2790 | 0.3986 | 0.5335 | 0.031* | |
H4B | 0.3850 | 0.2555 | 0.5701 | 0.031* | |
C5 | 0.3495 (3) | 0.0946 (5) | 0.3740 (3) | 0.0301 (8) | |
H5A | 0.4385 | 0.1058 | 0.4124 | 0.036* | |
H5B | 0.3313 | 0.0694 | 0.2879 | 0.036* | |
C6 | 0.3024 (3) | −0.0531 (5) | 0.4327 (3) | 0.0302 (8) | |
H6A | 0.2856 | −0.1576 | 0.3810 | 0.036* | |
H6B | 0.3636 | −0.0836 | 0.5111 | 0.036* | |
C7 | 0.1402 (3) | 0.2903 (5) | 0.1815 (3) | 0.0292 (8) | |
H7A | 0.1818 | 0.3999 | 0.1752 | 0.035* | |
H7B | 0.1799 | 0.1949 | 0.1528 | 0.035* | |
C8 | 0.0086 (3) | 0.3021 (5) | 0.1006 (3) | 0.0253 (7) | |
C9 | −0.0819 (3) | 0.3776 (6) | 0.1361 (4) | 0.0334 (9) | |
H9 | −0.0625 | 0.4208 | 0.2154 | 0.040* | |
C10 | −0.2006 (3) | 0.3904 (6) | 0.0562 (4) | 0.0381 (9) | |
H10 | −0.2613 | 0.4418 | 0.0817 | 0.046* | |
C11 | −0.2310 (3) | 0.3292 (6) | −0.0595 (4) | 0.0372 (9) | |
H11 | −0.3119 | 0.3384 | −0.1136 | 0.045* | |
C12 | −0.1416 (4) | 0.2540 (6) | −0.0956 (3) | 0.0376 (9) | |
H12 | −0.1613 | 0.2116 | −0.1751 | 0.045* | |
C13 | −0.0236 (3) | 0.2404 (5) | −0.0160 (3) | 0.0308 (8) | |
H13 | 0.0364 | 0.1877 | −0.0418 | 0.037* | |
C14 | 0.2644 (3) | 0.0669 (6) | 0.6694 (3) | 0.0296 (7) | |
H14A | 0.2059 | −0.0208 | 0.6777 | 0.035* | |
H14B | 0.3413 | 0.0062 | 0.6777 | 0.035* | |
C15 | 0.2872 (3) | 0.1989 (5) | 0.7685 (3) | 0.0279 (8) | |
C16 | 0.4021 (3) | 0.2126 (7) | 0.8542 (4) | 0.0423 (10) | |
H16 | 0.4672 | 0.1467 | 0.8457 | 0.051* | |
C17 | 0.4230 (4) | 0.3220 (8) | 0.9525 (4) | 0.0583 (15) | |
H17 | 0.5025 | 0.3317 | 1.0096 | 0.070* | |
C18 | 0.3295 (4) | 0.4162 (7) | 0.9678 (4) | 0.0504 (12) | |
H18 | 0.3433 | 0.4867 | 1.0368 | 0.060* | |
C19 | 0.2154 (4) | 0.4068 (6) | 0.8812 (4) | 0.0391 (10) | |
H19 | 0.1514 | 0.4762 | 0.8889 | 0.047* | |
C20 | 0.1932 (3) | 0.2974 (5) | 0.7832 (3) | 0.0319 (8) | |
H20 | 0.1137 | 0.2893 | 0.7259 | 0.038* | |
C21 | 0.5785 (10) | 0.1697 (18) | 0.2341 (9) | 0.143 (4)* | |
H21A | 0.5069 | 0.2449 | 0.2059 | 0.214* | |
H21B | 0.5560 | 0.0510 | 0.2051 | 0.214* | |
H21C | 0.6410 | 0.2130 | 0.2036 | 0.214* | |
H1A | 0.324 (4) | 0.357 (6) | 0.366 (3) | 0.025 (10)* | |
H2 | 0.158 (4) | −0.084 (7) | 0.479 (4) | 0.034 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0224 (4) | 0.0371 (5) | 0.0355 (5) | −0.0052 (3) | 0.0086 (3) | 0.0044 (4) |
Cl2 | 0.0283 (4) | 0.0250 (4) | 0.0649 (6) | 0.0003 (4) | 0.0194 (4) | 0.0047 (5) |
N1 | 0.0197 (13) | 0.0292 (18) | 0.0253 (15) | −0.0032 (12) | 0.0053 (11) | −0.0008 (13) |
N2 | 0.0236 (13) | 0.0214 (15) | 0.0313 (16) | −0.0023 (11) | 0.0074 (11) | −0.0016 (13) |
C1 | 0.0158 (14) | 0.0280 (19) | 0.0260 (17) | −0.0002 (12) | 0.0051 (12) | −0.0036 (14) |
C2 | 0.0205 (13) | 0.0317 (19) | 0.0230 (16) | −0.0035 (14) | 0.0037 (12) | −0.0025 (15) |
C3 | 0.0223 (13) | 0.0260 (16) | 0.0227 (16) | 0.0026 (14) | 0.0061 (11) | −0.0045 (15) |
C4 | 0.0250 (15) | 0.0272 (19) | 0.0215 (17) | −0.0013 (13) | 0.0021 (12) | −0.0056 (15) |
C5 | 0.0216 (14) | 0.037 (2) | 0.0323 (18) | 0.0022 (14) | 0.0102 (13) | −0.0030 (16) |
C6 | 0.0280 (17) | 0.027 (2) | 0.034 (2) | 0.0069 (14) | 0.0079 (14) | −0.0064 (16) |
C7 | 0.0290 (17) | 0.033 (2) | 0.0255 (18) | −0.0029 (14) | 0.0098 (14) | −0.0003 (15) |
C8 | 0.0294 (16) | 0.0223 (18) | 0.0246 (18) | −0.0050 (13) | 0.0096 (13) | 0.0021 (14) |
C9 | 0.0305 (17) | 0.039 (2) | 0.0288 (18) | −0.0013 (16) | 0.0072 (14) | −0.0043 (17) |
C10 | 0.0304 (18) | 0.040 (2) | 0.041 (2) | 0.0007 (16) | 0.0086 (16) | −0.0019 (19) |
C11 | 0.0307 (17) | 0.036 (2) | 0.035 (2) | −0.0043 (16) | −0.0022 (14) | 0.0057 (18) |
C12 | 0.045 (2) | 0.038 (2) | 0.0242 (18) | −0.0110 (18) | 0.0058 (15) | −0.0015 (17) |
C13 | 0.0361 (18) | 0.028 (2) | 0.0274 (19) | −0.0022 (16) | 0.0100 (15) | −0.0005 (16) |
C14 | 0.0317 (15) | 0.0302 (18) | 0.0268 (17) | 0.0051 (16) | 0.0100 (13) | 0.0008 (17) |
C15 | 0.0264 (15) | 0.032 (2) | 0.0246 (17) | 0.0029 (14) | 0.0080 (13) | 0.0012 (15) |
C16 | 0.0272 (17) | 0.058 (3) | 0.042 (2) | 0.0044 (18) | 0.0115 (15) | −0.014 (2) |
C17 | 0.0295 (19) | 0.084 (4) | 0.053 (3) | 0.002 (2) | 0.0026 (18) | −0.035 (3) |
C18 | 0.040 (2) | 0.063 (3) | 0.047 (3) | −0.003 (2) | 0.0130 (18) | −0.029 (2) |
C19 | 0.0331 (18) | 0.046 (3) | 0.040 (2) | 0.0085 (18) | 0.0162 (16) | −0.010 (2) |
C20 | 0.0256 (16) | 0.036 (2) | 0.032 (2) | 0.0035 (15) | 0.0074 (14) | 0.0004 (16) |
O1—C21 | 1.401 (10) | C8—C13 | 1.388 (5) |
O1—H1 | 0.8400 | C8—C9 | 1.396 (5) |
N1—C5 | 1.492 (5) | C9—C10 | 1.395 (5) |
N1—C1 | 1.507 (4) | C9—H9 | 0.9500 |
N1—C4 | 1.507 (4) | C10—C11 | 1.379 (6) |
N1—H1A | 0.94 (4) | C10—H10 | 0.9500 |
N2—C2 | 1.495 (4) | C11—C12 | 1.387 (6) |
N2—C3 | 1.512 (5) | C11—H11 | 0.9500 |
N2—C6 | 1.512 (4) | C12—C13 | 1.388 (5) |
N2—H2 | 0.92 (5) | C12—H12 | 0.9500 |
C1—C7 | 1.522 (5) | C13—H13 | 0.9500 |
C1—C2 | 1.543 (5) | C14—C15 | 1.508 (5) |
C1—H1B | 1.0000 | C14—H14A | 0.9900 |
C2—H2A | 0.9900 | C14—H14B | 0.9900 |
C2—H2B | 0.9900 | C15—C16 | 1.388 (5) |
C3—C14 | 1.525 (5) | C15—C20 | 1.398 (5) |
C3—C4 | 1.532 (5) | C16—C17 | 1.392 (6) |
C3—H3 | 1.0000 | C16—H16 | 0.9500 |
C4—H4A | 0.9900 | C17—C18 | 1.377 (6) |
C4—H4B | 0.9900 | C17—H17 | 0.9500 |
C5—C6 | 1.532 (5) | C18—C19 | 1.384 (6) |
C5—H5A | 0.9900 | C18—H18 | 0.9500 |
C5—H5B | 0.9900 | C19—C20 | 1.387 (6) |
C6—H6A | 0.9900 | C19—H19 | 0.9500 |
C6—H6B | 0.9900 | C20—H20 | 0.9500 |
C7—C8 | 1.517 (5) | C21—H21A | 0.9800 |
C7—H7A | 0.9900 | C21—H21B | 0.9800 |
C7—H7B | 0.9900 | C21—H21C | 0.9800 |
C21—O1—H1 | 124.7 | C8—C7—H7B | 108.8 |
C5—N1—C1 | 111.2 (3) | C1—C7—H7B | 108.8 |
C5—N1—C4 | 108.7 (3) | H7A—C7—H7B | 107.7 |
C1—N1—C4 | 109.0 (3) | C13—C8—C9 | 117.9 (3) |
C5—N1—H1A | 112 (2) | C13—C8—C7 | 118.9 (3) |
C1—N1—H1A | 107 (2) | C9—C8—C7 | 123.2 (3) |
C4—N1—H1A | 109 (2) | C10—C9—C8 | 120.5 (4) |
C2—N2—C3 | 109.3 (3) | C10—C9—H9 | 119.7 |
C2—N2—C6 | 109.5 (3) | C8—C9—H9 | 119.7 |
C3—N2—C6 | 110.9 (3) | C11—C10—C9 | 120.8 (4) |
C2—N2—H2 | 116 (3) | C11—C10—H10 | 119.6 |
C3—N2—H2 | 106 (3) | C9—C10—H10 | 119.6 |
C6—N2—H2 | 105 (3) | C10—C11—C12 | 119.0 (3) |
N1—C1—C7 | 110.6 (3) | C10—C11—H11 | 120.5 |
N1—C1—C2 | 107.2 (3) | C12—C11—H11 | 120.5 |
C7—C1—C2 | 113.2 (3) | C11—C12—C13 | 120.2 (4) |
N1—C1—H1B | 108.6 | C11—C12—H12 | 119.9 |
C7—C1—H1B | 108.6 | C13—C12—H12 | 119.9 |
C2—C1—H1B | 108.6 | C8—C13—C12 | 121.5 (3) |
N2—C2—C1 | 107.8 (3) | C8—C13—H13 | 119.2 |
N2—C2—H2A | 110.1 | C12—C13—H13 | 119.2 |
C1—C2—H2A | 110.1 | C15—C14—C3 | 112.6 (3) |
N2—C2—H2B | 110.1 | C15—C14—H14A | 109.1 |
C1—C2—H2B | 110.1 | C3—C14—H14A | 109.1 |
H2A—C2—H2B | 108.5 | C15—C14—H14B | 109.1 |
N2—C3—C14 | 110.5 (3) | C3—C14—H14B | 109.1 |
N2—C3—C4 | 106.6 (2) | H14A—C14—H14B | 107.8 |
C14—C3—C4 | 114.3 (3) | C16—C15—C20 | 118.5 (3) |
N2—C3—H3 | 108.4 | C16—C15—C14 | 119.5 (3) |
C14—C3—H3 | 108.4 | C20—C15—C14 | 121.7 (3) |
C4—C3—H3 | 108.4 | C15—C16—C17 | 120.7 (4) |
N1—C4—C3 | 108.4 (3) | C15—C16—H16 | 119.7 |
N1—C4—H4A | 110.0 | C17—C16—H16 | 119.7 |
C3—C4—H4A | 110.0 | C18—C17—C16 | 120.6 (4) |
N1—C4—H4B | 110.0 | C18—C17—H17 | 119.7 |
C3—C4—H4B | 110.0 | C16—C17—H17 | 119.7 |
H4A—C4—H4B | 108.4 | C17—C18—C19 | 119.1 (4) |
N1—C5—C6 | 108.6 (3) | C17—C18—H18 | 120.5 |
N1—C5—H5A | 110.0 | C19—C18—H18 | 120.5 |
C6—C5—H5A | 110.0 | C18—C19—C20 | 120.8 (4) |
N1—C5—H5B | 110.0 | C18—C19—H19 | 119.6 |
C6—C5—H5B | 110.0 | C20—C19—H19 | 119.6 |
H5A—C5—H5B | 108.4 | C19—C20—C15 | 120.3 (3) |
N2—C6—C5 | 107.4 (3) | C19—C20—H20 | 119.9 |
N2—C6—H6A | 110.2 | C15—C20—H20 | 119.9 |
C5—C6—H6A | 110.2 | O1—C21—H21A | 109.5 |
N2—C6—H6B | 110.2 | O1—C21—H21B | 109.5 |
C5—C6—H6B | 110.2 | H21A—C21—H21B | 109.5 |
H6A—C6—H6B | 108.5 | O1—C21—H21C | 109.5 |
C8—C7—C1 | 113.7 (3) | H21A—C21—H21C | 109.5 |
C8—C7—H7A | 108.8 | H21B—C21—H21C | 109.5 |
C1—C7—H7A | 108.8 | ||
C5—N1—C1—C7 | −76.2 (4) | C1—C7—C8—C13 | −146.2 (3) |
C4—N1—C1—C7 | 164.0 (3) | C1—C7—C8—C9 | 36.1 (5) |
C5—N1—C1—C2 | 47.7 (3) | C13—C8—C9—C10 | −0.1 (6) |
C4—N1—C1—C2 | −72.1 (3) | C7—C8—C9—C10 | 177.6 (4) |
C3—N2—C2—C1 | 49.2 (3) | C8—C9—C10—C11 | −0.2 (6) |
C6—N2—C2—C1 | −72.6 (3) | C9—C10—C11—C12 | 0.2 (6) |
N1—C1—C2—N2 | 19.9 (3) | C10—C11—C12—C13 | 0.2 (6) |
C7—C1—C2—N2 | 142.2 (3) | C9—C8—C13—C12 | 0.5 (5) |
C2—N2—C3—C14 | 162.0 (3) | C7—C8—C13—C12 | −177.4 (3) |
C6—N2—C3—C14 | −77.0 (3) | C11—C12—C13—C8 | −0.5 (6) |
C2—N2—C3—C4 | −73.3 (3) | N2—C3—C14—C15 | −177.2 (2) |
C6—N2—C3—C4 | 47.7 (4) | C4—C3—C14—C15 | 62.6 (4) |
C5—N1—C4—C3 | −73.3 (3) | C3—C14—C15—C16 | −123.7 (4) |
C1—N1—C4—C3 | 48.1 (4) | C3—C14—C15—C20 | 62.5 (4) |
N2—C3—C4—N1 | 20.5 (3) | C20—C15—C16—C17 | 0.0 (7) |
C14—C3—C4—N1 | 142.8 (3) | C14—C15—C16—C17 | −174.1 (5) |
C1—N1—C5—C6 | −69.7 (4) | C15—C16—C17—C18 | 1.2 (9) |
C4—N1—C5—C6 | 50.3 (3) | C16—C17—C18—C19 | −2.9 (9) |
C2—N2—C6—C5 | 50.7 (4) | C17—C18—C19—C20 | 3.3 (8) |
C3—N2—C6—C5 | −70.1 (4) | C18—C19—C20—C15 | −2.2 (7) |
N1—C5—C6—N2 | 16.8 (4) | C16—C15—C20—C19 | 0.5 (6) |
N1—C1—C7—C8 | −176.4 (3) | C14—C15—C20—C19 | 174.4 (4) |
C2—C1—C7—C8 | 63.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl1 | 0.94 (4) | 2.03 (4) | 2.967 (3) | 176 (4) |
C5—H5A···O1 | 0.99 | 2.51 | 3.331 (7) | 140 |
N2—H2···Cl2i | 0.92 (5) | 2.18 (5) | 3.045 (3) | 157 (4) |
C6—H6A···Cl1i | 0.99 | 2.75 | 3.563 (4) | 139 |
O1—H1···Cl2ii | 0.82 | 2.38 | 3.201 (4) | 180 |
C6—H6B···O1ii | 0.99 | 2.41 | 3.151 (9) | 131 |
C14—H14B···O1ii | 0.99 | 2.68 | 3.389 (7) | 129 |
C6—H6B···Cl1ii | 0.99 | 2.94 | 3.715 (4) | 136 |
C4—H4A···O1iii | 0.99 | 2.51 | 3.329 (8) | 140 |
C3—H3···Cl2iv | 0.99 | 2.68 | 3.526 (4) | 142 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1/2, −z+1; (iii) −x+1, y+1/2, −z+1; (iv) −x, y−1/2, −z+1. |