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The crystal structures of the title compounds, [Cu(C15H11N2O2)2(C14H15N)2] and [Cu(C15H11N2O2)2(C14H15N)2]·2CHCl3, respectively, have been determined. The red disolvate complex affords a square-planar CuN4 coordination environment in which the CuII atom lies on a centre of symmetry. The blue solvent-free complex affords a distorted square-pyramidal CuN4O coordination environment and adjacent molecules form centrosymmetric dimers. A comparison of the different crystal structures focuses on the role of the solvent molecules in supramolecular assemblies of the copper(II) complexes.
Supporting information
CCDC references: 269013; 269014
Treatment of equimolar quantities of copper(II) acetate (0.454 g, 2.50 mmol), 5,5-diphenylhydantoin (1.26 g, 5.00 mmol) and 2,2-diphenylethylamine (0.99 g, 5.00 mmol) in ethanol (100 ml) at 323 K for 2 h gave rise to crude precipitates. Red–violet plate-like crystals of (I) were obtained from a solution in chloroform–methanol (4:1 v/v) at 298 K over a period of several days. IR (KBr): 1644 cm−1 (amide I band); m.p. 629 K (decomposition). Recrystallization of the crude precipitates from a solution in chloroform–methanol (4:1 v/v) at 283 K overnight yielded only a small amount of blue–violet plate-like crystals of the solvent-free complex, (II). IR (KBr): 1645 cm−1 (amide I band); m.p. 605 K (decomposition).
All H atoms were placed in calculated positions, with C—H = N—H = 0.95 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2Ueq(parent atom). The C atoms of the phenyl groups, viz. C4–C9, C10–C15, C18–C23 and C24–C29 for (I), and C4–C9, C10–C15, C18–C23, C24–C29, C33–C38, C39–C44, C47–C52 and C53–C58 for (II), were treated as rigid groups of anisotropic atoms. The intensity of the data was relatively weak, similar to some analogous mononuclear copper complexes with large organic ligands. The largest hole in the difference map of (II) is near atom Cu1, at (0.9919, 0.4909, 0.2953).
For both compounds, data collection: WinAFC Diffractometer Control Software (Rigaku, 1999); cell refinement: WinAFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.
Crystal data top
[Cu(C15H11N2O2)2(C14H15N)2]·2CHCl3 | F(000) = 2476.0 |
Mr = 1199.34 | Dx = 1.393 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 25 reflections |
a = 19.37 (1) Å | θ = 10.3–12.6° |
b = 29.796 (7) Å | µ = 0.72 mm−1 |
c = 9.910 (3) Å | T = 298 K |
V = 5720 (4) Å3 | Plate-like, red–violet |
Z = 4 | 0.41 × 0.16 × 0.10 mm |
Data collection top
Rigaku AFC-7R diffractometer | Rint = 0.021 |
ω/2θ scans | θmax = 27.5° |
Absorption correction: ψ scan (North et al., 1968) | h = −10→25 |
Tmin = 0.872, Tmax = 0.931 | k = 0→38 |
8516 measured reflections | l = −12→5 |
6565 independent reflections | 3 standard reflections every 150 reflections |
3338 reflections with I > 2σ(I) | intensity decay: 0.2% |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.050 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.163 | (Δ/σ)max < 0.001 |
S = 0.99 | Δρmax = 0.43 e Å−3 |
3338 reflections | Δρmin = −0.46 e Å−3 |
302 parameters | |
Crystal data top
[Cu(C15H11N2O2)2(C14H15N)2]·2CHCl3 | V = 5720 (4) Å3 |
Mr = 1199.34 | Z = 4 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 19.37 (1) Å | µ = 0.72 mm−1 |
b = 29.796 (7) Å | T = 298 K |
c = 9.910 (3) Å | 0.41 × 0.16 × 0.10 mm |
Data collection top
Rigaku AFC-7R diffractometer | 3338 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.021 |
Tmin = 0.872, Tmax = 0.931 | 3 standard reflections every 150 reflections |
8516 measured reflections | intensity decay: 0.2% |
6565 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 302 parameters |
wR(F2) = 0.163 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.43 e Å−3 |
3338 reflections | Δρmin = −0.46 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.5000 | 0.5000 | 0.5000 | 0.0307 (1) | |
Cl1 | 0.14371 (8) | 0.44923 (5) | 0.42211 (2) | 0.1146 (6) | |
Cl2 | 0.1733 (1) | 0.37426 (8) | 0.5972 (2) | 0.1334 (7) | |
Cl3 | 0.17950 (7) | 0.36416 (6) | 0.3122 (2) | 0.1019 (5) | |
O1 | 0.5246 (1) | 0.51803 (8) | 0.1754 (2) | 0.0439 (6) | |
O2 | 0.3656 (1) | 0.43479 (8) | 0.4037 (2) | 0.0395 (6) | |
N1 | 0.4545 (1) | 0.48014 (9) | 0.3279 (3) | 0.0318 (6) | |
N2 | 0.4543 (2) | 0.46060 (9) | 0.1070 (3) | 0.0346 (6) | |
N3 | 0.4891 (2) | 0.43761 (9) | 0.5727 (3) | 0.0392 (7) | |
C1 | 0.4814 (2) | 0.4887 (1) | 0.1992 (4) | 0.0334 (8) | |
C2 | 0.4025 (2) | 0.4493 (1) | 0.3137 (4) | 0.0331 (7) | |
C3 | 0.3996 (2) | 0.4330 (1) | 0.1652 (3) | 0.0314 (7) | |
C4 | 0.3313 (1) | 0.44243 (8) | 0.0926 (2) | 0.0375 (8) | |
C5 | 0.2762 (1) | 0.46458 (9) | 0.1527 (2) | 0.055 (1) | |
C6 | 0.2169 (1) | 0.4736 (1) | 0.0784 (3) | 0.074 (1) | |
C7 | 0.2128 (1) | 0.4605 (1) | −0.0559 (3) | 0.075 (2) | |
C8 | 0.2679 (2) | 0.4383 (1) | −0.1160 (2) | 0.067 (1) | |
C9 | 0.3272 (1) | 0.42931 (9) | −0.0418 (2) | 0.051 (1) | |
C10 | 0.4162 (1) | 0.38285 (5) | 0.1652 (3) | 0.0341 (7) | |
C11 | 0.36363 (9) | 0.35262 (7) | 0.1946 (3) | 0.0417 (8) | |
C12 | 0.3778 (1) | 0.30693 (7) | 0.2008 (3) | 0.050 (1) | |
C13 | 0.4444 (1) | 0.29147 (6) | 0.1776 (3) | 0.059 (1) | |
C14 | 0.4970 (1) | 0.32170 (8) | 0.1482 (3) | 0.059 (1) | |
C15 | 0.4828 (1) | 0.36739 (7) | 0.1419 (3) | 0.0480 (10) | |
C16 | 0.5351 (2) | 0.4026 (1) | 0.5163 (4) | 0.0427 (9) | |
C17 | 0.5388 (2) | 0.3603 (1) | 0.6065 (4) | 0.0431 (9) | |
C18 | 0.4681 (1) | 0.34290 (8) | 0.6445 (2) | 0.0387 (8) | |
C19 | 0.4542 (1) | 0.33384 (9) | 0.7793 (2) | 0.053 (1) | |
C20 | 0.3889 (2) | 0.3193 (1) | 0.8178 (2) | 0.066 (1) | |
C21 | 0.3375 (1) | 0.31388 (9) | 0.7214 (3) | 0.066 (1) | |
C22 | 0.3513 (1) | 0.32295 (9) | 0.5865 (3) | 0.061 (1) | |
C23 | 0.4166 (1) | 0.33746 (9) | 0.5480 (2) | 0.0494 (10) | |
C24 | 0.5871 (1) | 0.32564 (8) | 0.5414 (3) | 0.0477 (10) | |
C25 | 0.5617 (1) | 0.28857 (9) | 0.4721 (4) | 0.072 (1) | |
C26 | 0.6071 (2) | 0.25845 (9) | 0.4122 (4) | 0.097 (2) | |
C27 | 0.6779 (2) | 0.2654 (1) | 0.4216 (4) | 0.097 (2) | |
C28 | 0.7033 (1) | 0.3024 (1) | 0.4909 (4) | 0.087 (2) | |
C29 | 0.6579 (1) | 0.3326 (1) | 0.5508 (3) | 0.070 (1) | |
C30 | 0.1934 (2) | 0.4010 (2) | 0.4437 (6) | 0.072 (1) | |
H1 | 0.4690 | 0.4589 | 0.0157 | 0.0416* | |
H2 | 0.2790 | 0.4737 | 0.2448 | 0.0668* | |
H3 | 0.1792 | 0.4889 | 0.1197 | 0.0870* | |
H4 | 0.1722 | 0.4667 | −0.1064 | 0.0899* | |
H5 | 0.2651 | 0.4295 | −0.2076 | 0.0825* | |
H6 | 0.3649 | 0.4142 | −0.0826 | 0.0626* | |
H7 | 0.3180 | 0.3632 | 0.2107 | 0.0501* | |
H8 | 0.3418 | 0.2862 | 0.2211 | 0.0597* | |
H9 | 0.4541 | 0.2602 | 0.1820 | 0.0710* | |
H10 | 0.5425 | 0.3111 | 0.1323 | 0.0712* | |
H11 | 0.5187 | 0.3881 | 0.1219 | 0.0581* | |
H12 | 0.4967 | 0.4388 | 0.6670 | 0.0474* | |
H13 | 0.4427 | 0.4286 | 0.5555 | 0.0474* | |
H14 | 0.5184 | 0.3942 | 0.4297 | 0.0514* | |
H15 | 0.5802 | 0.4148 | 0.5076 | 0.0514* | |
H16 | 0.5602 | 0.3693 | 0.6883 | 0.0520* | |
H17 | 0.4893 | 0.3375 | 0.8452 | 0.0636* | |
H18 | 0.3794 | 0.3131 | 0.9099 | 0.0798* | |
H19 | 0.2928 | 0.3040 | 0.7474 | 0.0795* | |
H20 | 0.3162 | 0.3193 | 0.5204 | 0.0730* | |
H21 | 0.4262 | 0.3437 | 0.4558 | 0.0593* | |
H22 | 0.5133 | 0.2838 | 0.4659 | 0.0860* | |
H23 | 0.5897 | 0.2331 | 0.3650 | 0.1183* | |
H24 | 0.7089 | 0.2448 | 0.3804 | 0.1161* | |
H25 | 0.7516 | 0.3072 | 0.4968 | 0.1047* | |
H26 | 0.6752 | 0.3579 | 0.5977 | 0.0825* | |
H27 | 0.2406 | 0.4092 | 0.4449 | 0.0864* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0421 (3) | 0.0223 (2) | 0.0279 (3) | −0.0042 (3) | −0.0015 (3) | −0.0007 (3) |
Cl1 | 0.0811 (10) | 0.0693 (9) | 0.193 (2) | 0.0002 (8) | −0.023 (1) | 0.021 (1) |
Cl2 | 0.115 (1) | 0.189 (2) | 0.096 (1) | −0.005 (1) | −0.004 (1) | −0.025 (1) |
Cl3 | 0.0743 (9) | 0.110 (1) | 0.121 (1) | −0.0162 (9) | −0.0226 (9) | 0.050 (1) |
O1 | 0.055 (2) | 0.044 (1) | 0.032 (1) | −0.021 (1) | 0.004 (1) | −0.002 (1) |
O2 | 0.042 (1) | 0.040 (1) | 0.037 (1) | −0.006 (1) | 0.007 (1) | 0.001 (1) |
N1 | 0.040 (2) | 0.027 (1) | 0.029 (1) | −0.007 (1) | 0.002 (1) | −0.002 (1) |
N2 | 0.043 (2) | 0.032 (1) | 0.028 (1) | −0.009 (1) | 0.004 (1) | −0.002 (1) |
N3 | 0.057 (2) | 0.027 (1) | 0.033 (2) | −0.006 (1) | −0.002 (1) | 0.002 (1) |
C1 | 0.038 (2) | 0.029 (2) | 0.032 (2) | −0.003 (1) | −0.001 (1) | 0.000 (1) |
C2 | 0.037 (2) | 0.025 (2) | 0.038 (2) | 0.001 (1) | 0.000 (2) | −0.002 (1) |
C3 | 0.035 (2) | 0.025 (2) | 0.034 (2) | −0.003 (1) | −0.002 (1) | −0.001 (1) |
C4 | 0.043 (2) | 0.029 (2) | 0.040 (2) | −0.003 (1) | −0.005 (2) | 0.003 (1) |
C5 | 0.049 (2) | 0.051 (2) | 0.066 (3) | 0.007 (2) | −0.007 (2) | 0.006 (2) |
C6 | 0.045 (3) | 0.071 (3) | 0.106 (4) | 0.013 (2) | −0.005 (3) | 0.021 (3) |
C7 | 0.062 (3) | 0.067 (3) | 0.097 (4) | −0.020 (3) | −0.036 (3) | 0.037 (3) |
C8 | 0.081 (3) | 0.058 (3) | 0.062 (3) | −0.015 (2) | −0.032 (3) | 0.012 (2) |
C9 | 0.059 (3) | 0.047 (2) | 0.048 (2) | −0.004 (2) | −0.017 (2) | 0.002 (2) |
C10 | 0.043 (2) | 0.029 (2) | 0.031 (2) | 0.000 (1) | −0.004 (2) | −0.003 (1) |
C11 | 0.046 (2) | 0.034 (2) | 0.045 (2) | −0.006 (2) | −0.001 (2) | −0.002 (2) |
C12 | 0.061 (3) | 0.033 (2) | 0.056 (2) | −0.008 (2) | −0.003 (2) | −0.002 (2) |
C13 | 0.078 (3) | 0.031 (2) | 0.068 (3) | 0.009 (2) | −0.011 (2) | −0.003 (2) |
C14 | 0.056 (2) | 0.048 (2) | 0.074 (3) | 0.018 (2) | 0.003 (2) | −0.005 (2) |
C15 | 0.046 (2) | 0.039 (2) | 0.059 (3) | 0.002 (2) | −0.003 (2) | −0.004 (2) |
C16 | 0.050 (2) | 0.031 (2) | 0.047 (2) | −0.004 (2) | −0.003 (2) | 0.006 (2) |
C17 | 0.050 (2) | 0.035 (2) | 0.045 (2) | −0.004 (2) | −0.010 (2) | 0.004 (2) |
C18 | 0.046 (2) | 0.025 (2) | 0.045 (2) | 0.002 (2) | −0.004 (2) | 0.001 (1) |
C19 | 0.067 (3) | 0.045 (2) | 0.046 (2) | −0.002 (2) | −0.001 (2) | −0.003 (2) |
C20 | 0.086 (3) | 0.061 (3) | 0.052 (3) | −0.002 (3) | 0.024 (3) | −0.004 (2) |
C21 | 0.055 (3) | 0.053 (3) | 0.089 (4) | −0.004 (2) | 0.016 (3) | −0.001 (3) |
C22 | 0.049 (2) | 0.055 (2) | 0.080 (3) | −0.005 (2) | −0.011 (2) | −0.001 (2) |
C23 | 0.056 (2) | 0.043 (2) | 0.049 (2) | −0.010 (2) | −0.007 (2) | 0.007 (2) |
C24 | 0.046 (2) | 0.039 (2) | 0.057 (2) | 0.004 (2) | 0.000 (2) | 0.010 (2) |
C25 | 0.055 (3) | 0.046 (2) | 0.115 (5) | −0.001 (2) | 0.013 (3) | −0.016 (3) |
C26 | 0.080 (4) | 0.065 (3) | 0.147 (6) | 0.008 (3) | 0.017 (4) | −0.033 (4) |
C27 | 0.084 (4) | 0.086 (4) | 0.121 (5) | 0.036 (3) | 0.024 (4) | −0.005 (4) |
C28 | 0.055 (3) | 0.117 (5) | 0.090 (4) | 0.017 (3) | 0.004 (3) | 0.002 (4) |
C29 | 0.055 (3) | 0.077 (3) | 0.078 (3) | −0.002 (2) | −0.004 (2) | 0.001 (3) |
C30 | 0.042 (2) | 0.081 (3) | 0.092 (4) | −0.008 (2) | −0.008 (2) | 0.016 (3) |
Geometric parameters (Å, º) top
Cu1—N1 | 2.009 (3) | C13—C14 | 1.390 (3) |
Cu1—N3 | 2.005 (3) | C13—H9 | 0.950 |
Cl1—C30 | 1.742 (5) | C14—C15 | 1.390 (3) |
Cl2—C30 | 1.761 (6) | C14—H10 | 0.950 |
Cl3—C30 | 1.725 (6) | C15—H11 | 0.950 |
O1—C1 | 1.232 (4) | C16—C17 | 1.547 (5) |
O2—C2 | 1.222 (4) | C16—H14 | 0.950 |
N1—C1 | 1.401 (4) | C16—H15 | 0.950 |
N1—C2 | 1.372 (4) | C17—C18 | 1.512 (4) |
N2—C1 | 1.346 (4) | C17—C24 | 1.534 (4) |
N2—C3 | 1.460 (4) | C17—H16 | 0.950 |
N2—H1 | 0.950 | C18—C19 | 1.390 (3) |
N3—C16 | 1.482 (4) | C18—C23 | 1.390 (3) |
N3—H12 | 0.950 | C19—C20 | 1.390 (4) |
N3—H13 | 0.950 | C19—H17 | 0.950 |
C2—C3 | 1.549 (5) | C20—C21 | 1.390 (4) |
C3—C4 | 1.532 (4) | C20—H18 | 0.950 |
C3—C10 | 1.529 (3) | C21—C22 | 1.390 (4) |
C4—C5 | 1.390 (4) | C21—H19 | 0.950 |
C4—C9 | 1.390 (3) | C22—C23 | 1.390 (3) |
C5—C6 | 1.390 (4) | C22—H20 | 0.950 |
C5—H2 | 0.950 | C23—H21 | 0.950 |
C6—C7 | 1.390 (5) | C24—C25 | 1.390 (4) |
C6—H3 | 0.950 | C24—C29 | 1.390 (4) |
C7—C8 | 1.390 (4) | C25—C26 | 1.390 (4) |
C7—H4 | 0.950 | C25—H22 | 0.950 |
C8—C9 | 1.390 (4) | C26—C27 | 1.390 (5) |
C8—H5 | 0.950 | C26—H23 | 0.950 |
C9—H6 | 0.950 | C27—C28 | 1.390 (5) |
C10—C11 | 1.390 (3) | C27—H24 | 0.950 |
C10—C15 | 1.390 (3) | C28—C29 | 1.390 (4) |
C11—C12 | 1.390 (3) | C28—H25 | 0.950 |
C11—H7 | 0.950 | C29—H26 | 0.950 |
C12—C13 | 1.390 (4) | C30—H27 | 0.950 |
C12—H8 | 0.950 | | |
| | | |
N1—Cu1—N1i | 180.0 | C13—C14—H10 | 120.0 |
N1—Cu1—N3 | 89.2 (1) | C15—C14—H10 | 120.0 |
N1—Cu1—N3i | 90.8 (1) | C10—C15—C14 | 120.0 (2) |
N3—Cu1—N3i | 180.0 | C10—C15—H11 | 119.9 |
Cu1—N1—C1 | 123.8 (2) | C14—C15—H11 | 120.1 |
Cu1—N1—C2 | 127.3 (2) | N3—C16—C17 | 112.6 (3) |
C1—N1—C2 | 107.6 (3) | N3—C16—H14 | 108.7 |
C1—N2—C3 | 111.4 (3) | N3—C16—H15 | 108.5 |
C1—N2—H1 | 124.3 | C17—C16—H14 | 108.8 |
C3—N2—H1 | 124.3 | C17—C16—H15 | 108.7 |
Cu1—N3—C16 | 117.0 (2) | H14—C16—H15 | 109.3 |
Cu1—N3—H12 | 107.6 | C16—C17—C18 | 112.3 (3) |
Cu1—N3—H13 | 107.3 | C16—C17—C24 | 109.5 (3) |
C16—N3—H12 | 107.8 | C16—C17—H16 | 106.4 |
C16—N3—H13 | 107.5 | C18—C17—C24 | 115.2 (3) |
H12—N3—H13 | 109.5 | C18—C17—H16 | 106.3 |
O1—C1—N1 | 123.8 (3) | C24—C17—H16 | 106.5 |
O1—C1—N2 | 125.2 (3) | C17—C18—C19 | 118.7 (2) |
N1—C1—N2 | 111.1 (3) | C17—C18—C23 | 121.2 (2) |
O2—C2—N1 | 126.3 (3) | C19—C18—C23 | 120.0 (2) |
O2—C2—C3 | 124.2 (3) | C18—C19—C20 | 120.0 (2) |
N1—C2—C3 | 109.4 (3) | C18—C19—H17 | 120.0 |
N2—C3—C2 | 100.0 (2) | C20—C19—H17 | 120.0 |
N2—C3—C4 | 109.8 (2) | C19—C20—C21 | 120.0 (2) |
N2—C3—C10 | 113.4 (2) | C19—C20—H18 | 120.1 |
C2—C3—C4 | 114.9 (2) | C21—C20—H18 | 119.9 |
C2—C3—C10 | 107.3 (2) | C20—C21—C22 | 120.0 (2) |
C4—C3—C10 | 111.1 (2) | C20—C21—H19 | 120.1 |
C3—C4—C5 | 123.3 (2) | C22—C21—H19 | 119.9 |
C3—C4—C9 | 116.6 (2) | C21—C22—C23 | 120.0 (2) |
C5—C4—C9 | 120.0 (2) | C21—C22—H20 | 120.1 |
C4—C5—C6 | 120.0 (2) | C23—C22—H20 | 119.9 |
C4—C5—H2 | 120.1 | C18—C23—C22 | 120.0 (2) |
C6—C5—H2 | 119.9 | C18—C23—H21 | 119.9 |
C5—C6—C7 | 120.0 (2) | C22—C23—H21 | 120.1 |
C5—C6—H3 | 119.9 | C17—C24—C25 | 121.8 (2) |
C7—C6—H3 | 120.1 | C17—C24—C29 | 118.2 (3) |
C6—C7—C8 | 120.0 (2) | C25—C24—C29 | 120.0 (2) |
C6—C7—H4 | 119.8 | C24—C25—C26 | 120.0 (2) |
C8—C7—H4 | 120.2 | C24—C25—H22 | 119.9 |
C7—C8—C9 | 120.0 (2) | C26—C25—H22 | 120.1 |
C7—C8—H5 | 119.9 | C25—C26—C27 | 120.0 (3) |
C9—C8—H5 | 120.1 | C25—C26—H23 | 119.9 |
C4—C9—C8 | 120.0 (2) | C27—C26—H23 | 120.1 |
C4—C9—H6 | 119.9 | C26—C27—C28 | 120.0 (3) |
C8—C9—H6 | 120.1 | C26—C27—H24 | 119.9 |
C3—C10—C11 | 118.7 (2) | C28—C27—H24 | 120.1 |
C3—C10—C15 | 121.3 (2) | C27—C28—C29 | 120.0 (2) |
C11—C10—C15 | 120.0 (2) | C27—C28—H25 | 119.9 |
C10—C11—C12 | 120.0 (2) | C29—C28—H25 | 120.1 |
C10—C11—H7 | 120.0 | C24—C29—C28 | 120.0 (3) |
C12—C11—H7 | 120.0 | C24—C29—H26 | 120.1 |
C11—C12—C13 | 120.0 (2) | C28—C29—H26 | 119.9 |
C11—C12—H8 | 120.0 | Cl1—C30—Cl2 | 110.9 (3) |
C13—C12—H8 | 120.0 | Cl1—C30—Cl3 | 110.3 (3) |
C12—C13—C14 | 120.0 (2) | Cl1—C30—H27 | 108.8 |
C12—C13—H9 | 120.0 | Cl2—C30—Cl3 | 109.3 (3) |
C14—C13—H9 | 120.0 | Cl2—C30—H27 | 108.6 |
C13—C14—C15 | 120.0 (2) | Cl3—C30—H27 | 108.9 |
| | | |
Cu1—N1—C1—O1 | −18.9 (5) | C4—C3—C10—C11 | −44.1 (3) |
Cu1—N1—C1—N2 | 160.4 (2) | C4—C3—C10—C15 | 138.6 (3) |
Cu1—N1—C2—O2 | 15.3 (5) | C4—C5—C6—C7 | 0.0 (4) |
Cu1—N1—C2—C3 | −161.7 (2) | C4—C9—C8—C7 | 0.0 (4) |
Cu1—N1i—C1i—O1i | 18.9 (5) | C5—C4—C3—C10 | 123.3 (3) |
Cu1—N1i—C1i—N2i | −160.4 (2) | C5—C4—C9—C8 | 0.0 (4) |
Cu1—N1i—C2i—O2i | −15.3 (5) | C5—C6—C7—C8 | 0.0 (5) |
Cu1—N1i—C2i—C3i | 161.7 (2) | C6—C5—C4—C9 | 0.0 (4) |
Cu1—N3—C16—C17 | 162.3 (2) | C6—C7—C8—C9 | 0.0 (5) |
Cu1—N3i—C16i—C17i | −162.3 (2) | C9—C4—C3—C10 | −59.4 (3) |
O1—C1—N1—C2 | 173.1 (3) | C10—C11—C12—C13 | 0.0 (4) |
O1—C1—N2—C3 | −174.3 (3) | C10—C15—C14—C13 | 0.0 (4) |
O2—C2—N1—C1 | −177.3 (3) | C11—C10—C15—C14 | 0.0 (4) |
O2—C2—C3—N2 | −179.1 (3) | C11—C12—C13—C14 | 0.0 (4) |
O2—C2—C3—C10 | −60.5 (4) | C12—C11—C10—C15 | 0.0 (4) |
N1—Cu1—N3i—C16i | 106.8 (2) | C12—C13—C14—C15 | 0.0 (4) |
N1—C1—N2—C3 | 6.4 (4) | C16—C17—C18—C19 | −130.1 (3) |
N1—C2—C3—N2 | −2.0 (3) | C16—C17—C18—C23 | 47.7 (4) |
N1—C2—C3—C4 | −119.4 (3) | C16—C17—C24—C25 | −102.2 (4) |
N1—C2—C3—C10 | 116.6 (3) | C16—C17—C24—C29 | 76.6 (4) |
N2—C1—N1—C2 | −7.6 (4) | C17—C18—C19—C20 | 177.8 (3) |
N2—C3—C4—C5 | −110.4 (3) | C17—C18—C23—C22 | −177.7 (3) |
N2—C3—C4—C9 | 66.9 (3) | C17—C24—C25—C26 | 178.8 (3) |
N2—C3—C10—C11 | −168.3 (2) | C17—C24—C29—C28 | −178.8 (3) |
N2—C3—C10—C15 | 14.4 (4) | C18—C17—C24—C25 | 25.5 (4) |
N3—Cu1—N1—C1 | −130.9 (3) | C18—C17—C24—C29 | −155.7 (3) |
N3—Cu1—N1—C2 | 34.6 (3) | C18—C19—C20—C21 | 0.0 (4) |
N3—Cu1—N1i—C1i | −49.1 (3) | C18—C23—C22—C21 | 0.0 (4) |
N3—Cu1—N1i—C2i | 145.4 (3) | C19—C18—C17—C24 | 103.7 (3) |
N3—C16—C17—C24 | 179.8 (3) | C19—C18—C23—C22 | 0.0 (4) |
C1—N1—C2—C3 | 5.7 (3) | C19—C20—C21—C22 | 0.0 (4) |
C1—N2—C3—C2 | −2.7 (3) | C20—C19—C18—C23 | 0.0 (4) |
C1—N2—C3—C4 | 118.5 (3) | C20—C21—C22—C23 | 0.0 (4) |
C1—N2—C3—C10 | −116.6 (3) | C23—C18—C17—C24 | −78.6 (4) |
C2—C3—C4—C5 | 1.3 (4) | C24—C25—C26—C27 | 0.0 (5) |
C2—C3—C4—C9 | 178.6 (2) | C24—C29—C28—C27 | 0.0 (5) |
C2—C3—C10—C11 | 82.2 (3) | C25—C24—C29—C28 | 0.0 (5) |
C2—C3—C10—C15 | −95.1 (3) | C25—C26—C27—C28 | 0.0 (6) |
C3—C4—C5—C6 | 177.2 (3) | C26—C25—C24—C29 | 0.0 (5) |
C3—C4—C9—C8 | −177.4 (2) | C26—C27—C28—C29 | 0.0 (6) |
C3—C10—C11—C12 | −177.3 (2) | C26—C27—C28—C29 | 0.0 (6) |
C3—C10—C15—C14 | 177.2 (3) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1···O1ii | 0.95 | 2.02 | 2.900 (3) | 153 |
N3—H12···O1i | 0.95 | 2.06 | 2.837 (3) | 137 |
N3—H13···O2 | 0.95 | 2.13 | 2.922 (3) | 140 |
C30—H27···O2 | 0.95 | 2.57 | 3.507 (5) | 170 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z. |
Crystal data top
[Cu(C15H11N2O2)2(C14H15N)2] | Z = 2 |
Mr = 960.63 | F(000) = 1006 |
Triclinic, P1 | Dx = 1.327 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.7107 Å |
a = 14.313 (4) Å | Cell parameters from 25 reflections |
b = 15.888 (5) Å | θ = 10.0–12.4° |
c = 11.863 (4) Å | µ = 0.51 mm−1 |
α = 90.13 (3)° | T = 298 K |
β = 95.00 (3)° | Plate-like, blue–violet |
γ = 63.58 (2)° | 0.50 × 0.40 × 0.20 mm |
V = 2404.7 (14) Å3 | |
Data collection top
Rigaku AFC-7R diffractometer | Rint = 0.087 |
ω/2θ scans | θmax = 27.5° |
Absorption correction: ψ scan (North et al., 1968) | h = −18→18 |
Tmin = 0.783, Tmax = 0.903 | k = −20→20 |
12233 measured reflections | l = −6→15 |
12233 independent reflections | 3 standard reflections every 150 reflections |
11075 reflections with I > 0σ(I) | intensity decay: 0.3% |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.069 | w = 1/[σ2(Fo2) + (0.0502P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.161 | (Δ/σ)max < 0.001 |
S = 0.85 | Δρmax = 0.62 e Å−3 |
11075 reflections | Δρmin = −1.31 e Å−3 |
527 parameters | |
Crystal data top
[Cu(C15H11N2O2)2(C14H15N)2] | γ = 63.58 (2)° |
Mr = 960.63 | V = 2404.7 (14) Å3 |
Triclinic, P1 | Z = 2 |
a = 14.313 (4) Å | Mo Kα radiation |
b = 15.888 (5) Å | µ = 0.51 mm−1 |
c = 11.863 (4) Å | T = 298 K |
α = 90.13 (3)° | 0.50 × 0.40 × 0.20 mm |
β = 95.00 (3)° | |
Data collection top
Rigaku AFC-7R diffractometer | 11075 reflections with I > 0σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.087 |
Tmin = 0.783, Tmax = 0.903 | 3 standard reflections every 150 reflections |
12233 measured reflections | intensity decay: 0.3% |
12233 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.069 | 527 parameters |
wR(F2) = 0.161 | H-atom parameters constrained |
S = 0.85 | Δρmax = 0.62 e Å−3 |
11075 reflections | Δρmin = −1.31 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.99199 (5) | 0.48877 (4) | 0.29269 (5) | 0.0246 (2) | |
O1 | 1.0577 (2) | 0.4010 (2) | 0.0607 (3) | 0.0412 (9) | |
O2 | 0.7685 (3) | 0.4529 (2) | 0.2396 (3) | 0.0397 (9) | |
O3 | 1.1150 (2) | 0.4528 (2) | 0.5536 (3) | 0.0298 (8) | |
O4 | 1.1108 (2) | 0.6262 (2) | 0.2463 (3) | 0.0349 (8) | |
N1 | 0.9244 (3) | 0.4360 (3) | 0.1786 (3) | 0.0279 (9) | |
N2 | 0.9004 (3) | 0.4027 (3) | −0.0037 (3) | 0.0324 (10) | |
N3 | 0.9143 (3) | 0.6129 (3) | 0.2026 (3) | 0.0278 (9) | |
N4 | 1.0937 (3) | 0.5284 (3) | 0.3785 (3) | 0.0235 (9) | |
N5 | 1.2063 (3) | 0.5348 (3) | 0.5203 (3) | 0.0314 (10) | |
N6 | 1.0715 (3) | 0.3589 (3) | 0.3699 (3) | 0.0317 (10) | |
C1 | 0.9685 (4) | 0.4116 (3) | 0.0750 (4) | 0.030 (1) | |
C2 | 0.8292 (4) | 0.4377 (3) | 0.1662 (4) | 0.031 (1) | |
C3 | 0.8029 (3) | 0.4189 (3) | 0.0426 (4) | 0.025 (1) | |
C4 | 0.7880 (3) | 0.3298 (2) | 0.0300 (3) | 0.034 (1) | |
C5 | 0.8239 (3) | 0.2610 (3) | 0.1168 (2) | 0.072 (2) | |
C6 | 0.8201 (4) | 0.1761 (2) | 0.0992 (3) | 0.092 (3) | |
C7 | 0.7802 (4) | 0.1599 (2) | −0.0053 (4) | 0.063 (2) | |
C8 | 0.7443 (3) | 0.2287 (3) | −0.0921 (3) | 0.059 (2) | |
C9 | 0.7481 (3) | 0.3137 (2) | −0.0744 (3) | 0.049 (1) | |
C10 | 0.7094 (2) | 0.5085 (2) | −0.0082 (3) | 0.030 (1) | |
C11 | 0.6111 (3) | 0.5302 (2) | 0.0261 (3) | 0.043 (1) | |
C12 | 0.5255 (2) | 0.6140 (3) | −0.0119 (4) | 0.057 (2) | |
C13 | 0.5381 (3) | 0.6760 (2) | −0.0843 (4) | 0.068 (2) | |
C14 | 0.6364 (3) | 0.6544 (2) | −0.1186 (3) | 0.057 (2) | |
C15 | 0.7221 (2) | 0.5706 (3) | −0.0806 (3) | 0.044 (1) | |
C16 | 0.8022 (4) | 0.6693 (3) | 0.2186 (4) | 0.033 (1) | |
C17 | 0.7472 (4) | 0.7552 (3) | 0.1361 (4) | 0.033 (1) | |
C18 | 0.6293 (2) | 0.8074 (3) | 0.1473 (3) | 0.039 (1) | |
C19 | 0.5650 (3) | 0.8633 (3) | 0.0552 (3) | 0.058 (2) | |
C20 | 0.4577 (3) | 0.9138 (3) | 0.0619 (3) | 0.073 (2) | |
C21 | 0.4148 (2) | 0.9085 (3) | 0.1607 (4) | 0.068 (2) | |
C22 | 0.4791 (3) | 0.8526 (3) | 0.2528 (3) | 0.081 (2) | |
C23 | 0.5864 (3) | 0.8020 (3) | 0.2462 (3) | 0.077 (2) | |
C24 | 0.8010 (3) | 0.8194 (2) | 0.1466 (3) | 0.038 (1) | |
C25 | 0.7791 (3) | 0.8839 (3) | 0.2317 (3) | 0.058 (2) | |
C26 | 0.8346 (4) | 0.9366 (3) | 0.2466 (4) | 0.074 (2) | |
C27 | 0.9119 (3) | 0.9250 (3) | 0.1763 (4) | 0.082 (2) | |
C28 | 0.9338 (3) | 0.8605 (3) | 0.0912 (4) | 0.077 (2) | |
C29 | 0.8784 (3) | 0.8077 (3) | 0.0763 (3) | 0.057 (2) | |
C30 | 1.1366 (3) | 0.5020 (3) | 0.4901 (4) | 0.025 (1) | |
C31 | 1.1328 (3) | 0.5871 (3) | 0.3411 (4) | 0.027 (1) | |
C32 | 1.2061 (3) | 0.6000 (3) | 0.4340 (4) | 0.027 (1) | |
C33 | 1.1617 (3) | 0.6985 (2) | 0.4796 (3) | 0.032 (1) | |
C34 | 1.0631 (3) | 0.7685 (3) | 0.4410 (3) | 0.061 (2) | |
C35 | 1.0255 (3) | 0.8566 (2) | 0.4874 (4) | 0.086 (2) | |
C36 | 1.0864 (4) | 0.8748 (2) | 0.5724 (4) | 0.068 (2) | |
C37 | 1.1851 (4) | 0.8048 (3) | 0.6111 (3) | 0.072 (2) | |
C38 | 1.2227 (2) | 0.7166 (3) | 0.5647 (3) | 0.056 (2) | |
C39 | 1.3152 (2) | 0.5693 (3) | 0.3915 (3) | 0.034 (1) | |
C40 | 1.3475 (3) | 0.6353 (2) | 0.3584 (3) | 0.052 (2) | |
C41 | 1.4448 (3) | 0.6058 (3) | 0.3175 (4) | 0.072 (2) | |
C42 | 1.5098 (2) | 0.5104 (3) | 0.3096 (3) | 0.066 (2) | |
C43 | 1.4775 (3) | 0.4444 (2) | 0.3426 (4) | 0.075 (2) | |
C44 | 1.3801 (3) | 0.4739 (2) | 0.3836 (4) | 0.058 (2) | |
C45 | 1.1778 (4) | 0.3075 (3) | 0.3330 (4) | 0.040 (1) | |
C46 | 1.2445 (4) | 0.2093 (4) | 0.3910 (4) | 0.039 (1) | |
C47 | 1.3600 (2) | 0.1808 (3) | 0.3729 (3) | 0.043 (1) | |
C48 | 1.4149 (3) | 0.2214 (3) | 0.4356 (3) | 0.061 (2) | |
C49 | 1.5179 (3) | 0.1979 (3) | 0.4167 (4) | 0.078 (2) | |
C50 | 1.5660 (2) | 0.1339 (3) | 0.3352 (4) | 0.076 (2) | |
C51 | 1.5111 (3) | 0.0934 (3) | 0.2725 (3) | 0.072 (2) | |
C52 | 1.4081 (3) | 0.1168 (3) | 0.2914 (3) | 0.054 (2) | |
C53 | 1.2101 (3) | 0.1341 (2) | 0.3606 (3) | 0.041 (1) | |
C54 | 1.2504 (3) | 0.0531 (3) | 0.4303 (3) | 0.054 (2) | |
C55 | 1.2255 (3) | −0.0200 (2) | 0.4026 (4) | 0.066 (2) | |
C56 | 1.1603 (3) | −0.0122 (3) | 0.3051 (4) | 0.072 (2) | |
C57 | 1.1200 (3) | 0.0688 (3) | 0.2354 (3) | 0.074 (2) | |
C58 | 1.1449 (3) | 0.1419 (2) | 0.2632 (3) | 0.060 (2) | |
H1 | 0.9141 | 0.3877 | −0.0800 | 0.0386* | |
H2 | 0.8510 | 0.2720 | 0.1882 | 0.0871* | |
H3 | 0.8445 | 0.1291 | 0.1584 | 0.1109* | |
H4 | 0.7775 | 0.1019 | −0.0175 | 0.0752* | |
H5 | 0.7171 | 0.2177 | −0.1636 | 0.0711* | |
H6 | 0.7237 | 0.3607 | −0.1338 | 0.0593* | |
H7 | 0.6025 | 0.4878 | 0.0756 | 0.0515* | |
H8 | 0.4583 | 0.6287 | 0.0116 | 0.0685* | |
H9 | 0.4795 | 0.7332 | −0.1103 | 0.0812* | |
H10 | 0.6450 | 0.6967 | −0.1681 | 0.0681* | |
H11 | 0.7893 | 0.5558 | −0.1040 | 0.0522* | |
H12 | 0.9491 | 0.6505 | 0.2225 | 0.0331* | |
H13 | 0.9189 | 0.5997 | 0.1246 | 0.0331* | |
H14 | 0.7678 | 0.6303 | 0.2079 | 0.0397* | |
H15 | 0.7970 | 0.6905 | 0.2939 | 0.0397* | |
H16 | 0.7549 | 0.7321 | 0.0619 | 0.0388* | |
H17 | 0.5944 | 0.8670 | −0.0123 | 0.0701* | |
H18 | 0.4138 | 0.9520 | −0.0011 | 0.0879* | |
H19 | 0.3414 | 0.9430 | 0.1652 | 0.0807* | |
H20 | 0.4497 | 0.8489 | 0.3203 | 0.0979* | |
H21 | 0.6303 | 0.7639 | 0.3092 | 0.0925* | |
H22 | 0.7263 | 0.8918 | 0.2797 | 0.0701* | |
H23 | 0.8196 | 0.9807 | 0.3047 | 0.0880* | |
H24 | 0.9498 | 0.9611 | 0.1864 | 0.0983* | |
H25 | 0.9866 | 0.8526 | 0.0431 | 0.0923* | |
H26 | 0.8933 | 0.7637 | 0.0181 | 0.0684* | |
H27 | 1.2502 | 0.5178 | 0.5894 | 0.0375* | |
H28 | 1.0215 | 0.7561 | 0.3827 | 0.0732* | |
H29 | 0.9580 | 0.9045 | 0.4608 | 0.1035* | |
H30 | 1.0606 | 0.9351 | 0.6041 | 0.0813* | |
H31 | 1.2265 | 0.8173 | 0.6693 | 0.0859* | |
H32 | 1.2900 | 0.6689 | 0.5911 | 0.0676* | |
H33 | 1.3031 | 0.7005 | 0.3638 | 0.0630* | |
H34 | 1.4670 | 0.6509 | 0.2949 | 0.0869* | |
H35 | 1.5763 | 0.4903 | 0.2816 | 0.0787* | |
H36 | 1.5218 | 0.3792 | 0.3372 | 0.0898* | |
H37 | 1.3580 | 0.4288 | 0.4062 | 0.0698* | |
H38 | 1.0772 | 0.3656 | 0.4496 | 0.0380* | |
H39 | 1.0336 | 0.3237 | 0.3523 | 0.0380* | |
H40 | 1.1712 | 0.3000 | 0.2537 | 0.0480* | |
H41 | 1.2142 | 0.3446 | 0.3484 | 0.0480* | |
H42 | 1.2391 | 0.2174 | 0.4699 | 0.0468* | |
H43 | 1.3820 | 0.2650 | 0.4915 | 0.0733* | |
H44 | 1.5555 | 0.2256 | 0.4597 | 0.0940* | |
H45 | 1.6365 | 0.1179 | 0.3225 | 0.0920* | |
H46 | 1.5441 | 0.0497 | 0.2169 | 0.0871* | |
H47 | 1.3706 | 0.0891 | 0.2486 | 0.0647* | |
H48 | 1.2948 | 0.0479 | 0.4970 | 0.0651* | |
H49 | 1.2529 | −0.0753 | 0.4503 | 0.0795* | |
H50 | 1.1432 | −0.0622 | 0.2862 | 0.0863* | |
H51 | 1.0755 | 0.0741 | 0.1688 | 0.0883* | |
H52 | 1.1174 | 0.1972 | 0.2155 | 0.0720* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0241 (3) | 0.0258 (3) | 0.0235 (3) | −0.0109 (3) | 0.0019 (3) | −0.0015 (3) |
O1 | 0.026 (2) | 0.060 (2) | 0.043 (2) | −0.024 (2) | 0.006 (2) | −0.004 (2) |
O2 | 0.045 (2) | 0.063 (2) | 0.022 (2) | −0.031 (2) | 0.015 (2) | −0.009 (2) |
O3 | 0.035 (2) | 0.033 (2) | 0.024 (2) | −0.016 (2) | 0.003 (1) | 0.004 (1) |
O4 | 0.040 (2) | 0.048 (2) | 0.021 (2) | −0.024 (2) | 0.000 (2) | 0.008 (2) |
N1 | 0.030 (2) | 0.036 (2) | 0.016 (2) | −0.014 (2) | 0.000 (2) | 0.000 (2) |
N2 | 0.033 (2) | 0.049 (3) | 0.018 (2) | −0.021 (2) | 0.006 (2) | −0.006 (2) |
N3 | 0.026 (2) | 0.029 (2) | 0.026 (2) | −0.012 (2) | −0.003 (2) | 0.005 (2) |
N4 | 0.022 (2) | 0.031 (2) | 0.019 (2) | −0.013 (2) | 0.001 (2) | 0.005 (2) |
N5 | 0.028 (2) | 0.039 (2) | 0.027 (2) | −0.015 (2) | −0.003 (2) | 0.004 (2) |
N6 | 0.030 (2) | 0.031 (2) | 0.030 (2) | −0.011 (2) | −0.003 (2) | 0.001 (2) |
C1 | 0.037 (3) | 0.034 (3) | 0.026 (3) | −0.022 (2) | 0.001 (2) | 0.000 (2) |
C2 | 0.037 (3) | 0.036 (3) | 0.020 (3) | −0.017 (2) | −0.002 (2) | 0.004 (2) |
C3 | 0.028 (3) | 0.040 (3) | 0.015 (2) | −0.021 (2) | 0.006 (2) | −0.005 (2) |
C4 | 0.039 (3) | 0.033 (3) | 0.034 (3) | −0.020 (2) | 0.006 (2) | −0.003 (2) |
C5 | 0.123 (6) | 0.053 (4) | 0.051 (4) | −0.053 (4) | −0.009 (4) | 0.004 (3) |
C6 | 0.181 (8) | 0.066 (5) | 0.046 (4) | −0.073 (5) | −0.007 (5) | 0.001 (4) |
C7 | 0.086 (5) | 0.045 (4) | 0.065 (4) | −0.034 (4) | 0.003 (4) | −0.022 (3) |
C8 | 0.073 (4) | 0.055 (4) | 0.052 (4) | −0.034 (4) | −0.007 (3) | −0.007 (3) |
C9 | 0.079 (4) | 0.054 (4) | 0.032 (3) | −0.045 (3) | 0.009 (3) | −0.009 (3) |
C10 | 0.032 (3) | 0.035 (3) | 0.028 (3) | −0.019 (2) | 0.004 (2) | −0.006 (2) |
C11 | 0.037 (3) | 0.044 (3) | 0.051 (4) | −0.019 (3) | 0.011 (3) | −0.003 (3) |
C12 | 0.041 (4) | 0.059 (4) | 0.070 (4) | −0.020 (3) | 0.009 (3) | −0.001 (3) |
C13 | 0.047 (4) | 0.057 (4) | 0.087 (5) | −0.015 (3) | −0.011 (4) | 0.009 (4) |
C14 | 0.065 (4) | 0.058 (4) | 0.048 (4) | −0.030 (4) | −0.007 (3) | 0.021 (3) |
C15 | 0.045 (3) | 0.055 (4) | 0.044 (3) | −0.031 (3) | 0.010 (3) | 0.002 (3) |
C16 | 0.032 (3) | 0.031 (3) | 0.033 (3) | −0.010 (2) | 0.006 (2) | 0.004 (2) |
C17 | 0.035 (3) | 0.027 (3) | 0.028 (3) | −0.007 (2) | 0.004 (2) | 0.001 (2) |
C18 | 0.037 (3) | 0.023 (3) | 0.047 (3) | −0.005 (2) | 0.003 (3) | −0.001 (2) |
C19 | 0.041 (3) | 0.066 (4) | 0.044 (4) | −0.003 (3) | 0.002 (3) | 0.005 (3) |
C20 | 0.042 (4) | 0.076 (5) | 0.072 (5) | −0.002 (4) | −0.010 (3) | −0.007 (4) |
C21 | 0.032 (3) | 0.046 (4) | 0.116 (6) | −0.009 (3) | 0.010 (4) | −0.027 (4) |
C22 | 0.045 (4) | 0.094 (6) | 0.084 (5) | −0.009 (4) | 0.025 (4) | 0.017 (4) |
C23 | 0.040 (4) | 0.090 (5) | 0.073 (5) | −0.003 (4) | 0.013 (3) | 0.026 (4) |
C24 | 0.030 (3) | 0.033 (3) | 0.037 (3) | −0.002 (2) | −0.003 (2) | 0.010 (2) |
C25 | 0.054 (4) | 0.045 (4) | 0.073 (5) | −0.019 (3) | 0.009 (3) | −0.015 (3) |
C26 | 0.054 (4) | 0.054 (4) | 0.111 (6) | −0.022 (4) | 0.012 (4) | −0.034 (4) |
C27 | 0.063 (5) | 0.045 (4) | 0.141 (8) | −0.029 (4) | −0.002 (5) | 0.015 (5) |
C28 | 0.066 (5) | 0.065 (5) | 0.108 (6) | −0.034 (4) | 0.020 (4) | 0.021 (4) |
C29 | 0.064 (4) | 0.056 (4) | 0.058 (4) | −0.029 (3) | 0.021 (3) | 0.004 (3) |
C30 | 0.021 (2) | 0.026 (3) | 0.026 (3) | −0.008 (2) | 0.005 (2) | −0.001 (2) |
C31 | 0.024 (3) | 0.034 (3) | 0.021 (3) | −0.011 (2) | 0.005 (2) | −0.011 (2) |
C32 | 0.030 (3) | 0.036 (3) | 0.019 (2) | −0.019 (2) | 0.002 (2) | 0.001 (2) |
C33 | 0.040 (3) | 0.047 (3) | 0.023 (3) | −0.030 (3) | 0.011 (2) | −0.004 (2) |
C34 | 0.045 (4) | 0.048 (4) | 0.074 (5) | −0.009 (3) | −0.002 (3) | −0.016 (3) |
C35 | 0.056 (4) | 0.060 (5) | 0.125 (7) | −0.013 (4) | −0.001 (4) | −0.018 (5) |
C36 | 0.089 (5) | 0.058 (4) | 0.073 (5) | −0.043 (4) | 0.033 (4) | −0.023 (4) |
C37 | 0.113 (6) | 0.068 (5) | 0.057 (4) | −0.057 (5) | 0.024 (4) | −0.029 (4) |
C38 | 0.065 (4) | 0.059 (4) | 0.046 (4) | −0.030 (3) | −0.003 (3) | −0.007 (3) |
C39 | 0.024 (3) | 0.054 (3) | 0.026 (3) | −0.019 (3) | 0.000 (2) | 0.000 (2) |
C40 | 0.038 (3) | 0.067 (4) | 0.057 (4) | −0.026 (3) | 0.010 (3) | 0.010 (3) |
C41 | 0.048 (4) | 0.112 (6) | 0.069 (5) | −0.044 (4) | 0.013 (3) | 0.020 (4) |
C42 | 0.035 (4) | 0.118 (6) | 0.045 (4) | −0.034 (4) | 0.007 (3) | 0.002 (4) |
C43 | 0.043 (4) | 0.081 (5) | 0.090 (5) | −0.016 (4) | 0.024 (4) | −0.016 (4) |
C44 | 0.045 (4) | 0.057 (4) | 0.075 (5) | −0.022 (3) | 0.021 (3) | −0.016 (3) |
C45 | 0.036 (3) | 0.026 (3) | 0.043 (3) | −0.001 (2) | 0.002 (2) | 0.002 (2) |
C46 | 0.038 (3) | 0.037 (3) | 0.032 (3) | −0.007 (3) | 0.006 (2) | −0.002 (2) |
C47 | 0.044 (3) | 0.027 (3) | 0.047 (3) | −0.005 (3) | −0.006 (3) | 0.010 (3) |
C48 | 0.058 (4) | 0.065 (4) | 0.051 (4) | −0.021 (4) | −0.006 (3) | −0.005 (3) |
C49 | 0.055 (5) | 0.092 (6) | 0.086 (6) | −0.034 (4) | −0.012 (4) | 0.012 (5) |
C50 | 0.038 (4) | 0.075 (5) | 0.097 (6) | −0.008 (4) | 0.005 (4) | 0.020 (4) |
C51 | 0.055 (4) | 0.056 (4) | 0.092 (6) | −0.007 (4) | 0.033 (4) | −0.005 (4) |
C52 | 0.051 (4) | 0.046 (4) | 0.062 (4) | −0.018 (3) | 0.012 (3) | −0.003 (3) |
C53 | 0.031 (3) | 0.037 (3) | 0.047 (3) | −0.007 (3) | 0.006 (3) | 0.003 (3) |
C54 | 0.048 (4) | 0.035 (3) | 0.069 (4) | −0.010 (3) | 0.004 (3) | 0.013 (3) |
C55 | 0.057 (4) | 0.050 (4) | 0.093 (5) | −0.023 (3) | 0.018 (4) | 0.007 (4) |
C56 | 0.053 (4) | 0.049 (4) | 0.120 (7) | −0.023 (4) | 0.030 (4) | −0.021 (4) |
C57 | 0.062 (4) | 0.062 (5) | 0.092 (6) | −0.024 (4) | −0.001 (4) | −0.022 (4) |
C58 | 0.059 (4) | 0.045 (4) | 0.067 (4) | −0.018 (3) | −0.003 (3) | −0.006 (3) |
Geometric parameters (Å, º) top
Cu1—O3i | 2.397 (4) | C23—H21 | 0.950 |
Cu1—N1 | 1.990 (4) | C24—C25 | 1.390 (5) |
Cu1—N3 | 2.030 (3) | C24—C29 | 1.390 (6) |
Cu1—N4 | 2.026 (4) | C25—C26 | 1.390 (7) |
Cu1—N6 | 2.032 (4) | C25—H22 | 0.950 |
O1—C1 | 1.238 (7) | C26—C27 | 1.390 (7) |
O2—C2 | 1.232 (6) | C26—H23 | 0.950 |
O3—C30 | 1.237 (7) | C27—C28 | 1.390 (7) |
O4—C31 | 1.232 (6) | C27—H24 | 0.950 |
N1—C1 | 1.405 (6) | C28—C29 | 1.390 (8) |
N1—C2 | 1.345 (7) | C28—H25 | 0.950 |
N2—C1 | 1.343 (7) | C29—H26 | 0.950 |
N2—C3 | 1.459 (7) | C31—C32 | 1.532 (7) |
N2—H1 | 0.950 | C32—C33 | 1.522 (6) |
N3—C16 | 1.478 (6) | C32—C39 | 1.545 (6) |
N3—H12 | 0.950 | C33—C34 | 1.390 (4) |
N3—H13 | 0.950 | C33—C38 | 1.390 (5) |
N4—C30 | 1.392 (5) | C34—C35 | 1.390 (6) |
N4—C31 | 1.374 (7) | C34—H28 | 0.950 |
N5—C30 | 1.340 (7) | C35—C36 | 1.390 (7) |
N5—C32 | 1.457 (7) | C35—H29 | 0.950 |
N5—H27 | 0.950 | C36—C37 | 1.390 (5) |
N6—C45 | 1.478 (6) | C36—H30 | 0.950 |
N6—H38 | 0.950 | C37—C38 | 1.390 (6) |
N6—H39 | 0.950 | C37—H31 | 0.950 |
C2—C3 | 1.544 (6) | C38—H32 | 0.950 |
C3—C4 | 1.528 (7) | C39—C40 | 1.390 (6) |
C3—C10 | 1.532 (4) | C39—C44 | 1.390 (4) |
C4—C5 | 1.390 (5) | C40—C41 | 1.390 (6) |
C4—C9 | 1.390 (5) | C40—H33 | 0.950 |
C5—C6 | 1.390 (7) | C41—C42 | 1.390 (6) |
C5—H2 | 0.950 | C41—H34 | 0.950 |
C6—C7 | 1.390 (6) | C42—C43 | 1.390 (7) |
C6—H3 | 0.950 | C42—H35 | 0.950 |
C7—C8 | 1.390 (5) | C43—C44 | 1.390 (6) |
C7—H4 | 0.950 | C43—H36 | 0.950 |
C8—C9 | 1.390 (6) | C44—H37 | 0.950 |
C8—H5 | 0.950 | C45—C46 | 1.544 (6) |
C9—H6 | 0.950 | C45—H40 | 0.950 |
C10—C11 | 1.390 (5) | C45—H41 | 0.950 |
C10—C15 | 1.390 (6) | C46—C47 | 1.541 (6) |
C11—C12 | 1.390 (4) | C46—C53 | 1.515 (8) |
C11—H7 | 0.950 | C46—H42 | 0.950 |
C12—C13 | 1.390 (6) | C47—C48 | 1.390 (7) |
C12—H8 | 0.950 | C47—C52 | 1.390 (5) |
C13—C14 | 1.390 (6) | C48—C49 | 1.390 (7) |
C13—H9 | 0.950 | C48—H43 | 0.950 |
C14—C15 | 1.390 (4) | C49—C50 | 1.390 (7) |
C14—H10 | 0.950 | C49—H44 | 0.950 |
C15—H11 | 0.950 | C50—C51 | 1.390 (7) |
C16—C17 | 1.536 (6) | C50—H45 | 0.950 |
C16—H14 | 0.950 | C51—C52 | 1.390 (7) |
C16—H15 | 0.950 | C51—H46 | 0.950 |
C17—C18 | 1.532 (5) | C52—H47 | 0.950 |
C17—C24 | 1.526 (8) | C53—C54 | 1.390 (5) |
C17—H16 | 0.950 | C53—C58 | 1.390 (5) |
C18—C19 | 1.390 (4) | C54—C55 | 1.390 (7) |
C18—C23 | 1.390 (6) | C54—H48 | 0.950 |
C19—C20 | 1.390 (5) | C55—C56 | 1.390 (7) |
C19—H17 | 0.950 | C55—H49 | 0.950 |
C20—C21 | 1.390 (6) | C56—C57 | 1.390 (6) |
C20—H18 | 0.950 | C56—H50 | 0.950 |
C21—C22 | 1.390 (6) | C57—C58 | 1.390 (7) |
C21—H19 | 0.950 | C57—H51 | 0.950 |
C22—C23 | 1.390 (6) | C58—H52 | 0.950 |
C22—H20 | 0.950 | | |
| | | |
O3i—Cu1—N1 | 109.8 (1) | C17—C24—C29 | 119.5 (3) |
O3i—Cu1—N3 | 92.2 (1) | C25—C24—C29 | 120.0 (4) |
O3i—Cu1—N4 | 86.7 (1) | C24—C25—C26 | 120.0 (4) |
O3i—Cu1—N6 | 91.9 (1) | C24—C25—H22 | 120.0 |
N1—Cu1—N3 | 86.9 (2) | C26—C25—H22 | 120.0 |
N1—Cu1—N4 | 163.5 (2) | C25—C26—C27 | 120.0 (4) |
N1—Cu1—N6 | 89.1 (2) | C25—C26—H23 | 120.0 |
N3—Cu1—N4 | 93.7 (2) | C27—C26—H23 | 120.0 |
N3—Cu1—N6 | 175.0 (2) | C26—C27—C28 | 120.0 (5) |
N4—Cu1—N6 | 89.2 (2) | C26—C27—H24 | 120.0 |
Cu1—N1—C1 | 117.1 (4) | C28—C27—H24 | 120.0 |
Cu1—N1—C2 | 132.8 (3) | C27—C28—C29 | 120.0 (4) |
C1—N1—C2 | 108.0 (4) | C27—C28—H25 | 120.0 |
C1—N2—C3 | 111.6 (4) | C29—C28—H25 | 120.0 |
C1—N2—H1 | 124.2 | C24—C29—C28 | 120.0 (4) |
C3—N2—H1 | 124.2 | C24—C29—H26 | 120.0 |
Cu1—N3—C16 | 117.1 (3) | C28—C29—H26 | 120.0 |
Cu1—N3—H12 | 107.5 | O3—C30—N4 | 124.7 (5) |
Cu1—N3—H13 | 107.6 | O3—C30—N5 | 123.7 (4) |
C16—N3—H12 | 107.5 | N4—C30—N5 | 111.7 (5) |
C16—N3—H13 | 107.5 | O4—C31—N4 | 125.0 (5) |
H12—N3—H13 | 109.5 | O4—C31—C32 | 123.8 (5) |
Cu1—N4—C30 | 125.9 (4) | N4—C31—C32 | 111.2 (4) |
Cu1—N4—C31 | 128.0 (3) | N5—C32—C31 | 98.9 (4) |
C30—N4—C31 | 106.1 (4) | N5—C32—C33 | 108.9 (3) |
C30—N5—C32 | 111.6 (4) | N5—C32—C39 | 112.7 (3) |
C30—N5—H27 | 124.2 | C31—C32—C33 | 113.5 (3) |
C32—N5—H27 | 124.2 | C31—C32—C39 | 109.7 (3) |
Cu1—N6—C45 | 112.0 (3) | C33—C32—C39 | 112.5 (4) |
Cu1—N6—H38 | 108.8 | C32—C33—C34 | 122.4 (4) |
Cu1—N6—H39 | 108.9 | C32—C33—C38 | 117.6 (3) |
C45—N6—H38 | 108.8 | C34—C33—C38 | 120.0 (3) |
C45—N6—H39 | 108.9 | C33—C34—C35 | 120.0 (4) |
H38—N6—H39 | 109.5 | C33—C34—H28 | 120.0 |
O1—C1—N1 | 123.4 (5) | C35—C34—H28 | 120.0 |
O1—C1—N2 | 126.1 (4) | C34—C35—C36 | 120.0 (3) |
N1—C1—N2 | 110.5 (5) | C34—C35—H29 | 120.0 |
O2—C2—N1 | 127.0 (4) | C36—C35—H29 | 120.0 |
O2—C2—C3 | 122.7 (5) | C35—C36—C37 | 120.0 (3) |
N1—C2—C3 | 110.3 (4) | C35—C36—H30 | 119.9 |
N2—C3—C2 | 99.5 (4) | C37—C36—H30 | 120.1 |
N2—C3—C4 | 108.3 (3) | C36—C37—C38 | 120.0 (4) |
N2—C3—C10 | 112.5 (4) | C36—C37—H31 | 119.9 |
C2—C3—C4 | 113.7 (4) | C38—C37—H31 | 120.1 |
C2—C3—C10 | 107.6 (3) | C33—C38—C37 | 120.0 (3) |
C4—C3—C10 | 114.3 (4) | C33—C38—H32 | 120.0 |
C3—C4—C5 | 121.0 (4) | C37—C38—H32 | 120.0 |
C3—C4—C9 | 118.6 (3) | C32—C39—C40 | 121.2 (3) |
C5—C4—C9 | 120.0 (4) | C32—C39—C44 | 118.8 (4) |
C4—C5—C6 | 120.0 (3) | C40—C39—C44 | 120.0 (3) |
C4—C5—H2 | 120.0 | C39—C40—C41 | 120.0 (3) |
C6—C5—H2 | 120.0 | C39—C40—H33 | 120.0 |
C5—C6—C7 | 120.0 (3) | C41—C40—H33 | 120.0 |
C5—C6—H3 | 120.1 | C40—C41—C42 | 120.0 (5) |
C7—C6—H3 | 119.9 | C40—C41—H34 | 120.0 |
C6—C7—C8 | 120.0 (4) | C42—C41—H34 | 120.0 |
C6—C7—H4 | 120.1 | C41—C42—C43 | 120.0 (4) |
C8—C7—H4 | 119.9 | C41—C42—H35 | 120.0 |
C7—C8—C9 | 120.0 (3) | C43—C42—H35 | 120.0 |
C7—C8—H5 | 120.1 | C42—C43—C44 | 120.0 (3) |
C9—C8—H5 | 119.9 | C42—C43—H36 | 120.0 |
C4—C9—C8 | 120.0 (3) | C44—C43—H36 | 120.0 |
C4—C9—H6 | 120.0 | C39—C44—C43 | 120.0 (4) |
C8—C9—H6 | 120.0 | C39—C44—H37 | 120.0 |
C3—C10—C11 | 118.1 (3) | C43—C44—H37 | 120.0 |
C3—C10—C15 | 121.7 (3) | N6—C45—C46 | 115.0 (5) |
C11—C10—C15 | 120.0 (2) | N6—C45—H40 | 108.1 |
C10—C11—C12 | 120.0 (4) | N6—C45—H41 | 108.1 |
C10—C11—H7 | 120.0 | C46—C45—H40 | 108.1 |
C12—C11—H7 | 120.0 | C46—C45—H41 | 108.0 |
C11—C12—C13 | 120.0 (3) | H40—C45—H41 | 109.3 |
C11—C12—H8 | 120.0 | C45—C46—C47 | 107.5 (5) |
C13—C12—H8 | 120.0 | C45—C46—C53 | 116.4 (4) |
C12—C13—C14 | 120.0 (3) | C45—C46—H42 | 106.2 |
C12—C13—H9 | 120.0 | C47—C46—C53 | 113.6 (3) |
C14—C13—H9 | 120.0 | C47—C46—H42 | 106.4 |
C13—C14—C15 | 120.0 (4) | C53—C46—H42 | 106.1 |
C13—C14—H10 | 120.0 | C46—C47—C48 | 120.0 (4) |
C15—C14—H10 | 120.0 | C46—C47—C52 | 120.0 (4) |
C10—C15—C14 | 120.0 (3) | C48—C47—C52 | 120.0 (4) |
C10—C15—H11 | 120.0 | C47—C48—C49 | 120.0 (4) |
C14—C15—H11 | 120.0 | C47—C48—H43 | 120.0 |
N3—C16—C17 | 113.0 (4) | C49—C48—H43 | 120.0 |
N3—C16—H14 | 108.6 | C48—C49—C50 | 120.0 (5) |
N3—C16—H15 | 108.5 | C48—C49—H44 | 119.9 |
C17—C16—H14 | 108.7 | C50—C49—H44 | 120.1 |
C17—C16—H15 | 108.6 | C49—C50—C51 | 120.0 (4) |
H14—C16—H15 | 109.4 | C49—C50—H45 | 119.9 |
C16—C17—C18 | 112.0 (4) | C51—C50—H45 | 120.1 |
C16—C17—C24 | 111.3 (4) | C50—C51—C52 | 120.0 (4) |
C16—C17—H16 | 106.7 | C50—C51—H46 | 119.9 |
C18—C17—C24 | 112.9 (3) | C52—C51—H46 | 120.1 |
C18—C17—H16 | 106.7 | C47—C52—C51 | 120.0 (4) |
C24—C17—H16 | 106.8 | C47—C52—H47 | 120.0 |
C17—C18—C19 | 117.7 (4) | C51—C52—H47 | 120.0 |
C17—C18—C23 | 122.3 (3) | C46—C53—C54 | 117.9 (4) |
C19—C18—C23 | 120.0 (3) | C46—C53—C58 | 122.0 (3) |
C18—C19—C20 | 120.0 (3) | C54—C53—C58 | 120.0 (4) |
C18—C19—H17 | 120.0 | C53—C54—C55 | 120.0 (3) |
C20—C19—H17 | 120.0 | C53—C54—H48 | 120.0 |
C19—C20—C21 | 120.0 (3) | C55—C54—H48 | 120.0 |
C19—C20—H18 | 120.0 | C54—C55—C56 | 120.0 (3) |
C21—C20—H18 | 120.0 | C54—C55—H49 | 120.0 |
C20—C21—C22 | 120.0 (3) | C56—C55—H49 | 120.0 |
C20—C21—H19 | 120.0 | C55—C56—C57 | 120.0 (4) |
C22—C21—H19 | 120.0 | C55—C56—H50 | 120.0 |
C21—C22—C23 | 120.0 (4) | C57—C56—H50 | 120.0 |
C21—C22—H20 | 120.0 | C56—C57—C58 | 120.0 (4) |
C23—C22—H20 | 120.0 | C56—C57—H51 | 120.0 |
C18—C23—C22 | 120.0 (3) | C58—C57—H51 | 120.0 |
C18—C23—H21 | 120.0 | C53—C58—C57 | 120.0 (3) |
C22—C23—H21 | 120.0 | C53—C58—H52 | 120.0 |
C17—C24—C25 | 120.3 (4) | C57—C58—H52 | 120.0 |
| | | |
Cu1—N1—C1—O1 | 17.0 (6) | C10—C15—C14—C13 | 0.0 (6) |
Cu1—N1—C1—N2 | −162.7 (3) | C11—C10—C15—C14 | 0.0 (6) |
Cu1—N1—C2—O2 | −20.2 (8) | C11—C12—C13—C14 | 0.0 (6) |
Cu1—N1—C2—C3 | 158.9 (3) | C12—C11—C10—C15 | 0.0 (6) |
Cu1—N3—C16—C17 | −172.7 (3) | C12—C13—C14—C15 | 0.0 (6) |
Cu1—N4—C30—O3 | −2.8 (5) | C16—C17—C18—C19 | −157.4 (4) |
Cu1—N4—C30—N5 | 176.0 (2) | C16—C17—C18—C23 | 24.2 (6) |
Cu1—N4—C31—O4 | 0.3 (6) | C16—C17—C24—C25 | −81.9 (4) |
Cu1—N4—C31—C32 | 178.9 (2) | C16—C17—C24—C29 | 92.9 (4) |
Cu1—N6—C45—C46 | 178.1 (4) | C17—C18—C19—C20 | −178.5 (4) |
O1—C1—N1—C2 | −177.3 (5) | C17—C18—C23—C22 | 178.4 (5) |
O1—C1—N2—C3 | 179.2 (5) | C17—C24—C25—C26 | 174.7 (3) |
O2—C2—N1—C1 | 177.2 (5) | C17—C24—C29—C28 | −174.8 (3) |
O2—C2—C3—N2 | −178.0 (4) | C18—C17—C24—C25 | 45.0 (5) |
O2—C2—C3—C4 | −63.1 (5) | C18—C17—C24—C29 | −140.2 (3) |
O2—C2—C3—C10 | 64.6 (6) | C18—C19—C20—C21 | 0.0 (7) |
O3—C30—N4—C31 | 176.2 (4) | C18—C23—C22—C21 | 0.0 (8) |
O3—C30—N5—C32 | −172.9 (4) | C19—C18—C17—C24 | 76.1 (5) |
O4—C31—N4—C30 | −178.6 (4) | C19—C18—C23—C22 | 0.0 (7) |
O4—C31—C32—N5 | −177.0 (4) | C19—C20—C21—C22 | 0.0 (7) |
O4—C31—C32—C33 | 67.8 (5) | C20—C19—C18—C23 | 0.0 (7) |
O4—C31—C32—C39 | −59.0 (5) | C20—C21—C22—C23 | 0.0 (8) |
N1—Cu1—N3—C16 | 78.7 (3) | C23—C18—C17—C24 | −102.4 (5) |
N1—Cu1—N4—C30 | −122.3 (5) | C24—C25—C26—C27 | 0.0 (5) |
N1—Cu1—N4—C31 | 59.0 (6) | C24—C29—C28—C27 | 0.0 (5) |
N1—Cu1—N6—C45 | 96.1 (3) | C25—C24—C29—C28 | 0.0 (5) |
N1—C1—N2—C3 | −1.1 (5) | C25—C26—C27—C28 | 0.0 (6) |
N1—C2—C3—N2 | 2.8 (5) | C26—C25—C24—C29 | 0.0 (5) |
N1—C2—C3—C4 | 117.7 (4) | C26—C27—C28—C29 | 0.0 (6) |
N1—C2—C3—C10 | −114.6 (4) | C30—N4—C31—C32 | 0.0 (4) |
N2—C1—N1—C2 | 3.1 (5) | C30—N5—C32—C31 | −7.4 (4) |
N2—C3—C4—C5 | 92.6 (4) | C30—N5—C32—C33 | 111.3 (4) |
N2—C3—C4—C9 | −80.3 (4) | C30—N5—C32—C39 | −123.1 (4) |
N2—C3—C10—C11 | 177.8 (4) | C31—C32—C33—C34 | 1.1 (6) |
N2—C3—C10—C15 | −6.6 (6) | C31—C32—C33—C38 | 179.7 (4) |
N3—Cu1—N1—C1 | 79.3 (3) | C31—C32—C39—C40 | 104.1 (5) |
N3—Cu1—N1—C2 | −82.0 (4) | C31—C32—C39—C44 | −74.1 (5) |
N3—Cu1—N4—C30 | 146.0 (3) | C32—C33—C34—C35 | 178.6 (4) |
N3—Cu1—N4—C31 | −32.7 (3) | C32—C33—C38—C37 | −178.7 (4) |
N3—C16—C17—C18 | 174.9 (4) | C32—C39—C40—C41 | −178.1 (4) |
N3—C16—C17—C24 | −57.6 (5) | C32—C39—C44—C43 | 178.2 (4) |
N4—Cu1—N1—C1 | −13.4 (7) | C33—C32—C39—C40 | −23.2 (5) |
N4—Cu1—N1—C2 | −174.7 (5) | C33—C32—C39—C44 | 158.6 (3) |
N4—Cu1—N3—C16 | −117.8 (3) | C33—C34—C35—C36 | 0.0 (7) |
N4—Cu1—N6—C45 | −67.5 (3) | C33—C38—C37—C36 | 0.0 (7) |
N4—C30—N5—C32 | 8.3 (5) | C34—C33—C32—C39 | 126.4 (4) |
N4—C31—C32—N5 | 4.3 (4) | C34—C33—C38—C37 | 0.0 (6) |
N4—C31—C32—C33 | −110.9 (4) | C34—C35—C36—C37 | 0.0 (8) |
N4—C31—C32—C39 | 122.3 (4) | C35—C34—C33—C38 | 0.0 (6) |
N5—C30—N4—C31 | −5.0 (4) | C35—C36—C37—C38 | 0.0 (8) |
N5—C32—C33—C34 | −108.0 (4) | C38—C33—C32—C39 | −55.0 (5) |
N5—C32—C33—C38 | 70.7 (5) | C39—C40—C41—C42 | 0.0 (6) |
N5—C32—C39—C40 | −146.8 (4) | C39—C44—C43—C42 | 0.0 (6) |
N5—C32—C39—C44 | 35.0 (5) | C40—C39—C44—C43 | 0.0 (6) |
N6—Cu1—N1—C1 | −97.7 (3) | C40—C41—C42—C43 | 0.0 (6) |
N6—Cu1—N1—C2 | 101.0 (4) | C41—C40—C39—C44 | 0.0 (6) |
N6—Cu1—N4—C30 | −38.0 (3) | C41—C42—C43—C44 | 0.0 (6) |
N6—Cu1—N4—C31 | 143.3 (3) | C45—C46—C47—C48 | 75.4 (5) |
N6—C45—C46—C47 | −162.0 (4) | C45—C46—C47—C52 | −102.5 (5) |
N6—C45—C46—C53 | 69.3 (6) | C45—C46—C53—C54 | −164.2 (4) |
C1—N1—C2—C3 | −3.7 (5) | C45—C46—C53—C58 | 19.3 (6) |
C1—N2—C3—C2 | −1.0 (5) | C46—C47—C48—C49 | −177.9 (4) |
C1—N2—C3—C4 | −120.0 (4) | C46—C47—C52—C51 | 177.9 (4) |
C1—N2—C3—C10 | 112.7 (4) | C46—C53—C54—C55 | −176.6 (4) |
C2—C3—C4—C5 | −17.0 (5) | C46—C53—C58—C57 | 176.4 (4) |
C2—C3—C4—C9 | 170.1 (4) | C47—C46—C53—C54 | 70.1 (5) |
C2—C3—C10—C11 | −73.5 (5) | C47—C46—C53—C58 | −106.4 (4) |
C2—C3—C10—C15 | 102.1 (5) | C47—C48—C49—C50 | 0.0 (6) |
C3—C4—C5—C6 | −172.9 (4) | C47—C52—C51—C50 | 0.0 (6) |
C3—C4—C9—C8 | 173.0 (4) | C48—C47—C46—C53 | −154.2 (4) |
C3—C10—C11—C12 | 175.7 (4) | C48—C47—C52—C51 | 0.0 (6) |
C3—C10—C15—C14 | −175.5 (4) | C48—C49—C50—C51 | 0.0 (7) |
C4—C3—C10—C11 | 53.8 (5) | C49—C48—C47—C52 | 0.0 (6) |
C4—C3—C10—C15 | −130.6 (4) | C49—C50—C51—C52 | 0.0 (7) |
C4—C5—C6—C7 | 0.0 (7) | C52—C47—C46—C53 | 27.8 (5) |
C4—C9—C8—C7 | 0.0 (6) | C53—C54—C55—C56 | 0.0 (6) |
C5—C4—C3—C10 | −141.1 (4) | C53—C58—C57—C56 | 0.0 (6) |
C5—C4—C9—C8 | 0.0 (6) | C54—C53—C58—C57 | 0.0 (6) |
C5—C6—C7—C8 | 0.0 (7) | C54—C55—C56—C57 | 0.0 (7) |
C6—C5—C4—C9 | 0.0 (6) | C55—C54—C53—C58 | 0.0 (6) |
C6—C7—C8—C9 | 0.0 (7) | C55—C56—C57—C58 | 0.0 (7) |
C9—C4—C3—C10 | 45.9 (5) | C55—C56—C57—C58 | 0.0 (7) |
C10—C11—C12—C13 | 0.0 (6) | | |
Symmetry code: (i) −x+2, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1···O4ii | 0.95 | 2.00 | 2.915 (6) | 160 |
N3—H12···O4 | 0.95 | 2.17 | 2.915 (6) | 135 |
N5—H27···O2i | 0.95 | 2.09 | 2.857 (5) | 136 |
N6—H39···O3 | 0.95 | 2.07 | 2.817 (5) | 134 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+1, −z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Cu(C15H11N2O2)2(C14H15N)2]·2CHCl3 | [Cu(C15H11N2O2)2(C14H15N)2] |
Mr | 1199.34 | 960.63 |
Crystal system, space group | Orthorhombic, Pbca | Triclinic, P1 |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 19.37 (1), 29.796 (7), 9.910 (3) | 14.313 (4), 15.888 (5), 11.863 (4) |
α, β, γ (°) | 90, 90, 90 | 90.13 (3), 95.00 (3), 63.58 (2) |
V (Å3) | 5720 (4) | 2404.7 (14) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.72 | 0.51 |
Crystal size (mm) | 0.41 × 0.16 × 0.10 | 0.50 × 0.40 × 0.20 |
|
Data collection |
Diffractometer | Rigaku AFC-7R diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.872, 0.931 | 0.783, 0.903 |
No. of measured, independent and observed reflections | 8516, 6565, 3338 [I > 2σ(I)] | 12233, 12233, 11075 [I > 0σ(I)] |
Rint | 0.021 | 0.087 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.163, 0.99 | 0.069, 0.161, 0.85 |
No. of reflections | 3338 | 11075 |
No. of parameters | 302 | 527 |
No. of restraints | ? | ? |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.46 | 0.62, −1.31 |
Selected geometric parameters (Å, º) for (I) topCu1—N1 | 2.009 (3) | Cu1—N3 | 2.005 (3) |
| | | |
N1—Cu1—N3 | 89.2 (1) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1···O1i | 0.95 | 2.02 | 2.900 (3) | 153 |
N3—H12···O1ii | 0.95 | 2.06 | 2.837 (3) | 137 |
N3—H13···O2 | 0.95 | 2.13 | 2.922 (3) | 140 |
C30—H27···O2 | 0.95 | 2.57 | 3.507 (5) | 170 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1. |
Selected geometric parameters (Å, º) for (II) topCu1—O3i | 2.397 (4) | Cu1—N4 | 2.026 (4) |
Cu1—N1 | 1.990 (4) | Cu1—N6 | 2.032 (4) |
Cu1—N3 | 2.030 (3) | | |
| | | |
O3i—Cu1—N1 | 109.8 (1) | N1—Cu1—N4 | 163.5 (2) |
O3i—Cu1—N3 | 92.2 (1) | N1—Cu1—N6 | 89.1 (2) |
O3i—Cu1—N4 | 86.7 (1) | N3—Cu1—N4 | 93.7 (2) |
O3i—Cu1—N6 | 91.9 (1) | N3—Cu1—N6 | 175.0 (2) |
N1—Cu1—N3 | 86.9 (2) | N4—Cu1—N6 | 89.2 (2) |
Symmetry code: (i) −x+2, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1···O4ii | 0.95 | 2.00 | 2.915 (6) | 160 |
N3—H12···O4 | 0.95 | 2.17 | 2.915 (6) | 135 |
N5—H27···O2i | 0.95 | 2.09 | 2.857 (5) | 136 |
N6—H39···O3 | 0.95 | 2.07 | 2.817 (5) | 134 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+1, −z. |
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In recent years, studies of supramolecular self-assembling metal–organic frameworks of metal complexes have been extensively carried out, with the aim of rational construction of desired crystal structures and fine-tuning of their functions (Eddaoudi et al., 2001; Evans et al., 2002; Yaghi et al., 1998). In particular, host–guest inclusion of small molecules and hydrogen-bonded flexible self-assemblies enable the realisation of appropriate crystal packing containing guest molecules (Holman et al., 2001), which depends on the novelty of the secondary building units as a synthon. In this respect, for example, vapochromic switching of optoelectronic properties may be one of the most promising strategies for the preparation of functional materials (Kato et al., 2002; Fernandez et al., 2003). It is well known that copper(II) complexes exhibit a remarkable variety in their coordination geometries and corresponding optoelectronic properties. Some copper(II) complexes incorporating monodentate 5,5-diphenylhydantoinate ligands have been studied previously. In the solid state, most of the related complexes afford a four-coordinated square-planar CuN4 coordination geometry (Akitsu, Komorita & Urushiyama, 2001) with the aid of crystal-packing forces. Appropriate steric factors of the ligands can lead to a tetrahedrally distorted square-planar CuN4 coordination geometry (Akitsu et al., 2003) or a five-coordinated square-pyramidal CuN4O coordination geometry (Akitsu et al., 1997). To date, structural regulation by other means, such as solvent in the crystal (Tynan et al., 2004), has not been observed for analogous complexes. We report here a structural comparison of trans-bis(2,2-diphenylethylamine)bis(5,5-diphenylhydantoinato)copper(II)chloroform disolvate, (I), and dimeric trans-bis(2,2-diphenylethylamine)bis(5,5-diphenylhydantoinato)copper(II), (II).
Complex (I), the chloroform disolvate, affords a square-planar CuN4 coordination geometry, in which the Cu atom lies on an inversion centre (Fig. 1). Both the neutral 2,2-diphenylethylamine ligands and the anionic deprotonated 5,5-diphenylhydantoinate ligands act as monodentate ligands with N-atom donors, and they are coordinated on trans sites with respect to the Cu atom. The Cu—N bond distances (Table 1) are within the range found in related complexes, some of which are planar and some of which exhibit some tetrahedral distortion, viz. the Cu—N(imide) distances range from 1.975 (5) to 2.05 (1) Å, whereas the Cu—N(amine) distances range from 1.97 (1) to 2.030 (4) Å (Akitsu, Komorita & Kushi, 2001; Akitsu et al., 2003; Akitsu & Einaga, 2004). The cis-N1—Cu1—N3 angles are close to right angles. The dihedral angle between the Cu1/N1/N3/N1i/N3i mean plane of the coordination sphere and the N1/C1/N2/C2/C3 plane of the ligands is 139.4 (1)°, and those between the five-membered C3/C2/N1/C1/N2 ring of the 5,5-diphenylhydantoinate ligand and the connecting phenyl groups, i.e. C4/C5/C6/C7/C8/C9 and C10/C11/C12/C13/C14/C15, are 57.7 (1) and 123.0 (1)°, respectively [symmetry code: (i) 1 − x, 1 − y, 1 − z].
The solvent-free complex, (II), affords a slightly distorted pyramidal CuN4 coordination geometry (Fig. 2) and adjacent molecules form centrosymmetric dimers, with Cu1—O3iii 2.397 (4) Å [symmetry code: (iii) 2 − x, 1 − y, 1 − z] (Fig. 3). The Cu—N bond distances are also within the range found in related complexes (Table 3). The dihedral angle between the N1/Cu1/N3 and N4/Cu1/N6 planes is 16.69 (1)°. The Cu atom deviates slightly from the N1/N3/N4/N6 plane, by 0.178 (2) Å. The dihedral angle between the Cu1/N1/N3/N4/N6 and N1/C1/N2/C2/C3 planes is 94.7 (2)°, while that between the Cu1/N1/N3/N4/N6 and N4/C30/N5/C31/C32 planes is 35.2 (2)°. Although the planarity of the coordination environment is broken, the sp2 character of the N-donor atoms of the 5,5-diphenylhydantoinate ligands is still maintained; the C1—N1—C3 and C30—N4—C31 bond angles are 108.0 (5) and 106.2 (5)°, respectively.
To the best of our knowledge, this is the first case of related complexes which exhibit different coordination geometries in the presence or absence of solvent molecules in the crystal. In the crystal structure of (I), four intramolecular hydrogen bonds are formed around the coordination sphere, i.e. N3—H13···O2 and N3—H12···O1i (Table 2). Furthermore, adjacent molecules are linked by double complementary intermolecular N2—H1···O1ii hydrogen bonds along the crystallographic b axis [N···O 2.900 (3) Å; symmetry code: (ii) 1 − x, 1 − y, −z]. The chloroform solvent molecules also play an important role in stabilizing the crystal packing of (I) via a C30—H27···O2 hydrogen bond [C···O 3.507 (5) Å]. On the other hand, the crystal-packing mode of (II) is quite different. Only two intramolecular hydrogen bonds, namely N3—H12···O4 and N6—H39···O3, are formed on one side of the coordination sphere (Table 4). Moreover, intermolecular hydrogen bonds, i.e. N5—H27···O2iii and N2—H1···O4iv, link adjacent molecules to form hydrogen-bonded networks [symmetry codes: (iii) 2 − x, 1 − y, 1 − z; (iv) 2 − x, 1 − y, −z].