Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104026575/sq1180sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104026575/sq1180Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104026575/sq1180IIsup3.hkl |
CCDC references: 259021; 259022
For the preparation of (I), treatment of equimolar quantities of copper(II) acetate (0.91 g, 5.00 mmol), R-1-phenylethylamine (1.21 g, 10.0 mmol) and 3,5-dichlorosalicylaldehyde (1.91 g, 10.0 mmol) in methanol (150 ml) at 318 K for 2 h gave rise to a brown precipitate. Plate-like brown crystals were grown by the slow evaporation of a methanol solution at 278 K overnight. Analysis found: C 55.37, H 3.98, N 4.09%; calculated for C30H24Cl4CuN2O2: C 55.44, H 3.72, N 4.31%. IR (KBr): 1623 cm−1 (C=N). m.p. 556 K (decomposed). The same preparation procedure was used for (II), except that 3-ethoxysalicylaldehyde (1.66 g, 10.0 mmol) was used instead of 3,5-diclrorosalicylaldehyde. Analysis found: C 67.84, H 6.12, N 4.59%; calculated for C34H36CuN2O4: C 68.04, H 6.05, N 4.67%; IR (KBr): 1636 cm−1 (C=N). m.p. 542 K (decomposed).
H atoms were placed in calculated positions (with C—H = 0.950 Å) and were 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, namely C1–C6, C10–C15, C16–C21 and C25–C30 for (I), and C1–C6, C10–C15, C16–C21, C25–C30, C35–C40, C44–C49, C50–C55 and C59–C64 for (II), were treated as rigid groups of anisotropic atoms. Because of the remarkable plate-like shape and relatively poor quality of crystals for (II), we employed the present data as the best result. Since we do not have another good single-crystal, we could not recollect the data.
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.
[Cu(C15H12Cl2NO)2] | F(000) = 662.0 |
Mr = 649.86 | Dx = 1.521 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: P 2yb | Cell parameters from 25 reflections |
a = 11.166 (5) Å | θ = 10.2–14.8° |
b = 14.852 (7) Å | µ = 1.18 mm−1 |
c = 8.636 (4) Å | T = 297 K |
β = 97.89 (4)° | Plate, brown |
V = 1418.6 (11) Å3 | 0.30 × 0.30 × 0.20 mm |
Z = 2 |
Rigaku AFC-7R diffractometer | Rint = 0.020 |
ω–2θ scans | θmax = 27.5° |
Absorption correction: ψ scan (North et al., 1968) | h = −5→14 |
Tmin = 0.709, Tmax = 0.790 | k = 0→19 |
3771 measured reflections | l = −11→11 |
3387 independent reflections | 3 standard reflections every 150 reflections |
2958 reflections with I > 2σ(I) | intensity decay: 0.1% |
Refinement on F2 | w = 1/[σ2(Fo2) + (0.0497P)2 + 0.597P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.034 | (Δ/σ)max = 0.002 |
wR(F2) = 0.093 | Δρmax = 0.63 e Å−3 |
S = 1.05 | Δρmin = −0.50 e Å−3 |
2958 reflections | Absolute structure: Flack (1983), 3387 Friedel pairs |
304 parameters | Absolute structure parameter: −0.01 (2) |
H-atom parameters constrained |
[Cu(C15H12Cl2NO)2] | V = 1418.6 (11) Å3 |
Mr = 649.86 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 11.166 (5) Å | µ = 1.18 mm−1 |
b = 14.852 (7) Å | T = 297 K |
c = 8.636 (4) Å | 0.30 × 0.30 × 0.20 mm |
β = 97.89 (4)° |
Rigaku AFC-7R diffractometer | 2958 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.020 |
Tmin = 0.709, Tmax = 0.790 | 3 standard reflections every 150 reflections |
3771 measured reflections | intensity decay: 0.1% |
3387 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.093 | Δρmax = 0.63 e Å−3 |
S = 1.05 | Δρmin = −0.50 e Å−3 |
2958 reflections | Absolute structure: Flack (1983), 3387 Friedel pairs |
304 parameters | Absolute structure parameter: −0.01 (2) |
Refinement. Refinement using reflections with F2 > 0.0 σ(F2). The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
Cu1 | −0.43069 (4) | −0.39418 (3) | −0.81436 (5) | 0.0292 (1) | |
Cl1 | −0.0308 (2) | −0.6253 (1) | −0.2394 (2) | 0.0815 (6) | |
Cl2 | −0.0998 (1) | −0.2891 (1) | −0.4671 (2) | 0.0550 (3) | |
Cl3 | −0.6764 (1) | −0.3227 (1) | −1.6221 (1) | 0.0476 (3) | |
Cl4 | −0.83029 (9) | −0.3584 (1) | −1.0607 (1) | 0.0514 (3) | |
O1 | −0.3205 (3) | −0.3636 (2) | −0.6361 (3) | 0.0343 (6) | |
O2 | −0.5777 (2) | −0.3766 (2) | −0.9449 (3) | 0.0339 (7) | |
N1 | −0.4876 (3) | −0.5024 (3) | −0.7085 (4) | 0.0323 (7) | |
N2 | −0.3317 (3) | −0.3519 (3) | −0.9741 (4) | 0.0295 (7) | |
C1 | −0.2622 (2) | −0.4233 (2) | −0.5367 (3) | 0.0313 (8) | |
C2 | −0.1517 (2) | −0.3970 (2) | −0.4551 (3) | 0.0385 (8) | |
C3 | −0.0828 (2) | −0.4581 (2) | −0.3588 (3) | 0.045 (1) | |
C4 | −0.1242 (3) | −0.5455 (2) | −0.3440 (4) | 0.048 (1) | |
C5 | −0.2347 (3) | −0.5718 (2) | −0.4255 (4) | 0.048 (1) | |
C6 | −0.3037 (2) | −0.5107 (2) | −0.5219 (3) | 0.0364 (9) | |
C7 | −0.4202 (4) | −0.5414 (3) | −0.5973 (5) | 0.0375 (10) | |
C8 | −0.6029 (4) | −0.5447 (3) | −0.7783 (5) | 0.0343 (9) | |
C9 | −0.6561 (4) | −0.6118 (4) | −0.6732 (6) | 0.046 (1) | |
C10 | −0.5881 (3) | −0.5857 (2) | −0.9364 (3) | 0.0368 (9) | |
C11 | −0.6860 (2) | −0.5847 (2) | −1.0546 (4) | 0.049 (1) | |
C12 | −0.6754 (3) | −0.6227 (3) | −1.1992 (3) | 0.058 (1) | |
C13 | −0.5669 (4) | −0.6617 (3) | −1.2256 (3) | 0.061 (2) | |
C14 | −0.4690 (3) | −0.6627 (3) | −1.1074 (4) | 0.055 (1) | |
C15 | −0.4795 (2) | −0.6248 (2) | −0.9628 (3) | 0.042 (1) | |
C16 | −0.5943 (2) | −0.3588 (2) | −1.0980 (2) | 0.0328 (8) | |
C17 | −0.7133 (2) | −0.3534 (2) | −1.1698 (3) | 0.0347 (9) | |
C18 | −0.7380 (2) | −0.3408 (3) | −1.3305 (3) | 0.0386 (10) | |
C19 | −0.6437 (2) | −0.3336 (2) | −1.4194 (2) | 0.0365 (9) | |
C20 | −0.5246 (2) | −0.3389 (2) | −1.3476 (3) | 0.0329 (9) | |
C21 | −0.4999 (2) | −0.3515 (2) | −1.1869 (3) | 0.0311 (8) | |
C22 | −0.3736 (4) | −0.3445 (3) | −1.1191 (5) | 0.0331 (9) | |
C23 | −0.2004 (4) | −0.3379 (3) | −0.9222 (5) | 0.0325 (9) | |
C24 | −0.1327 (4) | −0.2871 (4) | −1.0360 (6) | 0.043 (1) | |
C25 | −0.1387 (3) | −0.4273 (2) | −0.8757 (4) | 0.040 (1) | |
C26 | −0.0286 (3) | −0.4245 (3) | −0.7787 (5) | 0.058 (2) | |
C27 | 0.0299 (3) | −0.5041 (4) | −0.7289 (5) | 0.082 (2) | |
C28 | −0.0216 (5) | −0.5865 (3) | −0.7761 (6) | 0.094 (3) | |
C29 | −0.1317 (5) | −0.5893 (2) | −0.8731 (7) | 0.094 (3) | |
C30 | −0.1903 (3) | −0.5098 (3) | −0.9229 (5) | 0.059 (1) | |
H1 | −0.0072 | −0.4401 | −0.3031 | 0.0538* | |
H2 | −0.2631 | −0.6316 | −0.4154 | 0.0572* | |
H3 | −0.4496 | −0.5963 | −0.5602 | 0.0451* | |
H4 | −0.6601 | −0.4973 | −0.7983 | 0.0411* | |
H5 | −0.6685 | −0.5830 | −0.5784 | 0.0553* | |
H6 | −0.7311 | −0.6335 | −0.7248 | 0.0553* | |
H7 | −0.6018 | −0.6608 | −0.6507 | 0.0553* | |
H8 | −0.7602 | −0.5581 | −1.0365 | 0.0583* | |
H9 | −0.7424 | −0.6220 | −1.2800 | 0.0701* | |
H10 | −0.5597 | −0.6877 | −1.3244 | 0.0730* | |
H11 | −0.3948 | −0.6894 | −1.1254 | 0.0655* | |
H12 | −0.4126 | −0.6255 | −0.8820 | 0.0506* | |
H13 | −0.8194 | −0.3372 | −1.3796 | 0.0463* | |
H14 | −0.4602 | −0.3340 | −1.4083 | 0.0395* | |
H15 | −0.3168 | −0.3333 | −1.1892 | 0.0398* | |
H16 | −0.1944 | −0.3025 | −0.8298 | 0.0390* | |
H17 | −0.0508 | −0.2794 | −0.9913 | 0.0518* | |
H18 | −0.1360 | −0.3203 | −1.1305 | 0.0518* | |
H19 | −0.1691 | −0.2298 | −1.0573 | 0.0518* | |
H20 | 0.0066 | −0.3681 | −0.7464 | 0.0699* | |
H21 | 0.1052 | −0.5021 | −0.6627 | 0.0989* | |
H22 | 0.0184 | −0.6409 | −0.7421 | 0.1134* | |
H23 | −0.1670 | −0.6457 | −0.9054 | 0.1125* | |
H24 | −0.2655 | −0.5117 | −0.9891 | 0.0710* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0276 (2) | 0.0322 (2) | 0.0267 (2) | −0.0016 (2) | 0.0001 (2) | 0.0028 (2) |
Cl1 | 0.071 (1) | 0.076 (1) | 0.087 (1) | 0.0217 (9) | −0.0264 (9) | 0.0226 (10) |
Cl2 | 0.0543 (7) | 0.0502 (8) | 0.0556 (7) | −0.0159 (6) | −0.0100 (6) | −0.0042 (6) |
Cl3 | 0.0562 (7) | 0.0596 (8) | 0.0251 (5) | 0.0054 (6) | −0.0009 (5) | 0.0012 (5) |
Cl4 | 0.0264 (4) | 0.0864 (10) | 0.0422 (6) | 0.0013 (5) | 0.0073 (4) | 0.0024 (6) |
O1 | 0.038 (1) | 0.033 (2) | 0.030 (1) | −0.004 (1) | −0.004 (1) | 0.002 (1) |
O2 | 0.028 (1) | 0.047 (2) | 0.026 (1) | 0.000 (1) | 0.0005 (10) | 0.005 (1) |
N1 | 0.032 (2) | 0.035 (2) | 0.030 (2) | −0.002 (2) | 0.004 (1) | −0.001 (1) |
N2 | 0.024 (1) | 0.033 (2) | 0.031 (2) | 0.002 (1) | 0.003 (1) | −0.003 (1) |
C1 | 0.032 (2) | 0.033 (2) | 0.028 (2) | 0.000 (2) | 0.003 (2) | −0.001 (2) |
C2 | 0.037 (2) | 0.045 (2) | 0.032 (2) | −0.001 (2) | −0.002 (2) | −0.005 (2) |
C3 | 0.034 (2) | 0.060 (3) | 0.037 (2) | 0.005 (2) | −0.010 (2) | −0.005 (2) |
C4 | 0.048 (3) | 0.053 (3) | 0.039 (3) | 0.014 (2) | −0.008 (2) | 0.009 (2) |
C5 | 0.054 (3) | 0.042 (3) | 0.043 (3) | 0.002 (2) | −0.009 (2) | 0.013 (2) |
C6 | 0.038 (2) | 0.036 (2) | 0.033 (2) | 0.000 (2) | −0.003 (2) | 0.003 (2) |
C7 | 0.042 (2) | 0.034 (2) | 0.035 (2) | −0.007 (2) | −0.001 (2) | 0.006 (2) |
C8 | 0.032 (2) | 0.035 (2) | 0.036 (2) | −0.001 (2) | 0.003 (2) | 0.001 (2) |
C9 | 0.041 (2) | 0.054 (3) | 0.043 (2) | −0.014 (2) | 0.006 (2) | 0.002 (2) |
C10 | 0.044 (2) | 0.030 (2) | 0.035 (2) | −0.009 (2) | 0.002 (2) | 0.002 (2) |
C11 | 0.051 (3) | 0.048 (3) | 0.043 (3) | −0.009 (2) | −0.006 (2) | 0.002 (2) |
C12 | 0.072 (4) | 0.058 (3) | 0.042 (3) | −0.017 (3) | −0.007 (3) | 0.000 (3) |
C13 | 0.095 (5) | 0.047 (3) | 0.040 (3) | −0.010 (3) | 0.010 (3) | −0.005 (2) |
C14 | 0.071 (4) | 0.042 (3) | 0.054 (3) | −0.001 (3) | 0.021 (3) | −0.006 (2) |
C15 | 0.049 (3) | 0.032 (2) | 0.047 (3) | −0.001 (2) | 0.011 (2) | −0.004 (2) |
C16 | 0.032 (2) | 0.037 (2) | 0.028 (2) | 0.000 (2) | 0.001 (2) | −0.002 (2) |
C17 | 0.028 (2) | 0.043 (2) | 0.034 (2) | 0.000 (2) | 0.006 (2) | 0.001 (2) |
C18 | 0.033 (2) | 0.046 (3) | 0.035 (2) | −0.001 (2) | −0.001 (2) | 0.001 (2) |
C19 | 0.044 (2) | 0.040 (2) | 0.025 (2) | 0.006 (2) | 0.000 (2) | −0.001 (2) |
C20 | 0.036 (2) | 0.038 (2) | 0.026 (2) | 0.003 (2) | 0.008 (2) | 0.001 (2) |
C21 | 0.027 (2) | 0.036 (2) | 0.030 (2) | 0.001 (2) | 0.005 (1) | −0.001 (2) |
C22 | 0.029 (2) | 0.039 (2) | 0.031 (2) | 0.002 (2) | 0.004 (2) | −0.004 (2) |
C23 | 0.022 (2) | 0.037 (2) | 0.038 (2) | 0.002 (2) | 0.003 (2) | −0.004 (2) |
C24 | 0.029 (2) | 0.051 (3) | 0.049 (3) | −0.004 (2) | 0.005 (2) | 0.004 (2) |
C25 | 0.034 (2) | 0.048 (3) | 0.041 (2) | 0.013 (2) | 0.014 (2) | 0.006 (2) |
C26 | 0.042 (3) | 0.078 (4) | 0.053 (3) | 0.023 (3) | −0.001 (2) | 0.003 (3) |
C27 | 0.068 (4) | 0.108 (6) | 0.068 (4) | 0.052 (4) | 0.001 (3) | 0.015 (4) |
C28 | 0.093 (6) | 0.082 (6) | 0.116 (6) | 0.060 (5) | 0.041 (5) | 0.047 (5) |
C29 | 0.094 (6) | 0.052 (4) | 0.143 (8) | 0.028 (4) | 0.044 (5) | 0.022 (5) |
C30 | 0.048 (3) | 0.042 (3) | 0.089 (4) | 0.010 (2) | 0.016 (3) | 0.010 (3) |
Cu1—O1 | 1.890 (3) | C12—C13 | 1.390 (6) |
Cu1—O2 | 1.878 (3) | C12—H9 | 0.950 |
Cu1—N1 | 1.995 (4) | C13—C14 | 1.390 (4) |
Cu1—N2 | 1.984 (4) | C13—H10 | 0.950 |
Cl1—C4 | 1.747 (4) | C14—C15 | 1.390 (5) |
Cl2—C2 | 1.712 (3) | C14—H11 | 0.950 |
Cl3—C19 | 1.746 (2) | C15—H12 | 0.950 |
Cl4—C17 | 1.714 (3) | C16—C17 | 1.390 (3) |
O1—C1 | 1.340 (4) | C16—C21 | 1.390 (3) |
O2—C16 | 1.336 (3) | C17—C18 | 1.390 (3) |
N1—C7 | 1.275 (6) | C18—C19 | 1.390 (3) |
N1—C8 | 1.484 (5) | C18—H13 | 0.950 |
N2—C22 | 1.280 (5) | C19—C20 | 1.390 (3) |
N2—C23 | 1.488 (5) | C20—C21 | 1.390 (3) |
C1—C2 | 1.390 (4) | C20—H14 | 0.950 |
C1—C6 | 1.390 (4) | C21—C22 | 1.455 (4) |
C2—C3 | 1.390 (4) | C22—H15 | 0.950 |
C3—C4 | 1.390 (4) | C23—C24 | 1.521 (7) |
C3—H1 | 0.950 | C23—C25 | 1.524 (6) |
C4—C5 | 1.390 (4) | C23—H16 | 0.950 |
C5—C6 | 1.390 (4) | C24—H17 | 0.950 |
C5—H2 | 0.950 | C24—H18 | 0.950 |
C6—C7 | 1.446 (5) | C24—H19 | 0.950 |
C7—H3 | 0.950 | C25—C26 | 1.390 (4) |
C8—C9 | 1.523 (7) | C25—C30 | 1.390 (5) |
C8—C10 | 1.525 (5) | C26—C27 | 1.390 (6) |
C8—H4 | 0.950 | C26—H20 | 0.950 |
C9—H5 | 0.950 | C27—C28 | 1.390 (7) |
C9—H6 | 0.950 | C27—H21 | 0.950 |
C9—H7 | 0.950 | C28—C29 | 1.390 (7) |
C10—C11 | 1.390 (4) | C28—H22 | 0.950 |
C10—C15 | 1.390 (4) | C29—C30 | 1.390 (5) |
C11—C12 | 1.390 (5) | C29—H23 | 0.950 |
C11—H8 | 0.950 | C30—H24 | 0.950 |
O1—Cu1—O2 | 150.9 (1) | C14—C13—H10 | 120.0 |
O1—Cu1—N1 | 91.9 (1) | C13—C14—C15 | 120.0 (3) |
O1—Cu1—N2 | 97.3 (1) | C13—C14—H11 | 120.0 |
O2—Cu1—N1 | 94.6 (1) | C15—C14—H11 | 120.0 |
O2—Cu1—N2 | 93.6 (1) | C10—C15—C14 | 120.0 (2) |
N1—Cu1—N2 | 144.7 (2) | C10—C15—H12 | 120.0 |
Cu1—O1—C1 | 124.6 (2) | C14—C15—H12 | 120.0 |
Cu1—O2—C16 | 127.8 (2) | O2—C16—C17 | 116.6 (2) |
Cu1—N1—C7 | 121.3 (3) | O2—C16—C21 | 123.3 (2) |
Cu1—N1—C8 | 117.9 (3) | C17—C16—C21 | 120.0 (2) |
C7—N1—C8 | 120.2 (4) | Cl4—C17—C16 | 120.4 (2) |
Cu1—N2—C22 | 122.9 (3) | Cl4—C17—C18 | 119.5 (2) |
Cu1—N2—C23 | 117.0 (2) | C16—C17—C18 | 120.0 (2) |
C22—N2—C23 | 119.7 (4) | C17—C18—C19 | 120.0 (2) |
O1—C1—C2 | 117.2 (2) | C17—C18—H13 | 120.0 |
O1—C1—C6 | 122.6 (2) | C19—C18—H13 | 120.0 |
C2—C1—C6 | 120.0 (2) | Cl3—C19—C18 | 119.4 (2) |
Cl2—C2—C1 | 121.1 (2) | Cl3—C19—C20 | 120.6 (2) |
Cl2—C2—C3 | 118.9 (2) | C18—C19—C20 | 120.0 (2) |
C1—C2—C3 | 120.0 (2) | C19—C20—C21 | 120.0 (2) |
C2—C3—C4 | 120.0 (2) | C19—C20—H14 | 120.0 |
C2—C3—H1 | 120.0 | C21—C20—H14 | 120.0 |
C4—C3—H1 | 120.0 | C16—C21—C20 | 120.0 (2) |
Cl1—C4—C3 | 119.9 (2) | C16—C21—C22 | 123.4 (2) |
Cl1—C4—C5 | 119.8 (2) | C20—C21—C22 | 116.1 (2) |
C3—C4—C5 | 120.0 (3) | N2—C22—C21 | 126.3 (4) |
C4—C5—C6 | 120.0 (2) | N2—C22—H15 | 116.9 |
C4—C5—H2 | 120.0 | C21—C22—H15 | 116.9 |
C6—C5—H2 | 120.0 | N2—C23—C24 | 115.5 (3) |
C1—C6—C5 | 120.0 (2) | N2—C23—C25 | 110.5 (3) |
C1—C6—C7 | 122.9 (3) | N2—C23—H16 | 106.5 |
C5—C6—C7 | 117.0 (3) | C24—C23—C25 | 110.9 (3) |
N1—C7—C6 | 126.7 (4) | C24—C23—H16 | 106.5 |
N1—C7—H3 | 116.6 | C25—C23—H16 | 106.5 |
C6—C7—H3 | 116.7 | C23—C24—H17 | 109.5 |
N1—C8—C9 | 115.0 (3) | C23—C24—H18 | 109.5 |
N1—C8—C10 | 109.7 (3) | C23—C24—H19 | 109.5 |
N1—C8—H4 | 106.6 | H17—C24—H18 | 109.5 |
C9—C8—C10 | 111.8 (4) | H17—C24—H19 | 109.5 |
C9—C8—H4 | 106.6 | H18—C24—H19 | 109.5 |
C10—C8—H4 | 106.6 | C23—C25—C26 | 117.6 (3) |
C8—C9—H5 | 109.5 | C23—C25—C30 | 122.4 (3) |
C8—C9—H6 | 109.5 | C26—C25—C30 | 120.0 (3) |
C8—C9—H7 | 109.5 | C25—C26—C27 | 120.0 (3) |
H5—C9—H6 | 109.5 | C25—C26—H20 | 120.0 |
H5—C9—H7 | 109.5 | C27—C26—H20 | 120.0 |
H6—C9—H7 | 109.4 | C26—C27—C28 | 120.0 (3) |
C8—C10—C11 | 118.8 (3) | C26—C27—H21 | 120.0 |
C8—C10—C15 | 121.2 (3) | C28—C27—H21 | 120.0 |
C11—C10—C15 | 120.0 (3) | C27—C28—C29 | 120.0 (4) |
C10—C11—C12 | 120.0 (3) | C27—C28—H22 | 120.0 |
C10—C11—H8 | 120.0 | C29—C28—H22 | 120.0 |
C12—C11—H8 | 120.0 | C28—C29—C30 | 120.0 (3) |
C11—C12—C13 | 120.0 (3) | C28—C29—H23 | 120.0 |
C11—C12—H9 | 120.0 | C30—C29—H23 | 120.0 |
C13—C12—H9 | 120.0 | C25—C30—C29 | 120.0 (3) |
C12—C13—C14 | 120.0 (3) | C25—C30—H24 | 120.0 |
C12—C13—H10 | 120.0 | C29—C30—H24 | 120.0 |
Cu1—O1—C1—C2 | 153.3 (2) | N2—C22—C21—C16 | 6.6 (7) |
Cu1—O1—C1—C6 | −21.9 (4) | N2—C22—C21—C20 | 178.5 (4) |
Cu1—O2—C16—C17 | 176.7 (3) | N2—C23—C25—C26 | −159.5 (3) |
Cu1—O2—C16—C21 | 1.0 (5) | N2—C23—C25—C30 | 18.6 (5) |
Cu1—N1—C7—C6 | 6.7 (6) | C1—C2—C3—C4 | 0.0 (4) |
Cu1—N1—C8—C9 | −166.1 (3) | C1—C6—C5—C4 | 0.0 (5) |
Cu1—N1—C8—C10 | 66.9 (4) | C2—C1—C6—C5 | 0.0 (4) |
Cu1—N2—C22—C21 | 10.0 (7) | C2—C1—C6—C7 | 177.0 (3) |
Cu1—N2—C23—C24 | −167.4 (3) | C2—C3—C4—C5 | 0.0 (5) |
Cu1—N2—C23—C25 | 65.7 (4) | C3—C2—C1—C6 | 0.0 (4) |
Cl1—C4—C3—C2 | 173.3 (2) | C3—C4—C5—C6 | 0.0 (5) |
Cl1—C4—C5—C6 | −173.3 (3) | C4—C5—C6—C7 | −177.1 (3) |
Cl2—C2—C1—O1 | 6.2 (4) | C6—C7—N1—C8 | 177.4 (4) |
Cl2—C2—C1—C6 | −178.4 (2) | C7—N1—C8—C9 | 23.0 (6) |
Cl2—C2—C3—C4 | 178.4 (2) | C7—N1—C8—C10 | −104.1 (4) |
Cl3—C19—C18—C17 | 177.3 (3) | C8—C10—C11—C12 | −179.2 (3) |
Cl3—C19—C20—C21 | −177.2 (3) | C8—C10—C15—C14 | 179.2 (3) |
Cl4—C17—C16—O2 | 6.4 (5) | C9—C8—C10—C11 | 85.4 (4) |
Cl4—C17—C16—C21 | −177.8 (3) | C9—C8—C10—C15 | −93.8 (4) |
Cl4—C17—C18—C19 | 177.8 (3) | C10—C11—C12—C13 | 0.0 (6) |
O1—Cu1—O2—C16 | 123.0 (3) | C10—C15—C14—C13 | 0.0 (5) |
O1—Cu1—N1—C7 | −25.3 (4) | C11—C10—C15—C14 | 0.0 (5) |
O1—Cu1—N1—C8 | 163.9 (3) | C11—C12—C13—C14 | 0.0 (6) |
O1—Cu1—N2—C22 | −168.8 (4) | C12—C11—C10—C15 | 0.0 (5) |
O1—Cu1—N2—C23 | 17.7 (3) | C12—C13—C14—C15 | 0.0 (6) |
O1—C1—C2—C3 | −175.4 (3) | C16—C17—C18—C19 | 0.0 (5) |
O1—C1—C6—C5 | 175.1 (3) | C16—C21—C20—C19 | 0.0 (5) |
O1—C1—C6—C7 | −7.9 (5) | C17—C16—C21—C20 | 0.0 (5) |
O2—Cu1—O1—C1 | 136.1 (3) | C17—C16—C21—C22 | 171.6 (4) |
O2—Cu1—N1—C7 | −176.8 (4) | C17—C18—C19—C20 | 0.0 (5) |
O2—Cu1—N1—C8 | 12.3 (3) | C18—C17—C16—C21 | 0.0 (5) |
O2—Cu1—N2—C22 | −15.9 (4) | C18—C19—C20—C21 | 0.0 (5) |
O2—Cu1—N2—C23 | 170.7 (3) | C19—C20—C21—C22 | −172.2 (3) |
O2—C16—C17—C18 | −175.9 (3) | C21—C22—N2—C23 | −176.7 (4) |
O2—C16—C21—C20 | 175.6 (3) | C22—N2—C23—C24 | 18.9 (6) |
O2—C16—C21—C22 | −12.8 (5) | C22—N2—C23—C25 | −108.0 (4) |
N1—Cu1—O1—C1 | 33.2 (3) | C23—C25—C26—C27 | 178.1 (4) |
N1—Cu1—O2—C16 | −134.7 (3) | C23—C25—C30—C29 | −178.0 (4) |
N1—Cu1—N2—C22 | 87.3 (4) | C24—C23—C25—C26 | 71.2 (5) |
N1—Cu1—N2—C23 | −86.2 (4) | C24—C23—C25—C30 | −110.8 (4) |
N1—C7—C6—C1 | 15.6 (7) | C25—C26—C27—C28 | 0.0 (6) |
N1—C7—C6—C5 | −167.3 (4) | C25—C30—C29—C28 | 0.0 (8) |
N1—C8—C10—C11 | −145.8 (3) | C26—C25—C30—C29 | 0.0 (6) |
N1—C8—C10—C15 | 35.0 (5) | C26—C27—C28—C29 | 0.0 (8) |
N2—Cu1—O1—C1 | −112.7 (3) | C27—C26—C25—C30 | 0.0 (6) |
N2—Cu1—O2—C16 | 10.9 (3) | C27—C28—C29—C30 | 0.0 (8) |
N2—Cu1—N1—C7 | 80.3 (4) | C27—C28—C29—C30 | 0.0 (8) |
N2—Cu1—N1—C8 | −90.6 (4) |
[Cu(C17H18NO2)2] | F(000) = 1260.0 |
Mr = 600.20 | Dx = 1.306 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: P 2yb | Cell parameters from 25 reflections |
a = 9.227 (4) Å | θ = 10.5–12.0° |
b = 42.38 (1) Å | µ = 0.76 mm−1 |
c = 8.035 (3) Å | T = 298 K |
β = 103.67 (3)° | Plate, brown |
V = 3053.0 (19) Å3 | 0.40 × 0.30 × 0.20 mm |
Z = 4 |
Rigaku AFC-7R diffractometer | Rint = 0.161 |
ω–2θ scans | θmax = 27.5° |
Absorption correction: ψ scan (North et al., 1968) | h = −4→11 |
Tmin = 0.762, Tmax = 0.860 | k = 0→55 |
7924 measured reflections | l = −10→10 |
7100 independent reflections | 3 standard reflections every 150 reflections |
3976 reflections with I > 2σ(I) | intensity decay: 0.8% |
Refinement on F2 | w = 1/[σ2(Fo2) + (0.1162P)2 + 4.3366P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.066 | (Δ/σ)max < 0.001 |
wR(F2) = 0.242 | Δρmax = 0.69 e Å−3 |
S = 1.02 | Δρmin = −0.77 e Å−3 |
3976 reflections | Absolute structure: Flack (1983), ? Friedel pairs |
644 parameters | Absolute structure parameter: −0.04 (3) |
H-atom parameters constrained |
[Cu(C17H18NO2)2] | V = 3053.0 (19) Å3 |
Mr = 600.20 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.227 (4) Å | µ = 0.76 mm−1 |
b = 42.38 (1) Å | T = 298 K |
c = 8.035 (3) Å | 0.40 × 0.30 × 0.20 mm |
β = 103.67 (3)° |
Rigaku AFC-7R diffractometer | 3976 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.161 |
Tmin = 0.762, Tmax = 0.860 | 3 standard reflections every 150 reflections |
7924 measured reflections | intensity decay: 0.8% |
7100 independent reflections |
R[F2 > 2σ(F2)] = 0.066 | H-atom parameters constrained |
wR(F2) = 0.242 | Δρmax = 0.69 e Å−3 |
S = 1.02 | Δρmin = −0.77 e Å−3 |
3976 reflections | Absolute structure: Flack (1983), ? Friedel pairs |
644 parameters | Absolute structure parameter: −0.04 (3) |
Refinement. Refinement using reflections with F2 > 0.0 σ(F2). The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.0807 (1) | 0.81450 (3) | −0.0383 (2) | 0.0534 (4) | |
Cu2 | −0.0532 (1) | 1.05037 (3) | 0.5388 (2) | 0.0533 (4) | |
O1 | 0.0208 (9) | 0.7768 (2) | −0.162 (1) | 0.061 (2) | |
O2 | 0.0643 (9) | 0.8591 (2) | −0.022 (1) | 0.069 (2) | |
O3 | −0.041 (1) | 0.7339 (3) | −0.393 (1) | 0.077 (3) | |
O4 | −0.0195 (10) | 0.9156 (2) | 0.005 (1) | 0.063 (2) | |
O5 | 0.0047 (9) | 1.0857 (2) | 0.685 (1) | 0.064 (2) | |
O6 | −0.0267 (9) | 1.0064 (2) | 0.517 (1) | 0.057 (2) | |
O7 | 0.052 (1) | 1.1277 (3) | 0.927 (1) | 0.081 (3) | |
O8 | 0.0618 (9) | 0.9481 (2) | 0.481 (1) | 0.063 (2) | |
N1 | −0.057 (1) | 0.8086 (2) | 0.115 (1) | 0.052 (2) | |
N2 | 0.2808 (10) | 0.8159 (3) | −0.088 (1) | 0.057 (2) | |
N3 | 0.053 (1) | 1.0655 (2) | 0.367 (1) | 0.055 (2) | |
N4 | −0.239 (1) | 1.0463 (2) | 0.617 (1) | 0.055 (2) | |
C1 | −0.178 (1) | 0.7617 (3) | −0.033 (1) | 0.049 (2) | |
C2 | −0.296 (1) | 0.7405 (3) | −0.037 (2) | 0.057 (3) | |
C3 | −0.332 (1) | 0.7177 (3) | −0.163 (2) | 0.060 (3) | |
C4 | −0.249 (1) | 0.7153 (3) | −0.285 (2) | 0.063 (3) | |
C5 | −0.131 (1) | 0.7358 (3) | −0.283 (2) | 0.056 (3) | |
C6 | −0.094 (1) | 0.7580 (3) | −0.156 (1) | 0.050 (2) | |
C7 | −0.154 (1) | 0.7857 (3) | 0.097 (1) | 0.048 (2) | |
C8 | −0.043 (1) | 0.8313 (3) | 0.257 (1) | 0.057 (3) | |
C9 | 0.100 (1) | 0.8254 (4) | 0.387 (2) | 0.088 (4) | |
C10 | −0.178 (1) | 0.8343 (3) | 0.334 (1) | 0.057 (3) | |
C11 | −0.294 (1) | 0.8542 (3) | 0.259 (1) | 0.061 (3) | |
C12 | −0.419 (2) | 0.8584 (4) | 0.329 (2) | 0.080 (4) | |
C13 | −0.422 (2) | 0.8437 (5) | 0.477 (2) | 0.094 (5) | |
C14 | −0.313 (2) | 0.8235 (4) | 0.550 (2) | 0.084 (4) | |
C15 | −0.188 (1) | 0.8176 (4) | 0.484 (2) | 0.076 (3) | |
C16 | 0.293 (1) | 0.8739 (3) | −0.095 (2) | 0.055 (3) | |
C17 | 0.387 (1) | 0.8996 (3) | −0.118 (2) | 0.067 (3) | |
C18 | 0.340 (2) | 0.9297 (3) | −0.106 (2) | 0.074 (4) | |
C19 | 0.204 (1) | 0.9368 (3) | −0.069 (2) | 0.062 (3) | |
C20 | 0.114 (1) | 0.9120 (3) | −0.040 (1) | 0.054 (3) | |
C21 | 0.156 (1) | 0.8803 (3) | −0.051 (1) | 0.049 (2) | |
C22 | 0.347 (1) | 0.8429 (3) | −0.105 (2) | 0.060 (3) | |
C23 | 0.366 (1) | 0.7875 (3) | −0.107 (2) | 0.056 (3) | |
C24 | 0.316 (1) | 0.7728 (3) | −0.284 (1) | 0.075 (4) | |
C25 | 0.368 (1) | 0.7651 (3) | 0.040 (2) | 0.053 (3) | |
C26 | 0.445 (1) | 0.7733 (3) | 0.205 (2) | 0.064 (3) | |
C27 | 0.464 (2) | 0.7529 (4) | 0.341 (2) | 0.076 (4) | |
C28 | 0.408 (2) | 0.7236 (4) | 0.315 (2) | 0.083 (4) | |
C29 | 0.329 (2) | 0.7140 (3) | 0.155 (2) | 0.082 (4) | |
C30 | 0.308 (1) | 0.7348 (3) | 0.019 (2) | 0.065 (3) | |
C31 | −0.082 (2) | 0.7140 (4) | −0.538 (2) | 0.081 (4) | |
C32 | 0.041 (2) | 0.7163 (4) | −0.634 (2) | 0.095 (5) | |
C33 | −0.071 (1) | 0.9470 (3) | 0.021 (1) | 0.065 (3) | |
C34 | −0.220 (2) | 0.9444 (3) | 0.067 (2) | 0.074 (4) | |
C35 | 0.185 (1) | 1.1083 (3) | 0.549 (2) | 0.056 (3) | |
C36 | 0.297 (1) | 1.1311 (3) | 0.557 (2) | 0.066 (3) | |
C37 | 0.334 (1) | 1.1519 (3) | 0.693 (2) | 0.066 (3) | |
C38 | 0.253 (1) | 1.1509 (3) | 0.822 (2) | 0.062 (3) | |
C39 | 0.142 (1) | 1.1294 (3) | 0.811 (2) | 0.059 (3) | |
C40 | 0.106 (1) | 1.1057 (3) | 0.679 (1) | 0.052 (3) | |
C41 | 0.149 (1) | 1.0885 (3) | 0.402 (2) | 0.054 (3) | |
C42 | 0.030 (1) | 1.0520 (3) | 0.187 (1) | 0.060 (3) | |
C43 | −0.110 (1) | 1.0328 (4) | 0.143 (2) | 0.091 (5) | |
C44 | 0.167 (1) | 1.0344 (3) | 0.168 (1) | 0.056 (3) | |
C45 | 0.220 (2) | 1.0392 (4) | 0.024 (2) | 0.092 (5) | |
C46 | 0.344 (3) | 1.0231 (5) | 0.001 (3) | 0.114 (7) | |
C47 | 0.420 (2) | 1.0031 (5) | 0.128 (3) | 0.106 (6) | |
C48 | 0.365 (2) | 0.9971 (4) | 0.267 (2) | 0.093 (5) | |
C49 | 0.239 (2) | 1.0122 (3) | 0.289 (2) | 0.072 (3) | |
C50 | −0.248 (1) | 0.9890 (3) | 0.594 (1) | 0.055 (3) | |
C51 | −0.338 (1) | 0.9627 (3) | 0.620 (2) | 0.068 (3) | |
C52 | −0.294 (1) | 0.9324 (3) | 0.599 (2) | 0.070 (3) | |
C53 | −0.160 (1) | 0.9277 (3) | 0.552 (2) | 0.063 (3) | |
C54 | −0.070 (1) | 0.9519 (3) | 0.527 (1) | 0.050 (3) | |
C55 | −0.113 (1) | 0.9829 (2) | 0.547 (1) | 0.051 (2) | |
C56 | −0.303 (1) | 1.0190 (3) | 0.626 (2) | 0.059 (3) | |
C57 | −0.306 (1) | 1.0759 (3) | 0.661 (2) | 0.059 (3) | |
C58 | −0.437 (2) | 1.0721 (3) | 0.745 (2) | 0.083 (4) | |
C59 | −0.351 (1) | 1.0961 (3) | 0.502 (2) | 0.059 (3) | |
C60 | −0.305 (1) | 1.1272 (3) | 0.507 (2) | 0.069 (3) | |
C61 | −0.353 (2) | 1.1466 (3) | 0.362 (2) | 0.086 (4) | |
C62 | −0.440 (2) | 1.1355 (4) | 0.214 (2) | 0.078 (4) | |
C63 | −0.484 (2) | 1.1045 (4) | 0.207 (2) | 0.077 (4) | |
C64 | −0.438 (1) | 1.0848 (3) | 0.349 (2) | 0.063 (3) | |
C65 | 0.110 (2) | 0.9164 (3) | 0.462 (2) | 0.065 (3) | |
C66 | 0.259 (2) | 0.9185 (3) | 0.417 (2) | 0.087 (4) | |
C67 | 0.063 (2) | 1.1520 (3) | 1.050 (2) | 0.077 (4) | |
C68 | −0.065 (2) | 1.1482 (4) | 1.132 (2) | 0.095 (5) | |
H1 | −0.3525 | 0.7419 | 0.0472 | 0.0694* | |
H2 | −0.4127 | 0.7037 | −0.1653 | 0.0722* | |
H3 | −0.2725 | 0.6993 | −0.3711 | 0.0765* | |
H4 | −0.2135 | 0.7847 | 0.1781 | 0.0582* | |
H5 | −0.0310 | 0.8514 | 0.2097 | 0.0689* | |
H6 | 0.0940 | 0.8054 | 0.4398 | 0.1069* | |
H7 | 0.1803 | 0.8252 | 0.3325 | 0.1069* | |
H8 | 0.1146 | 0.8414 | 0.4717 | 0.1069* | |
H9 | −0.2884 | 0.8654 | 0.1579 | 0.0734* | |
H10 | −0.4999 | 0.8714 | 0.2725 | 0.0964* | |
H11 | −0.5023 | 0.8476 | 0.5290 | 0.1141* | |
H12 | −0.3202 | 0.8129 | 0.6520 | 0.1017* | |
H13 | −0.1125 | 0.8029 | 0.5367 | 0.0922* | |
H14 | 0.4812 | 0.8957 | −0.1422 | 0.0816* | |
H15 | 0.4028 | 0.9466 | −0.1222 | 0.0900* | |
H16 | 0.1725 | 0.9580 | −0.0641 | 0.0755* | |
H17 | 0.4438 | 0.8413 | −0.1265 | 0.0719* | |
H18 | 0.4662 | 0.7941 | −0.0960 | 0.0682* | |
H19 | 0.2152 | 0.7656 | −0.3002 | 0.0908* | |
H20 | 0.3211 | 0.7879 | −0.3687 | 0.0908* | |
H21 | 0.3779 | 0.7553 | −0.2928 | 0.0908* | |
H22 | 0.4856 | 0.7941 | 0.2244 | 0.0773* | |
H23 | 0.5178 | 0.7593 | 0.4525 | 0.0914* | |
H24 | 0.4232 | 0.7092 | 0.4083 | 0.0998* | |
H25 | 0.2883 | 0.6931 | 0.1386 | 0.0993* | |
H26 | 0.2517 | 0.7284 | −0.0910 | 0.0795* | |
H27 | −0.0909 | 0.6928 | −0.5021 | 0.0973* | |
H28 | −0.1739 | 0.7206 | −0.6089 | 0.0973* | |
H29 | 0.1326 | 0.7094 | −0.5607 | 0.1136* | |
H30 | 0.0171 | 0.7034 | −0.7322 | 0.1136* | |
H31 | 0.0506 | 0.7376 | −0.6658 | 0.1136* | |
H32 | −0.0018 | 0.9579 | 0.1093 | 0.0782* | |
H33 | −0.0814 | 0.9580 | −0.0837 | 0.0782* | |
H34 | −0.2564 | 0.9650 | 0.0805 | 0.0897* | |
H35 | −0.2880 | 0.9337 | −0.0215 | 0.0897* | |
H36 | −0.2083 | 0.9331 | 0.1714 | 0.0897* | |
H37 | 0.3486 | 1.1322 | 0.4665 | 0.0800* | |
H38 | 0.4129 | 1.1667 | 0.7000 | 0.0806* | |
H39 | 0.2758 | 1.1651 | 0.9161 | 0.0750* | |
H40 | 0.2033 | 1.0926 | 0.3166 | 0.0650* | |
H41 | 0.0167 | 1.0694 | 0.1099 | 0.0730* | |
H42 | −0.1920 | 1.0454 | 0.1539 | 0.1081* | |
H43 | −0.1251 | 1.0254 | 0.0287 | 0.1081* | |
H44 | −0.1004 | 1.0153 | 0.2189 | 0.1081* | |
H45 | 0.1699 | 1.0539 | −0.0610 | 0.1101* | |
H46 | 0.3771 | 1.0258 | −0.1015 | 0.1354* | |
H47 | 0.5109 | 0.9937 | 0.1179 | 0.1272* | |
H48 | 0.4147 | 0.9822 | 0.3510 | 0.1122* | |
H49 | 0.1998 | 1.0076 | 0.3866 | 0.0877* | |
H50 | −0.4291 | 0.9664 | 0.6519 | 0.0830* | |
H51 | −0.3535 | 0.9149 | 0.6179 | 0.0845* | |
H52 | −0.1302 | 0.9066 | 0.5360 | 0.0767* | |
H53 | −0.3963 | 1.0194 | 0.6571 | 0.0723* | |
H54 | −0.2299 | 1.0870 | 0.7397 | 0.0718* | |
H55 | −0.4725 | 1.0925 | 0.7677 | 0.1007* | |
H56 | −0.5159 | 1.0611 | 0.6697 | 0.1007* | |
H57 | −0.4067 | 1.0609 | 0.8491 | 0.1007* | |
H58 | −0.2414 | 1.1354 | 0.6087 | 0.0829* | |
H59 | −0.3230 | 1.1681 | 0.3680 | 0.1033* | |
H60 | −0.4688 | 1.1487 | 0.1161 | 0.0958* | |
H61 | −0.5480 | 1.0964 | 0.1051 | 0.0935* | |
H62 | −0.4660 | 1.0632 | 0.3403 | 0.0763* | |
H63 | 0.1199 | 0.9053 | 0.5670 | 0.0796* | |
H64 | 0.0411 | 0.9059 | 0.3738 | 0.0796* | |
H65 | 0.2952 | 0.8980 | 0.4049 | 0.1053* | |
H66 | 0.2492 | 0.9300 | 0.3143 | 0.1053* | |
H67 | 0.3280 | 0.9292 | 0.5076 | 0.1053* | |
H68 | 0.1549 | 1.1499 | 1.1341 | 0.0931* | |
H69 | 0.0592 | 1.1719 | 0.9971 | 0.0931* | |
H70 | −0.0593 | 1.1642 | 1.2172 | 0.1149* | |
H71 | −0.1554 | 1.1501 | 1.0489 | 0.1149* | |
H72 | −0.0596 | 1.1281 | 1.1861 | 0.1149* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0516 (7) | 0.0481 (8) | 0.0627 (9) | −0.0010 (6) | 0.0179 (6) | 0.0007 (7) |
Cu2 | 0.0565 (7) | 0.0449 (7) | 0.0603 (9) | −0.0043 (6) | 0.0175 (6) | 0.0000 (7) |
O1 | 0.054 (4) | 0.065 (5) | 0.071 (5) | −0.011 (4) | 0.025 (4) | −0.007 (4) |
O2 | 0.053 (5) | 0.062 (6) | 0.099 (7) | 0.003 (4) | 0.033 (5) | 0.008 (5) |
O3 | 0.077 (6) | 0.092 (7) | 0.071 (5) | −0.020 (5) | 0.032 (5) | −0.033 (5) |
O4 | 0.068 (5) | 0.050 (5) | 0.073 (5) | 0.002 (4) | 0.022 (4) | −0.002 (4) |
O5 | 0.062 (5) | 0.070 (5) | 0.065 (5) | −0.014 (4) | 0.027 (4) | −0.017 (4) |
O6 | 0.061 (4) | 0.045 (4) | 0.068 (5) | −0.006 (3) | 0.021 (4) | 0.003 (4) |
O7 | 0.099 (7) | 0.071 (6) | 0.081 (6) | −0.021 (5) | 0.038 (5) | −0.021 (5) |
O8 | 0.076 (5) | 0.043 (4) | 0.071 (5) | 0.006 (4) | 0.020 (4) | −0.003 (4) |
N1 | 0.057 (5) | 0.036 (4) | 0.060 (5) | 0.005 (4) | 0.008 (4) | 0.001 (4) |
N2 | 0.057 (5) | 0.059 (5) | 0.057 (5) | 0.005 (5) | 0.015 (4) | 0.002 (5) |
N3 | 0.058 (5) | 0.052 (5) | 0.056 (6) | −0.001 (4) | 0.013 (4) | −0.002 (4) |
N4 | 0.063 (5) | 0.049 (5) | 0.053 (5) | −0.008 (4) | 0.012 (4) | 0.007 (4) |
C1 | 0.049 (5) | 0.040 (5) | 0.060 (6) | 0.011 (4) | 0.018 (5) | 0.004 (5) |
C2 | 0.056 (6) | 0.048 (6) | 0.067 (7) | −0.001 (5) | 0.015 (5) | 0.006 (5) |
C3 | 0.050 (6) | 0.047 (6) | 0.082 (8) | −0.009 (5) | 0.014 (6) | 0.001 (6) |
C4 | 0.065 (7) | 0.061 (8) | 0.060 (7) | −0.003 (6) | 0.009 (6) | −0.003 (6) |
C5 | 0.054 (6) | 0.056 (7) | 0.057 (6) | 0.000 (5) | 0.012 (5) | −0.007 (5) |
C6 | 0.045 (5) | 0.044 (6) | 0.058 (6) | 0.001 (4) | 0.006 (4) | −0.006 (5) |
C7 | 0.052 (6) | 0.042 (5) | 0.055 (6) | 0.003 (4) | 0.020 (5) | −0.002 (5) |
C8 | 0.057 (6) | 0.060 (6) | 0.059 (6) | 0.006 (5) | 0.024 (5) | −0.003 (5) |
C9 | 0.068 (8) | 0.10 (1) | 0.091 (10) | −0.021 (7) | 0.012 (7) | −0.023 (9) |
C10 | 0.061 (6) | 0.047 (6) | 0.061 (7) | −0.007 (5) | 0.010 (5) | −0.005 (5) |
C11 | 0.066 (7) | 0.053 (6) | 0.063 (7) | 0.003 (5) | 0.013 (5) | 0.002 (5) |
C12 | 0.066 (8) | 0.086 (10) | 0.086 (9) | 0.011 (7) | 0.016 (7) | −0.018 (8) |
C13 | 0.076 (9) | 0.11 (1) | 0.10 (1) | −0.003 (9) | 0.035 (9) | −0.03 (1) |
C14 | 0.10 (1) | 0.088 (10) | 0.072 (8) | −0.010 (8) | 0.043 (8) | −0.004 (7) |
C15 | 0.087 (8) | 0.086 (9) | 0.059 (7) | −0.002 (8) | 0.026 (6) | 0.007 (7) |
C16 | 0.050 (6) | 0.060 (7) | 0.057 (7) | −0.003 (5) | 0.015 (5) | 0.001 (5) |
C17 | 0.055 (6) | 0.066 (8) | 0.083 (9) | −0.020 (6) | 0.021 (6) | 0.006 (7) |
C18 | 0.075 (8) | 0.059 (8) | 0.089 (10) | −0.015 (6) | 0.024 (7) | 0.006 (7) |
C19 | 0.065 (7) | 0.051 (7) | 0.071 (8) | −0.007 (5) | 0.016 (6) | 0.002 (6) |
C20 | 0.057 (6) | 0.058 (7) | 0.047 (6) | −0.007 (5) | 0.009 (5) | 0.005 (5) |
C21 | 0.061 (6) | 0.038 (5) | 0.047 (6) | −0.001 (4) | 0.013 (5) | 0.005 (4) |
C22 | 0.052 (6) | 0.070 (8) | 0.058 (7) | 0.001 (6) | 0.015 (5) | 0.006 (6) |
C23 | 0.043 (6) | 0.066 (7) | 0.063 (7) | 0.009 (5) | 0.021 (5) | 0.007 (6) |
C24 | 0.086 (9) | 0.092 (9) | 0.054 (7) | 0.029 (7) | 0.029 (6) | 0.000 (6) |
C25 | 0.048 (6) | 0.049 (6) | 0.066 (7) | 0.006 (4) | 0.022 (5) | 0.007 (5) |
C26 | 0.069 (7) | 0.058 (7) | 0.068 (8) | 0.019 (6) | 0.022 (6) | −0.003 (6) |
C27 | 0.091 (9) | 0.082 (10) | 0.059 (7) | 0.013 (7) | 0.030 (7) | 0.005 (7) |
C28 | 0.090 (10) | 0.076 (9) | 0.09 (1) | 0.012 (8) | 0.037 (8) | 0.026 (8) |
C29 | 0.091 (10) | 0.059 (8) | 0.10 (1) | −0.010 (7) | 0.029 (8) | 0.008 (8) |
C30 | 0.065 (7) | 0.057 (7) | 0.073 (8) | −0.001 (5) | 0.014 (6) | −0.001 (6) |
C31 | 0.082 (9) | 0.09 (1) | 0.077 (10) | −0.003 (8) | 0.024 (7) | −0.017 (8) |
C32 | 0.11 (1) | 0.10 (1) | 0.07 (1) | −0.01 (1) | 0.032 (9) | −0.028 (9) |
C33 | 0.073 (8) | 0.053 (7) | 0.066 (8) | 0.014 (6) | 0.012 (6) | −0.004 (6) |
C34 | 0.076 (8) | 0.070 (8) | 0.073 (9) | 0.016 (7) | 0.013 (7) | −0.002 (7) |
C35 | 0.056 (6) | 0.049 (6) | 0.064 (7) | 0.002 (5) | 0.017 (5) | 0.007 (5) |
C36 | 0.053 (6) | 0.048 (6) | 0.100 (10) | 0.000 (5) | 0.025 (6) | 0.008 (7) |
C37 | 0.060 (7) | 0.040 (6) | 0.095 (9) | −0.008 (5) | 0.010 (6) | 0.005 (6) |
C38 | 0.076 (8) | 0.038 (6) | 0.071 (8) | −0.003 (5) | 0.016 (6) | −0.001 (5) |
C39 | 0.066 (7) | 0.049 (7) | 0.061 (7) | −0.004 (5) | 0.012 (5) | −0.002 (5) |
C40 | 0.044 (5) | 0.049 (6) | 0.062 (7) | −0.003 (4) | 0.012 (5) | 0.008 (5) |
C41 | 0.047 (6) | 0.053 (6) | 0.066 (7) | −0.003 (5) | 0.024 (5) | 0.004 (5) |
C42 | 0.076 (7) | 0.061 (6) | 0.044 (5) | 0.006 (6) | 0.015 (5) | 0.004 (5) |
C43 | 0.059 (8) | 0.14 (1) | 0.069 (8) | 0.021 (8) | −0.003 (6) | −0.023 (9) |
C44 | 0.062 (6) | 0.053 (7) | 0.057 (7) | −0.009 (5) | 0.022 (5) | −0.004 (5) |
C45 | 0.12 (1) | 0.09 (1) | 0.08 (1) | −0.013 (9) | 0.050 (9) | −0.008 (8) |
C46 | 0.15 (2) | 0.08 (1) | 0.14 (2) | −0.02 (1) | 0.10 (2) | −0.02 (1) |
C47 | 0.079 (10) | 0.09 (1) | 0.17 (2) | −0.013 (9) | 0.06 (1) | −0.04 (1) |
C48 | 0.062 (8) | 0.08 (1) | 0.14 (1) | −0.001 (7) | 0.030 (9) | −0.027 (10) |
C49 | 0.071 (8) | 0.059 (7) | 0.088 (9) | 0.007 (6) | 0.023 (7) | −0.006 (6) |
C50 | 0.055 (6) | 0.054 (6) | 0.054 (6) | −0.005 (5) | 0.009 (5) | 0.002 (5) |
C51 | 0.066 (7) | 0.059 (8) | 0.078 (8) | −0.014 (6) | 0.018 (6) | 0.012 (6) |
C52 | 0.070 (8) | 0.051 (7) | 0.083 (9) | −0.020 (6) | 0.009 (7) | 0.004 (6) |
C53 | 0.069 (8) | 0.052 (7) | 0.066 (8) | −0.005 (5) | 0.010 (6) | 0.003 (6) |
C54 | 0.057 (7) | 0.046 (6) | 0.045 (6) | 0.000 (5) | 0.007 (5) | −0.003 (5) |
C55 | 0.062 (6) | 0.026 (5) | 0.063 (7) | −0.008 (4) | 0.010 (5) | 0.004 (4) |
C56 | 0.045 (6) | 0.065 (8) | 0.067 (7) | −0.007 (5) | 0.013 (5) | 0.009 (6) |
C57 | 0.065 (7) | 0.057 (7) | 0.060 (7) | 0.009 (5) | 0.023 (5) | −0.004 (5) |
C58 | 0.078 (9) | 0.089 (10) | 0.092 (9) | 0.019 (7) | 0.039 (8) | 0.019 (8) |
C59 | 0.061 (6) | 0.051 (6) | 0.069 (7) | −0.002 (5) | 0.023 (6) | 0.001 (5) |
C60 | 0.076 (8) | 0.056 (7) | 0.077 (8) | 0.003 (6) | 0.024 (7) | −0.004 (7) |
C61 | 0.10 (1) | 0.057 (8) | 0.11 (1) | −0.005 (7) | 0.031 (9) | 0.008 (8) |
C62 | 0.088 (9) | 0.071 (9) | 0.083 (9) | 0.019 (7) | 0.033 (8) | 0.005 (7) |
C63 | 0.090 (9) | 0.073 (9) | 0.068 (8) | 0.014 (7) | 0.019 (7) | 0.001 (7) |
C64 | 0.079 (8) | 0.046 (6) | 0.063 (7) | −0.003 (5) | 0.013 (6) | −0.007 (5) |
C65 | 0.084 (9) | 0.047 (7) | 0.063 (7) | 0.013 (6) | 0.012 (6) | −0.001 (5) |
C66 | 0.10 (1) | 0.073 (9) | 0.09 (1) | 0.027 (8) | 0.030 (9) | 0.004 (8) |
C67 | 0.12 (1) | 0.048 (7) | 0.065 (9) | −0.004 (7) | 0.019 (8) | −0.016 (7) |
C68 | 0.11 (1) | 0.08 (1) | 0.10 (1) | 0.021 (10) | 0.04 (1) | 0.007 (10) |
Cu1—O1 | 1.895 (9) | C29—H25 | 0.950 |
Cu1—O2 | 1.90 (1) | C30—H26 | 0.950 |
Cu1—N1 | 1.98 (1) | C31—C32 | 1.51 (2) |
Cu1—N2 | 1.980 (10) | C31—H27 | 0.950 |
Cu2—O5 | 1.899 (9) | C31—H28 | 0.950 |
Cu2—O6 | 1.891 (8) | C32—H29 | 0.950 |
Cu2—N3 | 1.98 (1) | C32—H30 | 0.950 |
Cu2—N4 | 1.97 (1) | C32—H31 | 0.950 |
O1—C6 | 1.33 (1) | C33—C34 | 1.51 (2) |
O2—C21 | 1.29 (1) | C33—H32 | 0.950 |
O3—C5 | 1.36 (2) | C33—H33 | 0.950 |
O3—C31 | 1.41 (2) | C34—H34 | 0.950 |
O4—C20 | 1.37 (2) | C34—H35 | 0.950 |
O4—C33 | 1.43 (2) | C34—H36 | 0.950 |
O5—C40 | 1.28 (1) | C35—C36 | 1.41 (2) |
O6—C55 | 1.33 (1) | C35—C40 | 1.40 (2) |
O7—C39 | 1.39 (2) | C35—C41 | 1.43 (2) |
O7—C67 | 1.41 (2) | C36—C37 | 1.38 (2) |
O8—C54 | 1.36 (2) | C36—H37 | 0.950 |
O8—C65 | 1.43 (2) | C37—C38 | 1.42 (2) |
N1—C7 | 1.30 (1) | C37—H38 | 0.950 |
N1—C8 | 1.48 (1) | C38—C39 | 1.35 (2) |
N2—C22 | 1.32 (2) | C38—H39 | 0.950 |
N2—C23 | 1.47 (2) | C39—C40 | 1.44 (2) |
N3—C41 | 1.30 (1) | C41—H40 | 0.950 |
N3—C42 | 1.53 (1) | C42—C43 | 1.49 (2) |
N4—C56 | 1.31 (2) | C42—C44 | 1.51 (2) |
N4—C57 | 1.48 (2) | C42—H41 | 0.950 |
C1—C2 | 1.41 (2) | C43—H42 | 0.950 |
C1—C6 | 1.40 (2) | C43—H43 | 0.950 |
C1—C7 | 1.44 (2) | C43—H44 | 0.950 |
C2—C3 | 1.38 (2) | C44—C45 | 1.37 (2) |
C2—H1 | 0.950 | C44—C49 | 1.40 (2) |
C3—C4 | 1.38 (2) | C45—C46 | 1.39 (3) |
C3—H2 | 0.950 | C45—H45 | 0.950 |
C4—C5 | 1.39 (2) | C46—C47 | 1.38 (3) |
C4—H3 | 0.950 | C46—H46 | 0.950 |
C5—C6 | 1.37 (2) | C47—C48 | 1.36 (3) |
C7—H4 | 0.950 | C47—H47 | 0.950 |
C8—C9 | 1.49 (2) | C48—C49 | 1.38 (2) |
C8—C10 | 1.52 (2) | C48—H48 | 0.950 |
C8—H5 | 0.950 | C49—H49 | 0.950 |
C9—H6 | 0.950 | C50—C51 | 1.43 (2) |
C9—H7 | 0.950 | C50—C55 | 1.41 (2) |
C9—H8 | 0.950 | C50—C56 | 1.41 (2) |
C10—C11 | 1.38 (2) | C51—C52 | 1.37 (2) |
C10—C15 | 1.42 (2) | C51—H50 | 0.950 |
C11—C12 | 1.41 (2) | C52—C53 | 1.39 (2) |
C11—H9 | 0.950 | C52—H51 | 0.950 |
C12—C13 | 1.34 (2) | C53—C54 | 1.37 (2) |
C12—H10 | 0.950 | C53—H52 | 0.950 |
C13—C14 | 1.35 (2) | C54—C55 | 1.39 (2) |
C13—H11 | 0.950 | C56—H53 | 0.950 |
C14—C15 | 1.40 (2) | C57—C58 | 1.53 (2) |
C14—H12 | 0.950 | C57—C59 | 1.51 (2) |
C15—H13 | 0.950 | C57—H54 | 0.950 |
C16—C17 | 1.43 (2) | C58—H55 | 0.950 |
C16—C21 | 1.42 (2) | C58—H56 | 0.950 |
C16—C22 | 1.41 (2) | C58—H57 | 0.950 |
C17—C18 | 1.36 (2) | C59—C60 | 1.38 (2) |
C17—H14 | 0.950 | C59—C64 | 1.39 (2) |
C18—C19 | 1.39 (2) | C60—C61 | 1.41 (2) |
C18—H15 | 0.950 | C60—H58 | 0.950 |
C19—C20 | 1.39 (2) | C61—C62 | 1.36 (2) |
C19—H16 | 0.950 | C61—H59 | 0.950 |
C20—C21 | 1.41 (2) | C62—C63 | 1.37 (2) |
C22—H17 | 0.950 | C62—H60 | 0.950 |
C23—C24 | 1.52 (2) | C63—C64 | 1.39 (2) |
C23—C25 | 1.51 (2) | C63—H61 | 0.950 |
C23—H18 | 0.950 | C64—H62 | 0.950 |
C24—H19 | 0.950 | C65—C66 | 1.50 (2) |
C24—H20 | 0.950 | C65—H63 | 0.950 |
C24—H21 | 0.950 | C65—H64 | 0.950 |
C25—C26 | 1.39 (2) | C66—H65 | 0.950 |
C25—C30 | 1.39 (2) | C66—H66 | 0.950 |
C26—C27 | 1.37 (2) | C66—H67 | 0.950 |
C26—H22 | 0.950 | C67—C68 | 1.49 (2) |
C27—C28 | 1.34 (2) | C67—H68 | 0.950 |
C27—H23 | 0.950 | C67—H69 | 0.950 |
C28—C29 | 1.38 (2) | C68—H70 | 0.950 |
C28—H24 | 0.950 | C68—H71 | 0.950 |
C29—C30 | 1.38 (2) | C68—H72 | 0.950 |
O1—Cu1—O2 | 148.9 (3) | C31—C32—H31 | 109.4 |
O1—Cu1—N1 | 94.0 (4) | H29—C32—H30 | 109.3 |
O1—Cu1—N2 | 95.2 (4) | H29—C32—H31 | 109.2 |
O2—Cu1—N1 | 90.5 (4) | H30—C32—H31 | 109.9 |
O2—Cu1—N2 | 94.4 (4) | O4—C33—C34 | 107 (1) |
N1—Cu1—N2 | 153.4 (4) | O4—C33—H32 | 110.0 |
O5—Cu2—O6 | 144.0 (3) | O4—C33—H33 | 110.2 |
O5—Cu2—N3 | 93.5 (4) | C34—C33—H32 | 110.0 |
O5—Cu2—N4 | 90.6 (4) | C34—C33—H33 | 110.0 |
O6—Cu2—N3 | 99.2 (4) | H32—C33—H33 | 109.4 |
O6—Cu2—N4 | 94.8 (4) | C33—C34—H34 | 109.4 |
N3—Cu2—N4 | 150.0 (4) | C33—C34—H35 | 109.7 |
Cu1—O1—C6 | 128.3 (8) | C33—C34—H36 | 109.4 |
Cu1—O2—C21 | 127.8 (8) | H34—C34—H35 | 109.6 |
C5—O3—C31 | 119 (1) | H34—C34—H36 | 109.1 |
C20—O4—C33 | 117.7 (10) | H35—C34—H36 | 109.7 |
Cu2—O5—C40 | 127.2 (8) | C36—C35—C40 | 121 (1) |
Cu2—O6—C55 | 128.7 (8) | C36—C35—C41 | 117 (1) |
C39—O7—C67 | 118 (1) | C40—C35—C41 | 121 (1) |
C54—O8—C65 | 117.4 (10) | C35—C36—C37 | 120 (1) |
Cu1—N1—C7 | 123.3 (8) | C35—C36—H37 | 119.5 |
Cu1—N1—C8 | 116.5 (7) | C37—C36—H37 | 119.7 |
C7—N1—C8 | 120 (1) | C36—C37—C38 | 119 (1) |
Cu1—N2—C22 | 121.6 (9) | C36—C37—H38 | 120.5 |
Cu1—N2—C23 | 123.0 (8) | C38—C37—H38 | 120.3 |
C22—N2—C23 | 115.4 (10) | C37—C38—C39 | 119 (1) |
Cu2—N3—C41 | 121.5 (8) | C37—C38—H39 | 120.4 |
Cu2—N3—C42 | 123.8 (7) | C39—C38—H39 | 119.9 |
C41—N3—C42 | 114 (1) | O7—C39—C38 | 123 (1) |
Cu2—N4—C56 | 122.3 (9) | O7—C39—C40 | 112 (1) |
Cu2—N4—C57 | 116.6 (8) | C38—C39—C40 | 123 (1) |
C56—N4—C57 | 121 (1) | O5—C40—C35 | 126 (1) |
C2—C1—C6 | 117 (1) | O5—C40—C39 | 118 (1) |
C2—C1—C7 | 117 (1) | C35—C40—C39 | 115 (1) |
C6—C1—C7 | 125 (1) | N3—C41—C35 | 129.4 (12) |
C1—C2—C3 | 121 (1) | N3—C41—H40 | 115.6 |
C1—C2—H1 | 119.4 | C35—C41—H40 | 115.7 |
C3—C2—H1 | 119.5 | N3—C42—C43 | 110.7 (10) |
C2—C3—C4 | 119 (1) | N3—C42—C44 | 110.3 (8) |
C2—C3—H2 | 120.2 | N3—C42—H41 | 107.2 |
C4—C3—H2 | 120.1 | C43—C42—C44 | 113 (1) |
C3—C4—C5 | 120 (1) | C43—C42—H41 | 107.3 |
C3—C4—H3 | 119.8 | C44—C42—H41 | 107.3 |
C5—C4—H3 | 119.8 | C42—C43—H42 | 109.6 |
O3—C5—C4 | 123 (1) | C42—C43—H43 | 109.7 |
O3—C5—C6 | 116.4 (10) | C42—C43—H44 | 109.3 |
C4—C5—C6 | 120 (1) | H42—C43—H43 | 109.6 |
O1—C6—C1 | 122.2 (10) | H42—C43—H44 | 109.1 |
O1—C6—C5 | 116 (1) | H43—C43—H44 | 109.5 |
C1—C6—C5 | 121.3 (10) | C42—C44—C45 | 118 (1) |
N1—C7—C1 | 126 (1) | C42—C44—C49 | 122 (1) |
N1—C7—H4 | 116.8 | C45—C44—C49 | 118 (1) |
C1—C7—H4 | 117.0 | C44—C45—C46 | 120 (1) |
N1—C8—C9 | 109.6 (10) | C44—C45—H45 | 119.5 |
N1—C8—C10 | 115.9 (9) | C46—C45—H45 | 119.8 |
N1—C8—H5 | 105.7 | C45—C46—C47 | 119 (2) |
C9—C8—C10 | 113 (1) | C45—C46—H46 | 120.0 |
C9—C8—H5 | 105.5 | C47—C46—H46 | 120.3 |
C10—C8—H5 | 105.6 | C46—C47—C48 | 119 (1) |
C8—C9—H6 | 109.2 | C46—C47—H47 | 120.0 |
C8—C9—H7 | 109.5 | C48—C47—H47 | 120.1 |
C8—C9—H8 | 109.7 | C47—C48—C49 | 121 (1) |
H6—C9—H7 | 109.2 | C47—C48—H48 | 119.6 |
H6—C9—H8 | 109.4 | C49—C48—H48 | 119.3 |
H7—C9—H8 | 109.7 | C44—C49—C48 | 119 (1) |
C8—C10—C11 | 119 (1) | C44—C49—H49 | 119.9 |
C8—C10—C15 | 121 (1) | C48—C49—H49 | 120.6 |
C11—C10—C15 | 118 (1) | C51—C50—C55 | 118 (1) |
C10—C11—C12 | 121 (1) | C51—C50—C56 | 115 (1) |
C10—C11—H9 | 119.1 | C55—C50—C56 | 126 (1) |
C12—C11—H9 | 119.3 | C50—C51—C52 | 121 (1) |
C11—C12—C13 | 118 (1) | C50—C51—H50 | 119.2 |
C11—C12—H10 | 120.4 | C52—C51—H50 | 119.5 |
C13—C12—H10 | 120.7 | C51—C52—C53 | 118 (1) |
C12—C13—C14 | 120 (1) | C51—C52—H51 | 120.9 |
C12—C13—H11 | 119.3 | C53—C52—H51 | 120.9 |
C14—C13—H11 | 120.0 | C52—C53—C54 | 122 (1) |
C13—C14—C15 | 122 (1) | C52—C53—H52 | 118.4 |
C13—C14—H12 | 118.5 | C54—C53—H52 | 118.6 |
C15—C14—H12 | 118.5 | O8—C54—C53 | 124 (1) |
C10—C15—C14 | 117 (1) | O8—C54—C55 | 116 (1) |
C10—C15—H13 | 121.5 | C53—C54—C55 | 119 (1) |
C14—C15—H13 | 121.4 | O6—C55—C50 | 120.8 (10) |
C17—C16—C21 | 119 (1) | O6—C55—C54 | 119 (1) |
C17—C16—C22 | 117 (1) | C50—C55—C54 | 120 (1) |
C21—C16—C22 | 122 (1) | N4—C56—C50 | 126 (1) |
C16—C17—C18 | 119 (1) | N4—C56—H53 | 116.7 |
C16—C17—H14 | 120.3 | C50—C56—H53 | 116.5 |
C18—C17—H14 | 120.1 | N4—C57—C58 | 116 (1) |
C17—C18—C19 | 122 (1) | N4—C57—C59 | 109 (1) |
C17—C18—H15 | 118.8 | N4—C57—H54 | 106.9 |
C19—C18—H15 | 118.8 | C58—C57—C59 | 110 (1) |
C18—C19—C20 | 118 (1) | C58—C57—H54 | 107.0 |
C18—C19—H16 | 120.7 | C59—C57—H54 | 106.9 |
C20—C19—H16 | 120.7 | C57—C58—H55 | 109.4 |
O4—C20—C19 | 124 (1) | C57—C58—H56 | 109.5 |
O4—C20—C21 | 113 (1) | C57—C58—H57 | 109.8 |
C19—C20—C21 | 121 (1) | H55—C58—H56 | 109.1 |
O2—C21—C16 | 124 (1) | H55—C58—H57 | 109.4 |
O2—C21—C20 | 117 (1) | H56—C58—H57 | 109.7 |
C16—C21—C20 | 118 (1) | C57—C59—C60 | 119 (1) |
N2—C22—C16 | 128 (1) | C57—C59—C64 | 122 (1) |
N2—C22—H17 | 115.7 | C60—C59—C64 | 117 (1) |
C16—C22—H17 | 115.9 | C59—C60—C61 | 119 (1) |
N2—C23—C24 | 112.5 (9) | C59—C60—H58 | 119.8 |
N2—C23—C25 | 110 (1) | C61—C60—H58 | 120.3 |
N2—C23—H18 | 106.4 | C60—C61—C62 | 121 (1) |
C24—C23—C25 | 114 (1) | C60—C61—H59 | 119.3 |
C24—C23—H18 | 106.3 | C62—C61—H59 | 118.9 |
C25—C23—H18 | 106.5 | C61—C62—C63 | 118 (1) |
C23—C24—H19 | 109.4 | C61—C62—H60 | 121.0 |
C23—C24—H20 | 109.8 | C63—C62—H60 | 120.6 |
C23—C24—H21 | 109.5 | C62—C63—C64 | 120 (1) |
H19—C24—H20 | 109.4 | C62—C63—H61 | 119.7 |
H19—C24—H21 | 109.1 | C64—C63—H61 | 119.5 |
H20—C24—H21 | 109.6 | C59—C64—C63 | 121 (1) |
C23—C25—C26 | 119.6 (10) | C59—C64—H62 | 119.3 |
C23—C25—C30 | 123 (1) | C63—C64—H62 | 119.4 |
C26—C25—C30 | 116 (1) | O8—C65—C66 | 107 (1) |
C25—C26—C27 | 122 (1) | O8—C65—H63 | 109.9 |
C25—C26—H22 | 118.7 | O8—C65—H64 | 110.1 |
C27—C26—H22 | 118.5 | C66—C65—H63 | 110.2 |
C26—C27—C28 | 118 (1) | C66—C65—H64 | 109.8 |
C26—C27—H23 | 120.6 | H63—C65—H64 | 109.7 |
C28—C27—H23 | 120.6 | C65—C66—H65 | 109.7 |
C27—C28—C29 | 121 (1) | C65—C66—H66 | 109.9 |
C27—C28—H24 | 119.3 | C65—C66—H67 | 109.1 |
C29—C28—H24 | 119.4 | H65—C66—H66 | 110.1 |
C28—C29—C30 | 119 (1) | H65—C66—H67 | 108.9 |
C28—C29—H25 | 120.3 | H66—C66—H67 | 109.2 |
C30—C29—H25 | 120.2 | O7—C67—C68 | 107 (1) |
C25—C30—C29 | 120 (1) | O7—C67—H68 | 109.3 |
C25—C30—H26 | 119.2 | O7—C67—H69 | 110.2 |
C29—C30—H26 | 119.8 | C68—C67—H68 | 110.1 |
O3—C31—C32 | 107 (1) | C68—C67—H69 | 110.3 |
O3—C31—H27 | 109.8 | H68—C67—H69 | 109.4 |
O3—C31—H28 | 110.4 | C67—C68—H70 | 109.1 |
C32—C31—H27 | 110.0 | C67—C68—H71 | 109.8 |
C32—C31—H28 | 110.3 | C67—C68—H72 | 109.5 |
H27—C31—H28 | 109.2 | H70—C68—H71 | 109.7 |
C31—C32—H29 | 109.4 | H70—C68—H72 | 108.7 |
C31—C32—H30 | 109.7 | H71—C68—H72 | 109.9 |
Cu1—O1—C6—C1 | −9 (1) | C1—C6—C5—C4 | −3 (1) |
Cu1—O1—C6—C5 | 167.1 (8) | C1—C7—N1—C8 | −178.9 (9) |
Cu1—O2—C21—C16 | −2 (1) | C2—C1—C6—C5 | 4 (1) |
Cu1—O2—C21—C20 | 176.3 (7) | C2—C3—C4—C5 | 0 (1) |
Cu1—N1—C7—C1 | 0 (1) | C3—C2—C1—C6 | −2 (1) |
Cu1—N1—C8—C9 | −70 (1) | C3—C2—C1—C7 | 176 (1) |
Cu1—N1—C8—C10 | 159.3 (7) | C3—C4—C5—C6 | 1 (1) |
Cu1—N2—C22—C16 | −1 (1) | C4—C5—O3—C31 | 11 (1) |
Cu1—N2—C23—C24 | 80 (1) | C5—O3—C31—C32 | −178 (1) |
Cu1—N2—C23—C25 | −48 (1) | C5—C6—C1—C7 | −175 (1) |
Cu2—O5—C40—C35 | 8 (1) | C6—C5—O3—C31 | −172 (1) |
Cu2—O5—C40—C39 | −174.7 (7) | C7—N1—C8—C9 | 108.2 (11) |
Cu2—O6—C55—C50 | 3 (1) | C7—N1—C8—C10 | −22 (1) |
Cu2—O6—C55—C54 | −178.3 (7) | C8—C10—C11—C12 | −178 (1) |
Cu2—N3—C41—C35 | −6 (1) | C8—C10—C15—C14 | 176 (1) |
Cu2—N3—C42—C43 | 15 (1) | C9—C8—C10—C11 | 147 (1) |
Cu2—N3—C42—C44 | −111.3 (10) | C9—C8—C10—C15 | −31 (1) |
Cu2—N4—C56—C50 | 4 (1) | C10—C11—C12—C13 | 2 (2) |
Cu2—N4—C57—C58 | −171.8 (7) | C10—C15—C14—C13 | 1 (2) |
Cu2—N4—C57—C59 | 63.4 (10) | C11—C10—C15—C14 | −2 (1) |
O1—Cu1—O2—C21 | −102 (1) | C11—C12—C13—C14 | −4 (2) |
O1—Cu1—N1—C7 | −4.8 (9) | C12—C11—C10—C15 | 0 (1) |
O1—Cu1—N1—C8 | 173.3 (7) | C12—C13—C14—C15 | 2 (2) |
O1—Cu1—N2—C22 | 147.4 (9) | C16—C17—C18—C19 | 0 (2) |
O1—Cu1—N2—C23 | −33.1 (8) | C16—C21—C20—C19 | 0 (1) |
O1—C6—C1—C2 | −179.8 (10) | C16—C22—N2—C23 | 179 (1) |
O1—C6—C1—C7 | 0 (1) | C17—C16—C21—C20 | 3 (1) |
O1—C6—C5—O3 | 4 (1) | C17—C18—C19—C20 | 1 (2) |
O1—C6—C5—C4 | 179 (1) | C18—C17—C16—C21 | −3 (1) |
O2—Cu1—O1—C6 | −87 (1) | C18—C17—C16—C22 | −178 (1) |
O2—Cu1—N1—C7 | 144.4 (8) | C18—C19—C20—C21 | −1 (1) |
O2—Cu1—N1—C8 | −37.5 (7) | C19—C20—O4—C33 | 0 (1) |
O2—Cu1—N2—C22 | −3.0 (9) | C20—O4—C33—C34 | 178.5 (9) |
O2—Cu1—N2—C23 | 176.6 (8) | C20—C21—C16—C22 | 178 (1) |
O2—C21—C16—C17 | −177 (1) | C21—C20—O4—C33 | 179.6 (9) |
O2—C21—C16—C22 | −2 (1) | C22—N2—C23—C24 | −99 (1) |
O2—C21—C20—O4 | 1 (1) | C22—N2—C23—C25 | 131.2 (10) |
O2—C21—C20—C19 | −179 (1) | C23—C25—C26—C27 | −172 (1) |
O3—C5—C4—C3 | 176 (1) | C23—C25—C30—C29 | 171 (1) |
O3—C5—C6—C1 | −179.1 (10) | C24—C23—C25—C26 | 164 (1) |
O4—C20—C19—C18 | 176 (1) | C24—C23—C25—C30 | −9 (1) |
O4—C20—C21—C16 | −179.4 (9) | C25—C26—C27—C28 | 0 (2) |
O5—Cu2—O6—C55 | 98.4 (10) | C25—C30—C29—C28 | 1 (2) |
O5—Cu2—N3—C41 | 13.0 (9) | C26—C25—C30—C29 | −2 (1) |
O5—Cu2—N3—C42 | −166.2 (8) | C26—C27—C28—C29 | −1 (2) |
O5—Cu2—N4—C56 | −148.8 (9) | C27—C26—C25—C30 | 1 (1) |
O5—Cu2—N4—C57 | 33.5 (7) | C27—C28—C29—C30 | 0 (2) |
O5—C40—C35—C36 | −178 (1) | C35—C36—C37—C38 | −2 (1) |
O5—C40—C35—C41 | 3 (1) | C35—C40—C39—C38 | −6 (1) |
O5—C40—C39—O7 | −2 (1) | C35—C41—N3—C42 | 172 (1) |
O5—C40—C39—C38 | 176 (1) | C36—C35—C40—C39 | 4 (1) |
O6—Cu2—O5—C40 | 96 (1) | C36—C37—C38—C39 | 0 (1) |
O6—Cu2—N3—C41 | −133.2 (9) | C37—C36—C35—C40 | 0 (1) |
O6—Cu2—N3—C42 | 47.6 (8) | C37—C36—C35—C41 | 177 (1) |
O6—Cu2—N4—C56 | −4.5 (9) | C37—C38—C39—C40 | 3 (1) |
O6—Cu2—N4—C57 | 177.8 (7) | C38—C39—O7—C67 | 8 (1) |
O6—C55—C50—C51 | 178 (1) | C39—O7—C67—C68 | 168 (1) |
O6—C55—C50—C56 | −4 (1) | C39—C40—C35—C41 | −173 (1) |
O6—C55—C54—O8 | 1 (1) | C40—C39—O7—C67 | −172.1 (10) |
O6—C55—C54—C53 | −178.0 (10) | C41—N3—C42—C43 | −163 (1) |
O7—C39—C38—C37 | −176 (1) | C41—N3—C42—C44 | 69 (1) |
O7—C39—C40—C35 | 174.3 (10) | C42—C44—C45—C46 | −179 (1) |
O8—C54—C53—C52 | 179 (1) | C42—C44—C49—C48 | −179 (1) |
O8—C54—C55—C50 | 179.6 (9) | C43—C42—C44—C45 | 100 (1) |
N1—Cu1—O1—C6 | 9.9 (9) | C43—C42—C44—C49 | −76 (1) |
N1—Cu1—O2—C21 | 158.8 (9) | C44—C45—C46—C47 | −2 (2) |
N1—Cu1—N2—C22 | −102 (1) | C44—C49—C48—C47 | 0 (2) |
N1—Cu1—N2—C23 | 76 (1) | C45—C44—C49—C48 | 3 (1) |
N1—C7—C1—C2 | −175 (1) | C45—C46—C47—C48 | 5 (2) |
N1—C7—C1—C6 | 4 (1) | C46—C45—C44—C49 | −1 (2) |
N1—C8—C10—C11 | −84 (1) | C46—C47—C48—C49 | −3 (2) |
N1—C8—C10—C15 | 96 (1) | C50—C51—C52—C53 | 0 (1) |
N2—Cu1—O1—C6 | 164.9 (9) | C50—C55—C54—C53 | 0 (1) |
N2—Cu1—O2—C21 | 5.0 (9) | C50—C56—N4—C57 | −177 (1) |
N2—Cu1—N1—C7 | −114 (1) | C51—C50—C55—C54 | 0 (1) |
N2—Cu1—N1—C8 | 63 (1) | C51—C52—C53—C54 | 0 (1) |
N2—C22—C16—C17 | 179.9 (14) | C52—C51—C50—C55 | 0 (1) |
N2—C22—C16—C21 | 5 (1) | C52—C51—C50—C56 | −177 (1) |
N2—C23—C25—C26 | −67 (1) | C52—C53—C54—C55 | 0 (1) |
N2—C23—C25—C30 | 118 (1) | C53—C54—O8—C65 | −1 (1) |
N3—Cu2—O5—C40 | −14.4 (9) | C54—O8—C65—C66 | −178.1 (9) |
N3—Cu2—O6—C55 | −152.6 (9) | C54—C55—C50—C56 | 177.1 (10) |
N3—Cu2—N4—C56 | 113 (1) | C55—C54—O8—C65 | 178.8 (9) |
N3—Cu2—N4—C57 | −64 (1) | C56—N4—C57—C58 | 10 (1) |
N3—C41—C35—C36 | 178 (1) | C56—N4—C57—C59 | −114 (1) |
N3—C41—C35—C40 | −3 (1) | C57—C59—C60—C61 | −176 (1) |
N3—C42—C44—C45 | −134 (1) | C57—C59—C64—C63 | 176 (1) |
N3—C42—C44—C49 | 48 (1) | C58—C57—C59—C60 | 103.3 (12) |
N4—Cu2—O5—C40 | −164.6 (9) | C58—C57—C59—C64 | −76 (1) |
N4—Cu2—O6—C55 | 0.7 (9) | C59—C60—C61—C62 | −1 (2) |
N4—Cu2—N3—C41 | 110.2 (10) | C59—C64—C63—C62 | 2 (2) |
N4—Cu2—N3—C42 | −69 (1) | C60—C59—C64—C63 | −3 (2) |
N4—C56—C50—C51 | 177 (1) | C60—C61—C62—C63 | 1 (2) |
N4—C56—C50—C55 | 0 (1) | C61—C60—C59—C64 | 2 (2) |
N4—C57—C59—C60 | −128 (1) | C61—C62—C63—C64 | −1 (2) |
N4—C57—C59—C64 | 51 (1) | C61—C62—C63—C64 | −1 (2) |
C1—C2—C3—C4 | 0 (1) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Cu(C15H12Cl2NO)2] | [Cu(C17H18NO2)2] |
Mr | 649.86 | 600.20 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21 |
Temperature (K) | 297 | 298 |
a, b, c (Å) | 11.166 (5), 14.852 (7), 8.636 (4) | 9.227 (4), 42.38 (1), 8.035 (3) |
β (°) | 97.89 (4) | 103.67 (3) |
V (Å3) | 1418.6 (11) | 3053.0 (19) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.18 | 0.76 |
Crystal size (mm) | 0.30 × 0.30 × 0.20 | 0.40 × 0.30 × 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 | 0.709, 0.790 | 0.762, 0.860 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3771, 3387, 2958 | 7924, 7100, 3976 |
Rint | 0.020 | 0.161 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.093, 1.05 | 0.066, 0.242, 1.02 |
No. of reflections | 2958 | 3976 |
No. of parameters | 304 | 644 |
No. of restraints | ? | ? |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.63, −0.50 | 0.69, −0.77 |
Absolute structure | Flack (1983), 3387 Friedel pairs | Flack (1983), ? Friedel pairs |
Absolute structure parameter | −0.01 (2) | −0.04 (3) |
Computer programs: WinAFC Diffractometer Control Software (Rigaku, 1999), WinAFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 2001), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), TEXSAN.
Cu1—O1 | 1.890 (3) | Cu1—N2 | 1.984 (4) |
Cu1—O2 | 1.878 (3) | N1—C7 | 1.275 (6) |
Cu1—N1 | 1.995 (4) | N2—C22 | 1.280 (5) |
O1—Cu1—O2 | 150.9 (1) | O2—Cu1—N1 | 94.6 (1) |
O1—Cu1—N1 | 91.9 (1) | O2—Cu1—N2 | 93.6 (1) |
O1—Cu1—N2 | 97.3 (1) | N1—Cu1—N2 | 144.7 (2) |
C7—N1—C8—C10 | −104.1 (4) | C22—N2—C23—C25 | −108.0 (4) |
Cu1—O1 | 1.895 (9) | Cu2—N3 | 1.98 (1) |
Cu1—O2 | 1.90 (1) | Cu2—N4 | 1.97 (1) |
Cu1—N1 | 1.98 (1) | N1—C7 | 1.30 (1) |
Cu1—N2 | 1.980 (10) | N2—C22 | 1.32 (2) |
Cu2—O5 | 1.899 (9) | N3—C41 | 1.30 (1) |
Cu2—O6 | 1.891 (8) | N4—C56 | 1.31 (2) |
O1—Cu1—O2 | 148.9 (3) | O5—Cu2—O6 | 144.0 (3) |
O1—Cu1—N1 | 94.0 (4) | O5—Cu2—N3 | 93.5 (4) |
O1—Cu1—N2 | 95.2 (4) | O5—Cu2—N4 | 90.6 (4) |
O2—Cu1—N1 | 90.5 (4) | O6—Cu2—N3 | 99.2 (4) |
O2—Cu1—N2 | 94.4 (4) | O6—Cu2—N4 | 94.8 (4) |
N1—Cu1—N2 | 153.4 (4) | N3—Cu2—N4 | 150.0 (4) |
C7—N1—C8—C10 | −22 (1) | C41—N3—C42—C44 | 69 (1) |
Recent developments in functional switching materials (Sato et al., 2003) have shown that a good way to discover candidate metal complexes is to examine compounds that show any changes between two or more states, such as structural phase transitions, isomerism, mixed-valences and spin crossover. In this respect, bis(N-alkylsalicylideneimine)copper(II) complexes are potentially good examples, because some of them exhibit thermally induced structural phase transitions (Yamada, 1999), and structural isomers can be isolated (Chia et al., 1977). In addition, chirality (Barron & Buckingham, 2001) provides several structural and electronic modifications, and absolute asymmetric catalytic reactions (Nozaki et al., 1968) are also often susceptible to external physical influence (Avalos et al., 1998). For example, complexes incorporating 1-phenylethylamine ligands are suitable for studying the correlation between molecular structures and electronic properties (Akitsu et al., 2001; Akitsu et al., 2003), and optically active bis(N-alkylsalicylideneimine) complexes of CuII (Li et al., 1987), ZnII (Evans & Luneau, 2002; Sakiyama et al., 1990), PdII (Brunner et al., 2000) and RhV (Kühn et al., 1997) have been investigated in terms of stereochemistry, catalytic applications and second-harmonic generation. In this paper, we report the crystal structures of the title compounds, (I) and (II), having 1-phenylethylamine groups.
Both (I) (Table 1 and Fig. 1) and (II) (Table 2, and Figs. 2 and 3) adopt a compressed tetrahedral trans-[CuN2O2] coordination geometry. Both 1-phenylethylamine groups are folded along the molecular axis through the salicylideneaminate moiety, and the molecule of (I) adopts an umbrella conformation. On the other hand, complex (II), which crystallizes in the monoclinic system (space group P21 with Z = 4) contains two crystallographically independent molecules, which we denote molecules 1 (Cu1) and 2 (Cu2). The overall structure of molecule 1 differs from that of molecule 2. For both molecules of (II), one of the two 1-phenylethylamine groups is folded along the salicylideneaminate moiety, while the other is located towards the outside of the molecule. As the bond angles around the coordination environment show, complex (II) also adopts a tetrahedral trans-[CuN2O2] coordination geometry, which is closer to a tetrahedron than (I). The dihedral angles between the N1/Cu1/O1 and N2/Cu1/O2 planes are 45.0 (1)° for (I), and the dihedral angles between the N1/Cu1/O1 and N2/Cu1/O2 planes and the N3/Cu2/O5 and N4/Cu2/O6 planes are 39.80 (1) and 45.33 (1)°, respectively, for (II).
The degree of distortion of the trans-[CuN2O2] coordination environment in (I) and (II) results from both electronic effects of the 3,5-substituents and steric effects of the 1-phenylethylamine groups. However, these effects are complicated. For example, even 2-butylamine (Cheeseman et al., 1965) or 2-propylamine (Orioli & Sacconi, 1966) moieties can lead to a tetrahedral environment. In contrast, more bulky diphenylethylamine groups result in a planar environment (Fernandez et al., 2000). Most of the geometric parameters for (I) and (II) are comparable to analogous tetrahedral CuIIcomplexes (Yamada, 1999). Nevertheless only R-1-phenylethylamine was used for our preparations. The absolute configurations of the crystals of (I) and (II) examined were found to be Δ(R,R) and Λ(R,R), respectively. Both the related Cl-substituted ZnII complex (Evans & Luneau, 2001) and the CuII complex without 3-ethoxy substituents (Li et al., 1987) were reported to have Λ(R,R) configurations. Intra- and intermolecular hydrogen bonds are not detectable within van der Waals radii (Bondi, 1964) for either (I) or (II), and hence the crystal packing is dominated by weak van der Waals forces. Since no significant intermolecular interactions are found in either crystal, the factors determining the absolute configuration of the coordination environment are obscure at present.
In addition, DSC (differential scanning calorimetry) curves obtained by heating the brown precipitates of (I) and (II) showed endothermic peaks at 419 and 386 K, respectively. By analogy with similar CuII and NiII complexes (Yamada, 1999; Akitsu & Einaga, 2004; Arai et al., 1972), these features are attributed to thermally induced structural phase transitions. The structural change seems to be irreversible for both cases, though there are no intermolecular hydrogen bonds in the crystals. Moreover, whether conversion occurs between Λ(R,R) or Δ(R,R) forms during the phase transition is still unclear.