Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011540/cv6040sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011540/cv6040Isup2.hkl |
CCDC reference: 170869
To a refluxing solution of the ligand (0.639 g, 1.78 mmol) in 1:1 water/ethanol (10 ml) mixture was added dropwise an aqueous solution of copper perchlorate hexahydrate (0.661 g, 1.78 mmol, 5 ml). The mixture, now a deep blue colour, was heated for a further 5 min then acetonitrile (\sim1 ml) was added and the solution allowed to cool. The dark blue crystals that formed, after further cooling (in refrigerator) were collected by filtration, washed with a small amount of water then ethanol prior to being air dried. Yield = 0.50 g (45%). λmaxCH3CN, 648 nm, ε = 311.51 M-1 cm-1, µ = 2.13 B·M. at 18°C. Microanalysis for C20H34Cl2N6CuO8, calculated: C 38.68, H 5.52, N 13.53; found: C 38.55, H 5.34, N 13.42.
Suitable crystals of the complex were grown by slow evaporation of a solution of the complex in \sim5% acetonitrile/water mixture.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control; data reduction: TEXSAN (Molecular Structure Corporation, 1992-1997); program(s) used to solve structure: PATTYy in DIRDIF92 (Beurskens et al., 1992); program(s) used to refine structure: Xtal3.4 CRYLSQ (Hall et al., 1995); molecular graphics: Xtal3.4 PIG ORTEP; software used to prepare material for publication: Xtal3.4 BONDLA CIFIO.
Fig. 1. The complex cation of the title compound with displacement ellipsoids at the 50% probability level. |
[Cu(C20H34N6)](ClO4)2 | Dx = 1.607 Mg m−3 |
Mr = 620.98 | Cu Kα radiation, λ = 1.5418 Å |
Orthorhombic, Pbca | Cell parameters from 25 reflections |
a = 12.978 (2) Å | θ = 48.6–49.8° |
b = 16.518 (2) Å | µ = 3.64 mm−1 |
c = 23.950 (4) Å | T = 213 K |
V = 5134 (1) Å3 | Irregular, blue |
Z = 8 | 0.40 × 0.28 × 0.20 mm |
F(000) = 2584.00 |
Rigaku AFC-6R diffractometer | 3263 reflections with F2 > 1.5σ(F2) |
Radiation source: Rigaku rotating anode | Rint = 0 |
Graphite monochromator | θmax = 60.1°, θmin = 1.9° |
ω–2θ scans | h = 0→14 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→18 |
Tmin = 0.382, Tmax = 0.483 | l = 0→26 |
4291 measured reflections | 3 standard reflections every 150 reflections |
3823 independent reflections | intensity decay: 0.5% |
Refinement on F2 | 334 parameters |
Least-squares matrix: full | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.054 | w = 1/[σ2(Fo2) + (0.1Fo2)2] |
wR(F2) = 0.165 | (Δ/σ)max = 0.0003 |
S = 1.38 | Δρmax = 1.20 e Å−3 |
3263 reflections | Δρmin = −0.55 e Å−3 |
[Cu(C20H34N6)](ClO4)2 | V = 5134 (1) Å3 |
Mr = 620.98 | Z = 8 |
Orthorhombic, Pbca | Cu Kα radiation |
a = 12.978 (2) Å | µ = 3.64 mm−1 |
b = 16.518 (2) Å | T = 213 K |
c = 23.950 (4) Å | 0.40 × 0.28 × 0.20 mm |
Rigaku AFC-6R diffractometer | 3263 reflections with F2 > 1.5σ(F2) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0 |
Tmin = 0.382, Tmax = 0.483 | θmax = 60.1° |
4291 measured reflections | 3 standard reflections every 150 reflections |
3823 independent reflections | intensity decay: 0.5% |
R[F2 > 2σ(F2)] = 0.054 | 334 parameters |
wR(F2) = 0.165 | H-atom parameters not refined |
S = 1.38 | Δρmax = 1.20 e Å−3 |
3263 reflections | Δρmin = −0.55 e Å−3 |
Experimental. The scan width was (1.20 + 0.30tanθ)° with an ω scan speed of 32° per minute (up to 5 scans to achieve I/σ(I) > 10). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1. Data can only be collected to 2θ 120° on a AFC6R diffractometer when the evacuated beam tunnel in used. Mass attenuation coefficients for absorption from International Tables for X-ray Crystallography, Vol IV (1974) Table 2.1 C. |
x | y | z | Uiso*/Ueq | ||
Cu | 0.16186 (4) | −0.00140 (3) | 0.12678 (2) | 0.0211 (4) | |
Cl1 | −0.35065 (8) | 0.04176 (8) | 0.11549 (5) | 0.0423 (7) | |
Cl2 | −0.41164 (8) | −0.28659 (6) | −0.27905 (5) | 0.0400 (6) | |
O11 | −0.4288 (3) | 0.0894 (3) | 0.14298 (19) | 0.075 (3) | |
O12 | −0.2791 (4) | 0.0166 (3) | 0.1562 (2) | 0.093 (4) | |
O13 | −0.2996 (3) | 0.0904 (3) | 0.07510 (17) | 0.075 (3) | |
O14 | −0.3983 (3) | −0.0255 (3) | 0.0899 (2) | 0.084 (3) | |
O21 | −0.3395 (4) | −0.2251 (3) | −0.2759 (2) | 0.089 (3) | |
O22 | −0.3669 (3) | −0.3631 (2) | −0.26532 (18) | 0.069 (3) | |
O23 | −0.4516 (5) | −0.2871 (3) | −0.3334 (2) | 0.111 (4) | |
O24 | −0.4930 (6) | −0.2724 (4) | −0.2432 (3) | 0.157 (6) | |
N1 | 0.2295 (2) | 0.07895 (18) | 0.17890 (13) | 0.0236 (16) | |
N2 | 0.2440 (3) | 0.06738 (18) | 0.06230 (13) | 0.0264 (17) | |
N3 | 0.3004 (3) | −0.06548 (19) | 0.13277 (14) | 0.0257 (17) | |
N4 | 0.0271 (2) | 0.0265 (2) | 0.16738 (13) | 0.0244 (17) | |
N5 | 0.0712 (2) | −0.0849 (2) | 0.09150 (13) | 0.0251 (17) | |
N6 | −0.0604 (3) | −0.1683 (2) | 0.10945 (15) | 0.034 (2) | |
C1 | 0.2911 (3) | 0.1401 (2) | 0.14838 (17) | 0.030 (2) | |
C2 | 0.2521 (3) | 0.1478 (2) | 0.08901 (17) | 0.032 (2) | |
C3 | 0.3473 (3) | 0.0299 (3) | 0.05528 (18) | 0.033 (2) | |
C4 | 0.3502 (3) | −0.0574 (2) | 0.07673 (18) | 0.030 (2) | |
C5 | 0.3632 (3) | −0.0265 (3) | 0.17784 (18) | 0.031 (2) | |
C6 | 0.2951 (3) | 0.0253 (3) | 0.21475 (16) | 0.028 (2) | |
C7 | 0.1896 (4) | 0.0746 (3) | 0.00866 (18) | 0.039 (2) | |
C8 | 0.2860 (4) | −0.1529 (2) | 0.1457 (2) | 0.038 (2) | |
C9 | 0.1466 (3) | 0.1196 (3) | 0.21298 (18) | 0.030 (2) | |
C10 | 0.0581 (3) | 0.0623 (3) | 0.22223 (16) | 0.030 (2) | |
C11 | −0.0309 (3) | −0.0496 (3) | 0.17436 (17) | 0.031 (2) | |
C12 | −0.0075 (3) | −0.1007 (2) | 0.12460 (15) | 0.026 (2) | |
C13 | −0.0110 (3) | −0.1981 (2) | 0.06251 (17) | 0.031 (2) | |
C14 | −0.0341 (4) | −0.2651 (3) | 0.0287 (2) | 0.044 (3) | |
C15 | 0.0285 (4) | −0.2757 (3) | −0.0175 (2) | 0.046 (3) | |
C16 | 0.1090 (4) | −0.2229 (3) | −0.0310 (2) | 0.040 (3) | |
C17 | 0.1307 (3) | −0.1568 (3) | 0.00347 (17) | 0.031 (2) | |
C18 | 0.0696 (3) | −0.1458 (2) | 0.05065 (16) | 0.026 (2) | |
C19 | −0.1509 (4) | −0.2018 (3) | 0.1377 (2) | 0.048 (3) | |
C20 | −0.0322 (4) | 0.0844 (3) | 0.1331 (2) | 0.038 (3) | |
H1a | 0.28600 | 0.19090 | 0.16680 | 0.03700* | |
H1b | 0.36160 | 0.12340 | 0.14800 | 0.03700* | |
H2a | 0.18650 | 0.17290 | 0.08940 | 0.03900* | |
H2b | 0.29900 | 0.18030 | 0.06820 | 0.03900* | |
H3a | 0.39650 | 0.06090 | 0.07510 | 0.04100* | |
H3b | 0.36420 | 0.02960 | 0.01660 | 0.04100* | |
H4a | 0.42010 | −0.07380 | 0.07970 | 0.03800* | |
H4b | 0.31520 | −0.09110 | 0.05100 | 0.03800* | |
H5a | 0.41500 | 0.00660 | 0.16110 | 0.03700* | |
H5b | 0.39570 | −0.06730 | 0.19970 | 0.03700* | |
H6a | 0.33610 | 0.05750 | 0.23870 | 0.03500* | |
H6b | 0.25160 | −0.00890 | 0.23670 | 0.03500* | |
H7a | 0.22630 | 0.10980 | −0.01550 | 0.04800* | |
H7b | 0.18390 | 0.02260 | −0.00840 | 0.04800* | |
H7c | 0.12200 | 0.09570 | 0.01460 | 0.04800* | |
H8a | 0.35050 | −0.17890 | 0.14710 | 0.04600* | |
H8b | 0.24440 | −0.17690 | 0.11730 | 0.04600* | |
H8c | 0.25180 | −0.15800 | 0.18070 | 0.04600* | |
H9a | 0.17410 | 0.13550 | 0.24800 | 0.03800* | |
H9b | 0.12220 | 0.16600 | 0.19360 | 0.03800* | |
H10a | 0.07900 | 0.02020 | 0.24710 | 0.03700* | |
H10b | 0.00150 | 0.09060 | 0.23810 | 0.03700* | |
H11a | −0.01100 | −0.07620 | 0.20760 | 0.03700* | |
H11b | −0.10330 | −0.03820 | 0.17590 | 0.03700* | |
H14 | −0.08820 | −0.30150 | 0.03750 | 0.05200* | |
H15 | 0.01540 | −0.32020 | −0.04190 | 0.05500* | |
H16 | 0.14890 | −0.23160 | −0.06330 | 0.04800* | |
H17 | 0.18570 | −0.12060 | −0.00500 | 0.03800* | |
H19a | −0.13300 | −0.21490 | 0.17530 | 0.06000* | |
H19b | −0.20440 | −0.16290 | 0.13760 | 0.06000* | |
H19c | −0.17250 | −0.24930 | 0.11890 | 0.06000* | |
H20a | 0.00650 | 0.13270 | 0.12840 | 0.04600* | |
H20b | −0.04620 | 0.06120 | 0.09750 | 0.04600* | |
H20c | −0.09560 | 0.09660 | 0.15120 | 0.04600* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0232 (4) | 0.0214 (4) | 0.0187 (4) | −0.0018 (2) | 0.0002 (2) | −0.0030 (2) |
Cl1 | 0.0364 (6) | 0.0650 (8) | 0.0257 (6) | −0.0084 (5) | 0.0014 (4) | 0.0081 (5) |
Cl2 | 0.0421 (6) | 0.0358 (6) | 0.0420 (7) | 0.0039 (4) | 0.0007 (5) | 0.0065 (5) |
O11 | 0.060 (2) | 0.090 (3) | 0.074 (3) | −0.011 (2) | 0.022 (2) | −0.015 (3) |
O12 | 0.068 (3) | 0.133 (4) | 0.078 (3) | 0.001 (3) | −0.028 (3) | 0.042 (3) |
O13 | 0.083 (3) | 0.073 (3) | 0.069 (3) | 0.017 (2) | 0.044 (2) | 0.037 (2) |
O14 | 0.066 (3) | 0.108 (4) | 0.078 (3) | −0.026 (3) | 0.007 (2) | −0.038 (3) |
O21 | 0.091 (3) | 0.061 (3) | 0.116 (4) | −0.026 (2) | −0.033 (3) | 0.001 (3) |
O22 | 0.084 (3) | 0.050 (2) | 0.071 (3) | 0.025 (2) | 0.002 (2) | 0.013 (2) |
O23 | 0.164 (5) | 0.076 (3) | 0.093 (4) | −0.029 (3) | −0.076 (4) | 0.023 (3) |
O24 | 0.156 (5) | 0.120 (4) | 0.195 (7) | 0.077 (4) | 0.127 (5) | 0.075 (5) |
N1 | 0.0263 (17) | 0.0227 (15) | 0.0217 (17) | 0.0001 (13) | 0.0008 (14) | −0.0035 (13) |
N2 | 0.0370 (18) | 0.0215 (16) | 0.0206 (16) | −0.0005 (14) | −0.0009 (14) | 0.0015 (13) |
N3 | 0.0275 (17) | 0.0229 (17) | 0.0269 (18) | 0.0029 (14) | −0.0004 (14) | 0.0003 (13) |
N4 | 0.0240 (17) | 0.0268 (16) | 0.0222 (17) | 0.0008 (14) | 0.0026 (13) | −0.0030 (14) |
N5 | 0.0276 (17) | 0.0248 (16) | 0.0230 (17) | −0.0049 (13) | −0.0012 (14) | −0.0039 (14) |
N6 | 0.036 (2) | 0.035 (2) | 0.0319 (19) | −0.0102 (16) | −0.0046 (16) | −0.0009 (16) |
C1 | 0.040 (2) | 0.0203 (19) | 0.029 (2) | −0.0029 (17) | 0.0011 (19) | −0.0024 (17) |
C2 | 0.041 (2) | 0.022 (2) | 0.032 (2) | −0.0028 (17) | 0.0041 (19) | −0.0001 (17) |
C3 | 0.031 (2) | 0.042 (2) | 0.028 (2) | −0.0096 (19) | 0.0078 (17) | −0.001 (2) |
C4 | 0.031 (2) | 0.029 (2) | 0.031 (2) | 0.0028 (16) | −0.0008 (17) | −0.0104 (18) |
C5 | 0.028 (2) | 0.033 (2) | 0.032 (2) | 0.0033 (18) | −0.0108 (18) | −0.0035 (19) |
C6 | 0.028 (2) | 0.034 (2) | 0.023 (2) | −0.0023 (18) | −0.0048 (16) | −0.0012 (18) |
C7 | 0.060 (3) | 0.035 (2) | 0.024 (2) | −0.000 (2) | −0.006 (2) | 0.0064 (18) |
C8 | 0.045 (3) | 0.023 (2) | 0.046 (3) | 0.0011 (18) | −0.008 (2) | 0.004 (2) |
C9 | 0.032 (2) | 0.032 (2) | 0.027 (2) | −0.0000 (17) | 0.0011 (17) | −0.0103 (18) |
C10 | 0.030 (2) | 0.038 (2) | 0.023 (2) | −0.0020 (17) | 0.0041 (17) | −0.0085 (17) |
C11 | 0.026 (2) | 0.039 (2) | 0.026 (2) | −0.0088 (18) | 0.0083 (17) | −0.0008 (18) |
C12 | 0.025 (2) | 0.030 (2) | 0.025 (2) | −0.0043 (17) | −0.0043 (16) | 0.0028 (17) |
C13 | 0.037 (2) | 0.030 (2) | 0.025 (2) | −0.0051 (17) | −0.0034 (18) | −0.0034 (18) |
C14 | 0.049 (3) | 0.039 (3) | 0.044 (3) | −0.011 (2) | −0.006 (2) | −0.005 (2) |
C15 | 0.066 (3) | 0.032 (2) | 0.041 (3) | −0.008 (2) | −0.016 (2) | −0.015 (2) |
C16 | 0.049 (3) | 0.040 (3) | 0.030 (2) | 0.003 (2) | −0.009 (2) | −0.009 (2) |
C17 | 0.038 (2) | 0.031 (2) | 0.025 (2) | −0.0015 (18) | −0.0046 (18) | −0.0057 (18) |
C18 | 0.035 (2) | 0.024 (2) | 0.019 (2) | −0.0006 (17) | −0.0072 (17) | −0.0023 (16) |
C19 | 0.041 (3) | 0.056 (3) | 0.047 (3) | −0.023 (2) | 0.007 (2) | −0.004 (3) |
C20 | 0.039 (3) | 0.035 (2) | 0.039 (3) | 0.008 (2) | 0.002 (2) | −0.001 (2) |
Cu—N1 | 2.022 (3) | C4—H4a | 0.950 |
Cu—N2 | 2.194 (3) | C4—H4b | 0.946 |
Cu—N3 | 2.091 (3) | C5—C6 | 1.515 (6) |
Cu—N4 | 2.053 (3) | C5—H5a | 0.955 |
Cu—N5 | 2.000 (3) | C5—H5b | 0.952 |
Cl1—O11 | 1.443 (5) | C6—H6a | 0.946 |
Cl1—O12 | 1.409 (5) | C6—H6b | 0.956 |
Cl1—O13 | 1.421 (4) | C7—H7a | 0.948 |
Cl1—O14 | 1.411 (5) | C7—H7b | 0.954 |
Cl2—O21 | 1.383 (5) | C7—H7c | 0.955 |
Cl2—O22 | 1.428 (4) | C8—H8a | 0.942 |
Cl2—O23 | 1.401 (6) | C8—H8b | 0.955 |
Cl2—O24 | 1.381 (8) | C8—H8c | 0.952 |
N1—C1 | 1.481 (5) | C9—C10 | 1.504 (6) |
N1—C6 | 1.499 (5) | C9—H9a | 0.949 |
N1—C9 | 1.508 (5) | C9—H9b | 0.950 |
N2—C2 | 1.479 (5) | C10—H10a | 0.955 |
N2—C3 | 1.486 (5) | C10—H10b | 0.950 |
N2—C7 | 1.470 (6) | C11—C12 | 1.492 (6) |
N3—C4 | 1.496 (5) | C11—H11a | 0.946 |
N3—C5 | 1.498 (5) | C11—H11b | 0.958 |
N3—C8 | 1.488 (5) | C13—C14 | 1.404 (6) |
N4—C10 | 1.496 (5) | C13—C18 | 1.386 (6) |
N4—C11 | 1.475 (5) | C14—C15 | 1.383 (7) |
N4—C20 | 1.477 (6) | C14—H14 | 0.948 |
N5—C12 | 1.319 (5) | C15—C16 | 1.399 (7) |
N5—C18 | 1.403 (5) | C15—H15 | 0.955 |
N6—C12 | 1.359 (5) | C16—C17 | 1.398 (6) |
N6—C13 | 1.384 (5) | C16—H16 | 0.942 |
N6—C19 | 1.464 (6) | C17—C18 | 1.392 (6) |
C1—C2 | 1.515 (6) | C17—H17 | 0.952 |
C1—H1a | 0.951 | C19—H19a | 0.955 |
C1—H1b | 0.955 | C19—H19b | 0.946 |
C2—H2a | 0.946 | C19—H19c | 0.947 |
C2—H2b | 0.952 | C20—H20a | 0.949 |
C3—C4 | 1.532 (6) | C20—H20b | 0.952 |
C3—H3a | 0.946 | C20—H20c | 0.951 |
C3—H3b | 0.952 | ||
N1—Cu—N2 | 83.33 (12) | N3—C5—C6 | 110.3 (3) |
N1—Cu—N3 | 85.23 (13) | N3—C5—H5a | 109.1 |
N1—Cu—N4 | 85.97 (13) | N3—C5—H5b | 109.5 |
N1—Cu—N5 | 165.60 (13) | C6—C5—H5a | 109.3 |
N2—Cu—N3 | 83.84 (12) | C6—C5—H5b | 109.7 |
N2—Cu—N4 | 129.11 (12) | H5a—C5—H5b | 108.9 |
N2—Cu—N5 | 110.22 (12) | N1—C6—C5 | 109.3 (3) |
N3—Cu—N4 | 144.42 (13) | N1—C6—H6a | 109.6 |
N3—Cu—N5 | 100.68 (13) | N1—C6—H6b | 109.2 |
N4—Cu—N5 | 81.62 (13) | C5—C6—H6a | 110.1 |
O11—Cl1—O12 | 107.9 (3) | C5—C6—H6b | 109.3 |
O11—Cl1—O13 | 109.2 (3) | H6a—C6—H6b | 109.3 |
O11—Cl1—O14 | 108.6 (3) | N2—C7—H7a | 110.0 |
O12—Cl1—O13 | 109.3 (3) | N2—C7—H7b | 109.8 |
O12—Cl1—O14 | 110.9 (3) | N2—C7—H7c | 109.9 |
O13—Cl1—O14 | 110.7 (3) | H7a—C7—H7b | 109.3 |
O21—Cl2—O22 | 111.2 (3) | H7a—C7—H7c | 109.2 |
O21—Cl2—O23 | 107.8 (3) | H7b—C7—H7c | 108.7 |
O21—Cl2—O24 | 111.0 (3) | N3—C8—H8a | 109.8 |
O22—Cl2—O23 | 111.1 (3) | N3—C8—H8b | 109.0 |
O22—Cl2—O24 | 108.5 (3) | N3—C8—H8c | 109.2 |
O23—Cl2—O24 | 107.2 (4) | H8a—C8—H8b | 109.7 |
Cu—N1—C1 | 112.2 (2) | H8a—C8—H8c | 110.0 |
Cu—N1—C6 | 102.3 (2) | H8b—C8—H8c | 109.1 |
Cu—N1—C9 | 108.5 (2) | N1—C9—C10 | 110.1 (3) |
C1—N1—C6 | 112.2 (3) | N1—C9—H9a | 109.5 |
C1—N1—C9 | 110.4 (3) | N1—C9—H9b | 109.4 |
C6—N1—C9 | 111.0 (3) | C10—C9—H9a | 109.4 |
Cu—N2—C2 | 101.3 (2) | C10—C9—H9b | 109.0 |
Cu—N2—C3 | 107.6 (2) | H9a—C9—H9b | 109.5 |
Cu—N2—C7 | 115.1 (3) | N4—C10—C9 | 108.9 (3) |
C2—N2—C3 | 111.0 (3) | N4—C10—H10a | 109.6 |
C2—N2—C7 | 109.8 (3) | N4—C10—H10b | 109.8 |
C3—N2—C7 | 111.6 (3) | C9—C10—H10a | 109.5 |
Cu—N3—C4 | 105.4 (2) | C9—C10—H10b | 109.9 |
Cu—N3—C5 | 107.4 (2) | H10a—C10—H10b | 109.2 |
Cu—N3—C8 | 113.4 (3) | N4—C11—C12 | 106.7 (3) |
C4—N3—C5 | 111.9 (3) | N4—C11—H11a | 110.6 |
C4—N3—C8 | 109.1 (3) | N4—C11—H11b | 109.8 |
C5—N3—C8 | 109.6 (3) | C12—C11—H11a | 110.7 |
Cu—N4—C10 | 106.0 (2) | C12—C11—H11b | 110.0 |
Cu—N4—C11 | 107.3 (2) | H11a—C11—H11b | 109.1 |
Cu—N4—C20 | 109.0 (3) | N5—C12—N6 | 113.2 (3) |
C10—N4—C11 | 112.0 (3) | N5—C12—C11 | 121.7 (4) |
C10—N4—C20 | 111.9 (3) | N6—C12—C11 | 125.1 (4) |
C11—N4—C20 | 110.4 (3) | N6—C13—C14 | 130.5 (4) |
Cu—N5—C12 | 109.8 (3) | N6—C13—C18 | 107.1 (3) |
Cu—N5—C18 | 142.9 (3) | C14—C13—C18 | 122.3 (4) |
C12—N5—C18 | 105.4 (3) | C13—C14—C15 | 115.8 (4) |
C12—N6—C13 | 105.9 (3) | C13—C14—H14 | 122.0 |
C12—N6—C19 | 126.3 (4) | C15—C14—H14 | 122.2 |
C13—N6—C19 | 127.7 (4) | C14—C15—C16 | 123.0 (4) |
N1—C1—C2 | 109.9 (3) | C14—C15—H15 | 118.9 |
N1—C1—H1a | 109.6 | C16—C15—H15 | 118.1 |
N1—C1—H1b | 109.0 | C15—C16—C17 | 120.1 (4) |
C2—C1—H1a | 109.7 | C15—C16—H16 | 120.4 |
C2—C1—H1b | 109.6 | C17—C16—H16 | 119.5 |
H1a—C1—H1b | 109.0 | C16—C17—C18 | 117.8 (4) |
N2—C2—C1 | 110.7 (3) | C16—C17—H17 | 121.0 |
N2—C2—H2a | 109.5 | C18—C17—H17 | 121.2 |
N2—C2—H2b | 109.0 | N5—C18—C13 | 108.3 (3) |
C1—C2—H2a | 109.2 | N5—C18—C17 | 130.6 (4) |
C1—C2—H2b | 109.0 | C13—C18—C17 | 121.0 (4) |
H2a—C2—H2b | 109.5 | N6—C19—H19a | 109.0 |
N2—C3—C4 | 112.1 (3) | N6—C19—H19b | 109.3 |
N2—C3—H3a | 109.1 | N6—C19—H19c | 109.3 |
N2—C3—H3b | 108.7 | H19a—C19—H19b | 109.6 |
C4—C3—H3a | 108.9 | H19a—C19—H19c | 109.4 |
C4—C3—H3b | 108.4 | H19b—C19—H19c | 110.1 |
H3a—C3—H3b | 109.6 | N4—C20—H20a | 109.5 |
N3—C4—C3 | 112.0 (3) | N4—C20—H20b | 109.7 |
N3—C4—H4a | 108.7 | N4—C20—H20c | 109.6 |
N3—C4—H4b | 109.0 | H20a—C20—H20b | 109.4 |
C3—C4—H4a | 108.5 | H20a—C20—H20c | 109.5 |
C3—C4—H4b | 108.9 | H20b—C20—H20c | 109.2 |
H4a—C4—H4b | 109.9 |
Experimental details
Crystal data | |
Chemical formula | [Cu(C20H34N6)](ClO4)2 |
Mr | 620.98 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 213 |
a, b, c (Å) | 12.978 (2), 16.518 (2), 23.950 (4) |
V (Å3) | 5134 (1) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 3.64 |
Crystal size (mm) | 0.40 × 0.28 × 0.20 |
Data collection | |
Diffractometer | Rigaku AFC-6R diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.382, 0.483 |
No. of measured, independent and observed [F2 > 1.5σ(F2)] reflections | 4291, 3823, 3263 |
Rint | 0 |
θmax (°) | 60.1 |
(sin θ/λ)max (Å−1) | 0.562 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.165, 1.38 |
No. of reflections | 3263 |
No. of parameters | 334 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 1.20, −0.55 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992), MSC/AFC Diffractometer Control, TEXSAN (Molecular Structure Corporation, 1992-1997), PATTYy in DIRDIF92 (Beurskens et al., 1992), Xtal3.4 CRYLSQ (Hall et al., 1995), Xtal3.4 PIG ORTEP, Xtal3.4 BONDLA CIFIO.
Cu—N1 | 2.022 (3) | Cu—N4 | 2.053 (3) |
Cu—N2 | 2.194 (3) | Cu—N5 | 2.000 (3) |
Cu—N3 | 2.091 (3) | ||
N1—Cu—N2 | 83.33 (12) | N2—Cu—N4 | 129.11 (12) |
N1—Cu—N3 | 85.23 (13) | N2—Cu—N5 | 110.22 (12) |
N1—Cu—N4 | 85.97 (13) | N3—Cu—N4 | 144.42 (13) |
N1—Cu—N5 | 165.60 (13) | N3—Cu—N5 | 100.68 (13) |
N2—Cu—N3 | 83.84 (12) | N4—Cu—N5 | 81.62 (13) |
Galactose oxidase is a non-blue copper-dependent oxidase isolated from Dactylium dendroides (Ogel et al., 1994) and structurally characterized (Ito et al., 1992). This enzyme achieves the stereo selective oxidation of primary alcohols, such as D-galactose. There has been some interest in the potential utility of this enzyme as a biosensor (Hasebe & Uchiyama, 2000). Extensive spectroscopic investigations have probed the mechanism of catalysis indicating a pH dependence of the redox reaction providing evidence for a phenolic amino acid residue initiating the catalytic cycle by abstraction of an H atom from a neighbouring group (Reynolds et al., 1997).
Recently, this enzyme has attracted our interest and we have prepared structural model complexes (Daly & Martin, 2001) containing the square-based pyramidal geometry about the CuII ion, as observed in the native enzyme. Unfortunately, we were unable to structurally characterize the ligand containing the phenol moiety in the solid state; however, the title complex is the N-methyl derivative coordinated to a CuII ion.
If the coordination of CuII is described as distorted square-pyramidal the N1, N3, N4 and N5 atoms would constitute the base plane and N2, which has the longest bond to CuII (Table 1), is the apical atom. Deviations from the least-squares plane through N1, N3, N4 and N5 are 0.191 (4), -0.262 (5), -0.226 (4) and 0.200 (4) Å, respectively, so that there is a significant tetrahedral distortion from planarity. Cu and N2 are 0.381 (1) and 2.350 (4) Å from this plane. This pentadentate ligand coordinates in a different conformation in the octahedral Ni complex (Daly et al., 2001) which has acetonitrile as the sixth ligand. There, N2, N3, N4 and N5 are in a square plane, with N1 at the apex.
An alternative trigonal-bipyramidal description arises from considering N2, N3 and N4 as the trianglar entity. In this description, N1, N5 and Cu are 1.842 (3), -2.101 (4) and -0.180 (1) Å, respectively, from this equatorial plane.