Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802016288/ya6131sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802016288/ya6131Isup2.hkl |
CCDC reference: 198305
2-Mehtylimidazole (2M-ImH) (Merck), 2,2'-dimethoxypropane (Aldrich), cupric oxide (Merck), trifluoromethylsulfonic acid (Aldrich) and organic solvents of reagent grade were used as received. Cu(CF3SO3)2·6H2O was prepared from CuO and CF3SO3H. Tetrakis(2-methylimidazolo)bis(trifluoromethylsulfonato)copper(II), Cu(2—CH3—ImH)4(CF3SO3)2, was prepared by the following procedure: Cu(CF3SO3)2·6H2O (1 mmole) and 2-methylimidazole (4 mmole) were dissolved in acetonitrile containing 5% of 2,2-dimethoxypropane. After stirring the mixture at room temperature for two hours, diethyl ether was added dropwise until precipitate began to appear. The solution was stored in a refrigerator for two days yielding dark blue crystal, yield, 83%.
The H atoms were generated geometrically with C—H bonds of 0.96 Å and N—H bonds of 0.90 Å. They were included in the final refinement in the riding motion approximation with fixed isotropic temperature factors of 0.12 Å2 for the methyl H atoms and 0.08 Å2 for all other hydrogen atoms.
Data collection: CAD-4-PC Software (Enraf-Nonius, 1992); cell refinement: CAD-4-PC; data reduction: XCAD4 (Harms, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 1998); software used to prepare material for publication: SHELXL97.
[Cu(CH3C3H3N2)4(CF3SO3)2] | F(000) = 1404 |
Mr = 690.11 | Dx = 1.572 Mg m−3 |
Monoclinic, P21/c | Melting point: 465-471°K (decomposed) K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 18.763 (4) Å | Cell parameters from 25 reflections |
b = 10.674 (2) Å | θ = 10.0–13.5° |
c = 16.064 (3) Å | µ = 0.98 mm−1 |
β = 115.02 (3)° | T = 293 K |
V = 2915.3 (12) Å3 | Prism, dark blue |
Z = 4 | 0.32 × 0.22 × 0.16 mm |
Enraf-Nonius CAD-4 diffractometer | 2600 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.035 |
Graphite monochromator | θmax = 25.0°, θmin = 2.2° |
ω scans | h = −22→20 |
Absorption correction: ψ scan (North et al, 1968) | k = −12→0 |
Tmin = 0.742, Tmax = 0.855 | l = 0→19 |
5291 measured reflections | 3 standard reflections every 120 min |
5092 independent reflections | intensity decay: 15% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.001P)2 + 10.P] where P = (Fo2 + 2Fc2)/3 |
5092 reflections | (Δ/σ)max = 0.001 |
370 parameters | Δρmax = 0.65 e Å−3 |
0 restraints | Δρmin = −0.49 e Å−3 |
[Cu(CH3C3H3N2)4(CF3SO3)2] | V = 2915.3 (12) Å3 |
Mr = 690.11 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 18.763 (4) Å | µ = 0.98 mm−1 |
b = 10.674 (2) Å | T = 293 K |
c = 16.064 (3) Å | 0.32 × 0.22 × 0.16 mm |
β = 115.02 (3)° |
Enraf-Nonius CAD-4 diffractometer | 2600 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al, 1968) | Rint = 0.035 |
Tmin = 0.742, Tmax = 0.855 | 3 standard reflections every 120 min |
5291 measured reflections | intensity decay: 15% |
5092 independent reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.65 e Å−3 |
5092 reflections | Δρmin = −0.49 e Å−3 |
370 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.74186 (4) | 0.01102 (6) | 0.49439 (5) | 0.0488 (2) | |
S1 | 0.58212 (9) | −0.04278 (14) | 0.24141 (10) | 0.0498 (4) | |
S2 | 0.92442 (10) | −0.03064 (17) | 0.77262 (13) | 0.0654 (5) | |
O1 | 0.5818 (3) | 0.0295 (5) | 0.1674 (3) | 0.0858 (15) | |
O2 | 0.6205 (2) | 0.0126 (5) | 0.3308 (3) | 0.0748 (13) | |
O3 | 0.6012 (3) | −0.1719 (4) | 0.2370 (3) | 0.0731 (14) | |
O4 | 0.9068 (3) | −0.1597 (4) | 0.7713 (3) | 0.0804 (15) | |
O5 | 0.9318 (4) | 0.0342 (6) | 0.8531 (4) | 0.129 (2) | |
O6 | 0.8784 (3) | 0.0292 (5) | 0.6862 (4) | 0.1055 (19) | |
F1 | 0.4361 (3) | −0.0957 (6) | 0.1374 (4) | 0.134 (2) | |
F2 | 0.4684 (3) | −0.1156 (6) | 0.2813 (3) | 0.124 (2) | |
F3 | 0.4520 (3) | 0.0641 (6) | 0.2218 (4) | 0.140 (2) | |
F4 | 1.0275 (3) | −0.0904 (6) | 0.7119 (3) | 0.1232 (19) | |
F5 | 1.0480 (3) | 0.0840 (6) | 0.7778 (4) | 0.142 (2) | |
F6 | 1.0717 (3) | −0.0817 (6) | 0.8555 (4) | 0.146 (2) | |
N1 | 0.7836 (4) | 0.1576 (5) | 0.4510 (4) | 0.0662 (16) | |
N2 | 0.8510 (4) | 0.2945 (6) | 0.4151 (4) | 0.091 (2) | |
H2A | 0.8931 | 0.3303 | 0.4117 | 0.080* | |
N3 | 0.8098 (3) | −0.1128 (5) | 0.4690 (3) | 0.0500 (12) | |
N4 | 0.8664 (3) | −0.2362 (5) | 0.4070 (4) | 0.0647 (15) | |
H4D | 0.8812 | −0.2689 | 0.3651 | 0.080* | |
N5 | 0.6917 (3) | −0.1350 (4) | 0.5274 (3) | 0.0471 (12) | |
N6 | 0.6431 (3) | −0.2677 (5) | 0.5922 (4) | 0.0637 (15) | |
H6A | 0.6283 | −0.3018 | 0.6337 | 0.080* | |
N7 | 0.6723 (3) | 0.1269 (5) | 0.5275 (3) | 0.0618 (15) | |
N8 | 0.6235 (4) | 0.2653 (6) | 0.5862 (4) | 0.0775 (18) | |
H8D | 0.6213 | 0.3322 | 0.6192 | 0.080* | |
C1 | 0.8500 (4) | 0.1947 (7) | 0.4613 (5) | 0.069 (2) | |
C2 | 0.7681 (6) | 0.3289 (8) | 0.3681 (6) | 0.112 (3) | |
H2B | 0.7500 | 0.4027 | 0.3309 | 0.080* | |
C3 | 0.7280 (5) | 0.2489 (7) | 0.3864 (5) | 0.080 (2) | |
H3A | 0.6716 | 0.2481 | 0.3623 | 0.080* | |
C4 | 0.9252 (4) | 0.1348 (8) | 0.5179 (5) | 0.089 (2) | |
H4A | 0.9166 | 0.0644 | 0.5496 | 0.120* | |
H4B | 0.9491 | 0.1069 | 0.4788 | 0.120* | |
H4C | 0.9593 | 0.1939 | 0.5618 | 0.120* | |
C5 | 0.8232 (3) | −0.1334 (6) | 0.3953 (4) | 0.0529 (16) | |
C6 | 0.8830 (4) | −0.2852 (7) | 0.4920 (5) | 0.081 (2) | |
H6B | 0.9147 | −0.3574 | 0.5194 | 0.080* | |
C7 | 0.8483 (4) | −0.2109 (6) | 0.5296 (5) | 0.0654 (18) | |
H7A | 0.8484 | −0.2221 | 0.5889 | 0.080* | |
C8 | 0.7977 (4) | −0.0578 (7) | 0.3119 (4) | 0.0671 (19) | |
H8A | 0.8159 | −0.0954 | 0.2702 | 0.120* | |
H8B | 0.7413 | −0.0541 | 0.2836 | 0.120* | |
H8C | 0.8186 | 0.0254 | 0.3268 | 0.120* | |
C9 | 0.6793 (3) | −0.1577 (6) | 0.6022 (4) | 0.0441 (14) | |
C10 | 0.6305 (4) | −0.3186 (6) | 0.5092 (4) | 0.0652 (19) | |
H10A | 0.6062 | −0.3978 | 0.4851 | 0.080* | |
C11 | 0.6595 (4) | −0.2361 (6) | 0.4693 (4) | 0.0546 (16) | |
H11A | 0.6579 | −0.2442 | 0.4089 | 0.080* | |
C14 | 0.5592 (4) | 0.1849 (8) | 0.5312 (5) | 0.081 (2) | |
H14A | 0.5062 | 0.1921 | 0.5252 | 0.080* | |
C12 | 0.7011 (4) | −0.0778 (7) | 0.6844 (4) | 0.0647 (19) | |
H12A | 0.6845 | −0.1171 | 0.7270 | 0.120* | |
H12B | 0.7571 | −0.0665 | 0.7129 | 0.120* | |
H12C | 0.6759 | 0.0022 | 0.6666 | 0.120* | |
C13 | 0.6846 (4) | 0.2239 (6) | 0.5789 (5) | 0.0640 (18) | |
C15 | 0.5876 (4) | 0.1037 (7) | 0.4932 (4) | 0.0653 (19) | |
H15A | 0.5579 | 0.0399 | 0.4504 | 0.080* | |
C16 | 0.7612 (4) | 0.2851 (7) | 0.6266 (5) | 0.086 (2) | |
H16A | 0.7573 | 0.3545 | 0.6625 | 0.120* | |
H16B | 0.7984 | 0.2253 | 0.6662 | 0.120* | |
H16C | 0.7785 | 0.3145 | 0.5817 | 0.120* | |
C17 | 0.4791 (4) | −0.0474 (8) | 0.2193 (5) | 0.075 (2) | |
C18 | 1.0230 (4) | −0.0294 (8) | 0.7802 (6) | 0.077 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0737 (5) | 0.0365 (4) | 0.0618 (4) | −0.0011 (4) | 0.0534 (4) | −0.0014 (4) |
S1 | 0.0641 (10) | 0.0526 (10) | 0.0459 (9) | −0.0089 (7) | 0.0361 (8) | −0.0047 (7) |
S2 | 0.0746 (11) | 0.0566 (11) | 0.0901 (13) | 0.0147 (9) | 0.0591 (11) | 0.0153 (10) |
O1 | 0.111 (4) | 0.082 (4) | 0.081 (3) | −0.023 (3) | 0.057 (3) | 0.019 (3) |
O2 | 0.075 (3) | 0.095 (4) | 0.053 (2) | −0.010 (3) | 0.024 (2) | −0.031 (3) |
O3 | 0.113 (4) | 0.058 (3) | 0.076 (3) | 0.012 (3) | 0.067 (3) | −0.006 (2) |
O4 | 0.111 (4) | 0.068 (3) | 0.094 (4) | −0.008 (3) | 0.073 (3) | 0.003 (3) |
O5 | 0.159 (5) | 0.126 (5) | 0.151 (5) | 0.009 (4) | 0.114 (5) | −0.051 (4) |
O6 | 0.081 (3) | 0.111 (4) | 0.129 (5) | 0.029 (3) | 0.048 (3) | 0.059 (4) |
F1 | 0.093 (4) | 0.182 (6) | 0.099 (4) | −0.057 (4) | 0.014 (3) | −0.024 (4) |
F2 | 0.103 (4) | 0.182 (6) | 0.122 (4) | −0.025 (4) | 0.081 (3) | 0.026 (4) |
F3 | 0.101 (4) | 0.142 (5) | 0.186 (6) | 0.049 (4) | 0.071 (4) | 0.004 (4) |
F4 | 0.103 (4) | 0.182 (5) | 0.124 (4) | −0.001 (4) | 0.086 (3) | −0.027 (4) |
F5 | 0.119 (4) | 0.129 (5) | 0.193 (6) | −0.045 (4) | 0.082 (4) | 0.002 (4) |
F6 | 0.090 (4) | 0.215 (7) | 0.115 (4) | 0.064 (4) | 0.026 (3) | 0.043 (4) |
N1 | 0.095 (4) | 0.052 (3) | 0.071 (4) | −0.020 (3) | 0.054 (4) | −0.007 (3) |
N2 | 0.109 (6) | 0.092 (5) | 0.073 (4) | −0.042 (4) | 0.040 (4) | 0.023 (4) |
N3 | 0.054 (3) | 0.058 (3) | 0.050 (3) | 0.003 (3) | 0.034 (3) | 0.001 (3) |
N4 | 0.066 (4) | 0.083 (4) | 0.056 (4) | 0.016 (3) | 0.037 (3) | −0.009 (3) |
N5 | 0.063 (3) | 0.046 (3) | 0.048 (3) | −0.002 (2) | 0.039 (3) | 0.005 (2) |
N6 | 0.067 (4) | 0.076 (4) | 0.052 (4) | −0.023 (3) | 0.029 (3) | 0.012 (3) |
N7 | 0.103 (5) | 0.045 (3) | 0.057 (3) | 0.008 (3) | 0.054 (3) | −0.007 (3) |
N8 | 0.104 (5) | 0.073 (4) | 0.063 (4) | 0.033 (4) | 0.042 (4) | −0.015 (3) |
C1 | 0.087 (6) | 0.069 (5) | 0.075 (5) | −0.025 (4) | 0.056 (5) | −0.015 (4) |
C2 | 0.156 (10) | 0.082 (6) | 0.097 (7) | 0.008 (6) | 0.054 (7) | 0.044 (5) |
C3 | 0.088 (6) | 0.069 (5) | 0.085 (6) | 0.009 (4) | 0.039 (5) | 0.021 (4) |
C4 | 0.066 (5) | 0.098 (6) | 0.089 (6) | 0.005 (5) | 0.019 (4) | −0.003 (5) |
C5 | 0.037 (3) | 0.071 (4) | 0.057 (4) | −0.003 (3) | 0.026 (3) | −0.013 (3) |
C6 | 0.087 (5) | 0.077 (5) | 0.081 (6) | 0.033 (4) | 0.038 (5) | 0.009 (4) |
C7 | 0.070 (4) | 0.073 (5) | 0.065 (4) | 0.011 (4) | 0.039 (4) | 0.006 (4) |
C8 | 0.066 (4) | 0.094 (5) | 0.046 (4) | 0.000 (4) | 0.028 (3) | 0.005 (4) |
C9 | 0.042 (3) | 0.056 (4) | 0.042 (3) | −0.002 (3) | 0.026 (3) | 0.007 (3) |
C10 | 0.079 (5) | 0.066 (4) | 0.053 (4) | −0.026 (4) | 0.030 (4) | −0.003 (3) |
C11 | 0.074 (4) | 0.049 (4) | 0.050 (4) | −0.007 (3) | 0.035 (3) | −0.003 (3) |
C14 | 0.066 (5) | 0.104 (6) | 0.080 (5) | 0.012 (5) | 0.036 (4) | −0.005 (5) |
C12 | 0.065 (4) | 0.093 (5) | 0.045 (4) | −0.006 (4) | 0.032 (3) | −0.003 (4) |
C13 | 0.097 (5) | 0.047 (4) | 0.068 (5) | 0.009 (4) | 0.055 (4) | 0.004 (3) |
C15 | 0.063 (4) | 0.085 (5) | 0.070 (4) | −0.006 (4) | 0.048 (4) | −0.018 (4) |
C16 | 0.089 (6) | 0.083 (6) | 0.074 (5) | −0.037 (5) | 0.023 (4) | −0.008 (4) |
C17 | 0.065 (5) | 0.090 (6) | 0.077 (5) | −0.011 (4) | 0.038 (4) | −0.002 (5) |
C18 | 0.068 (5) | 0.088 (6) | 0.080 (5) | 0.011 (4) | 0.035 (4) | 0.007 (5) |
Cu1—N1 | 2.002 (5) | N6—H6A | 0.9001 |
Cu1—N3 | 1.994 (5) | N7—C13 | 1.283 (8) |
Cu1—N5 | 2.004 (4) | N7—C15 | 1.467 (8) |
Cu1—N7 | 2.026 (5) | N8—C13 | 1.280 (8) |
Cu1—O2 | 2.651 (4) | N8—C14 | 1.439 (9) |
Cu1—O6 | 3.069 (6) | N8—H8D | 0.9000 |
S1—O1 | 1.416 (4) | C1—C4 | 1.463 (9) |
S1—O2 | 1.434 (4) | C2—C3 | 1.253 (10) |
S1—O3 | 1.434 (4) | C2—H2B | 0.9599 |
S1—C17 | 1.812 (7) | C3—H3A | 0.9600 |
S2—O4 | 1.415 (5) | C4—H4A | 0.9600 |
S2—O5 | 1.421 (5) | C4—H4B | 0.9599 |
S2—O6 | 1.438 (5) | C4—H4C | 0.9600 |
S2—C18 | 1.802 (7) | C5—C8 | 1.461 (8) |
F1—C17 | 1.322 (8) | C6—C7 | 1.322 (8) |
F2—C17 | 1.317 (8) | C6—H6B | 0.9599 |
F3—C17 | 1.302 (9) | C7—H7A | 0.9600 |
F4—C18 | 1.308 (8) | C8—H8A | 0.9600 |
F5—C18 | 1.305 (9) | C8—H8B | 0.9599 |
F6—C18 | 1.295 (8) | C8—H8C | 0.9599 |
N1—C1 | 1.250 (8) | C9—C12 | 1.475 (8) |
N1—C3 | 1.482 (8) | C10—C11 | 1.335 (8) |
N2—C1 | 1.303 (8) | C10—H10A | 0.9601 |
N2—C2 | 1.458 (10) | C11—H11A | 0.9600 |
N2—H2A | 0.9000 | C14—C15 | 1.298 (9) |
N3—C5 | 1.329 (7) | C14—H14A | 0.9600 |
N3—C7 | 1.404 (8) | C12—H12A | 0.9601 |
N4—C5 | 1.330 (7) | C12—H12B | 0.9600 |
N4—C6 | 1.369 (8) | C12—H12C | 0.9600 |
N4—H4D | 0.9000 | C13—C16 | 1.465 (9) |
N5—C9 | 1.340 (6) | C15—H15A | 0.9600 |
N5—C11 | 1.387 (7) | C16—H16A | 0.9600 |
N6—C9 | 1.332 (7) | C16—H16B | 0.9600 |
N6—C10 | 1.365 (8) | C16—H16C | 0.9600 |
N3—Cu1—N1 | 94.0 (2) | H4A—C4—H4B | 109.5 |
N3—Cu1—N5 | 87.19 (18) | C1—C4—H4C | 109.7 |
N1—Cu1—N5 | 175.0 (2) | H4A—C4—H4C | 109.5 |
N3—Cu1—N7 | 175.4 (2) | H4B—C4—H4C | 109.5 |
N1—Cu1—N7 | 90.3 (2) | N3—C5—N4 | 110.1 (6) |
N5—Cu1—N7 | 88.8 (2) | N3—C5—C8 | 127.9 (6) |
N1—Cu1—O2 | 87.0 (2) | N4—C5—C8 | 122.0 (5) |
N3—Cu1—O2 | 99.05 (17) | C7—C6—N4 | 106.1 (6) |
N5—Cu1—O2 | 87.97 (18) | C7—C6—H6B | 127.1 |
N7—Cu1—O2 | 82.96 (18) | N4—C6—H6B | 126.7 |
N1—Cu1—O6 | 91.0 (2) | C6—C7—N3 | 109.9 (6) |
N3—Cu1—O6 | 84.99 (18) | C6—C7—H7A | 125.7 |
N5—Cu1—O6 | 93.97 (17) | N3—C7—H7A | 124.4 |
N7—Cu1—O6 | 93.13 (19) | C5—C8—H8A | 109.5 |
O2—Cu1—O6 | 175.61 (14) | C5—C8—H8B | 109.0 |
O1—S1—O3 | 113.2 (3) | H8A—C8—H8B | 109.5 |
O1—S1—O2 | 116.0 (3) | C5—C8—H8C | 109.9 |
O3—S1—O2 | 114.6 (3) | H8A—C8—H8C | 109.5 |
O1—S1—C17 | 103.0 (3) | H8B—C8—H8C | 109.5 |
O3—S1—C17 | 103.4 (3) | N6—C9—N5 | 108.9 (5) |
O2—S1—C17 | 104.4 (3) | N6—C9—C12 | 123.5 (5) |
O4—S2—O5 | 114.8 (4) | N5—C9—C12 | 127.6 (5) |
O4—S2—O6 | 112.1 (4) | C11—C10—N6 | 105.6 (6) |
O5—S2—O6 | 116.7 (4) | C11—C10—H10A | 127.5 |
O4—S2—C18 | 103.6 (4) | N6—C10—H10A | 126.9 |
O5—S2—C18 | 103.5 (4) | C10—C11—N5 | 109.9 (5) |
O6—S2—C18 | 104.0 (3) | C10—C11—H11A | 125.4 |
C1—N1—C3 | 104.6 (6) | N5—C11—H11A | 124.7 |
C1—N1—Cu1 | 135.7 (6) | C15—C14—N8 | 106.5 (6) |
C3—N1—Cu1 | 119.6 (5) | C15—C14—H14A | 128.3 |
C1—N2—C2 | 103.4 (6) | N8—C14—H14A | 125.2 |
C1—N2—H2A | 127.3 | C9—C12—H12A | 109.5 |
C2—N2—H2A | 129.3 | C9—C12—H12B | 109.5 |
C5—N3—C7 | 104.9 (5) | H12A—C12—H12B | 109.5 |
C5—N3—Cu1 | 132.1 (4) | C9—C12—H12C | 109.4 |
C7—N3—Cu1 | 122.6 (4) | H12A—C12—H12C | 109.5 |
C5—N4—C6 | 108.9 (5) | H12B—C12—H12C | 109.5 |
C5—N4—H4D | 125.2 | N8—C13—N7 | 114.4 (7) |
C6—N4—H4D | 125.9 | N8—C13—C16 | 121.2 (7) |
C9—N5—C11 | 105.8 (5) | N7—C13—C16 | 124.5 (7) |
C9—N5—Cu1 | 131.1 (4) | C14—C15—N7 | 107.8 (6) |
C11—N5—Cu1 | 123.1 (4) | C14—C15—H15A | 125.6 |
C9—N6—C10 | 109.7 (5) | N7—C15—H15A | 126.7 |
C9—N6—H6A | 124.6 | C13—C16—H16A | 110.6 |
C10—N6—H6A | 125.6 | C13—C16—H16B | 109.2 |
C13—N7—C15 | 104.5 (5) | H16A—C16—H16B | 109.5 |
C13—N7—Cu1 | 134.5 (5) | C13—C16—H16C | 108.7 |
C15—N7—Cu1 | 120.9 (4) | H16A—C16—H16C | 109.5 |
C13—N8—C14 | 106.8 (6) | H16B—C16—H16C | 109.5 |
C13—N8—H8D | 126.3 | F3—C17—F2 | 107.1 (7) |
C14—N8—H8D | 126.9 | F3—C17—F1 | 107.8 (7) |
N1—C1—N2 | 115.9 (8) | F2—C17—F1 | 108.3 (7) |
N1—C1—C4 | 126.1 (7) | F3—C17—S1 | 111.6 (6) |
N2—C1—C4 | 117.9 (7) | F2—C17—S1 | 111.0 (6) |
C3—C2—N2 | 108.8 (7) | F1—C17—S1 | 110.9 (5) |
C3—C2—H2B | 128.0 | F6—C18—F5 | 107.8 (7) |
N2—C2—H2B | 123.2 | F6—C18—F4 | 107.4 (7) |
C2—C3—N1 | 107.3 (7) | F5—C18—F4 | 106.6 (7) |
C2—C3—H3A | 125.5 | F6—C18—S2 | 111.0 (6) |
N1—C3—H3A | 127.3 | F5—C18—S2 | 112.1 (6) |
C1—C4—H4A | 109.8 | F4—C18—S2 | 111.6 (6) |
C1—C4—H4B | 108.9 |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O5i | 0.90 | 2.02 | 2.812 (7) | 146 |
N4—H4D···O4ii | 0.90 | 1.92 | 2.822 (6) | 177 |
N6—H6A···O3iii | 0.90 | 1.95 | 2.826 (6) | 164 |
N8—H8D···O1iv | 0.90 | 1.95 | 2.823 (7) | 162 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y−1/2, z−1/2; (iii) x, −y−1/2, z+1/2; (iv) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(CH3C3H3N2)4(CF3SO3)2] |
Mr | 690.11 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 18.763 (4), 10.674 (2), 16.064 (3) |
β (°) | 115.02 (3) |
V (Å3) | 2915.3 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.98 |
Crystal size (mm) | 0.32 × 0.22 × 0.16 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al, 1968) |
Tmin, Tmax | 0.742, 0.855 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5291, 5092, 2600 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.126, 1.04 |
No. of reflections | 5092 |
No. of parameters | 370 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.65, −0.49 |
Computer programs: CAD-4-PC Software (Enraf-Nonius, 1992), CAD-4-PC, XCAD4 (Harms, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Bruker, 1998), SHELXL97.
Cu1—N1 | 2.002 (5) | Cu1—N7 | 2.026 (5) |
Cu1—N3 | 1.994 (5) | Cu1—O2 | 2.651 (4) |
Cu1—N5 | 2.004 (4) | Cu1—O6 | 3.069 (6) |
N3—Cu1—N1 | 94.0 (2) | N5—Cu1—O2 | 87.97 (18) |
N3—Cu1—N5 | 87.19 (18) | N7—Cu1—O2 | 82.96 (18) |
N1—Cu1—N5 | 175.0 (2) | N1—Cu1—O6 | 91.0 (2) |
N3—Cu1—N7 | 175.4 (2) | N3—Cu1—O6 | 84.99 (18) |
N1—Cu1—N7 | 90.3 (2) | N5—Cu1—O6 | 93.97 (17) |
N5—Cu1—N7 | 88.8 (2) | N7—Cu1—O6 | 93.13 (19) |
N1—Cu1—O2 | 87.0 (2) | O2—Cu1—O6 | 175.61 (14) |
N3—Cu1—O2 | 99.05 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O5i | 0.90 | 2.02 | 2.812 (7) | 146.0 |
N4—H4D···O4ii | 0.90 | 1.92 | 2.822 (6) | 176.8 |
N6—H6A···O3iii | 0.90 | 1.95 | 2.826 (6) | 164.0 |
N8—H8D···O1iv | 0.90 | 1.95 | 2.823 (7) | 162.1 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y−1/2, z−1/2; (iii) x, −y−1/2, z+1/2; (iv) x, −y+1/2, z+1/2. |
Coordination chemistry of copper complexes has been the focus of numerous studies, since it can provide important clues for better understanding the structures and probable mechanisms of reactions involving copper-containing metalloproteins (Kaim & Schwederski, 1991). The structures of copper complexes are affected by various factors (Hathaway, 1987), such as ligand field stabilization energies, the Pauling electroneutrality principle, Jahn-Teller effect, counter-ion effects, steric effects, etc. Considerable research effort has been focused on low molecular weight Cu(II)–imidazole complexes in order to understand their stereochemistry and the interactions of histidyl residues with copper ions (Ohtsu et al., 2001; Wang et al., 1999; Jian et al., 1999). The structures and bonding properties of Cu(II)–imidazole chromophores have been studied by X-ray diffraction and electronic spectra in our earlier work (Liu & Su, 1995; Su et al., 1995). The study of the title complex, (I), was undertaken in order to compare its structure with that of its analogue, [Cu(ImH)4(CF3SO3)2] (where ImH = imidazole), and thus consider the effect of substitution at the imidazole ligands on the structure of complex.
Fig. 1 shows an ORTEP (Johnson, 1965) drawing of the title complex and Table 1 lists the distances and angles involving the Cu atom. The Cu atom has an octahedral coordination, with bond angles indicating relatively slight distortions (12 angles from 82.96 to 99.05° and three angles, 175.0–175.6°), and equatorial Cu—N bonds in the normal range typical for Cu—N coordination (1.994–2.026 Å). Both axial Cu—O bonds are much longer than one would expect for normal Cu—O coordination bonds; in addition, one of the Cu—O distances (Cu1—O6 3.069 (6) Å) is significantly longer than the other (Cu1—O2 2.651 (4) Å), which is very different from the geometry of other Cu(II)–imidazole complexes, which have long but almost identical axial bonds, e.g. 2.593 Å in [Cu(ImH)4(CF3SO3)2] (Liu & Su, 1995), 2.625 Å in [Cu(ImH)4(ClO4)2] (Ivarsson, 1973), 2.574 Å in [Cu(ImH)4(SO4)2] (Fransson & Lundberg, 1972) and 2.566 Å in [Cu(ImH)4(NO3)2] (McFadden et al., 1976).
It was found that the conformations of the imidazole ligands in tetrakis-imidazole and tetrakis-monosubstituted imidazole copper(II) complexes are mainly affected by the donor abilities of both the imidazole ligands and the counter ions. For the title complex, the dihedral angles between the imidazole rings and the equatorial CuN4 plane are 47.2 (2), 47.8 (3), 51.9 (3) and 51.3 (2)°, respectively. The dihedral angles for the analog with unsubstituted imidazole and the same anion, [Cu(ImH)4(CF3SO3)2], fall into two categories; one pair of trans imidazole rings is almost perpendicular to the equatorial plane (88.2°) and another is tilted by 59.4° (Liu & Su, 1995). Complexes with very weak σ-donor anions such as [Cu(ImH)4(ClO4)2] (Ivarsson, 1973), tend to have a perpendicular and a parallel pair of imidazole ligands, forming the dihedral angles of 94.3 and 18.7° with the metal coordination plane, respectively. Corresponding complexes with relatively stronger σ-donor anions have all four imidazole rings perpendicular to the equatorial plane, e.g., 98.6 and 94.6° in [Cu(ImH)4(NO3)2] (McFadden et al.,1976).
A view of the packing is shown in Fig. 2. The discrete complexes are connected by hydrogen bonding between N atoms of imidazole ligands and O atoms of trifluoromethylsulfonate to form layers parallel to the bc plane.