Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107026753/sk3135sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107026753/sk3135Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107026753/sk3135IIsup3.hkl |
CCDC references: 659113; 659114
[Cu(phen)2](ClO4)2 and [Cu(bipy)2](ClO4)2 were prepared by reacting Cu(ClO4)2 with phen or bipy in 1:2 molar ratio in ethanol. The products separated out of the reaction mixtures and were washed with ethanol and dried under reduced pressure. For the preparation of (I), a solution of N,N'-dimethylimidazolidine-2-selone (30.0 mg, 0.17 mmol) in MeCN (2 ml) was added dropwise at room temperature to a solution of [Cu(phen)2](ClO4)2 (53.0 mg, 0.085 mmol) in MeCN (3 ml). The colour of the reaction mixture turned green immediately. Crystals of the title compound were obtained by slow evaporation of the solvent (52.0 mg 76.5% yield). Analysis found (calculated for C29H26Cl2CuN6O8Se): C 43.20 (43.54), H 3.30 (3.27), N 10.35 (10.50)%. For the preparation of (II), a solution of imidazolidine-2-thione (30.0 mg, 029 mmol) in MeCN (3 ml) was added dropwise at room temperature to a solution of [Cu(bipy)2](ClO4)2 (83.4 mg, 0.145 mmol) in MeCN (3 ml). The colour of the reaction mixture turned green immediately. Crystals of the title compound were obtained by slow evaporation of the solvent (88.0 mg, 89.6% yield). Analysis found (calculated for C23H22Cl2CuN6O8S): C 40.60 (40.81), H 3.25 (3.28), N 12.35 (12.41), S 4.52 (4.74)%.
NH and NMe H atoms were located in difference Fourier syntheses. The NH H atoms were then refined subject to an N—H distance restraint of 0.90 (2) Å and with Uiso(H) = 1.2Ueq(N); NMe H atoms were refined as part of a rigid rotating group with Uiso(H) = 1.5Ueq(C). All other H atoms were included in calculated positions and refined using a riding model with Uiso(H) = 1.2Ueq(C). Similarity restraints were applied to the Cl—O distances in (I).
The intermediate value of 0.41 (3) for the Flack parameter of (I) suggests that the crystal selected was a racemic twin with approximately equal amounts of each twin component.
For both compounds, data collection: STADI4 (Stoe & Cie, 1996); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: enCIFer (Allen et al., 2004), PLATON (Spek, 2003) and publCIF (Westrip, 2007).
[Cu(C12H8N2)2(C5H10N2Se)](ClO4)2 | F(000) = 1612 |
Mr = 799.96 | Dx = 1.703 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 11.606 (6) Å | θ = 12.5–13.9° |
b = 12.155 (2) Å | µ = 2.10 mm−1 |
c = 22.120 (4) Å | T = 150 K |
V = 3120.5 (18) Å3 | Column, green |
Z = 4 | 0.51 × 0.14 × 0.10 mm |
Stoe Stadi-4 four-circle diffractometer | 2621 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.052 |
Graphite monochromator | θmax = 25.1°, θmin = 2.5° |
ω/θ scans | h = −2→13 |
Absorption correction: numerical (X-RED; Stoe & Cie, 1996) | k = 0→14 |
Tmin = 0.700, Tmax = 0.830 | l = 0→26 |
3878 measured reflections | 3 standard reflections every 60 min |
3511 independent reflections | intensity decay: random variation +−5% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: included in calculated positions, except for N-Me (found from delta-F) |
R[F2 > 2σ(F2)] = 0.074 | H-atom parameters constrained |
wR(F2) = 0.144 | w = 1/[σ2(Fo2) + 24.56P] where P = (Fo2 + 2Fc2)/3 |
S = 1.23 | (Δ/σ)max = 0.001 |
3511 reflections | Δρmax = 0.80 e Å−3 |
427 parameters | Δρmin = −0.67 e Å−3 |
147 restraints | Absolute structure: Flack (1983), 780 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.41 (3) |
[Cu(C12H8N2)2(C5H10N2Se)](ClO4)2 | V = 3120.5 (18) Å3 |
Mr = 799.96 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 11.606 (6) Å | µ = 2.10 mm−1 |
b = 12.155 (2) Å | T = 150 K |
c = 22.120 (4) Å | 0.51 × 0.14 × 0.10 mm |
Stoe Stadi-4 four-circle diffractometer | 2621 reflections with I > 2σ(I) |
Absorption correction: numerical (X-RED; Stoe & Cie, 1996) | Rint = 0.052 |
Tmin = 0.700, Tmax = 0.830 | 3 standard reflections every 60 min |
3878 measured reflections | intensity decay: random variation +−5% |
3511 independent reflections |
R[F2 > 2σ(F2)] = 0.074 | H-atom parameters constrained |
wR(F2) = 0.144 | w = 1/[σ2(Fo2) + 24.56P] where P = (Fo2 + 2Fc2)/3 |
S = 1.23 | Δρmax = 0.80 e Å−3 |
3511 reflections | Δρmin = −0.67 e Å−3 |
427 parameters | Absolute structure: Flack (1983), 780 Friedel pairs |
147 restraints | Absolute structure parameter: 0.41 (3) |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.14068 (15) | 0.67758 (13) | 0.00636 (7) | 0.0239 (4) | |
Se1 | −0.06144 (13) | 0.65302 (13) | 0.04170 (7) | 0.0338 (4) | |
N1 | −0.1010 (11) | 0.4356 (10) | 0.0812 (6) | 0.039 (3) | |
N2 | −0.0145 (12) | 0.5357 (11) | 0.1509 (6) | 0.043 (4) | |
N1A | 0.1896 (9) | 0.5310 (8) | 0.0357 (5) | 0.019 (2) | |
N1B | 0.0983 (10) | 0.8274 (8) | −0.0236 (4) | 0.025 (3) | |
N8A | 0.2523 (10) | 0.7291 (9) | 0.0764 (5) | 0.024 (3) | |
N8B | 0.2065 (9) | 0.6641 (9) | −0.0808 (4) | 0.024 (3) | |
C1 | −0.0563 (14) | 0.5337 (12) | 0.0956 (6) | 0.029 (3) | |
C2A | 0.1556 (13) | 0.4345 (10) | 0.0128 (6) | 0.031 (3) | |
H2AA | 0.1115 | 0.4326 | −0.0234 | 0.037* | |
C2B | 0.0425 (13) | 0.9058 (10) | 0.0051 (6) | 0.030 (3) | |
H2BA | 0.0158 | 0.8904 | 0.0448 | 0.035* | |
C2 | −0.0890 (17) | 0.3599 (14) | 0.1331 (9) | 0.069 (6) | |
H2A | −0.0438 | 0.2940 | 0.1219 | 0.083* | |
H2B | −0.1654 | 0.3364 | 0.1483 | 0.083* | |
C3A | 0.1854 (12) | 0.3347 (11) | 0.0425 (6) | 0.031 (3) | |
H3AA | 0.1618 | 0.2663 | 0.0258 | 0.038* | |
C3B | 0.0203 (13) | 1.0089 (11) | −0.0183 (6) | 0.032 (3) | |
H3BA | −0.0195 | 1.0628 | 0.0048 | 0.038* | |
C3 | −0.0273 (16) | 0.4270 (13) | 0.1788 (8) | 0.052 (5) | |
H3A | −0.0725 | 0.4319 | 0.2167 | 0.062* | |
H3B | 0.0490 | 0.3946 | 0.1881 | 0.062* | |
C4A | 0.2466 (12) | 0.3363 (13) | 0.0941 (6) | 0.029 (3) | |
H4AA | 0.2664 | 0.2693 | 0.1136 | 0.035* | |
C4B | 0.0572 (13) | 1.0311 (11) | −0.0758 (6) | 0.027 (3) | |
H4BA | 0.0436 | 1.1013 | −0.0932 | 0.033* | |
C4 | −0.1544 (16) | 0.4001 (15) | 0.0252 (8) | 0.068 (6) | |
H4A | −0.1426 | 0.4564 | −0.0059 | 0.102* | |
H4B | −0.2371 | 0.3892 | 0.0316 | 0.102* | |
H4C | −0.1194 | 0.3308 | 0.0119 | 0.102* | |
C5A | 0.2815 (13) | 0.4375 (11) | 0.1193 (6) | 0.027 (3) | |
C5B | 0.1151 (12) | 0.9501 (11) | −0.1089 (5) | 0.023 (3) | |
C5 | 0.0314 (13) | 0.6300 (15) | 0.1827 (7) | 0.051 (5) | |
H5A | 0.0257 | 0.6953 | 0.1569 | 0.077* | |
H5B | 0.1124 | 0.6166 | 0.1929 | 0.077* | |
H5C | −0.0128 | 0.6420 | 0.2199 | 0.077* | |
C6A | 0.2527 (12) | 0.5344 (11) | 0.0863 (6) | 0.020 (3) | |
C6B | 0.1324 (12) | 0.8472 (11) | −0.0803 (5) | 0.024 (3) | |
C7A | 0.2863 (12) | 0.6382 (11) | 0.1097 (6) | 0.023 (3) | |
C7B | 0.1887 (12) | 0.7625 (10) | −0.1113 (6) | 0.021 (3) | |
C9A | 0.2835 (12) | 0.8261 (12) | 0.0970 (6) | 0.031 (3) | |
H9A | 0.2584 | 0.8896 | 0.0757 | 0.037* | |
C9B | 0.2600 (13) | 0.5841 (13) | −0.1080 (6) | 0.030 (4) | |
H9B | 0.2712 | 0.5169 | −0.0868 | 0.036* | |
C10A | 0.3509 (13) | 0.8409 (12) | 0.1480 (6) | 0.030 (3) | |
H10A | 0.3740 | 0.9126 | 0.1601 | 0.037* | |
C10B | 0.3021 (13) | 0.5930 (12) | −0.1679 (6) | 0.032 (4) | |
H10B | 0.3428 | 0.5335 | −0.1858 | 0.039* | |
C11A | 0.3838 (14) | 0.7505 (12) | 0.1809 (6) | 0.033 (3) | |
H11A | 0.4299 | 0.7599 | 0.2161 | 0.040* | |
C11B | 0.2840 (13) | 0.6880 (12) | −0.1999 (6) | 0.030 (3) | |
H11B | 0.3096 | 0.6941 | −0.2406 | 0.036* | |
C12A | 0.3506 (12) | 0.6459 (11) | 0.1635 (6) | 0.029 (3) | |
C12B | 0.2278 (12) | 0.7749 (11) | −0.1721 (6) | 0.024 (3) | |
C13A | 0.3763 (13) | 0.5465 (12) | 0.1953 (6) | 0.033 (3) | |
H13A | 0.4164 | 0.5504 | 0.2327 | 0.039* | |
C13B | 0.2076 (12) | 0.8823 (11) | −0.1986 (6) | 0.025 (3) | |
H13B | 0.2321 | 0.8952 | −0.2390 | 0.031* | |
C14A | 0.3449 (12) | 0.4476 (12) | 0.1735 (6) | 0.028 (3) | |
H14A | 0.3659 | 0.3830 | 0.1950 | 0.034* | |
C14B | 0.1566 (13) | 0.9629 (12) | −0.1689 (6) | 0.031 (3) | |
H14B | 0.1474 | 1.0320 | −0.1883 | 0.037* | |
Cl1 | 0.0915 (3) | 1.0784 (3) | 0.14224 (15) | 0.0303 (9) | |
O1 | 0.1762 (8) | 1.0799 (8) | 0.0951 (4) | 0.036 (3) | |
O2 | 0.0995 (11) | 0.9775 (7) | 0.1751 (5) | 0.063 (4) | |
O3 | −0.0213 (7) | 1.0883 (9) | 0.1163 (5) | 0.044 (3) | |
O4 | 0.1106 (9) | 1.1699 (7) | 0.1823 (4) | 0.042 (3) | |
Cl2 | 0.5385 (3) | 0.1680 (3) | 0.14352 (16) | 0.0367 (9) | |
O5 | 0.4999 (10) | 0.2082 (8) | 0.0860 (4) | 0.048 (3) | |
O6 | 0.5548 (12) | 0.0535 (7) | 0.1415 (6) | 0.075 (4) | |
O7 | 0.4506 (11) | 0.1907 (12) | 0.1875 (4) | 0.090 (6) | |
O8 | 0.6399 (12) | 0.2210 (12) | 0.1618 (6) | 0.116 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0288 (9) | 0.0211 (8) | 0.0217 (8) | 0.0049 (9) | 0.0008 (8) | 0.0019 (7) |
Se1 | 0.0278 (8) | 0.0404 (9) | 0.0331 (7) | 0.0089 (8) | 0.0055 (8) | 0.0105 (7) |
N1 | 0.026 (8) | 0.041 (8) | 0.050 (8) | 0.002 (7) | 0.006 (7) | 0.002 (7) |
N2 | 0.036 (8) | 0.057 (9) | 0.035 (7) | 0.004 (8) | −0.003 (7) | 0.011 (7) |
N1A | 0.016 (6) | 0.021 (6) | 0.020 (5) | −0.007 (5) | −0.003 (5) | −0.001 (5) |
N1B | 0.036 (7) | 0.008 (5) | 0.030 (6) | 0.006 (6) | −0.002 (5) | 0.007 (5) |
N8A | 0.028 (7) | 0.022 (6) | 0.024 (6) | 0.005 (6) | 0.006 (6) | −0.006 (5) |
N8B | 0.023 (6) | 0.026 (6) | 0.022 (5) | 0.001 (6) | −0.001 (5) | 0.002 (6) |
C1 | 0.025 (8) | 0.037 (8) | 0.024 (7) | 0.012 (8) | 0.005 (7) | −0.010 (7) |
C2A | 0.032 (9) | 0.028 (7) | 0.032 (7) | 0.005 (7) | 0.000 (7) | −0.004 (6) |
C2B | 0.035 (9) | 0.026 (6) | 0.027 (7) | 0.016 (7) | 0.006 (7) | −0.003 (5) |
C2 | 0.058 (14) | 0.032 (10) | 0.117 (16) | 0.001 (10) | 0.010 (12) | 0.014 (10) |
C3A | 0.037 (8) | 0.025 (6) | 0.038 (6) | 0.017 (7) | 0.012 (6) | −0.011 (6) |
C3B | 0.040 (10) | 0.028 (6) | 0.027 (6) | 0.008 (7) | −0.013 (6) | −0.003 (5) |
C3 | 0.050 (12) | 0.051 (11) | 0.055 (11) | 0.019 (9) | 0.018 (8) | 0.030 (8) |
C4A | 0.022 (8) | 0.029 (5) | 0.036 (6) | 0.010 (7) | 0.016 (5) | 0.005 (5) |
C4B | 0.023 (8) | 0.023 (6) | 0.035 (6) | −0.001 (6) | −0.013 (6) | 0.003 (5) |
C4 | 0.047 (12) | 0.061 (12) | 0.096 (16) | −0.013 (11) | −0.006 (12) | −0.034 (11) |
C5A | 0.028 (8) | 0.029 (5) | 0.025 (6) | 0.023 (6) | 0.005 (5) | 0.000 (5) |
C5B | 0.023 (8) | 0.025 (5) | 0.020 (5) | −0.002 (6) | −0.011 (5) | 0.009 (4) |
C5 | 0.017 (9) | 0.104 (15) | 0.032 (8) | −0.002 (10) | 0.000 (7) | −0.016 (10) |
C6A | 0.023 (8) | 0.024 (5) | 0.013 (6) | 0.008 (6) | 0.013 (5) | 0.001 (4) |
C6B | 0.024 (7) | 0.027 (6) | 0.020 (5) | 0.003 (7) | −0.003 (5) | 0.006 (4) |
C7A | 0.022 (8) | 0.029 (5) | 0.019 (6) | −0.009 (6) | 0.008 (5) | 0.007 (5) |
C7B | 0.024 (8) | 0.018 (5) | 0.022 (5) | −0.015 (5) | 0.000 (6) | −0.002 (4) |
C9A | 0.029 (8) | 0.026 (8) | 0.037 (7) | 0.007 (8) | −0.001 (6) | 0.001 (7) |
C9B | 0.035 (9) | 0.034 (9) | 0.022 (6) | 0.002 (8) | 0.003 (7) | 0.000 (6) |
C10A | 0.035 (8) | 0.027 (5) | 0.030 (6) | −0.007 (8) | 0.007 (6) | −0.002 (6) |
C10B | 0.040 (10) | 0.029 (6) | 0.027 (6) | 0.004 (7) | 0.015 (7) | −0.008 (5) |
C11A | 0.035 (10) | 0.039 (5) | 0.026 (7) | −0.006 (7) | −0.001 (6) | 0.002 (5) |
C11B | 0.032 (9) | 0.037 (6) | 0.022 (6) | 0.000 (7) | 0.003 (6) | −0.002 (5) |
C12A | 0.020 (7) | 0.032 (4) | 0.035 (7) | 0.006 (7) | −0.007 (6) | 0.003 (5) |
C12B | 0.019 (8) | 0.031 (5) | 0.021 (5) | −0.003 (6) | −0.003 (6) | 0.001 (5) |
C13A | 0.024 (9) | 0.042 (5) | 0.031 (7) | −0.001 (7) | 0.002 (6) | 0.014 (5) |
C13B | 0.013 (7) | 0.038 (6) | 0.026 (6) | −0.008 (6) | −0.003 (6) | 0.010 (5) |
C14A | 0.018 (8) | 0.039 (5) | 0.029 (6) | 0.001 (7) | 0.005 (5) | 0.018 (5) |
C14B | 0.032 (9) | 0.031 (6) | 0.029 (6) | 0.003 (7) | −0.006 (6) | 0.016 (5) |
Cl1 | 0.036 (2) | 0.0304 (19) | 0.0246 (17) | 0.0007 (18) | 0.0027 (17) | 0.0046 (16) |
O1 | 0.049 (7) | 0.027 (5) | 0.030 (5) | −0.009 (5) | 0.019 (5) | −0.001 (5) |
O2 | 0.086 (11) | 0.037 (6) | 0.066 (8) | 0.012 (7) | 0.012 (8) | 0.028 (6) |
O3 | 0.024 (6) | 0.056 (7) | 0.052 (7) | −0.003 (6) | −0.008 (5) | −0.017 (6) |
O4 | 0.052 (7) | 0.046 (6) | 0.027 (5) | −0.011 (7) | −0.003 (5) | −0.013 (5) |
Cl2 | 0.050 (2) | 0.0249 (18) | 0.0354 (19) | −0.002 (2) | −0.0018 (18) | −0.0006 (17) |
O5 | 0.076 (9) | 0.050 (7) | 0.017 (5) | 0.003 (7) | −0.011 (6) | 0.009 (5) |
O6 | 0.098 (11) | 0.028 (6) | 0.099 (10) | 0.027 (8) | −0.001 (10) | 0.013 (7) |
O7 | 0.084 (11) | 0.141 (14) | 0.045 (7) | 0.073 (12) | 0.011 (8) | −0.003 (9) |
O8 | 0.115 (15) | 0.152 (15) | 0.083 (10) | −0.086 (14) | −0.027 (11) | 0.031 (10) |
Cu1—N1A | 1.980 (10) | C5A—C14A | 1.411 (19) |
Cu1—N1B | 1.999 (10) | C5A—C6A | 1.425 (18) |
Cu1—N8B | 2.080 (10) | C5B—C6B | 1.416 (17) |
Cu1—N8A | 2.114 (11) | C5B—C14B | 1.420 (18) |
Cu1—Se1 | 2.491 (3) | C5—H5A | 0.9800 |
Se1—C1 | 1.878 (14) | C5—H5B | 0.9800 |
N1—C1 | 1.340 (18) | C5—H5C | 0.9800 |
N1—C4 | 1.451 (19) | C6A—C7A | 1.418 (18) |
N1—C2 | 1.48 (2) | C6B—C7B | 1.398 (18) |
N2—C1 | 1.317 (17) | C7A—C12A | 1.409 (18) |
N2—C5 | 1.447 (19) | C7B—C12B | 1.428 (17) |
N2—C3 | 1.467 (18) | C9A—C10A | 1.385 (18) |
N1A—C6A | 1.337 (16) | C9A—H9A | 0.9500 |
N1A—C2A | 1.338 (15) | C9B—C10B | 1.417 (18) |
N1B—C2B | 1.316 (15) | C9B—H9B | 0.9500 |
N1B—C6B | 1.336 (14) | C10A—C11A | 1.371 (19) |
N8A—C9A | 1.316 (17) | C10A—H10A | 0.9500 |
N8A—C7A | 1.385 (16) | C10B—C11B | 1.370 (18) |
N8B—C9B | 1.301 (17) | C10B—H10B | 0.9500 |
N8B—C7B | 1.389 (16) | C11A—C12A | 1.384 (19) |
C2A—C3A | 1.423 (18) | C11A—H11A | 0.9500 |
C2A—H2AA | 0.9500 | C11B—C12B | 1.386 (19) |
C2B—C3B | 1.380 (17) | C11B—H11B | 0.9500 |
C2B—H2BA | 0.9500 | C12A—C13A | 1.429 (18) |
C2—C3 | 1.48 (2) | C12B—C13B | 1.451 (18) |
C2—H2A | 0.9900 | C13A—C14A | 1.346 (19) |
C2—H2B | 0.9900 | C13A—H13A | 0.9500 |
C3A—C4A | 1.344 (19) | C13B—C14B | 1.320 (19) |
C3A—H3AA | 0.9500 | C13B—H13B | 0.9500 |
C3B—C4B | 1.370 (18) | C14A—H14A | 0.9500 |
C3B—H3BA | 0.9500 | C14B—H14B | 0.9500 |
C3—H3A | 0.9900 | Cl1—O2 | 1.429 (8) |
C3—H3B | 0.9900 | Cl1—O3 | 1.434 (8) |
C4A—C5A | 1.41 (2) | Cl1—O1 | 1.434 (8) |
C4A—H4AA | 0.9500 | Cl1—O4 | 1.439 (8) |
C4B—C5B | 1.399 (18) | Cl2—O8 | 1.401 (10) |
C4B—H4BA | 0.9500 | Cl2—O6 | 1.406 (8) |
C4—H4A | 0.9800 | Cl2—O5 | 1.434 (8) |
C4—H4B | 0.9800 | Cl2—O7 | 1.437 (9) |
C4—H4C | 0.9800 | ||
N1A—Cu1—N1B | 177.6 (5) | C14A—C5A—C6A | 119.0 (13) |
N1A—Cu1—N8B | 97.4 (4) | C4B—C5B—C6B | 117.1 (12) |
N1B—Cu1—N8B | 81.6 (4) | C4B—C5B—C14B | 125.1 (12) |
N1A—Cu1—N8A | 81.4 (4) | C6B—C5B—C14B | 117.8 (13) |
N1B—Cu1—N8A | 97.1 (4) | N2—C5—H5A | 109.5 |
N8B—Cu1—N8A | 118.5 (4) | N2—C5—H5B | 109.5 |
N1A—Cu1—Se1 | 93.4 (3) | H5A—C5—H5B | 109.5 |
N1B—Cu1—Se1 | 88.9 (3) | N2—C5—H5C | 109.5 |
N8B—Cu1—Se1 | 128.8 (3) | H5A—C5—H5C | 109.5 |
N8A—Cu1—Se1 | 112.5 (3) | H5B—C5—H5C | 109.5 |
C1—Se1—Cu1 | 105.2 (5) | N1A—C6A—C7A | 118.9 (12) |
C1—N1—C4 | 129.3 (13) | N1A—C6A—C5A | 122.1 (12) |
C1—N1—C2 | 109.5 (13) | C7A—C6A—C5A | 118.9 (12) |
C4—N1—C2 | 121.3 (14) | N1B—C6B—C7B | 117.7 (12) |
C1—N2—C5 | 127.0 (14) | N1B—C6B—C5B | 122.5 (12) |
C1—N2—C3 | 109.7 (14) | C7B—C6B—C5B | 119.8 (11) |
C5—N2—C3 | 123.1 (13) | N8A—C7A—C12A | 123.2 (12) |
C6A—N1A—C2A | 120.4 (11) | N8A—C7A—C6A | 115.9 (11) |
C6A—N1A—Cu1 | 113.8 (8) | C12A—C7A—C6A | 120.9 (12) |
C2A—N1A—Cu1 | 125.5 (9) | N8B—C7B—C6B | 117.8 (11) |
C2B—N1B—C6B | 117.9 (11) | N8B—C7B—C12B | 120.0 (12) |
C2B—N1B—Cu1 | 128.4 (9) | C6B—C7B—C12B | 122.2 (12) |
C6B—N1B—Cu1 | 113.7 (9) | N8A—C9A—C10A | 123.7 (14) |
C9A—N8A—C7A | 116.9 (11) | N8A—C9A—H9A | 118.2 |
C9A—N8A—Cu1 | 133.5 (10) | C10A—C9A—H9A | 118.2 |
C7A—N8A—Cu1 | 109.1 (8) | N8B—C9B—C10B | 122.7 (14) |
C9B—N8B—C7B | 119.4 (11) | N8B—C9B—H9B | 118.6 |
C9B—N8B—Cu1 | 131.5 (9) | C10B—C9B—H9B | 118.6 |
C7B—N8B—Cu1 | 109.1 (8) | C11A—C10A—C9A | 119.1 (14) |
N2—C1—N1 | 112.3 (13) | C11A—C10A—H10A | 120.5 |
N2—C1—Se1 | 126.0 (12) | C9A—C10A—H10A | 120.5 |
N1—C1—Se1 | 121.6 (10) | C11B—C10B—C9B | 119.7 (14) |
N1A—C2A—C3A | 120.0 (13) | C11B—C10B—H10B | 120.2 |
N1A—C2A—H2AA | 120.0 | C9B—C10B—H10B | 120.2 |
C3A—C2A—H2AA | 120.0 | C10A—C11A—C12A | 120.7 (13) |
N1B—C2B—C3B | 124.7 (13) | C10A—C11A—H11A | 119.7 |
N1B—C2B—H2BA | 117.7 | C12A—C11A—H11A | 119.7 |
C3B—C2B—H2BA | 117.7 | C10B—C11B—C12B | 119.0 (13) |
N1—C2—C3 | 103.5 (13) | C10B—C11B—H11B | 120.5 |
N1—C2—H2A | 111.1 | C12B—C11B—H11B | 120.5 |
C3—C2—H2A | 111.1 | C11A—C12A—C7A | 116.4 (12) |
N1—C2—H2B | 111.1 | C11A—C12A—C13A | 125.6 (12) |
C3—C2—H2B | 111.1 | C7A—C12A—C13A | 118.1 (13) |
H2A—C2—H2B | 109.0 | C11B—C12B—C7B | 119.2 (13) |
C4A—C3A—C2A | 120.5 (14) | C11B—C12B—C13B | 125.7 (13) |
C4A—C3A—H3AA | 119.7 | C7B—C12B—C13B | 115.1 (13) |
C2A—C3A—H3AA | 119.7 | C14A—C13A—C12A | 121.4 (13) |
C4B—C3B—C2B | 117.9 (14) | C14A—C13A—H13A | 119.3 |
C4B—C3B—H3BA | 121.0 | C12A—C13A—H13A | 119.3 |
C2B—C3B—H3BA | 121.0 | C14B—C13B—C12B | 122.6 (13) |
N2—C3—C2 | 104.9 (14) | C14B—C13B—H13B | 118.7 |
N2—C3—H3A | 110.8 | C12B—C13B—H13B | 118.7 |
C2—C3—H3A | 110.8 | C13A—C14A—C5A | 121.6 (13) |
N2—C3—H3B | 110.8 | C13A—C14A—H14A | 119.2 |
C2—C3—H3B | 110.8 | C5A—C14A—H14A | 119.2 |
H3A—C3—H3B | 108.9 | C13B—C14B—C5B | 122.4 (13) |
C3A—C4A—C5A | 120.0 (14) | C13B—C14B—H14B | 118.8 |
C3A—C4A—H4AA | 120.0 | C5B—C14B—H14B | 118.8 |
C5A—C4A—H4AA | 120.0 | O2—Cl1—O3 | 109.6 (7) |
C3B—C4B—C5B | 119.9 (13) | O2—Cl1—O1 | 109.6 (6) |
C3B—C4B—H4BA | 120.0 | O3—Cl1—O1 | 109.5 (6) |
C5B—C4B—H4BA | 120.0 | O2—Cl1—O4 | 109.9 (6) |
N1—C4—H4A | 109.5 | O3—Cl1—O4 | 108.9 (6) |
N1—C4—H4B | 109.5 | O1—Cl1—O4 | 109.4 (6) |
H4A—C4—H4B | 109.5 | O8—Cl2—O6 | 110.6 (9) |
N1—C4—H4C | 109.5 | O8—Cl2—O5 | 111.2 (7) |
H4A—C4—H4C | 109.5 | O6—Cl2—O5 | 110.5 (7) |
H4B—C4—H4C | 109.5 | O8—Cl2—O7 | 108.2 (8) |
C4A—C5A—C14A | 124.1 (13) | O6—Cl2—O7 | 107.9 (8) |
C4A—C5A—C6A | 116.8 (12) | O5—Cl2—O7 | 108.3 (7) |
C5—N2—C1—N1 | −174.7 (14) | C5A—C6A—C7A—N8A | −177.9 (13) |
C3—N2—C1—N1 | 1.8 (18) | N1A—C6A—C7A—C12A | 178.5 (13) |
C5—N2—C1—Se1 | 3 (2) | C5A—C6A—C7A—C12A | 2 (2) |
C3—N2—C1—Se1 | 179.3 (12) | C9B—N8B—C7B—C6B | −179.1 (12) |
C4—N1—C1—N2 | −179.7 (15) | C9B—N8B—C7B—C12B | 1 (2) |
C2—N1—C1—N2 | 0.1 (18) | N1B—C6B—C7B—N8B | −0.7 (19) |
C4—N1—C1—Se1 | 3 (2) | C5B—C6B—C7B—N8B | 178.3 (12) |
C2—N1—C1—Se1 | −177.5 (11) | N1B—C6B—C7B—C12B | 179.5 (12) |
C6A—N1A—C2A—C3A | 1 (2) | C5B—C6B—C7B—C12B | −1 (2) |
C6B—N1B—C2B—C3B | −2 (2) | C7A—N8A—C9A—C10A | 2 (2) |
C1—N1—C2—C3 | −1.9 (18) | C7B—N8B—C9B—C10B | 0 (2) |
C4—N1—C2—C3 | 177.9 (14) | N8A—C9A—C10A—C11A | −3 (2) |
N1A—C2A—C3A—C4A | 1 (2) | N8B—C9B—C10B—C11B | −2 (2) |
N1B—C2B—C3B—C4B | 1 (2) | C9A—C10A—C11A—C12A | 0 (2) |
C1—N2—C3—C2 | −2.9 (19) | C9B—C10B—C11B—C12B | 2 (2) |
C5—N2—C3—C2 | 173.7 (14) | C10A—C11A—C12A—C7A | 2 (2) |
N1—C2—C3—N2 | 2.8 (18) | C10A—C11A—C12A—C13A | −177.7 (15) |
C2A—C3A—C4A—C5A | 0 (2) | N8A—C7A—C12A—C11A | −3 (2) |
C2B—C3B—C4B—C5B | 0 (2) | C6A—C7A—C12A—C11A | 177.0 (14) |
C3A—C4A—C5A—C14A | 179.4 (13) | N8A—C7A—C12A—C13A | 177.3 (13) |
C3A—C4A—C5A—C6A | −2 (2) | C6A—C7A—C12A—C13A | −3 (2) |
C3B—C4B—C5B—C6B | 0 (2) | C10B—C11B—C12B—C7B | −1 (2) |
C3B—C4B—C5B—C14B | 179.5 (14) | C10B—C11B—C12B—C13B | 176.5 (14) |
C2A—N1A—C6A—C7A | −179.4 (13) | N8B—C7B—C12B—C11B | 0 (2) |
C2A—N1A—C6A—C5A | −3 (2) | C6B—C7B—C12B—C11B | 179.4 (13) |
C4A—C5A—C6A—N1A | 4 (2) | N8B—C7B—C12B—C13B | −178.2 (12) |
C14A—C5A—C6A—N1A | −177.7 (12) | C6B—C7B—C12B—C13B | 1.6 (19) |
C4A—C5A—C6A—C7A | −179.8 (13) | C11A—C12A—C13A—C14A | −176.9 (16) |
C14A—C5A—C6A—C7A | −2 (2) | C7A—C12A—C13A—C14A | 3 (2) |
C2B—N1B—C6B—C7B | −178.2 (13) | C11B—C12B—C13B—C14B | −177.8 (15) |
C2B—N1B—C6B—C5B | 3 (2) | C7B—C12B—C13B—C14B | 0 (2) |
C4B—C5B—C6B—N1B | −2 (2) | C12A—C13A—C14A—C5A | −2 (2) |
C14B—C5B—C6B—N1B | 178.9 (13) | C4A—C5A—C14A—C13A | 179.7 (14) |
C4B—C5B—C6B—C7B | 179.4 (12) | C6A—C5A—C14A—C13A | 2 (2) |
C14B—C5B—C6B—C7B | 0 (2) | C12B—C13B—C14B—C5B | −1 (2) |
C9A—N8A—C7A—C12A | 0 (2) | C4B—C5B—C14B—C13B | −177.9 (14) |
C9A—N8A—C7A—C6A | −179.4 (13) | C6B—C5B—C14B—C13B | 2 (2) |
N1A—C6A—C7A—N8A | −1.6 (18) |
[Cu(C10H8N2)2(C3H6N2S)](ClO4)2 | F(000) = 1380 |
Mr = 676.97 | Dx = 1.636 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 58 reflections |
a = 11.493 (7) Å | θ = 12.5–14.5° |
b = 11.861 (9) Å | µ = 1.12 mm−1 |
c = 20.166 (10) Å | T = 150 K |
V = 2749 (3) Å3 | Ingot, green |
Z = 4 | 0.54 × 0.27 × 0.18 mm |
Stoe Stadi-4 four-circle diffractometer | 3420 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 25.1°, θmin = 2.7° |
ω/θ scans | h = −6→13 |
Absorption correction: numerical (X-RED; Stoe & Cie, 1996) | k = 0→14 |
Tmin = 0.747, Tmax = 0.840 | l = 0→23 |
4959 measured reflections | 3 standard reflections every 60 min |
3932 independent reflections | intensity decay: random variation +/−6% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: included in calculated positions; except for N-H (found in delta-F) |
R[F2 > 2σ(F2)] = 0.061 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.164 | w = 1/[σ2(Fo2) + (0.084P)2 + 11.27P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.004 |
3932 reflections | Δρmax = 1.18 e Å−3 |
377 parameters | Δρmin = −0.56 e Å−3 |
2 restraints | Absolute structure: Flack (1983), 1186 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.00 (3) |
[Cu(C10H8N2)2(C3H6N2S)](ClO4)2 | V = 2749 (3) Å3 |
Mr = 676.97 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 11.493 (7) Å | µ = 1.12 mm−1 |
b = 11.861 (9) Å | T = 150 K |
c = 20.166 (10) Å | 0.54 × 0.27 × 0.18 mm |
Stoe Stadi-4 four-circle diffractometer | 3420 reflections with I > 2σ(I) |
Absorption correction: numerical (X-RED; Stoe & Cie, 1996) | Rint = 0.024 |
Tmin = 0.747, Tmax = 0.840 | 3 standard reflections every 60 min |
4959 measured reflections | intensity decay: random variation +/−6% |
3932 independent reflections |
R[F2 > 2σ(F2)] = 0.061 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.164 | w = 1/[σ2(Fo2) + (0.084P)2 + 11.27P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | Δρmax = 1.18 e Å−3 |
3932 reflections | Δρmin = −0.56 e Å−3 |
377 parameters | Absolute structure: Flack (1983), 1186 Friedel pairs |
2 restraints | Absolute structure parameter: 0.00 (3) |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.96775 (8) | 0.91289 (8) | 0.24280 (4) | 0.0358 (3) | |
S1 | 0.9224 (2) | 0.72098 (16) | 0.22395 (10) | 0.0407 (6) | |
N1 | 0.7710 (7) | 0.6768 (6) | 0.1268 (3) | 0.042 (2) | |
N1A | 0.8532 (6) | 1.0305 (5) | 0.2796 (3) | 0.0323 (17) | |
N1B | 1.0403 (6) | 0.8705 (5) | 0.3285 (3) | 0.0353 (19) | |
N2 | 0.6996 (7) | 0.7828 (6) | 0.2041 (3) | 0.041 (2) | |
N8A | 0.8936 (6) | 0.9646 (5) | 0.1587 (3) | 0.0343 (19) | |
N8B | 1.1380 (6) | 0.9586 (5) | 0.2231 (3) | 0.036 (2) | |
C1 | 0.7915 (8) | 0.7291 (7) | 0.1835 (4) | 0.036 (3) | |
C2 | 0.6538 (10) | 0.7063 (8) | 0.1005 (4) | 0.054 (3) | |
C2A | 0.8478 (8) | 1.0708 (7) | 0.3423 (4) | 0.039 (3) | |
C2B | 0.9823 (9) | 0.8208 (7) | 0.3791 (4) | 0.047 (3) | |
C3 | 0.5977 (9) | 0.7619 (8) | 0.1612 (5) | 0.052 (3) | |
C3A | 0.7747 (8) | 1.1572 (7) | 0.3604 (4) | 0.038 (3) | |
C3B | 1.0354 (9) | 0.7944 (7) | 0.4378 (4) | 0.047 (3) | |
C4A | 0.7084 (8) | 1.2078 (7) | 0.3130 (4) | 0.044 (3) | |
C4B | 1.1526 (10) | 0.8186 (8) | 0.4450 (5) | 0.056 (3) | |
C5A | 0.7131 (7) | 1.1672 (6) | 0.2484 (4) | 0.037 (2) | |
C5B | 1.2121 (8) | 0.8678 (7) | 0.3934 (4) | 0.042 (3) | |
C6A | 0.7867 (6) | 1.0798 (6) | 0.2331 (3) | 0.031 (2) | |
C6B | 1.1541 (7) | 0.8941 (6) | 0.3355 (4) | 0.035 (2) | |
C7A | 0.8058 (7) | 1.0353 (6) | 0.1650 (4) | 0.033 (2) | |
C7B | 1.2099 (8) | 0.9447 (6) | 0.2759 (4) | 0.037 (3) | |
C9A | 0.9182 (8) | 0.9202 (7) | 0.0986 (4) | 0.042 (3) | |
C9B | 1.1809 (9) | 1.0071 (7) | 0.1683 (4) | 0.044 (3) | |
C10A | 0.8531 (9) | 0.9482 (7) | 0.0432 (4) | 0.046 (3) | |
C10B | 1.2963 (8) | 1.0428 (8) | 0.1638 (5) | 0.047 (3) | |
C11A | 0.7601 (9) | 1.0201 (7) | 0.0495 (4) | 0.048 (3) | |
C11B | 1.3678 (9) | 1.0253 (8) | 0.2169 (5) | 0.054 (3) | |
C12A | 0.7347 (8) | 1.0636 (6) | 0.1114 (4) | 0.040 (3) | |
C12B | 1.3261 (8) | 0.9759 (7) | 0.2738 (4) | 0.043 (3) | |
H1 | 0.840 (4) | 0.654 (7) | 0.111 (4) | 0.0500* | |
H5AA | 0.66560 | 1.19980 | 0.21490 | 0.0450* | |
H2 | 0.699 (8) | 0.807 (7) | 0.2465 (17) | 0.0490* | |
H4AA | 0.65970 | 1.26980 | 0.32390 | 0.0520* | |
H2B | 0.61040 | 0.63830 | 0.08650 | 0.0650* | |
H2C | 0.65920 | 0.75950 | 0.06280 | 0.0650* | |
H3AA | 0.77040 | 1.18120 | 0.40520 | 0.0460* | |
H3A | 0.55810 | 0.83320 | 0.14920 | 0.0620* | |
H3B | 0.54120 | 0.71080 | 0.18290 | 0.0620* | |
H2AA | 0.89650 | 1.03810 | 0.37520 | 0.0470* | |
H9AA | 0.98130 | 0.86900 | 0.09430 | 0.0500* | |
H5BA | 1.29280 | 0.88360 | 0.39760 | 0.0510* | |
H4BA | 1.19150 | 0.80130 | 0.48520 | 0.0680* | |
H3BA | 0.99290 | 0.76020 | 0.47280 | 0.0570* | |
H2BA | 0.90210 | 0.80380 | 0.37360 | 0.0570* | |
H9BA | 1.13110 | 1.01750 | 0.13120 | 0.0520* | |
H10A | 0.87270 | 0.91780 | 0.00100 | 0.0550* | |
H10B | 1.32450 | 1.07840 | 0.12470 | 0.0560* | |
H11A | 0.71410 | 1.03960 | 0.01210 | 0.0580* | |
H11B | 1.44710 | 1.04740 | 0.21450 | 0.0650* | |
H12A | 0.66970 | 1.11200 | 0.11740 | 0.0480* | |
H12B | 1.37570 | 0.96340 | 0.31080 | 0.0520* | |
Cl1 | 0.92029 (19) | 0.60874 (17) | −0.01995 (8) | 0.0404 (6) | |
O1 | 0.9866 (6) | 0.5334 (5) | −0.0602 (3) | 0.053 (2) | |
O2 | 0.9693 (7) | 0.6148 (8) | 0.0446 (3) | 0.084 (3) | |
O3 | 0.8035 (7) | 0.5678 (8) | −0.0143 (4) | 0.079 (3) | |
O4 | 0.9191 (7) | 0.7161 (6) | −0.0490 (4) | 0.071 (3) | |
Cl2 | 0.57729 (18) | 0.85245 (17) | 0.37624 (9) | 0.0366 (6) | |
O5 | 0.6038 (7) | 0.9054 (7) | 0.3145 (3) | 0.076 (3) | |
O6 | 0.5155 (7) | 0.9312 (7) | 0.4150 (3) | 0.081 (3) | |
O7 | 0.5067 (7) | 0.7602 (7) | 0.3633 (5) | 0.088 (4) | |
O8 | 0.6832 (6) | 0.8203 (7) | 0.4081 (4) | 0.070 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0329 (5) | 0.0419 (5) | 0.0327 (4) | 0.0017 (5) | 0.0028 (4) | 0.0067 (4) |
S1 | 0.0391 (11) | 0.0356 (9) | 0.0474 (11) | 0.0044 (10) | 0.0002 (10) | 0.0068 (8) |
N1 | 0.049 (5) | 0.044 (4) | 0.032 (3) | −0.004 (4) | 0.003 (3) | 0.000 (3) |
N1A | 0.024 (3) | 0.040 (3) | 0.033 (3) | −0.001 (3) | 0.001 (3) | 0.005 (3) |
N1B | 0.039 (4) | 0.031 (3) | 0.036 (3) | 0.000 (3) | 0.004 (3) | 0.001 (3) |
N2 | 0.035 (4) | 0.052 (4) | 0.036 (3) | −0.001 (4) | 0.003 (3) | −0.003 (3) |
N8A | 0.040 (4) | 0.031 (3) | 0.032 (3) | 0.000 (3) | 0.004 (3) | 0.006 (3) |
N8B | 0.035 (4) | 0.031 (3) | 0.042 (4) | 0.001 (3) | 0.007 (3) | −0.007 (3) |
C1 | 0.038 (5) | 0.037 (4) | 0.034 (4) | −0.001 (4) | 0.005 (4) | 0.009 (3) |
C2 | 0.064 (7) | 0.058 (5) | 0.041 (5) | −0.003 (5) | −0.009 (5) | 0.001 (4) |
C2A | 0.038 (5) | 0.049 (5) | 0.030 (4) | −0.003 (4) | −0.005 (4) | 0.000 (3) |
C2B | 0.047 (6) | 0.050 (5) | 0.045 (5) | 0.006 (5) | −0.003 (5) | 0.011 (4) |
C3 | 0.049 (6) | 0.055 (5) | 0.051 (5) | 0.005 (5) | 0.001 (5) | 0.009 (4) |
C3A | 0.033 (5) | 0.046 (5) | 0.036 (4) | −0.008 (4) | 0.004 (4) | −0.001 (3) |
C3B | 0.050 (6) | 0.056 (5) | 0.035 (4) | 0.008 (5) | 0.007 (4) | 0.017 (4) |
C4A | 0.041 (5) | 0.038 (4) | 0.052 (5) | −0.001 (4) | 0.015 (4) | 0.000 (4) |
C4B | 0.063 (7) | 0.057 (6) | 0.049 (5) | 0.012 (6) | −0.004 (5) | 0.007 (4) |
C5A | 0.031 (4) | 0.041 (4) | 0.039 (4) | −0.002 (4) | 0.002 (4) | 0.017 (4) |
C5B | 0.037 (5) | 0.051 (5) | 0.039 (4) | 0.008 (4) | −0.001 (4) | −0.002 (4) |
C6A | 0.028 (4) | 0.034 (4) | 0.031 (3) | −0.011 (4) | 0.004 (3) | 0.006 (3) |
C6B | 0.035 (4) | 0.035 (4) | 0.035 (4) | 0.011 (4) | 0.002 (3) | −0.004 (3) |
C7A | 0.035 (5) | 0.022 (3) | 0.042 (4) | −0.006 (4) | −0.007 (4) | 0.011 (3) |
C7B | 0.036 (5) | 0.030 (4) | 0.044 (4) | 0.002 (4) | 0.002 (4) | 0.001 (3) |
C9A | 0.047 (5) | 0.041 (4) | 0.038 (4) | −0.010 (5) | 0.010 (4) | 0.000 (3) |
C9B | 0.049 (6) | 0.043 (4) | 0.039 (4) | 0.003 (4) | 0.008 (4) | 0.006 (4) |
C10A | 0.059 (6) | 0.041 (4) | 0.037 (4) | −0.012 (5) | 0.012 (4) | 0.004 (3) |
C10B | 0.043 (5) | 0.051 (5) | 0.047 (5) | −0.011 (5) | 0.020 (5) | −0.004 (4) |
C11A | 0.055 (6) | 0.047 (5) | 0.043 (5) | −0.018 (5) | −0.005 (4) | 0.008 (4) |
C11B | 0.043 (5) | 0.052 (5) | 0.066 (6) | −0.006 (5) | 0.017 (5) | −0.025 (5) |
C12A | 0.042 (5) | 0.036 (4) | 0.042 (4) | −0.007 (4) | −0.005 (4) | 0.011 (3) |
C12B | 0.039 (5) | 0.039 (4) | 0.051 (5) | −0.003 (4) | −0.002 (4) | −0.006 (4) |
Cl1 | 0.0430 (11) | 0.0530 (11) | 0.0251 (8) | 0.0040 (10) | −0.0003 (8) | 0.0021 (8) |
O1 | 0.050 (4) | 0.060 (4) | 0.049 (3) | 0.000 (4) | 0.003 (3) | −0.011 (3) |
O2 | 0.075 (5) | 0.149 (7) | 0.029 (3) | 0.040 (6) | −0.019 (3) | −0.016 (4) |
O3 | 0.058 (5) | 0.113 (6) | 0.066 (4) | −0.017 (5) | 0.016 (4) | −0.018 (4) |
O4 | 0.071 (5) | 0.074 (4) | 0.068 (4) | 0.023 (4) | 0.019 (4) | 0.024 (4) |
Cl2 | 0.0304 (10) | 0.0500 (11) | 0.0293 (8) | 0.0011 (10) | −0.0002 (8) | −0.0026 (8) |
O5 | 0.078 (5) | 0.097 (5) | 0.053 (4) | 0.014 (5) | 0.021 (4) | 0.022 (4) |
O6 | 0.068 (5) | 0.109 (6) | 0.066 (4) | 0.031 (5) | −0.010 (4) | −0.052 (4) |
O7 | 0.044 (5) | 0.069 (5) | 0.151 (8) | −0.009 (4) | −0.003 (5) | −0.007 (5) |
O8 | 0.046 (4) | 0.099 (6) | 0.064 (4) | 0.014 (4) | −0.013 (4) | 0.008 (4) |
Cu1—S1 | 2.366 (3) | C4B—C5B | 1.375 (13) |
Cu1—N1A | 2.057 (7) | C5A—C6A | 1.373 (10) |
Cu1—N1B | 1.984 (6) | C5B—C6B | 1.380 (12) |
Cu1—N8A | 1.995 (6) | C6A—C7A | 1.488 (10) |
Cu1—N8B | 2.069 (7) | C6B—C7B | 1.489 (11) |
Cl1—O1 | 1.428 (7) | C7A—C12A | 1.396 (12) |
Cl1—O2 | 1.420 (7) | C7B—C12B | 1.387 (13) |
Cl1—O3 | 1.432 (9) | C9A—C10A | 1.385 (12) |
Cl1—O4 | 1.402 (7) | C9B—C10B | 1.395 (14) |
Cl2—O5 | 1.427 (7) | C10A—C11A | 1.373 (14) |
Cl2—O6 | 1.410 (8) | C10B—C11B | 1.366 (14) |
Cl2—O7 | 1.387 (9) | C11A—C12A | 1.382 (12) |
Cl2—O8 | 1.428 (8) | C11B—C12B | 1.375 (13) |
S1—C1 | 1.714 (9) | C2—H2B | 0.9900 |
N1—C2 | 1.489 (14) | C2—H2C | 0.9900 |
N1—C1 | 1.322 (10) | C2A—H2AA | 0.9500 |
N1A—C2A | 1.353 (10) | C2B—H2BA | 0.9500 |
N1A—C6A | 1.344 (9) | C3—H3A | 0.9900 |
N1B—C6B | 1.345 (11) | C3—H3B | 0.9900 |
N1B—C2B | 1.354 (11) | C3A—H3AA | 0.9500 |
N2—C1 | 1.302 (12) | C3B—H3BA | 0.9500 |
N2—C3 | 1.477 (13) | C4A—H4AA | 0.9500 |
N8A—C7A | 1.318 (10) | C4B—H4BA | 0.9500 |
N8A—C9A | 1.351 (10) | C5A—H5AA | 0.9500 |
N8B—C7B | 1.358 (11) | C5B—H5BA | 0.9500 |
N8B—C9B | 1.340 (11) | C9A—H9AA | 0.9500 |
N1—H1 | 0.90 (5) | C9B—H9BA | 0.9500 |
N2—H2 | 0.90 (4) | C10A—H10A | 0.9500 |
C2—C3 | 1.533 (14) | C10B—H10B | 0.9500 |
C2A—C3A | 1.375 (12) | C11A—H11A | 0.9500 |
C2B—C3B | 1.368 (12) | C11B—H11B | 0.9500 |
C3A—C4A | 1.362 (12) | C12A—H12A | 0.9500 |
C3B—C4B | 1.385 (15) | C12B—H12B | 0.9500 |
C4A—C5A | 1.390 (11) | ||
S1—Cu1—N1A | 124.72 (19) | C5B—C6B—C7B | 124.5 (8) |
S1—Cu1—N1B | 89.35 (18) | N1B—C6B—C5B | 120.8 (7) |
S1—Cu1—N8A | 93.73 (18) | C6A—C7A—C12A | 122.9 (7) |
S1—Cu1—N8B | 115.44 (18) | N8A—C7A—C12A | 121.8 (7) |
N1A—Cu1—N1B | 97.3 (3) | N8A—C7A—C6A | 115.3 (7) |
N1A—Cu1—N8A | 79.9 (3) | N8B—C7B—C6B | 114.8 (7) |
N1A—Cu1—N8B | 119.8 (2) | C6B—C7B—C12B | 123.2 (7) |
N1B—Cu1—N8A | 176.7 (2) | N8B—C7B—C12B | 122.0 (7) |
N1B—Cu1—N8B | 80.6 (3) | N8A—C9A—C10A | 121.1 (8) |
N8A—Cu1—N8B | 99.2 (3) | N8B—C9B—C10B | 122.3 (8) |
O1—Cl1—O2 | 109.9 (5) | C9A—C10A—C11A | 119.7 (8) |
O1—Cl1—O3 | 109.5 (5) | C9B—C10B—C11B | 118.4 (9) |
O1—Cl1—O4 | 109.7 (4) | C10A—C11A—C12A | 118.7 (8) |
O2—Cl1—O3 | 108.4 (5) | C10B—C11B—C12B | 120.6 (9) |
O2—Cl1—O4 | 109.9 (5) | C7A—C12A—C11A | 119.1 (8) |
O3—Cl1—O4 | 109.4 (5) | C7B—C12B—C11B | 118.4 (8) |
O5—Cl2—O6 | 107.4 (5) | N1—C2—H2C | 112.00 |
O5—Cl2—O7 | 107.9 (5) | C3—C2—H2B | 112.00 |
O5—Cl2—O8 | 109.1 (5) | N1—C2—H2B | 111.00 |
O6—Cl2—O7 | 109.4 (5) | C3—C2—H2C | 111.00 |
O6—Cl2—O8 | 110.9 (5) | H2B—C2—H2C | 109.00 |
O7—Cl2—O8 | 111.9 (5) | N1A—C2A—H2AA | 119.00 |
Cu1—S1—C1 | 102.5 (3) | C3A—C2A—H2AA | 119.00 |
C1—N1—C2 | 111.0 (7) | N1B—C2B—H2BA | 119.00 |
Cu1—N1A—C6A | 114.1 (5) | C3B—C2B—H2BA | 119.00 |
Cu1—N1A—C2A | 127.3 (6) | N2—C3—H3B | 111.00 |
C2A—N1A—C6A | 118.2 (7) | N2—C3—H3A | 111.00 |
Cu1—N1B—C2B | 124.1 (6) | H3A—C3—H3B | 109.00 |
Cu1—N1B—C6B | 116.6 (5) | C2—C3—H3A | 111.00 |
C2B—N1B—C6B | 119.4 (7) | C2—C3—H3B | 111.00 |
C1—N2—C3 | 112.0 (7) | C2A—C3A—H3AA | 121.00 |
C7A—N8A—C9A | 119.6 (7) | C4A—C3A—H3AA | 120.00 |
Cu1—N8A—C7A | 116.2 (5) | C2B—C3B—H3BA | 121.00 |
Cu1—N8A—C9A | 123.6 (5) | C4B—C3B—H3BA | 121.00 |
C7B—N8B—C9B | 118.4 (7) | C3A—C4A—H4AA | 121.00 |
Cu1—N8B—C9B | 128.2 (6) | C5A—C4A—H4AA | 121.00 |
Cu1—N8B—C7B | 113.2 (5) | C5B—C4B—H4BA | 120.00 |
C1—N1—H1 | 107 (5) | C3B—C4B—H4BA | 120.00 |
C2—N1—H1 | 138 (5) | C4A—C5A—H5AA | 120.00 |
C3—N2—H2 | 127 (6) | C6A—C5A—H5AA | 120.00 |
C1—N2—H2 | 118 (6) | C6B—C5B—H5BA | 120.00 |
S1—C1—N1 | 122.8 (7) | C4B—C5B—H5BA | 120.00 |
N1—C1—N2 | 111.2 (8) | N8A—C9A—H9AA | 119.00 |
S1—C1—N2 | 126.0 (6) | C10A—C9A—H9AA | 119.00 |
N1—C2—C3 | 101.4 (7) | N8B—C9B—H9BA | 119.00 |
N1A—C2A—C3A | 122.7 (8) | C10B—C9B—H9BA | 119.00 |
N1B—C2B—C3B | 122.2 (9) | C11A—C10A—H10A | 120.00 |
N2—C3—C2 | 101.9 (8) | C9A—C10A—H10A | 120.00 |
C2A—C3A—C4A | 119.0 (8) | C9B—C10B—H10B | 121.00 |
C2B—C3B—C4B | 118.5 (9) | C11B—C10B—H10B | 121.00 |
C3A—C4A—C5A | 118.9 (8) | C10A—C11A—H11A | 121.00 |
C3B—C4B—C5B | 119.5 (9) | C12A—C11A—H11A | 121.00 |
C4A—C5A—C6A | 119.7 (7) | C10B—C11B—H11B | 120.00 |
C4B—C5B—C6B | 119.7 (9) | C12B—C11B—H11B | 120.00 |
N1A—C6A—C7A | 114.0 (6) | C7A—C12A—H12A | 120.00 |
C5A—C6A—C7A | 124.5 (6) | C11A—C12A—H12A | 120.00 |
N1A—C6A—C5A | 121.5 (6) | C11B—C12B—H12B | 121.00 |
N1B—C6B—C7B | 114.7 (7) | C7B—C12B—H12B | 121.00 |
C2—N1—C1—S1 | −175.4 (6) | C3B—C4B—C5B—C6B | 1.0 (13) |
C2—N1—C1—N2 | 6.4 (10) | C4A—C5A—C6A—C7A | −175.1 (7) |
C1—N1—C2—C3 | −13.8 (9) | C4A—C5A—C6A—N1A | 1.4 (11) |
C6A—N1A—C2A—C3A | 2.1 (12) | C4B—C5B—C6B—N1B | −1.1 (12) |
C2A—N1A—C6A—C5A | −1.3 (11) | C4B—C5B—C6B—C7B | −178.4 (8) |
C2A—N1A—C6A—C7A | 175.5 (7) | N1A—C6A—C7A—C12A | 170.8 (7) |
C6B—N1B—C2B—C3B | 0.6 (12) | N1A—C6A—C7A—N8A | −7.7 (10) |
C2B—N1B—C6B—C5B | 0.3 (11) | C5A—C6A—C7A—C12A | −12.5 (12) |
C2B—N1B—C6B—C7B | 177.8 (7) | C5A—C6A—C7A—N8A | 169.0 (7) |
C3—N2—C1—S1 | −173.4 (7) | N1B—C6B—C7B—N8B | −0.6 (9) |
C3—N2—C1—N1 | 4.7 (10) | C5B—C6B—C7B—C12B | −3.3 (12) |
C1—N2—C3—C2 | −13.0 (9) | N1B—C6B—C7B—C12B | 179.3 (7) |
C9A—N8A—C7A—C6A | −179.6 (7) | C5B—C6B—C7B—N8B | 176.9 (7) |
C9A—N8A—C7A—C12A | 1.9 (11) | N8A—C7A—C12A—C11A | −2.8 (12) |
C7A—N8A—C9A—C10A | 0.4 (12) | C6A—C7A—C12A—C11A | 178.8 (7) |
C9B—N8B—C7B—C6B | 177.8 (7) | N8B—C7B—C12B—C11B | 1.9 (12) |
C9B—N8B—C7B—C12B | −2.0 (11) | C6B—C7B—C12B—C11B | −177.9 (8) |
C7B—N8B—C9B—C10B | 0.4 (12) | N8A—C9A—C10A—C11A | −1.6 (13) |
N1—C2—C3—N2 | 14.9 (8) | N8B—C9B—C10B—C11B | 1.3 (14) |
N1A—C2A—C3A—C4A | −2.9 (13) | C9A—C10A—C11A—C12A | 0.6 (13) |
N1B—C2B—C3B—C4B | −0.7 (13) | C9B—C10B—C11B—C12B | −1.4 (14) |
C2A—C3A—C4A—C5A | 2.8 (13) | C10A—C11A—C12A—C7A | 1.5 (13) |
C2B—C3B—C4B—C5B | −0.2 (13) | C10B—C11B—C12B—C7B | −0.2 (13) |
C3A—C4A—C5A—C6A | −2.1 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.90 (5) | 2.05 (7) | 2.913 (11) | 160 (7) |
N2—H2···O5 | 0.90 (4) | 2.11 (7) | 2.878 (10) | 143 (7) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Cu(C12H8N2)2(C5H10N2Se)](ClO4)2 | [Cu(C10H8N2)2(C3H6N2S)](ClO4)2 |
Mr | 799.96 | 676.97 |
Crystal system, space group | Orthorhombic, P212121 | Orthorhombic, P212121 |
Temperature (K) | 150 | 150 |
a, b, c (Å) | 11.606 (6), 12.155 (2), 22.120 (4) | 11.493 (7), 11.861 (9), 20.166 (10) |
V (Å3) | 3120.5 (18) | 2749 (3) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 2.10 | 1.12 |
Crystal size (mm) | 0.51 × 0.14 × 0.10 | 0.54 × 0.27 × 0.18 |
Data collection | ||
Diffractometer | Stoe Stadi-4 four-circle diffractometer | Stoe Stadi-4 four-circle diffractometer |
Absorption correction | Numerical (X-RED; Stoe & Cie, 1996) | Numerical (X-RED; Stoe & Cie, 1996) |
Tmin, Tmax | 0.700, 0.830 | 0.747, 0.840 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3878, 3511, 2621 | 4959, 3932, 3420 |
Rint | 0.052 | 0.024 |
(sin θ/λ)max (Å−1) | 0.596 | 0.596 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.074, 0.144, 1.23 | 0.061, 0.164, 1.01 |
No. of reflections | 3511 | 3932 |
No. of parameters | 427 | 377 |
No. of restraints | 147 | 2 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
w = 1/[σ2(Fo2) + 24.56P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.084P)2 + 11.27P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.80, −0.67 | 1.18, −0.56 |
Absolute structure | Flack (1983), 780 Friedel pairs | Flack (1983), 1186 Friedel pairs |
Absolute structure parameter | 0.41 (3) | 0.00 (3) |
Computer programs: STADI4 (Stoe & Cie, 1996), STADI4, X-RED (Stoe & Cie, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), Mercury (Macrae et al., 2006), enCIFer (Allen et al., 2004), PLATON (Spek, 2003) and publCIF (Westrip, 2007).
Cu1—N1A | 1.980 (10) | Cu1—N8A | 2.114 (11) |
Cu1—N1B | 1.999 (10) | Cu1—Se1 | 2.491 (3) |
Cu1—N8B | 2.080 (10) | ||
N1A—Cu1—N1B | 177.6 (5) | N8B—Cu1—N8A | 118.5 (4) |
N1A—Cu1—N8B | 97.4 (4) | N1A—Cu1—Se1 | 93.4 (3) |
N1B—Cu1—N8B | 81.6 (4) | N1B—Cu1—Se1 | 88.9 (3) |
N1A—Cu1—N8A | 81.4 (4) | N8B—Cu1—Se1 | 128.8 (3) |
N1B—Cu1—N8A | 97.1 (4) | N8A—Cu1—Se1 | 112.5 (3) |
Cu1—S1 | 2.366 (3) | Cu1—N8A | 1.995 (6) |
Cu1—N1A | 2.057 (7) | Cu1—N8B | 2.069 (7) |
Cu1—N1B | 1.984 (6) | ||
S1—Cu1—N1A | 124.72 (19) | N1A—Cu1—N8A | 79.9 (3) |
S1—Cu1—N1B | 89.35 (18) | N1A—Cu1—N8B | 119.8 (2) |
S1—Cu1—N8A | 93.73 (18) | N1B—Cu1—N8A | 176.7 (2) |
S1—Cu1—N8B | 115.44 (18) | N1B—Cu1—N8B | 80.6 (3) |
N1A—Cu1—N1B | 97.3 (3) | N8A—Cu1—N8B | 99.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.90 (5) | 2.05 (7) | 2.913 (11) | 160 (7) |
N2—H2···O5 | 0.90 (4) | 2.11 (7) | 2.878 (10) | 143 (7) |
Copper plays an important role in redox-active metalloproteins where evidence for metal–sulfur coordination is consistent with a chemical environment favouring the copper(I) state (Karlin et al., 1982; Lippard & Berg, 1994). Thio- and seleno-amido ligands, –NR–CS(Se)–, react with copper(II) salts yielding S– and Se-bonded copper(I) complexes. In particular, several copper(I) complexes have been prepared and structurally characterized by reacting ligands such as imidazolidine-, thiazolidine-, benzothiazole- and oxazolidine-2-thione and, when possible, also their -2-selone parent compounds with CuII salts (Hussein et al., 1985; Devillanova et al., 1986; Battaglia et al. 1979). One approach to studying the redox and coordination chemistry of CuII in the presence of soft reducing S– or Se-ketonic donors is to consider complexes of polydentate ligands containing N atoms in which copper is stabilized in the oxidation state two (McKee, 1993).
To preserve the CuII oxidation state in the reaction with thiourea and other reducing ligands, Montenero & Pelizzi (1972) have used as starting material copper(II) chelated complexes with π-acceptor ligands such as 1,10-phenanthroline (phen) and 2,2'-bipyridine (bipy). Here we report the synthesis and structural characterization of (dimethylimidazolidine-2-selone-κSe)bis(1,10-phenanthroline- κ2N,N')copper(II) bis(perchlorate), (I), and bis(2,2'-bipyridyl-κ2N,N')(imidazolidine-2-thione-κS)copper(II) bis(perchlorate), (II).
The CuII centre in (I) is coordinated in a distorted trigonal–bipyramidal (TBP) environment by four N donors from the two phen ligands and by an Se atom from the dimethylimidazolidine-2-selone ligand (Fig. 1 [the atom labelling in the phen ligands does not match that in CIF/text; please supply correctly labelled figure]). The equatorial plane is defined by the Se atom and by two N donors (N8A and N8B) from different phen ligands, with angles subtended at Cu1 ranging from 112.5 (3) to 128.8 (3)°. The axial sites are occupied by the two remaining N donors (N1A and N1B) from each phen ligand and the N1A—Cu1—N1B angle is 177.6 (5)°. Owing to the narrow bite angle of the phen ligands (ca 80°) which bridge pairs of axial and equatorial sites, the N1A—Cu1—N1B vector deviates significantly from orthogonality with the equatorial plane. A TBP coordination geometry is not common in the case of CuII complexes, particularly when they contain ligands with reducing properties (Barclay et al., 1963; Ferrari et al., 1973, 1975). Thus (I) represents, to our knowledge, the only case of a structurally characterized CuII mixed-ligand complex featuring a TBP coordination geometry in which the coordination environment contains an Se-atom donor and chelating ligands such as 1,10-phenanthroline (phen) and 2,2'-bipyridine (bipy) with strong π-conjugation properties.
The Cu—N distances range from 1.980 (10) to 2.114 (11) Å, while the Cu—Se distance is 2.491 (3) Å (Table 1). Each phen ligand participates in one long and one short Cu—N bond to the metal, an asymmetry that we attribute to the steric congestion between the two bidentate ligands. This congestion is also expressed in the high degree of twist between the phen units; the dihedral angle between the least-squares mean planes through the five-membered rings Cu1/N1A/C6A/C7A/N8A and Cu1/N1B/C6B/C7B/N8B is 59.6 (3)°. The N—C—C—N torsion angles are essentially zero, indicating that there is no twisting of this unit in either phen ligand. The dihedral angle between the plane through the dimethylimidazolidine-2-selone ring and that through the phen ligand containing atoms N1A and N8A [16.3 (6)°] is much smaller than the corresponding dihedral angle involving the other phen ligand [57.4 (4)°], and therefore only the former is involved in a possible π–π stacking with the N1A–C6A ring [the centroid–centroid distance is 3.506 (10) Å and the perpendicular distance 3.466 (10) Å].
Intermolecular π–π contacts with a centroid–centroid distance of 3.829 (10) Å between the imidazolidine ring in one cation and the central ring (C5B–C7B/C12B–C14B) of the phen ligand in a neighbouring cation at (1/2 + x, 3/2 - y, -z) (Fig. 2) give rise to chains running along the a axis in (I). The mutual inclination of these rings is only 1.6 (6)° and the perpendicular distance is 3.515 (10) Å.
In (II), the CuII centre also occupies a distorted trigonal–bipyramidal (TBP) environment, similarly consisting of four N donors from two bipy ligands but with the fifth site occupied by an S-atom donor from an imidazolidine-2-thione ligand (Fig. 3). The equatorial plane is defined by coordination from the S atom and atoms N1A and N8B from different bipy ligands; the angles subtended at Cu1 occupy a somewhat narrower range between 115.44 (18) and 124.72 (19)°, and the axial donors N1B and N8A subtend an angle of 176.7 (2)° at Cu1. The principal deviation from ideal trigonal–bipyamidal geometry is the result of the narrow bite angle of the bipy ligand; there is a significant deviation from orthogonality between the equatorial plane and the N1B—Cu1—N8A vector.
The Cu—N distances range from 1.984 (6) to 2.069 (7) Å, while the Cu—S distance is 2.366 (3) Å (Table 2). This latter is of the same order of magnitude as that found in CuI–thiourea complexes (Okaya & Knobler, 1964), a feature also observed in CuII–thiourea complexes containing coordinated bipy or phen-chelating ligands (Ferrari et al., 1973, 1975). This observation suggests charge transfer to the metal centre by the chelating ligands through a π-donor effect. The same pattern of asymmetry seen in (I) appears in the Cu—N distances, and in the twist between the Cu1/N1A/C6A/C7A/N8A and Cu1/N1B/C6B/C7B/N8B rings [61.2 (2)°)]. While the N—C—C—N torsion angle in one ligand is essentially zero as in (I), the value of -7.7 (10)° for N1A—C6A—C7A–N8A indicates a slight twist for the other. There are again marked differences in the dihedral angles between the imidazolidine ring and the five-membered rings formed by the coordination of the two bipy ligands. For the Cu1/N1A/C6A/C7A/N8A ring this angle is 59.2 (2)°, but the lower value of 30.9 (3)° suggests the possibility of π–π interaction between the imidazolidine and C7A–C12A rings; the relevant centroid–centroid distance is 3.559 (7) Å, the perpendicular distance is 3.455 (7) Å and the rings are mutually inclined at 24.1 (3)°.
A major difference between the two structures arises from the presence of imidazolidine N—H hydrogen-bond donors in (II) instead of the NMe groups in (I). This leads to the formation of two N—H···O hydrogen bonds to perchlorate O atoms (Fig. 3 and Table 3).
The imidazolidine ring and a pyridyl ring in two neighbouring cations related by the symmetry operation (2 - x, -1/2 + y, 1/2 - z) are involved in intermolecular π–π contacts with a centroid–centroid distance of 3.820 (10) Å to form chains of cations (Fig. 4) running along the b axis in (II). The rings are inclined to each other at an angle of only 6.7 (6)° and the perpendicular distance is 3.392 (10) Å.