Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106054163/dn3030sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106054163/dn3030Isup2.hkl |
CCDC reference: 638305
The title complex was obtained as a by-product in the preparation of [Cu3(dpyam)2(µ-NCS)2(µ-OOCCH3)4] by adding Cu(O2CCH3)2.nH2O (1.5 mmol) to a warm solution of dpyam (1.0 mmol) in dimethylformamide (DMF) (10.0 ml). A solution of NaNCS (1.0 mmol) in DMF (5.0 ml) was then added and the resulting green solution was allowed to evaporate slowly at room temperature. After several days, green crystals of (I) were formed. The crystals were filtered off, washed with mother liquor and dried in air. IR data (KBr, ν, cm-1): 2084 (vs), 1654 (s), 1589 (s), 1556 (s), 1486 (vs), 1424 (s), 1237 (m), 1160 (m), 1019 (m), 784 (m).
H atoms attached to atoms N3 and N6 were located in difference Fourier maps and refined with a DFIX (SHELXTL; Sheldrick, 2000b) restraint of N—H = 0.86 (1) Å. All H atoms attached to C atoms were fixed geometrically and treated as riding, with C—H = 0.93 Å (aromatic) or 0.96 Å (methyl), and with Uiso(H) = 1.2Ueq(aromatic) or 1.5Ueq(methyl).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000b); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL (Sheldrick 2000b) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL.
[Cu2(C2H3O2)3(NCS)(C10H9N3)2] | V = 1505.09 (4) Å3 |
Mr = 704.70 | Z = 2 |
Triclinic, P1 | F(000) = 720 |
Hall symbol: -P 1 | Dx = 1.555 Mg m−3 |
a = 9.6949 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.4915 (2) Å | θ = 1.3–30.4° |
c = 16.9001 (2) Å | µ = 1.54 mm−1 |
α = 97.645 (1)° | T = 273 K |
β = 101.458 (1)° | Polygon, green |
γ = 113.215 (1)° | 0.30 × 0.18 × 0.08 mm |
Siemens SMART CCD area-detector diffractometer | 5440 independent reflections |
Radiation source: fine-focus sealed tube | 4510 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ω scans | θmax = 25.4°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000a) | h = −11→11 |
Tmin = 0.732, Tmax = 0.891 | k = −12→8 |
8178 measured reflections | l = −19→20 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0423P)2 + 1.2895P] where P = (Fo2 + 2Fc2)/3 |
5440 reflections | (Δ/σ)max = 0.001 |
399 parameters | Δρmax = 0.34 e Å−3 |
2 restraints | Δρmin = −0.49 e Å−3 |
[Cu2(C2H3O2)3(NCS)(C10H9N3)2] | γ = 113.215 (1)° |
Mr = 704.70 | V = 1505.09 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.6949 (2) Å | Mo Kα radiation |
b = 10.4915 (2) Å | µ = 1.54 mm−1 |
c = 16.9001 (2) Å | T = 273 K |
α = 97.645 (1)° | 0.30 × 0.18 × 0.08 mm |
β = 101.458 (1)° |
Siemens SMART CCD area-detector diffractometer | 5440 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000a) | 4510 reflections with I > 2σ(I) |
Tmin = 0.732, Tmax = 0.891 | Rint = 0.021 |
8178 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 2 restraints |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.34 e Å−3 |
5440 reflections | Δρmin = −0.49 e Å−3 |
399 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 | 0.65426 (4) | 0.43795 (4) | 0.31247 (2) | 0.02719 (11) | |
Cu2 | 0.49437 (5) | 0.71429 (4) | 0.14258 (2) | 0.03208 (12) | |
S1 | 0.11020 (11) | 0.07683 (10) | 0.21812 (7) | 0.0524 (3) | |
O1 | 0.7660 (2) | 0.3883 (2) | 0.23370 (13) | 0.0326 (5) | |
O2 | 0.9782 (3) | 0.4853 (3) | 0.34124 (14) | 0.0432 (6) | |
O3 | 0.6492 (3) | 0.5871 (2) | 0.25150 (13) | 0.0344 (5) | |
O4 | 0.7010 (3) | 0.8018 (2) | 0.22820 (13) | 0.0344 (5) | |
O5 | 0.3752 (3) | 0.6718 (3) | 0.22647 (15) | 0.0406 (6) | |
O6 | 0.4062 (4) | 0.8763 (3) | 0.19568 (17) | 0.0546 (7) | |
N1 | 0.6402 (3) | 0.5470 (3) | 0.41686 (15) | 0.0289 (6) | |
N2 | 0.6877 (3) | 0.3020 (3) | 0.37880 (16) | 0.0309 (6) | |
N3 | 0.8092 (3) | 0.4802 (3) | 0.50463 (16) | 0.0316 (6) | |
N4 | 0.3479 (3) | 0.5391 (3) | 0.05710 (16) | 0.0321 (6) | |
N5 | 0.5758 (3) | 0.8142 (3) | 0.05899 (16) | 0.0302 (6) | |
N6 | 0.3664 (3) | 0.6495 (3) | −0.05682 (17) | 0.0368 (7) | |
N7 | 0.4131 (3) | 0.2952 (3) | 0.25318 (18) | 0.0409 (7) | |
C1 | 0.5591 (4) | 0.6271 (4) | 0.4093 (2) | 0.0361 (8) | |
H1 | 0.4898 | 0.6104 | 0.3582 | 0.043* | |
C2 | 0.5748 (5) | 0.7317 (4) | 0.4736 (2) | 0.0443 (9) | |
H2 | 0.5165 | 0.7837 | 0.4664 | 0.053* | |
C3 | 0.6804 (5) | 0.7577 (4) | 0.5499 (2) | 0.0486 (9) | |
H3 | 0.6965 | 0.8304 | 0.5938 | 0.058* | |
C4 | 0.7600 (4) | 0.6758 (4) | 0.5599 (2) | 0.0419 (8) | |
H4 | 0.8298 | 0.6914 | 0.6107 | 0.050* | |
C5 | 0.7346 (4) | 0.5671 (3) | 0.49191 (19) | 0.0287 (7) | |
C6 | 0.7732 (4) | 0.3457 (3) | 0.45805 (19) | 0.0284 (7) | |
C7 | 0.8302 (4) | 0.2590 (4) | 0.4971 (2) | 0.0386 (8) | |
H7 | 0.8892 | 0.2912 | 0.5523 | 0.046* | |
C8 | 0.7977 (5) | 0.1273 (4) | 0.4528 (3) | 0.0552 (11) | |
H8 | 0.8370 | 0.0698 | 0.4774 | 0.066* | |
C9 | 0.7054 (5) | 0.0788 (4) | 0.3707 (2) | 0.0529 (10) | |
H9 | 0.6810 | −0.0113 | 0.3398 | 0.063* | |
C10 | 0.6516 (4) | 0.1679 (3) | 0.3367 (2) | 0.0414 (8) | |
H10 | 0.5876 | 0.1352 | 0.2825 | 0.050* | |
C11 | 0.2836 (4) | 0.4185 (4) | 0.0848 (2) | 0.0384 (8) | |
H11 | 0.3168 | 0.4230 | 0.1411 | 0.046* | |
C12 | 0.1726 (4) | 0.2913 (4) | 0.0339 (2) | 0.0443 (9) | |
H12 | 0.1322 | 0.2108 | 0.0549 | 0.053* | |
C13 | 0.1218 (5) | 0.2856 (4) | −0.0500 (2) | 0.0478 (9) | |
H13 | 0.0444 | 0.2012 | −0.0857 | 0.057* | |
C14 | 0.1859 (4) | 0.4046 (4) | −0.0804 (2) | 0.0425 (8) | |
H14 | 0.1532 | 0.4014 | −0.1365 | 0.051* | |
C15 | 0.3021 (4) | 0.5317 (3) | −0.02479 (19) | 0.0305 (7) | |
C16 | 0.4981 (4) | 0.7779 (3) | −0.02211 (18) | 0.0288 (7) | |
C17 | 0.5478 (4) | 0.8682 (4) | −0.0755 (2) | 0.0367 (8) | |
H17 | 0.4918 | 0.8422 | −0.1311 | 0.044* | |
C18 | 0.6791 (4) | 0.9945 (4) | −0.0449 (2) | 0.0407 (8) | |
H18 | 0.7138 | 1.0550 | −0.0795 | 0.049* | |
C19 | 0.7603 (4) | 1.0312 (4) | 0.0388 (2) | 0.0434 (9) | |
H19 | 0.8504 | 1.1162 | 0.0608 | 0.052* | |
C20 | 0.7057 (4) | 0.9410 (4) | 0.0879 (2) | 0.0393 (8) | |
H20 | 0.7597 | 0.9671 | 0.1439 | 0.047* | |
C21 | 0.9122 (4) | 0.4239 (3) | 0.2670 (2) | 0.0319 (7) | |
C22 | 1.0019 (5) | 0.3883 (5) | 0.2110 (3) | 0.0545 (10) | |
H22A | 1.1090 | 0.4577 | 0.2297 | 0.082* | |
H22B | 0.9572 | 0.3891 | 0.1551 | 0.082* | |
H22C | 0.9963 | 0.2953 | 0.2126 | 0.082* | |
C23 | 0.7351 (4) | 0.7197 (3) | 0.26862 (19) | 0.0294 (7) | |
C24 | 0.8841 (4) | 0.7883 (4) | 0.3382 (2) | 0.0485 (10) | |
H24A | 0.8607 | 0.8061 | 0.3900 | 0.073* | |
H24B | 0.9524 | 0.8768 | 0.3288 | 0.073* | |
H24C | 0.9343 | 0.7256 | 0.3401 | 0.073* | |
C25 | 0.3538 (4) | 0.7851 (4) | 0.2360 (2) | 0.0387 (8) | |
C26 | 0.2705 (6) | 0.8090 (5) | 0.2987 (3) | 0.0678 (13) | |
H26A | 0.3458 | 0.8719 | 0.3493 | 0.102* | |
H26B | 0.2090 | 0.7194 | 0.3096 | 0.102* | |
H26C | 0.2035 | 0.8510 | 0.2772 | 0.102* | |
C27 | 0.2882 (4) | 0.2042 (3) | 0.2387 (2) | 0.0343 (7) | |
H5 | 0.866 (4) | 0.497 (4) | 0.5537 (13) | 0.034 (9)* | |
H15 | 0.329 (4) | 0.637 (4) | −0.1093 (12) | 0.042 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0318 (2) | 0.0273 (2) | 0.0202 (2) | 0.01257 (16) | 0.00274 (15) | 0.00595 (15) |
Cu2 | 0.0356 (2) | 0.0328 (2) | 0.0199 (2) | 0.00848 (17) | 0.00413 (16) | 0.00678 (16) |
S1 | 0.0348 (5) | 0.0399 (5) | 0.0647 (7) | 0.0051 (4) | 0.0030 (5) | 0.0071 (5) |
O1 | 0.0327 (12) | 0.0411 (13) | 0.0209 (11) | 0.0168 (10) | 0.0009 (9) | 0.0045 (9) |
O2 | 0.0363 (13) | 0.0502 (15) | 0.0295 (14) | 0.0127 (11) | −0.0020 (11) | 0.0016 (11) |
O3 | 0.0451 (13) | 0.0329 (12) | 0.0269 (12) | 0.0196 (11) | 0.0060 (10) | 0.0098 (9) |
O4 | 0.0380 (13) | 0.0321 (12) | 0.0282 (12) | 0.0140 (10) | −0.0002 (10) | 0.0098 (9) |
O5 | 0.0509 (15) | 0.0411 (14) | 0.0349 (13) | 0.0212 (12) | 0.0165 (11) | 0.0139 (11) |
O6 | 0.080 (2) | 0.0583 (17) | 0.0510 (17) | 0.0435 (16) | 0.0320 (15) | 0.0291 (14) |
N1 | 0.0311 (14) | 0.0293 (13) | 0.0237 (13) | 0.0111 (11) | 0.0065 (11) | 0.0068 (11) |
N2 | 0.0354 (14) | 0.0272 (13) | 0.0250 (14) | 0.0116 (11) | 0.0025 (11) | 0.0048 (11) |
N3 | 0.0349 (15) | 0.0307 (14) | 0.0218 (14) | 0.0132 (12) | −0.0024 (12) | 0.0012 (11) |
N4 | 0.0341 (14) | 0.0337 (14) | 0.0265 (14) | 0.0138 (12) | 0.0064 (11) | 0.0065 (11) |
N5 | 0.0296 (14) | 0.0337 (14) | 0.0230 (13) | 0.0112 (12) | 0.0037 (11) | 0.0065 (11) |
N6 | 0.0381 (16) | 0.0397 (16) | 0.0181 (14) | 0.0071 (13) | −0.0016 (12) | 0.0052 (12) |
N7 | 0.0339 (16) | 0.0429 (17) | 0.0335 (16) | 0.0097 (14) | −0.0013 (13) | 0.0073 (13) |
C1 | 0.0361 (18) | 0.045 (2) | 0.0341 (18) | 0.0224 (16) | 0.0103 (15) | 0.0169 (15) |
C2 | 0.058 (2) | 0.045 (2) | 0.046 (2) | 0.0335 (19) | 0.0222 (19) | 0.0151 (17) |
C3 | 0.068 (3) | 0.042 (2) | 0.037 (2) | 0.026 (2) | 0.0155 (19) | 0.0039 (16) |
C4 | 0.055 (2) | 0.0406 (19) | 0.0245 (17) | 0.0196 (17) | 0.0046 (16) | 0.0026 (14) |
C5 | 0.0321 (16) | 0.0277 (16) | 0.0236 (16) | 0.0103 (13) | 0.0073 (13) | 0.0064 (12) |
C6 | 0.0295 (16) | 0.0296 (16) | 0.0253 (16) | 0.0126 (13) | 0.0053 (13) | 0.0078 (13) |
C7 | 0.045 (2) | 0.0383 (19) | 0.0296 (18) | 0.0195 (16) | −0.0006 (15) | 0.0090 (14) |
C8 | 0.070 (3) | 0.044 (2) | 0.054 (3) | 0.034 (2) | 0.000 (2) | 0.0138 (19) |
C9 | 0.074 (3) | 0.036 (2) | 0.041 (2) | 0.027 (2) | −0.001 (2) | 0.0024 (16) |
C10 | 0.055 (2) | 0.0267 (17) | 0.0316 (19) | 0.0135 (16) | 0.0015 (16) | 0.0030 (14) |
C11 | 0.043 (2) | 0.0360 (18) | 0.0357 (19) | 0.0161 (16) | 0.0093 (16) | 0.0143 (15) |
C12 | 0.047 (2) | 0.0331 (19) | 0.051 (2) | 0.0133 (16) | 0.0177 (18) | 0.0123 (16) |
C13 | 0.044 (2) | 0.0352 (19) | 0.047 (2) | 0.0076 (16) | 0.0071 (18) | −0.0046 (16) |
C14 | 0.044 (2) | 0.040 (2) | 0.0291 (18) | 0.0123 (17) | 0.0005 (16) | −0.0018 (15) |
C15 | 0.0316 (17) | 0.0344 (17) | 0.0235 (16) | 0.0141 (14) | 0.0053 (13) | 0.0042 (13) |
C16 | 0.0292 (16) | 0.0361 (17) | 0.0214 (15) | 0.0164 (14) | 0.0031 (13) | 0.0060 (13) |
C17 | 0.0415 (19) | 0.047 (2) | 0.0233 (17) | 0.0202 (16) | 0.0069 (14) | 0.0128 (14) |
C18 | 0.045 (2) | 0.045 (2) | 0.038 (2) | 0.0187 (17) | 0.0159 (16) | 0.0215 (16) |
C19 | 0.041 (2) | 0.0381 (19) | 0.042 (2) | 0.0081 (16) | 0.0065 (16) | 0.0146 (16) |
C20 | 0.0340 (18) | 0.0404 (19) | 0.0299 (18) | 0.0073 (15) | −0.0006 (14) | 0.0071 (15) |
C21 | 0.0349 (18) | 0.0288 (16) | 0.0296 (18) | 0.0145 (14) | 0.0036 (14) | 0.0049 (13) |
C22 | 0.046 (2) | 0.064 (3) | 0.050 (2) | 0.025 (2) | 0.0117 (19) | −0.002 (2) |
C23 | 0.0313 (16) | 0.0365 (18) | 0.0240 (16) | 0.0169 (14) | 0.0091 (13) | 0.0095 (13) |
C24 | 0.0320 (19) | 0.053 (2) | 0.051 (2) | 0.0122 (17) | −0.0021 (17) | 0.0221 (19) |
C25 | 0.0403 (19) | 0.053 (2) | 0.0294 (18) | 0.0251 (17) | 0.0107 (15) | 0.0132 (16) |
C26 | 0.085 (3) | 0.082 (3) | 0.073 (3) | 0.056 (3) | 0.049 (3) | 0.032 (3) |
C27 | 0.0353 (19) | 0.0348 (18) | 0.0282 (17) | 0.0144 (16) | 0.0011 (14) | 0.0060 (14) |
Cu1—O3 | 1.996 (2) | C4—C5 | 1.414 (4) |
Cu1—N2 | 2.011 (3) | C4—H4 | 0.9300 |
Cu1—O1 | 2.013 (2) | C6—C7 | 1.406 (4) |
Cu1—N1 | 2.030 (3) | C7—C8 | 1.363 (5) |
Cu1—N7 | 2.150 (3) | C7—H7 | 0.9300 |
Cu2—N4 | 1.976 (3) | C8—C9 | 1.395 (6) |
Cu2—N5 | 1.976 (3) | C8—H8 | 0.9300 |
Cu2—O5 | 1.989 (2) | C9—C10 | 1.372 (5) |
Cu2—O4 | 1.999 (2) | C9—H9 | 0.9300 |
Cu2—O6 | 2.339 (3) | C10—H10 | 0.9300 |
S1—C27 | 1.645 (3) | C11—C12 | 1.370 (5) |
O1—C21 | 1.295 (4) | C11—H11 | 0.9300 |
O2—C21 | 1.240 (4) | C12—C13 | 1.391 (5) |
O3—C23 | 1.264 (4) | C12—H12 | 0.9300 |
O4—C23 | 1.268 (4) | C13—C14 | 1.377 (5) |
O5—C25 | 1.280 (4) | C13—H13 | 0.9300 |
O6—C25 | 1.250 (4) | C14—C15 | 1.412 (4) |
N1—C5 | 1.344 (4) | C14—H14 | 0.9300 |
N1—C1 | 1.360 (4) | C16—C17 | 1.409 (4) |
N2—C6 | 1.337 (4) | C17—C18 | 1.367 (5) |
N2—C10 | 1.362 (4) | C17—H17 | 0.9300 |
N3—C5 | 1.382 (4) | C18—C19 | 1.394 (5) |
N3—C6 | 1.393 (4) | C18—H18 | 0.9300 |
N3—H5 | 0.852 (18) | C19—C20 | 1.362 (5) |
N4—C15 | 1.349 (4) | C19—H19 | 0.9300 |
N4—C11 | 1.364 (4) | C20—H20 | 0.9300 |
N5—C16 | 1.348 (4) | C21—C22 | 1.510 (5) |
N5—C20 | 1.362 (4) | C22—H22A | 0.9600 |
N6—C15 | 1.383 (4) | C22—H22B | 0.9600 |
N6—C16 | 1.387 (4) | C22—H22C | 0.9600 |
N6—H15 | 0.860 (18) | C23—C24 | 1.506 (5) |
N7—C27 | 1.160 (4) | C24—H24A | 0.9600 |
C1—C2 | 1.377 (5) | C24—H24B | 0.9600 |
C1—H1 | 0.9300 | C24—H24C | 0.9600 |
C2—C3 | 1.395 (5) | C25—C26 | 1.507 (5) |
C2—H2 | 0.9300 | C26—H26A | 0.9600 |
C3—C4 | 1.369 (5) | C26—H26B | 0.9600 |
C3—H3 | 0.9300 | C26—H26C | 0.9600 |
O3—Cu1—N2 | 173.03 (10) | C7—C8—H8 | 120.1 |
O3—Cu1—O1 | 86.58 (9) | C9—C8—H8 | 120.1 |
N2—Cu1—O1 | 90.75 (10) | C10—C9—C8 | 118.1 (3) |
O3—Cu1—N1 | 91.91 (10) | C10—C9—H9 | 121.0 |
N2—Cu1—N1 | 87.77 (10) | C8—C9—H9 | 121.0 |
O1—Cu1—N1 | 154.89 (10) | N2—C10—C9 | 123.0 (3) |
O3—Cu1—N7 | 93.57 (11) | N2—C10—H10 | 118.5 |
N2—Cu1—N7 | 93.31 (11) | C9—C10—H10 | 118.5 |
O1—Cu1—N7 | 103.31 (10) | N4—C11—C12 | 123.2 (3) |
N1—Cu1—N7 | 101.80 (11) | N4—C11—H11 | 118.4 |
N4—Cu2—N5 | 92.41 (11) | C12—C11—H11 | 118.4 |
N4—Cu2—O5 | 95.05 (11) | C11—C12—C13 | 118.2 (3) |
N5—Cu2—O5 | 156.16 (11) | C11—C12—H12 | 120.9 |
N4—Cu2—O4 | 142.76 (10) | C13—C12—H12 | 120.9 |
N5—Cu2—O4 | 94.46 (10) | C14—C13—C12 | 120.1 (3) |
O5—Cu2—O4 | 93.21 (10) | C14—C13—H13 | 119.9 |
N4—Cu2—O6 | 120.17 (11) | C12—C13—H13 | 119.9 |
N5—Cu2—O6 | 96.50 (10) | C13—C14—C15 | 118.8 (3) |
O5—Cu2—O6 | 60.28 (9) | C13—C14—H14 | 120.6 |
O4—Cu2—O6 | 95.34 (10) | C15—C14—H14 | 120.6 |
C21—O1—Cu1 | 114.53 (19) | N4—C15—N6 | 120.9 (3) |
C23—O3—Cu1 | 131.0 (2) | N4—C15—C14 | 121.3 (3) |
C23—O4—Cu2 | 116.6 (2) | N6—C15—C14 | 117.8 (3) |
C25—O5—Cu2 | 97.3 (2) | N5—C16—N6 | 121.5 (3) |
C25—O6—Cu2 | 82.2 (2) | N5—C16—C17 | 121.4 (3) |
C5—N1—C1 | 118.1 (3) | N6—C16—C17 | 117.1 (3) |
C5—N1—Cu1 | 121.4 (2) | C18—C17—C16 | 119.5 (3) |
C1—N1—Cu1 | 118.9 (2) | C18—C17—H17 | 120.3 |
C6—N2—C10 | 118.2 (3) | C16—C17—H17 | 120.3 |
C6—N2—Cu1 | 122.3 (2) | C17—C18—C19 | 119.1 (3) |
C10—N2—Cu1 | 117.8 (2) | C17—C18—H18 | 120.5 |
C5—N3—C6 | 129.1 (3) | C19—C18—H18 | 120.5 |
C5—N3—H5 | 116 (2) | C20—C19—C18 | 119.1 (3) |
C6—N3—H5 | 112 (2) | C20—C19—H19 | 120.5 |
C15—N4—C11 | 118.3 (3) | C18—C19—H19 | 120.5 |
C15—N4—Cu2 | 125.2 (2) | N5—C20—C19 | 123.1 (3) |
C11—N4—Cu2 | 116.4 (2) | N5—C20—H20 | 118.4 |
C16—N5—C20 | 117.9 (3) | C19—C20—H20 | 118.4 |
C16—N5—Cu2 | 124.2 (2) | O2—C21—O1 | 122.6 (3) |
C20—N5—Cu2 | 117.0 (2) | O2—C21—C22 | 120.5 (3) |
C15—N6—C16 | 130.8 (3) | O1—C21—C22 | 116.9 (3) |
C15—N6—H15 | 115 (2) | C21—C22—H22A | 109.5 |
C16—N6—H15 | 113 (2) | C21—C22—H22B | 109.5 |
C27—N7—Cu1 | 162.6 (3) | H22A—C22—H22B | 109.5 |
N1—C1—C2 | 123.1 (3) | C21—C22—H22C | 109.5 |
N1—C1—H1 | 118.4 | H22A—C22—H22C | 109.5 |
C2—C1—H1 | 118.4 | H22B—C22—H22C | 109.5 |
C1—C2—C3 | 118.3 (3) | O3—C23—O4 | 122.0 (3) |
C1—C2—H2 | 120.8 | O3—C23—C24 | 121.4 (3) |
C3—C2—H2 | 120.8 | O4—C23—C24 | 116.6 (3) |
C4—C3—C2 | 119.7 (3) | C23—C24—H24A | 109.5 |
C4—C3—H3 | 120.1 | C23—C24—H24B | 109.5 |
C2—C3—H3 | 120.1 | H24A—C24—H24B | 109.5 |
C3—C4—C5 | 118.9 (3) | C23—C24—H24C | 109.5 |
C3—C4—H4 | 120.5 | H24A—C24—H24C | 109.5 |
C5—C4—H4 | 120.5 | H24B—C24—H24C | 109.5 |
N1—C5—N3 | 120.3 (3) | O6—C25—O5 | 120.2 (3) |
N1—C5—C4 | 121.6 (3) | O6—C25—C26 | 120.9 (3) |
N3—C5—C4 | 118.1 (3) | O5—C25—C26 | 118.8 (3) |
N2—C6—N3 | 120.5 (3) | C25—C26—H26A | 109.5 |
N2—C6—C7 | 121.7 (3) | C25—C26—H26B | 109.5 |
N3—C6—C7 | 117.8 (3) | H26A—C26—H26B | 109.5 |
C8—C7—C6 | 119.1 (3) | C25—C26—H26C | 109.5 |
C8—C7—H7 | 120.5 | H26A—C26—H26C | 109.5 |
C6—C7—H7 | 120.5 | H26B—C26—H26C | 109.5 |
C7—C8—C9 | 119.8 (3) | N7—C27—S1 | 179.2 (3) |
O3—Cu1—O1—C21 | 109.1 (2) | C1—N1—C5—N3 | 174.5 (3) |
N2—Cu1—O1—C21 | −64.5 (2) | Cu1—N1—C5—N3 | −19.9 (4) |
N1—Cu1—O1—C21 | 21.9 (4) | C1—N1—C5—C4 | −5.2 (5) |
N7—Cu1—O1—C21 | −158.1 (2) | Cu1—N1—C5—C4 | 160.5 (3) |
O1—Cu1—O3—C23 | −99.2 (3) | C6—N3—C5—N1 | −19.5 (5) |
N1—Cu1—O3—C23 | 55.7 (3) | C6—N3—C5—C4 | 160.1 (3) |
N7—Cu1—O3—C23 | 157.7 (3) | C3—C4—C5—N1 | 3.3 (5) |
N4—Cu2—O4—C23 | −38.1 (3) | C3—C4—C5—N3 | −176.3 (3) |
N5—Cu2—O4—C23 | −138.0 (2) | C10—N2—C6—N3 | −178.0 (3) |
O5—Cu2—O4—C23 | 64.6 (2) | Cu1—N2—C6—N3 | 16.9 (4) |
O6—Cu2—O4—C23 | 125.0 (2) | C10—N2—C6—C7 | 2.2 (5) |
N4—Cu2—O5—C25 | −122.1 (2) | Cu1—N2—C6—C7 | −162.9 (3) |
N5—Cu2—O5—C25 | −14.3 (4) | C5—N3—C6—N2 | 21.5 (5) |
O4—Cu2—O5—C25 | 94.3 (2) | C5—N3—C6—C7 | −158.7 (3) |
O6—Cu2—O5—C25 | 0.0 (2) | N2—C6—C7—C8 | 0.2 (5) |
N4—Cu2—O6—C25 | 77.6 (2) | N3—C6—C7—C8 | −179.6 (4) |
N5—Cu2—O6—C25 | 174.2 (2) | C6—C7—C8—C9 | −1.8 (6) |
O5—Cu2—O6—C25 | 0.0 (2) | C7—C8—C9—C10 | 0.8 (7) |
O4—Cu2—O6—C25 | −90.6 (2) | C6—N2—C10—C9 | −3.3 (6) |
O3—Cu1—N1—C5 | −133.4 (2) | Cu1—N2—C10—C9 | 162.6 (3) |
N2—Cu1—N1—C5 | 39.6 (2) | C8—C9—C10—N2 | 1.8 (7) |
O1—Cu1—N1—C5 | −47.4 (4) | C15—N4—C11—C12 | −1.4 (5) |
N7—Cu1—N1—C5 | 132.5 (2) | Cu2—N4—C11—C12 | 175.6 (3) |
O3—Cu1—N1—C1 | 32.1 (2) | N4—C11—C12—C13 | −0.8 (6) |
N2—Cu1—N1—C1 | −154.8 (2) | C11—C12—C13—C14 | 1.8 (6) |
O1—Cu1—N1—C1 | 118.1 (3) | C12—C13—C14—C15 | −0.6 (6) |
N7—Cu1—N1—C1 | −61.9 (3) | C11—N4—C15—N6 | −178.2 (3) |
O1—Cu1—N2—C6 | 116.8 (3) | Cu2—N4—C15—N6 | 5.1 (4) |
N1—Cu1—N2—C6 | −38.1 (3) | C11—N4—C15—C14 | 2.6 (5) |
N7—Cu1—N2—C6 | −139.8 (3) | Cu2—N4—C15—C14 | −174.0 (3) |
O1—Cu1—N2—C10 | −48.4 (3) | C16—N6—C15—N4 | 13.8 (5) |
N1—Cu1—N2—C10 | 156.7 (3) | C16—N6—C15—C14 | −167.0 (3) |
N7—Cu1—N2—C10 | 55.0 (3) | C13—C14—C15—N4 | −1.6 (5) |
N5—Cu2—N4—C15 | −18.2 (3) | C13—C14—C15—N6 | 179.2 (3) |
O5—Cu2—N4—C15 | 139.1 (3) | C20—N5—C16—N6 | 178.8 (3) |
O4—Cu2—N4—C15 | −118.8 (3) | Cu2—N5—C16—N6 | −12.7 (4) |
O6—Cu2—N4—C15 | 80.7 (3) | C20—N5—C16—C17 | −0.7 (5) |
N5—Cu2—N4—C11 | 165.1 (2) | Cu2—N5—C16—C17 | 167.8 (2) |
O5—Cu2—N4—C11 | −37.6 (3) | C15—N6—C16—N5 | −9.7 (5) |
O4—Cu2—N4—C11 | 64.5 (3) | C15—N6—C16—C17 | 169.9 (3) |
O6—Cu2—N4—C11 | −95.9 (2) | N5—C16—C17—C18 | 1.1 (5) |
N4—Cu2—N5—C16 | 21.9 (3) | N6—C16—C17—C18 | −178.5 (3) |
O5—Cu2—N5—C16 | −86.4 (4) | C16—C17—C18—C19 | −0.4 (5) |
O4—Cu2—N5—C16 | 165.2 (3) | C17—C18—C19—C20 | −0.6 (6) |
O6—Cu2—N5—C16 | −98.9 (3) | C16—N5—C20—C19 | −0.3 (5) |
N4—Cu2—N5—C20 | −169.6 (3) | Cu2—N5—C20—C19 | −169.6 (3) |
O5—Cu2—N5—C20 | 82.2 (4) | C18—C19—C20—N5 | 1.0 (6) |
O4—Cu2—N5—C20 | −26.2 (3) | Cu1—O1—C21—O2 | −0.9 (4) |
O6—Cu2—N5—C20 | 69.7 (3) | Cu1—O1—C21—C22 | 179.5 (3) |
O3—Cu1—N7—C27 | −159.3 (10) | Cu1—O3—C23—O4 | −169.8 (2) |
N2—Cu1—N7—C27 | 21.8 (10) | Cu1—O3—C23—C24 | 10.4 (5) |
O1—Cu1—N7—C27 | 113.4 (10) | Cu2—O4—C23—O3 | 5.5 (4) |
N1—Cu1—N7—C27 | −66.6 (10) | Cu2—O4—C23—C24 | −174.8 (2) |
C5—N1—C1—C2 | 3.1 (5) | Cu2—O6—C25—O5 | 0.0 (3) |
Cu1—N1—C1—C2 | −162.9 (3) | Cu2—O6—C25—C26 | 177.5 (4) |
N1—C1—C2—C3 | 0.8 (6) | Cu2—O5—C25—O6 | 0.0 (4) |
C1—C2—C3—C4 | −2.7 (6) | Cu2—O5—C25—C26 | −177.5 (3) |
C2—C3—C4—C5 | 0.7 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H5···O2i | 0.85 (2) | 2.02 (2) | 2.862 (3) | 168 |
N6—H15···O1ii | 0.86 (2) | 2.06 (2) | 2.915 (3) | 178 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C2H3O2)3(NCS)(C10H9N3)2] |
Mr | 704.70 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 273 |
a, b, c (Å) | 9.6949 (2), 10.4915 (2), 16.9001 (2) |
α, β, γ (°) | 97.645 (1), 101.458 (1), 113.215 (1) |
V (Å3) | 1505.09 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.54 |
Crystal size (mm) | 0.30 × 0.18 × 0.08 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000a) |
Tmin, Tmax | 0.732, 0.891 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8178, 5440, 4510 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.099, 1.05 |
No. of reflections | 5440 |
No. of parameters | 399 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.49 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXTL (Sheldrick, 2000b), SHELXTL (Sheldrick 2000b) and PLATON (Spek, 2003).
Cu1—O3 | 1.996 (2) | Cu2—N4 | 1.976 (3) |
Cu1—N2 | 2.011 (3) | Cu2—N5 | 1.976 (3) |
Cu1—O1 | 2.013 (2) | Cu2—O5 | 1.989 (2) |
Cu1—N1 | 2.030 (3) | Cu2—O4 | 1.999 (2) |
Cu1—N7 | 2.150 (3) | Cu2—O6 | 2.339 (3) |
O3—Cu1—N2 | 173.03 (10) | N4—Cu2—N5 | 92.41 (11) |
O3—Cu1—O1 | 86.58 (9) | N4—Cu2—O5 | 95.05 (11) |
N2—Cu1—O1 | 90.75 (10) | N5—Cu2—O5 | 156.16 (11) |
O3—Cu1—N1 | 91.91 (10) | N4—Cu2—O4 | 142.76 (10) |
N2—Cu1—N1 | 87.77 (10) | N5—Cu2—O4 | 94.46 (10) |
O1—Cu1—N1 | 154.89 (10) | O5—Cu2—O4 | 93.21 (10) |
O3—Cu1—N7 | 93.57 (11) | N4—Cu2—O6 | 120.17 (11) |
N2—Cu1—N7 | 93.31 (11) | N5—Cu2—O6 | 96.50 (10) |
O1—Cu1—N7 | 103.31 (10) | O5—Cu2—O6 | 60.28 (9) |
N1—Cu1—N7 | 101.80 (11) | O4—Cu2—O6 | 95.34 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H5···O2i | 0.852 (18) | 2.022 (18) | 2.862 (3) | 168.40 |
N6—H15···O1ii | 0.860 (18) | 2.055 (18) | 2.915 (3) | 177.80 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z. |
The coordination chemistry of copper(II) complexes with various carboxylates has been investigated for many years. Carboxylate chemistry is interesting for two reasons. Firstly, carboxylates play a vital role as ligands in biochemical systems involving mono-, di- or polymetallic active sites, and secondly, polynuclear carboxylates are very good probes for exchange-coupling interactions between adjacent metal ions. Carboxylate groups are known to assume different bridging conformations and the important types are syn–syn, anti–anti and syn–anti (Colacio et al., 1993). It may be noted that structurally characterized examples of syn–anti configuration are far less numerous than those with the syn–syn configuration (Sen et al., 1998). We report here the synthesis and crystal structure of a new syn–anti configuration acetate-bridged complex, [Cu2(dpyam)2(µ-O2CCH3)(O2CCH3)2(NCS)], (I).
The structure of (I) consists of a dinuclear [Cu2(dpyam)2(µ-O2CCH3)(O2CCH3)2(NCS)] unit. The Cu atoms are bridged unsymmetrically by an acetate group in a syn–anti arrangement (Fig. 1). Atoms Cu1 and Cu2 are five-coordinated, with a basal plane consisting of two N atoms of the dpyam ligand and two O atoms of two different acetate ligands. The axial positions of Cu1 and Cu2 are coordinated by N and O atoms from thiocyanate and acetate molecules, respectively (Table 1), leading to a square-pyramidal geometry. The square bases of the copper chromophores are non-planar, with tetrahedral twists of 25.7 (1) and 43.7 (1)° for Cu1 and Cu2, respectively. The Cu atoms lie above the basal plane, at 0.280 (1) Å towards N7 for Cu1 and 0.112 (1) Å towards O6 for Cu2.
The distortion of a square pyramid can be best described by the structural parameter τ (τ = 0 for a square pyramid and τ = 1 for a trigonal bipyramid; Addison et al., 1984), which in this case has values of 0.30 and 0.22 for Cu1 and Cu2, respectively. The copper chromophores can be described as having a distorted square-pyramidal geometry, with a high tetrahedral twist of the square bases. The Cu···Cu distance is 4.800 (3) Å. The dihedral angles between the pyridine rings of the dpyam ligands are 20.9 (1)° for Cu1 and 12.0 (1)° for Cu2. The molecular structure and bridging configuration of (I) are very similar to those of the closely related complexes [Cu(dpyam)(µ-O2CH)(OH2)]n(NO3)n (Youngme et al., 2005) and {[Cu(dpa)(µ-O2CCH3)](ClO4)·0.5THF}n with a single carboxylate bridge (Tanase et al., 2005).
Analysis of the crystal packing of (I) shows hydrogen-bonding interactions between the N—H of the amide and the coordinated and uncoordinated O atoms of the acetate anions, with N—H···O contacts of 2.915 (3) and 2.862 (3) Å. A plot of the hydrogen-bond system forming a one-dimensional structure is given in Fig. 2 and details are given in Table 2. Classical N3—H5···O2i [symmetry code: (i) -x + 2, -y + 1, -z + 1] and N6—H15···O1ii [symmetry code: (ii) -x + 1, -y + 1, -z] intermolecular hydrogen bonds between adjacent dimeric units link them into a one-dimensional chain. The resulting motifs, A and B, in the formalism of graph-set analysis of hydrogen-bond patterns (Etter et al., 1990), are characterized as R22(15) [N3, H5, O2i, C21i, O1i, Cu1i, N1i, C5i, N3i, H5i, O2, C21, Cu1, N1 and C5] and R22(20) [N6, H15, O1ii, Cu1ii, O3ii, C23ii, O4ii, Cu2ii, N4ii, C15ii, N6ii, H15ii, O1, Cu1, O3, C23, O4, Cu2, N4 and C15], respectively.