Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807059247/lh2563sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807059247/lh2563Isup2.hkl |
CCDC reference: 672753
To a solution of Cu(OAc)2(0.14 g, 0.6 mmol) in Dimethyl sulphoxide (3 ml) a suspension of sodium azide(0.039 g, 0.6 mmol) in the ethanol (15 ml) was added and the mixture was stirred for 2 h at 333 K. The solution was filtered after cooled and allowed to stand at room temperature without disturbing, black crystals of of the title compound were obtained after about 3 weeks.
After being located in a difference map, all H-atoms were fixed geometrically at ideal positions and allowed to ride on the parent C atoms with C—H = 0.96Å and Uiso(H)= 1.5Ueq(C).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).
[Cu3(C2H3O2)2(N3)4(C2H6OS)2] | Z = 1 |
Mr = 633.13 | F(000) = 317 |
Triclinic, P1 | Dx = 1.855 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.5205 (9) Å | Cell parameters from 2542 reflections |
b = 8.6624 (9) Å | θ = 2.4–27.0° |
c = 9.4999 (10) Å | µ = 3.02 mm−1 |
α = 90.386 (2)° | T = 293 K |
β = 112.687 (1)° | Block, black |
γ = 116.261 (1)° | 0.30 × 0.20 × 0.20 mm |
V = 566.66 (10) Å3 |
Bruker SMART-CCD diffractometer | 2182 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.060 |
Graphite monochromator | θmax = 27.0°, θmin = 2.4° |
ϕ and ω scans | h = −10→7 |
3467 measured reflections | k = −7→11 |
2404 independent reflections | l = −10→12 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.052P)2 + 0.3521P] where P = (Fo2 + 2Fc2)/3 |
2404 reflections | (Δ/σ)max < 0.001 |
145 parameters | Δρmax = 0.60 e Å−3 |
0 restraints | Δρmin = −0.65 e Å−3 |
[Cu3(C2H3O2)2(N3)4(C2H6OS)2] | γ = 116.261 (1)° |
Mr = 633.13 | V = 566.66 (10) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.5205 (9) Å | Mo Kα radiation |
b = 8.6624 (9) Å | µ = 3.02 mm−1 |
c = 9.4999 (10) Å | T = 293 K |
α = 90.386 (2)° | 0.30 × 0.20 × 0.20 mm |
β = 112.687 (1)° |
Bruker SMART-CCD diffractometer | 2182 reflections with I > 2σ(I) |
3467 measured reflections | Rint = 0.060 |
2404 independent reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.60 e Å−3 |
2404 reflections | Δρmin = −0.65 e Å−3 |
145 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 | 0.81687 (5) | 0.81565 (4) | −0.06003 (4) | 0.03025 (14) | |
Cu2 | 0.5000 | 0.5000 | 0.0000 | 0.03156 (15) | |
C1 | 0.7810 (8) | 1.1353 (5) | 0.2360 (6) | 0.0673 (12) | |
H1A | 0.8966 | 1.1839 | 0.2199 | 0.101* | |
H1B | 0.8111 | 1.1893 | 0.3382 | 0.101* | |
H1C | 0.6854 | 1.1577 | 0.1586 | 0.101* | |
C2 | 0.4761 (7) | 0.8594 (7) | 0.2395 (6) | 0.0707 (13) | |
H2A | 0.4049 | 0.9054 | 0.1643 | 0.106* | |
H2B | 0.5099 | 0.9132 | 0.3429 | 0.106* | |
H2C | 0.3974 | 0.7341 | 0.2218 | 0.106* | |
C3 | 0.2979 (6) | 0.5365 (6) | −0.4771 (4) | 0.0630 (12) | |
H3A | 0.2879 | 0.4330 | −0.5259 | 0.095* | |
H3B | 0.3458 | 0.6318 | −0.5264 | 0.095* | |
H3C | 0.1722 | 0.5130 | −0.4879 | 0.095* | |
C4 | 0.4350 (5) | 0.5860 (4) | −0.3071 (4) | 0.0361 (6) | |
N1 | 1.0712 (4) | 0.9551 (4) | 0.1239 (3) | 0.0449 (7) | |
N2 | 1.1240 (4) | 0.9351 (4) | 0.2578 (3) | 0.0421 (6) | |
N3 | 1.1756 (6) | 0.9171 (6) | 0.3806 (4) | 0.0691 (11) | |
N4 | 0.2460 (4) | 0.4183 (3) | 0.0089 (3) | 0.0328 (5) | |
N5 | 0.1232 (4) | 0.4496 (4) | −0.0825 (3) | 0.0379 (6) | |
N6 | 0.0095 (5) | 0.4816 (5) | −0.1649 (5) | 0.0624 (9) | |
O1 | 0.6009 (3) | 0.7171 (3) | −0.2653 (3) | 0.0432 (6) | |
O2 | 0.3755 (3) | 0.4928 (3) | −0.2207 (3) | 0.0406 (5) | |
O3 | 0.6177 (4) | 0.8295 (3) | 0.0499 (3) | 0.0430 (5) | |
S1 | 0.68907 (12) | 0.90584 (11) | 0.22039 (10) | 0.0401 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0237 (2) | 0.0250 (2) | 0.0280 (2) | 0.00378 (15) | 0.00743 (15) | 0.00848 (14) |
Cu2 | 0.0225 (3) | 0.0298 (3) | 0.0332 (3) | 0.0057 (2) | 0.0115 (2) | 0.0083 (2) |
C1 | 0.080 (3) | 0.0306 (19) | 0.068 (3) | 0.009 (2) | 0.031 (2) | −0.0018 (18) |
C2 | 0.057 (3) | 0.079 (3) | 0.062 (3) | 0.014 (2) | 0.035 (2) | −0.008 (2) |
C3 | 0.046 (2) | 0.071 (3) | 0.0320 (18) | 0.007 (2) | 0.0030 (16) | 0.0070 (17) |
C4 | 0.0317 (15) | 0.0350 (16) | 0.0304 (14) | 0.0103 (13) | 0.0097 (12) | 0.0041 (12) |
N1 | 0.0338 (14) | 0.0375 (15) | 0.0345 (14) | 0.0031 (12) | 0.0040 (11) | 0.0176 (11) |
N2 | 0.0356 (14) | 0.0370 (15) | 0.0372 (15) | 0.0090 (12) | 0.0101 (12) | 0.0122 (11) |
N3 | 0.071 (2) | 0.076 (3) | 0.0393 (18) | 0.026 (2) | 0.0150 (17) | 0.0256 (17) |
N4 | 0.0251 (12) | 0.0272 (12) | 0.0428 (14) | 0.0099 (10) | 0.0148 (11) | 0.0109 (10) |
N5 | 0.0316 (13) | 0.0317 (13) | 0.0458 (15) | 0.0109 (11) | 0.0175 (12) | 0.0118 (11) |
N6 | 0.052 (2) | 0.070 (2) | 0.073 (2) | 0.0381 (19) | 0.0230 (18) | 0.0342 (19) |
O1 | 0.0344 (12) | 0.0334 (11) | 0.0305 (11) | −0.0018 (10) | 0.0059 (9) | 0.0056 (9) |
O2 | 0.0282 (11) | 0.0391 (12) | 0.0337 (11) | 0.0031 (10) | 0.0094 (9) | 0.0067 (9) |
O3 | 0.0450 (13) | 0.0400 (13) | 0.0407 (12) | 0.0177 (11) | 0.0188 (11) | 0.0008 (10) |
S1 | 0.0395 (4) | 0.0351 (4) | 0.0384 (4) | 0.0163 (4) | 0.0118 (3) | 0.0031 (3) |
Cu1—O1 | 1.933 (2) | C2—H2B | 0.9600 |
Cu1—N4i | 1.970 (2) | C2—H2C | 0.9600 |
Cu1—N1 | 1.986 (3) | C3—C4 | 1.500 (4) |
Cu1—N1ii | 2.002 (3) | C3—H3A | 0.9600 |
Cu1—O3 | 2.351 (2) | C3—H3B | 0.9600 |
Cu2—O2 | 1.936 (2) | C3—H3C | 0.9600 |
Cu2—O2i | 1.936 (2) | C4—O2 | 1.245 (4) |
Cu2—N4i | 1.995 (2) | C4—O1 | 1.259 (4) |
Cu2—N4 | 1.995 (2) | N1—N2 | 1.217 (4) |
Cu2—O3 | 2.542 (2) | N1—Cu1ii | 2.002 (3) |
C1—S1 | 1.765 (4) | N2—N3 | 1.116 (4) |
C1—H1A | 0.9600 | N4—N5 | 1.215 (4) |
C1—H1B | 0.9600 | N4—Cu1i | 1.970 (2) |
C1—H1C | 0.9600 | N5—N6 | 1.133 (4) |
C2—S1 | 1.760 (5) | O3—S1 | 1.517 (2) |
C2—H2A | 0.9600 | ||
O1—Cu1—N4i | 92.49 (11) | H2A—C2—H2C | 109.5 |
O1—Cu1—N1 | 166.25 (11) | H2B—C2—H2C | 109.5 |
N4i—Cu1—N1 | 98.17 (11) | C4—C3—H3A | 109.5 |
O1—Cu1—N1ii | 89.72 (10) | C4—C3—H3B | 109.5 |
N4i—Cu1—N1ii | 165.71 (13) | H3A—C3—H3B | 109.5 |
N1—Cu1—N1ii | 77.84 (12) | C4—C3—H3C | 109.5 |
O1—Cu1—O3 | 91.09 (10) | H3A—C3—H3C | 109.5 |
N4i—Cu1—O3 | 87.19 (10) | H3B—C3—H3C | 109.5 |
N1—Cu1—O3 | 98.06 (12) | O2—C4—O1 | 126.0 (3) |
N1ii—Cu1—O3 | 106.90 (12) | O2—C4—C3 | 117.2 (3) |
O2—Cu2—O2i | 180.00 (15) | O1—C4—C3 | 116.8 (3) |
O2—Cu2—N4i | 90.66 (10) | N2—N1—Cu1 | 129.6 (2) |
O2i—Cu2—N4i | 89.34 (10) | N2—N1—Cu1ii | 124.8 (2) |
O2—Cu2—N4 | 89.34 (10) | Cu1—N1—Cu1ii | 102.16 (11) |
O2i—Cu2—N4 | 90.66 (10) | N3—N2—N1 | 178.7 (4) |
N4i—Cu2—N4 | 180.0 | N5—N4—Cu1i | 122.3 (2) |
S1—C1—H1A | 109.5 | N5—N4—Cu2 | 120.7 (2) |
S1—C1—H1B | 109.5 | Cu1i—N4—Cu2 | 104.04 (11) |
H1A—C1—H1B | 109.5 | N6—N5—N4 | 178.3 (4) |
S1—C1—H1C | 109.5 | C4—O1—Cu1 | 128.8 (2) |
H1A—C1—H1C | 109.5 | C4—O2—Cu2 | 131.9 (2) |
H1B—C1—H1C | 109.5 | S1—O3—Cu1 | 124.36 (14) |
S1—C2—H2A | 109.5 | O3—S1—C2 | 104.30 (19) |
S1—C2—H2B | 109.5 | O3—S1—C1 | 105.62 (19) |
H2A—C2—H2B | 109.5 | C2—S1—C1 | 97.6 (3) |
S1—C2—H2C | 109.5 | ||
O1—Cu1—N1—N2 | −175.2 (4) | N4i—Cu1—O1—C4 | 35.2 (3) |
N4i—Cu1—N1—N2 | −34.7 (4) | N1—Cu1—O1—C4 | 176.1 (5) |
N1ii—Cu1—N1—N2 | 159.2 (5) | N1ii—Cu1—O1—C4 | −158.9 (3) |
O3—Cu1—N1—N2 | 53.6 (4) | O3—Cu1—O1—C4 | −52.0 (3) |
O1—Cu1—N1—Cu1ii | 25.6 (6) | O1—C4—O2—Cu2 | −1.5 (6) |
N4i—Cu1—N1—Cu1ii | 166.06 (14) | C3—C4—O2—Cu2 | 177.6 (3) |
N1ii—Cu1—N1—Cu1ii | 0.0 | N4i—Cu2—O2—C4 | −34.0 (3) |
O3—Cu1—N1—Cu1ii | −105.65 (14) | N4—Cu2—O2—C4 | 146.0 (3) |
O2—Cu2—N4—N5 | −27.1 (3) | O1—Cu1—O3—S1 | −177.11 (17) |
O2i—Cu2—N4—N5 | 152.9 (3) | N4i—Cu1—O3—S1 | 90.44 (18) |
O2—Cu2—N4—Cu1i | 114.98 (12) | N1—Cu1—O3—S1 | −7.41 (19) |
O2i—Cu2—N4—Cu1i | −65.02 (12) | N1ii—Cu1—O3—S1 | −87.08 (18) |
O2—C4—O1—Cu1 | 1.1 (5) | Cu1—O3—S1—C2 | −173.7 (2) |
C3—C4—O1—Cu1 | −178.1 (3) | Cu1—O3—S1—C1 | 83.9 (2) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu3(C2H3O2)2(N3)4(C2H6OS)2] |
Mr | 633.13 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.5205 (9), 8.6624 (9), 9.4999 (10) |
α, β, γ (°) | 90.386 (2), 112.687 (1), 116.261 (1) |
V (Å3) | 566.66 (10) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 3.02 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART-CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3467, 2404, 2182 |
Rint | 0.060 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.099, 1.11 |
No. of reflections | 2404 |
No. of parameters | 145 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.60, −0.65 |
Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).
Cu1—O1 | 1.933 (2) | Cu1—O3 | 2.351 (2) |
Cu1—N4i | 1.970 (2) | Cu2—O2 | 1.936 (2) |
Cu1—N1 | 1.986 (3) | Cu2—N4 | 1.995 (2) |
Cu1—N1ii | 2.002 (3) | Cu2—O3 | 2.542 (2) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, −y+2, −z. |
The crystal structure and some properties of Cu(II)-azido coordination polymers have been previously reported (Goher et al., 1999; Goher et al., 2002; Liu et al., 2007; Song et al., 2007). We report here the synthesis and crystal structure of the title one-dimensional Copper(II)-azido coordination polymer(I) (Fig. 1). In (I) one unique CuII atom is six-coordinated while the other is is five-coordinated. Crystallographically independent CuII atoms are bridged by two O atoms from acetate ligands, one µ2-O atom from a DMSO ligand and one µ2-N atom of an azido ion, while the symmetry related CuII atoms are bridged by two µ2-N atoms from two azido ligands to from a one-dimensional polymer. In the absence of any direction specific interactions the the crystal structure is stabilized by Van der Waals interactions.