Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051586/cf2156sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051586/cf2156Isup2.hkl |
CCDC reference: 667223
Key indicators
- Single-crystal X-ray study
- T = 298 K
- R factor = 0.031
- wR factor = 0.089
- Data-to-parameter ratio = 12.6
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
2-Benzothiazolylthioacetic acid (0.225 g, 1 mmol) and potassium hydroxide (0.06 g, 1 mmol) dissolved in water (10 ml) were added to a 1:1 methanol– water (10 ml) solution of CuCl2.2H2O (0.5 mmol). To this mixture was added a solution of imidazole (0.5 mmol) in methanol (4 ml). The blue solution was set aside for one week for the growth of blue block-shapped crystals.
H atoms on C and N atoms were positoned geometrically and refined using a riding model (C—H = 0.93 Å for C—Haromatic, C—H = 0.97 Å for C—Haliphatic and N—H = 0.86 Å) with Uiso(H) = 1.2Ueq(C,N)
The recognition of strong antitumor activity of the trans-bis(acetato)bis(imidazole)copper(II) complex caused a growing interest in the synthesis and characterization of new compounds of this type (Tamura et al., 1987; Raptopoulu et al., 1998). We report here the synthesis and crystal stucture of a new copper(II) complex [Cu(bttaa)2(Him)2] (where bttaa = 2-benzothiazolylthioacetate and Him = imidazole).
In the title complex, the CuII atom lying on an inversion centre, is coordinated by two imidazole nitrogen atoms and two carboxylate oxygen atoms. The Cu1···O2 separation of 2.767 Å indicates a weak interaction. Therefore, the title compound can be regarded as a pseudo-six-coordinate complex. This geometry around copper is typical of complexes of CuII with carboxylates and aromatic amines or imidazole (Battaglia et al., 1983; Houser et al., 2005; Ying et al., 2004; Noro et al., 2005). The length of Cu—O1 is in the normal range for a carboxylate group coordinated to copper in monodentate mode, and the Cu—N2 distance of 1.970 Å is similar to those observed for imidazole coordinated to copper(II) (Dobrzynska et al., 2002; Xu et al., 2005).
The supramolecular architecture is stabilized by an extensive 2-D network of intermolecular hydrogen bonds (N—H···O) involving imidazole N3 and bttaa O1 atoms.
For related literature, see: Tamura et al. (1987); Raptopoulu et al. (1998); Battaglia et al. (1983); Houser & Cheng (2005); Ying et al. (2004); Noro et al. (2005); Dobrzynska et al. (2002); Xu et al. (2005).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL (Bruker, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
[Cu(C9H6NO2S2)2(C3H4N2)2] | F(000) = 662 |
Mr = 648.24 | Dx = 1.684 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.086 (3) Å | Cell parameters from 2567 reflections |
b = 12.050 (3) Å | θ = 2.6–27.6° |
c = 10.521 (3) Å | µ = 1.23 mm−1 |
β = 91.281 (3)° | T = 298 K |
V = 1278.4 (6) Å3 | Block, blue |
Z = 2 | 0.31 × 0.23 × 0.15 mm |
Bruker SMART CCD diffractometer | 2250 independent reflections |
Radiation source: fine-focus sealed tube | 1768 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
φ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −9→11 |
Tmin = 0.702, Tmax = 0.837 | k = −12→14 |
6476 measured reflections | l = −11→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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0469P)2 + 0.8447P] where P = (Fo2 + 2Fc2)/3 |
2250 reflections | (Δ/σ)max < 0.001 |
178 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
[Cu(C9H6NO2S2)2(C3H4N2)2] | V = 1278.4 (6) Å3 |
Mr = 648.24 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.086 (3) Å | µ = 1.23 mm−1 |
b = 12.050 (3) Å | T = 298 K |
c = 10.521 (3) Å | 0.31 × 0.23 × 0.15 mm |
β = 91.281 (3)° |
Bruker SMART CCD diffractometer | 2250 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 1768 reflections with I > 2σ(I) |
Tmin = 0.702, Tmax = 0.837 | Rint = 0.026 |
6476 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.43 e Å−3 |
2250 reflections | Δρmin = −0.26 e Å−3 |
178 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 | 0.5000 | 1.0000 | 0.0000 | 0.02612 (16) | |
N1 | 0.1790 (2) | 1.1037 (2) | 0.4327 (2) | 0.0350 (6) | |
N2 | 0.5031 (2) | 0.9149 (2) | 0.1598 (2) | 0.0306 (6) | |
N3 | 0.5472 (3) | 0.7866 (2) | 0.3026 (3) | 0.0429 (7) | |
H3 | 0.5779 | 0.7268 | 0.3370 | 0.052* | |
O1 | 0.35753 (19) | 1.09765 (16) | 0.06651 (17) | 0.0297 (5) | |
O2 | 0.2287 (2) | 0.97582 (18) | −0.0341 (2) | 0.0438 (6) | |
S1 | 0.09591 (8) | 0.95164 (7) | 0.27425 (7) | 0.0356 (2) | |
S2 | 0.12226 (8) | 1.19910 (6) | 0.21074 (7) | 0.0355 (2) | |
C1 | 0.2436 (3) | 1.0601 (2) | 0.0281 (3) | 0.0291 (6) | |
C2 | 0.1223 (3) | 1.1293 (3) | 0.0589 (3) | 0.0340 (7) | |
H2A | 0.0453 | 1.0811 | 0.0541 | 0.041* | |
H2B | 0.1110 | 1.1850 | −0.0071 | 0.041* | |
C3 | 0.1361 (3) | 1.0878 (2) | 0.3167 (3) | 0.0312 (7) | |
C4 | 0.1860 (3) | 1.0024 (3) | 0.4970 (3) | 0.0325 (7) | |
C5 | 0.1485 (3) | 0.9090 (3) | 0.4248 (3) | 0.0310 (7) | |
C6 | 0.1636 (3) | 0.8019 (3) | 0.4724 (3) | 0.0380 (8) | |
H6 | 0.1410 | 0.7404 | 0.4232 | 0.046* | |
C7 | 0.2133 (3) | 0.7898 (3) | 0.5949 (3) | 0.0445 (8) | |
H7 | 0.2260 | 0.7190 | 0.6282 | 0.053* | |
C8 | 0.2446 (3) | 0.8817 (3) | 0.6688 (3) | 0.0468 (9) | |
H8 | 0.2750 | 0.8714 | 0.7520 | 0.056* | |
C9 | 0.2317 (3) | 0.9881 (3) | 0.6217 (3) | 0.0415 (8) | |
H9 | 0.2532 | 1.0491 | 0.6723 | 0.050* | |
C10 | 0.5633 (3) | 0.8185 (3) | 0.1828 (3) | 0.0369 (7) | |
H10 | 0.6104 | 0.7787 | 0.1230 | 0.044* | |
C11 | 0.4737 (3) | 0.8653 (3) | 0.3607 (3) | 0.0485 (9) | |
H11 | 0.4470 | 0.8649 | 0.4447 | 0.058* | |
C12 | 0.4469 (3) | 0.9442 (3) | 0.2732 (3) | 0.0423 (8) | |
H12 | 0.3981 | 1.0084 | 0.2871 | 0.051* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0296 (3) | 0.0238 (3) | 0.0250 (3) | 0.0048 (2) | 0.0015 (2) | 0.0009 (2) |
N1 | 0.0394 (15) | 0.0286 (14) | 0.0373 (14) | 0.0021 (11) | 0.0031 (12) | −0.0042 (12) |
N2 | 0.0298 (13) | 0.0320 (14) | 0.0301 (13) | 0.0031 (11) | 0.0013 (10) | 0.0070 (11) |
N3 | 0.0392 (16) | 0.0440 (17) | 0.0456 (16) | 0.0033 (13) | 0.0004 (13) | 0.0229 (13) |
O1 | 0.0316 (11) | 0.0277 (11) | 0.0298 (10) | 0.0058 (9) | 0.0004 (8) | −0.0015 (9) |
O2 | 0.0503 (14) | 0.0364 (13) | 0.0447 (13) | −0.0035 (10) | 0.0046 (11) | −0.0134 (10) |
S1 | 0.0399 (5) | 0.0299 (4) | 0.0368 (4) | −0.0038 (3) | −0.0006 (3) | −0.0031 (3) |
S2 | 0.0383 (4) | 0.0258 (4) | 0.0425 (5) | 0.0060 (3) | 0.0045 (3) | −0.0019 (3) |
C1 | 0.0355 (17) | 0.0263 (16) | 0.0255 (14) | 0.0018 (13) | 0.0007 (13) | 0.0054 (13) |
C2 | 0.0333 (17) | 0.0340 (18) | 0.0347 (16) | 0.0013 (13) | −0.0022 (13) | 0.0009 (14) |
C3 | 0.0278 (15) | 0.0257 (16) | 0.0404 (17) | 0.0051 (12) | 0.0096 (13) | −0.0008 (13) |
C4 | 0.0288 (16) | 0.0344 (17) | 0.0346 (16) | 0.0014 (13) | 0.0070 (13) | −0.0023 (14) |
C5 | 0.0253 (15) | 0.0356 (17) | 0.0324 (16) | −0.0024 (12) | 0.0059 (12) | −0.0019 (13) |
C6 | 0.0373 (18) | 0.0326 (18) | 0.0445 (19) | −0.0076 (14) | 0.0066 (15) | 0.0010 (15) |
C7 | 0.044 (2) | 0.040 (2) | 0.049 (2) | −0.0029 (15) | 0.0113 (16) | 0.0151 (16) |
C8 | 0.049 (2) | 0.059 (2) | 0.0330 (17) | −0.0030 (17) | 0.0013 (15) | 0.0056 (17) |
C9 | 0.044 (2) | 0.045 (2) | 0.0355 (18) | −0.0025 (15) | 0.0017 (14) | −0.0065 (15) |
C10 | 0.0378 (18) | 0.0353 (18) | 0.0375 (17) | 0.0039 (14) | 0.0007 (14) | 0.0069 (14) |
C11 | 0.0365 (18) | 0.071 (3) | 0.0383 (18) | 0.0105 (17) | 0.0098 (15) | 0.0213 (18) |
C12 | 0.0363 (18) | 0.051 (2) | 0.0395 (18) | 0.0130 (15) | 0.0093 (14) | 0.0111 (16) |
Cu1—N2i | 1.970 (2) | C1—C2 | 1.521 (4) |
Cu1—N2 | 1.970 (2) | C2—H2A | 0.970 |
Cu1—O1i | 1.9961 (19) | C2—H2B | 0.970 |
Cu1—O1 | 1.9961 (19) | C4—C9 | 1.391 (4) |
N1—C3 | 1.300 (4) | C4—C5 | 1.404 (4) |
N1—C4 | 1.397 (4) | C5—C6 | 1.392 (4) |
N2—C10 | 1.330 (4) | C6—C7 | 1.380 (4) |
N2—C12 | 1.378 (4) | C6—H6 | 0.930 |
N3—C10 | 1.332 (4) | C7—C8 | 1.385 (5) |
N3—C11 | 1.358 (4) | C7—H7 | 0.930 |
N3—H3 | 0.860 | C8—C9 | 1.380 (5) |
O1—C1 | 1.291 (3) | C8—H8 | 0.930 |
O2—C1 | 1.216 (3) | C9—H9 | 0.930 |
S1—C5 | 1.737 (3) | C10—H10 | 0.930 |
S1—C3 | 1.746 (3) | C11—C12 | 1.346 (4) |
S2—C3 | 1.748 (3) | C11—H11 | 0.930 |
S2—C2 | 1.806 (3) | C12—H12 | 0.930 |
N2i—Cu1—N2 | 180.0 | C9—C4—N1 | 125.2 (3) |
N2i—Cu1—O1i | 90.30 (9) | C9—C4—C5 | 119.4 (3) |
N2—Cu1—O1i | 89.70 (9) | N1—C4—C5 | 115.3 (3) |
N2i—Cu1—O1 | 89.70 (9) | C6—C5—C4 | 121.5 (3) |
N2—Cu1—O1 | 90.30 (9) | C6—C5—S1 | 129.1 (2) |
O1i—Cu1—O1 | 180.0 | C4—C5—S1 | 109.3 (2) |
C3—N1—C4 | 109.8 (2) | C7—C6—C5 | 117.9 (3) |
C10—N2—C12 | 105.2 (2) | C7—C6—H6 | 121.0 |
C10—N2—Cu1 | 127.4 (2) | C5—C6—H6 | 121.0 |
C12—N2—Cu1 | 127.4 (2) | C6—C7—C8 | 120.9 (3) |
C10—N3—C11 | 107.7 (3) | C6—C7—H7 | 119.6 |
C10—N3—H3 | 126.2 | C8—C7—H7 | 119.6 |
C11—N3—H3 | 126.2 | C9—C8—C7 | 121.5 (3) |
C1—O1—Cu1 | 109.05 (17) | C9—C8—H8 | 119.2 |
C5—S1—C3 | 88.84 (14) | C7—C8—H8 | 119.2 |
C3—S2—C2 | 101.87 (14) | C8—C9—C4 | 118.7 (3) |
O2—C1—O1 | 124.0 (3) | C8—C9—H9 | 120.7 |
O2—C1—C2 | 118.8 (3) | C4—C9—H9 | 120.7 |
O1—C1—C2 | 117.1 (3) | N2—C10—N3 | 111.0 (3) |
C1—C2—S2 | 117.4 (2) | N2—C10—H10 | 124.5 |
C1—C2—H2A | 108.0 | N3—C10—H10 | 124.5 |
S2—C2—H2A | 108.0 | C12—C11—N3 | 106.8 (3) |
C1—C2—H2B | 108.0 | C12—C11—H11 | 126.6 |
S2—C2—H2B | 108.0 | N3—C11—H11 | 126.6 |
H2A—C2—H2B | 107.2 | C11—C12—N2 | 109.3 (3) |
N1—C3—S1 | 116.7 (2) | C11—C12—H12 | 125.3 |
N1—C3—S2 | 120.4 (2) | N2—C12—H12 | 125.3 |
S1—C3—S2 | 122.89 (18) | ||
N2i—Cu1—N2—C10 | 35 (100) | C3—N1—C4—C5 | 0.8 (4) |
O1i—Cu1—N2—C10 | −11.8 (3) | C9—C4—C5—C6 | −4.0 (4) |
O1—Cu1—N2—C10 | 168.2 (3) | N1—C4—C5—C6 | 173.3 (3) |
N2i—Cu1—N2—C12 | −148 (100) | C9—C4—C5—S1 | 179.9 (2) |
O1i—Cu1—N2—C12 | 165.9 (3) | N1—C4—C5—S1 | −2.8 (3) |
O1—Cu1—N2—C12 | −14.1 (3) | C3—S1—C5—C6 | −172.7 (3) |
N2i—Cu1—O1—C1 | 85.13 (18) | C3—S1—C5—C4 | 2.9 (2) |
N2—Cu1—O1—C1 | −94.87 (18) | C4—C5—C6—C7 | 1.9 (4) |
O1i—Cu1—O1—C1 | −55 (100) | S1—C5—C6—C7 | 177.0 (2) |
Cu1—O1—C1—O2 | 2.9 (3) | C5—C6—C7—C8 | 1.3 (5) |
Cu1—O1—C1—C2 | −174.60 (19) | C6—C7—C8—C9 | −2.3 (5) |
O2—C1—C2—S2 | 145.5 (2) | C7—C8—C9—C4 | 0.1 (5) |
O1—C1—C2—S2 | −36.9 (3) | N1—C4—C9—C8 | −174.0 (3) |
C3—S2—C2—C1 | −60.2 (3) | C5—C4—C9—C8 | 3.0 (5) |
C4—N1—C3—S1 | 1.6 (3) | C12—N2—C10—N3 | 0.3 (4) |
C4—N1—C3—S2 | −177.7 (2) | Cu1—N2—C10—N3 | 178.4 (2) |
C5—S1—C3—N1 | −2.8 (2) | C11—N3—C10—N2 | −0.1 (4) |
C5—S1—C3—S2 | 176.57 (19) | C10—N3—C11—C12 | −0.1 (4) |
C2—S2—C3—N1 | 159.1 (2) | N3—C11—C12—N2 | 0.3 (4) |
C2—S2—C3—S1 | −20.2 (2) | C10—N2—C12—C11 | −0.3 (4) |
C3—N1—C4—C9 | 177.9 (3) | Cu1—N2—C12—C11 | −178.4 (2) |
Symmetry code: (i) −x+1, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O1ii | 0.86 | 1.96 | 2.819 | 174 |
Symmetry code: (ii) −x+1, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C9H6NO2S2)2(C3H4N2)2] |
Mr | 648.24 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 10.086 (3), 12.050 (3), 10.521 (3) |
β (°) | 91.281 (3) |
V (Å3) | 1278.4 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.23 |
Crystal size (mm) | 0.31 × 0.23 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.702, 0.837 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6476, 2250, 1768 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.089, 1.00 |
No. of reflections | 2250 |
No. of parameters | 178 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.26 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Bruker, 1997).
Cu1—N2 | 1.970 (2) | Cu1—O1 | 1.9961 (19) |
N2i—Cu1—N2 | 180.0 | N2—Cu1—O1i | 89.70 (9) |
N2i—Cu1—O1i | 90.30 (9) | O1i—Cu1—O1 | 180.0 |
Symmetry code: (i) −x+1, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O1ii | 0.86 | 1.96 | 2.819 | 174 |
Symmetry code: (ii) −x+1, y−1/2, −z+1/2. |
The recognition of strong antitumor activity of the trans-bis(acetato)bis(imidazole)copper(II) complex caused a growing interest in the synthesis and characterization of new compounds of this type (Tamura et al., 1987; Raptopoulu et al., 1998). We report here the synthesis and crystal stucture of a new copper(II) complex [Cu(bttaa)2(Him)2] (where bttaa = 2-benzothiazolylthioacetate and Him = imidazole).
In the title complex, the CuII atom lying on an inversion centre, is coordinated by two imidazole nitrogen atoms and two carboxylate oxygen atoms. The Cu1···O2 separation of 2.767 Å indicates a weak interaction. Therefore, the title compound can be regarded as a pseudo-six-coordinate complex. This geometry around copper is typical of complexes of CuII with carboxylates and aromatic amines or imidazole (Battaglia et al., 1983; Houser et al., 2005; Ying et al., 2004; Noro et al., 2005). The length of Cu—O1 is in the normal range for a carboxylate group coordinated to copper in monodentate mode, and the Cu—N2 distance of 1.970 Å is similar to those observed for imidazole coordinated to copper(II) (Dobrzynska et al., 2002; Xu et al., 2005).
The supramolecular architecture is stabilized by an extensive 2-D network of intermolecular hydrogen bonds (N—H···O) involving imidazole N3 and bttaa O1 atoms.