Bis[(1,3-benzothia­zol-2-ylsulfan­yl)acetato-κO]bis­(imidazole-κN³)copper(II)

In the title complex, [Cu(C₉H₆NO₂S₂)₂(C₃H₄N₂)₂], the Cu^II atom, lying on an inversion centre, is coordinated by two O atoms and two N atoms in a geometry deviating slightly from square planar. Inter­molecular hydrogen bonds link the complex mol­ecules into a layer structure.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• R factor = 0.031
• wR factor = 0.089
• Data-to-parameter ratio = 12.6

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S1. Comment

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 Cu^II 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 Cu^II 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.

Related literature

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).

S2. Experimental

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.

S3. Refinement

H atoms on C and N atoms were positoned geometrically and refined using a riding model (C—H = 0.93 Å for C—H_aromatic, C—H = 0.97 Å for C—H_aliphatic and N—H = 0.86 Å) with U_iso(H) = 1.2U_eq(C,N)

Computing details

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).

Figures

	Fig. 1. The molecular structure of (I) with the atom-numbering scheme and 30% displacement ellipsoids (arbitrary spheres for the H atoms). Atoms with the suffix A are generated by the symmetry operation (-x + 1, -y + 2, -z).
	Fig. 2. The 2-D network structure of compound (I) (methylene H atoms are omitted for clarity). Hydrogen bonds are shown as dashed lines.

Bis[(1,3-benzothiazol-2-ylsulfanyl)acetato-κO]bis(imidazole-κN³)copper(II)

Crystal data

[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) Å^3	Block, blue
Z = 2	0.31 × 0.23 × 0.15 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.089	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0469P)^2 + 0.8447P] where P = (Fo^2 + 2Fc^2)/3
2250 reflections	(Δ/σ)max < 0.001
178 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Cu1—N2^i	1.970 (2)	C1—C2	1.521 (4)
Cu1—N2	1.970 (2)	C2—H2A	0.970
Cu1—O1^i	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
N2^i—Cu1—N2	180.0	C9—C4—N1	125.2 (3)
N2^i—Cu1—O1^i	90.30 (9)	C9—C4—C5	119.4 (3)
N2—Cu1—O1^i	89.70 (9)	N1—C4—C5	115.3 (3)
N2^i—Cu1—O1	89.70 (9)	C6—C5—C4	121.5 (3)
N2—Cu1—O1	90.30 (9)	C6—C5—S1	129.1 (2)
O1^i—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)
N2^i—Cu1—N2—C10	35 (100)	C3—N1—C4—C5	0.8 (4)
O1^i—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)
N2^i—Cu1—N2—C12	−148 (100)	C9—C4—C5—S1	179.9 (2)
O1^i—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)
N2^i—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)
O1^i—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.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1^ii	0.86	1.96	2.819	174

Symmetry code: (ii) −x+1, y−1/2, −z+1/2.