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Acta Cryst. (2007). E63, m1881    [ doi:10.1107/S1600536807027948 ]

Tetra-[mu]-acetato-[kappa]8O:O'-bis[(2-amino-1,3-benzothiazole-[kappa]N)copper(II)] butanol disolvate

Y.-F. Sun, J.-R. Lu and Z.-B. Zheng

Abstract top

The title compound, [Cu2(C2H3O2)4(C7H6N2S)2]·2C4H10O, exhibits distorted square-pyramidal coordination geometry around each CuII atom, with the basal plane comprising O atoms from four bridging acetate ligands and the apical position occupied by the thiazole N atom of 2-aminobenzothiazole. The dinuclear complex lies on a crystallographic centre of inversion and has a Cu...Cu distance of 2.6850 (14) Å. Complexes are linked into one-dimensional chains by a combination of intermolecular O-H...O and N-H...O hydrogen bonds involving the butanol solvent molecules.

Comment top

Interest in the study of compounds containing the benzothiazole group has increased on account of their broad spectrum of biological activities (Rana et al., 2007), and also their potential applications in the areas of sensors (Kim et al., 2005), non-linear optics, laser dyes, electroluminescent devices (Costa et al., 2006) and as chelating agents (Usman et al., 2003). A large number of copper compounds with diverse ligands have been synthesized and studied as potential therapeutic agents (Wu et al., 2003) and catalysts (Marko et al., 1996).

In the title compound (Fig. 1), each CuII ion is five-coordinated, with a coordination geometry that is best described as distorted square pyramidal. Four O atoms of bridging acetate ligands construct the basal plane of the square pyramid. The 2-aminobenzothiazole molecules are coordinated to CuII through their thiazole N atom and occupy the axial position. Four acetate ligands act as bridges to connect the two CuII centers into a dinuclear complex across a crystallographic centre of inversion. All the geometrical parameters lie within expected ranges.

The complexes are linked into one-dimensional chains by a combination of intermolecular O—H···O and N—H···O hydrogen bonds involving the butane solvent molecules (Fig. 2).

Related literature top

For general literature concerning applications of benzothiazole compounds, see: Rana et al. (2007); Kim et al. (2005); Costa et al. (2006); Wu et al. (2003); Marko et al. (1996). Similar coordination geometry has been observed for a related dinuclear CuII complex containing 2-amino-5-chloropyridine (Liu et al., 2003). Other reported 2-aminobenzothiazole complexes with CuII contain either six-coordinate (Sieroń & Bukowska-Strżyzewska, 1999, 2000; Sieroń, 2007) or four-coordinate CuII (Usman et al., 2003).

Experimental top

A solution of 2-aminobenzothiazole (2 mmol) in butanol (10 ml) was added dropwise to Cu(OAc)2·2H2O (1 mmol in 10 ml of butanol) with stirring. The resulting solution was left to stand at room temperature and black crystals were obtained after several days.

Refinement top

All H atoms were visible in a difference Fourier map. The methyl H atoms were constrained to an ideal geometry with C—H distances of 0.96 Å and Uiso(H) = 1.5Ueq(C). The hydroxyl H atoms were treated as riding atoms with O—H distances normalized to 0.85 Å and with Uiso(H) = 1.5Ueq(O). All other H atoms were placed geometrically and constrained to ride on their parent atoms with C—H distances of 0.93–0.97 Å and N—H distances of 0.90 Å, and with Uiso(H) = 1.2Ueq(C/N). The C—C bonds and 1,3-distances in the butanol molecule were restrained to 1.50 (1) and 2.45 (2) Å, respectively.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound showing displacement ellipsoids at the 50% probability level. H atoms are omitted.
[Figure 2] Fig. 2. The chain structure in the title compound formed via hydrogen bonds (dashed lines). H atoms are omitted.
Tetra-µ-acetato-κ8O:O'-bis[(2-amino-1,3-benzothiazole-κN)copper(II)] butanol disolvate top
Crystal data top
[Cu2(C2H3O2)4(C7H6N2S)2]·2C4H10OF000 = 844
Mr = 811.89Dx = 1.410 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8320 reflections
a = 10.0998 (17) Åθ = 2.2–25.7º
b = 11.465 (2) ŵ = 1.28 mm−1
c = 16.514 (3) ÅT = 273 (2) K
β = 91.242 (7)ºBlock, black
V = 1911.8 (6) Å30.32 × 0.21 × 0.12 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer		3353 independent reflections
Radiation source: fine-focus sealed tube3000 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.044
T = 273(2) Kθmax = 25.0º
φ and ω scansθmin = 2.0º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −12→11
Tmin = 0.686, Tmax = 0.862k = −13→13
20441 measured reflectionsl = −19→19
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.084H-atom parameters constrained
wR(F2) = 0.249  w = 1/[σ2(Fo2) + (0.0643P)2 + 21.2639P]
where P = (Fo2 + 2Fc2)/3
S = 1.15(Δ/σ)max = 0.001
3353 reflectionsΔρmax = 0.97 e Å−3
217 parametersΔρmin = −1.00 e Å−3
5 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Cu2(C2H3O2)4(C7H6N2S)2]·2C4H10OV = 1911.8 (6) Å3
Mr = 811.89Z = 2
Monoclinic, P21/cMo Kα
a = 10.0998 (17) ŵ = 1.28 mm−1
b = 11.465 (2) ÅT = 273 (2) K
c = 16.514 (3) Å0.32 × 0.21 × 0.12 mm
β = 91.242 (7)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		3353 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3000 reflections with I > 2σ(I)
Tmin = 0.686, Tmax = 0.862Rint = 0.044
20441 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0845 restraints
wR(F2) = 0.249H-atom parameters constrained
S = 1.15  w = 1/[σ2(Fo2) + (0.0643P)2 + 21.2639P]
where P = (Fo2 + 2Fc2)/3
3353 reflectionsΔρmax = 0.97 e Å−3
217 parametersΔρmin = −1.00 e Å−3
Special details top

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 (Å2) top
xyzUiso*/Ueq
Cu10.93063 (11)0.90286 (8)0.98271 (6)0.0418 (4)
S10.7442 (3)0.5375 (2)0.9140 (2)0.0706 (8)
O11.0552 (7)0.8231 (6)1.0602 (4)0.0611 (18)
O21.0644 (7)0.8793 (6)0.8988 (4)0.0616 (18)
O30.8344 (7)1.0149 (6)0.9128 (4)0.0620 (18)
O40.8287 (7)0.9547 (6)1.0754 (4)0.0624 (18)
O50.0282 (10)0.3940 (7)0.8688 (6)0.088 (3)
H50.00370.32990.88960.131*
N10.9877 (9)0.6283 (8)0.9201 (7)0.074 (3)
H1A1.04400.68910.92400.111*
H1B1.02080.55710.91000.111*
N20.8107 (7)0.7502 (6)0.9518 (5)0.0491 (18)
C10.8607 (10)0.6475 (8)0.9296 (6)0.050 (2)
C20.6731 (9)0.7435 (8)0.9545 (6)0.051 (2)
C30.6197 (11)0.6342 (9)0.9356 (7)0.060 (3)
C40.4832 (12)0.6167 (12)0.9369 (9)0.085 (4)
H4A0.44720.54420.92390.102*
C50.4020 (12)0.7085 (12)0.9576 (10)0.092 (4)
H5A0.31080.69770.95960.110*
C60.4558 (12)0.8154 (11)0.9753 (9)0.081 (4)
H6A0.39990.87710.98750.097*
C70.5897 (11)0.8339 (9)0.9754 (7)0.063 (3)
H7A0.62430.90650.98930.076*
C80.8556 (10)1.1205 (8)0.9024 (6)0.051 (2)
C90.7718 (14)1.1838 (11)0.8413 (9)0.093 (5)
H9A0.70821.13100.81760.139*
H9B0.82681.21470.79980.139*
H9C0.72631.24660.86730.139*
C100.8488 (10)1.0437 (9)1.1167 (6)0.054 (2)
C110.7607 (14)1.0663 (13)1.1869 (8)0.089 (4)
H11A0.69981.00271.19230.134*
H11B0.71211.13731.17770.134*
H11C0.81361.07361.23560.134*
C120.0949 (18)0.3587 (19)0.7984 (11)0.129 (6)
H12A0.07850.41250.75400.154*
H12B0.06840.28090.78170.154*
C130.236 (2)0.361 (3)0.8257 (12)0.220 (15)
H13A0.25700.43760.84820.264*
H13B0.25090.30380.86780.264*
C140.325 (2)0.337 (3)0.7572 (13)0.30 (3)
H14A0.34490.40910.72930.359*
H14B0.28050.28510.71890.359*
C150.449 (2)0.282 (3)0.7884 (18)0.27 (2)
H15A0.50610.26710.74420.410*
H15B0.42790.21040.81510.410*
H15C0.49180.33420.82620.410*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0566 (7)0.0260 (5)0.0427 (6)−0.0058 (4)−0.0026 (4)−0.0019 (4)
S10.0751 (18)0.0379 (13)0.099 (2)−0.0159 (12)0.0041 (15)−0.0175 (13)
O10.079 (5)0.036 (3)0.067 (4)−0.003 (3)−0.016 (4)0.011 (3)
O20.078 (5)0.049 (4)0.059 (4)−0.011 (3)0.015 (3)−0.013 (3)
O30.070 (4)0.046 (4)0.069 (4)−0.005 (3)−0.020 (4)0.009 (3)
O40.068 (4)0.057 (4)0.063 (4)−0.016 (3)0.011 (3)−0.006 (4)
O50.127 (7)0.041 (4)0.095 (6)0.004 (4)0.022 (6)−0.004 (4)
N10.065 (6)0.039 (5)0.117 (8)−0.001 (4)0.014 (5)−0.014 (5)
N20.052 (4)0.032 (4)0.063 (5)−0.004 (3)−0.002 (4)−0.001 (3)
C10.064 (6)0.032 (4)0.054 (5)−0.004 (4)0.003 (4)−0.006 (4)
C20.055 (5)0.038 (5)0.058 (5)−0.007 (4)−0.006 (4)0.007 (4)
C30.068 (6)0.042 (5)0.069 (6)−0.016 (5)−0.005 (5)0.006 (5)
C40.072 (8)0.068 (8)0.112 (11)−0.027 (7)−0.015 (7)0.002 (7)
C50.056 (7)0.080 (9)0.139 (13)−0.008 (6)−0.004 (7)0.014 (9)
C60.067 (7)0.054 (7)0.123 (11)0.000 (6)0.002 (7)0.003 (7)
C70.072 (7)0.033 (5)0.086 (8)−0.003 (5)−0.001 (6)−0.007 (5)
C80.062 (6)0.039 (5)0.051 (5)0.001 (4)−0.006 (4)0.011 (4)
C90.110 (10)0.059 (7)0.107 (10)0.002 (7)−0.048 (8)0.026 (7)
C100.061 (6)0.054 (6)0.048 (5)−0.003 (5)0.003 (4)−0.008 (4)
C110.101 (10)0.103 (10)0.066 (7)−0.016 (8)0.030 (7)−0.013 (7)
C120.145 (16)0.131 (16)0.111 (13)−0.019 (13)0.019 (12)−0.008 (12)
C130.20 (3)0.31 (4)0.15 (2)0.05 (3)0.02 (2)0.09 (3)
C140.38 (5)0.37 (6)0.14 (2)0.19 (5)−0.06 (3)−0.06 (3)
C150.14 (2)0.44 (6)0.24 (4)0.03 (3)0.00 (2)0.12 (4)
Geometric parameters (Å, °) top
Cu1—O41.956 (7)C6—C71.369 (15)
Cu1—O31.970 (7)C6—H6A0.930
Cu1—O21.975 (7)C7—H7A0.930
Cu1—O11.996 (7)C8—O1i1.260 (11)
Cu1—N22.183 (7)C8—C91.491 (13)
Cu1—Cu1i2.6862 (19)C9—H9A0.960
S1—C31.720 (12)C9—H9B0.960
S1—C11.740 (9)C9—H9C0.960
O1—C8i1.260 (11)C10—O2i1.274 (12)
O2—C10i1.274 (12)C10—C111.499 (15)
O3—C81.242 (11)C11—H11A0.960
O4—C101.241 (12)C11—H11B0.960
O5—C121.415 (18)C11—H11C0.960
O5—H50.850C12—C131.487 (10)
N1—C11.314 (12)C12—H12A0.970
N1—H1A0.900C12—H12B0.970
N1—H1B0.900C13—C141.482 (10)
N2—C11.336 (11)C13—H13A0.970
N2—C21.394 (12)C13—H13B0.970
C2—C71.383 (14)C14—C151.483 (10)
C2—C31.397 (13)C14—H14A0.970
C3—C41.394 (15)C14—H14B0.970
C4—C51.383 (19)C15—H15A0.960
C4—H4A0.930C15—H15B0.960
C5—C61.370 (18)C15—H15C0.960
C5—H5A0.930
O4—Cu1—O390.0 (3)C6—C7—C2119.4 (10)
O4—Cu1—O2166.1 (3)C6—C7—H7A120.3
O3—Cu1—O290.8 (3)C2—C7—H7A120.3
O4—Cu1—O188.4 (3)O3—C8—O1i123.8 (8)
O3—Cu1—O1166.1 (3)O3—C8—C9118.1 (9)
O2—Cu1—O187.4 (3)O1i—C8—C9118.1 (9)
O4—Cu1—N297.4 (3)C8—C9—H9A109.5
O3—Cu1—N297.0 (3)C8—C9—H9B109.5
O2—Cu1—N296.4 (3)H9A—C9—H9B109.5
O1—Cu1—N297.0 (3)C8—C9—H9C109.5
O4—Cu1—Cu1i82.1 (2)H9A—C9—H9C109.5
O3—Cu1—Cu1i80.4 (2)H9B—C9—H9C109.5
O2—Cu1—Cu1i84.3 (2)O4—C10—O2i124.3 (9)
O1—Cu1—Cu1i85.7 (2)O4—C10—C11118.3 (10)
N2—Cu1—Cu1i177.3 (2)O2i—C10—C11117.3 (9)
C3—S1—C189.8 (5)C10—C11—H11A109.5
C8i—O1—Cu1120.9 (6)C10—C11—H11B109.5
C10i—O2—Cu1122.0 (6)H11A—C11—H11B109.5
C8—O3—Cu1129.2 (6)C10—C11—H11C109.5
C10—O4—Cu1126.7 (7)H11A—C11—H11C109.5
C12—O5—H5103.5H11B—C11—H11C109.5
C1—N1—H1A118.6O5—C12—C13102.5 (14)
C1—N1—H1B122.8O5—C12—H12A111.3
H1A—N1—H1B118.6C13—C12—H12A111.3
C1—N2—C2110.1 (8)O5—C12—H12B111.3
C1—N2—Cu1124.0 (6)C13—C12—H12B111.3
C2—N2—Cu1125.8 (6)H12A—C12—H12B109.2
N1—C1—N2123.8 (8)C14—C13—C12110.8 (14)
N1—C1—S1121.3 (7)C14—C13—H13A109.5
N2—C1—S1114.9 (7)C12—C13—H13A109.5
C7—C2—N2125.4 (8)C14—C13—H13B109.5
C7—C2—C3119.6 (9)C12—C13—H13B109.5
N2—C2—C3115.0 (9)H13A—C13—H13B108.1
C4—C3—C2120.2 (11)C13—C14—C15109.4 (14)
C4—C3—S1129.6 (9)C13—C14—H14A109.8
C2—C3—S1110.1 (8)C15—C14—H14A109.8
C5—C4—C3119.1 (11)C13—C14—H14B109.8
C5—C4—H4A120.5C15—C14—H14B109.8
C3—C4—H4A120.5H14A—C14—H14B108.2
C6—C5—C4120.0 (11)C14—C15—H15A109.5
C6—C5—H5A120.0C14—C15—H15B109.5
C4—C5—H5A120.0H15A—C15—H15B109.5
C7—C6—C5121.7 (12)C14—C15—H15C109.5
C7—C6—H6A119.1H15A—C15—H15C109.5
C5—C6—H6A119.1H15B—C15—H15C109.5
O4—Cu1—O1—C8i−80.3 (8)C2—N2—C1—N1178.5 (10)
O3—Cu1—O1—C8i3.3 (18)Cu1—N2—C1—N1−3.5 (14)
O2—Cu1—O1—C8i86.3 (8)C2—N2—C1—S1−1.7 (10)
N2—Cu1—O1—C8i−177.6 (8)Cu1—N2—C1—S1176.4 (4)
Cu1i—Cu1—O1—C8i1.9 (8)C3—S1—C1—N1−178.7 (10)
O4—Cu1—O2—C10i−20.0 (18)C3—S1—C1—N21.5 (8)
O3—Cu1—O2—C10i73.2 (8)C1—N2—C2—C7179.9 (10)
O1—Cu1—O2—C10i−92.9 (8)Cu1—N2—C2—C71.9 (14)
N2—Cu1—O2—C10i170.3 (8)C1—N2—C2—C31.0 (12)
Cu1i—Cu1—O2—C10i−7.0 (8)Cu1—N2—C2—C3−177.0 (7)
O4—Cu1—O3—C883.1 (9)C7—C2—C3—C40.7 (16)
O2—Cu1—O3—C8−82.9 (9)N2—C2—C3—C4179.6 (10)
O1—Cu1—O3—C80(2)C7—C2—C3—S1−178.8 (8)
N2—Cu1—O3—C8−179.4 (9)N2—C2—C3—S10.1 (11)
Cu1i—Cu1—O3—C81.2 (9)C1—S1—C3—C4179.7 (12)
O3—Cu1—O4—C10−79.9 (9)C1—S1—C3—C2−0.8 (8)
O2—Cu1—O4—C1013.4 (19)C2—C3—C4—C5−0.5 (19)
O1—Cu1—O4—C1086.3 (9)S1—C3—C4—C5179.0 (11)
N2—Cu1—O4—C10−176.9 (9)C3—C4—C5—C61(2)
Cu1i—Cu1—O4—C100.4 (8)C4—C5—C6—C7−2(2)
O4—Cu1—N2—C1−138.9 (8)C5—C6—C7—C22(2)
O3—Cu1—N2—C1130.2 (8)N2—C2—C7—C6179.7 (11)
O2—Cu1—N2—C138.6 (8)C3—C2—C7—C6−1.5 (17)
O1—Cu1—N2—C1−49.6 (8)Cu1—O3—C8—O1i−3.1 (16)
Cu1i—Cu1—N2—C1143 (4)Cu1—O3—C8—C9176.2 (9)
O4—Cu1—N2—C238.9 (8)Cu1—O4—C10—O2i5.0 (16)
O3—Cu1—N2—C2−52.0 (8)Cu1—O4—C10—C11−178.6 (8)
O2—Cu1—N2—C2−143.6 (7)O5—C12—C13—C14−175 (2)
O1—Cu1—N2—C2128.2 (7)C12—C13—C14—C15−152 (3)
Cu1i—Cu1—N2—C2−40 (5)
Symmetry codes: (i) −x+2, −y+2, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O20.902.233.002 (11)144
N1—H1B···O5ii0.901.992.850 (12)159
O5—H5···O1iii0.852.042.885 (10)180
Symmetry codes: (ii) x+1, y, z; (iii) −x+1, −y+1, −z+2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O20.902.233.002 (11)144
N1—H1B···O5i0.901.992.850 (12)159
O5—H5···O1ii0.852.042.885 (10)180
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+2.
Acknowledgements top

This project was supported by the Foundation of Taishan University (grant No. Y04–2-02)

references
References top

Bruker (1997). SMART, SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Costa, S. P. G., Batista, R. M. F., Sousa, A. M. R. C. & Raposo, M. M. M. (2006). Mater. Sci. Forum, 514–516, 147–151.

Kim, Y. H., Youk, J. S., Kim, S. H. & Chang, S. K. (2005). Bull. Korean Chem. Soc. 26, 47–50.

Liu, B., Chen, Z. F., Hu, R. X., Liang, H. & Yu, K. B. (2003). Chin. J. Inorg. Chem. 19, 387–390. (In Chinese.)

Marko, I. E., Giles, P. R., Tsukazaki, M., Brown, S. M. & Urch, C. J. (1996). Science, 274, 2044–2046.

Rana, A., Siddiqui, N. & Khan, S. A. (2007). Indian J. Pharm. Sci. 69, 10–17.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Sieroń, L. (2007). Acta Cryst. E63, m598–m600.

Sieroń, L. & Bukowska-Strżyzewska, M. (1999). Acta Cryst. C55, 167–169.

Sieroń, L. & Bukowska-Strzyżewska, M. (2000). Acta Cryst. C56, 19–21.

Usman, A., Fun, H.-K., Chantrapromma, S., Zhang, M., Chen, Z.-F., Tang, Y.-Z., Shi, S.-M. & Liang, H. (2003). Acta Cryst. E59, m41–m43.

Wu, G. G., Wang, G. P., Fu, X. C. & Zhu, L. G. (2003). Molecules, 8, 287–296.