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Acta Cryst. (2007). E63, m2466    [ doi:10.1107/S1600536807042560 ]

Dibromidobis(6-methyl-3-phenyl-s-triazolo[3,4-b][1,3,4]thiadiazole-[kappa]N1)copper(II)

H.-Q. Liu

Abstract top

In the title complex, [CuBr2(C10H8N4S)2], the CuII atom is located on an inversion centre and displays a distorted square-planar coordination geometry. The dihedral angle between the fused-ring system and its phenyl substituent is 2.1 (3)°. Intermolecular C-H...Br hydrogen bonds and [pi]-[pi] contacts [with an interplanar separation of 3.513 (3) Å] form a supramolecular network structure.

Comment top

The molecular structure of 2-methyl-5-phenyl-s-triazolo(3,4 − b)-1,3,4-thiadiazole (Fornies-Marquina et al., 1974) and its substituted derivatives (Molina et al., 1989; Huang et al., 2005; Naveen et al., 2006) have been reported; however, no metal complexes of the ligand have been reported. In this paper, we report the crystal structure of the title compound, (I), a Cu complex obtained by the reaction of 2-methyl-5-phenyl-s-triazolo(3,4 − b)-1,3,4-thiadiazole with copper(II) bromide in methanol solution.

As illustrated in Fig. 1, the CuII atom lies on an inversion centre and has a distorted square-planar geometry with two N atoms from two 2-methyl-5-phenyl-s-triazolo(3,4 − b)-1,3,4-thiadiazole ligands and two bromine atoms (Table 1). There are intramolecular C—H···N interactions. The molecules are connected through C—H···Br hydrogen bonding and π-π stacking interactions between the phenyl ring and triazolo ring, forming a supramolecular network structure (Table 2). The centroid-centroid distance of stacked rings is 3.513 (3) Å.

Related literature top

For related literature, see: Fornies-Marquina et al. (1974); Molina et al. (1989); Huang et al. (2005); Naveen et al. (2006).

Experimental top

The title complex was prepared by the addition of copper(II) bromide (0.0568 g, 0.25 mmol) to a hot methanol solution (10 ml) of 2-methyl-5-phenyl-s-triazolo(3,4 − b)-1,3,4-thiadiazole (0.085 g, 0.48 mmol). The resulting solution was filtered, and blue block crystals were obtained at room temperature on slow evaporation of the solvent over several days.

Refinement top

H atoms were placed at calculated positions and were treated as riding on the parent C atoms with C—H = 0.93–0.97 and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); 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, 2004); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level. Unlabelled atoms and atoms with the suffix A are related to the labelled atoms by the symmetry operator (1 − x, 1 − y, −z).
Dibromidobis(6-methyl-3-phenyl-s-triazolo[3,4-b][1,3,4]thiadiazole-κN1)\ copper(II) top
Crystal data top
[CuBr2(C10H8N4S)2]Z = 1
Mr = 655.89F000 = 323
Triclinic, P1Dx = 1.869 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 6.8286 (10) ÅCell parameters from 1927 reflections
b = 8.5231 (13) Åθ = 1.9–25.2º
c = 11.3654 (16) ŵ = 4.57 mm−1
α = 98.442 (2)ºT = 298 (2) K
β = 105.614 (2)ºBlock, blue
γ = 108.859 (2)º0.44 × 0.31 × 0.22 mm
V = 582.69 (15) Å3
Data collection top
Bruker APEXII area-detector
diffractometer		1927 independent reflections
Radiation source: fine-focus sealed tube1430 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.101
T = 298(2) Kθmax = 25.2º
φ and ω scansθmin = 1.9º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→8
Tmin = 0.196, Tmax = 0.366k = −10→10
3511 measured reflectionsl = −13→13
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)] = 0.041H-atom parameters constrained
wR(F2) = 0.106  w = 1/[σ2(Fo2) + (0.0555P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.89(Δ/σ)max < 0.001
1927 reflectionsΔρmax = 0.74 e Å−3
152 parametersΔρmin = −0.82 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[CuBr2(C10H8N4S)2]γ = 108.859 (2)º
Mr = 655.89V = 582.69 (15) Å3
Triclinic, P1Z = 1
a = 6.8286 (10) ÅMo Kα
b = 8.5231 (13) ŵ = 4.57 mm−1
c = 11.3654 (16) ÅT = 298 (2) K
α = 98.442 (2)º0.44 × 0.31 × 0.22 mm
β = 105.614 (2)º
Data collection top
Bruker APEXII area-detector
diffractometer		1927 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1430 reflections with I > 2σ(I)
Tmin = 0.196, Tmax = 0.366Rint = 0.101
3511 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.041152 parameters
wR(F2) = 0.106H-atom parameters constrained
S = 0.89Δρmax = 0.74 e Å−3
1927 reflectionsΔρmin = −0.82 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
Br10.85241 (9)0.72698 (7)0.06813 (5)0.0689 (3)
Cu10.50000.50000.00000.0354 (2)
S10.3985 (2)0.08848 (13)0.13106 (10)0.0422 (3)
N10.5615 (6)0.4521 (4)0.1695 (3)0.0372 (9)
N20.6696 (6)0.5812 (4)0.2825 (3)0.0373 (8)
N30.6000 (6)0.3339 (4)0.3277 (3)0.0313 (8)
N40.5775 (6)0.1935 (4)0.3769 (3)0.0364 (8)
C10.8741 (8)0.7801 (6)0.5408 (4)0.0427 (11)
H10.86170.83710.47710.051*
C20.9722 (8)0.8728 (6)0.6678 (4)0.0488 (12)
H21.02510.99200.68930.059*
C30.9893 (8)0.7859 (7)0.7602 (4)0.0482 (12)
H31.05390.84780.84450.058*
C50.8168 (8)0.5183 (6)0.6051 (4)0.0412 (11)
H40.76610.39920.58480.049*
C60.7953 (7)0.6014 (5)0.5107 (4)0.0321 (9)
C40.9144 (9)0.6115 (6)0.7317 (4)0.0498 (12)
H60.92800.55510.79580.060*
C80.5198 (7)0.3057 (5)0.2006 (4)0.0349 (10)
C90.4788 (8)0.0574 (6)0.2846 (4)0.0410 (11)
C100.4271 (9)−0.1187 (6)0.3017 (5)0.0628 (15)
H17A0.4735−0.11340.39020.094*
H17B0.5029−0.17390.26130.094*
H17C0.2715−0.18290.26450.094*
C70.6928 (7)0.5087 (5)0.3755 (4)0.0321 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0591 (4)0.0724 (4)0.0373 (3)−0.0128 (3)0.0003 (3)0.0209 (3)
Cu10.0443 (5)0.0328 (4)0.0219 (4)0.0077 (3)0.0087 (3)0.0071 (3)
S10.0511 (8)0.0350 (6)0.0336 (6)0.0126 (5)0.0102 (6)0.0056 (5)
N10.045 (2)0.0359 (19)0.0236 (17)0.0093 (17)0.0078 (17)0.0070 (15)
N20.045 (2)0.0343 (19)0.0250 (18)0.0103 (17)0.0083 (17)0.0049 (15)
N30.038 (2)0.0324 (19)0.0257 (17)0.0148 (16)0.0108 (16)0.0095 (15)
N40.041 (2)0.039 (2)0.0342 (19)0.0186 (17)0.0131 (18)0.0151 (17)
C10.047 (3)0.046 (3)0.032 (2)0.017 (2)0.012 (2)0.007 (2)
C20.046 (3)0.050 (3)0.036 (3)0.011 (2)0.008 (2)−0.005 (2)
C30.042 (3)0.070 (3)0.027 (2)0.019 (3)0.011 (2)0.000 (2)
C50.048 (3)0.043 (2)0.032 (2)0.016 (2)0.014 (2)0.007 (2)
C60.034 (2)0.040 (2)0.025 (2)0.016 (2)0.013 (2)0.0071 (18)
C40.057 (3)0.066 (3)0.028 (2)0.023 (3)0.016 (2)0.015 (2)
C80.038 (3)0.036 (2)0.029 (2)0.012 (2)0.014 (2)0.0072 (18)
C90.042 (3)0.044 (3)0.043 (3)0.021 (2)0.014 (2)0.018 (2)
C100.073 (4)0.046 (3)0.063 (4)0.025 (3)0.006 (3)0.021 (3)
C70.032 (2)0.037 (2)0.029 (2)0.0130 (19)0.0116 (19)0.0100 (18)
Geometric parameters (Å, °) top
Br1—Cu12.3834 (6)C1—H10.930
Cu1—N1i1.990 (3)C2—C31.372 (7)
Cu1—N11.990 (3)C2—H20.930
Cu1—Br1i2.3834 (6)C3—C41.362 (7)
S1—C81.722 (4)C3—H30.930
S1—C91.770 (5)C5—C61.372 (6)
N1—C81.311 (5)C5—C41.397 (6)
N1—N21.398 (4)C5—H40.930
N2—C71.300 (5)C6—C71.477 (5)
N3—C81.353 (5)C4—H60.930
N3—C71.372 (5)C9—C101.482 (6)
N3—N41.376 (4)C10—H17A0.960
N4—C91.287 (6)C10—H17B0.960
C1—C61.394 (6)C10—H17C0.960
C1—C21.400 (6)
N1i—Cu1—N1180C6—C5—C4120.4 (4)
N1i—Cu1—Br189.18 (10)C6—C5—H4119.8
N1—Cu1—Br190.82 (10)C4—C5—H4119.8
N1i—Cu1—Br1i90.82 (10)C5—C6—C1119.9 (4)
N1—Cu1—Br1i89.18 (10)C5—C6—C7122.5 (4)
Br1—Cu1—Br1i180C1—C6—C7117.6 (4)
C8—S1—C987.4 (2)C3—C4—C5119.2 (4)
C8—N1—N2106.6 (3)C3—C4—H6120.4
C8—N1—Cu1130.2 (3)C5—C4—H6120.4
N2—N1—Cu1123.2 (2)N1—C8—N3110.1 (4)
C7—N2—N1108.2 (3)N1—C8—S1140.1 (3)
C8—N3—C7106.1 (3)N3—C8—S1109.8 (3)
C8—N3—N4117.9 (3)N4—C9—C10123.5 (4)
C7—N3—N4135.9 (3)N4—C9—S1116.5 (3)
C9—N4—N3108.2 (3)C10—C9—S1119.9 (4)
C6—C1—C2119.4 (4)C9—C10—H17A109.5
C6—C1—H1120.3C9—C10—H17B109.5
C2—C1—H1120.3H17A—C10—H17B109.5
C3—C2—C1119.3 (4)C9—C10—H17C109.5
C3—C2—H2120.3H17A—C10—H17C109.5
C1—C2—H2120.3H17B—C10—H17C109.5
C4—C3—C2121.7 (4)N2—C7—N3109.0 (3)
C4—C3—H3119.1N2—C7—C6124.9 (4)
C2—C3—H3119.1N3—C7—C6126.1 (4)
Symmetry codes: (i) −x+1, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C10—H17C···Br1ii0.962.903.769 (5)151
C1—H1···N20.932.562.871 (5)100
C5—H4···N40.932.453.122 (6)129
Symmetry codes: (ii) x−1, y−1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C10—H17C···Br1i0.962.903.769 (5)151
C1—H1···N20.932.562.871 (5)100
C5—H4···N40.932.453.122 (6)129
Symmetry codes: (i) x−1, y−1, z.
Acknowledgements top

The author thanks the Scientific and Technical Key Leading Project of Guangdong Province of China (grant No. B05119) for supporting this study.

references
References top

Bruker (2004). APEX2 (Version 6.01), SAINT (Version 7.23A) and SHELXTL (Version 5.1). Bruker AXS Inc., Madison, Wisconsin, USA.

Fornies-Marquina, J. M., Courseille, C. & Elguero, J. (1974). Cryst. Struct. Commun. 3, 7–9.

Huang, X.-B., Liu, M.-C., Zhang, L.-X., Zhang, A.-J., Xu, Y.-L. & Hu, M.-L. (2005). Acta Cryst. E61, o2233–o2234.

Molina, P., Arques, A., Alias, M. A., Llamas Saiz, A. L. & Foces-Foces, C. (1989). Liebigs Ann. Chem. 1111, 1055–1059.

Naveen, S., Swamy, S. N., Basappa, initials?, Swamy, B. P., Anandalwar, S. M., Prasad, J. S. & Rangappa, K. S. (2006). Anal. Sci. 22, x221–x222.

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

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