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Acta Cryst. (2007). E63, m2297    [ doi:10.1107/S1600536807038524 ]

Dichloridobis(methanol-[kappa]O)bis(6-methyl-3-phenyl-1,2,4-triazolo[3,4-b][1,3,4]thiadiazole-[kappa]N1)cadmium(II)

P.-Z. Hong, W.-D. Song and Z.-H. Wu

Abstract top

The title complex, [CdCl2(C10H8N4S)2(CH4O)2], a neutral mononuclear molecule, consists of a CdII ion, two 6-methyl-3-phenyl-1,2,4-triazolo[3,4-b][1,3,4]thiadiazole ligands, two chloride ligands and two coordinated methanol molecules. The CdII ion, located on a center of symmetry, displays a distorted octahedral coordination geometry. A supramolecular network structure is formed by intermolecular O-H...Cl hydrogen bonds and [pi]-[pi] contacts [centroid-centroid distance 3.613 (7) Å].

Comment top

The molecular structure of 6-methyl-3-phenyl-[1,2,4]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 these ligands have so far been reported. In this paper, we report the crystal structure of the title compound, (I), a Cd complex obtained by the reaction of 6-methyl-3-phenyl-[1,2,4]triazolo(3,4 − b)-1,3,4-thiadiazole with cadmium chloride in methanol solution.

As illustrated in Fig. 1, the CdII atom, which is a neutral mononuclear molecule, lies on a centre of symmetry and has a distorted octahedral geometry with six coordinating atoms: two N atoms from two 6-methyl-3-phenyl-[1,2,4]triazolo(3,4 − b)-1,3,4-thiadiazole, two O from two methanol molecules and two chlorine atoms (Table 1). The structural components are connected through O—H···Cl hydrogen bonding involving the coordinating methanol molecules as donors and the Cl atoms as acceptors and π-π stacking interactions between the phenyl and triazolo rings, thus forming a supramolecular network structure (Fig. 2; Table 2). The centroid-centroid distance of adjacent phenyl and triazolo rings (at 1 − x,-y,1 − z) is 3.613 (7) Å, indicating a normal π-π interaction.

Related literature top

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

For related literature, see: Huang et al. (2005).

Experimental top

The title complex was prepared by the addition of a stoichiometric amount of cadmium chloride (1 mmol) to a hot methanol solution (10 ml) of 2-methyl-5-phenyl-s-triazolo(3,4 − b)-1,3,4-thiadiazole (1 mmol). The resulting solution was filtered, and yellow blocky crystals were obtained on slow evaporation of the solvent over several days at room temperature.

Refinement top

Carbon-bound and hydroxyl H atoms were placed at calculated positions and were treated as riding on the parent C atoms with C—H = 0.93–0.97 or O—H = 0.82 Å, and with Uiso(H) = 1.2 or 1.5 Ueq(C, O). The terminal methyl and hydroxyl groups were also allowed free rotation.

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 structure of (I), showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level. Unlabelled atoms are related to the labelled atoms by the symmetry operator (−x, 2 − y, −z).
[Figure 2] Fig. 2. A packing view of (I), showing the intermolecular hydrogen bonding interactions as broken lines.
Dichloridobis(methanol-κO)bis(6-methyl-3-phenyl-1,2,4-\ triazolo[3,4-b][1,3,4]thiadiazole-κN1)cadmium(II) top
Crystal data top
[CdCl2(C10H8N4S)2(CH4O)2]Z = 1
Mr = 679.91F000 = 342
Triclinic, P1Dx = 1.714 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 6.7576 (9) ÅCell parameters from 2400 reflections
b = 8.6138 (11) Åθ = 1.4–28.0º
c = 12.1019 (15) ŵ = 1.23 mm−1
α = 95.5880 (10)ºT = 291 (2) K
β = 104.0370 (10)ºBlock, yellow
γ = 102.4960 (10)º0.44 × 0.31 × 0.22 mm
V = 658.81 (15) Å3
Data collection top
Bruker APEX II area-detector
diffractometer		2386 independent reflections
Radiation source: fine-focus sealed tube2327 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.011
T = 291(2) Kθmax = 25.5º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→8
Tmin = 0.633, Tmax = 0.764k = −10→10
4509 measured reflectionsl = −14→14
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)] = 0.019H-atom parameters constrained
wR(F2) = 0.051  w = 1/[σ2(Fo2) + (0.0249P)2 + 0.3405P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max < 0.001
2386 reflectionsΔρmax = 0.46 e Å−3
171 parametersΔρmin = −0.45 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[CdCl2(C10H8N4S)2(CH4O)2]γ = 102.4960 (10)º
Mr = 679.91V = 658.81 (15) Å3
Triclinic, P1Z = 1
a = 6.7576 (9) ÅMo Kα
b = 8.6138 (11) ŵ = 1.23 mm−1
c = 12.1019 (15) ÅT = 291 (2) K
α = 95.5880 (10)º0.44 × 0.31 × 0.22 mm
β = 104.0370 (10)º
Data collection top
Bruker APEX II area-detector
diffractometer		2386 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2327 reflections with I > 2σ(I)
Tmin = 0.633, Tmax = 0.764Rint = 0.011
4509 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.019171 parameters
wR(F2) = 0.051H-atom parameters constrained
S = 1.12Δρmax = 0.46 e Å−3
2386 reflectionsΔρmin = −0.45 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
Cd10.00001.00000.00000.02382 (7)
Cl10.21045 (8)0.79569 (6)−0.04065 (4)0.03678 (13)
S1−0.03252 (8)0.61793 (6)0.16761 (4)0.03174 (12)
O10.3105 (2)1.20734 (17)0.02416 (13)0.0378 (3)
H1A0.39611.1971−0.02450.057*
N10.0945 (3)0.9611 (2)0.19295 (13)0.0293 (4)
N20.1805 (3)1.0753 (2)0.29327 (14)0.0287 (3)
C70.1962 (3)0.9992 (2)0.38328 (16)0.0257 (4)
N30.1205 (2)0.83616 (18)0.34395 (13)0.0249 (3)
N40.0906 (3)0.69736 (19)0.39330 (14)0.0280 (3)
C10.3662 (3)1.2428 (3)0.52946 (18)0.0343 (4)
H10.36961.30280.46980.041*
C20.4460 (4)1.3187 (3)0.6438 (2)0.0411 (5)
H20.50061.42980.66000.049*
C30.4446 (3)1.2307 (3)0.73328 (18)0.0410 (5)
H30.49881.28220.80930.049*
C40.3625 (4)1.0656 (3)0.70944 (18)0.0400 (5)
H40.36221.00610.76960.048*
C50.2802 (3)0.9882 (3)0.59548 (17)0.0336 (4)
H50.22440.87730.57970.040*
C60.2815 (3)1.0772 (2)0.50492 (16)0.0266 (4)
C100.0617 (3)0.8198 (2)0.22672 (15)0.0265 (4)
C80.0103 (3)0.5756 (2)0.31026 (16)0.0292 (4)
C9−0.0456 (4)0.4066 (3)0.33259 (19)0.0425 (5)
H9A0.00250.40460.41380.064*
H9B0.02030.34150.29150.064*
H9C−0.19570.36490.30690.064*
C110.3701 (4)1.3467 (3)0.1099 (2)0.0519 (6)
H10A0.25101.39140.10770.078*
H10B0.48141.42500.09530.078*
H10C0.41791.31760.18460.078*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.02905 (11)0.02292 (11)0.01872 (10)0.00580 (8)0.00528 (7)0.00425 (7)
Cl10.0386 (3)0.0388 (3)0.0361 (3)0.0168 (2)0.0112 (2)0.0022 (2)
S10.0461 (3)0.0253 (2)0.0220 (2)0.0082 (2)0.0065 (2)0.00352 (19)
O10.0324 (8)0.0315 (8)0.0454 (9)0.0019 (6)0.0123 (7)−0.0034 (6)
N10.0398 (9)0.0263 (8)0.0215 (8)0.0093 (7)0.0066 (7)0.0040 (6)
N20.0361 (9)0.0262 (8)0.0229 (8)0.0077 (7)0.0067 (7)0.0024 (6)
C70.0270 (9)0.0270 (9)0.0240 (9)0.0083 (8)0.0077 (7)0.0036 (7)
N30.0309 (8)0.0254 (8)0.0193 (7)0.0085 (7)0.0066 (6)0.0058 (6)
N40.0349 (9)0.0270 (8)0.0247 (8)0.0095 (7)0.0094 (7)0.0091 (7)
C10.0363 (11)0.0329 (11)0.0320 (10)0.0079 (9)0.0070 (9)0.0042 (9)
C20.0391 (12)0.0353 (11)0.0410 (12)0.0058 (9)0.0046 (9)−0.0075 (10)
C30.0365 (11)0.0537 (14)0.0268 (10)0.0108 (10)0.0036 (9)−0.0089 (10)
C40.0432 (12)0.0532 (14)0.0242 (10)0.0129 (11)0.0091 (9)0.0072 (9)
C50.0380 (11)0.0349 (11)0.0267 (10)0.0073 (9)0.0081 (8)0.0042 (8)
C60.0240 (9)0.0323 (10)0.0230 (9)0.0089 (8)0.0055 (7)0.0006 (8)
C100.0328 (10)0.0279 (10)0.0200 (9)0.0097 (8)0.0068 (7)0.0049 (7)
C80.0353 (10)0.0297 (10)0.0247 (9)0.0105 (8)0.0082 (8)0.0084 (8)
C90.0642 (15)0.0284 (11)0.0323 (11)0.0081 (10)0.0096 (10)0.0089 (9)
C110.0438 (13)0.0419 (14)0.0585 (16)0.0012 (11)0.0091 (11)−0.0136 (11)
Geometric parameters (Å, °) top
Cd1—N1i2.3438 (16)C1—C61.390 (3)
Cd1—N12.3438 (16)C1—C21.394 (3)
Cd1—O1i2.3785 (14)C1—H10.9300
Cd1—O12.3785 (14)C2—C31.382 (3)
Cd1—Cl12.5721 (5)C2—H20.9300
Cd1—Cl1i2.5721 (5)C3—C41.383 (3)
S1—C101.731 (2)C3—H30.9300
S1—C81.7672 (19)C4—C51.394 (3)
O1—C111.423 (3)C4—H40.9300
O1—H1A0.9300C5—C61.398 (3)
N1—C101.313 (3)C5—H50.9300
N1—N21.399 (2)C8—C91.491 (3)
N2—C71.319 (3)C9—H9A0.9600
C7—N31.379 (2)C9—H9B0.9600
C7—C61.476 (2)C9—H9C0.9600
N3—C101.362 (2)C11—H10A0.9600
N3—N41.386 (2)C11—H10B0.9600
N4—C81.299 (3)C11—H10C0.9600
N1i—Cd1—N1180.00 (8)C3—C2—C1120.7 (2)
N1i—Cd1—O1i93.09 (6)C3—C2—H2119.7
N1—Cd1—O1i86.91 (6)C1—C2—H2119.7
N1i—Cd1—O186.91 (6)C2—C3—C4119.8 (2)
N1—Cd1—O193.09 (6)C2—C3—H3120.1
O1i—Cd1—O1180.0C4—C3—H3120.1
N1i—Cd1—Cl193.32 (4)C3—C4—C5120.1 (2)
N1—Cd1—Cl186.68 (4)C3—C4—H4119.9
O1i—Cd1—Cl192.17 (4)C5—C4—H4119.9
O1—Cd1—Cl187.83 (4)C4—C5—C6120.1 (2)
N1i—Cd1—Cl1i86.68 (4)C4—C5—H5120.0
N1—Cd1—Cl1i93.32 (4)C6—C5—H5120.0
O1i—Cd1—Cl1i87.83 (4)C1—C6—C5119.51 (18)
O1—Cd1—Cl1i92.17 (4)C1—C6—C7118.98 (18)
Cl1—Cd1—Cl1i180.00 (2)C5—C6—C7121.51 (18)
C10—S1—C887.32 (9)N1—C10—N3110.67 (16)
C11—O1—Cd1122.51 (14)N1—C10—S1139.33 (15)
C11—O1—H1A118.8N3—C10—S1110.00 (14)
Cd1—O1—H1A118.7N4—C8—C9122.19 (18)
C10—N1—N2106.37 (15)N4—C8—S1117.17 (15)
C10—N1—Cd1124.10 (12)C9—C8—S1120.63 (15)
N2—N1—Cd1129.41 (12)C8—C9—H9A109.5
C7—N2—N1108.57 (15)C8—C9—H9B109.5
N2—C7—N3108.37 (16)H9A—C9—H9B109.5
N2—C7—C6125.23 (17)C8—C9—H9C109.5
N3—C7—C6126.40 (17)H9A—C9—H9C109.5
C10—N3—C7106.01 (15)H9B—C9—H9C109.5
C10—N3—N4117.68 (15)O1—C11—H10A109.5
C7—N3—N4136.30 (15)O1—C11—H10B109.5
C8—N4—N3107.80 (15)H10A—C11—H10B109.5
C6—C1—C2119.8 (2)O1—C11—H10C109.5
C6—C1—H1120.1H10A—C11—H10C109.5
C2—C1—H1120.1H10B—C11—H10C109.5
Symmetry codes: (i) −x, −y+2, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···Cl1ii0.932.573.2005 (16)126
Symmetry codes: (ii) −x+1, −y+2, −z.
Table 1
Selected geometric parameters (Å, °) top
Cd1—N12.3438 (16)Cd1—Cl12.5721 (5)
Cd1—O12.3785 (14)
N1i—Cd1—O1i93.09 (6)N1—Cd1—Cl186.68 (4)
N1i—Cd1—O186.91 (6)O1i—Cd1—Cl192.17 (4)
N1—Cd1—O193.09 (6)O1—Cd1—Cl187.83 (4)
N1i—Cd1—Cl193.32 (4)
Symmetry codes: (i) −x, −y+2, −z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···Cl1ii0.932.573.2005 (16)126
Symmetry codes: (ii) −x+1, −y+2, −z.
Acknowledgements top

The authors thank the Scientific and Technical Key Leading Project of Guangdong Province of China (grant No. B05119) and the Foundation for Excellent Persons over Introduction of [please check; is there a clearer way of translating this?] Zhanjiang and Guangdong Ocean University for supporting this study.

references
References top

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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. de la M. & Foces-Foces, C. (1989). Liebigs Ann. Chem. 1111, 1055–1059.

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

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