The title compound, [Cd2(NCS)4(C8H8N2)4], is a centrosymmetric

dinuclear cadmium(II) complex in which each two

metal ions are linked by a pair of thiocyanate N:S-bridges. Two

2-methylbenzimidazole N-atom donors and one terminal

thiocyanate N atom complete a highly distorted squarepyramidal

geometry around the Cd atom. In the crystal

structure, two N—H� � �S hydrogen-bonding interactions

occur, resulting in a three-dimensional polymeric structure.

The apical 2-methylbenzimidazole ring and its symmetryrelated

counterpart are arranged in an antiparallel manner

with a centroid–centroid separation of 3.6050 (14) A ° , indicative

of a �–� interaction

Ahaker, S.

Khaledi, H.

Mohd Ali, H.

UM Digital Repository

Di-l-thiocyanato-j2N:S;j2S:N-bis[bis(2-methyl-1H-benzimidazole-jN3)-(thiocyanato-jN)cadmium(II)]Shayma A. Shaker, Hamid Khaledi* and Hapipah Mohd AliDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, MalaysiaCorrespondence e-mail: khaledi@siswa.um.edu.myReceived 12 October 2010; accepted 19 October 2010Key indicators: single-crystal X-ray study; T = 100 K; mean (C–C) = 0.003 A˚;R factor = 0.021; wR factor = 0.047; data-to-parameter ratio = 14.2.The title compound, [Cd2(NCS)4(C8H8N2)4], is a centrosym-metric dinuclear cadmium(II) complex in which each twometal ions are linked by a pair of thiocyanate N:S-bridges. Two2-methylbenzimidazole N-atom donors and one terminalthiocyanate N atom complete a highly distorted square-pyramidal geometry around the Cd atom. In the crystalstructure, two N—H  S hydrogen-bonding interactionsoccur, resulting in a three-dimensional polymeric structure.The apical 2-methylbenzimidazole ring and its symmetry-related counterpart are arranged in an antiparallel mannerwith a centroid–centroid separation of 3.6050 (14) A˚, indica-tive of a – interaction.Related literatureFor cadmium complexes having a [Cd2(2-NCS)2(NCS)2] unit,see: Gou et al. (2008); Govor et al. (2008); Shi et al. (2004).ExperimentalCrystal data[Cd2(NCS)4(C8H8N2)4]Mr = 985.78Monoclinic, C2=ca = 18.1519 (11) A˚b = 10.2098 (6) A˚c = 21.7385 (13) A˚ = 97.864 (1)V = 3990.8 (4) A˚3Z = 4Mo K radiation = 1.32 mm1T = 100 K0.38  0.20  0.13 mmData collectionBruker APEXII CCDdiffractometerAbsorption correction: multi-scan(SADABS; Sheldrick, 1996)Tmin = 0.634, Tmax = 0.8479361 measured reflections3593 independent reflections3213 reflections with I > 2(I)Rint = 0.022RefinementR[F 2 > 2(F 2)] = 0.021wR(F 2) = 0.047S = 1.033593 reflections253 parameters3 restraintsH atoms treated by a mixture ofindependent and constrainedrefinementmax = 0.35 e A˚3min = 0.31 e A˚3Table 1Hydrogen-bond geometry (A˚, ).D—H  A D—H H  A D  A D—H  AN2—H2N  S1i 0.86 (2) 2.45 (2) 3.273 (2) 163 (2)N4—H4N  S1ii 0.84 (2) 2.48 (2) 3.281 (2) 159 (2)Symmetry codes: (i) xþ 32; yþ 12;zþ 32; (ii) x  12; y 12; z.Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT(Bruker, 2007); data reduction: SAINT; program(s) used to solvestructure: SHELXS97 (Sheldrick, 2008); program(s) used to refinestructure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP inSHELXTL (Sheldrick, 2008); software used to prepare material forpublication: SHELXL97 and publCIF (Westrip, 2010).The authors thank University of Malaya for funding thisstudy (UMRG grant RG024/09BIO).Supplementary data and figures for this paper are available from theIUCr electronic archives (Reference: PK2278).ReferencesBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin,USA.Gou, L., Wu, Q. R., Hu, H. M., Qin, T., Xue, G. L., Yang, M. L. & Tang, Z. X.(2008). Polyhedron, 27, 1517–1526.Govor, E. V., Lysenko, A. B., Domasevitch, K. V., Rusanov, E. B. & Chernega,A. N. (2008). Acta Cryst. C64, m117–m120.Sheldrick, G. M. (1996). SADABS. University of Go¨ttingen, Germany.Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.Shi, Q., Xu, L. J., Ji, J. X., Li, Y. M., Wang, R. H., Zhou, Z. Y., Cao, R., Hong,M. C. & Chan, A. S. C. (2004). Inorg. Chem. Commun. 7, 1254–1257.Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.metal-organic compoundsm1464 A. Shaker et al. doi:10.1107/S1600536810042443 Acta Cryst. (2010). E66, m1464Acta Crystallographica Section EStructure ReportsOnlineISSN 1600-5368supplementary materialssupplementary materialssup-1Acta Cryst. (2010). E66, m1464    [ doi:10.1107/S1600536810042443 ]Di- -thiocyanato- 2N:S; 2S:N-bis[bis(2-methyl-1H-benzimidazole- N3)(thiocyanato-N)cadmium(II)]S. A. Shaker, H. Khaledi and H. Mohd AliCommentThe title compound is a mixed-ligand cadmium(II) complex with thiocyanate and 2-methylbenzimidazole. The thiocyanateions act as either bridging or terminal ligands. The pairs of the former, link each two metal ions into a centrosymmetricdinuclear complex. The resulting eight-membered Cd2(µ2-NCS)2 ring is almost planar (r.m.s = 0.015), unlike the chairconformation observed in most of the similar structures (Gou et al. 2008; Govor et al. 2008; Shi et al. 2004). The terminalthiocyanate ligand forms two types of hydrogen bond with the amine hydrogen atoms (Fig. 2), leading to an infinite three-dimensional network. Two 2-methylbenzimidazole ligands, one in the apical position and the other one equatorially posi-tioned, complete the penta-coordinate cadmium(II) complex in a highly distorted square pyramidal geometry (τ = 0.26). Theapical 2-methylbenzimidazole ring and its symmetry related counterpart at (-x+1, -y, -z+1) are arranged in an antiparallelmanner with separation of 3.6050 (14) Å, indicative of a π-π interaction.ExperimentalAn ethanolic solution (15 ml) of 2-methylbenzimidazole (1.32 g, 10 mmol) was added to an aqueous solution (20 ml) ofCdCl2. H2O (0.5 g, 2.5 mmol) followed by addition of an aqueous solution (15 ml) of KSCN (0.49 g, 5 mmol). The mixturewas heated in a water bath for 30 min with constant stirring. The resulting precipitate was filtered off and recrystallizedfrom ethanol to give the colorless crystals of the title cadmium(II) complex.RefinementThe C-bound hydrogen atoms were placed in idealized locations (C—H = 0.95–0.98 Å) and refined as riding on theirparent carbon atoms. The N-bound hydrogen atoms were located in a difference Fourier map and were refined with distancerestraints of N—H 0.88 (2) Å. U(H) were set to either 1.2 Ueq of the parent atom, or 1.5 Ueq(C) for methyl H. An additionalrigid-bond type restraint (DELU in SHELXL97) was placed on the displacement parameters of S1 and C17.FiguresFig. 1. The molecular structure of the title compound showing displacement ellipsoids at the50% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius. The unla-belled atoms are generated by the symmetry operation (–x + 1, –y + 1, –z + 1).supplementary materialssup-2Fig. 2. A view of the hydrogen bonding interactions (dashed lines). C-bound hydrogen atomshave been omitted for clarity. Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) x + 1/2, y + 1/2, z;(iii) -x + 3/2, -y + 3/2, -z + 1/2; (iv) -x+3/2, y - 1/2, - z+3/2.Di-µ-thiocyanato-κ2N:S;κ2S:N- bis[bis(2-methyl-1H-benzimidazole-κN3)(thiocyanato- κN)cadmium(II)]Crystal data[Cd2(NCS)4(C8H8N2)4] F(000) = 1968Mr = 985.78 Dx = 1.641 Mg m−3Monoclinic, C2/c Mo Kα radiation, λ = 0.71073 ÅHall symbol: -C 2yc Cell parameters from 4666 reflectionsa = 18.1519 (11) Å θ = 2.3–30.1°b = 10.2098 (6) Å µ = 1.32 mm−1c = 21.7385 (13) Å T = 100 Kβ = 97.864 (1)° Block, colorlessV = 3990.8 (4) Å3 0.38 × 0.20 × 0.13 mmZ = 4Data collectionBruker APEXII CCDdiffractometer 3593 independent reflectionsRadiation source: fine-focus sealed tube 3213 reflections with I > 2σ(I)graphite Rint = 0.022φ and ω scans θmax = 25.2°, θmin = 2.3°Absorption correction: multi-scan(SADABS; Sheldrick, 1996) h = −21→21Tmin = 0.634, Tmax = 0.847 k = −12→89361 measured reflections l = −26→26RefinementRefinement on F2Primary atom site location: structure-invariant directmethodsLeast-squares matrix: full Secondary atom site location: difference Fourier mapR[F2 > 2σ(F2)] = 0.021Hydrogen site location: inferred from neighbouringsiteswR(F2) = 0.047H atoms treated by a mixture of independent andconstrained refinementS = 1.03w = 1/[σ2(Fo2) + (0.0169P)2 + 6.0676P]where P = (Fo2 + 2Fc2)/33593 reflections (Δ/σ)max = 0.003supplementary materialssup-3253 parameters Δρmax = 0.35 e Å−33 restraints Δρmin = −0.31 e Å−3Special detailsGeometry. 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 mat-rix. 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; correlationsbetween e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment ofcell 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, convention-al 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 largeas 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)x y z Uiso*/UeqCd1 0.611050 (9) 0.354819 (16) 0.590885 (7) 0.01561 (6)S1 0.88100 (3) 0.33657 (6) 0.67126 (3) 0.02608 (15)S2 0.63546 (3) 0.42113 (7) 0.47897 (3) 0.02741 (16)N1 0.62322 (10) 0.41831 (19) 0.69141 (9) 0.0181 (4)N2 0.63781 (11) 0.5391 (2) 0.77688 (9) 0.0211 (5)H2N 0.6364 (14) 0.609 (2) 0.7982 (11) 0.025*N3 0.57608 (10) 0.14637 (19) 0.58946 (8) 0.0166 (4)N4 0.50684 (11) −0.0294 (2) 0.59628 (9) 0.0193 (4)H4N 0.4715 (12) −0.075 (2) 0.6062 (11) 0.023*N5 0.73824 (11) 0.3290 (2) 0.60377 (10) 0.0258 (5)N6 0.49556 (11) 0.4528 (2) 0.57293 (9) 0.0227 (5)C1 0.57531 (15) 0.6482 (2) 0.68162 (12) 0.0279 (6)H1A 0.5852 0.6462 0.6384 0.042*H1B 0.5953 0.7293 0.7014 0.042*H1C 0.5215 0.6444 0.6826 0.042*C2 0.61150 (12) 0.5342 (2) 0.71553 (11) 0.0195 (5)C3 0.67023 (13) 0.4198 (2) 0.79411 (11) 0.0199 (5)C4 0.70777 (13) 0.3741 (3) 0.85017 (11) 0.0256 (6)H4 0.7157 0.4277 0.8862 0.031*C5 0.73278 (13) 0.2465 (3) 0.85032 (11) 0.0267 (6)H5 0.7590 0.2115 0.8875 0.032*C6 0.72085 (13) 0.1674 (3) 0.79777 (11) 0.0244 (6)H6 0.7376 0.0791 0.8004 0.029*C7 0.68519 (13) 0.2141 (2) 0.74170 (11) 0.0207 (5)H7 0.6782 0.1606 0.7056 0.025*C8 0.66004 (12) 0.3433 (2) 0.74051 (10) 0.0180 (5)C9 0.47424 (14) 0.1670 (2) 0.65538 (11) 0.0235 (6)H9A 0.5070 0.1980 0.6921 0.035*H9B 0.4369 0.1074 0.6683 0.035*H9C 0.4493 0.2419 0.6333 0.035*supplementary materialssup-4C10 0.51909 (12) 0.0964 (2) 0.61350 (10) 0.0180 (5)C11 0.55900 (12) −0.0656 (2) 0.55862 (10) 0.0179 (5)C12 0.57193 (13) −0.1818 (2) 0.52880 (11) 0.0215 (5)H12 0.5417 −0.2570 0.5316 0.026*C13 0.63096 (14) −0.1828 (2) 0.49486 (11) 0.0224 (5)H13 0.6421 −0.2610 0.4743 0.027*C14 0.67477 (13) −0.0712 (2) 0.49010 (11) 0.0221 (5)H14 0.7146 −0.0752 0.4660 0.027*C15 0.66144 (13) 0.0441 (2) 0.51961 (10) 0.0191 (5)H15 0.6914 0.1194 0.5164 0.023*C16 0.60252 (12) 0.0460 (2) 0.55436 (10) 0.0162 (5)C17 0.79736 (13) 0.3327 (2) 0.63127 (11) 0.0190 (5)C18 0.55777 (13) 0.4945 (2) 0.44892 (10) 0.0181 (5)Atomic displacement parameters (Å2)U11 U22 U33 U12 U13 U23Cd1 0.01419 (9) 0.01624 (10) 0.01592 (9) −0.00017 (7) 0.00037 (6) −0.00061 (7)S1 0.0177 (3) 0.0296 (4) 0.0292 (3) −0.0058 (3) −0.0026 (3) 0.0120 (3)S2 0.0179 (3) 0.0383 (4) 0.0273 (3) 0.0099 (3) 0.0080 (3) 0.0139 (3)N1 0.0166 (10) 0.0187 (11) 0.0187 (10) 0.0004 (8) 0.0009 (8) −0.0010 (9)N2 0.0222 (11) 0.0219 (12) 0.0193 (11) 0.0006 (9) 0.0026 (9) −0.0070 (9)N3 0.0148 (9) 0.0179 (10) 0.0169 (9) −0.0008 (8) 0.0016 (8) 0.0001 (8)N4 0.0176 (10) 0.0214 (11) 0.0190 (10) −0.0059 (8) 0.0024 (8) 0.0023 (9)N5 0.0183 (11) 0.0351 (13) 0.0245 (11) 0.0003 (9) 0.0043 (9) 0.0033 (10)N6 0.0210 (11) 0.0283 (12) 0.0188 (10) 0.0040 (9) 0.0031 (9) −0.0008 (9)C1 0.0305 (14) 0.0229 (14) 0.0288 (13) 0.0028 (11) −0.0010 (12) −0.0035 (12)C2 0.0150 (11) 0.0213 (13) 0.0223 (12) −0.0009 (10) 0.0027 (10) −0.0012 (11)C3 0.0160 (12) 0.0262 (14) 0.0181 (12) −0.0029 (10) 0.0043 (10) −0.0003 (11)C4 0.0209 (13) 0.0399 (17) 0.0162 (12) −0.0057 (11) 0.0033 (10) −0.0021 (11)C5 0.0186 (13) 0.0414 (17) 0.0202 (13) 0.0015 (11) 0.0023 (10) 0.0108 (12)C6 0.0185 (12) 0.0260 (14) 0.0298 (14) 0.0029 (10) 0.0071 (11) 0.0095 (11)C7 0.0177 (12) 0.0222 (14) 0.0222 (12) 0.0005 (10) 0.0027 (10) 0.0000 (11)C8 0.0138 (11) 0.0215 (13) 0.0185 (12) −0.0012 (10) 0.0018 (9) 0.0018 (10)C9 0.0232 (13) 0.0284 (15) 0.0197 (12) −0.0038 (11) 0.0061 (10) −0.0028 (11)C10 0.0164 (12) 0.0220 (13) 0.0148 (11) −0.0014 (10) −0.0002 (10) 0.0035 (10)C11 0.0178 (12) 0.0211 (13) 0.0139 (11) −0.0015 (10) −0.0016 (9) 0.0039 (10)C12 0.0248 (13) 0.0182 (13) 0.0198 (12) −0.0046 (10) −0.0025 (10) 0.0013 (10)C13 0.0256 (13) 0.0197 (13) 0.0206 (12) 0.0024 (10) −0.0010 (11) −0.0029 (10)C14 0.0194 (12) 0.0262 (14) 0.0208 (12) 0.0011 (10) 0.0032 (10) −0.0010 (11)C15 0.0174 (12) 0.0184 (13) 0.0210 (12) −0.0023 (10) 0.0002 (10) 0.0004 (10)C16 0.0156 (11) 0.0176 (12) 0.0141 (11) 0.0004 (9) −0.0023 (9) 0.0016 (10)C17 0.0201 (12) 0.0184 (13) 0.0193 (12) −0.0006 (10) 0.0061 (10) 0.0050 (10)C18 0.0177 (12) 0.0207 (13) 0.0164 (12) −0.0015 (10) 0.0048 (10) 0.0004 (10)Geometric parameters (Å, °)Cd1—N3 2.2199 (19) C3—C8 1.394 (3)Cd1—N1 2.2611 (19) C4—C5 1.379 (4)supplementary materialssup-5Cd1—N5 2.302 (2) C4—H4 0.9500Cd1—N6 2.307 (2) C5—C6 1.392 (4)Cd1—S2 2.6207 (7) C5—H5 0.9500S1—C17 1.644 (2) C6—C7 1.385 (3)S2—C18 1.651 (2) C6—H6 0.9500N1—C2 1.323 (3) C7—C8 1.394 (3)N1—C8 1.406 (3) C7—H7 0.9500N2—C2 1.355 (3) C9—C10 1.488 (3)N2—C3 1.382 (3) C9—H9A 0.9800N2—H2N 0.856 (17) C9—H9B 0.9800N3—C10 1.323 (3) C9—H9C 0.9800N3—C16 1.401 (3) C11—C12 1.388 (3)N4—C10 1.347 (3) C11—C16 1.396 (3)N4—C11 1.384 (3) C12—C13 1.382 (3)N4—H4N 0.844 (16) C12—H12 0.9500N5—C17 1.155 (3) C13—C14 1.401 (3)N6—C18i 1.152 (3) C13—H13 0.9500C1—C2 1.482 (3) C14—C15 1.378 (3)C1—H1A 0.9800 C14—H14 0.9500C1—H1B 0.9800 C15—C16 1.391 (3)C1—H1C 0.9800 C15—H15 0.9500C3—C4 1.393 (3) C18—N6i 1.152 (3)N3—Cd1—N1 106.16 (7) C4—C5—H5 118.9N3—Cd1—N5 99.90 (7) C6—C5—H5 118.9N1—Cd1—N5 87.22 (7) C7—C6—C5 121.6 (2)N3—Cd1—N6 99.32 (7) C7—C6—H6 119.2N1—Cd1—N6 90.32 (7) C5—C6—H6 119.2N5—Cd1—N6 160.55 (7) C6—C7—C8 117.1 (2)N3—Cd1—S2 108.61 (5) C6—C7—H7 121.5N1—Cd1—S2 144.74 (5) C8—C7—H7 121.5N5—Cd1—S2 81.28 (5) C3—C8—C7 120.6 (2)N6—Cd1—S2 89.77 (5) C3—C8—N1 108.9 (2)C18—S2—Cd1 103.94 (8) C7—C8—N1 130.5 (2)C2—N1—C8 105.77 (19) C10—C9—H9A 109.5C2—N1—Cd1 129.77 (16) C10—C9—H9B 109.5C8—N1—Cd1 123.42 (15) H9A—C9—H9B 109.5C2—N2—C3 108.3 (2) C10—C9—H9C 109.5C2—N2—H2N 122.1 (18) H9A—C9—H9C 109.5C3—N2—H2N 129.4 (18) H9B—C9—H9C 109.5C10—N3—C16 106.11 (19) N3—C10—N4 111.5 (2)C10—N3—Cd1 126.99 (16) N3—C10—C9 125.3 (2)C16—N3—Cd1 126.17 (15) N4—C10—C9 123.2 (2)C10—N4—C11 108.57 (19) N4—C11—C12 132.7 (2)C10—N4—H4N 123.9 (18) N4—C11—C16 105.1 (2)C11—N4—H4N 127.4 (18) C12—C11—C16 122.2 (2)C17—N5—Cd1 154.70 (19) C13—C12—C11 116.7 (2)C18i—N6—Cd1 164.86 (18) C13—C12—H12 121.7C2—C1—H1A 109.5 C11—C12—H12 121.7supplementary materialssup-6C2—C1—H1B 109.5 C12—C13—C14 121.5 (2)H1A—C1—H1B 109.5 C12—C13—H13 119.2C2—C1—H1C 109.5 C14—C13—H13 119.2H1A—C1—H1C 109.5 C15—C14—C13 121.5 (2)H1B—C1—H1C 109.5 C15—C14—H14 119.2N1—C2—N2 111.7 (2) C13—C14—H14 119.2N1—C2—C1 126.1 (2) C14—C15—C16 117.5 (2)N2—C2—C1 122.2 (2) C14—C15—H15 121.2N2—C3—C4 132.2 (2) C16—C15—H15 121.2N2—C3—C8 105.3 (2) C15—C16—C11 120.5 (2)C4—C3—C8 122.4 (2) C15—C16—N3 130.7 (2)C5—C4—C3 116.1 (2) C11—C16—N3 108.8 (2)C5—C4—H4 121.9 N5—C17—S1 179.1 (2)C3—C4—H4 121.9 N6i—C18—S2 178.5 (2)C4—C5—C6 122.2 (2)Symmetry codes: (i) −x+1, −y+1, −z+1.Hydrogen-bond geometry (Å, °)D—H···A D—H H···A D···A D—H···AN2—H2N···S1ii 0.86 (2) 2.44 (2) 3.273 (2) 163 (2)N4—H4N···S1iii 0.84 (2) 2.48 (2) 3.281 (2) 159 (2)Symmetry codes: (ii) −x+3/2, y+1/2, −z+3/2; (iii) x−1/2, y−1/2, z.supplementary materialssup-7Fig. 1supplementary materialssup-8Fig. 2

Di--thiocyanato-2N: S; 2S: N-bis [bis (2-methyl-1H-benzimidazole-N3)(thiocyanato-N) cadmium (II)]

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Di--thiocyanato-2N: S; 2S: N-bis [bis (2-methyl-1H-benzimidazole-N3)(thiocyanato-N) cadmium (II)]

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