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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): m993.
Published online 2010 July 21. doi:  10.1107/S1600536810028448
PMCID: PMC3007206

Dibromido[1,1′-dibenzyl-2,2′-(sulfane­diyl­dimethyl­ene)di-1H-benzimidazole]­cadmium(II) dimethyl­formamide solvate

Abstract

In the title compound, [CdBr2(C30H26N4S)]·C3H7NO, both the complex and solvent mol­ecule lie on a crystallographic mirror plane. The CdII ion is coordinated in a disorted square-pyramidal CdBr2N2S environment with one of the Br atoms in the apical site. In the crystal structure, the benzimidazole ring systems are involved in weak inter­molecular π–π stacking inter­actions [centroid–centroid distances = 3.606 (2) and 3.753 (2) Å]. Further stabilization is provided by weak inter­molecular C—H(...)O hydrogen bonds. The methyl H atoms of the dimethyl­formamide solvent mol­ecule are disordered about a mirror plane.

Related literature

For background to the synthesis and for related structures of 1,3-bis­(benzimidazol-2-yl)-2-thia­propane and its derivatives, see: Dagdigian et al. (1979 [triangle]); Agh-Atabay et al.(2004 [triangle]); Wu et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m993-scheme1.jpg

Experimental

Crystal data

  • [CdBr2(C30H26N4S)]·C3H7NO
  • M r = 819.92
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m993-efi1.jpg
  • a = 9.7437 (8) Å
  • b = 16.7792 (14) Å
  • c = 10.5931 (9) Å
  • β = 110.029 (1)°
  • V = 1627.1 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 3.23 mm−1
  • T = 296 K
  • 0.36 × 0.32 × 0.28 mm

Data collection

  • Bruker APEXII area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2006 [triangle]) T min = 0.390, T max = 0.465
  • 9062 measured reflections
  • 3305 independent reflections
  • 2742 reflections with I > 2σ(I)
  • R int = 0.027

Refinement

  • R[F 2 > 2σ(F 2)] = 0.029
  • wR(F 2) = 0.077
  • S = 1.05
  • 3305 reflections
  • 211 parameters
  • H-atom parameters constrained
  • Δρmax = 0.78 e Å−3
  • Δρmin = −0.64 e Å−3

Data collection: APEX2 (Bruker, 2006 [triangle]); cell refinement: SAINT (Bruker, 2006 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810028448/lh5084sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810028448/lh5084Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors acknowledge financial support and a grant from the Qing Lan Talent Engineering Funds of Lanzhou Jiaotong University.

supplementary crystallographic information

Comment

The asymmetric unit of the title complex is shown in Fig. 1. The CdII ion is coordinated by one tridentate 1,3-bis(1-benzylbenzimidazol-2-yl)-2-thiapropane ligand and two bromide ions in a distorted square-pyramidal geometry. In the crystal structure, the benzimidazole ring systems are involved in weak intermolecular π–π stacking interactions [centroid–centroid distances = 3.606 (2) and 3.753 (2) Å].

Experimental

To a stirred solution of 1,3-bis(1-benzylbenzimidazol-2-yl)-2-thiapropane (0.237 g, 0.50 mmol) in hot MeOH (10 ml) was added Cd(C6H2N3O7)2 (0.154 g, 0.25 mmol) and KBr(0.059 g, 0.50 mmol) in MeOH (5 ml). A yellow crystalline product formed rapidly. The precipitate was filtered off, washed with MeOH and absolute Et2O, and dried in vacuo. The dried precipitate was dissolved in DMF resulting in a yellow solution. The deep yellow crystals suitable for X-ray diffraction studies were obtained by ether diffusion into a solution of the title compound in DMF after several days at room temperature. Yield, 0.29 g (73%). (found: C, 54.16; H, 4.49; N,9.63. Calcd.: C, 54.22; H, 4.55; N, 9.58)

Refinement

All H atoms were visible in difference Fourier maps and were subsequently refined in a riding-model approximation with C—H distances ranging from 0.93 to 0.97Å and Uiso(H) = 1.2 Ueq(C) or Uiso(H) = 1.5Ueq(Cmethyl).

Figures

Fig. 1.
The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity [symmetry code (A): x, -y+1/2, z].

Crystal data

[CdBr2(C30H26N4S)]·C3H7NOF(000) = 816
Mr = 819.92Dx = 1.674 Mg m3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 3975 reflections
a = 9.7437 (8) Åθ = 2.2–27.3°
b = 16.7792 (14) ŵ = 3.23 mm1
c = 10.5931 (9) ÅT = 296 K
β = 110.029 (1)°Block, yellow
V = 1627.1 (2) Å30.36 × 0.32 × 0.28 mm
Z = 2

Data collection

Bruker APEXII area-detector diffractometer3305 independent reflections
Radiation source: fine-focus sealed tube2742 reflections with I > 2σ(I)
graphiteRint = 0.027
ω scansθmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2006)h = −11→12
Tmin = 0.390, Tmax = 0.465k = −20→20
9062 measured reflectionsl = −13→6

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.077w = 1/[σ2(Fo2) + (0.0374P)2 + 0.7961P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
3305 reflectionsΔρmax = 0.78 e Å3
211 parametersΔρmin = −0.64 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0025 (4)

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 (Å2)

xyzUiso*/UeqOcc. (<1)
Br10.53761 (5)0.25000.42042 (5)0.05529 (15)
Br20.95622 (6)0.25000.72708 (5)0.05828 (15)
C11.0172 (3)0.16482 (17)0.2726 (3)0.0434 (7)
H1A0.95620.18320.18440.052*
H1B1.10100.13770.26300.052*
C20.9329 (3)0.10786 (16)0.3253 (3)0.0343 (6)
C30.9688 (3)−0.01196 (18)0.1929 (3)0.0410 (7)
H3A1.0153−0.06200.22950.049*
H3B1.04000.02070.17140.049*
C40.8399 (3)−0.02804 (19)0.0656 (3)0.0444 (7)
C50.7349 (5)0.0278 (3)0.0121 (4)0.0949 (16)
H50.74290.07770.05230.114*
C60.6156 (6)0.0109 (4)−0.1025 (5)0.117 (2)
H60.54390.0493−0.13760.140*
C70.6033 (5)−0.0607 (3)−0.1629 (4)0.0825 (13)
H70.5234−0.0716−0.23950.099*
C80.7068 (5)−0.1163 (3)−0.1119 (3)0.0691 (11)
H80.6985−0.1656−0.15390.083*
C90.8260 (4)−0.1008 (2)0.0029 (3)0.0545 (8)
H90.8967−0.13980.03760.065*
C100.8378 (3)−0.00630 (16)0.3597 (3)0.0343 (6)
C110.7924 (3)−0.08440 (17)0.3631 (3)0.0432 (7)
H110.8186−0.12480.31570.052*
C120.7067 (3)−0.09879 (19)0.4403 (3)0.0491 (7)
H120.6721−0.15010.44360.059*
C130.6703 (3)−0.03818 (19)0.5139 (3)0.0468 (7)
H130.6136−0.05060.56620.056*
C140.7157 (3)0.03915 (18)0.5110 (3)0.0421 (7)
H140.69120.07910.56030.051*
C150.8005 (3)0.05523 (17)0.4308 (3)0.0351 (6)
C160.6054 (6)0.25001.0757 (6)0.0683 (14)
H160.53340.25001.11480.082*
C170.4073 (8)0.25000.8662 (7)0.111 (3)
H17A0.39120.27630.78190.166*0.50
H17B0.35530.27760.91520.166*0.50
H17C0.37280.19610.85020.166*0.50
C180.6637 (11)0.25000.8761 (10)0.133 (3)
H18A0.65470.20140.82600.199*0.50
H18B0.76070.25400.94050.199*0.50
H18C0.64520.29460.81580.199*0.50
Cd10.81788 (3)0.25000.46873 (3)0.04091 (11)
N10.8612 (2)0.12589 (13)0.4073 (2)0.0359 (5)
N20.9223 (2)0.02893 (13)0.2940 (2)0.0355 (5)
N30.5618 (5)0.25000.9435 (5)0.0682 (12)
O10.7309 (5)0.25001.1506 (5)0.1167 (18)
S11.07918 (11)0.25000.38353 (10)0.0414 (2)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0422 (3)0.0582 (3)0.0688 (3)0.0000.0232 (2)0.000
Br20.0716 (3)0.0552 (3)0.0480 (3)0.0000.0204 (2)0.000
C10.0503 (17)0.0394 (16)0.0495 (16)−0.0028 (13)0.0285 (14)−0.0058 (13)
C20.0313 (13)0.0363 (15)0.0343 (13)0.0002 (11)0.0099 (11)−0.0025 (11)
C30.0445 (16)0.0412 (16)0.0406 (15)0.0036 (13)0.0189 (13)−0.0089 (12)
C40.0488 (17)0.0510 (18)0.0343 (15)0.0001 (14)0.0156 (13)−0.0017 (12)
C50.096 (3)0.082 (3)0.070 (3)0.035 (3)−0.018 (2)−0.023 (2)
C60.099 (4)0.139 (5)0.071 (3)0.049 (4)−0.023 (3)−0.013 (3)
C70.067 (3)0.132 (4)0.041 (2)−0.013 (3)0.0088 (18)−0.010 (2)
C80.083 (3)0.081 (3)0.0469 (19)−0.034 (2)0.027 (2)−0.0184 (19)
C90.066 (2)0.055 (2)0.0441 (17)−0.0117 (16)0.0214 (16)−0.0056 (14)
C100.0282 (13)0.0381 (14)0.0342 (14)0.0013 (11)0.0075 (11)0.0008 (11)
C110.0428 (16)0.0383 (16)0.0468 (16)0.0023 (13)0.0131 (13)0.0017 (13)
C120.0426 (16)0.0401 (17)0.0612 (19)−0.0004 (13)0.0134 (15)0.0135 (14)
C130.0357 (15)0.0560 (19)0.0510 (18)0.0053 (14)0.0179 (14)0.0176 (14)
C140.0362 (14)0.0488 (17)0.0434 (16)0.0070 (13)0.0164 (13)0.0046 (13)
C150.0268 (13)0.0409 (15)0.0353 (14)0.0014 (11)0.0077 (11)0.0006 (11)
C160.049 (3)0.071 (4)0.077 (4)0.0000.011 (3)0.000
C170.075 (5)0.161 (8)0.077 (4)0.0000.001 (4)0.000
C180.134 (8)0.157 (9)0.136 (7)0.0000.083 (6)0.000
Cd10.04412 (19)0.03567 (18)0.0520 (2)0.0000.02820 (15)0.000
N10.0345 (12)0.0377 (12)0.0394 (12)−0.0018 (10)0.0175 (10)−0.0041 (10)
N20.0356 (12)0.0363 (12)0.0355 (12)−0.0006 (10)0.0132 (10)−0.0036 (9)
N30.057 (3)0.073 (3)0.073 (3)0.0000.020 (2)0.000
O10.062 (3)0.149 (5)0.116 (4)0.0000.002 (3)0.000
S10.0379 (5)0.0342 (5)0.0486 (6)0.0000.0104 (4)0.000

Geometric parameters (Å, °)

Br1—Cd12.6004 (6)C10—C151.397 (4)
Br2—Cd12.6038 (6)C11—C121.376 (4)
C1—C21.488 (4)C11—H110.9300
C1—S11.817 (3)C12—C131.399 (5)
C1—H1A0.9700C12—H120.9300
C1—H1B0.9700C13—C141.375 (4)
C2—N11.322 (3)C13—H130.9300
C2—N21.360 (3)C14—C151.399 (4)
C3—N21.468 (3)C14—H140.9300
C3—C41.519 (4)C15—N11.385 (3)
C3—H3A0.9700C16—O11.208 (7)
C3—H3B0.9700C16—N31.316 (7)
C4—C51.360 (5)C16—H160.9300
C4—C91.374 (4)C17—N31.446 (8)
C5—C61.393 (6)C17—H17A0.9600
C5—H50.9300C17—H17B0.9600
C6—C71.347 (7)C17—H17C0.9600
C6—H60.9300C18—N31.408 (9)
C7—C81.344 (6)C18—H18A0.9600
C7—H70.9300C18—H18B0.9600
C8—C91.389 (5)C18—H18C0.9600
C8—H80.9300Cd1—N12.264 (2)
C9—H90.9300Cd1—N1i2.264 (2)
C10—N21.380 (3)Cd1—S12.9784 (11)
C10—C111.387 (4)S1—C1i1.817 (3)
C2—C1—S1111.48 (19)C12—C13—H13119.1
C2—C1—H1A109.3C13—C14—C15117.2 (3)
S1—C1—H1A109.3C13—C14—H14121.4
C2—C1—H1B109.3C15—C14—H14121.4
S1—C1—H1B109.3N1—C15—C10109.2 (2)
H1A—C1—H1B108.0N1—C15—C14130.7 (3)
N1—C2—N2111.7 (2)C10—C15—C14120.1 (3)
N1—C2—C1125.7 (2)O1—C16—N3125.8 (6)
N2—C2—C1122.6 (2)O1—C16—H16117.1
N2—C3—C4111.3 (2)N3—C16—H16117.1
N2—C3—H3A109.4N3—C17—H17A109.5
C4—C3—H3A109.4N3—C17—H17B109.5
N2—C3—H3B109.4H17A—C17—H17B109.5
C4—C3—H3B109.4N3—C17—H17C109.5
H3A—C3—H3B108.0H17A—C17—H17C109.5
C5—C4—C9118.4 (3)H17B—C17—H17C109.5
C5—C4—C3121.5 (3)N3—C18—H18A109.5
C9—C4—C3120.1 (3)N3—C18—H18B109.5
C4—C5—C6120.4 (4)H18A—C18—H18B109.5
C4—C5—H5119.8N3—C18—H18C109.5
C6—C5—H5119.8H18A—C18—H18C109.5
C7—C6—C5120.6 (5)H18B—C18—H18C109.5
C7—C6—H6119.7N1—Cd1—N1i133.74 (11)
C5—C6—H6119.7N1—Cd1—Br1103.31 (6)
C8—C7—C6119.7 (4)N1i—Cd1—Br1103.31 (6)
C8—C7—H7120.2N1—Cd1—Br2102.82 (6)
C6—C7—H7120.2N1i—Cd1—Br2102.82 (6)
C7—C8—C9120.6 (4)Br1—Cd1—Br2109.732 (19)
C7—C8—H8119.7N1—Cd1—S169.50 (5)
C9—C8—H8119.7N1i—Cd1—S169.50 (5)
C4—C9—C8120.3 (4)Br1—Cd1—S1152.80 (3)
C4—C9—H9119.9Br2—Cd1—S197.46 (3)
C8—C9—H9119.9C2—N1—C15106.0 (2)
N2—C10—C11131.9 (3)C2—N1—Cd1126.29 (18)
N2—C10—C15105.4 (2)C15—N1—Cd1127.02 (17)
C11—C10—C15122.7 (3)C2—N2—C10107.6 (2)
C12—C11—C10116.4 (3)C2—N2—C3128.0 (2)
C12—C11—H11121.8C10—N2—C3123.7 (2)
C10—C11—H11121.8C16—N3—C18120.8 (6)
C11—C12—C13121.7 (3)C16—N3—C17119.8 (5)
C11—C12—H12119.2C18—N3—C17119.4 (6)
C13—C12—H12119.2C1i—S1—C1103.7 (2)
C14—C13—C12121.9 (3)C1i—S1—Cd193.83 (10)
C14—C13—H13119.1C1—S1—Cd193.83 (10)
S1—C1—C2—N125.0 (4)N1i—Cd1—N1—C25.0 (3)
S1—C1—C2—N2−154.3 (2)Br1—Cd1—N1—C2128.6 (2)
N2—C3—C4—C542.8 (5)Br2—Cd1—N1—C2−117.2 (2)
N2—C3—C4—C9−136.2 (3)S1—Cd1—N1—C2−23.9 (2)
C9—C4—C5—C60.8 (7)N1i—Cd1—N1—C15−164.51 (14)
C3—C4—C5—C6−178.2 (5)Br1—Cd1—N1—C15−40.9 (2)
C4—C5—C6—C7−0.8 (9)Br2—Cd1—N1—C1573.3 (2)
C5—C6—C7—C80.2 (9)S1—Cd1—N1—C15166.6 (2)
C6—C7—C8—C90.4 (7)N1—C2—N2—C100.2 (3)
C5—C4—C9—C8−0.3 (5)C1—C2—N2—C10179.7 (2)
C3—C4—C9—C8178.7 (3)N1—C2—N2—C3170.8 (2)
C7—C8—C9—C4−0.3 (5)C1—C2—N2—C3−9.7 (4)
N2—C10—C11—C12−179.7 (3)C11—C10—N2—C2179.8 (3)
C15—C10—C11—C120.4 (4)C15—C10—N2—C2−0.3 (3)
C10—C11—C12—C13−1.4 (4)C11—C10—N2—C38.7 (4)
C11—C12—C13—C141.2 (5)C15—C10—N2—C3−171.4 (2)
C12—C13—C14—C150.1 (4)C4—C3—N2—C2−100.7 (3)
N2—C10—C15—N10.3 (3)C4—C3—N2—C1068.5 (3)
C11—C10—C15—N1−179.8 (2)O1—C16—N3—C180.000 (6)
N2—C10—C15—C14−179.0 (2)O1—C16—N3—C17180.000 (4)
C11—C10—C15—C140.9 (4)C2—C1—S1—C1i−128.05 (17)
C13—C14—C15—N1179.8 (3)C2—C1—S1—Cd1−33.2 (2)
C13—C14—C15—C10−1.1 (4)N1—Cd1—S1—C1i131.08 (12)
N2—C2—N1—C150.0 (3)N1i—Cd1—S1—C1i−27.04 (12)
C1—C2—N1—C15−179.5 (3)Br1—Cd1—S1—C1i52.02 (10)
N2—C2—N1—Cd1−171.33 (16)Br2—Cd1—S1—C1i−127.98 (10)
C1—C2—N1—Cd19.2 (4)N1—Cd1—S1—C127.03 (12)
C10—C15—N1—C2−0.2 (3)N1i—Cd1—S1—C1−131.08 (12)
C14—C15—N1—C2179.0 (3)Br1—Cd1—S1—C1−52.02 (10)
C10—C15—N1—Cd1171.06 (17)Br2—Cd1—S1—C1127.98 (10)
C14—C15—N1—Cd1−9.8 (4)

Symmetry codes: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1—H1A···O1ii0.972.383.004 (5)122

Symmetry codes: (ii) x, y, z−1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH5084).

References

  • Agh-Atabay, N. M., Baykal, A. & Somer, M. (2004). Transition Met. Chem.29, 159–163.
  • Bruker (2006). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA
  • Dagdigian, J. V. & Reed, C. A. (1979). Inorg. Chem.18, 2624–2626.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wu, H. L., Wang, K. T., Yun, R. R. & Huang, X. C. (2009). Synth. React. Inorg. Met.-Org. Chem.39, 629–632.

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