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Acta Cryst. (2009). E65, m613    [ doi:10.1107/S1600536809015943 ]

Bis{[mu]-1,3-bis[(benzimidazol-1-yl)methyl]benzene-[kappa]2N3:N3'}bis[dichloridozinc(II)] dimethylformamide disolvate

L.-Z. Zhao, P. Li, B.-L. Cao and S. W. Ng

Abstract top

In the title compound, [Zn2Cl4(C22H18N4)2]·2C3H7NO, the 1,3-bis[(benzimidazol-1-yl)methyl]benzene ligand bridges two ZnCl2 units, forming a centrosymmetric dinuclear molecule. The ZnII atom shows a distorted tetrahedral coordination within a Cl2N2 donor set.

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Related literature top

For the crystal structure of 1,3-bis((benzimidazol-1-yl)methyl)benzene, which was isolated as the malonic acid co-crystal, see: Aakeröy et al. (2005). For related metal complexes, see: Fan et al. (2006); Raehm et al. (2003).

Experimental top

The compound was prepared from a mixture of boric acid (0.17 g), zinc chloride (0.27 g), 1,3-bis((benzimidazol-1-yl)methyl)benzene (0.45 g) in DMF (3.6 ml) and water (0.2 ml). The mixture was sealed in 25-ml Teflon-lined stainless-steel vessel, which was heated at 423 K for 5 days. The vessel was then cooled to room temperature slowly. Crystals were picked out manually.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.99 Å) and were included in the refinement in the riding model approximation, with U(H) fixed at 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of [ZnCl2(C22H18N4)]2.2DMF at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. Only one DMF molecule is shown. Unlabelled non-H atoms are related by a centre of inversion.
Bis{µ-1,3-bis[(benzimidazol-1-yl)methyl]benzene- κ2N3:N3'}bis[dichloridozinc(II)] dimethylformamide disolvate top
Crystal data top
[Zn2Cl4(C22H18N4)2]·2C3H7NOF000 = 2256
Mr = 1095.54Dx = 1.454 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 4135 reflections
a = 24.0069 (5) Åθ = 2.3–27.2º
b = 9.8217 (2) ŵ = 1.22 mm−1
c = 23.9723 (5) ÅT = 120 K
β = 117.695 (1)ºPrism, colorless
V = 5004.8 (2) Å30.30 × 0.20 × 0.10 mm
Z = 4
Data collection top
Bruker SMART APEX
diffractometer		5730 independent reflections
Radiation source: fine-focus sealed tube4449 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.034
T = 120 Kθmax = 27.5º
ω scansθmin = 1.9º
Absorption correction: Multi-scan
SADABS (Sheldrick, 1996)		h = −30→31
Tmin = 0.711, Tmax = 0.888k = −12→12
17166 measured reflectionsl = −31→28
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)] = 0.037H-atom parameters constrained
wR(F2) = 0.097  w = 1/[σ2(Fo2) + (0.0452P)2 + 5.1375P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
5730 reflectionsΔρmax = 0.92 e Å−3
309 parametersΔρmin = −0.57 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Zn2Cl4(C22H18N4)2]·2C3H7NOV = 5004.8 (2) Å3
Mr = 1095.54Z = 4
Monoclinic, C2/cMo Kα
a = 24.0069 (5) ŵ = 1.22 mm−1
b = 9.8217 (2) ÅT = 120 K
c = 23.9723 (5) Å0.30 × 0.20 × 0.10 mm
β = 117.695 (1)º
Data collection top
Bruker SMART APEX
diffractometer		5730 independent reflections
Absorption correction: Multi-scan
SADABS (Sheldrick, 1996)		4449 reflections with I > 2σ(I)
Tmin = 0.711, Tmax = 0.888Rint = 0.034
17166 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037309 parameters
wR(F2) = 0.097H-atom parameters constrained
S = 1.04Δρmax = 0.92 e Å−3
5730 reflectionsΔρmin = −0.57 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.499493 (12)0.24704 (3)0.615569 (12)0.01976 (9)
Cl10.54858 (3)0.40106 (6)0.69289 (3)0.02422 (14)
Cl20.54751 (3)0.05513 (6)0.61286 (3)0.03540 (17)
O10.28873 (14)0.6931 (3)0.61655 (11)0.0738 (8)
N10.46559 (9)0.32960 (19)0.52860 (9)0.0194 (4)
N20.42352 (9)0.33960 (19)0.42428 (9)0.0183 (4)
N30.16359 (9)0.2139 (2)0.36682 (9)0.0223 (4)
N40.08242 (9)0.2789 (2)0.38075 (9)0.0224 (4)
N50.37081 (12)0.8246 (2)0.67983 (10)0.0369 (6)
C10.43461 (10)0.4540 (2)0.50863 (10)0.0185 (5)
C20.42823 (11)0.5612 (2)0.54354 (11)0.0224 (5)
H20.44640.55740.58820.027*
C30.39418 (11)0.6732 (2)0.51009 (12)0.0263 (5)
H30.38870.74790.53220.032*
C40.36741 (11)0.6791 (2)0.44394 (12)0.0260 (5)
H40.34440.75790.42270.031*
C50.37366 (11)0.5743 (2)0.40925 (11)0.0232 (5)
H50.35560.57850.36460.028*
C60.40796 (10)0.4615 (2)0.44313 (11)0.0199 (5)
C70.45751 (11)0.2659 (2)0.47682 (11)0.0202 (5)
H70.47380.17790.47660.024*
C80.40337 (11)0.2955 (2)0.35930 (11)0.0206 (5)
H8A0.42200.20540.35950.025*
H8B0.41870.36110.33820.025*
C90.33254 (11)0.2861 (2)0.32330 (11)0.0209 (5)
C100.29914 (11)0.2108 (2)0.34747 (11)0.0208 (5)
H100.32150.16140.38560.025*
C110.23407 (11)0.2072 (2)0.31670 (11)0.0222 (5)
C120.20141 (12)0.2768 (3)0.25988 (12)0.0285 (6)
H120.15670.27420.23820.034*
C130.23399 (13)0.3496 (3)0.23511 (12)0.0338 (6)
H130.21170.39590.19610.041*
C140.29951 (12)0.3554 (3)0.26713 (11)0.0291 (6)
H140.32160.40730.25030.035*
C150.19950 (12)0.1274 (2)0.34467 (12)0.0257 (5)
H15A0.17020.06330.31260.031*
H15B0.23030.07300.38050.031*
C160.10264 (11)0.1968 (2)0.35076 (11)0.0223 (5)
H160.07660.13180.32060.027*
C170.13518 (11)0.3561 (2)0.42061 (11)0.0221 (5)
C180.14072 (12)0.4591 (2)0.46287 (11)0.0251 (5)
H180.10580.48700.46860.030*
C190.19923 (12)0.5187 (3)0.49612 (12)0.0285 (6)
H190.20470.58920.52540.034*
C200.25048 (12)0.4777 (3)0.48768 (12)0.0300 (6)
H200.28990.52140.51140.036*
C210.24572 (12)0.3754 (3)0.44588 (12)0.0283 (6)
H210.28080.34740.44050.034*
C220.18653 (11)0.3158 (2)0.41212 (11)0.0227 (5)
C230.31081 (17)0.7967 (4)0.64606 (15)0.0501 (9)
H230.28190.86430.64460.060*
C240.4155 (2)0.7252 (4)0.6803 (2)0.0749 (12)
H24A0.39290.65120.65100.112*
H24B0.43960.68830.72290.112*
H24C0.44430.76880.66720.112*
C250.3954 (2)0.9448 (4)0.71704 (16)0.0667 (12)
H25A0.36051.00250.71330.100*
H25B0.42110.99490.70200.100*
H25C0.42130.91920.76120.100*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.01891 (15)0.01906 (14)0.01959 (14)0.00064 (11)0.00751 (11)0.00179 (10)
Cl10.0220 (3)0.0268 (3)0.0201 (3)−0.0046 (2)0.0067 (2)−0.0007 (2)
Cl20.0442 (4)0.0243 (3)0.0351 (3)0.0130 (3)0.0162 (3)0.0053 (3)
O10.093 (2)0.0474 (15)0.0492 (14)−0.0216 (15)0.0061 (14)−0.0035 (12)
N10.0187 (10)0.0179 (10)0.0211 (9)0.0017 (8)0.0088 (8)0.0031 (8)
N20.0178 (10)0.0180 (9)0.0194 (9)0.0005 (8)0.0089 (8)0.0005 (7)
N30.0229 (11)0.0223 (10)0.0239 (10)−0.0048 (8)0.0126 (9)−0.0058 (8)
N40.0228 (10)0.0218 (10)0.0236 (10)−0.0057 (8)0.0116 (9)−0.0045 (8)
N50.0455 (15)0.0325 (13)0.0262 (11)−0.0073 (11)0.0112 (11)−0.0024 (10)
C10.0144 (11)0.0178 (11)0.0231 (11)−0.0012 (8)0.0085 (9)0.0003 (9)
C20.0172 (12)0.0240 (12)0.0237 (12)−0.0005 (9)0.0078 (10)−0.0013 (9)
C30.0247 (13)0.0203 (12)0.0344 (13)0.0034 (10)0.0143 (11)−0.0034 (10)
C40.0224 (13)0.0211 (12)0.0328 (13)0.0068 (10)0.0116 (11)0.0061 (10)
C50.0207 (12)0.0224 (12)0.0249 (12)0.0035 (9)0.0092 (10)0.0037 (9)
C60.0160 (11)0.0202 (12)0.0238 (12)−0.0021 (9)0.0096 (9)0.0001 (9)
C70.0168 (11)0.0186 (11)0.0248 (12)0.0005 (9)0.0094 (9)0.0031 (9)
C80.0229 (12)0.0219 (11)0.0199 (11)0.0008 (9)0.0123 (10)0.0003 (9)
C90.0247 (13)0.0202 (11)0.0203 (11)−0.0013 (9)0.0128 (10)−0.0025 (9)
C100.0243 (12)0.0180 (11)0.0198 (11)0.0005 (9)0.0099 (10)−0.0002 (9)
C110.0266 (13)0.0183 (11)0.0236 (12)−0.0034 (9)0.0132 (10)−0.0067 (9)
C120.0236 (13)0.0315 (14)0.0244 (12)−0.0035 (10)0.0062 (10)−0.0048 (10)
C130.0312 (15)0.0420 (16)0.0202 (12)−0.0028 (12)0.0051 (11)0.0071 (11)
C140.0290 (14)0.0343 (14)0.0240 (12)−0.0048 (11)0.0124 (11)0.0049 (11)
C150.0268 (13)0.0235 (13)0.0307 (13)−0.0033 (10)0.0166 (11)−0.0057 (10)
C160.0218 (12)0.0229 (12)0.0227 (12)−0.0063 (9)0.0106 (10)−0.0034 (9)
C170.0220 (12)0.0212 (12)0.0210 (11)−0.0034 (9)0.0082 (10)0.0000 (9)
C180.0274 (13)0.0227 (12)0.0264 (12)−0.0009 (10)0.0135 (11)−0.0037 (10)
C190.0316 (14)0.0248 (13)0.0251 (13)−0.0028 (11)0.0100 (11)−0.0058 (10)
C200.0250 (13)0.0295 (14)0.0311 (14)−0.0088 (11)0.0093 (11)−0.0077 (11)
C210.0235 (13)0.0293 (14)0.0323 (13)−0.0060 (10)0.0130 (11)−0.0050 (11)
C220.0256 (13)0.0206 (12)0.0225 (12)−0.0053 (10)0.0117 (10)−0.0033 (9)
C230.053 (2)0.0425 (18)0.0376 (17)−0.0103 (16)0.0071 (15)0.0080 (14)
C240.075 (3)0.078 (3)0.083 (3)0.007 (2)0.047 (3)−0.009 (2)
C250.094 (3)0.043 (2)0.0422 (19)−0.0191 (19)0.014 (2)−0.0115 (15)
Geometric parameters (Å, °) top
Zn1—N12.022 (2)C8—H8B0.9900
Zn1—N4i2.025 (2)C9—C141.383 (3)
Zn1—Cl12.2544 (6)C9—C101.399 (3)
Zn1—Cl22.2262 (7)C10—C111.384 (3)
O1—C231.211 (4)C10—H100.9500
N1—C71.321 (3)C11—C121.394 (4)
N1—C11.394 (3)C11—C151.506 (3)
N2—C71.349 (3)C12—C131.381 (4)
N2—C61.391 (3)C12—H120.9500
N2—C81.465 (3)C13—C141.394 (4)
N3—C161.339 (3)C13—H130.9500
N3—C221.389 (3)C14—H140.9500
N3—C151.474 (3)C15—H15A0.9900
N4—C161.314 (3)C15—H15B0.9900
N4—C171.403 (3)C16—H160.9500
N4—Zn1i2.025 (2)C17—C181.393 (3)
N5—C231.312 (4)C17—C221.397 (3)
N5—C251.431 (4)C18—C191.382 (3)
N5—C241.447 (5)C18—H180.9500
C1—C61.395 (3)C19—C201.396 (4)
C1—C21.397 (3)C19—H190.9500
C2—C31.382 (3)C20—C211.386 (4)
C2—H20.9500C20—H200.9500
C3—C41.408 (3)C21—C221.396 (3)
C3—H30.9500C21—H210.9500
C4—C51.375 (3)C23—H230.9500
C4—H40.9500C24—H24A0.9800
C5—C61.394 (3)C24—H24B0.9800
C5—H50.9500C24—H24C0.9800
C7—H70.9500C25—H25A0.9800
C8—C91.510 (3)C25—H25B0.9800
C8—H8A0.9900C25—H25C0.9800
N1—Zn1—N4i99.30 (8)C10—C11—C12119.4 (2)
N1—Zn1—Cl1112.62 (6)C10—C11—C15119.7 (2)
N1—Zn1—Cl2105.97 (6)C12—C11—C15120.9 (2)
N4i—Zn1—Cl1101.28 (6)C13—C12—C11120.0 (2)
N4i—Zn1—Cl2114.92 (6)C13—C12—H12120.0
Cl1—Zn1—Cl2120.81 (3)C11—C12—H12120.0
C7—N1—C1105.68 (18)C12—C13—C14120.2 (2)
C7—N1—Zn1126.28 (15)C12—C13—H13119.9
C1—N1—Zn1126.89 (15)C14—C13—H13119.9
C7—N2—C6107.21 (19)C9—C14—C13120.4 (2)
C7—N2—C8126.25 (19)C9—C14—H14119.8
C6—N2—C8126.44 (19)C13—C14—H14119.8
C16—N3—C22107.3 (2)N3—C15—C11113.3 (2)
C16—N3—C15124.6 (2)N3—C15—H15A108.9
C22—N3—C15127.7 (2)C11—C15—H15A108.9
C16—N4—C17105.0 (2)N3—C15—H15B108.9
C16—N4—Zn1i124.06 (16)C11—C15—H15B108.9
C17—N4—Zn1i128.75 (16)H15A—C15—H15B107.7
C23—N5—C25124.9 (3)N4—C16—N3113.5 (2)
C23—N5—C24117.5 (3)N4—C16—H16123.3
C25—N5—C24117.6 (3)N3—C16—H16123.3
N1—C1—C6109.0 (2)C18—C17—C22121.3 (2)
N1—C1—C2130.1 (2)C18—C17—N4129.7 (2)
C6—C1—C2120.9 (2)C22—C17—N4109.0 (2)
C3—C2—C1116.9 (2)C19—C18—C17117.1 (2)
C3—C2—H2121.6C19—C18—H18121.5
C1—C2—H2121.6C17—C18—H18121.5
C2—C3—C4121.6 (2)C18—C19—C20121.5 (2)
C2—C3—H3119.2C18—C19—H19119.3
C4—C3—H3119.2C20—C19—H19119.3
C5—C4—C3121.9 (2)C21—C20—C19122.1 (2)
C5—C4—H4119.0C21—C20—H20118.9
C3—C4—H4119.0C19—C20—H20118.9
C4—C5—C6116.3 (2)C20—C21—C22116.3 (2)
C4—C5—H5121.8C20—C21—H21121.9
C6—C5—H5121.8C22—C21—H21121.9
N2—C6—C5132.1 (2)N3—C22—C21133.0 (2)
N2—C6—C1105.54 (19)N3—C22—C17105.2 (2)
C5—C6—C1122.4 (2)C21—C22—C17121.8 (2)
N1—C7—N2112.6 (2)O1—C23—N5126.3 (4)
N1—C7—H7123.7O1—C23—H23116.8
N2—C7—H7123.7N5—C23—H23116.8
N2—C8—C9110.68 (19)N5—C24—H24A109.5
N2—C8—H8A109.5N5—C24—H24B109.5
C9—C8—H8A109.5H24A—C24—H24B109.5
N2—C8—H8B109.5N5—C24—H24C109.5
C9—C8—H8B109.5H24A—C24—H24C109.5
H8A—C8—H8B108.1H24B—C24—H24C109.5
C14—C9—C10118.9 (2)N5—C25—H25A109.5
C14—C9—C8120.7 (2)N5—C25—H25B109.5
C10—C9—C8120.4 (2)H25A—C25—H25B109.5
C11—C10—C9121.0 (2)N5—C25—H25C109.5
C11—C10—H10119.5H25A—C25—H25C109.5
C9—C10—H10119.5H25B—C25—H25C109.5
N4i—Zn1—N1—C7−101.91 (19)C9—C10—C11—C15−178.8 (2)
Cl2—Zn1—N1—C717.5 (2)C10—C11—C12—C13−0.6 (4)
Cl1—Zn1—N1—C7151.65 (17)C15—C11—C12—C13179.9 (2)
N4i—Zn1—N1—C164.00 (19)C11—C12—C13—C14−0.9 (4)
Cl2—Zn1—N1—C1−176.59 (17)C10—C9—C14—C13−0.2 (4)
Cl1—Zn1—N1—C1−42.44 (19)C8—C9—C14—C13−178.1 (2)
C7—N1—C1—C6−0.1 (2)C12—C13—C14—C91.3 (4)
Zn1—N1—C1—C6−168.31 (15)C16—N3—C15—C11128.1 (2)
C7—N1—C1—C2−179.8 (2)C22—N3—C15—C11−59.4 (3)
Zn1—N1—C1—C212.0 (3)C10—C11—C15—N3112.2 (2)
N1—C1—C2—C3−179.9 (2)C12—C11—C15—N3−68.3 (3)
C6—C1—C2—C30.5 (3)C17—N4—C16—N3−0.5 (3)
C1—C2—C3—C4−0.3 (4)Zn1i—N4—C16—N3−164.84 (16)
C2—C3—C4—C50.0 (4)C22—N3—C16—N40.6 (3)
C3—C4—C5—C60.0 (4)C15—N3—C16—N4174.3 (2)
C7—N2—C6—C5−179.8 (2)C16—N4—C17—C18179.7 (2)
C8—N2—C6—C5−3.4 (4)Zn1i—N4—C17—C18−17.1 (4)
C7—N2—C6—C10.0 (2)C16—N4—C17—C220.3 (3)
C8—N2—C6—C1176.4 (2)Zn1i—N4—C17—C22163.61 (17)
C4—C5—C6—N2180.0 (2)C22—C17—C18—C19−0.3 (4)
C4—C5—C6—C10.1 (3)N4—C17—C18—C19−179.6 (2)
N1—C1—C6—N20.0 (2)C17—C18—C19—C200.0 (4)
C2—C1—C6—N2179.7 (2)C18—C19—C20—C21−0.1 (4)
N1—C1—C6—C5179.9 (2)C19—C20—C21—C220.4 (4)
C2—C1—C6—C5−0.4 (4)C16—N3—C22—C21179.6 (3)
C1—N1—C7—N20.1 (3)C15—N3—C22—C216.1 (4)
Zn1—N1—C7—N2168.44 (15)C16—N3—C22—C17−0.3 (3)
C6—N2—C7—N1−0.1 (3)C15—N3—C22—C17−173.8 (2)
C8—N2—C7—N1−176.5 (2)C20—C21—C22—N3179.4 (3)
C7—N2—C8—C9115.4 (2)C20—C21—C22—C17−0.7 (4)
C6—N2—C8—C9−60.3 (3)C18—C17—C22—N3−179.4 (2)
N2—C8—C9—C14125.4 (2)N4—C17—C22—N30.0 (3)
N2—C8—C9—C10−52.4 (3)C18—C17—C22—C210.7 (4)
C14—C9—C10—C11−1.3 (4)N4—C17—C22—C21−179.9 (2)
C8—C9—C10—C11176.5 (2)C25—N5—C23—O1−176.3 (3)
C9—C10—C11—C121.7 (3)C24—N5—C23—O12.7 (5)
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1.
Acknowledgements top

We acknowledge support from the Scientific Research Projects of Higher Education of Inner Mongolia (NJzy08217) and the University of Malaya.

references
References top

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