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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): m758.
Published online 2008 May 3. doi:  10.1107/S1600536808006399
PMCID: PMC2961613

Bis[2-(1H-1,2,3-benzotriazol-1-yl)acetic acid-κN 3]dichloridozinc(II)

Abstract

In the title complex, [ZnCl2(C8H7N3O2)2], the ZnII atom is coordinated by two chloride ions and two N atoms in a distorted tetra­hedral coordination environment. In the crystal structure, mol­ecules are linked by inter­molecular C—H(...)O and O—H(...)O hydrogen bonds, forming a three-dimensional network.

Related literature

For synthesis of the organic ligand, see: Danan et al. (1997 [triangle]); Xu & Ye (2007 [triangle]).

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Object name is e-64-0m758-scheme1.jpg

Experimental

Crystal data

  • [ZnCl2(C8H7N3O2)2]
  • M r = 490.60
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m758-efi1.jpg
  • a = 8.0896 (16) Å
  • b = 9.6898 (19) Å
  • c = 12.703 (3) Å
  • α = 87.48 (3)°
  • β = 84.25 (3)°
  • γ = 83.95 (3)°
  • V = 984.7 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.55 mm−1
  • T = 293 (2) K
  • 0.3 × 0.2 × 0.1 mm

Data collection

  • Rigaku Mercury2 CCD diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.720, T max = 0.860
  • 10222 measured reflections
  • 4512 independent reflections
  • 4022 reflections with I > 2σ(I)
  • R int = 0.028

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.099
  • S = 1.09
  • 4512 reflections
  • 275 parameters
  • 2 restraints
  • H-atom parameters constrained
  • Δρmax = 0.63 e Å−3
  • Δρmin = −0.54 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; 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 I, global. DOI: 10.1107/S1600536808006399/pk2083sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808006399/pk2083Isup2.hkl

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

Acknowledgments

This work was supported by a Start-up Grant from Southeast University (to QY).

supplementary crystallographic information

Comment

Recently, we reported the structure of 2-(1H-benzo[d][1,2,3] triazol-1-yl)acetonitrile (Xu et al. (2007)). The reaction of it with ZnCl2 in ethanol-water solution gives the title complex. The zinc(II) center is coordinated by two nitrogen atoms from the benzotriazole rings and two terminal chloride anions in a distorted tetrahedral arrangement as shown in Fig. 1. The angle between the two benzotriazole rings is 62.98 (7)°.

From Fig. 2, it is easy to see that the structure is consolidated by extensive C—H···O and O—H···O hydrogen bonds. This hydrogen bonding with the π-π stacking between neighboring results to the formation of three-dimensional structure.

Experimental

The ligand, 2-(1H-benzo[d][1,2,3]triazol-1-yl)acetonitrile, was synthesized by the reaction of benzotriazole and bromoacetonitrile according to the procedure described in the literature (Danan et al. (1997)).

A mixture of 2-(1H-benzo[d][1,2,3]triazol-1-yl)acetonitrile (32 mg, 0.2 mmol), ZnCl2(40 mg, 0.3 mmol), ethanol(1 ml) and a few drops of water sealed in a glass tube maintained at 120 °C. Colorless crystals suitable for X-ray analysis were obtained after several days.

Refinement

Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on the C, O atoms to which they are bonded, with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(O).

Figures

Fig. 1.
The molecular structure of the compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
Fig. 2.
A packing diagram of the molecular packing of the title compound, viewed down the b axis.

Crystal data

[ZnCl2(C8H7N3O2)2]Z = 2
Mr = 490.60F000 = 496
Triclinic, P1Dx = 1.655 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 8.0896 (16) ÅCell parameters from 10272 reflections
b = 9.6898 (19) Åθ = 3.1–28.7º
c = 12.703 (3) ŵ = 1.56 mm1
α = 87.48 (3)ºT = 293 (2) K
β = 84.25 (3)ºBlock, colorless
γ = 83.95 (3)º0.3 × 0.2 × 0.1 mm
V = 984.7 (4) Å3

Data collection

Mercury2 CCD (2x2 bin mode) diffractometer4512 independent reflections
Radiation source: fine-focus sealed tube4022 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.028
Detector resolution: 13.6612 pixels mm-1θmax = 27.5º
T = 293(2) Kθmin = 3.1º
CCD_Profile_fitting scansh = −10→10
Absorption correction: multi-scan(CrystalClear; Rigaku, 2005)k = −12→12
Tmin = 0.720, Tmax = 0.860l = −16→16
10222 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.099  w = 1/[σ2(Fo2) + (0.0423P)2 + 0.762P] where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
4512 reflectionsΔρmax = 0.63 e Å3
275 parametersΔρmin = −0.54 e Å3
2 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

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 > 2σ(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*/Ueq
Zn1−0.24666 (3)0.21707 (3)0.28538 (2)0.03130 (10)
Cl1−0.49995 (9)0.21702 (8)0.23354 (6)0.04842 (18)
Cl2−0.17619 (9)0.06835 (7)0.41738 (5)0.04511 (17)
O10.4086 (3)0.4222 (3)−0.1108 (2)0.0764 (8)
H1C0.48840.4518−0.08740.115*
O2−0.5545 (3)0.9218 (2)0.3737 (2)0.0627 (6)
H2B−0.58590.98460.32010.061 (11)*
O3−0.3617 (3)0.7988 (2)0.26399 (16)0.0555 (6)
O40.2761 (3)0.4739 (3)0.05103 (16)0.0546 (6)
N1−0.2805 (3)0.6045 (2)0.41091 (17)0.0327 (4)
N2−0.0410 (3)0.2952 (2)0.09576 (17)0.0350 (5)
N30.0805 (3)0.2522 (2)0.02244 (16)0.0338 (4)
N4−0.3401 (3)0.4916 (2)0.37794 (17)0.0350 (5)
N5−0.0605 (3)0.1913 (2)0.16490 (16)0.0334 (4)
N6−0.2121 (3)0.4090 (2)0.33810 (17)0.0330 (4)
C10.2918 (4)−0.1020 (3)0.0338 (2)0.0470 (7)
H1A0.3714−0.16600.00040.048 (9)*
C20.1680 (4)0.6422 (3)0.3786 (2)0.0465 (7)
H2A0.25060.69850.38930.061 (10)*
C30.1993 (4)−0.1432 (3)0.1290 (2)0.0504 (7)
H3A0.2219−0.23300.15650.056 (10)*
C40.0791 (4)−0.0547 (3)0.1816 (2)0.0434 (6)
H4A0.0190−0.08200.24390.048 (9)*
C50.0517 (3)0.0791 (3)0.13594 (19)0.0329 (5)
C60.1357 (3)0.3460 (3)−0.0639 (2)0.0380 (6)
H6A0.04390.4144−0.07890.050 (9)*
H6B0.16980.2937−0.12720.051 (9)*
C70.0055 (4)0.6881 (3)0.4093 (2)0.0404 (6)
H7A−0.02560.77370.43970.042 (8)*
C80.2157 (3)0.5130 (3)0.3319 (2)0.0456 (7)
H8A0.32820.48760.31210.054 (9)*
C9−0.3956 (3)0.7224 (3)0.4457 (2)0.0375 (6)
H9A−0.34640.77270.49700.056 (10)*
H9B−0.49790.69000.47970.057 (10)*
C100.2827 (4)0.4195 (3)−0.0345 (2)0.0391 (6)
C110.1012 (3)0.4239 (3)0.3143 (2)0.0391 (6)
H11A0.13250.33810.28440.042 (8)*
C120.1438 (3)0.1188 (3)0.0429 (2)0.0323 (5)
C130.2670 (3)0.0281 (3)−0.0107 (2)0.0415 (6)
H13A0.32820.0552−0.07270.044 (8)*
C14−0.4354 (3)0.8186 (3)0.3517 (2)0.0360 (5)
C15−0.0664 (3)0.4692 (2)0.34439 (19)0.0313 (5)
C16−0.1116 (3)0.5972 (2)0.39085 (19)0.0311 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.03324 (16)0.02833 (16)0.03146 (16)−0.00575 (11)0.00609 (11)−0.00602 (11)
Cl10.0373 (3)0.0458 (4)0.0624 (5)−0.0034 (3)−0.0060 (3)−0.0035 (3)
Cl20.0551 (4)0.0419 (4)0.0363 (3)−0.0022 (3)0.0009 (3)0.0019 (3)
O10.0671 (16)0.100 (2)0.0642 (16)−0.0331 (15)0.0161 (12)−0.0134 (15)
O20.0577 (14)0.0495 (13)0.0762 (17)0.0028 (10)0.0081 (12)−0.0038 (12)
O30.0670 (14)0.0550 (13)0.0375 (11)0.0109 (11)0.0131 (10)−0.0053 (9)
O40.0568 (13)0.0696 (15)0.0398 (11)−0.0209 (11)0.0038 (10)−0.0117 (10)
N10.0334 (10)0.0284 (10)0.0360 (11)−0.0040 (8)0.0012 (8)−0.0081 (8)
N20.0393 (11)0.0324 (11)0.0317 (11)−0.0044 (9)0.0075 (9)−0.0042 (8)
N30.0337 (11)0.0345 (11)0.0318 (11)−0.0055 (8)0.0071 (8)−0.0037 (8)
N40.0323 (11)0.0330 (11)0.0400 (12)−0.0074 (8)0.0028 (9)−0.0100 (9)
N50.0383 (11)0.0279 (10)0.0321 (11)−0.0036 (8)0.0067 (9)−0.0025 (8)
N60.0320 (10)0.0291 (10)0.0384 (11)−0.0068 (8)0.0014 (9)−0.0074 (8)
C10.0420 (15)0.0468 (16)0.0484 (16)0.0110 (12)0.0016 (12)−0.0103 (13)
C20.0382 (14)0.0512 (17)0.0539 (17)−0.0206 (12)−0.0079 (13)0.0027 (13)
C30.0575 (18)0.0400 (16)0.0492 (17)0.0097 (13)0.0000 (14)0.0012 (13)
C40.0512 (16)0.0376 (14)0.0386 (14)−0.0014 (12)0.0051 (12)0.0023 (11)
C50.0348 (12)0.0324 (12)0.0306 (12)−0.0029 (10)0.0031 (10)−0.0053 (10)
C60.0429 (14)0.0397 (14)0.0303 (12)−0.0063 (11)0.0039 (10)0.0002 (10)
C70.0463 (15)0.0324 (13)0.0450 (15)−0.0125 (11)−0.0068 (12)−0.0032 (11)
C80.0297 (13)0.0563 (18)0.0498 (16)−0.0046 (12)0.0004 (12)0.0011 (13)
C90.0386 (14)0.0369 (13)0.0352 (13)0.0004 (11)0.0051 (11)−0.0115 (11)
C100.0445 (14)0.0359 (13)0.0364 (14)−0.0084 (11)0.0013 (10)0.0022 (11)
C110.0335 (13)0.0417 (14)0.0411 (14)−0.0010 (11)−0.0007 (11)−0.0055 (11)
C120.0304 (12)0.0343 (13)0.0319 (12)−0.0045 (10)0.0013 (9)−0.0044 (10)
C130.0337 (13)0.0514 (16)0.0367 (14)0.0003 (11)0.0069 (11)−0.0062 (12)
C140.0353 (13)0.0332 (12)0.0393 (14)−0.0078 (9)0.0051 (10)−0.0086 (10)
C150.0325 (12)0.0299 (12)0.0318 (12)−0.0064 (9)−0.0015 (9)−0.0019 (9)
C160.0326 (12)0.0301 (12)0.0310 (12)−0.0061 (9)−0.0014 (9)−0.0015 (9)

Geometric parameters (Å, °)

Zn1—N52.041 (2)C2—C71.367 (4)
Zn1—N62.059 (2)C2—C81.410 (4)
Zn1—Cl12.2142 (9)C2—H2A0.9295
Zn1—Cl22.2403 (10)C3—C41.369 (4)
O1—C101.336 (4)C3—H3A0.9301
O1—H1C0.8200C4—C51.402 (4)
O2—C141.332 (3)C4—H4A0.9297
O2—H2B0.9295C5—C121.394 (3)
O3—C141.223 (3)C6—C101.533 (4)
O4—C101.222 (3)C6—H6A0.9698
N1—N41.340 (3)C6—H6B0.9703
N1—C161.360 (3)C7—C161.402 (3)
N1—C91.451 (3)C7—H7A0.9301
N2—N51.318 (3)C8—C111.372 (4)
N2—N31.331 (3)C8—H8A0.9298
N3—C121.363 (3)C9—C141.521 (4)
N3—C61.459 (3)C9—H9A0.9703
N4—N61.314 (3)C9—H9B0.9702
N5—C51.379 (3)C11—C151.400 (4)
N6—C151.380 (3)C11—H11A0.9294
C1—C131.363 (4)C12—C131.401 (4)
C1—C31.422 (4)C13—H13A0.9300
C1—H1A0.9292C15—C161.395 (3)
N5—Zn1—N6101.73 (9)N3—C6—H6A109.6
N5—Zn1—Cl1113.50 (7)C10—C6—H6A109.7
N6—Zn1—Cl1110.90 (7)N3—C6—H6B109.5
N5—Zn1—Cl2107.14 (7)C10—C6—H6B109.4
N6—Zn1—Cl2104.41 (7)H6A—C6—H6B108.2
Cl1—Zn1—Cl2117.63 (4)C2—C7—C16115.2 (3)
C10—O1—H1C109.5C2—C7—H7A122.6
C14—O2—H2B119.5C16—C7—H7A122.3
N4—N1—C16111.2 (2)C11—C8—C2122.0 (3)
N4—N1—C9119.7 (2)C11—C8—H8A119.0
C16—N1—C9128.3 (2)C2—C8—H8A119.0
N5—N2—N3107.4 (2)N1—C9—C14110.2 (2)
N2—N3—C12111.6 (2)N1—C9—H9A109.7
N2—N3—C6120.6 (2)C14—C9—H9A109.7
C12—N3—C6127.7 (2)N1—C9—H9B109.6
N6—N4—N1107.55 (19)C14—C9—H9B109.5
N2—N5—C5109.6 (2)H9A—C9—H9B108.2
N2—N5—Zn1118.20 (16)O4—C10—O1125.3 (3)
C5—N5—Zn1132.12 (17)O4—C10—C6120.4 (2)
N4—N6—C15109.65 (19)O1—C10—C6114.2 (2)
N4—N6—Zn1120.39 (16)C8—C11—C15116.2 (3)
C15—N6—Zn1129.87 (17)C8—C11—H11A122.1
C13—C1—C3122.2 (3)C15—C11—H11A121.6
C13—C1—H1A118.7N3—C12—C5104.5 (2)
C3—C1—H1A119.1N3—C12—C13133.1 (2)
C7—C2—C8122.8 (3)C5—C12—C13122.4 (2)
C7—C2—H2A118.6C1—C13—C12115.8 (3)
C8—C2—H2A118.6C1—C13—H13A122.1
C4—C3—C1122.1 (3)C12—C13—H13A122.1
C4—C3—H3A119.1O3—C14—O2124.5 (3)
C1—C3—H3A118.8O3—C14—C9120.8 (2)
C3—C4—C5116.1 (3)O2—C14—C9114.6 (2)
C3—C4—H4A121.8N6—C15—C16106.8 (2)
C5—C4—H4A122.1N6—C15—C11132.0 (2)
N5—C5—C12106.9 (2)C16—C15—C11121.1 (2)
N5—C5—C4131.7 (2)N1—C16—C15104.7 (2)
C12—C5—C4121.4 (2)N1—C16—C7132.6 (2)
N3—C6—C10110.5 (2)C15—C16—C7122.7 (2)
N5—N2—N3—C12−0.4 (3)C16—N1—C9—C1481.9 (3)
N5—N2—N3—C6−177.9 (2)N3—C6—C10—O4−48.2 (4)
C16—N1—N4—N61.1 (3)N3—C6—C10—O1134.4 (3)
C9—N1—N4—N6171.8 (2)C2—C8—C11—C150.6 (4)
N3—N2—N5—C50.4 (3)N2—N3—C12—C50.3 (3)
N3—N2—N5—Zn1−176.82 (16)C6—N3—C12—C5177.6 (2)
N6—Zn1—N5—N2−47.2 (2)N2—N3—C12—C13178.1 (3)
Cl1—Zn1—N5—N272.01 (19)C6—N3—C12—C13−4.6 (5)
Cl2—Zn1—N5—N2−156.44 (17)N5—C5—C12—N30.0 (3)
N6—Zn1—N5—C5136.3 (2)C4—C5—C12—N3178.8 (2)
Cl1—Zn1—N5—C5−104.5 (2)N5—C5—C12—C13−178.2 (2)
Cl2—Zn1—N5—C527.1 (2)C4—C5—C12—C130.7 (4)
N1—N4—N6—C15−0.4 (3)C3—C1—C13—C12−0.4 (4)
N1—N4—N6—Zn1176.54 (15)N3—C12—C13—C1−177.6 (3)
N5—Zn1—N6—N4148.39 (19)C5—C12—C13—C1−0.1 (4)
Cl1—Zn1—N6—N427.4 (2)N1—C9—C14—O3−6.9 (4)
Cl2—Zn1—N6—N4−100.26 (19)N1—C9—C14—O2172.8 (2)
N5—Zn1—N6—C15−35.3 (2)N4—N6—C15—C16−0.4 (3)
Cl1—Zn1—N6—C15−156.3 (2)Zn1—N6—C15—C16−176.95 (17)
Cl2—Zn1—N6—C1576.0 (2)N4—N6—C15—C11179.4 (3)
C13—C1—C3—C40.3 (5)Zn1—N6—C15—C112.8 (4)
C1—C3—C4—C50.3 (5)C8—C11—C15—N6179.5 (3)
N2—N5—C5—C12−0.2 (3)C8—C11—C15—C16−0.8 (4)
Zn1—N5—C5—C12176.47 (18)N4—N1—C16—C15−1.3 (3)
N2—N5—C5—C4−178.9 (3)C9—N1—C16—C15−170.9 (2)
Zn1—N5—C5—C4−2.2 (4)N4—N1—C16—C7179.4 (3)
C3—C4—C5—N5177.8 (3)C9—N1—C16—C79.7 (5)
C3—C4—C5—C12−0.7 (4)N6—C15—C16—N11.0 (3)
N2—N3—C6—C1092.5 (3)C11—C15—C16—N1−178.8 (2)
C12—N3—C6—C10−84.5 (3)N6—C15—C16—C7−179.6 (2)
C8—C2—C7—C16−0.1 (4)C11—C15—C16—C70.6 (4)
C7—C2—C8—C11−0.1 (5)C2—C7—C16—N1179.1 (3)
N4—N1—C9—C14−87.0 (3)C2—C7—C16—C15−0.1 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1C···O4i0.822.203.015 (4)171
O2—H2B···Cl1ii0.932.593.348 (3)139
C6—H6A···O4iii0.972.693.586 (4)153

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z; (iii) −x, −y+1, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PK2083).

References

  • Danan, A., Charon, D., Kirkiacharian, S., Bories, C. & Loiseau, P. M. (1997). Farmaco, 52, 227–229. [PubMed]
  • Rigaku (2005). CrystalClear Version 1.4.0. Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Xu, X.-B. & Ye, Q. (2007). Acta Cryst. E63, o4607.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography