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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): m593.
Published online 2010 April 30. doi:  10.1107/S1600536810015138
PMCID: PMC2979197

Dichlorido[N-(2-pyridylmethyl­idene)benzene-1,4-diamine]zinc(II)

Abstract

In the title compound, [ZnCl2(C12H11N3)], the ZnII atom is four-coordinated by two N atoms from an N-(2-pyridylmethyl­ene)benzene-1,4-diamine ligand and two Cl atoms in a distorted tetra­hedral geometry. In the crystal, the complex mol­ecules are connected by N—H(...)Cl and C—H(...)Cl hydrogen bonds into a two-dimensional layer structure parallel to (110).

Related literature

For general background to zinc(II) complexes with Schiff base ligands, see: Su et al. (1999 [triangle]); Ye et al. (2005 [triangle]).

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Object name is e-66-0m593-scheme1.jpg

Experimental

Crystal data

  • [ZnCl2(C12H11N3)]
  • M r = 333.53
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m593-efi1.jpg
  • a = 7.5004 (15) Å
  • b = 9.1168 (18) Å
  • c = 10.186 (2) Å
  • α = 84.36 (3)°
  • β = 82.27 (3)°
  • γ = 74.19 (3)°
  • V = 662.7 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.24 mm−1
  • T = 293 K
  • 0.20 × 0.18 × 0.16 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.645, T max = 0.699
  • 6557 measured reflections
  • 3000 independent reflections
  • 2345 reflections with I > 2σ(I)
  • R int = 0.027

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.108
  • S = 0.93
  • 3000 reflections
  • 175 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.39 e Å−3
  • Δρmin = −0.37 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 1999 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810015138/hy2300sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810015138/hy2300Isup2.hkl

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

Acknowledgments

This work was supported by the National Natural Science Foundation of China (No. 60772019) and the Science and Technology Foundation of Education Office of Heilongjiang Province (No. 11541047).

supplementary crystallographic information

Comment

Based on the design and syntheses of zinc Schiff-base complexes and the potential applications of these materials as fluorescent probes (Su et al., 1999; Ye et al., 2005), the title compound has been obtained. As shown in Fig. 1, the asymmetric unit contains one ZnII ion, one N-(pyridin-2-ylmethylene)benzene-1,4-diamine ligand and two Cl atoms. The ZnII atom exhibits a distorted tetrahedral coordinate geometry formed by two N atoms from the ligand and two Cl atoms, with the Zn—N distances of 2.057 (3) and 2.070 (3)Å and the Zn—Cl distances of 2.2000 (13) and 2.2456 (12) Å. As shown in Fig. 2, the complex molecules are connected into a two-dimensional supramolecular layer-like structure via weak N—H···Cl and C—H···Cl hydrogen-bonding interactions (Table 1).

Experimental

The ligand was prepared according to the previous method (Ye et al., 2005). 1,4-Diaminobenzene (1.08 g, 10 mmol) was dissolved in methanol (20 ml), followed by addition of 2-pyridine carboxaldehyde (4.24 mg, 40 mmol). The mixture was stirred at room temperature for 2 h and filtered. The resulting yellow crystalline solid was washed with methanol several times and dried in air. A solution of ZnCl2.2H2O(14 mg, 0.08 mmol) in acetonitrile (5 ml) was allowed to diffuse slowly into a methylene chloride solution (10 ml) of the ligand (0.179 g, 0.625 mmol) in an H-shaped tube. Colorless crystals were obtained over a week.

Refinement

H atoms bonded to C3, C4 and C11 were located from a difference Fourier map and refined isotropically. The other H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 and N—H = 0.86 Å and with Uiso(H) = 1.2Ueq(C,N).

Figures

Fig. 1.
Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
A view of the two-dimensional layer-like structure in the title compound.

Crystal data

[ZnCl2(C12H11N3)]Z = 2
Mr = 333.53F(000) = 336
Triclinic, P1Dx = 1.671 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.5004 (15) ÅCell parameters from 2613 reflections
b = 9.1168 (18) Åθ = 3.2–26.5°
c = 10.186 (2) ŵ = 2.24 mm1
α = 84.36 (3)°T = 293 K
β = 82.27 (3)°Block, red
γ = 74.19 (3)°0.20 × 0.18 × 0.16 mm
V = 662.7 (3) Å3

Data collection

Rigaku R-AXIS RAPID diffractometer3000 independent reflections
Radiation source: fine-focus sealed tube2345 reflections with I > 2σ(I)
graphiteRint = 0.027
ω scansθmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = −9→9
Tmin = 0.645, Tmax = 0.699k = −11→11
6557 measured reflectionsl = −13→13

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 0.93w = 1/[σ2(Fo2) + (0.058P)2 + 0.9028P] where P = (Fo2 + 2Fc2)/3
3000 reflections(Δ/σ)max < 0.001
175 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = −0.36 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Zn10.27968 (6)0.38462 (4)0.24431 (4)0.03673 (14)
Cl20.09004 (13)0.22915 (11)0.26242 (10)0.0490 (2)
Cl40.55281 (14)0.29132 (12)0.13201 (10)0.0515 (3)
N40.1317 (4)0.6067 (3)0.2044 (3)0.0353 (6)
N60.2715 (4)0.4658 (3)0.4284 (3)0.0308 (6)
C2−0.0484 (6)0.8248 (5)0.0885 (4)0.0492 (9)
H2−0.09410.87040.00980.059*
C3−0.0912 (6)0.9047 (5)0.2008 (4)0.0508 (10)
C4−0.0201 (6)0.8340 (4)0.3174 (4)0.0455 (9)
C10.0631 (5)0.6763 (4)0.0925 (4)0.0433 (8)
H10.09120.62320.01570.052*
C110.5458 (6)0.1380 (4)0.6210 (4)0.0422 (8)
N110.5896 (5)0.0970 (4)0.8533 (3)0.0536 (9)
H110.65550.00520.84080.064*
H100.56980.13060.93140.064*
C90.4073 (5)0.3393 (4)0.7684 (3)0.0375 (7)
H80.38950.37640.85240.045*
C50.0910 (5)0.6854 (4)0.3156 (3)0.0342 (7)
C100.5160 (5)0.1897 (4)0.7488 (3)0.0366 (7)
C60.1730 (5)0.6044 (4)0.4344 (3)0.0357 (7)
H60.15360.65330.51310.043*
C80.3268 (5)0.4319 (4)0.6659 (3)0.0347 (7)
H70.25480.53060.68120.042*
C120.4640 (5)0.2327 (4)0.5178 (3)0.0382 (8)
H90.48450.19730.43300.046*
C70.3523 (4)0.3789 (4)0.5390 (3)0.0312 (7)
H50.604 (6)0.045 (5)0.601 (4)0.050 (12)*
H4−0.030 (7)0.890 (6)0.403 (5)0.070 (14)*
H3−0.189 (7)1.002 (6)0.196 (5)0.079 (16)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.0404 (2)0.0338 (2)0.0327 (2)−0.00136 (17)−0.00508 (16)−0.00900 (15)
Cl20.0465 (5)0.0419 (5)0.0599 (6)−0.0092 (4)−0.0042 (4)−0.0183 (4)
Cl40.0469 (5)0.0540 (5)0.0475 (5)−0.0026 (4)0.0052 (4)−0.0188 (4)
N40.0341 (15)0.0352 (15)0.0347 (14)−0.0062 (12)−0.0034 (12)−0.0027 (12)
N60.0322 (14)0.0299 (13)0.0291 (13)−0.0059 (11)−0.0029 (11)−0.0030 (10)
C20.051 (2)0.047 (2)0.049 (2)−0.0123 (18)−0.0147 (18)0.0131 (18)
C30.045 (2)0.038 (2)0.063 (3)0.0000 (17)−0.0106 (19)0.0056 (18)
C40.049 (2)0.0335 (18)0.052 (2)−0.0061 (16)−0.0058 (18)−0.0070 (16)
C10.042 (2)0.048 (2)0.0377 (18)−0.0097 (16)−0.0052 (15)0.0034 (16)
C110.054 (2)0.0295 (17)0.0401 (19)−0.0002 (16)−0.0105 (16)−0.0089 (15)
N110.077 (3)0.0386 (17)0.0373 (16)0.0017 (16)−0.0176 (16)0.0005 (13)
C90.043 (2)0.0383 (18)0.0299 (16)−0.0080 (15)−0.0015 (14)−0.0092 (14)
C50.0333 (17)0.0323 (16)0.0369 (17)−0.0084 (14)−0.0036 (14)−0.0024 (13)
C100.0409 (19)0.0344 (17)0.0348 (17)−0.0098 (15)−0.0049 (14)−0.0029 (14)
C60.0389 (19)0.0352 (17)0.0327 (16)−0.0079 (14)−0.0017 (14)−0.0089 (13)
C80.0386 (18)0.0311 (16)0.0334 (16)−0.0067 (14)−0.0006 (14)−0.0085 (13)
C120.045 (2)0.0345 (17)0.0333 (16)−0.0035 (15)−0.0057 (14)−0.0109 (14)
C70.0309 (16)0.0320 (16)0.0314 (15)−0.0084 (13)−0.0054 (13)−0.0026 (12)

Geometric parameters (Å, °)

Zn1—N42.057 (3)C11—C121.391 (5)
Zn1—N62.070 (3)C11—C101.396 (5)
Zn1—Cl42.2000 (13)C11—H50.87 (4)
Zn1—Cl22.2456 (12)N11—C101.371 (4)
N4—C11.343 (4)N11—H110.8600
N4—C51.356 (4)N11—H100.8600
N6—C61.281 (4)C9—C81.374 (5)
N6—C71.418 (4)C9—C101.403 (5)
C2—C31.370 (6)C9—H80.9300
C2—C11.384 (5)C5—C61.472 (5)
C2—H20.9300C6—H60.9300
C3—C41.394 (6)C8—C71.395 (4)
C3—H30.99 (5)C8—H70.9300
C4—C51.384 (5)C12—C71.387 (5)
C4—H41.03 (5)C12—H90.9300
C1—H10.9300
N4—Zn1—N681.72 (11)C10—C11—H5125 (3)
N4—Zn1—Cl4120.24 (9)C10—N11—H11120.0
N6—Zn1—Cl4118.70 (9)C10—N11—H10120.0
N4—Zn1—Cl2109.98 (9)H11—N11—H10120.0
N6—Zn1—Cl2108.64 (8)C8—C9—C10121.2 (3)
Cl4—Zn1—Cl2113.46 (4)C8—C9—H8119.4
C1—N4—C5118.7 (3)C10—C9—H8119.4
C1—N4—Zn1130.3 (3)N4—C5—C4122.1 (3)
C5—N4—Zn1110.8 (2)N4—C5—C6116.2 (3)
C6—N6—C7122.8 (3)C4—C5—C6121.7 (3)
C6—N6—Zn1111.6 (2)N11—C10—C11121.2 (3)
C7—N6—Zn1125.5 (2)N11—C10—C9120.4 (3)
C3—C2—C1119.9 (4)C11—C10—C9118.4 (3)
C3—C2—H2120.0N6—C6—C5119.3 (3)
C1—C2—H2120.0N6—C6—H6120.3
C2—C3—C4118.9 (4)C5—C6—H6120.3
C2—C3—H3116 (3)C9—C8—C7120.4 (3)
C4—C3—H3124 (3)C9—C8—H7119.8
C5—C4—C3118.7 (4)C7—C8—H7119.8
C5—C4—H4117 (3)C7—C12—C11121.2 (3)
C3—C4—H4124 (3)C7—C12—H9119.4
N4—C1—C2121.7 (4)C11—C12—H9119.4
N4—C1—H1119.1C12—C7—C8118.8 (3)
C2—C1—H1119.1C12—C7—N6117.2 (3)
C12—C11—C10120.0 (3)C8—C7—N6124.0 (3)
C12—C11—H5115 (3)
N6—Zn1—N4—C1179.7 (3)C3—C4—C5—N4−0.4 (6)
Cl4—Zn1—N4—C161.3 (3)C3—C4—C5—C6179.1 (3)
Cl2—Zn1—N4—C1−73.4 (3)C12—C11—C10—N11177.7 (4)
N6—Zn1—N4—C5−5.4 (2)C12—C11—C10—C9−1.9 (6)
Cl4—Zn1—N4—C5−123.9 (2)C8—C9—C10—N11−177.6 (3)
Cl2—Zn1—N4—C5101.5 (2)C8—C9—C10—C112.0 (5)
N4—Zn1—N6—C64.4 (2)C7—N6—C6—C5−178.8 (3)
Cl4—Zn1—N6—C6124.4 (2)Zn1—N6—C6—C5−2.7 (4)
Cl2—Zn1—N6—C6−104.0 (2)N4—C5—C6—N6−2.0 (5)
N4—Zn1—N6—C7−179.7 (3)C4—C5—C6—N6178.4 (3)
Cl4—Zn1—N6—C7−59.6 (3)C10—C9—C8—C7−0.3 (5)
Cl2—Zn1—N6—C772.0 (3)C10—C11—C12—C70.1 (6)
C1—C2—C3—C40.3 (6)C11—C12—C7—C81.7 (5)
C2—C3—C4—C5−0.1 (6)C11—C12—C7—N6−178.6 (3)
C5—N4—C1—C2−0.5 (5)C9—C8—C7—C12−1.6 (5)
Zn1—N4—C1—C2174.1 (3)C9—C8—C7—N6178.8 (3)
C3—C2—C1—N40.0 (6)C6—N6—C7—C12−176.7 (3)
C1—N4—C5—C40.7 (5)Zn1—N6—C7—C127.8 (4)
Zn1—N4—C5—C4−174.9 (3)C6—N6—C7—C83.0 (5)
C1—N4—C5—C6−178.8 (3)Zn1—N6—C7—C8−172.5 (2)
Zn1—N4—C5—C65.6 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N11—H10···Cl4i0.862.603.433 (4)164
N11—H11···Cl2ii0.862.643.470 (4)161
C3—H3···Cl4iii0.99 (5)2.89 (5)3.864 (4)169 (4)
C6—H6···Cl2iv0.932.833.658 (4)149

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2300).

References

  • Brandenburg, K. (1999). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Rigaku (1998). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Su, C.-Y., Yang, X.-P., Liao, S., Mak, T. C. W. & Kang, B.-S. (1999). Inorg. Chem. Commun.2, 383–385.
  • Ye, K.-Q., Wu, Y., Guo, J.-H., Sun, Y.-H. & Wang, Y. (2005). Chem. J. Chin. Univ.26, 93–96.

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