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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): m1257.
Published online 2010 September 15. doi:  10.1107/S1600536810036251
PMCID: PMC2983120

Poly[dichloridobis[μ-1-(4-pyridyl­meth­yl)-1,2,4-triazole]cadmium(II)]

Abstract

In the title coordination polymer, [CdCl2(C8H8N4)2]n, the CdII atom, lying on an inversion center, is coordinated by two Cl atoms and two triazole N atoms and two pyridyl N atoms from four 1-(4-pyridyl­meth­yl)-1,2,4-triazole (pmta) ligands in a distorted trans-CdCl2N4 octa­hedral arrangement. The bridg­ing pmta ligands, with a dihedral angle between the triazole and pyridyl rings of 71.86 (8)°, link the Cd atoms into a 44 sheet parallel to (An external file that holds a picture, illustration, etc.
Object name is e-66-m1257-efi1.jpg02). π–π inter­actions between the triazole rings [centroid–centroid distance = 3.428 (2) Å] connect the sheets.

Related literature

For our previous studies on the design and synthesis of some unsymmetric flexible ligands, see: Huang et al. (2006 [triangle]); Liu et al. (2005 [triangle]). For related structures, see: Li et al. (2009 [triangle]); Wang et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1257-scheme1.jpg

Experimental

Crystal data

  • [CdCl2(C8H8N4)2]
  • M r = 503.67
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1257-efi2.jpg
  • a = 7.5795 (5) Å
  • b = 16.9491 (10) Å
  • c = 8.2215 (5) Å
  • β = 113.325 (3)°
  • V = 969.86 (10) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.42 mm−1
  • T = 293 K
  • 0.20 × 0.18 × 0.04 mm

Data collection

  • Rigaku Mercury CCD diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2007 [triangle]) T min = 0.841, T max = 1.000
  • 6994 measured reflections
  • 2214 independent reflections
  • 2079 reflections with I > 2σ(I)
  • R int = 0.016

Refinement

  • R[F 2 > 2σ(F 2)] = 0.022
  • wR(F 2) = 0.048
  • S = 1.01
  • 2214 reflections
  • 124 parameters
  • H-atom parameters constrained
  • Δρmax = 0.78 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: CrystalClear (Rigaku, 2007 [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]) and DIAMOND (Brandenburg, 1999 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Selected bond lengths (Å)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810036251/hy2349sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810036251/hy2349Isup2.hkl

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

Acknowledgments

The authors thank the Fujian Provincial Science and Technology Innovation Foundation under grant No. 2007 F3038 for financial support.

supplementary crystallographic information

Comment

Recently, our group has focused on the design and synthesis of some unsymmetric flexible ligands (Huang et al., 2006; Liu et al., 2005), and we have got a heterocyclic ligand 1-(4-pyridylmethyl)-1,2,4-triazole (pmta). In order to explore the architectural styles and coordination chemistry of this kind of ligands, we selected cadmium chloride as representative subject for stereoregular coordination. Among our attempts, the title compound, a new coordination polymer, was obtained as crystals suitable for single-crystal X-ray analysis.

The title compound is isomorphic to the complex we have reported (Li et al., 2009; Wang et al., 2008). The crystallographic analysis reveals that the asymmetric unit contains one CdII atom lying on an inversion center, one Cl anion and one bridging pmta ligand, as shown in Fig. 1. The CdII atom lies in an octahedral [CdCl2N4] environment, with the axial positions occupied by two Cl atoms and the equatorial positions occupied by two trans triazole N atoms and two trans pyridyl N atoms, which belong to four different pmta ligands. The bond angles about Cd1 atom range from 85.82 (6) to 94.18 (6)° and deviate slightly from those of a perfect octahedron. Due to the existence of the –CH2– spacer between the triazole and pyridyl rings with a dihedral angle of 71.86 (8)°, sufficient flexibility makes it possible for pmta to be twisted to meet the requirment of coordination geometries of the Cd center.

As shown in Fig. 2, the title compound exhibits a two-dimensional rhombohedral sheet containing 36-membered sandglass rings. The sp3 configuration of C3 forces the pmta ligand to be non-linear, generating the non-linear grid sides and thereby the sandglass grids. Every complementary four [Cd4(pmta)4] grids are joined together by sharing the Cd apices, giving a 44 topology with a side length of 11.022 Å and diagonal measurements of 14.096 and 16.949 Å.

Experimental

A solution of pmta (0.021 g, 0.10 mmol) in MeOH (5 ml) was carefully layered on a solution of CdCl2.2.5H2O (0.023 g, 0.10 mmol) in H2O (5 ml). Diffusion between the two phases over a period of two weeks produced colorless block crystals.

Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (CH) and 0.97 (CH2) Å and with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The structure of the title compound, showing 30% probability displacement ellipsoids. H atoms have been omitted for clarity. [Symmetry codes: (A) -x, -y+1, -z; (B) -x+1, y-1/2, -z+1/2; (C) x-1, -y+3/2, z-1/2.]
Fig. 2.
The two-dimensional structure of the title compound, constructed of rhombus-shaped grids.

Crystal data

[CdCl2(C8H8N4)2]F(000) = 500
Mr = 503.67Dx = 1.725 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2546 reflections
a = 7.5795 (5) Åθ = 2.7–27.5°
b = 16.9491 (10) ŵ = 1.42 mm1
c = 8.2215 (5) ÅT = 293 K
β = 113.325 (3)°Prism, colorless
V = 969.86 (10) Å30.20 × 0.18 × 0.04 mm
Z = 2

Data collection

Rigaku Mercury CCD diffractometer2214 independent reflections
Radiation source: fine-focus sealed tube2079 reflections with I > 2σ(I)
graphiteRint = 0.016
ω scansθmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)h = −9→9
Tmin = 0.841, Tmax = 1.000k = −15→22
6994 measured reflectionsl = −9→10

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)] = 0.022Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.048H-atom parameters constrained
S = 1.00w = 1/[σ2(Fo2) + (0.016P)2 + 0.9435P] where P = (Fo2 + 2Fc2)/3
2214 reflections(Δ/σ)max < 0.001
124 parametersΔρmax = 0.78 e Å3
0 restraintsΔρmin = −0.23 e Å3

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

xyzUiso*/Ueq
Cd10.00000.50000.00000.02465 (6)
Cl10.18617 (7)0.53526 (3)−0.19411 (7)0.03766 (12)
N20.4333 (3)0.60582 (12)0.5065 (2)0.0416 (4)
C20.4379 (3)0.56302 (12)0.2553 (3)0.0309 (4)
H20.48220.55150.16740.037*
C30.7421 (3)0.62024 (12)0.4780 (3)0.0387 (5)
H3A0.80330.59210.41160.046*
H3B0.80160.60270.60000.046*
C40.7814 (3)0.70736 (11)0.4718 (3)0.0315 (4)
C50.6464 (3)0.76634 (13)0.4358 (3)0.0404 (5)
H50.51870.75400.41060.048*
C60.7022 (3)0.84449 (12)0.4373 (3)0.0385 (5)
H60.60940.88360.41410.046*
C71.0109 (3)0.80837 (14)0.5028 (4)0.0501 (6)
H71.13680.82210.52390.060*
C80.9684 (3)0.72969 (13)0.5070 (4)0.0496 (6)
H81.06460.69190.53320.060*
N30.2643 (2)0.54659 (10)0.2469 (2)0.0306 (4)
C10.2694 (3)0.57354 (12)0.4037 (3)0.0356 (4)
H10.16530.56950.43600.043*
N10.5399 (2)0.59858 (9)0.4081 (2)0.0309 (4)
N40.8817 (3)0.86600 (10)0.4702 (2)0.0351 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cd10.02100 (10)0.02176 (10)0.03014 (10)0.00065 (7)0.00902 (7)−0.00232 (7)
Cl10.0338 (3)0.0460 (3)0.0388 (3)0.0022 (2)0.0204 (2)0.0020 (2)
N20.0476 (11)0.0420 (11)0.0385 (10)−0.0133 (9)0.0205 (9)−0.0113 (8)
C20.0264 (9)0.0316 (10)0.0330 (10)−0.0031 (8)0.0097 (8)−0.0057 (8)
C30.0261 (10)0.0265 (10)0.0511 (13)−0.0061 (8)0.0022 (9)−0.0011 (9)
C40.0307 (10)0.0257 (9)0.0331 (10)−0.0049 (8)0.0073 (8)−0.0019 (8)
C50.0274 (10)0.0317 (11)0.0579 (14)−0.0051 (8)0.0125 (10)0.0022 (10)
C60.0320 (11)0.0276 (10)0.0534 (13)0.0007 (8)0.0141 (10)0.0039 (9)
C70.0315 (11)0.0284 (11)0.094 (2)−0.0065 (9)0.0285 (12)−0.0064 (12)
C80.0338 (12)0.0250 (11)0.0862 (19)−0.0009 (9)0.0197 (12)−0.0064 (11)
N30.0246 (8)0.0318 (9)0.0334 (8)−0.0030 (7)0.0095 (7)−0.0038 (7)
C10.0390 (11)0.0336 (11)0.0387 (11)−0.0064 (9)0.0202 (9)−0.0052 (9)
N10.0283 (8)0.0235 (8)0.0365 (9)−0.0051 (6)0.0082 (7)−0.0010 (7)
N40.0345 (9)0.0246 (8)0.0479 (10)−0.0036 (7)0.0180 (8)−0.0005 (7)

Geometric parameters (Å, °)

Cd1—N32.3531 (16)C4—C81.383 (3)
Cd1—N4i2.4183 (16)C5—C61.389 (3)
Cd1—Cl12.5842 (5)C5—H50.9300
N2—C11.313 (3)C6—N41.329 (3)
N2—N11.357 (3)C6—H60.9300
C2—N31.320 (2)C7—N41.333 (3)
C2—N11.330 (2)C7—C81.375 (3)
C2—H20.9300C7—H70.9300
C3—N11.454 (2)C8—H80.9300
C3—C41.511 (3)N3—C11.353 (3)
C3—H3A0.9700C1—H10.9300
C3—H3B0.9700N4—Cd1ii2.4183 (16)
C4—C51.376 (3)
N3iii—Cd1—N3180.0C5—C4—C3125.27 (19)
N3iii—Cd1—N4i85.82 (6)C8—C4—C3117.38 (19)
N3—Cd1—N4i94.18 (6)C4—C5—C6119.5 (2)
N3iii—Cd1—N4iv94.18 (6)C4—C5—H5120.2
N3—Cd1—N4iv85.82 (6)C6—C5—H5120.2
N4i—Cd1—N4iv180.00 (10)N4—C6—C5123.2 (2)
N3iii—Cd1—Cl191.79 (4)N4—C6—H6118.4
N3—Cd1—Cl188.21 (4)C5—C6—H6118.4
N4i—Cd1—Cl190.49 (5)N4—C7—C8123.7 (2)
N4iv—Cd1—Cl189.51 (5)N4—C7—H7118.1
N3iii—Cd1—Cl1iii88.21 (4)C8—C7—H7118.1
N3—Cd1—Cl1iii91.79 (4)C7—C8—C4119.4 (2)
N4i—Cd1—Cl1iii89.51 (5)C7—C8—H8120.3
N4iv—Cd1—Cl1iii90.49 (5)C4—C8—H8120.3
Cl1—Cd1—Cl1iii180.0C2—N3—C1103.13 (16)
C1—N2—N1102.33 (17)C2—N3—Cd1127.31 (13)
N3—C2—N1109.85 (18)C1—N3—Cd1128.94 (14)
N3—C2—H2125.1N2—C1—N3114.62 (19)
N1—C2—H2125.1N2—C1—H1122.7
N1—C3—C4115.10 (17)N3—C1—H1122.7
N1—C3—H3A108.5C2—N1—N2110.07 (17)
C4—C3—H3A108.5C2—N1—C3127.96 (19)
N1—C3—H3B108.5N2—N1—C3121.64 (18)
C4—C3—H3B108.5C6—N4—C7116.82 (18)
H3A—C3—H3B107.5C6—N4—Cd1ii125.95 (14)
C5—C4—C8117.34 (19)C7—N4—Cd1ii117.03 (14)

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x, −y+1, −z; (iv) x−1, −y+3/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2349).

References

  • Brandenburg, K. (1999). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Huang, M., Liu, P., Chen, Y., Wang, J. & Liu, Z. (2006). J. Mol. Struct.788, 211–217.
  • Li, Z.-L., Wang, J., Xu, X.-Z. & Ye, X. (2009). Acta Cryst. E65, m340. [PMC free article] [PubMed]
  • Liu, Z., Liu, P., Chen, Y., Wang, J. & Huang, M. (2005). Inorg. Chem. Commun.8, 212–215.
  • Rigaku (2007). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, J., Huang, M., Liu, P. & Cheng, W. (2008). J. Mol. Struct.875, 22–26.

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