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

Wang, J.; Li, Z.-L.; Xu, X.-Z.; Yan, W.-J.; Chi, H.-L.

doi:10.1107/S1600536810036251

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page m1257

doi:10.1107/S1600536810036251

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

Jian Wang,^a Zhu-Lai Li,^a ^* Xiu-Zhi Xu,^a Wen-Jin Yan ^a and Hui-Li Chi ^a

^aDepartment of Medicinal Chemistry, School of Pharmacy, Fujian Medical University, Fuzhou, Fujian 350004, People's Republic of China
^*Correspondence e-mail: lizhulai@126.com

(Received 25 August 2010; accepted 9 September 2010; online 15 September 2010)

In the title coordination polymer, [CdCl₂(C₈H₈N₄)₂]_n, the Cd^II 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 ( $[\overline{1}]$ 02). 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 ); Liu et al. (2005 ). For related structures, see: Li et al. (2009 ); Wang et al. (2008 ).

Experimental

Crystal data

[CdCl₂(C₈H₈N₄)₂]
M_r = 503.67
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.022
wR(F²) = 0.048
S = 1.01
2214 reflections
124 parameters
H-atom parameters constrained
Δρ_max = 0.78 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—N3	2.3531 (16)
Cd1—N4ⁱ	2.4183 (16)
Cd1—Cl1	2.5842 (5)
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

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

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

checkCIF report

Comment top

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 Cd^II atom lying on an inversion center, one Cl anion and one bridging pmta ligand, as shown in Fig. 1. The Cd^II 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.

Related literature top

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

Experimental top

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.

Computing details top

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	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.

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

Crystal data top

[CdCl₂(C₈H₈N₄)₂]	F(000) = 500
M_r = 503.67	D_x = 1.725 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2546 reflections
a = 7.5795 (5) Å	θ = 2.7–27.5°
b = 16.9491 (10) Å	µ = 1.42 mm⁻¹
c = 8.2215 (5) Å	T = 293 K
β = 113.325 (3)°	Prism, colorless
V = 969.86 (10) Å³	0.20 × 0.18 × 0.04 mm
Z = 2

Data collection top

Rigaku Mercury CCD diffractometer	2214 independent reflections
Radiation source: fine-focus sealed tube	2079 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	h = −9→9
T_min = 0.841, T_max = 1.000	k = −15→22
6994 measured reflections	l = −9→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.048	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.016P)² + 0.9435P] where P = (F_o² + 2F_c²)/3
2214 reflections	(Δ/σ)_max < 0.001
124 parameters	Δρ_max = 0.78 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

[CdCl₂(C₈H₈N₄)₂]	V = 969.86 (10) Å³
M_r = 503.67	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.5795 (5) Å	µ = 1.42 mm⁻¹
b = 16.9491 (10) Å	T = 293 K
c = 8.2215 (5) Å	0.20 × 0.18 × 0.04 mm
β = 113.325 (3)°

Data collection top

Rigaku Mercury CCD diffractometer	2214 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	2079 reflections with I > 2σ(I)
T_min = 0.841, T_max = 1.000	R_int = 0.016
6994 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	0 restraints
wR(F²) = 0.048	H-atom parameters constrained
S = 1.01	Δρ_max = 0.78 e Å⁻³
2214 reflections	Δρ_min = −0.23 e Å⁻³
124 parameters

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

	x	y	z	U_iso*/U_eq
Cd1	0.0000	0.5000	0.0000	0.02465 (6)
Cl1	0.18617 (7)	0.53526 (3)	−0.19411 (7)	0.03766 (12)
N2	0.4333 (3)	0.60582 (12)	0.5065 (2)	0.0416 (4)
C2	0.4379 (3)	0.56302 (12)	0.2553 (3)	0.0309 (4)
H2	0.4822	0.5515	0.1674	0.037*
C3	0.7421 (3)	0.62024 (12)	0.4780 (3)	0.0387 (5)
H3A	0.8033	0.5921	0.4116	0.046*
H3B	0.8016	0.6027	0.6000	0.046*
C4	0.7814 (3)	0.70736 (11)	0.4718 (3)	0.0315 (4)
C5	0.6464 (3)	0.76634 (13)	0.4358 (3)	0.0404 (5)
H5	0.5187	0.7540	0.4106	0.048*
C6	0.7022 (3)	0.84449 (12)	0.4373 (3)	0.0385 (5)
H6	0.6094	0.8836	0.4141	0.046*
C7	1.0109 (3)	0.80837 (14)	0.5028 (4)	0.0501 (6)
H7	1.1368	0.8221	0.5239	0.060*
C8	0.9684 (3)	0.72969 (13)	0.5070 (4)	0.0496 (6)
H8	1.0646	0.6919	0.5332	0.060*
N3	0.2643 (2)	0.54659 (10)	0.2469 (2)	0.0306 (4)
C1	0.2694 (3)	0.57354 (12)	0.4037 (3)	0.0356 (4)
H1	0.1653	0.5695	0.4360	0.043*
N1	0.5399 (2)	0.59858 (9)	0.4081 (2)	0.0309 (4)
N4	0.8817 (3)	0.86600 (10)	0.4702 (2)	0.0351 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.02100 (10)	0.02176 (10)	0.03014 (10)	0.00065 (7)	0.00902 (7)	−0.00232 (7)
Cl1	0.0338 (3)	0.0460 (3)	0.0388 (3)	0.0022 (2)	0.0204 (2)	0.0020 (2)
N2	0.0476 (11)	0.0420 (11)	0.0385 (10)	−0.0133 (9)	0.0205 (9)	−0.0113 (8)
C2	0.0264 (9)	0.0316 (10)	0.0330 (10)	−0.0031 (8)	0.0097 (8)	−0.0057 (8)
C3	0.0261 (10)	0.0265 (10)	0.0511 (13)	−0.0061 (8)	0.0022 (9)	−0.0011 (9)
C4	0.0307 (10)	0.0257 (9)	0.0331 (10)	−0.0049 (8)	0.0073 (8)	−0.0019 (8)
C5	0.0274 (10)	0.0317 (11)	0.0579 (14)	−0.0051 (8)	0.0125 (10)	0.0022 (10)
C6	0.0320 (11)	0.0276 (10)	0.0534 (13)	0.0007 (8)	0.0141 (10)	0.0039 (9)
C7	0.0315 (11)	0.0284 (11)	0.094 (2)	−0.0065 (9)	0.0285 (12)	−0.0064 (12)
C8	0.0338 (12)	0.0250 (11)	0.0862 (19)	−0.0009 (9)	0.0197 (12)	−0.0064 (11)
N3	0.0246 (8)	0.0318 (9)	0.0334 (8)	−0.0030 (7)	0.0095 (7)	−0.0038 (7)
C1	0.0390 (11)	0.0336 (11)	0.0387 (11)	−0.0064 (9)	0.0202 (9)	−0.0052 (9)
N1	0.0283 (8)	0.0235 (8)	0.0365 (9)	−0.0051 (6)	0.0082 (7)	−0.0010 (7)
N4	0.0345 (9)	0.0246 (8)	0.0479 (10)	−0.0036 (7)	0.0180 (8)	−0.0005 (7)

Geometric parameters (Å, º) top

Cd1—N3	2.3531 (16)	C4—C8	1.383 (3)
Cd1—N4ⁱ	2.4183 (16)	C5—C6	1.389 (3)
Cd1—Cl1	2.5842 (5)	C5—H5	0.9300
N2—C1	1.313 (3)	C6—N4	1.329 (3)
N2—N1	1.357 (3)	C6—H6	0.9300
C2—N3	1.320 (2)	C7—N4	1.333 (3)
C2—N1	1.330 (2)	C7—C8	1.375 (3)
C2—H2	0.9300	C7—H7	0.9300
C3—N1	1.454 (2)	C8—H8	0.9300
C3—C4	1.511 (3)	N3—C1	1.353 (3)
C3—H3A	0.9700	C1—H1	0.9300
C3—H3B	0.9700	N4—Cd1ⁱⁱ	2.4183 (16)
C4—C5	1.376 (3)

N3ⁱⁱⁱ—Cd1—N3	180.0	C5—C4—C3	125.27 (19)
N3ⁱⁱⁱ—Cd1—N4ⁱ	85.82 (6)	C8—C4—C3	117.38 (19)
N3—Cd1—N4ⁱ	94.18 (6)	C4—C5—C6	119.5 (2)
N3ⁱⁱⁱ—Cd1—N4^iv	94.18 (6)	C4—C5—H5	120.2
N3—Cd1—N4^iv	85.82 (6)	C6—C5—H5	120.2
N4ⁱ—Cd1—N4^iv	180.00 (10)	N4—C6—C5	123.2 (2)
N3ⁱⁱⁱ—Cd1—Cl1	91.79 (4)	N4—C6—H6	118.4
N3—Cd1—Cl1	88.21 (4)	C5—C6—H6	118.4
N4ⁱ—Cd1—Cl1	90.49 (5)	N4—C7—C8	123.7 (2)
N4^iv—Cd1—Cl1	89.51 (5)	N4—C7—H7	118.1
N3ⁱⁱⁱ—Cd1—Cl1ⁱⁱⁱ	88.21 (4)	C8—C7—H7	118.1
N3—Cd1—Cl1ⁱⁱⁱ	91.79 (4)	C7—C8—C4	119.4 (2)
N4ⁱ—Cd1—Cl1ⁱⁱⁱ	89.51 (5)	C7—C8—H8	120.3
N4^iv—Cd1—Cl1ⁱⁱⁱ	90.49 (5)	C4—C8—H8	120.3
Cl1—Cd1—Cl1ⁱⁱⁱ	180.0	C2—N3—C1	103.13 (16)
C1—N2—N1	102.33 (17)	C2—N3—Cd1	127.31 (13)
N3—C2—N1	109.85 (18)	C1—N3—Cd1	128.94 (14)
N3—C2—H2	125.1	N2—C1—N3	114.62 (19)
N1—C2—H2	125.1	N2—C1—H1	122.7
N1—C3—C4	115.10 (17)	N3—C1—H1	122.7
N1—C3—H3A	108.5	C2—N1—N2	110.07 (17)
C4—C3—H3A	108.5	C2—N1—C3	127.96 (19)
N1—C3—H3B	108.5	N2—N1—C3	121.64 (18)
C4—C3—H3B	108.5	C6—N4—C7	116.82 (18)
H3A—C3—H3B	107.5	C6—N4—Cd1ⁱⁱ	125.95 (14)
C5—C4—C8	117.34 (19)	C7—N4—Cd1ⁱⁱ	117.03 (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.

Experimental details

Crystal data
Chemical formula	[CdCl₂(C₈H₈N₄)₂]
M_r	503.67
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.5795 (5), 16.9491 (10), 8.2215 (5)
β (°)	113.325 (3)
V (Å³)	969.86 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.42
Crystal size (mm)	0.20 × 0.18 × 0.04

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2007)
T_min, T_max	0.841, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6994, 2214, 2079
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.048, 1.01
No. of reflections	2214
No. of parameters	124
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.78, −0.23

Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cd1—N3	2.3531 (16)	Cd1—Cl1	2.5842 (5)
Cd1—N4ⁱ	2.4183 (16)

Symmetry code: (i) −x+1, y−1/2, −z+1/2.

Acknowledgements

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

References

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