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

Li, Z.-L.; Wang, J.; Xu, X.-Z.; Ye, X.

doi:10.1107/S160053680900645X

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page m340

doi:10.1107/S160053680900645X

Open

access

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

Zhu-Lai Li,^a Jian Wang,^a ^* Xiu-Zhi Xu ^a and Xiao Ye ^a

^aFaculty of Pharmacy Fujian Medical University, Fuzhou, Fujian 350004, People's Republic of China
^*Correspondence e-mail: wangjian7777@msn.com

(Received 12 January 2009; accepted 22 February 2009; online 28 February 2009)

The title coordination polymer, [CuCl₂(C₈H₈N₄)₂]_n, arose from a layer-separated diffusion synthesis at room temperature. The Cu atom (site symmetry $[\overline{1}]$ ) is coordinated by two chloride ions and four N atoms (two from triazole rings and two from pyridyl rings) in a distorted trans-CuCl₂N₄ octahedral arrangement. The bridging 1-(4-pyridylmethyl)-1H-1,2,4-triazole ligands [dihedral angle between the triazole and pyridine rings = 68.08 (8)°] result in a two-dimensional 4⁴ sheet structure in the crystal.

Related literature

For background on the synthesis and structures of coordination polymers, see: Carlucci et al. (2000 , 2004 ); Effendy et al. (2003 ); Evans et al. (1999 ); Huang et al. (2006 ); Liu et al. (2005 ); Moulton & Zaworotko (2001 ); Ranford et al. (1999 ); Sharma & Rogers (1999 ).

Experimental

Crystal data

[CuCl₂(C₈H₈N₄)₂]
M_r = 454.81
Monoclinic, P 2₁ /n
a = 7.5112 (5) Å
b = 16.0876 (9) Å
c = 8.3390 (6) Å
β = 116.469 (2)°
V = 902.03 (10) Å³
Z = 2
Mo Kα radiation
μ = 1.53 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.15 mm

Data collection

Siemens SMART diffractometer
Absorption correction: multi-scan (SADABS; Siemens, 1996 ) T_min = 0.88, T_max = 1.00 (expected range = 0.700–0.795)
6345 measured reflections
2067 independent reflections
1864 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.087
S = 1.01
2067 reflections
124 parameters
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N3	2.034 (2)
Cu1—N4ⁱ	2.087 (2)
Cu1—Cl1	2.7167 (7)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680900645X/hb2898sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680900645X/hb2898Isup2.hkl

checkCIF report

Comment top

In the research of supramolecular chemistry, a great interest has recently been focused on the crystal engineering of coordination frameworks due to their intriguing architectures, new topologies, intertwining phenomena and potential applications in microelectronics, nonlinear optics, ion exchange, molecular selection, molecular separation and recognition (Carlucci et al., 2000; Evans et al., 1999; Ranford et al., 1999; Sharma et al., 1999). The structural motifs of coordination polymers rest on several factors, but the choice of appropriate ligands is no doubt the key factor because it has an obvious influence on the topologies of coordination polymers and behavior of the molecules. Some flexible ligands, such as bis(triazole), bis(benzotriazole) and bis(pyridyl) alkyl, have been utilized to construct coordination polymers with aesthetics and useful properties (Moulton et al., 2001; Carlucci et al., 2004; Effendy et al., 2003), but the symmetry greatly limits the novelty and variety of the configuration.

Recently, our group have focused on the design and synthesis of some flexible unsymmetric ligands(Liu et al., 2005; Huang et al., 2006), and we have got a new heterocyclic ligand pyta [pyta = N-(4-pyridylmethyl)(1,2,4-triazole)]. In order to explore the architectural styles and other chemistry of this kind of ligands, we selected copper chloride as representative subject for stereoregular coordination. Among our attempts, a new polymer, namely [Cu(pyta)₂Cl₂]n,(I), was obtained as crystals suitable for single-crystal X-ray analysis.

The crystal structure of (I) is illustrated in Fig.1. The asymmetric unit contains one copper atom lying on an inversion centre, one chloride ion donor and one pyta bridging group. The Cu(II) center lies in an octahedral [CuN₄Cl₂] environment with the axial positions occupied by two chloride ions and the equatorial positions occupied by two trans triazolium nitrogen atoms and two trans pyridyl nitrogen atoms, each of which respectively belongs to four different pyta ligands. The bond angles about the Cu(1) octahedron range from 87.20 (8)° to 92.80 (8)° and deviate slightly from those of a perfect octahedron. The Cu—N bond lengths are in the range 2.034 (2) - 2.087 (2) Å. Due to the existence of the CH₂ spacer between the triazole and the pyridyl ring, sufficient flexibility make it possible for pyta to be twisted to meet the requirment of coordination geometries of Cu(II) center with the N(1)—C(3)—C(4) torsion angle 115.6 (2)° and the dihedral angle 68.08 (8)°.

The polymer results in an infinite two-dimensional rhombohedral sheet containing 36-membered sandglass rings, as shown in Fig.2. The sp-3 configuration of C(3) forces the pyta ligand to be non-linear, generating the nonlinear grid sides and thereby the sandglass grids. Every complementary four [Cu₄(pyta)₄] grids are joined together by sharing the copper apices to give the 4⁴ two-dimensional structure with a side length of 10.495 Å and a diagonal measurement of about 13.483 × 16.088 Å.

Related literature top

For background on the synthesis and structures of coordination polymers, see: Carlucci et al. (2000, 2004); Effendy et al. (2003); Evans et al. (1999); Huang et al. (2006); Liu et al. (2005); Moulton & Zaworotko (2001); Ranford et al. (1999); Sharma & Rogers (1999).

Experimental top

A solution of pyta (0.016 g, 0.10 mmol) in MeOH (5 ml) was carefully layered on a solution of CuCl₂.2H₂O (0.017 g, 0.10 mmol) in H₂O (5 ml). Diffusion between the two phases over about twenty days produced blue prisms of (I) (yield 0.013 g, 28.6%). Anal. Calcd for C₁₆H₁₆N₈Cl₂Cu (%): C, 32.16; H, 2.74; N, 19.02. Found: C, 32.78; H, 2.45; N, 19.30. IR (KBr, cm^-1): 3700–3500 (s), 2374 (m), 1488 (m), 1425 (s), 1409 (s), 1273 (m), 1185 (m), 1169 (m), 1025 (s), 1011 (m), 783 (m), 659 (w), 452 (w).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the asymmetric unit of (I), showing 50% probability displacement ellipsoids, expanded to show the Cu geometry. Symmetry codes: (i) 1–x, –y, 1–z; (ii) 1/2–x, y–1/2, 3/2–z; (iii) x+1/2, 1/2–y, z–1/2; (iv) 1/2–x, 1/2+y, 3/2–z.
	Fig. 2. The two-dimensional extended structure of (I), constructed of rhombus-shaped grids.

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

Crystal data top

[CuCl₂(C₈H₈N₄)₂]	F(000) = 462
M_r = 454.81	D_x = 1.674 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2134 reflections
a = 7.5112 (5) Å	θ = 2.7–27.5°
b = 16.0876 (9) Å	µ = 1.53 mm⁻¹
c = 8.3390 (6) Å	T = 293 K
β = 116.469 (2)°	Prism, blue
V = 902.03 (10) Å³	0.30 × 0.20 × 0.15 mm
Z = 2

Data collection top

Siemens SMART diffractometer	2067 independent reflections
Radiation source: fine-focus sealed tube	1864 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Siemens, 1996)	h = −9→6
T_min = 0.88, T_max = 1.00	k = −20→16
6345 measured reflections	l = −10→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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0347P)² + 1.5333P] where P = (F_o² + 2F_c²)/3
2067 reflections	(Δ/σ)_max < 0.001
124 parameters	Δρ_max = 0.81 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

[CuCl₂(C₈H₈N₄)₂]	V = 902.03 (10) Å³
M_r = 454.81	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.5112 (5) Å	µ = 1.53 mm⁻¹
b = 16.0876 (9) Å	T = 293 K
c = 8.3390 (6) Å	0.30 × 0.20 × 0.15 mm
β = 116.469 (2)°

Data collection top

Siemens SMART diffractometer	2067 independent reflections
Absorption correction: multi-scan (SADABS; Siemens, 1996)	1864 reflections with I > 2σ(I)
T_min = 0.88, T_max = 1.00	R_int = 0.017
6345 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.01	Δρ_max = 0.81 e Å⁻³
2067 reflections	Δρ_min = −0.56 e Å⁻³
124 parameters

Special details top

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 > σ(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) top

	x	y	z	U_iso*/U_eq
Cu1	0.5000	0.0000	0.5000	0.02592 (13)
Cl1	0.10912 (10)	0.03685 (4)	0.30125 (10)	0.03818 (18)
C1	0.6294 (4)	0.07131 (16)	0.8758 (4)	0.0365 (6)
H1A	0.7634	0.0666	0.9032	0.044*
C2	0.3175 (4)	0.06044 (15)	0.7390 (4)	0.0307 (5)
H2A	0.1881	0.0482	0.6555	0.037*
C3	0.2381 (5)	0.12190 (16)	0.9732 (4)	0.0355 (6)
H3A	0.3014	0.1057	1.0984	0.043*
H3B	0.1159	0.0902	0.9147	0.043*
C4	0.1852 (4)	0.21295 (15)	0.9625 (3)	0.0291 (5)
C5	0.2897 (4)	0.27713 (16)	0.9343 (4)	0.0358 (6)
H5A	0.3987	0.2659	0.9130	0.043*
C6	0.2312 (4)	0.35851 (16)	0.9379 (4)	0.0337 (6)
H6A	0.3050	0.4011	0.9211	0.040*
C7	−0.0305 (4)	0.31581 (17)	0.9856 (4)	0.0403 (7)
H7A	−0.1439	0.3284	0.9991	0.048*
C8	0.0212 (4)	0.23381 (17)	0.9888 (5)	0.0419 (7)
H8A	−0.0534	0.1925	1.0084	0.050*
N1	0.3680 (4)	0.09900 (13)	0.8939 (3)	0.0322 (5)
N2	0.5650 (4)	0.10725 (15)	0.9833 (3)	0.0378 (5)
N3	0.4802 (3)	0.04199 (13)	0.7215 (3)	0.0300 (5)
N4	0.0740 (3)	0.37867 (12)	0.9642 (3)	0.0279 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0367 (2)	0.0165 (2)	0.0367 (2)	−0.00556 (16)	0.0272 (2)	−0.00450 (16)
Cl1	0.0402 (4)	0.0381 (4)	0.0442 (4)	−0.0050 (3)	0.0260 (3)	−0.0017 (3)
C1	0.0337 (14)	0.0291 (13)	0.0474 (16)	0.0011 (11)	0.0189 (12)	−0.0053 (11)
C2	0.0349 (13)	0.0266 (12)	0.0366 (13)	−0.0025 (10)	0.0214 (11)	−0.0046 (10)
C3	0.0505 (16)	0.0232 (12)	0.0460 (16)	0.0040 (11)	0.0334 (14)	−0.0026 (11)
C4	0.0387 (14)	0.0217 (11)	0.0313 (13)	0.0030 (10)	0.0196 (11)	−0.0027 (9)
C5	0.0411 (15)	0.0286 (12)	0.0522 (17)	0.0053 (11)	0.0337 (14)	0.0005 (11)
C6	0.0393 (14)	0.0264 (12)	0.0478 (16)	0.0000 (11)	0.0305 (13)	0.0015 (11)
C7	0.0376 (15)	0.0259 (13)	0.071 (2)	0.0007 (11)	0.0364 (15)	−0.0021 (13)
C8	0.0444 (16)	0.0223 (12)	0.073 (2)	−0.0047 (11)	0.0383 (16)	−0.0034 (12)
N1	0.0439 (13)	0.0221 (10)	0.0374 (12)	0.0032 (9)	0.0243 (11)	−0.0023 (8)
N2	0.0409 (13)	0.0329 (12)	0.0409 (13)	−0.0017 (10)	0.0195 (11)	−0.0107 (10)
N3	0.0321 (11)	0.0252 (10)	0.0396 (12)	−0.0018 (8)	0.0223 (10)	−0.0039 (9)
N4	0.0330 (11)	0.0195 (9)	0.0375 (11)	0.0024 (8)	0.0212 (10)	0.0018 (8)

Geometric parameters (Å, º) top

Cu1—N3	2.034 (2)	C3—H3A	0.9700
Cu1—N3ⁱ	2.034 (2)	C3—H3B	0.9700
Cu1—N4ⁱⁱ	2.087 (2)	C4—C5	1.379 (4)
Cu1—N4ⁱⁱⁱ	2.087 (2)	C4—C8	1.386 (4)
Cu1—Cl1	2.7167 (7)	C5—C6	1.385 (4)
Cu1—Cl1ⁱ	2.7167 (7)	C5—H5A	0.9300
C1—N2	1.327 (4)	C6—N4	1.334 (3)
C1—N3	1.359 (4)	C6—H6A	0.9300
C1—H1A	0.9300	C7—N4	1.340 (3)
C2—N1	1.327 (3)	C7—C8	1.372 (4)
C2—N3	1.327 (3)	C7—H7A	0.9300
C2—H2A	0.9300	C8—H8A	0.9300
C3—N1	1.450 (3)	N1—N2	1.334 (3)
C3—C4	1.510 (3)	N4—Cu1^iv	2.0870 (19)

N3—Cu1—N3ⁱ	180.0	H3A—C3—H3B	107.4
N3—Cu1—N4ⁱⁱ	92.80 (8)	C5—C4—C8	117.3 (2)
N3ⁱ—Cu1—N4ⁱⁱ	87.20 (8)	C5—C4—C3	125.6 (2)
N3—Cu1—N4ⁱⁱⁱ	87.20 (8)	C8—C4—C3	117.0 (2)
N3ⁱ—Cu1—N4ⁱⁱⁱ	92.80 (8)	C4—C5—C6	119.6 (2)
N4ⁱⁱ—Cu1—N4ⁱⁱⁱ	180.0	C4—C5—H5A	120.2
N3—Cu1—Cl1	89.14 (6)	C6—C5—H5A	120.2
N3ⁱ—Cu1—Cl1	90.86 (6)	N4—C6—C5	123.1 (2)
N4ⁱⁱ—Cu1—Cl1	90.41 (6)	N4—C6—H6A	118.5
N4ⁱⁱⁱ—Cu1—Cl1	89.59 (6)	C5—C6—H6A	118.5
N3—Cu1—Cl1ⁱ	90.86 (6)	N4—C7—C8	123.4 (2)
N3ⁱ—Cu1—Cl1ⁱ	89.14 (6)	N4—C7—H7A	118.3
N4ⁱⁱ—Cu1—Cl1ⁱ	89.59 (6)	C8—C7—H7A	118.3
N4ⁱⁱⁱ—Cu1—Cl1ⁱ	90.41 (6)	C7—C8—C4	119.6 (2)
Cl1—Cu1—Cl1ⁱ	180.0	C7—C8—H8A	120.2
N2—C1—N3	113.3 (2)	C4—C8—H8A	120.2
N2—C1—H1A	123.4	C2—N1—N2	110.8 (2)
N3—C1—H1A	123.4	C2—N1—C3	127.2 (2)
N1—C2—N3	109.5 (2)	N2—N1—C3	121.6 (2)
N1—C2—H2A	125.3	C1—N2—N1	103.1 (2)
N3—C2—H2A	125.3	C2—N3—C1	103.3 (2)
N1—C3—C4	115.6 (2)	C2—N3—Cu1	128.15 (19)
N1—C3—H3A	108.4	C1—N3—Cu1	127.69 (18)
C4—C3—H3A	108.4	C6—N4—C7	116.9 (2)
N1—C3—H3B	108.4	C6—N4—Cu1^iv	124.24 (17)
C4—C3—H3B	108.4	C7—N4—Cu1^iv	118.55 (17)

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

Experimental details

Crystal data
Chemical formula	[CuCl₂(C₈H₈N₄)₂]
M_r	454.81
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.5112 (5), 16.0876 (9), 8.3390 (6)
β (°)	116.469 (2)
V (Å³)	902.03 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.53
Crystal size (mm)	0.30 × 0.20 × 0.15

Data collection
Diffractometer	Siemens SMART diffractometer
Absorption correction	Multi-scan (SADABS; Siemens, 1996)
T_min, T_max	0.88, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	6345, 2067, 1864
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.087, 1.01
No. of reflections	2067
No. of parameters	124
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.81, −0.56

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—N3	2.034 (2)	Cu1—Cl1	2.7167 (7)
Cu1—N4ⁱ	2.087 (2)

Symmetry code: (i) −x+1/2, y−1/2, −z+3/2.

References

Carlucci, L., Ciani, G., Moret, M., Proserpio, D. M. & Rizzato, S. (2000). Angew. Chem. Int. Ed. 39, 1506–1510. Web of Science CrossRef CAS Google Scholar
Carlucci, L., Ciani, G. & Proserpio, D. M. (2004). Chem. Commun. 4, 380–386. Web of Science CSD CrossRef Google Scholar
Effendy, Marchetti, F. & Pettinari, C. (2003). Inorg. Chem. 42, 112–117. Web of Science CSD CrossRef PubMed CAS Google Scholar
Evans, O. R., Xiong, R. G., Wang, Z. Y., Wong, G. K. & Lin, W. B. (1999). Angew. Chem. Int. Ed. 38, 536–538. CrossRef CAS Google Scholar
Huang, M., Liu, P., Chen, Y., Wang, J. & Liu, Z. (2006). J. Mol. Struct. 788, 211–217. Web of Science CrossRef CAS Google Scholar
Liu, Z., Liu, P., Chen, Y., Wang, J. & Huang, M. H. (2005). Inorg. Chem. Commun. 8, 212–215. Web of Science CSD CrossRef Google Scholar
Moulton, B. & Zaworotko, M. J. (2001). Chem. Rev. 101, 1629–1658. Web of Science CrossRef PubMed CAS Google Scholar
Ranford, J. D., Vittal, J. J. & Wu, D. (1999). Angew. Chem. Int. Ed. 38, 3498–3501. CrossRef CAS Google Scholar
Sharma, C. V. K. & Rogers, R. D. (1999). Chem. Commun. 1, 83–84. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART, SAINT and SADABS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar