catena-Poly[(chloridozinc)-μ-5-(1-methyl-1H-benzimidazol-2-yl-κN3)-1,2,3-triazol-1-ido-κ2N1:N3]

Sun, C.-G.; Song, J.-R.

doi:10.1107/S1600536812012706

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page m520

doi:10.1107/S1600536812012706

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catena-Poly[(chloridozinc)-μ-5-(1-methyl-1H-benzimidazol-2-yl-κN³)-1,2,3-triazol-1-ido-κ²N¹:N³]

Chen-Guang Sun ^a ^* and Ji-Rong Song ^a

^aSchool of Chemical Engineering, Northwest University, Xi'an 710069, Shaanxi, People's Republic of China
^*Correspondence e-mail: ssccgg2005@163.com

(Received 13 March 2012; accepted 23 March 2012; online 31 March 2012)

In the title complex, [Zn(C₁₀H₈N₅)Cl]_n, the Zn^II ion is four-coordinated by one Cl atom and three N atoms from two in situ-generated deprotonated 5-(1-methyl-1H-benzimidazol-2-yl-κN³)-1,2,3-triazol-1-ide ligands in a slightly distorted tetrahedral geometry. The Zn^II ions are bridged by the ligands, forming a helical chain along [001]. C—H⋯N and C—H⋯Cl hydrogen bonds and π–π interactions between the imidazole rings [centroid–centroid distance = 3.4244 (10) Å] assemble the chains into a three-dimensional supramolecular network.

Related literature

For general background to hydrothermal in situ reactions, see: Chen & Tong (2007 ); Zheng et al. (2009 ).

Experimental

Crystal data

[Zn(C₁₀H₈N₅)Cl]
M_r = 299.03
Tetragonal, P 4₂ /n
a = 16.0822 (1) Å
c = 9.0114 (2) Å
V = 2330.68 (6) Å³
Z = 8
Mo Kα radiation
μ = 2.32 mm⁻¹
T = 153 K
0.25 × 0.20 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.595, T_max = 0.801
6487 measured reflections
2511 independent reflections
2242 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.061
S = 1.05
2511 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N5ⁱ	0.93	2.49	3.274 (2)	142
C10—H10B⋯Cl1ⁱⁱ	0.96	2.81	3.744 (2)	165
Symmetry codes: (i) $[-y+1, x-{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+2, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, glogal. DOI: 10.1107/S1600536812012706/hy2526sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812012706/hy2526Isup2.hkl

checkCIF report

Comment top

Hydro(solvo)thermal in situ metal-ligand reactions, as a new bridge between coordination chemistry and organic synthetic chemistry, with advantages over conventional synthetic routes have attracted intensive interest in recent years (Chen & Tong, 2007). Some hydrothermal in situ metal-ligand decarboxylation reactions have been reported in the past (Zheng et al., 2009). According to our research, we found the 5-(1-methyl-1H-benzo[d]imidazol-2-yl)-3H-1,2,3-triazole- 4-carboxylic acid ligand is unstable, when the reaction temperature is high at 160°C. The title compound was obtained by in situ decarboxylation reaction. The Zn^II atom in the title compound is coordinated by one Cl atom and three N atoms from two deprotonated ligands in a distorted tetrahedral geometry (Fig. 1). The ligands bridge Zn atoms in a µ-κ³N,N':N' mode, forming a helical chain structure (Fig. 2). C—H···N and C—H···Cl hydrogen bonds (Table 1) and π–π interactions between the imidazole rings [centroid–centroid distance = 3.4244 (10) Å] assemble the chains into a three-dimensional supramolecular network (Fig. 3).

Related literature top

For general background to hydrothermal in situ reactions, see: Chen & Tong (2007); Zheng et al. (2009).

Experimental top

ZnCl₂ (0.5 mmol), 5-(1-methyl-1H-benzo[d]imidazol-2-yl)-3H- 1,2,3-triazole-4-carboxylic acid (0.25 mmol) and water (9 ml) were placed in a 15 ml Teflon-lined autoclave. The autoclave was heated at 433 K for 48 h. After the autoclave was cooled to room temperature, yellow block crystals were obtained (yield: ca 41.2% based on ligand). The initial ligand 5-(1-methyl-1H-benzo[d]imidazol-2-yl)-3H-1,2,3-triazole- 4-carboxylic acid was sythesized by refluxing N-methyl-1,2-benzenediamine dihydrochloride and 1H-1,2,3-triazole-4,5-dicarboxylic acid in a 1:1 ratio in HCl (4 mol/L).

Structure description top

For general background to hydrothermal in situ reactions, see: Chen & Tong (2007); Zheng et al. (2009).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title complex. Displacement ellipsoids are shown at the 50% probability level. [Symmetry code: (i) 1-y, -1/2+x, -1/2+z.]
	Fig. 2. The helical chain in the title complex along the c axis.
	Fig. 3. The three-dimensional supramolecular structure connected by hydrogen bonds (C—H···N: blue dashed lines; C—H···Cl: yellow dashed lines).

catena-Poly[(chloridozinc)-µ-5-(1-methyl-1H-benzimidazol- 2-yl-κN³)-1,2,3-triazol-1-ido-κ²N¹:N³] top

Crystal data top

[Zn(C₁₀H₈N₅)Cl]	D_x = 1.704 Mg m⁻³
M_r = 299.03	Melting point: 178 K
Tetragonal, P4₂/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 4bc	Cell parameters from 3164 reflections
a = 16.0822 (1) Å	θ = 2.8–27.6°
c = 9.0114 (2) Å	µ = 2.32 mm⁻¹
V = 2330.68 (6) Å³	T = 153 K
Z = 8	Block, yellow
F(000) = 1200	0.25 × 0.20 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	2511 independent reflections
Radiation source: fine-focus sealed tube	2242 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
φ and ω scans	θ_max = 27.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −20→19
T_min = 0.595, T_max = 0.801	k = −20→11
6487 measured reflections	l = −11→9

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0248P)² + 1.2538P] where P = (F_o² + 2F_c²)/3
2511 reflections	(Δ/σ)_max = 0.001
155 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[Zn(C₁₀H₈N₅)Cl]	Z = 8
M_r = 299.03	Mo Kα radiation
Tetragonal, P4₂/n	µ = 2.32 mm⁻¹
a = 16.0822 (1) Å	T = 153 K
c = 9.0114 (2) Å	0.25 × 0.20 × 0.10 mm
V = 2330.68 (6) Å³

Data collection top

Bruker APEXII CCD diffractometer	2511 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2242 reflections with I > 2σ(I)
T_min = 0.595, T_max = 0.801	R_int = 0.022
6487 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.061	H-atom parameters constrained
S = 1.05	Δρ_max = 0.28 e Å⁻³
2511 reflections	Δρ_min = −0.32 e Å⁻³
155 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
Zn1	0.885173 (13)	0.359714 (13)	0.23661 (2)	0.01485 (8)
Cl1	0.98564 (3)	0.32498 (3)	0.08256 (5)	0.02279 (12)
N4	0.86431 (9)	0.22361 (10)	0.63125 (16)	0.0164 (3)
N1	0.89656 (9)	0.46000 (9)	0.37457 (16)	0.0150 (3)
N3	0.87375 (10)	0.29967 (9)	0.43575 (16)	0.0158 (3)
C3	0.88790 (11)	0.43874 (11)	0.51738 (19)	0.0143 (4)
N2	0.88891 (9)	0.50546 (9)	0.60836 (16)	0.0156 (3)
N5	0.86571 (10)	0.22235 (10)	0.48211 (16)	0.0174 (3)
C9	0.89630 (11)	0.57556 (11)	0.5191 (2)	0.0171 (4)
C10	0.87849 (13)	0.50517 (12)	0.7694 (2)	0.0224 (4)
H10A	0.8203	0.5044	0.7931	0.034*
H10B	0.9035	0.5542	0.8106	0.034*
H10C	0.9048	0.4567	0.8102	0.034*
C2	0.87783 (11)	0.35173 (11)	0.5545 (2)	0.0146 (4)
C4	0.90207 (11)	0.54619 (11)	0.3728 (2)	0.0164 (4)
C8	0.89762 (13)	0.65991 (12)	0.5530 (2)	0.0242 (4)
H8	0.8937	0.6790	0.6501	0.029*
C1	0.87145 (12)	0.30313 (11)	0.6796 (2)	0.0175 (4)
H1	0.8719	0.3212	0.7776	0.021*
C7	0.90506 (14)	0.71385 (13)	0.4342 (2)	0.0294 (5)
H7	0.9049	0.7708	0.4519	0.035*
C6	0.91287 (14)	0.68529 (13)	0.2877 (2)	0.0269 (5)
H6	0.9187	0.7237	0.2113	0.032*
C5	0.91205 (12)	0.60159 (12)	0.2543 (2)	0.0207 (4)
H5	0.9179	0.5828	0.1573	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01681 (12)	0.01827 (12)	0.00945 (12)	−0.00095 (8)	−0.00090 (8)	0.00094 (8)
Cl1	0.0229 (2)	0.0266 (2)	0.0189 (2)	−0.0002 (2)	0.00538 (18)	−0.00207 (19)
N4	0.0217 (8)	0.0182 (8)	0.0093 (7)	0.0009 (7)	0.0008 (6)	0.0005 (6)
N1	0.0151 (7)	0.0163 (7)	0.0136 (7)	−0.0006 (6)	−0.0009 (6)	0.0009 (6)
N3	0.0202 (8)	0.0158 (8)	0.0115 (7)	−0.0012 (6)	−0.0002 (6)	0.0006 (6)
C3	0.0120 (8)	0.0170 (9)	0.0139 (8)	−0.0010 (7)	−0.0004 (7)	−0.0008 (7)
N2	0.0168 (7)	0.0164 (7)	0.0137 (8)	−0.0026 (6)	−0.0004 (6)	−0.0006 (6)
N5	0.0232 (8)	0.0181 (8)	0.0108 (7)	−0.0002 (7)	−0.0002 (6)	0.0029 (6)
C9	0.0143 (9)	0.0185 (9)	0.0185 (9)	−0.0004 (7)	−0.0013 (7)	0.0023 (7)
C10	0.0319 (11)	0.0227 (10)	0.0126 (9)	−0.0054 (9)	0.0021 (8)	−0.0028 (7)
C2	0.0142 (8)	0.0177 (9)	0.0119 (9)	0.0005 (7)	−0.0002 (7)	−0.0022 (7)
C4	0.0127 (8)	0.0177 (9)	0.0187 (9)	−0.0018 (7)	−0.0018 (7)	0.0013 (7)
C8	0.0301 (11)	0.0202 (10)	0.0222 (10)	−0.0013 (9)	−0.0004 (9)	−0.0028 (8)
C1	0.0222 (9)	0.0181 (9)	0.0121 (8)	0.0004 (8)	0.0011 (7)	−0.0018 (7)
C7	0.0396 (13)	0.0161 (10)	0.0325 (12)	−0.0029 (9)	−0.0025 (10)	0.0010 (9)
C6	0.0338 (12)	0.0214 (10)	0.0253 (11)	−0.0045 (9)	−0.0019 (9)	0.0084 (9)
C5	0.0210 (10)	0.0228 (10)	0.0184 (10)	−0.0022 (8)	−0.0020 (8)	0.0040 (8)

Geometric parameters (Å, º) top

Zn1—N4ⁱ	1.9920 (15)	C9—C8	1.391 (3)
Zn1—N1	2.0445 (15)	C9—C4	1.404 (3)
Zn1—N3	2.0461 (15)	C10—H10A	0.9600
Zn1—Cl1	2.2022 (5)	C10—H10B	0.9600
N4—N5	1.344 (2)	C10—H10C	0.9600
N4—C1	1.356 (2)	C2—C1	1.376 (3)
N4—Zn1ⁱⁱ	1.9920 (15)	C4—C5	1.400 (3)
N1—C3	1.339 (2)	C8—C7	1.383 (3)
N1—C4	1.389 (2)	C8—H8	0.9300
N3—N5	1.318 (2)	C1—H1	0.9300
N3—C2	1.360 (2)	C7—C6	1.403 (3)
C3—N2	1.351 (2)	C7—H7	0.9300
C3—C2	1.448 (2)	C6—C5	1.380 (3)
N2—C9	1.390 (2)	C6—H6	0.9300
N2—C10	1.461 (2)	C5—H5	0.9300

N4ⁱ—Zn1—N1	109.83 (6)	N2—C10—H10B	109.5
N4ⁱ—Zn1—N3	110.90 (6)	H10A—C10—H10B	109.5
N1—Zn1—N3	81.20 (6)	N2—C10—H10C	109.5
N4ⁱ—Zn1—Cl1	110.69 (5)	H10A—C10—H10C	109.5
N1—Zn1—Cl1	121.17 (4)	H10B—C10—H10C	109.5
N3—Zn1—Cl1	119.94 (5)	N3—C2—C1	106.92 (16)
N5—N4—C1	109.51 (15)	N3—C2—C3	114.77 (16)
N5—N4—Zn1ⁱⁱ	117.63 (12)	C1—C2—C3	138.31 (17)
C1—N4—Zn1ⁱⁱ	132.73 (12)	N1—C4—C5	130.65 (18)
C3—N1—C4	105.82 (15)	N1—C4—C9	108.71 (16)
C3—N1—Zn1	111.95 (12)	C5—C4—C9	120.64 (17)
C4—N1—Zn1	141.79 (12)	C7—C8—C9	116.31 (18)
N5—N3—C2	109.65 (14)	C7—C8—H8	121.8
N5—N3—Zn1	137.05 (12)	C9—C8—H8	121.8
C2—N3—Zn1	113.26 (12)	N4—C1—C2	106.21 (16)
N1—C3—N2	112.29 (16)	N4—C1—H1	126.9
N1—C3—C2	118.70 (16)	C2—C1—H1	126.9
N2—C3—C2	128.99 (16)	C8—C7—C6	122.04 (19)
C3—N2—C9	107.11 (15)	C8—C7—H7	119.0
C3—N2—C10	126.80 (16)	C6—C7—H7	119.0
C9—N2—C10	125.97 (16)	C5—C6—C7	121.60 (19)
N3—N5—N4	107.71 (14)	C5—C6—H6	119.2
N2—C9—C8	131.72 (17)	C7—C6—H6	119.2
N2—C9—C4	106.03 (16)	C6—C5—C4	117.12 (18)
C8—C9—C4	122.24 (17)	C6—C5—H5	121.4
N2—C10—H10A	109.5	C4—C5—H5	121.4

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N5ⁱⁱⁱ	0.93	2.49	3.274 (2)	142
C10—H10B···Cl1^iv	0.96	2.81	3.744 (2)	165

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

Experimental details

Crystal data
Chemical formula	[Zn(C₁₀H₈N₅)Cl]
M_r	299.03
Crystal system, space group	Tetragonal, P4₂/n
Temperature (K)	153
a, c (Å)	16.0822 (1), 9.0114 (2)
V (Å³)	2330.68 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.32
Crystal size (mm)	0.25 × 0.20 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.595, 0.801
No. of measured, independent and observed [I > 2σ(I)] reflections	6487, 2511, 2242
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.061, 1.05
No. of reflections	2511
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.32

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N5ⁱ	0.93	2.49	3.274 (2)	142
C10—H10B···Cl1ⁱⁱ	0.96	2.81	3.744 (2)	165

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

Acknowledgements

We thank the National Natural Science Foundation of China (grant No. 20803058) for generously supporting this study.

References

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, X.-M. & Tong, M.-L. (2007). Acc. Chem. Res. 40, 162–170. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zheng, Y.-Z., Zhang, Y.-B., Tong, M.-L., Xue, W. & Chen, X.-M. (2009). Dalton Trans. pp. 1396–1406. Web of Science CSD CrossRef Google Scholar

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