catena-Poly[[dibromidozinc(II)]-μ-3-(1H-benzimidazol-2-yl)[2,6-2H2]pyridine N-oxide]

Luo, H.-Z.; Ye, H.-Y.

doi:10.1107/S1600536807067281

metal-organic compounds

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Volume 64| Part 1| January 2008| Page m248

https://doi.org/10.1107/S1600536807067281

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catena-Poly[[dibromidozinc(II)]-μ-3-(1H-benzimidazol-2-yl)[2,6-²H₂]pyridine N-oxide]

Hui-Zhou Luo ^a and Heng-Yun Ye ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: hyye@seu.edu.cn

(Received 17 November 2007; accepted 17 December 2007; online 21 December 2007)

In the crystal structure of the title compound, [ZnBr₂(C₁₂H₇D₂N₃O)]_n, the Zn atoms are coordinated by two Br atoms and by one N atom and one O atom of two symmetry-related 3-(1H-benzimidazol-2-yl)[2,6-²H₂]pyridine N-oxide ligands in a slightly distorted tetrahedral geometry. The ZnBr₂ units are connected by the organic ligands into chains.

Related literature

For the deuteration effect (DEF) on physical properties, see: Akutagawa et al. (2004 ); Ye et al. (2007 ).

Experimental

Crystal data

[ZnBr₂(C₁₂H₇D₂N₃O)]
M_r = 438.42
Monoclinic, P 2₁ /n
a = 7.4071 (15) Å
b = 15.017 (3) Å
c = 12.174 (2) Å
β = 98.52 (3)°
V = 1339.2 (5) Å³
Z = 4
Mo Kα radiation
μ = 7.79 mm⁻¹
T = 293 (2) K
0.2 × 0.15 × 0.1 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.261, T_max = 0.463
13680 measured reflections
3070 independent reflections
2538 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.072
S = 1.09
3070 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1999 ); software used to prepare material for publication: SHELXTL

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807067281/nc2082sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807067281/nc2082Isup2.hkl

checkCIF report

Comment top

Recently, investigations on the effect of deuteration onto the physical properties like permittivity has become of increasing interest (Akutagawa, et al., 2004) and (Ye, et al., 2007). As a part of our ongoing investigations in this field we have determined the crystal structure of the title compound, poly bis(bromo)-(3-(1H-benzo[d]imidazole-2)–2,6-dideuterium-pyridine N-oxide)-zinc(II) (I).

In the crystal structure of the title compound the zinc atoms are coordinated by two bromo atoms and by one nitrogen atom and one oxygen atom of two symmetry related 3-(1H-benzo[d]imidazole-2)–2,6-dideuterium-pyridine ligands within slightly distorted tetrahedra (Fig. 1). The ZnBr₂ units are connected by the ligands into chains. The dihedral angle between the 1H-benzo[d]imidazole and the pyridine ring amount to 35.87 (8) °.

Related literature top

For deuteration effect (DEF) on physical properties, see: Akutagawa et al. (2004); Ye et al. (2007).

Experimental top

3-(1H-benzo[d]imidazole-2)–2,6-dideuterium-pyridine N-oxide (0.21 g 0.1 mmol) ZnBr₂ (0.027 g, 0.2 mmol), ethanol (0.8 ml) and water (0.4 ml) are transfered into a sealed Pyrex tube and heated at 100 °C for 2 d. On cooling colorless block-like crystals of the title compound are obtained, which are suitable for X-ray ananlysis.

Structure description top

For deuteration effect (DEF) on physical properties, see: Akutagawa et al. (2004); Ye et al. (2007).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 1999).

Figures top

Fig. 1. Crystal structure of the title compound with the atomic numbering scheme and displacement ellipsoids drawn at the 30% probability level. The H and D atoms are shown as spheres of arbitrary size. Symmetry code: A = 1.5 + x, -1/2 + y,1.5 + z.

catena-Poly[[dibromidozinc(II)]-µ-3-(1H-benzimidazol-2-yl)[2,6-^2^{H₂]pyridine N-oxide] top}

Crystal data top

[ZnBr₂(C₁₂H₇D₂N₃O)]	F(000) = 840
M_r = 438.42	D_x = 2.175 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 12253 reflections
a = 7.4071 (15) Å	θ = 3.0–27.5°
b = 15.017 (3) Å	µ = 7.79 mm⁻¹
c = 12.174 (2) Å	T = 293 K
β = 98.52 (3)°	Block, colorless
V = 1339.2 (5) Å³	0.2 × 0.15 × 0.1 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	3070 independent reflections
Radiation source: fine-focus sealed tube	2538 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −19→19
T_min = 0.261, T_max = 0.463	l = −15→15
13680 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.072	w = 1/[σ²(F_o²) + (0.0204P)² + 0.5716P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
3070 reflections	Δρ_max = 0.43 e Å⁻³
173 parameters	Δρ_min = −0.57 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0021 (3)

Crystal data top

[ZnBr₂(C₁₂H₇D₂N₃O)]	V = 1339.2 (5) Å³
M_r = 438.42	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.4071 (15) Å	µ = 7.79 mm⁻¹
b = 15.017 (3) Å	T = 293 K
c = 12.174 (2) Å	0.2 × 0.15 × 0.1 mm
β = 98.52 (3)°

Data collection top

Rigaku Mercury2 diffractometer	3070 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2538 reflections with I > 2σ(I)
T_min = 0.261, T_max = 0.463	R_int = 0.058
13680 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.072	H-atom parameters constrained
S = 1.09	Δρ_max = 0.43 e Å⁻³
3070 reflections	Δρ_min = −0.57 e Å⁻³
173 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	0.18024 (5)	0.76280 (2)	0.56995 (3)	0.02687 (12)
Br1	0.43934 (6)	0.68154 (3)	0.53737 (4)	0.05495 (15)
Br2	0.05935 (5)	0.71851 (2)	0.73359 (3)	0.03347 (12)
C1	0.2625 (4)	1.0321 (2)	0.4904 (3)	0.0270 (7)
C2	0.2551 (5)	1.0978 (2)	0.4096 (3)	0.0348 (8)
H2B	0.2762	1.1574	0.4277	0.042*
C3	0.2151 (5)	1.0700 (3)	0.3022 (3)	0.0376 (9)
H3A	0.2073	1.1119	0.2455	0.045*
C4	0.1855 (5)	0.9800 (3)	0.2749 (3)	0.0376 (9)
H4A	0.1610	0.9638	0.2004	0.045*
C5	0.1914 (5)	0.9149 (2)	0.3545 (3)	0.0333 (8)
H5A	0.1712	0.8554	0.3357	0.040*
C6	0.2292 (4)	0.9425 (2)	0.4644 (3)	0.0255 (7)
C7	0.2883 (4)	0.9521 (2)	0.6446 (3)	0.0242 (7)
C8	0.4011 (4)	0.8528 (2)	0.8000 (3)	0.0258 (7)
D2	0.4465	0.8148	0.7503	0.031*
C9	0.3176 (4)	0.9318 (2)	0.7629 (3)	0.0235 (7)
C10	0.2589 (4)	0.9895 (2)	0.8391 (3)	0.0290 (8)
H10A	0.2069	1.0440	0.8160	0.035*
C11	0.2781 (5)	0.9656 (2)	0.9485 (3)	0.0326 (8)
H11A	0.2391	1.0038	1.0003	0.039*
C12	0.3550 (4)	0.8850 (2)	0.9822 (3)	0.0312 (8)
D1	0.3645	0.8679	1.0562	0.037*
N1	0.2441 (3)	0.89347 (17)	0.5628 (2)	0.0246 (6)
N2	0.2984 (4)	1.03547 (18)	0.6041 (2)	0.0299 (6)
H2A	0.3232	1.0828	0.6431	0.036*
N3	0.4165 (4)	0.83101 (18)	0.9080 (2)	0.0282 (6)
O1	0.4873 (3)	0.75130 (15)	0.9391 (2)	0.0386 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0340 (2)	0.0198 (2)	0.0252 (2)	−0.00331 (15)	−0.00104 (17)	−0.00046 (15)
Br1	0.0509 (3)	0.0317 (2)	0.0885 (4)	0.00727 (18)	0.0311 (2)	0.0069 (2)
Br2	0.0438 (2)	0.0292 (2)	0.0269 (2)	−0.00230 (15)	0.00361 (15)	0.00400 (14)
C1	0.0279 (18)	0.0246 (18)	0.0273 (19)	−0.0010 (13)	0.0006 (14)	0.0017 (14)
C2	0.044 (2)	0.0230 (19)	0.038 (2)	−0.0001 (15)	0.0108 (16)	0.0038 (15)
C3	0.037 (2)	0.042 (2)	0.035 (2)	0.0040 (17)	0.0088 (16)	0.0182 (17)
C4	0.041 (2)	0.048 (3)	0.024 (2)	−0.0048 (17)	0.0054 (16)	0.0033 (17)
C5	0.041 (2)	0.030 (2)	0.028 (2)	−0.0040 (16)	0.0037 (15)	−0.0001 (15)
C6	0.0269 (17)	0.0226 (18)	0.0269 (19)	−0.0018 (13)	0.0038 (13)	0.0011 (14)
C7	0.0261 (17)	0.0191 (17)	0.0267 (18)	0.0004 (13)	0.0015 (13)	0.0009 (13)
C8	0.0300 (18)	0.0231 (18)	0.0225 (18)	−0.0030 (13)	−0.0019 (13)	−0.0046 (13)
C9	0.0239 (16)	0.0234 (18)	0.0220 (17)	−0.0039 (13)	−0.0007 (13)	−0.0014 (13)
C10	0.0313 (19)	0.0235 (19)	0.032 (2)	0.0028 (14)	0.0031 (15)	−0.0008 (14)
C11	0.038 (2)	0.032 (2)	0.027 (2)	0.0069 (15)	0.0039 (15)	−0.0022 (15)
C12	0.038 (2)	0.032 (2)	0.0216 (18)	0.0032 (15)	−0.0007 (14)	−0.0005 (15)
N1	0.0303 (15)	0.0196 (14)	0.0218 (15)	−0.0021 (11)	−0.0024 (11)	−0.0004 (11)
N2	0.0447 (18)	0.0187 (15)	0.0247 (16)	−0.0034 (12)	0.0002 (13)	−0.0023 (11)
N3	0.0295 (15)	0.0227 (15)	0.0284 (16)	0.0003 (11)	−0.0092 (12)	−0.0007 (12)
O1	0.0521 (16)	0.0247 (14)	0.0333 (15)	0.0125 (11)	−0.0125 (12)	−0.0008 (10)

Geometric parameters (Å, º) top

Zn1—O1ⁱ	1.987 (2)	C7—N1	1.333 (4)
Zn1—N1	2.023 (3)	C7—N2	1.352 (4)
Zn1—Br1	2.3569 (7)	C7—C9	1.457 (4)
Zn1—Br2	2.3960 (7)	C8—N3	1.343 (4)
C1—N2	1.371 (4)	C8—C9	1.383 (4)
C1—C2	1.388 (5)	C8—D2	0.9300
C1—C6	1.397 (4)	C9—C10	1.385 (4)
C2—C3	1.362 (5)	C10—C11	1.367 (5)
C2—H2B	0.9300	C10—H10A	0.9300
C3—C4	1.402 (5)	C11—C12	1.373 (5)
C3—H3A	0.9300	C11—H11A	0.9300
C4—C5	1.372 (5)	C12—N3	1.343 (4)
C4—H4A	0.9300	C12—D1	0.9300
C5—C6	1.389 (4)	N2—H2A	0.8600
C5—H5A	0.9300	N3—O1	1.339 (3)
C6—N1	1.397 (4)	O1—Zn1ⁱⁱ	1.987 (2)

O1ⁱ—Zn1—N1	102.35 (10)	N2—C7—C9	123.1 (3)
O1ⁱ—Zn1—Br1	108.47 (8)	N3—C8—C9	119.8 (3)
N1—Zn1—Br1	107.08 (8)	N3—C8—D2	120.1
O1ⁱ—Zn1—Br2	108.89 (8)	C9—C8—D2	120.1
N1—Zn1—Br2	115.04 (8)	C8—C9—C10	119.2 (3)
Br1—Zn1—Br2	114.22 (3)	C8—C9—C7	119.7 (3)
N2—C1—C2	132.1 (3)	C10—C9—C7	121.1 (3)
N2—C1—C6	105.4 (3)	C11—C10—C9	119.3 (3)
C2—C1—C6	122.5 (3)	C11—C10—H10A	120.3
C3—C2—C1	116.3 (3)	C9—C10—H10A	120.3
C3—C2—H2B	121.9	C10—C11—C12	120.1 (3)
C1—C2—H2B	121.9	C10—C11—H11A	120.0
C2—C3—C4	121.8 (3)	C12—C11—H11A	120.0
C2—C3—H3A	119.1	N3—C12—C11	119.9 (3)
C4—C3—H3A	119.1	N3—C12—D1	120.0
C5—C4—C3	122.1 (3)	C11—C12—D1	120.0
C5—C4—H4A	119.0	C7—N1—C6	105.8 (3)
C3—C4—H4A	119.0	C7—N1—Zn1	129.9 (2)
C4—C5—C6	116.7 (3)	C6—N1—Zn1	123.9 (2)
C4—C5—H5A	121.6	C7—N2—C1	108.7 (3)
C6—C5—H5A	121.6	C7—N2—H2A	125.6
C5—C6—N1	130.5 (3)	C1—N2—H2A	125.6
C5—C6—C1	120.6 (3)	O1—N3—C12	120.5 (3)
N1—C6—C1	108.9 (3)	O1—N3—C8	117.9 (3)
N1—C7—N2	111.1 (3)	C12—N3—C8	121.6 (3)
N1—C7—C9	125.8 (3)	N3—O1—Zn1ⁱⁱ	121.83 (19)

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

Experimental details

Crystal data
Chemical formula	[ZnBr₂(C₁₂H₇D₂N₃O)]
M_r	438.42
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.4071 (15), 15.017 (3), 12.174 (2)
β (°)	98.52 (3)
V (Å³)	1339.2 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.79
Crystal size (mm)	0.2 × 0.15 × 0.1

Data collection
Diffractometer	Rigaku Mercury2
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.261, 0.463
No. of measured, independent and observed [I > 2σ(I)] reflections	13680, 3070, 2538
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.072, 1.09
No. of reflections	3070
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.57

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1999).

Acknowledgements

This work was supported by a start-up grant from Southeast University to Professor Ren-Gen Xiong.

References

Akutagawa, T., Takeda, S., Hasegawa, T. & Nakamura, T. (2004). J. Am. Chem. Soc. 126, 291–294. Web of Science CrossRef PubMed CAS Google Scholar
Rigaku (2005). CrystalClear. Version 1.4.0. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1999). SHELXTL/PC. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ye, Q., Zhao, H., Qu, Z.-R., Fu, D.-W., Xiong, R.-G., Cui, Y.-P., Akutagawa, T., Hong Chan, P. W. & Nakamura, T. (2007). Angew. Chem. Int. Ed. 46, 6852–6856. Web of Science CSD CrossRef CAS Google Scholar

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