catena-Poly[[dichloridocobalt(II)]-μ-4,4′-bis­(benzimidazol-1-yl)biphen­yl]

Li, H.; Han, Q.; Yao, C.; Gong, Q.; Wei, Z.

doi:10.1107/S1600536811010671

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page m492

doi:10.1107/S1600536811010671

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catena-Poly[[dichloridocobalt(II)]-μ-4,4′-bis(benzimidazol-1-yl)biphenyl]

Hui Li,^a ^* Qiuping Han,^a Chenzhong Yao,^a Qiaojuan Gong ^a and Zhuangwei Wei ^a

^aDepartment of Applied Chemistry, Yuncheng University, Yuncheng, Shanxi 044000, People's Republic of China
^*Correspondence e-mail: lihuiwff@163.com

(Received 19 March 2011; accepted 22 March 2011; online 26 March 2011)

In the title compound, [CoCl₂(C₂₆H₁₈N₄)]_n, the Co^II atom (site symmetry 2) is tetrahedrally coordinated by two chloride ions and two N atoms from 4,4′-bis(benzimidazol-1-yl)biphenyl ligands: the complete ligand is generated by crystallographic twofold symmetry. The dihedral angle between the benzene rings is 34.67 (8)° and the angle between the benene ring and the adjacent benzimidazole ring system is 43.26 (10)°. The bridging ligand links the Co^II atoms into chains propagating in [ $[\overline{1}]$ 01].

Related literature

For background to benzimidazole-based ligands in crystal engineering, see: Jin et al. (2006 ); Li et al. (2009 ); Su et al. (2003 ).

Experimental

Crystal data

[CoCl₂(C₂₆H₁₈N₄)]
M_r = 516.27
Monoclinic, C 2/c
a = 12.878 (3) Å
b = 15.181 (3) Å
c = 11.136 (2) Å
β = 91.37 (3)°
V = 2176.5 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.06 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.15 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.776, T_max = 0.853
13945 measured reflections
2696 independent reflections
2361 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.124
S = 1.12
2696 reflections
150 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—N1	2.022 (2)
Co1—Cl1	2.2491 (8)

Data collection: CrystalClear (Rigaku/MSC, 2005); 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); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811010671/hb5820sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811010671/hb5820Isup2.hkl

checkCIF report

Comment top

Benzimidazole has been well used in crystal engineering, and a large number of benzimidazole-containing flexible ligands have been extensively studied (Su et al.,2003; Jin et al.,2006). However, to our knowledge, the research on benzimidazole ligands bearing rigid spacers is still less developed (Li et al.,2009).

Single-crystal X-ray diffraction analysis reveals that the title compound (I) crystallizes in the monoclinic space group C2/c. The geometry of the Co^II ion is surrounded by two benzoiimidazole rings of distinct L ligands and two chlorine anions, which illustrates a slightly distorted tetrahedral coordination environment (Fig. 1). Notably, as shown in Fig. 2, the four-coordinated Co^II center is bridged by the linear ligand L to form an infinite one-dimensional architecture. The dihedral angle between the biphenyl rings is 34.67 (8)°.

Related literature top

For background to bemzimidazole-based ligands in crystal engineering, see: Jin et al. (2006); Li et al. (2009); Su et al. (2003).

Experimental top

A mixture of CH₃OH and CHCl₃ (1:1, 8 ml), as a buffer layer, was carefully layered over a solution of 4,4'-Bis(benzimidazol-1-yl)terphenyl (L, 0.06 mmol) in CHCl₃ (6 ml). Then a solution of CoCl₂ (0.06 mmol) in CH₃OH (6 ml) was layered over the buffer layer, and the resultant reaction was left to stand at room temperature. After ca three weeks, blue block single crystals appeared at the boundary. Yield: ~40% (based on L).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radius. Atoms with suffix A are generated by (–x, y, 3/2–z).
	Fig. 2. The crystal packing for (I).

catena-Poly[[dichloridocobalt(II)]-µ-4,4'-bis(benzimidazol- 1-yl)biphenyl] top

Crystal data top

[CoCl₂(C₂₆H₁₈N₄)]	F(000) = 1052
M_r = 516.27	D_x = 1.576 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3011 reflections
a = 12.878 (3) Å	θ = 2.1–28.3°
b = 15.181 (3) Å	µ = 1.06 mm⁻¹
c = 11.136 (2) Å	T = 293 K
β = 91.37 (3)°	Block, blue
V = 2176.5 (8) Å³	0.25 × 0.20 × 0.15 mm
Z = 4

Data collection top

Rigaku Mercury CCD diffractometer	2696 independent reflections
Radiation source: fine-focus sealed tube	2361 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 9 pixels mm^-1	θ_max = 28.3°, θ_min = 2.1°
ω scans	h = −17→17
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −20→20
T_min = 0.776, T_max = 0.853	l = −14→14
13945 measured reflections

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0551P)² + 4.8457P] where P = (F_o² + 2F_c²)/3
2696 reflections	(Δ/σ)_max < 0.001
150 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.71 e Å⁻³

Crystal data top

[CoCl₂(C₂₆H₁₈N₄)]	V = 2176.5 (8) Å³
M_r = 516.27	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 12.878 (3) Å	µ = 1.06 mm⁻¹
b = 15.181 (3) Å	T = 293 K
c = 11.136 (2) Å	0.25 × 0.20 × 0.15 mm
β = 91.37 (3)°

Data collection top

Rigaku Mercury CCD diffractometer	2696 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	2361 reflections with I > 2σ(I)
T_min = 0.776, T_max = 0.853	R_int = 0.053
13945 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.124	H-atom parameters constrained
S = 1.12	Δρ_max = 0.48 e Å⁻³
2696 reflections	Δρ_min = −0.71 e Å⁻³
150 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
Co1	0.0000	0.40291 (3)	0.7500	0.01602 (16)
Cl1	0.03587 (6)	0.32578 (5)	0.91836 (7)	0.0311 (2)
N2	0.24698 (16)	0.52363 (14)	0.58018 (19)	0.0139 (4)
N1	0.11781 (16)	0.48022 (14)	0.69588 (19)	0.0151 (4)
C8	0.31898 (18)	0.52081 (17)	0.4838 (2)	0.0134 (5)
C11	0.46103 (18)	0.51614 (17)	0.2986 (2)	0.0140 (5)
C3	0.1150 (2)	0.61615 (17)	0.8273 (2)	0.0162 (5)
H3	0.0601	0.5985	0.8743	0.019*
C12	0.4046 (2)	0.59193 (17)	0.3225 (2)	0.0169 (5)
H12	0.4150	0.6419	0.2761	0.020*
C7	0.23231 (19)	0.59156 (16)	0.6623 (2)	0.0139 (5)
C13	0.3332 (2)	0.59502 (17)	0.4139 (2)	0.0172 (5)
H13	0.2955	0.6461	0.4278	0.021*
C1	0.17714 (19)	0.45999 (17)	0.6047 (2)	0.0153 (5)
H1	0.1715	0.4075	0.5620	0.018*
C10	0.44322 (18)	0.44110 (17)	0.3680 (2)	0.0145 (5)
H10	0.4781	0.3890	0.3514	0.017*
C9	0.37368 (19)	0.44371 (17)	0.4617 (2)	0.0151 (5)
H9	0.3638	0.3942	0.5093	0.018*
C2	0.15099 (19)	0.56315 (17)	0.7347 (2)	0.0138 (5)
C6	0.2823 (2)	0.67174 (17)	0.6813 (2)	0.0173 (5)
H6	0.3365	0.6901	0.6336	0.021*
C4	0.1643 (2)	0.69603 (18)	0.8462 (2)	0.0193 (5)
H4	0.1423	0.7328	0.9073	0.023*
C5	0.2473 (2)	0.72257 (17)	0.7745 (2)	0.0185 (5)
H5	0.2795	0.7762	0.7905	0.022*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0152 (3)	0.0153 (3)	0.0178 (3)	0.000	0.00656 (19)	0.000
Cl1	0.0347 (4)	0.0324 (4)	0.0267 (4)	0.0187 (3)	0.0143 (3)	0.0116 (3)
N2	0.0139 (10)	0.0151 (10)	0.0127 (10)	−0.0009 (8)	0.0033 (8)	−0.0021 (8)
N1	0.0146 (10)	0.0170 (10)	0.0138 (10)	−0.0027 (8)	0.0039 (8)	−0.0005 (8)
C8	0.0113 (10)	0.0178 (12)	0.0111 (11)	−0.0016 (9)	0.0032 (9)	0.0000 (9)
C11	0.0112 (11)	0.0184 (12)	0.0126 (12)	−0.0020 (9)	0.0041 (9)	0.0012 (9)
C3	0.0151 (11)	0.0207 (13)	0.0130 (12)	0.0016 (9)	0.0029 (10)	0.0012 (10)
C12	0.0169 (12)	0.0189 (12)	0.0152 (12)	0.0011 (9)	0.0045 (10)	0.0044 (10)
C7	0.0121 (11)	0.0163 (12)	0.0135 (12)	0.0027 (9)	0.0018 (9)	−0.0005 (9)
C13	0.0180 (12)	0.0177 (12)	0.0161 (12)	0.0046 (10)	0.0063 (10)	0.0030 (10)
C1	0.0168 (12)	0.0170 (12)	0.0124 (12)	−0.0024 (9)	0.0036 (10)	−0.0005 (9)
C10	0.0117 (11)	0.0144 (11)	0.0175 (13)	−0.0001 (9)	0.0002 (9)	−0.0015 (10)
C9	0.0158 (11)	0.0151 (12)	0.0144 (12)	−0.0029 (9)	0.0022 (9)	0.0018 (9)
C2	0.0129 (11)	0.0169 (12)	0.0116 (12)	−0.0007 (9)	0.0017 (9)	0.0006 (9)
C6	0.0153 (12)	0.0162 (12)	0.0205 (13)	−0.0013 (9)	0.0023 (10)	0.0036 (10)
C4	0.0216 (13)	0.0185 (13)	0.0177 (13)	0.0036 (10)	0.0009 (10)	−0.0023 (10)
C5	0.0214 (12)	0.0129 (11)	0.0214 (14)	0.0015 (10)	0.0011 (11)	0.0018 (10)

Geometric parameters (Å, º) top

Co1—N1	2.022 (2)	C3—H3	0.9300
Co1—N1ⁱ	2.022 (2)	C12—C13	1.388 (4)
Co1—Cl1ⁱ	2.2491 (8)	C12—H12	0.9300
Co1—Cl1	2.2491 (8)	C7—C6	1.391 (3)
N2—C1	1.352 (3)	C7—C2	1.404 (3)
N2—C7	1.394 (3)	C13—H13	0.9300
N2—C8	1.436 (3)	C1—H1	0.9300
N1—C1	1.321 (3)	C10—C9	1.392 (4)
N1—C2	1.395 (3)	C10—H10	0.9300
C8—C13	1.384 (3)	C9—H9	0.9300
C8—C9	1.391 (3)	C6—C5	1.378 (4)
C11—C12	1.390 (4)	C6—H6	0.9300
C11—C10	1.399 (3)	C4—C5	1.408 (4)
C11—C11ⁱⁱ	1.494 (5)	C4—H4	0.9300
C3—C4	1.383 (4)	C5—H5	0.9300
C3—C2	1.396 (4)

N1—Co1—N1ⁱ	109.02 (13)	N2—C7—C2	105.3 (2)
N1—Co1—Cl1ⁱ	101.21 (7)	C8—C13—C12	118.9 (2)
N1ⁱ—Co1—Cl1ⁱ	114.22 (7)	C8—C13—H13	120.5
N1—Co1—Cl1	114.22 (7)	C12—C13—H13	120.5
N1ⁱ—Co1—Cl1	101.21 (7)	N1—C1—N2	112.9 (2)
Cl1ⁱ—Co1—Cl1	117.25 (5)	N1—C1—H1	123.6
C1—N2—C7	107.1 (2)	N2—C1—H1	123.6
C1—N2—C8	125.1 (2)	C9—C10—C11	120.5 (2)
C7—N2—C8	127.8 (2)	C9—C10—H10	119.7
C1—N1—C2	105.6 (2)	C11—C10—H10	119.7
C1—N1—Co1	123.10 (18)	C8—C9—C10	119.6 (2)
C2—N1—Co1	131.16 (17)	C8—C9—H9	120.2
C13—C8—C9	120.7 (2)	C10—C9—H9	120.2
C13—C8—N2	119.5 (2)	N1—C2—C3	130.1 (2)
C9—C8—N2	119.7 (2)	N1—C2—C7	109.1 (2)
C12—C11—C10	118.4 (2)	C3—C2—C7	120.8 (2)
C12—C11—C11ⁱⁱ	120.15 (16)	C5—C6—C7	116.5 (2)
C10—C11—C11ⁱⁱ	121.49 (16)	C5—C6—H6	121.8
C4—C3—C2	117.3 (2)	C7—C6—H6	121.8
C4—C3—H3	121.3	C3—C4—C5	121.1 (2)
C2—C3—H3	121.3	C3—C4—H4	119.5
C13—C12—C11	121.8 (2)	C5—C4—H4	119.5
C13—C12—H12	119.1	C6—C5—C4	122.2 (3)
C11—C12—H12	119.1	C6—C5—H5	118.9
C6—C7—N2	132.6 (2)	C4—C5—H5	118.9
C6—C7—C2	122.0 (2)

N1ⁱ—Co1—N1—C1	−143.7 (2)	C8—N2—C1—N1	−177.9 (2)
Cl1ⁱ—Co1—N1—C1	−23.0 (2)	C12—C11—C10—C9	−2.5 (4)
Cl1—Co1—N1—C1	104.0 (2)	C11ⁱⁱ—C11—C10—C9	177.1 (3)
N1ⁱ—Co1—N1—C2	31.89 (19)	C13—C8—C9—C10	−0.2 (4)
Cl1ⁱ—Co1—N1—C2	152.6 (2)	N2—C8—C9—C10	179.8 (2)
Cl1—Co1—N1—C2	−80.5 (2)	C11—C10—C9—C8	2.2 (4)
C1—N2—C8—C13	135.7 (3)	C1—N1—C2—C3	179.4 (3)
C7—N2—C8—C13	−41.8 (4)	Co1—N1—C2—C3	3.3 (4)
C1—N2—C8—C9	−44.3 (4)	C1—N1—C2—C7	0.3 (3)
C7—N2—C8—C9	138.2 (3)	Co1—N1—C2—C7	−175.87 (17)
C10—C11—C12—C13	1.0 (4)	C4—C3—C2—N1	179.3 (2)
C11ⁱⁱ—C11—C12—C13	−178.6 (3)	C4—C3—C2—C7	−1.6 (4)
C1—N2—C7—C6	178.6 (3)	C6—C7—C2—N1	−178.9 (2)
C8—N2—C7—C6	−3.6 (4)	N2—C7—C2—N1	−0.3 (3)
C1—N2—C7—C2	0.1 (3)	C6—C7—C2—C3	1.8 (4)
C8—N2—C7—C2	178.0 (2)	N2—C7—C2—C3	−179.5 (2)
C9—C8—C13—C12	−1.3 (4)	N2—C7—C6—C5	−178.7 (3)
N2—C8—C13—C12	178.7 (2)	C2—C7—C6—C5	−0.5 (4)
C11—C12—C13—C8	0.8 (4)	C2—C3—C4—C5	0.2 (4)
C2—N1—C1—N2	−0.2 (3)	C7—C6—C5—C4	−0.9 (4)
Co1—N1—C1—N2	176.35 (16)	C3—C4—C5—C6	1.1 (4)
C7—N2—C1—N1	0.0 (3)

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

Experimental details

Crystal data
Chemical formula	[CoCl₂(C₂₆H₁₈N₄)]
M_r	516.27
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	12.878 (3), 15.181 (3), 11.136 (2)
β (°)	91.37 (3)
V (Å³)	2176.5 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.06
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.776, 0.853
No. of measured, independent and observed [I > 2σ(I)] reflections	13945, 2696, 2361
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.124, 1.12
No. of reflections	2696
No. of parameters	150
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.71

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Co1—N1

2.022 (2)

Co1—Cl1

2.2491 (8)

Acknowledgements

We thank the College Research Program of Yuncheng University (2008114) for funding.

References

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