Crystal structure of catena-poly[bis(formato-κO)bis­[μ2-1,1′-(1,4-phenyl­ene)bis­(1H-imidazole)-κ2N3:N3′]cobalt(II)]

Xu, G.-W.; Wang, Y.-N.; Xia, H.-X.; Wang, Z.-L.

doi:10.1107/S2056989015014255

metal-organic compounds

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Volume 71| Part 9| September 2015| Pages m156-m157

https://doi.org/10.1107/S2056989015014255

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Crystal structure of catena-poly[bis(formato-κO)bis[μ₂-1,1′-(1,4-phenylene)bis(1H-imidazole)-κ²N³:N^3′]cobalt(II)]

Guo-Wang Xu,^a Ye-Nan Wang,^b Hong-Xu Xia ^c and Zhong-Long Wang ^a ^*

^aCollege of Science, China Three Gorges University, Yichang 443002, People's Republic of China, ^bCollege of Mechanical and Power Engineering, China Three Gorges University, YiChang 443002, People's Republic of China, and ^cCollege of Materials and Chemical Engineering, China Three Gorges University, YiChang 443002, People's Republic of China
^*Correspondence e-mail: wzlsanxia@163.com

Edited by K. Fejfarova, Institute of Macromolecular Chemistry, AS CR, v.v.i, Czech Republic (Received 18 July 2015; accepted 28 July 2015; online 6 August 2015)

A red block-shaped crystal of the title compound, [Co(HCOO)₂(C₁₂H₁₀N₄)₂]_n, was obtained by the reaction of cobalt(II) nitrate hexahydrate, formic acid and 1,1′-(1,4-phenylene)bis(1H-imidazole) (bib) molecules. The asymmetric unit consists of one Co^II cation, one formate ligand and two halves of a bib ligand. The central Co^II cation, located on an inversion centre, is coordinated by two carboxylate O atoms and four N atoms from bib ligands, completing an octahedral coordination geometry. The Co^II centres are bridged by bib ligands, giving a two-dimensional net. Topologically, taking the Co^II atoms as nodes and the bib ligands as linkers, the two-dimensional structure can be simplified as a typical sql/Shubnikov tetragonal plane network. The structure features C—H⋯O hydrogen-bonding interactions between formate and bib ligands, resulting in a three-dimensional supramolecular network.

Keywords: crystal structure; Co complex; 1,4-bis(1-imidazolyl)benzene; hydrogen bonding.

CCDC reference: 1415558

1. Related literature

For metal–organic framework structures, see: Yang et al. (2011 , 2012 ); Guo & Sun (2012 ).

2. Experimental

2.1. Crystal data

[Co(CHO₂)₂(C₁₂H₁₀N₄)₂]
M_r = 569.44
Monoclinic, P 2₁ /c
a = 7.601 (6) Å
b = 11.715 (9) Å
c = 13.791 (10) Å
β = 99.017 (9)°
V = 1212.8 (16) Å³
Z = 2
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 293 K
0.20 × 0.18 × 0.17 mm

2.2. Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.732, T_max = 1
12595 measured reflections
2773 independent reflections
2059 reflections with I > 2σ(I)
R_int = 0.092

2.3. Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.121
S = 1.07
2773 reflections
178 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2ⁱ	0.93	2.40	3.330 (5)	173
C6—H6⋯O1ⁱ	0.93	2.49	3.383 (5)	161
C8—H8⋯O2ⁱⁱ	0.93	2.13	3.038 (5)	164
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ); molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1415558

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989015014255/ff2140sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015014255/ff2140Isup2.hkl

checkCIF report

Chemical context top

Many fantastic structures of metal-organic frameworks have been reported based on 1,4-bis(1-imidazolyl)benzene. A lot of the them were constructed by mixed ligands including carboxylate ligand, other N-donor molecule and wolframic acid or molybdic acid, see: Guo et al. (2012), Yang et al. (2011), Yang et al. (2012), Compared with those compounds constructed by mixed organic ligands, coordination polymers established by a single ligand, especially N-donor molecules, are much more useful and easier for understanding the theory of formation of supramolecules. Accordingly, we selected 1,4-bis(1-imidazolyl) benzene and cobalt(II), which always shows one or two coordinated ligands, to construct a new supramolecule and study the structure of the title compound.

Synthesis and crystallization top

The title complex was synthesized by the reaction of 1,4-bis(1-imidazolyl)benzene ( 10.5 mg, 0.05 mmol) in 8 ml of deionized water with cobalt(II) nitrate hexahydrate ( 29.1 mg, 0.1 mmol) in 20ml of methanol and the mixture was refluxed for 1 hour. To the above mixture, 0.5 ml of formic acid was added and the result fluid was placed in a Teflon-lined, stainless-steel reactor. The reactor was heated to 413 K for 96 hours. It was then cooled to room temperature. Red block crystals were isolated in 69% yield (based on bib ligand).

Refinement details top

All the hydrogen atoms in the molecule were identified from the difference electron density map, further idealized and treated as riding with a distance d(C—H)=0.93Å In all cases Uiso(H)=-1.2Ueq.

Related literature top

For metal–organic framework structures, see: Yang et al. (2011, 2012); Guo & Sun (2012).

Structure description top

For metal–organic framework structures, see: Yang et al. (2011, 2012); Guo & Sun (2012).

Synthesis and crystallization top

Refinement details top

All the hydrogen atoms in the molecule were identified from the difference electron density map, further idealized and treated as riding with a distance d(C—H)=0.93Å In all cases Uiso(H)=-1.2Ueq.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. A part of the crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 30% probability level, The H atoms have been removed for clarity. Symmetry codes: (A) -x, 2 - y, 1 - z; (B) 1 - x, 1 - y, -z.

catena-Poly[bis(formato-κO)bis[µ₂-1,1'-(1,4-phenylene)bis(1H-imidazole)-κ²N³:N^3']cobalt(II)] top

Crystal data top

[Co(CHO₂)₂(C₁₂H₁₀N₄)₂]	F(000) = 586
M_r = 569.44	D_x = 1.559 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.601 (6) Å	Cell parameters from 2599 reflections
b = 11.715 (9) Å	θ = 2.3–27.5°
c = 13.791 (10) Å	µ = 0.76 mm⁻¹
β = 99.017 (9)°	T = 293 K
V = 1212.8 (16) Å³	Block, red
Z = 2	0.20 × 0.18 × 0.17 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	2059 reflections with I > 2σ(I)
Detector resolution: 13.6612 pixels mm^-1	R_int = 0.092
φ and ω scans	θ_max = 27.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −9→9
T_min = 0.732, T_max = 1	k = −15→15
12595 measured reflections	l = −17→17
2773 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.053	H-atom parameters constrained
wR(F²) = 0.121	w = 1/[σ²(F_o²) + (0.0395P)² + 0.7123P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2773 reflections	Δρ_max = 0.33 e Å⁻³
178 parameters	Δρ_min = −0.41 e Å⁻³

Crystal data top

[Co(CHO₂)₂(C₁₂H₁₀N₄)₂]	V = 1212.8 (16) Å³
M_r = 569.44	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.601 (6) Å	µ = 0.76 mm⁻¹
b = 11.715 (9) Å	T = 293 K
c = 13.791 (10) Å	0.20 × 0.18 × 0.17 mm
β = 99.017 (9)°

Data collection top

Bruker SMART 1000 CCD diffractometer	2773 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	2059 reflections with I > 2σ(I)
T_min = 0.732, T_max = 1	R_int = 0.092
12595 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.121	H-atom parameters constrained
S = 1.07	Δρ_max = 0.33 e Å⁻³
2773 reflections	Δρ_min = −0.41 e Å⁻³
178 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.

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

	x	y	z	U_iso*/U_eq
Co1	0.0000	1.0000	0.0000	0.02562 (17)
O1	0.1750 (3)	1.11742 (17)	0.07673 (16)	0.0356 (5)
N4	0.3551 (3)	0.7072 (2)	0.0552 (2)	0.0357 (6)
N2	−0.0995 (4)	0.9605 (2)	0.29716 (18)	0.0327 (6)
N3	0.1856 (4)	0.8626 (2)	0.04773 (19)	0.0340 (6)
C4	−0.0494 (4)	0.9811 (2)	0.4001 (2)	0.0294 (6)
N1	−0.1089 (4)	0.9758 (2)	0.13562 (18)	0.0340 (6)
C6	−0.0753 (4)	0.8960 (3)	0.4668 (2)	0.0330 (7)
H6	−0.1252	0.8265	0.4446	0.040*
C11	0.4328 (5)	0.5795 (3)	−0.0706 (3)	0.0452 (9)
H11	0.3879	0.6324	−0.1184	0.054*
C5	0.0263 (4)	1.0845 (3)	0.4333 (2)	0.0336 (7)
H5	0.0442	1.1410	0.3885	0.040*
C1	−0.2136 (5)	0.8854 (3)	0.1559 (2)	0.0454 (9)
H1	−0.2780	0.8386	0.1087	0.055*
C10	0.4314 (4)	0.6030 (3)	0.0271 (2)	0.0361 (7)
C2	−0.2098 (5)	0.8742 (3)	0.2544 (2)	0.0459 (9)
H2	−0.2689	0.8198	0.2864	0.055*
C9	0.2525 (4)	0.7840 (2)	−0.0035 (2)	0.0343 (7)
H9	0.2326	0.7808	−0.0717	0.041*
C3	−0.0435 (4)	1.0190 (3)	0.2222 (2)	0.0346 (7)
H3	0.0318	1.0820	0.2310	0.041*
C13	0.3415 (5)	1.1113 (3)	0.0969 (2)	0.0422 (8)
H13	0.3948	1.0518	0.0675	0.051*
O2	0.4414 (4)	1.1735 (3)	0.1501 (2)	0.0710 (9)
C12	0.4980 (5)	0.5242 (3)	0.0977 (3)	0.0448 (9)
H12	0.4969	0.5402	0.1636	0.054*
C7	0.2476 (5)	0.8367 (3)	0.1452 (3)	0.0527 (10)
H7	0.2220	0.8785	0.1986	0.063*
C8	0.3512 (5)	0.7414 (3)	0.1518 (3)	0.0494 (10)
H8	0.4076	0.7064	0.2088	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0335 (3)	0.0221 (3)	0.0210 (3)	0.0044 (2)	0.0034 (2)	−0.0006 (2)
O1	0.0393 (13)	0.0303 (11)	0.0360 (12)	0.0005 (10)	0.0022 (10)	−0.0054 (10)
N4	0.0356 (15)	0.0274 (13)	0.0432 (16)	0.0054 (11)	0.0030 (12)	−0.0014 (12)
N2	0.0405 (15)	0.0345 (13)	0.0238 (13)	−0.0026 (11)	0.0080 (11)	−0.0009 (11)
N3	0.0392 (15)	0.0287 (13)	0.0324 (14)	0.0093 (11)	0.0006 (11)	0.0020 (11)
C4	0.0326 (16)	0.0344 (16)	0.0215 (13)	0.0027 (13)	0.0057 (12)	−0.0011 (12)
N1	0.0426 (15)	0.0347 (14)	0.0254 (12)	0.0002 (11)	0.0082 (11)	−0.0004 (11)
C6	0.0431 (18)	0.0277 (15)	0.0283 (15)	−0.0018 (13)	0.0062 (14)	−0.0029 (13)
C11	0.054 (2)	0.0387 (18)	0.043 (2)	0.0143 (17)	0.0071 (17)	0.0073 (16)
C5	0.0444 (19)	0.0303 (16)	0.0268 (15)	−0.0013 (14)	0.0080 (14)	0.0061 (13)
C1	0.052 (2)	0.058 (2)	0.0268 (16)	−0.0157 (18)	0.0059 (15)	−0.0035 (16)
C10	0.0327 (17)	0.0296 (16)	0.0461 (19)	0.0053 (13)	0.0063 (14)	0.0000 (14)
C2	0.058 (2)	0.051 (2)	0.0287 (17)	−0.0178 (18)	0.0064 (16)	0.0003 (16)
C9	0.0393 (18)	0.0290 (15)	0.0343 (17)	0.0070 (14)	0.0046 (14)	0.0017 (13)
C3	0.0447 (19)	0.0346 (17)	0.0258 (15)	0.0006 (14)	0.0100 (13)	0.0012 (13)
C13	0.045 (2)	0.0397 (19)	0.0398 (19)	−0.0021 (16)	0.0017 (16)	−0.0043 (15)
O2	0.0624 (19)	0.078 (2)	0.0664 (19)	−0.0092 (16)	−0.0096 (15)	−0.0266 (17)
C12	0.057 (2)	0.0379 (18)	0.0400 (18)	0.0143 (16)	0.0079 (17)	0.0024 (15)
C7	0.064 (3)	0.047 (2)	0.043 (2)	0.0232 (19)	−0.0058 (18)	−0.0095 (17)
C8	0.063 (3)	0.043 (2)	0.0364 (19)	0.0180 (18)	−0.0110 (17)	−0.0037 (16)

Geometric parameters (Å, º) top

Co1—O1ⁱ	2.083 (2)	N3—C7	1.387 (4)
Co1—O1	2.083 (2)	C4—C5	1.387 (4)
Co1—N3ⁱ	2.173 (3)	C4—C6	1.391 (4)
Co1—N3	2.173 (3)	N1—C3	1.320 (4)
Co1—N1	2.179 (3)	N1—C1	1.379 (4)
Co1—N1ⁱ	2.179 (3)	C6—C5ⁱⁱ	1.389 (4)
O1—C13	1.254 (4)	C11—C10	1.377 (5)
N4—C9	1.369 (4)	C11—C12ⁱⁱⁱ	1.397 (4)
N4—C8	1.396 (4)	C5—C6ⁱⁱ	1.389 (4)
N4—C10	1.431 (4)	C1—C2	1.361 (5)
N2—C3	1.363 (4)	C10—C12	1.379 (4)
N2—C2	1.385 (4)	C13—O2	1.212 (4)
N2—C4	1.432 (4)	C12—C11ⁱⁱⁱ	1.397 (4)
N3—C9	1.311 (4)	C7—C8	1.360 (5)

O1ⁱ—Co1—O1	180.0	C9—N3—Co1	130.2 (2)
O1ⁱ—Co1—N3ⁱ	90.15 (11)	C7—N3—Co1	124.2 (2)
O1—Co1—N3ⁱ	89.84 (11)	C5—C4—C6	120.1 (3)
O1ⁱ—Co1—N3	89.85 (11)	C5—C4—N2	120.4 (3)
O1—Co1—N3	90.16 (11)	C6—C4—N2	119.5 (3)
N3ⁱ—Co1—N3	180.00 (13)	C3—N1—C1	105.0 (3)
O1ⁱ—Co1—N1	92.97 (10)	C3—N1—Co1	125.9 (2)
O1—Co1—N1	87.03 (10)	C1—N1—Co1	125.6 (2)
N3ⁱ—Co1—N1	92.33 (10)	C5ⁱⁱ—C6—C4	119.6 (3)
N3—Co1—N1	87.67 (10)	C10—C11—C12ⁱⁱⁱ	119.7 (3)
O1ⁱ—Co1—N1ⁱ	87.04 (10)	C4—C5—C6ⁱⁱ	120.2 (3)
O1—Co1—N1ⁱ	92.96 (10)	C2—C1—N1	110.7 (3)
N3ⁱ—Co1—N1ⁱ	87.67 (10)	C11—C10—C12	119.9 (3)
N3—Co1—N1ⁱ	92.33 (10)	C11—C10—N4	120.1 (3)
N1—Co1—N1ⁱ	180.0	C12—C10—N4	119.9 (3)
C13—O1—Co1	128.1 (2)	C1—C2—N2	105.7 (3)
C9—N4—C8	106.2 (3)	N3—C9—N4	112.1 (3)
C9—N4—C10	128.2 (3)	N1—C3—N2	112.0 (3)
C8—N4—C10	125.0 (3)	O2—C13—O1	127.9 (4)
C3—N2—C2	106.5 (3)	C10—C12—C11ⁱⁱⁱ	120.3 (3)
C3—N2—C4	127.0 (3)	C8—C7—N3	110.4 (3)
C2—N2—C4	126.5 (3)	C7—C8—N4	105.8 (3)
C9—N3—C7	105.5 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2^iv	0.93	2.40	3.330 (5)	173
C3—H3···O1	0.93	2.57	3.026 (4)	111
C6—H6···O1^iv	0.93	2.49	3.383 (5)	161
C8—H8···O2^v	0.93	2.13	3.038 (5)	164

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2ⁱ	0.93	2.40	3.330 (5)	173
C3—H3···O1	0.93	2.57	3.026 (4)	111
C6—H6···O1ⁱ	0.93	2.49	3.383 (5)	161
C8—H8···O2ⁱⁱ	0.93	2.13	3.038 (5)	164

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

Acknowledgements

This work was supported financially by the Graduate Student Research Innovation Fund of CTGU (CX2014094) and the Training Excellent Masters Thesis Fund of CTGU (Nos. PY2015074 and PY2015030), China.

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