metal-organic compounds
catena-poly[bis(formato-κO)bis[μ2-1,1′-(1,4-phenylene)bis(1H-imidazole)-κ2N3:N3′]cobalt(II)]
ofaCollege 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
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 consists of one CoII cation, one formate ligand and two halves of a bib ligand. The central CoII 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 CoII centres are bridged by bib ligands, giving a two-dimensional net. Topologically, taking the CoII 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.
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
|
2.3. Refinement
|
|
Data collection: SMART (Bruker, 2007); cell 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
https://doi.org/10.1107/S2056989015014255/ff2140sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015014255/ff2140Isup2.hkl
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.
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).
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.
For metal–organic framework structures, see: Yang et al. (2011, 2012); Guo & Sun (2012).
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).
detailsAll the hydrogen atoms in the molecule were identified from the difference
further idealized and treated as riding with a distance d(C—H)=0.93Å In all cases Uiso(H)=-1.2Ueq.Data collection: SMART (Bruker, 2007); cell
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).[Co(CHO2)2(C12H10N4)2] | F(000) = 586 |
Mr = 569.44 | Dx = 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 |
Bruker SMART 1000 CCD diffractometer | 2059 reflections with I > 2σ(I) |
Detector resolution: 13.6612 pixels mm-1 | Rint = 0.092 |
φ and ω scans | θmax = 27.5°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | h = −9→9 |
Tmin = 0.732, Tmax = 1 | k = −15→15 |
12595 measured reflections | l = −17→17 |
2773 independent reflections |
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(Fo2) + (0.0395P)2 + 0.7123P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
2773 reflections | Δρmax = 0.33 e Å−3 |
178 parameters | Δρmin = −0.41 e Å−3 |
[Co(CHO2)2(C12H10N4)2] | V = 1212.8 (16) Å3 |
Mr = 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)° |
Bruker SMART 1000 CCD diffractometer | 2773 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | 2059 reflections with I > 2σ(I) |
Tmin = 0.732, Tmax = 1 | Rint = 0.092 |
12595 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.33 e Å−3 |
2773 reflections | Δρmin = −0.41 e Å−3 |
178 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O2iv | 0.93 | 2.40 | 3.330 (5) | 173 |
C3—H3···O1 | 0.93 | 2.57 | 3.026 (4) | 111 |
C6—H6···O1iv | 0.93 | 2.49 | 3.383 (5) | 161 |
C8—H8···O2v | 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. |
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.
References
Bruker (2007). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Guo, M. & Sun, Z.-M. (2012). J. Mater. Chem. 22, 15939–15946. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Yang, Q.-X., Chen, X.-Q., Cui, J., Hu, J., Zhang, M.-D., Qin, L., Wang, G.-F., Lu, Q.-Y. & Zheng, H.-G. (2012). Cryst. Growth Des. 12, 4072–4082. Web of Science CSD CrossRef CAS Google Scholar
Yang, G.-S., Zang, H.-Y., Lan, Y.-Q., Wang, X.-L., Jiang, C.-J., Su, Z.-M. & Zhu, L.-D. (2011). CrystEngComm, 13, 1461–1466. Web of Science CSD CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.