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A new coordination polymer (CP), namely poly[(μ-4,4′-bipyridine)(μ3-3,4′-oxydibenzoato)cobalt(II)], [Co(C14H8O5)(C10H8N2)]n or [Co(3,4′-obb)(4,4′-bipy)]n (1), was prepared by the self-assembly of Co(NO3)2·6H2O with the rarely used 3,4′-oxydibenzoic acid (3,4′-obbH2) ligand and 4,4′-bipyridine (4,4′-bipy) under solvothermal conditions, and has been structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography and powder X-ray diffraction (PXRD). Single-crystal X-ray diffraction reveals that each CoII ion is six-coordinated by four O atoms from three 3,4′-obb2− ligands, of which two function as monodentate ligands and the other as a bidentate ligand, and by two N atoms from bridging 4,4′-bipy ligands, thereby forming a distorted octahedral CoN2O4 coordination geometry. Adjacent crystallographically equivalent CoII ions are bridged by the O atoms of 3,4′-obb2− ligands, affording an eight-membered Co2O4C2 ring which is further extended into a two-dimensional [Co(3,4′-obb)]n sheet along the ab plane via 3,4′-obb2− functioning as a bidentate bridging ligand. The planes are interlinked into a three-dimensional [Co(3,4′-obb)(4,4′-bipy)]n network by 4,4′-bipy ligands acting as pillars along the c axis. Magnetic investigations on CP 1 disclose an antiferromagnetic coupling within the dimeric Co2 unit and a metamagnetic behaviour at low temperature resulting from intermolecular π–π interactions between the parallel 4,4′-bipy ligands.
Supporting information
CCDC reference: 1907853
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).
Poly[(µ-4,4'-bipyridine)(µ
3-3,4'-oxydibenzoato)cobalt(II)]
top
Crystal data top
[Co(C14H8O5)(C10H8N2)] | F(000) = 964 |
Mr = 471.32 | Dx = 1.472 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.506 (2) Å | Cell parameters from 1768 reflections |
b = 22.483 (4) Å | θ = 2.8–26.1° |
c = 10.684 (4) Å | µ = 0.85 mm−1 |
β = 111.37 (4)° | T = 293 K |
V = 2126.5 (12) Å3 | Block, purple |
Z = 4 | 0.21 × 0.09 × 0.07 mm |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 2389 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.085 |
φ and ω scans | θmax = 25.0°, θmin = 2.9° |
Absorption correction: multi-scan sadabs | h = −11→9 |
| k = −26→26 |
12164 measured reflections | l = −9→12 |
3745 independent reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.058 | H-atom parameters constrained |
wR(F2) = 0.162 | w = 1/[σ2(Fo2) + (0.0599P)2 + 0.1676P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
3745 reflections | Δρmax = 0.57 e Å−3 |
289 parameters | Δρmin = −0.43 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Single crystals of 1 suitable for X-ray diffraction analysis
were mounted on a glass rod, and the crystal data were
collected on a Bruker APEX2 CCD diffractometer with a Mo Kα sealed tube (λ =
0.71073 Å ) at 293 K, using the ω scan mode. The structures were solved
using the direct method and expanded using Fourier difference techniques with
the SHELXTL-2014 program package. The non-hydrogen atoms were refined
anisotropically with anisotropic displacement coefficients, while hydrogen
atoms were introduced as fixed contributors. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Co1 | −0.06841 (6) | 0.94729 (3) | 0.12087 (6) | 0.0272 (2) | |
O1 | 0.0752 (4) | 0.91931 (16) | 0.0342 (3) | 0.0434 (9) | |
O2 | 0.1004 (4) | 0.96484 (15) | −0.1411 (3) | 0.0397 (9) | |
O3 | 0.3947 (5) | 0.71635 (19) | −0.1786 (6) | 0.0937 (17) | |
O4 | 0.7636 (4) | 0.57417 (15) | −0.2848 (4) | 0.0436 (9) | |
O5 | 0.9066 (4) | 0.64244 (15) | −0.3209 (4) | 0.0443 (9) | |
N1 | 0.1227 (4) | 0.95217 (17) | 0.3091 (4) | 0.0315 (10) | |
N2 | 0.7454 (4) | 0.94525 (17) | 0.9305 (4) | 0.0317 (10) | |
C1 | 0.2331 (6) | 0.9137 (3) | 0.3333 (6) | 0.0541 (16) | |
H1 | 0.2272 | 0.8861 | 0.2668 | 0.065* | |
C2 | 0.3570 (6) | 0.9117 (3) | 0.4511 (5) | 0.0534 (16) | |
H2 | 0.4316 | 0.8833 | 0.4617 | 0.064* | |
C3 | 0.3718 (5) | 0.9511 (2) | 0.5527 (5) | 0.0303 (11) | |
C4 | 0.2558 (6) | 0.9921 (3) | 0.5269 (5) | 0.0539 (17) | |
H4 | 0.2590 | 1.0202 | 0.5917 | 0.065* | |
C5 | 0.1364 (6) | 0.9915 (3) | 0.4065 (5) | 0.0480 (15) | |
H5 | 0.0610 | 1.0199 | 0.3919 | 0.058* | |
C6 | 0.5017 (5) | 0.9496 (2) | 0.6830 (4) | 0.0277 (11) | |
C7 | 0.6237 (6) | 0.9116 (2) | 0.7042 (5) | 0.0458 (14) | |
H7 | 0.6261 | 0.8867 | 0.6355 | 0.055* | |
C8 | 0.7409 (5) | 0.9108 (2) | 0.8271 (5) | 0.0435 (14) | |
H8 | 0.8210 | 0.8849 | 0.8387 | 0.052* | |
C9 | 0.5072 (5) | 0.9858 (2) | 0.7894 (5) | 0.0402 (13) | |
H9 | 0.4298 | 1.0127 | 0.7802 | 0.048* | |
C10 | 0.6279 (5) | 0.9816 (2) | 0.9085 (5) | 0.0406 (13) | |
H10 | 0.6278 | 1.0058 | 0.9790 | 0.049* | |
C11 | 0.1149 (5) | 0.9212 (2) | −0.0653 (5) | 0.0272 (11) | |
C12 | 0.1868 (5) | 0.8668 (2) | −0.0953 (5) | 0.0388 (13) | |
C13 | 0.2553 (8) | 0.8683 (3) | −0.1877 (7) | 0.078 (2) | |
H13 | 0.2528 | 0.9037 | −0.2336 | 0.093* | |
C14 | 0.1891 (7) | 0.8138 (3) | −0.0293 (6) | 0.0585 (17) | |
H14 | 0.1421 | 0.8110 | 0.0330 | 0.070* | |
C15 | 0.2626 (8) | 0.7640 (3) | −0.0566 (7) | 0.073 (2) | |
H15 | 0.2654 | 0.7283 | −0.0118 | 0.087* | |
C16 | 0.3288 (8) | 0.7683 (3) | −0.1482 (8) | 0.072 (2) | |
C17 | 0.3279 (9) | 0.8201 (3) | −0.2161 (9) | 0.099 (3) | |
H17 | 0.3743 | 0.8226 | −0.2789 | 0.118* | |
C18 | 0.5468 (8) | 0.7172 (3) | −0.1573 (8) | 0.067 (2) | |
C19 | 0.6437 (10) | 0.7565 (4) | −0.0694 (9) | 0.105 (3) | |
H19 | 0.6085 | 0.7848 | −0.0245 | 0.126* | |
C20 | 0.7940 (9) | 0.7528 (4) | −0.0498 (10) | 0.130 (4) | |
H20 | 0.8625 | 0.7783 | 0.0110 | 0.156* | |
C21 | 0.8447 (8) | 0.7118 (3) | −0.1193 (8) | 0.097 (3) | |
H21 | 0.9467 | 0.7109 | −0.1071 | 0.116* | |
C22 | 0.7473 (6) | 0.6724 (2) | −0.2063 (6) | 0.0478 (15) | |
C23 | 0.5962 (7) | 0.6743 (2) | −0.2251 (6) | 0.0519 (16) | |
H23 | 0.5286 | 0.6474 | −0.2820 | 0.062* | |
C24 | 0.8081 (6) | 0.6272 (2) | −0.2759 (5) | 0.0367 (12) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0240 (4) | 0.0301 (4) | 0.0239 (4) | 0.0009 (3) | 0.0045 (3) | 0.0004 (3) |
O1 | 0.0371 (19) | 0.060 (3) | 0.038 (2) | 0.0094 (19) | 0.0193 (17) | −0.0011 (19) |
O2 | 0.050 (2) | 0.031 (2) | 0.031 (2) | 0.0033 (17) | 0.0070 (17) | −0.0014 (17) |
O3 | 0.088 (3) | 0.049 (3) | 0.174 (5) | 0.004 (3) | 0.084 (4) | −0.022 (3) |
O4 | 0.051 (2) | 0.035 (2) | 0.050 (2) | −0.0029 (19) | 0.0252 (19) | −0.0097 (19) |
O5 | 0.039 (2) | 0.039 (2) | 0.061 (3) | 0.0038 (17) | 0.0269 (19) | 0.0013 (19) |
N1 | 0.027 (2) | 0.033 (2) | 0.025 (2) | 0.0043 (19) | −0.0011 (17) | 0.0024 (19) |
N2 | 0.027 (2) | 0.034 (2) | 0.029 (2) | 0.0005 (19) | 0.0044 (18) | 0.001 (2) |
C1 | 0.048 (3) | 0.051 (4) | 0.042 (3) | 0.015 (3) | −0.008 (3) | −0.018 (3) |
C2 | 0.047 (3) | 0.057 (4) | 0.039 (3) | 0.019 (3) | −0.006 (3) | −0.009 (3) |
C3 | 0.024 (2) | 0.040 (3) | 0.024 (3) | 0.000 (2) | 0.006 (2) | −0.001 (2) |
C4 | 0.045 (3) | 0.071 (4) | 0.031 (3) | 0.025 (3) | −0.003 (3) | −0.016 (3) |
C5 | 0.038 (3) | 0.065 (4) | 0.030 (3) | 0.021 (3) | 0.000 (2) | −0.013 (3) |
C6 | 0.025 (2) | 0.032 (3) | 0.023 (3) | −0.002 (2) | 0.005 (2) | 0.001 (2) |
C7 | 0.040 (3) | 0.056 (4) | 0.033 (3) | 0.005 (3) | 0.003 (2) | −0.015 (3) |
C8 | 0.029 (3) | 0.045 (3) | 0.044 (3) | 0.011 (3) | −0.002 (2) | −0.013 (3) |
C9 | 0.030 (3) | 0.050 (3) | 0.034 (3) | 0.009 (3) | 0.003 (2) | −0.006 (3) |
C10 | 0.032 (3) | 0.048 (3) | 0.035 (3) | 0.004 (3) | 0.005 (2) | −0.005 (3) |
C11 | 0.015 (2) | 0.033 (3) | 0.028 (3) | 0.000 (2) | 0.000 (2) | −0.001 (2) |
C12 | 0.033 (3) | 0.033 (3) | 0.056 (4) | 0.000 (2) | 0.023 (3) | 0.000 (3) |
C13 | 0.111 (6) | 0.039 (4) | 0.123 (6) | 0.003 (4) | 0.089 (5) | 0.000 (4) |
C14 | 0.068 (4) | 0.055 (4) | 0.061 (4) | 0.010 (3) | 0.034 (3) | 0.008 (3) |
C15 | 0.096 (5) | 0.034 (3) | 0.111 (6) | 0.017 (4) | 0.065 (5) | 0.013 (4) |
C16 | 0.075 (5) | 0.049 (4) | 0.120 (6) | 0.007 (4) | 0.069 (5) | −0.005 (4) |
C17 | 0.138 (7) | 0.058 (5) | 0.157 (8) | −0.004 (5) | 0.122 (7) | −0.005 (5) |
C18 | 0.064 (4) | 0.053 (4) | 0.107 (6) | 0.007 (4) | 0.058 (4) | −0.010 (4) |
C19 | 0.100 (6) | 0.086 (6) | 0.145 (8) | 0.008 (5) | 0.062 (6) | −0.059 (6) |
C20 | 0.075 (5) | 0.129 (8) | 0.178 (9) | −0.006 (5) | 0.036 (6) | −0.119 (7) |
C21 | 0.060 (4) | 0.085 (6) | 0.139 (7) | −0.005 (4) | 0.030 (5) | −0.065 (5) |
C22 | 0.047 (3) | 0.044 (3) | 0.062 (4) | 0.004 (3) | 0.030 (3) | −0.011 (3) |
C23 | 0.059 (4) | 0.035 (3) | 0.071 (4) | 0.006 (3) | 0.035 (3) | 0.002 (3) |
C24 | 0.033 (3) | 0.042 (3) | 0.028 (3) | 0.008 (3) | 0.003 (2) | −0.001 (3) |
Geometric parameters (Å, º) top
Co1—O1 | 2.010 (3) | C6—C7 | 1.390 (6) |
Co1—O2i | 2.022 (3) | C7—C8 | 1.378 (6) |
Co1—O5ii | 2.150 (3) | C7—H7 | 0.9300 |
Co1—N2iii | 2.156 (4) | C8—H8 | 0.9300 |
Co1—N1 | 2.167 (4) | C9—C10 | 1.372 (7) |
Co1—O4ii | 2.230 (3) | C9—H9 | 0.9300 |
Co1—C24ii | 2.519 (5) | C10—H10 | 0.9300 |
O1—C11 | 1.251 (5) | C11—C12 | 1.492 (7) |
O2—C11 | 1.247 (5) | C12—C13 | 1.366 (8) |
O2—Co1i | 2.022 (3) | C12—C14 | 1.382 (7) |
O3—C18 | 1.379 (7) | C13—C17 | 1.376 (8) |
O3—C16 | 1.417 (7) | C13—H13 | 0.9300 |
O4—C24 | 1.258 (6) | C14—C15 | 1.406 (8) |
O4—Co1iv | 2.230 (3) | C14—H14 | 0.9300 |
O5—C24 | 1.246 (6) | C15—C16 | 1.346 (9) |
O5—Co1iv | 2.150 (3) | C15—H15 | 0.9300 |
N1—C1 | 1.311 (6) | C16—C17 | 1.372 (9) |
N1—C5 | 1.334 (6) | C17—H17 | 0.9300 |
N2—C10 | 1.334 (6) | C18—C19 | 1.371 (9) |
N2—C8 | 1.337 (6) | C18—C23 | 1.387 (8) |
N2—Co1v | 2.156 (4) | C19—C20 | 1.369 (10) |
C1—C2 | 1.376 (7) | C19—H19 | 0.9300 |
C1—H1 | 0.9300 | C20—C21 | 1.376 (9) |
C2—C3 | 1.368 (7) | C20—H20 | 0.9300 |
C2—H2 | 0.9300 | C21—C22 | 1.372 (8) |
C3—C4 | 1.385 (6) | C21—H21 | 0.9300 |
C3—C6 | 1.487 (6) | C22—C23 | 1.377 (7) |
C4—C5 | 1.371 (7) | C22—C24 | 1.494 (7) |
C4—H4 | 0.9300 | C23—H23 | 0.9300 |
C5—H5 | 0.9300 | C24—Co1iv | 2.519 (5) |
C6—C9 | 1.384 (6) | | |
| | | |
O1—Co1—O2i | 120.59 (15) | N2—C8—H8 | 118.3 |
O1—Co1—O5ii | 90.28 (14) | C7—C8—H8 | 118.3 |
O2i—Co1—O5ii | 148.10 (15) | C10—C9—C6 | 119.3 (5) |
O1—Co1—N2iii | 91.18 (14) | C10—C9—H9 | 120.3 |
O2i—Co1—N2iii | 91.04 (14) | C6—C9—H9 | 120.3 |
O5ii—Co1—N2iii | 96.54 (14) | N2—C10—C9 | 124.7 (5) |
O1—Co1—N1 | 87.88 (15) | N2—C10—H10 | 117.6 |
O2i—Co1—N1 | 87.65 (14) | C9—C10—H10 | 117.6 |
O5ii—Co1—N1 | 85.55 (14) | O2—C11—O1 | 125.6 (5) |
N2iii—Co1—N1 | 177.71 (15) | O2—C11—C12 | 117.1 (4) |
O1—Co1—O4ii | 149.23 (15) | O1—C11—C12 | 117.3 (4) |
O2i—Co1—O4ii | 90.16 (14) | C13—C12—C14 | 117.8 (5) |
O5ii—Co1—O4ii | 59.55 (13) | C13—C12—C11 | 120.8 (5) |
N2iii—Co1—O4ii | 86.84 (14) | C14—C12—C11 | 121.4 (5) |
N1—Co1—O4ii | 95.04 (14) | C12—C13—C17 | 123.3 (6) |
O1—Co1—C24ii | 119.79 (17) | C12—C13—H13 | 118.3 |
O2i—Co1—C24ii | 119.39 (17) | C17—C13—H13 | 118.3 |
O5ii—Co1—C24ii | 29.63 (14) | C12—C14—C15 | 119.9 (6) |
N2iii—Co1—C24ii | 92.62 (15) | C12—C14—H14 | 120.0 |
N1—Co1—C24ii | 89.66 (15) | C15—C14—H14 | 120.0 |
O4ii—Co1—C24ii | 29.93 (14) | C16—C15—C14 | 119.5 (6) |
C11—O1—Co1 | 147.8 (3) | C16—C15—H15 | 120.2 |
C11—O2—Co1i | 133.1 (3) | C14—C15—H15 | 120.2 |
C18—O3—C16 | 118.3 (5) | C15—C16—C17 | 122.1 (6) |
C24—O4—Co1iv | 87.9 (3) | C15—C16—O3 | 118.1 (6) |
C24—O5—Co1iv | 91.8 (3) | C17—C16—O3 | 119.8 (6) |
C1—N1—C5 | 116.1 (4) | C16—C17—C13 | 117.3 (6) |
C1—N1—Co1 | 119.3 (3) | C16—C17—H17 | 121.3 |
C5—N1—Co1 | 124.6 (3) | C13—C17—H17 | 121.3 |
C10—N2—C8 | 115.9 (4) | C19—C18—O3 | 121.7 (6) |
C10—N2—Co1v | 120.0 (3) | C19—C18—C23 | 122.3 (6) |
C8—N2—Co1v | 124.1 (3) | O3—C18—C23 | 115.9 (6) |
N1—C1—C2 | 124.0 (5) | C20—C19—C18 | 118.0 (7) |
N1—C1—H1 | 118.0 | C20—C19—H19 | 121.0 |
C2—C1—H1 | 118.0 | C18—C19—H19 | 121.0 |
C3—C2—C1 | 120.7 (5) | C19—C20—C21 | 120.6 (7) |
C3—C2—H2 | 119.6 | C19—C20—H20 | 119.7 |
C1—C2—H2 | 119.6 | C21—C20—H20 | 119.7 |
C2—C3—C4 | 115.4 (4) | C22—C21—C20 | 121.1 (7) |
C2—C3—C6 | 122.6 (4) | C22—C21—H21 | 119.5 |
C4—C3—C6 | 122.1 (4) | C20—C21—H21 | 119.5 |
C5—C4—C3 | 120.4 (5) | C21—C22—C23 | 119.3 (5) |
C5—C4—H4 | 119.8 | C21—C22—C24 | 119.3 (5) |
C3—C4—H4 | 119.8 | C23—C22—C24 | 121.4 (5) |
N1—C5—C4 | 123.4 (5) | C22—C23—C18 | 118.7 (6) |
N1—C5—H5 | 118.3 | C22—C23—H23 | 120.7 |
C4—C5—H5 | 118.3 | C18—C23—H23 | 120.7 |
C9—C6—C7 | 116.6 (4) | O5—C24—O4 | 120.7 (5) |
C9—C6—C3 | 121.7 (4) | O5—C24—C22 | 119.1 (5) |
C7—C6—C3 | 121.7 (4) | O4—C24—C22 | 120.1 (5) |
C8—C7—C6 | 120.0 (5) | O5—C24—Co1iv | 58.6 (3) |
C8—C7—H7 | 120.0 | O4—C24—Co1iv | 62.2 (3) |
C6—C7—H7 | 120.0 | C22—C24—Co1iv | 175.3 (4) |
N2—C8—C7 | 123.4 (5) | | |
Symmetry codes: (i) −x, −y+2, −z; (ii) x−1, −y+3/2, z+1/2; (iii) x−1, y, z−1; (iv) x+1, −y+3/2, z−1/2; (v) x+1, y, z+1. |
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