A new three-dimensional cobalt(II) coordination polymer based on V-shaped 3,4′-oxydibenzoate: synthesis, crystal structure and magnetic properties

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 Co^II 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 Co^II 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.

Computing details

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)(µ₃-3,4'-oxydibenzoato)cobalt(II)]

Crystal data

[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) Å^3	Block, purple
Z = 4	0.21 × 0.09 × 0.07 mm

Data collection

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

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.058	H-atom parameters constrained
wR(F^2) = 0.162	w = 1/[σ^2(Fo^2) + (0.0599P)^2 + 0.1676P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Co1—O1	2.010 (3)	C6—C7	1.390 (6)
Co1—O2^i	2.022 (3)	C7—C8	1.378 (6)
Co1—O5^ii	2.150 (3)	C7—H7	0.9300
Co1—N2^iii	2.156 (4)	C8—H8	0.9300
Co1—N1	2.167 (4)	C9—C10	1.372 (7)
Co1—O4^ii	2.230 (3)	C9—H9	0.9300
Co1—C24^ii	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—Co1^i	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—Co1^iv	2.230 (3)	C14—H14	0.9300
O5—C24	1.246 (6)	C15—C16	1.346 (9)
O5—Co1^iv	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—Co1^v	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—Co1^iv	2.519 (5)
C6—C9	1.384 (6)
O1—Co1—O2^i	120.59 (15)	N2—C8—H8	118.3
O1—Co1—O5^ii	90.28 (14)	C7—C8—H8	118.3
O2^i—Co1—O5^ii	148.10 (15)	C10—C9—C6	119.3 (5)
O1—Co1—N2^iii	91.18 (14)	C10—C9—H9	120.3
O2^i—Co1—N2^iii	91.04 (14)	C6—C9—H9	120.3
O5^ii—Co1—N2^iii	96.54 (14)	N2—C10—C9	124.7 (5)
O1—Co1—N1	87.88 (15)	N2—C10—H10	117.6
O2^i—Co1—N1	87.65 (14)	C9—C10—H10	117.6
O5^ii—Co1—N1	85.55 (14)	O2—C11—O1	125.6 (5)
N2^iii—Co1—N1	177.71 (15)	O2—C11—C12	117.1 (4)
O1—Co1—O4^ii	149.23 (15)	O1—C11—C12	117.3 (4)
O2^i—Co1—O4^ii	90.16 (14)	C13—C12—C14	117.8 (5)
O5^ii—Co1—O4^ii	59.55 (13)	C13—C12—C11	120.8 (5)
N2^iii—Co1—O4^ii	86.84 (14)	C14—C12—C11	121.4 (5)
N1—Co1—O4^ii	95.04 (14)	C12—C13—C17	123.3 (6)
O1—Co1—C24^ii	119.79 (17)	C12—C13—H13	118.3
O2^i—Co1—C24^ii	119.39 (17)	C17—C13—H13	118.3
O5^ii—Co1—C24^ii	29.63 (14)	C12—C14—C15	119.9 (6)
N2^iii—Co1—C24^ii	92.62 (15)	C12—C14—H14	120.0
N1—Co1—C24^ii	89.66 (15)	C15—C14—H14	120.0
O4^ii—Co1—C24^ii	29.93 (14)	C16—C15—C14	119.5 (6)
C11—O1—Co1	147.8 (3)	C16—C15—H15	120.2
C11—O2—Co1^i	133.1 (3)	C14—C15—H15	120.2
C18—O3—C16	118.3 (5)	C15—C16—C17	122.1 (6)
C24—O4—Co1^iv	87.9 (3)	C15—C16—O3	118.1 (6)
C24—O5—Co1^iv	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—Co1^v	120.0 (3)	C19—C18—C23	122.3 (6)
C8—N2—Co1^v	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—Co1^iv	58.6 (3)
C8—C7—H7	120.0	O4—C24—Co1^iv	62.2 (3)
C6—C7—H7	120.0	C22—C24—Co1^iv	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.