Magnetic properties of a new cobalt hydrogen vanadate with a dumortierite-like structure: Co_13.5(OH)₆(H_0.5VO_3.5)₂(VO₄)₆

The magnetic properties of a novel cobalt-based hydrogen vanadate, Co_13.5(OH)₆(H_0.5VO_3.5)₂(VO₄)₆, are reported. This new magnetic material was synthesized in single-crystal form using a conventional hydro­thermal method. Its crystal structure was determined from single-crystal X-ray diffraction data and was also characterized by scanning electron microscopy. Its crystal framework has a dumortierite-like structure consisting of large hexa­gonal and trigonal channels; the large hexa­gonal channels contain one-dimensional chains of face-sharing CoO₆ octa­hedra linked to the framework by rings of VO₄ tetra­hedra, while the trigonal channels are occupied by chains of disordered V₂O₄ pyramidal groups. The magnetic properties of this material were investigated by DC magnetic measurements, which indicate the occurrence of anti­ferromagnetic inter­actions.

Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015) and WinGX (Farrugia, 2012); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Cobalt hydroxide hydrogen vanadate

Crystal data

Co13.5(OH)6(H0.5VO3.5)2(VO4)6	Dx = 4.140 Mg m^−3
Mr = 1802.13	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63mc	Cell parameters from 1184 reflections
a = 12.837 (8) Å	θ = 3.2–35.0°
c = 5.064 (3) Å	µ = 10.09 mm^−1
V = 722.7 (7) Å^3	T = 293 K
Z = 1	Hexagonal prism, black
F(000) = 851.5	0.30 × 0.20 × 0.19 mm

Data collection

Bruker D8 VENTURE Super DUO diffractometer	1184 independent reflections
Radiation source: INCOATEC IµS micro-focus source	1155 reflections with I > 2σ(I)
Detector resolution: 10.4167 pixels mm^-1	Rint = 0.041
φ and ω scans	θmax = 35.0°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −20→20
Tmin = 0.619, Tmax = 0.747	k = −20→20
32344 measured reflections	l = −8→8

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0211P)^2 + 0.7866P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.015	(Δ/σ)max = 0.001
wR(F^2) = 0.043	Δρmax = 1.21 e Å^−3
S = 1.10	Δρmin = −0.47 e Å^−3
1184 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
63 parameters	Extinction coefficient: 0.0056 (6)
1 restraint	Absolute structure: Flack x determined using 521 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.020 (8)
Hydrogen site location: mixed

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. The software APEX3 was used for data collection and SAINT for cell refinement and data reduction. A total number of 32344 reflections were measured in the range of θ_min = 3.2 ° and θ_max = 35 °, of which 1184 were independent and 1155 reflections with I > 2σ(I). The crystal structure was solved by direct method with the SHELXS97 (Sheldrick, 1997) program and refined with SHELXL2014 (Sheldrick, 2015) program incorporated in the WinGX (Farrugia, 2012) package.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
V1	0.69852 (5)	0.84926 (2)	0.62349 (10)	0.00656 (10)
V2A	0.3333	0.6667	0.3690 (4)	0.0070 (4)	0.610 (5)
V2B	0.3333	0.6667	0.0920 (6)	0.0061 (5)	0.390 (5)
Co1	0.57335 (2)	0.64904 (3)	0.09342 (5)	0.00765 (8)
Co2	1.0000	1.0000	0.9265 (3)	0.0127 (2)	0.75
O1	0.65816 (17)	0.72332 (15)	0.4391 (4)	0.0098 (3)
O2	0.6119 (2)	0.80595 (12)	0.9087 (5)	0.0099 (4)
O3	0.8507 (2)	0.92536 (12)	0.6824 (7)	0.0145 (5)
O4	0.40426 (12)	0.59574 (12)	0.2403 (7)	0.0155 (5)
O5	0.3333	0.6667	0.720 (2)	0.0174 (19)	0.5
H5	0.3681	0.6319	0.7739	0.026*	0.1667
O6	0.52603 (12)	0.47397 (12)	0.2789 (5)	0.0090 (4)
H6	0.5536	0.4464	0.1584	0.013*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.0088 (2)	0.00597 (14)	0.0059 (2)	0.00438 (10)	−0.00049 (18)	−0.00024 (9)
V2A	0.0040 (4)	0.0040 (4)	0.0131 (7)	0.0020 (2)	0.000	0.000
V2B	0.0057 (6)	0.0057 (6)	0.0068 (9)	0.0029 (3)	0.000	0.000
Co1	0.00715 (13)	0.00836 (13)	0.00721 (13)	0.00369 (10)	0.00000 (11)	−0.00030 (13)
Co2	0.0041 (2)	0.0041 (2)	0.0298 (6)	0.00207 (11)	0.000	0.000
O1	0.0136 (7)	0.0082 (6)	0.0085 (7)	0.0060 (6)	−0.0016 (6)	−0.0005 (6)
O2	0.0140 (11)	0.0093 (7)	0.0080 (10)	0.0070 (5)	0.0024 (9)	0.0012 (4)
O3	0.0082 (10)	0.0132 (8)	0.0203 (13)	0.0041 (5)	−0.0014 (9)	−0.0007 (5)
O4	0.0092 (8)	0.0092 (8)	0.0293 (15)	0.0055 (9)	0.0016 (5)	−0.0016 (5)
O5	0.015 (3)	0.015 (3)	0.023 (5)	0.0073 (13)	0.000	0.000
O6	0.0093 (7)	0.0093 (7)	0.0086 (9)	0.0048 (9)	0.0009 (4)	−0.0009 (4)

Geometric parameters (Å, º)

V1—O1	1.7079 (18)	Co1—O6	2.222 (2)
V1—O1^i	1.7080 (18)	Co2—O3^vi	2.069 (3)
V1—O3	1.718 (3)	Co2—O3	2.069 (3)
V1—O2	1.736 (3)	Co2—O3^vii	2.070 (3)
V2A—O4	1.706 (3)	Co2—O3^viii	2.106 (3)
V2A—O4^ii	1.706 (3)	Co2—O3^ix	2.106 (3)
V2A—O4^i	1.706 (3)	Co2—O3^x	2.106 (3)
V2A—O5	1.777 (13)	O1—Co1^ix	2.0262 (17)
V2B—O4	1.747 (3)	O2—Co1^xi	2.0446 (13)
V2B—O4^i	1.747 (3)	O2—Co1^xii	2.0446 (13)
V2B—O4^ii	1.747 (3)	O3—Co2^xiii	2.106 (3)
V2B—O5^iii	1.884 (13)	O4—Co1^xiv	2.061 (2)
Co1—O1^iv	2.026 (2)	O5—H5	0.8200
Co1—O1	2.030 (2)	O6—Co1^ix	2.155 (2)
Co1—O2^iii	2.0447 (13)	O6—Co1^xv	2.155 (2)
Co1—O4	2.061 (2)	O6—Co1^xiv	2.222 (2)
Co1—O6^v	2.155 (2)	O6—H6	0.8643
O1—V1—O1^i	105.30 (13)	O1^iv—Co1—O6^v	87.39 (8)
O1—V1—O3	110.72 (9)	O1—Co1—O6^v	164.50 (8)
O1^i—V1—O3	110.72 (10)	O2^iii—Co1—O6^v	98.44 (9)
O1—V1—O2	108.01 (8)	O4—Co1—O6^v	83.34 (10)
O1^i—V1—O2	108.01 (9)	O1^iv—Co1—O6	89.59 (8)
O3—V1—O2	113.69 (15)	O1—Co1—O6	85.52 (8)
O4—V2A—O4^ii	106.33 (15)	O2^iii—Co1—O6	177.40 (9)
O4—V2A—O4^i	106.33 (15)	O4—Co1—O6	78.57 (9)
O4^ii—V2A—O4^i	106.33 (14)	O6^v—Co1—O6	78.99 (5)
O4—V2A—O5	112.45 (13)	O3^vi—Co2—O3	87.98 (14)
O4^ii—V2A—O5	112.45 (13)	O3^vi—Co2—O3^vii	87.98 (14)
O4^i—V2A—O5	112.45 (13)	O3—Co2—O3^vii	87.98 (14)
O4—V2B—O4^i	102.87 (17)	O3^vi—Co2—O3^viii	92.95 (7)
O4—V2B—O4^ii	102.87 (17)	O3—Co2—O3^viii	178.70 (16)
O4^i—V2B—O4^ii	102.87 (17)	O3^vii—Co2—O3^viii	92.96 (8)
O4—V2B—O5^iii	115.46 (14)	O3^vi—Co2—O3^ix	178.70 (16)
O4^i—V2B—O5^iii	115.46 (14)	O3—Co2—O3^ix	92.96 (7)
O4^ii—V2B—O5^iii	115.46 (14)	O3^vii—Co2—O3^ix	92.96 (7)
O1^iv—Co1—O1	91.98 (8)	O3^viii—Co2—O3^ix	86.09 (14)
O1^iv—Co1—O2^iii	90.67 (9)	O3^vi—Co2—O3^x	92.96 (7)
O1—Co1—O2^iii	97.06 (9)	O3—Co2—O3^x	92.95 (8)
O1^iv—Co1—O4	166.15 (8)	O3^vii—Co2—O3^x	178.70 (16)
O1—Co1—O4	94.20 (11)	O3^viii—Co2—O3^x	86.09 (14)
O2^iii—Co1—O4	100.84 (10)	O3^ix—Co2—O3^x	86.09 (14)

Symmetry codes: (i) x, x−y+1, z; (ii) −x+y, y, z; (iii) x, y, z−1; (iv) y, x, z−1/2; (v) −x+1, −y+1, z−1/2; (vi) −y+2, −x+2, z; (vii) −x+y+1, y, z; (viii) −x+2, −y+2, z+1/2; (ix) y, x, z+1/2; (x) x−y+1, −y+2, z+1/2; (xi) x, x−y+1, z+1; (xii) x, y, z+1; (xiii) −x+2, −y+2, z−1/2; (xiv) −y+1, −x+1, z; (xv) −x+1, −y+1, z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O4^xii	0.82	2.49	3.071 (11)	128
O5—H5···O6^xv	0.82	2.35	3.141 (3)	161
O6—H6···O4^v	0.86	2.32	3.137 (4)	159
O6—H6···O5^v	0.86	2.53	3.141 (3)	128

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