A polyoxometalate-based metal–organic poly­hedron constructed from a {V₅O₉Cl} building unit with rhombicubocta­hedral geometry

The design and construction of metal–organic polyhedra has received much attention by chemists due to the intriguing diversity of architectures and topologies that can be achieved. There are several crucial factors which should be considered for the construction of metal–organic polyhedra, such as the starting materials, reaction time and temperature, solvent and suitable organic ligands. Recently, polyoxometalates (POMs), serving as secondary building units to construct POM-based metal–organic polyhedra, have been the subject of much inter­est. The title compound, dodeca­kis­(di­methyl­ammonium) octa­kis­(μ-benzene-1,3,5-tri­carboxyl­ato)hexa-μ-chlorido-tetra­cosa-μ-oxido-triacontaoxidotriacontavanadium, (NH₂Me₂)₁₂[(V₅O₉Cl)₆(C₉H₃O₆)₈], was synthesized successfully by self-assembly of VOCl₃ and benzene-1,3,5-tri­carb­oxy­lic acid under solvothermal conditions. The title polyhedron has an rdo topology when the {V₅O₉Cl} building unit and the benzene-1,3,5-tri­carboxyl­ate (BTC³⁻) ligand were simplified into 4-connected and 3-connected vertices. Inter­estingly, when the {V₅O₉Cl} building unit and the BTC³⁻ ligand are considered as quadrangular and triangular faces, the structure displays rhombicubocta­hedral geometry with an outer diameter of 21.88 Å. The packing of the polyhedra produces a circular channel with a diameter of 8.2 Å. The title compound was characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, thermogravimetric analysis and powder X-ray diffraction.

Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Dodecakis(dimethylammonium) octakis(µ-benzene-1,3,5-tricarboxylato)hexa-µ-chlorido-tetracosa-µ-oxido-triacontaoxidotriacontavanadium

Crystal data

(C2H8N)12[(V5O9Cl)6(C9H3O6)8]	Mo Kα radiation, λ = 0.71073 Å
Mr = 4814.93	Cell parameters from 19592 reflections
Cubic, Fm3m	θ = 3.1–25.0°
a = 29.7184 (17) Å	µ = 1.14 mm^−1
V = 26247 (5) Å^3	T = 296 K
Z = 4	Block, green
F(000) = 9552	0.24 × 0.22 × 0.2 mm
Dx = 1.218 Mg m^−3

Data collection

Bruker APEXII Quazar diffractometer	1046 reflections with I > 2σ(I)
0.5° ω and 0.5° φ scans	Rint = 0.055
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θmax = 25.0°, θmin = 3.1°
Tmin = 0.768, Tmax = 0.796	h = −35→34
19592 measured reflections	k = −35→27
1201 independent reflections	l = −32→35

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2) + (0.0418P)^2 + 74.8854P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
1201 reflections	Δρmax = 0.27 e Å^−3
55 parameters	Δρmin = −0.30 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
V2	0.73802 (2)	0.500000	0.41711 (2)	0.01883 (17)
V1	0.68625 (3)	0.500000	0.500000	0.0221 (2)
O4	0.78500 (5)	0.54596 (5)	0.40056 (5)	0.0270 (4)
O2	0.70739 (6)	0.54202 (4)	0.45798 (4)	0.0216 (4)
O3	0.70869 (7)	0.500000	0.37254 (7)	0.0319 (5)
O1	0.63209 (14)	0.500000	0.500000	0.0381 (11)
C1	0.79992 (9)	0.58100 (6)	0.41900 (6)	0.0221 (6)
C3	0.85897 (7)	0.64103 (7)	0.41620 (10)	0.0252 (6)
H3	0.846200	0.653800	0.441755	0.030*
C2	0.83978 (9)	0.60281 (7)	0.39719 (7)	0.0229 (6)
Cl1	0.79363 (5)	0.500000	0.500000	0.0295 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V2	0.0137 (3)	0.0215 (3)	0.0212 (3)	0.000	−0.00207 (18)	0.000
V1	0.0111 (5)	0.0276 (3)	0.0276 (3)	0.000	0.000	0.000
O4	0.0244 (7)	0.0270 (8)	0.0298 (8)	−0.0073 (6)	0.0054 (6)	−0.0050 (6)
O2	0.0157 (10)	0.0245 (6)	0.0245 (6)	0.0019 (5)	−0.0019 (5)	0.0001 (8)
O3	0.0291 (11)	0.0379 (13)	0.0288 (12)	0.000	−0.0099 (9)	0.000
O1	0.014 (2)	0.0503 (17)	0.0503 (17)	0.000	0.000	0.000
C1	0.0203 (14)	0.0229 (9)	0.0229 (9)	0.0016 (8)	−0.0016 (8)	0.0015 (12)
C3	0.0255 (9)	0.0255 (9)	0.0246 (15)	−0.0006 (12)	0.0055 (9)	−0.0055 (9)
C2	0.0224 (15)	0.0232 (9)	0.0232 (9)	−0.0035 (8)	0.0035 (8)	−0.0026 (12)
Cl1	0.0185 (7)	0.0349 (5)	0.0349 (5)	0.000	0.000	0.000

Geometric parameters (Å, º)

V2—V1	2.9043 (7)	V1—O2^i	1.8747 (18)
V2—O4	2.0142 (14)	V1—O2^iii	1.8747 (18)
V2—O4^i	2.0143 (14)	V1—O1	1.610 (4)
V2—O2	1.9654 (9)	V1—Cl1	3.1910 (17)
V2—O2^i	1.9654 (9)	O4—C1	1.2575 (18)
V2—O3	1.585 (2)	C1—C2	1.498 (4)
V2—Cl1	2.9664 (9)	C3—C2^v	1.3908 (19)
V2—Cl1^ii	2.9664 (9)	C3—C2	1.3908 (19)
V2—Cl1^iii	2.9664 (9)	Cl1—Cl1^iii	0.000 (3)
V1—O2^iv	1.8747 (18)	Cl1—Cl1^ii	0.000 (3)
V1—O2	1.8746 (18)
V1—V2—Cl1^ii	65.84 (3)	O2^i—V1—V2^iv	112.80 (5)
V1—V2—Cl1	65.84 (3)	O2^iv—V1—V2^vii	112.80 (5)
V1—V2—Cl1^iii	65.84 (3)	O2^iii—V1—V2^vi	112.80 (5)
O4^i—V2—V1	125.05 (4)	O2—V1—V2	42.05 (3)
O4—V2—V1	125.05 (4)	O2^i—V1—V2	42.05 (3)
O4—V2—O4^i	85.39 (8)	O2—V1—V2^vi	42.05 (3)
O4—V2—Cl1^iii	79.43 (5)	O2^iii—V1—V2	112.80 (5)
O4—V2—Cl1^ii	79.43 (5)	O2^i—V1—V2^vii	42.05 (3)
O4^i—V2—Cl1^iii	79.43 (5)	O2^iii—V1—V2^vii	42.05 (3)
O4—V2—Cl1	79.43 (5)	O2—V1—V2^iv	112.80 (5)
O4^i—V2—Cl1	79.43 (5)	O2^iv—V1—V2	112.80 (5)
O4^i—V2—Cl1^ii	79.43 (5)	O2^i—V1—V2^vi	112.80 (5)
O2—V2—V1	39.70 (5)	O2^iv—V1—V2^vi	42.05 (3)
O2^i—V2—V1	39.70 (5)	O2—V1—O2^iv	83.55 (4)
O2—V2—O4	92.35 (6)	O2^i—V1—O2^iii	83.55 (4)
O2—V2—O4^i	154.52 (7)	O2—V1—O2^i	83.55 (4)
O2^i—V2—O4^i	92.35 (6)	O2^iv—V1—O2^iii	83.55 (4)
O2^i—V2—O4	154.52 (7)	O2—V1—O2^iii	140.84 (12)
O2—V2—O2^i	78.91 (10)	O2^iv—V1—O2^i	140.84 (12)
O2^i—V2—Cl1	75.22 (5)	O2—V1—Cl1	70.42 (6)
O2—V2—Cl1^iii	75.22 (5)	O2^iii—V1—Cl1	70.42 (6)
O2—V2—Cl1	75.22 (5)	O2^i—V1—Cl1	70.42 (6)
O2^i—V2—Cl1^iii	75.22 (5)	O2^iv—V1—Cl1	70.42 (6)
O2—V2—Cl1^ii	75.22 (5)	O1—V1—V2^vii	121.984 (17)
O2^i—V2—Cl1^ii	75.22 (5)	O1—V1—V2^vi	121.984 (17)
O3—V2—V1	114.67 (8)	O1—V1—V2	121.984 (17)
O3—V2—O4^i	100.20 (7)	O1—V1—V2^iv	121.984 (17)
O3—V2—O4	100.20 (7)	O1—V1—O2^iv	109.58 (6)
O3—V2—O2	105.17 (8)	O1—V1—O2	109.58 (6)
O3—V2—O2^i	105.17 (8)	O1—V1—O2^i	109.58 (6)
O3—V2—Cl1^ii	179.49 (8)	O1—V1—O2^iii	109.58 (6)
O3—V2—Cl1	179.49 (8)	O1—V1—Cl1	180.0
O3—V2—Cl1^iii	179.49 (8)	C1—O4—V2	134.39 (15)
Cl1^iii—V2—Cl1	0.0	V2—O2—V2^vi	124.81 (9)
Cl1^iii—V2—Cl1^ii	0.0	V1—O2—V2	98.25 (6)
Cl1—V2—Cl1^ii	0.0	V1—O2—V2^vi	98.25 (6)
V2^vi—V1—V2^vii	116.03 (3)	O4^vi—C1—O4	126.7 (3)
V2—V1—V2^vi	73.706 (16)	O4—C1—C2	116.65 (13)
V2^iv—V1—V2^vii	73.706 (16)	O4^vi—C1—C2	116.65 (13)
V2^iv—V1—V2^vi	73.706 (16)	C2^v—C3—C2	120.3 (3)
V2—V1—V2^iv	116.03 (3)	C3^viii—C2—C1	120.13 (14)
V2—V1—V2^vii	73.706 (16)	C3—C2—C1	120.12 (14)
V2—V1—Cl1	58.016 (17)	C3^viii—C2—C3	119.7 (3)
V2^vii—V1—Cl1	58.016 (17)	V2—Cl1—V1	56.14 (2)
V2^iv—V1—Cl1	58.016 (17)	Cl1^ii—Cl1—V2	0 (10)
V2^vi—V1—Cl1	58.016 (17)	Cl1^iii—Cl1—V2	0 (10)
O2^iii—V1—V2^iv	42.05 (3)	Cl1^iii—Cl1—V1	0 (10)
O2^iv—V1—V2^iv	42.05 (3)	Cl1^ii—Cl1—V1	0 (10)
O2—V1—V2^vii	112.80 (5)	Cl1^iii—Cl1—Cl1^ii	0 (10)

Symmetry codes: (i) x, −y+1, z; (ii) x, −z+1, y; (iii) x, −y+1, −z+1; (iv) x, y, −z+1; (v) z+1/2, −x+3/2, −y+1; (vi) x, −z+1, −y+1; (vii) x, z, −y+1; (viii) −y+3/2, −z+1, x−1/2.