Crystal structure of guanidinium hexa­fluorido­vanadate(III), (CN₃H₆)₃[VF₆]: an unusual hybrid compound related to perovskite

Vanadium fluorides with novel crystal–chemical features and inter­esting physical properties can be prepared by solvothermal synthetic routes. The title compound, guanidinium hexa­fluorido­vanadate(III), has a cubic structure (space group Pa), exhibiting isolated regular VF₆ octa­hedral units, which are hydrogen bonded to protonated guanidinium moieties. Although the VF₆ octa­hedral units are not linked directly together, there are structural similarities between this crystal structure and those of the wider family of perovskite materials, in particular, hybrid perovskites based on extended ligands such as cyanide. In this context, the octa­hedral tilt system of the present compound is of inter­est and demonstrates that unusual tilt systems can be mediated via `mol­ecular' linkers which allow only supra­molecular rather than covalent inter­actions.

Computing details

Data collection: CrystalClear-SM Expert (Rigaku, 2014); cell refinement: CrystalClear-SM Expert (Rigaku, 2014); data reduction: CrystalClear-SM Expert (Rigaku, 2014); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012).

Triguanidinium hexafluoridovanadate(III)

Crystal data

(CH6N3)3[VF6]	Mo Kα radiation, λ = 0.71075 Å
Mr = 345.20	Cell parameters from 800 reflections
Cubic, Pa3	θ = 2.5–25.3°
a = 14.095 (3) Å	µ = 0.78 mm^−1
V = 2800.2 (18) Å^3	T = 173 K
Z = 8	Block, green
F(000) = 1408	0.08 × 0.07 × 0.05 mm
Dx = 1.638 Mg m^−3

Data collection

Rigaku SCXmini diffractometer	778 reflections with I > 2σ(I)
Detector resolution: 14.7059 pixels mm^-1	Rint = 0.093
profile data from φ–scans	θmax = 25.3°, θmin = 2.5°
Absorption correction: multi-scan	h = −16→16
Tmin = 0.727, Tmax = 1.000	k = −16→14
16185 measured reflections	l = −16→16
853 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	All H-atom parameters refined
wR(F^2) = 0.161	w = 1/[σ^2(Fo^2) + (0.089P)^2 + 0.3869P] where P = (Fo^2 + 2Fc^2)/3
S = 1.32	(Δ/σ)max < 0.001
853 reflections	Δρmax = 0.44 e Å^−3
83 parameters	Δρmin = −0.70 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.

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

	x	y	z	Uiso*/Ueq
V1	0.0000	0.0000	0.0000	0.0124 (5)
V2	0.0000	0.0000	0.5000	0.0125 (5)
F1	−0.02491 (10)	0.02779 (10)	0.13294 (10)	0.0191 (5)
F2	0.02648 (11)	0.02032 (10)	0.36612 (10)	0.0193 (5)
N1	0.02433 (19)	0.35925 (18)	0.25208 (15)	0.0254 (7)
N2	0.01649 (17)	0.22012 (18)	0.16926 (18)	0.0243 (6)
N3	0.04043 (18)	0.21871 (18)	0.33114 (17)	0.0248 (6)
C1	0.0273 (3)	0.2656 (2)	0.25114 (15)	0.0187 (7)
H1	0.0158 (19)	0.389 (2)	0.201 (2)	0.023 (7)*
H2	0.0294 (18)	0.391 (2)	0.304 (2)	0.023 (7)*
H3	0.008 (2)	0.255 (2)	0.117 (3)	0.030 (10)*
H4	0.013 (2)	0.165 (3)	0.171 (2)	0.023 (8)*
H5	0.038 (3)	0.248 (2)	0.383 (3)	0.040 (10)*
H6	0.0386 (19)	0.164 (2)	0.333 (2)	0.017 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.0124 (5)	0.0124 (5)	0.0124 (5)	0.0002 (2)	0.0002 (2)	0.0002 (2)
V2	0.0125 (5)	0.0125 (5)	0.0125 (5)	−0.0002 (2)	−0.0002 (2)	0.0002 (2)
F1	0.0222 (8)	0.0191 (8)	0.0159 (8)	0.0005 (7)	0.0016 (6)	−0.0009 (6)
F2	0.0223 (9)	0.0200 (8)	0.0157 (8)	−0.0014 (7)	0.0015 (6)	0.0007 (6)
N1	0.0413 (15)	0.0169 (14)	0.0179 (15)	−0.0017 (10)	−0.0005 (10)	−0.0010 (9)
N2	0.0387 (14)	0.0144 (12)	0.0199 (13)	−0.0015 (10)	0.0010 (10)	0.0001 (10)
N3	0.0390 (15)	0.0175 (13)	0.0179 (12)	0.0013 (10)	0.0001 (10)	0.0004 (10)
C1	0.0184 (14)	0.0199 (14)	0.0177 (15)	−0.0022 (12)	0.0020 (9)	−0.0011 (9)

Geometric parameters (Å, º)

V1—F1^i	1.9461 (15)	V2—F2	1.9448 (15)
V1—F1^ii	1.9461 (15)	N1—C1	1.321 (4)
V1—F1^iii	1.9461 (15)	N1—H1	0.85 (3)
V1—F1^iv	1.9461 (15)	N1—H2	0.86 (3)
V1—F1^v	1.9461 (15)	N2—C1	1.329 (4)
V1—F1	1.9462 (15)	N2—H3	0.89 (4)
V2—F2^vi	1.9448 (15)	N2—H4	0.78 (3)
V2—F2^vii	1.9448 (15)	N3—C1	1.320 (3)
V2—F2^viii	1.9448 (15)	N3—H5	0.84 (4)
V2—F2^ix	1.9448 (15)	N3—H6	0.77 (3)
V2—F2^x	1.9448 (15)
F1^i—V1—F1^ii	180.00 (13)	F2^vi—V2—F2^x	180.0
F1^i—V1—F1^iii	90.93 (6)	F2^vii—V2—F2^x	89.14 (6)
F1^ii—V1—F1^iii	89.07 (6)	F2^viii—V2—F2^x	90.86 (6)
F1^i—V1—F1^iv	89.07 (6)	F2^ix—V2—F2^x	89.14 (6)
F1^ii—V1—F1^iv	90.93 (6)	F2^vi—V2—F2	89.14 (6)
F1^iii—V1—F1^iv	89.07 (6)	F2^vii—V2—F2	90.86 (6)
F1^i—V1—F1^v	90.93 (6)	F2^viii—V2—F2	89.14 (6)
F1^ii—V1—F1^v	89.07 (6)	F2^ix—V2—F2	180.0
F1^iii—V1—F1^v	90.93 (6)	F2^x—V2—F2	90.86 (6)
F1^iv—V1—F1^v	180.00 (9)	C1—N1—H1	120 (2)
F1^i—V1—F1	89.07 (6)	C1—N1—H2	121.9 (19)
F1^ii—V1—F1	90.93 (6)	H1—N1—H2	118 (3)
F1^iii—V1—F1	180.0	C1—N2—H3	118.1 (19)
F1^iv—V1—F1	90.93 (6)	C1—N2—H4	118 (2)
F1^v—V1—F1	89.07 (6)	H3—N2—H4	124 (3)
F2^vi—V2—F2^vii	90.86 (6)	C1—N3—H5	119 (2)
F2^vi—V2—F2^viii	89.14 (6)	C1—N3—H6	122 (2)
F2^vii—V2—F2^viii	180.00 (8)	H5—N3—H6	117 (3)
F2^vi—V2—F2^ix	90.86 (6)	N3—C1—N2	121.1 (3)
F2^vii—V2—F2^ix	89.14 (6)	N3—C1—N1	119.7 (2)
F2^viii—V2—F2^ix	90.86 (6)	N2—C1—N1	119.1 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···F2^xi	0.85 (3)	2.16 (3)	2.906 (3)	147 (3)
N1—H2···F1^xi	0.86 (3)	2.12 (3)	2.876 (3)	146 (3)
N2—H3···F2^iv	0.89 (4)	2.03 (4)	2.879 (3)	159 (3)
N2—H4···F1	0.78 (3)	2.08 (3)	2.820 (3)	160 (3)
N3—H5···F1^x	0.84 (4)	2.13 (4)	2.919 (3)	157 (3)
N3—H6···F2	0.77 (3)	2.09 (3)	2.846 (3)	169 (3)

Symmetry codes: (iv) y, z, x; (x) y, −z+1/2, x+1/2; (xi) −x, y+1/2, −z+1/2.