Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109021325/fn3018sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109021325/fn3018Isup2.hkl |
Vanadium(III) hypophosphite was synthesized by a hydrothermal method. A mixture of deionzed water, vanadium(V) oxide, 50% hypophosphoric acid and lithium carbonate in a molar ratio of 10.437:0.1:2:0.428 was placed in a Teflon acid digestion bomb (23 ml, Parr Instruments), heated at 423 K for 48 h and cooled to room temperature over a period of 24 h. The green product was filtered off, washed with deionized water and dried at room temperature in a desiccator.
The comparison of the X-ray powder diffraction pattern of the synthesized product with the simulated one from this structure revealed that the title compound is present as a minor phase. The major phase remains unknown.
While lithium ions are not present in this structure, the presence of lithium carbonate seems to be necessary to obtain the title compound, as synthesis attempts performed without the lithium source were unsuccessful.
We assume that the hypophosphoric acid is responsible of the reduction of the vanadium ions observed during the synthesis (V5+ to V3+), as no other reducing agent is present.
The H atoms were located in a Fourier difference map and their positional parameters were refined freely, while their Uiso(H) values were fixed at 0.049 Å2. The refinement of the structure was carried out on a twinned crystal. The transformation matrix used is (001, 010, 100). The refined volume fractions are 94.7 and 5.3%. [Please check modifications to text, inline with data in CIF.]
Data collection: COLLECT (Nonius, 1998); cell refinement: DIRAX/LSQ (Duisenberg, 1992); data reduction: EVALCCD (Duisenberg, 1998); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).
V(H2PO2)3 | F(000) = 976 |
Mr = 491.8 | Dx = 2.11 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 9018 reflections |
a = 11.4985 (3) Å | θ = 2.9–27.5° |
b = 11.7771 (5) Å | µ = 1.88 mm−1 |
c = 11.5999 (4) Å | T = 293 K |
β = 99.807 (2)° | Prism, green |
V = 1547.89 (9) Å3 | 0.15 × 0.05 × 0.04 mm |
Z = 4 |
Nonius KappaCCD diffractometer | Rint = 0.117 |
CCD rotation images, thick slices scans | θmax = 27.5°, θmin = 3.6° |
20258 measured reflections | h = −14→14 |
3550 independent reflections | k = −15→13 |
2426 reflections with I > 2σ(I) | l = −15→15 |
Refinement on F2 | Only H-atom coordinates refined |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0199P)2 + 4.0183P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.053 | (Δ/σ)max = 0.006 |
wR(F2) = 0.091 | Δρmax = 0.50 e Å−3 |
S = 1.04 | Δρmin = −0.54 e Å−3 |
3550 reflections | Extinction correction: (SHELXL97; Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
219 parameters | Extinction coefficient: 0.0013 (3) |
0 restraints |
V(H2PO2)3 | V = 1547.89 (9) Å3 |
Mr = 491.8 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.4985 (3) Å | µ = 1.88 mm−1 |
b = 11.7771 (5) Å | T = 293 K |
c = 11.5999 (4) Å | 0.15 × 0.05 × 0.04 mm |
β = 99.807 (2)° |
Nonius KappaCCD diffractometer | 2426 reflections with I > 2σ(I) |
20258 measured reflections | Rint = 0.117 |
3550 independent reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.091 | Only H-atom coordinates refined |
S = 1.04 | Δρmax = 0.50 e Å−3 |
3550 reflections | Δρmin = −0.54 e Å−3 |
219 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
V1 | 0.24603 (7) | 0.18513 (6) | 0.69692 (7) | 0.01900 (19) | |
V2 | 0.22812 (6) | 0.20319 (7) | 0.18963 (7) | 0.0203 (2) | |
P1 | 0.35198 (11) | −0.02754 (11) | 0.30844 (13) | 0.0302 (3) | |
P2 | −0.04238 (10) | 0.22262 (11) | 0.06807 (11) | 0.0245 (3) | |
P3 | 0.47390 (11) | 0.34106 (12) | 0.23653 (12) | 0.0281 (3) | |
P4 | 0.30125 (14) | 0.08384 (12) | 0.95864 (12) | 0.0357 (4) | |
P5 | 0.23503 (15) | 0.41320 (12) | 0.84204 (14) | 0.0399 (4) | |
P6 | 0.11404 (12) | 0.20824 (14) | 0.42549 (12) | 0.0334 (3) | |
O1 | 0.2886 (3) | 0.5289 (3) | 0.8650 (3) | 0.0331 (8) | |
O2 | 0.3095 (3) | −0.1342 (3) | 0.3592 (3) | 0.0320 (8) | |
O3 | −0.1071 (3) | 0.3117 (3) | 0.1251 (3) | 0.0303 (8) | |
O4 | 0.2596 (3) | 0.1751 (3) | 1.0298 (3) | 0.0377 (9) | |
O5 | 0.3366 (3) | 0.1189 (3) | 0.8447 (3) | 0.0302 (8) | |
O6 | 0.6033 (3) | 0.3188 (3) | 0.2748 (3) | 0.0300 (8) | |
O7 | 0.2806 (3) | 0.3429 (3) | 0.7523 (3) | 0.0342 (9) | |
O8 | 0.2606 (3) | 0.0390 (3) | 0.2302 (4) | 0.0415 (10) | |
O9 | 0.1450 (3) | 0.2435 (3) | 0.5517 (3) | 0.0301 (8) | |
O10 | 0.0580 (3) | 0.1621 (3) | 0.1444 (3) | 0.0332 (9) | |
O11 | 0.2025 (3) | 0.2393 (4) | 0.3511 (3) | 0.0473 (11) | |
O12 | 0.3974 (3) | 0.2392 (3) | 0.2420 (3) | 0.0409 (10) | |
H1A | 0.401 (5) | 0.035 (5) | 0.403 (5) | 0.049* | |
H1B | 0.448 (5) | −0.043 (5) | 0.247 (5) | 0.049* | |
H2A | −0.118 (5) | 0.142 (5) | 0.003 (5) | 0.049* | |
H2B | −0.001 (5) | 0.278 (5) | −0.027 (5) | 0.049* | |
H3A | 0.451 (4) | 0.423 (5) | 0.311 (5) | 0.049* | |
H3B | 0.462 (5) | 0.387 (5) | 0.127 (5) | 0.049* | |
H4A | 0.205 (5) | 0.013 (5) | 0.935 (5) | 0.049* | |
H4B | 0.387 (4) | 0.013 (5) | 1.006 (5) | 0.049* | |
H5A | 0.224 (5) | 0.365 (5) | 0.936 (5) | 0.049* | |
H5B | 0.116 (5) | 0.411 (5) | 0.829 (5) | 0.049* | |
H6A | 0.091 (5) | 0.095 (5) | 0.421 (5) | 0.049* | |
H6B | 0.007 (5) | 0.249 (5) | 0.386 (5) | 0.049* |
U11 | U22 | U33 | U12 | U13 | U23 | |
V1 | 0.0206 (4) | 0.0182 (4) | 0.0190 (4) | −0.0005 (3) | 0.0058 (3) | −0.0008 (3) |
V2 | 0.0204 (4) | 0.0220 (4) | 0.0187 (4) | −0.0005 (3) | 0.0033 (3) | 0.0005 (4) |
P1 | 0.0271 (7) | 0.0223 (7) | 0.0383 (8) | −0.0031 (6) | −0.0028 (6) | 0.0086 (6) |
P2 | 0.0207 (6) | 0.0283 (7) | 0.0242 (7) | 0.0002 (5) | 0.0027 (5) | −0.0041 (6) |
P3 | 0.0204 (6) | 0.0313 (7) | 0.0329 (8) | 0.0017 (6) | 0.0050 (5) | 0.0047 (6) |
P4 | 0.0600 (10) | 0.0244 (7) | 0.0273 (8) | 0.0120 (7) | 0.0201 (7) | 0.0067 (6) |
P5 | 0.0637 (10) | 0.0181 (7) | 0.0469 (10) | −0.0038 (7) | 0.0351 (8) | −0.0032 (7) |
P6 | 0.0290 (7) | 0.0503 (9) | 0.0208 (7) | −0.0022 (7) | 0.0035 (5) | −0.0003 (7) |
O1 | 0.046 (2) | 0.0171 (17) | 0.034 (2) | 0.0030 (16) | 0.0025 (17) | −0.0014 (16) |
O2 | 0.045 (2) | 0.0203 (18) | 0.031 (2) | −0.0015 (16) | 0.0077 (16) | 0.0057 (15) |
O3 | 0.0289 (17) | 0.0278 (19) | 0.038 (2) | 0.0020 (16) | 0.0153 (15) | −0.0021 (16) |
O4 | 0.061 (2) | 0.032 (2) | 0.023 (2) | 0.0132 (19) | 0.0158 (18) | 0.0015 (16) |
O5 | 0.0291 (18) | 0.043 (2) | 0.0199 (18) | 0.0078 (16) | 0.0071 (15) | 0.0030 (16) |
O6 | 0.0160 (15) | 0.049 (2) | 0.0257 (18) | 0.0016 (16) | 0.0048 (13) | 0.0000 (17) |
O7 | 0.043 (2) | 0.027 (2) | 0.036 (2) | −0.0029 (17) | 0.0155 (17) | −0.0055 (16) |
O8 | 0.0305 (19) | 0.029 (2) | 0.059 (3) | 0.0004 (17) | −0.0079 (18) | 0.0171 (19) |
O9 | 0.0386 (19) | 0.0309 (19) | 0.0213 (18) | 0.0118 (16) | 0.0067 (15) | 0.0007 (15) |
O10 | 0.0246 (17) | 0.0252 (19) | 0.047 (2) | 0.0027 (15) | −0.0034 (16) | 0.0076 (17) |
O11 | 0.051 (2) | 0.068 (3) | 0.026 (2) | −0.016 (2) | 0.0163 (18) | −0.007 (2) |
O12 | 0.0247 (18) | 0.044 (2) | 0.050 (2) | −0.0100 (17) | −0.0043 (17) | 0.0121 (19) |
V1—O7 | 1.984 (3) | P3—O6 | 1.502 (3) |
V1—O1i | 1.991 (3) | P3—H3A | 1.35 (6) |
V1—O9 | 1.998 (3) | P3—H3B | 1.37 (6) |
V1—O6ii | 2.004 (3) | P4—O4 | 1.484 (4) |
V1—O3iii | 2.006 (3) | P4—O5 | 1.505 (4) |
V1—O5 | 2.007 (3) | P4—H4A | 1.38 (6) |
V2—O4iv | 1.976 (3) | P4—H4B | 1.34 (5) |
V2—O12 | 1.984 (3) | P5—O7 | 1.493 (4) |
V2—O11 | 1.990 (4) | P5—O1 | 1.500 (4) |
V2—O10 | 1.996 (3) | P5—H5A | 1.25 (6) |
V2—O8 | 2.010 (4) | P5—H5B | 1.36 (5) |
V2—O2v | 2.023 (3) | P6—O11 | 1.488 (4) |
P1—O8 | 1.488 (4) | P6—O9 | 1.505 (3) |
P1—O2 | 1.504 (3) | P6—H6A | 1.36 (6) |
P1—H1A | 1.36 (6) | P6—H6B | 1.32 (5) |
P1—H1B | 1.43 (5) | O1—V1vi | 1.991 (3) |
P2—O3 | 1.504 (3) | O2—V2vii | 2.023 (3) |
P2—O10 | 1.508 (3) | O3—V1viii | 2.006 (3) |
P2—H2A | 1.42 (5) | O4—V2ix | 1.976 (3) |
P2—H2B | 1.43 (5) | O6—V1x | 2.004 (3) |
P3—O12 | 1.495 (4) | ||
O7—V1—O1i | 177.79 (15) | O3—P2—H2B | 106 (2) |
O7—V1—O9 | 90.39 (15) | O10—P2—H2B | 110 (2) |
O1i—V1—O9 | 87.82 (14) | H2A—P2—H2B | 99 (3) |
O7—V1—O6ii | 90.56 (15) | O12—P3—O6 | 114.1 (2) |
O1i—V1—O6ii | 90.71 (15) | O12—P3—H3A | 112 (2) |
O9—V1—O6ii | 89.14 (14) | O6—P3—H3A | 103 (2) |
O7—V1—O3iii | 88.90 (14) | O12—P3—H3B | 113 (2) |
O1i—V1—O3iii | 89.90 (14) | O6—P3—H3B | 106 (2) |
O9—V1—O3iii | 93.05 (14) | H3A—P3—H3B | 108 (3) |
O6ii—V1—O3iii | 177.75 (15) | O4—P4—O5 | 116.8 (2) |
O7—V1—O5 | 92.36 (15) | O4—P4—H4A | 103 (2) |
O1i—V1—O5 | 89.51 (15) | O5—P4—H4A | 109 (2) |
O9—V1—O5 | 175.46 (15) | O4—P4—H4B | 121 (2) |
O6ii—V1—O5 | 87.22 (13) | O5—P4—H4B | 104 (2) |
O3iii—V1—O5 | 90.62 (14) | H4A—P4—H4B | 102 (3) |
O4iv—V2—O12 | 89.79 (17) | O7—P5—O1 | 116.4 (2) |
O4iv—V2—O11 | 176.70 (17) | O7—P5—H5A | 117 (3) |
O12—V2—O11 | 87.77 (16) | O1—P5—H5A | 111 (3) |
O4iv—V2—O10 | 92.31 (16) | O7—P5—H5B | 113 (2) |
O12—V2—O10 | 177.05 (15) | O1—P5—H5B | 114 (2) |
O11—V2—O10 | 90.21 (16) | H5A—P5—H5B | 81 (3) |
O4iv—V2—O8 | 90.13 (16) | O11—P6—O9 | 115.2 (2) |
O12—V2—O8 | 90.02 (15) | O11—P6—H6A | 112 (2) |
O11—V2—O8 | 92.08 (18) | O9—P6—H6A | 108 (2) |
O10—V2—O8 | 87.90 (14) | O11—P6—H6B | 113 (2) |
O4iv—V2—O2v | 87.75 (14) | O9—P6—H6B | 107 (2) |
O12—V2—O2v | 92.00 (15) | H6A—P6—H6B | 100 (3) |
O11—V2—O2v | 90.13 (17) | P5—O1—V1vi | 136.4 (2) |
O10—V2—O2v | 90.16 (14) | P1—O2—V2vii | 138.6 (2) |
O8—V2—O2v | 177.06 (15) | P2—O3—V1viii | 135.3 (2) |
O8—P1—O2 | 115.8 (2) | P4—O4—V2ix | 140.5 (2) |
O8—P1—H1A | 111 (2) | P4—O5—V1 | 132.7 (2) |
O2—P1—H1A | 105 (2) | P3—O6—V1x | 135.8 (2) |
O8—P1—H1B | 107 (2) | P5—O7—V1 | 132.1 (2) |
O2—P1—H1B | 115 (2) | P1—O8—V2 | 137.1 (2) |
H1A—P1—H1B | 103 (3) | P6—O9—V1 | 137.1 (2) |
O3—P2—O10 | 117.3 (2) | P2—O10—V2 | 131.1 (2) |
O3—P2—H2A | 113 (2) | P6—O11—V2 | 136.0 (3) |
O10—P2—H2A | 110 (2) | P3—O12—V2 | 135.4 (2) |
Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) x−1/2, −y+1/2, z+1/2; (iii) x+1/2, −y+1/2, z+1/2; (iv) x, y, z−1; (v) −x+1/2, y+1/2, −z+1/2; (vi) −x+1/2, y+1/2, −z+3/2; (vii) −x+1/2, y−1/2, −z+1/2; (viii) x−1/2, −y+1/2, z−1/2; (ix) x, y, z+1; (x) x+1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | V(H2PO2)3 |
Mr | 491.8 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 11.4985 (3), 11.7771 (5), 11.5999 (4) |
β (°) | 99.807 (2) |
V (Å3) | 1547.89 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.88 |
Crystal size (mm) | 0.15 × 0.05 × 0.04 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20258, 3550, 2426 |
Rint | 0.117 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.091, 1.04 |
No. of reflections | 3550 |
No. of parameters | 219 |
H-atom treatment | Only H-atom coordinates refined |
Δρmax, Δρmin (e Å−3) | 0.50, −0.54 |
Computer programs: COLLECT (Nonius, 1998), DIRAX/LSQ (Duisenberg, 1992), EVALCCD (Duisenberg, 1998), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2005), WinGX (Farrugia, 1999).
V1—O7 | 1.984 (3) | P1—H1B | 1.43 (5) |
V1—O5 | 2.007 (3) | P2—O10 | 1.508 (3) |
V2—O4i | 1.976 (3) | P4—O4 | 1.484 (4) |
V2—O2ii | 2.023 (3) | P5—H5A | 1.25 (6) |
O7—V1—O1iii | 177.79 (15) | O12—P3—O6 | 114.1 (2) |
O9—V1—O3iv | 93.05 (14) | H3A—P3—H3B | 108 (3) |
O9—V1—O5 | 175.46 (15) | O4—P4—H4A | 103 (2) |
O6v—V1—O5 | 87.22 (13) | O4—P4—H4B | 121 (2) |
O3—P2—O10 | 117.3 (2) | H5A—P5—H5B | 81 (3) |
Symmetry codes: (i) x, y, z−1; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+1/2, y−1/2, −z+3/2; (iv) x+1/2, −y+1/2, z+1/2; (v) x−1/2, −y+1/2, z+1/2. |
During the past few decades, several metal hypophosphite compounds have been reported in the literature, incorporating alkali, alkaline earth (Galigné & Dumas, 1973; Kuratieva et al., 2005), transition (Marcos et al., 1993, 1994; Kuratieva et al., 2002), lanthanide and group 14 metals. Several line of interest have led us to investigate this class of compounds. Among them are (i) the study of low-dimensional structures suitable for catalytic or ion-exchange properties supported by the low degree of connectivity of the oxoanion H2PO2- ; (ii) the characterization of lanthanide ions involving the use of the (H2PO2)- ligand (Seddon et al., 1999; Tanner et al., 1999, 2000); and (iii) the application of anhydrous metal hypophosphites as mild reducing agents, reagents in catalytic syntheses of organophosphorous compounds and antioxidants (Naumova et al., 2004a,b ?????). Another interest was the magnetic properties of some hypophosphite complexes of transtion metals (Marcos et al., 1992; Yoshida et al., 2009).
Although a number of crystal structures of hypophosphites are known, there is a lack of structural data for anhydrous transition metal hypophosphites. In fact, only two such compounds have been characterized by X-ray diffraction, namely Fe(H2PO2)3 (Kuratieva & Naumov, 2006), exhibiting a layered structure built up from iron hypophosphite chains, and Zn(H2PO2)2 (Tanner et al., 1997), comprising a two-dimensional structure.
At the same time and to the best of our knowledge, only one vanadium hypophosphite has been isolated. It is hydrated and exhibits a one-dimensional structure (Le Bail et al., 1994) where the metallic cation is involved in an oxovanadium group. The aim of our study is to enlarge the hypophosphite family compounds, especially for metals like vanadium, which adopts different coordination geometries.
Our study reports the first anhydrous vanadium phosphinate. The asymmetric unit (Fig. 1) contains two independent V atoms and six phosphinate ions, all situated on general positions. Atoms V1 and V2 both exhibit a slightly distorted octahedral geometry, where the mean values of the V—O bonds are 1.998 (3) Å and 1.997 (3) Å, respectively. The hypophosphite groups have pseudotetrahedral geometry. The bond distances and angles (Table 1) in the H2PO2- pseudotetrahedra are similar to those observed in other hypophosphite compounds. The VIIIO6 octahedra share all their vertices with six distinct pseudotetrahedra, and each H2PO2- anion has both of its O atoms linked to two adjacent metallic centers, acting as a bidentate bridging ligand. This type of connection involves the formation of V—O—P—O—V chains through the three directions of the space, leading therefore to a three-dimensional network. The junction of the V1, V2, O and P atoms along the a axis describes helicoidal chains, while along the c-axis direction it forms a sawtooth curve (Figs. 3a and 3b). Along the b axis, the V2—O—P—O—V2 chains follow a helicoidal pattern with an elliptical cross section and the V1—O—P—O—V1 chains might be assimilated to a sinusoid (Fig. 3c). While in the oxovanadium(IV) hypophosphite (Le Bail et al., 1994) the one-dimensional aspect of the structure is related to the anisotropic environment of the vanadium, in the title compound the three-dimensionality is favoured by the isotropic bonding scheme of the cation owing to its +3 oxidation state.