metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

A second polymorph of [H3N(CH2)3NH3][V4O10]

aSchool of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, Scotland
*Correspondence e-mail: pl@st-and.ac.uk

(Received 29 September 2006; accepted 3 October 2006; online 31 October 2006)

The title compound, propane-1,3-diammonium tetra­vanadate, (C3H12N2)[V4O10], represents a second polymorph of composition β-[H3N(CH2)3NH3][V4O10]. It differs from the α polymorph [Riou & Ferey (1995[Riou, D. & Ferey, G. (1995). J. Solid State Chem. 120, 137-145.]). J. Solid State Chem. 120, 137–145] in the conformation of the propane-1,3-diammonium dication which, in the present example, lies on a twofold axis and adopts a synsyn rather than a synanti conformation. The twofold symmetry of this conformation thus co-operates with the vanadium oxide framework to result in a higher symmetry for the resultant crystal, viz. C2/c versus P21/n. The overall unit-cell parameters for the two polymorphs are similar, and the inorganic layer within each is topologically identical, comprising edge-sharing VIVO5 square pyramids linked together via corner-sharing with VVO4 tetra­hedra. A key difference between the two polymorphs is a `head-to-head' versus `head-to-tail' stacking of the vanadyl groups in adjacent layers.

Comment

The title compound, β-[H3N(CH2)3NH3][V4O10], (I)[link], was prepared during a more general survey of the hydro­thermal chemistry of vanadium in the presence of organic templating agents and HF (Aldous et al., 2006[Aldous, D. W., Goff, R. J., Attfield, J. P. & Lightfoot, P. (2006). Inorg. Chem. In the press.]). Specifically, it arose from an attempt to prepare a structural analogue of an inter­esting polar material, [H3N(CH2)2NH3][VOF4(H2O)] (Stephens & Lightfoot, 2005[Stephens, N. F. & Lightfoot, P. (2005). J. Mater. Chem. 15, 4298-4300.]). An α polymorph of the same composition has been reported previously (Riou & Ferey, 1995[Riou, D. & Ferey, G. (1995). J. Solid State Chem. 120, 137-145.]). The different polymorphs arise from quite similar hydro­thermal reactions, both employing HF, but the α polymorph also

[Scheme 1]
included SiO2 in the reaction mixture and the synthesis being carried out at a higher temperature of 453 K and a lower pH of 4–5.

The α form has similar unit-cell parameters to (I)[link] [P21/n, a = 7.9991 (1) Å, b = 10.001 (1) Å and c = 15.703 (1) Å, and β = 100.49 (1)° at 298 K]. Although the structural units are the same in each case, the higher symmetry in (I)[link] is perhaps encouraged by the additional symmetry within the organic dication, which lies on a twofold axis in the β form (Fig. 1[link]). A projection of the unit cell of (I)[link] along the c axis, together with the corresponding view for the α form, is shown in Fig. 2[link].

There are two unique V sites in the structure of (I)[link], atom V1 being five-coordinated by O and atom V2 being four-coordinate. Bond-valence sum analysis (Brown & Altermatt, 1985[Brown, I. D. & Altermatt, D. (1985). Acta Cryst. B41, 244-247.]) shows these sites to be VIV and VV, respectively. The compound exhibits a layered crystal structure comprised of edge-sharing V1O5 square pyramids linked together via corner-sharing V2O4 tetra­hedra to form continuous inorganic sheets in the ab plane. These are separated by hydrogen-bonded organic cations along the c axis. Similar structural building units are known in vanadium oxide chemistry (Zavalij & Whittingham, 1999[Zavalij, P. Y. & Whittingham, M. S. (1999). Acta Cryst. B55, 627-663.]).

The most significant difference in the unit-cell parameters of the two forms is the considerable reduction in the c axis of the β form. A comparative view perpendicular to the c axis is shown in Fig. 3[link], and the difference in c dimensions may be explained by the more extensive hydrogen bonding in the β form (Table 2[link]), whereby each N—H bond acts as a donor. This difference in inter­layer hydrogen bonding is co-operative, with a different stacking of adjacent vanadium oxide layers, such that the vanadyl bonds of the VO5 pyramids take up a `head-to-head' arrangement in the β polymorph, in contrast with a `head-to-tail' configuration in the α polymorph. This leads to a short inter­layer O5⋯O5([-x, y, {1\over2}-z]) contact of 2.770 (3) Å in (I)[link], which does not occur in the α polymorph. We note that polymorphism has also been observed in two closely related compositions incorporating dications of ethyl­enediamine and piperazine (Zhang et al., 1996[Zhang, Y., Haushaler, R. C. & Clearfield, A. (1996). Inorg. Chem. 35, 4950-4956.]).

[Figure 1]
Figure 1
The asymmetric unit of compound (I)[link], with displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) −[{1\over 2}] + x, [{1\over 2}] + y, z; (ii) −[{1\over 2}] − x, [{1\over 2}] − y, − z; (iii) −x, 1 − y, −z; (iv) −1 − x, y, [{1\over 2}] − z.]
[Figure 2]
Figure 2
Projections of the structures of the α form (left) and the β form (right) down [001]. Note the relative positions and conformations of the organic cation.
[Figure 3]
Figure 3
Projections of the structures perpendicular to the c axis, showing the α form along [[\overline{1}][\overline{1}]0] (left) and the β form along [110] (right).

Experimental

Vanadium pentoxide (0.1819 g), water (5 ml) and a 48% solution of HF (0.5 ml) were heated in a polypropyl­ene bottle at 373 K for 1 h. To the resulting yellow solution was added ethyl­ene glycol (5 ml). Finally, propane-1,3-diamine (0.5 ml) was added to give a green solution of pH 10. This was heated in a polypropyl­ene bottle at 373 K for 5 d. The pH remained constant over this time. The final product was isolated as dark-blue crystals, filtered off, washed in water and allowed to dry overnight at room temperature. Elemental analysis confirmed phase purity; found: C 8.34, H 2.21, N 6.41%; (C3H12N2)[V4O10] requires: C 8.19, H 2.75, N 6.37%. Additionally, powder X-ray diffraction of the product at room temperature confirmed that the bulk material was the new β polymorph, with no indication of the presence of the α polymorph.

Crystal data
  • (C3H12N2)[V4O10]

  • Mr = 439.91

  • Monoclinic, C 2/c

  • a = 7.977 (3) Å

  • b = 10.099 (3) Å

  • c = 15.210 (5) Å

  • β = 104.075 (11)°

  • V = 1188.6 (7) Å3

  • Z = 4

  • Dx = 2.458 Mg m−3

  • Mo Kα radiation

  • μ = 3.10 mm−1

  • T = 93 (2) K

  • Needle, blue

  • 0.15 × 0.01 × 0.01 mm

Data collection
  • Rigaku Mercury70 (2 × 2 bin mode) CCD area-detector diffractometer

  • ω scans

  • Absorption correction: multi-scan (SADABS; Bruker, 1999[Bruker (1999). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.84, Tmax = 0.97

  • 3674 measured reflections

  • 1075 independent reflections

  • 997 reflections with I > 2σ(I)

  • Rint = 0.019

  • θmax = 25.3°

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.025

  • wR(F2) = 0.059

  • S = 1.13

  • 1075 reflections

  • 87 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0213P)2 + 5.2306P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 0.37 e Å−3

  • Δρmin = −0.36 e Å−3

Table 1
Selected bond lengths (Å)

V1—O1 1.635 (2)
V1—O2 1.705 (2)
V1—O3 1.737 (2)
V1—O4 1.838 (2)
V2—O5 1.607 (2)
V2—O2i 1.921 (2)
V2—O3ii 1.952 (2)
V2—O4 1.969 (2)
V2—O4iii 1.982 (2)
Symmetry codes: (i) [x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]; (ii) [-x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]; (iii) -x, -y+1, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯O1iv 0.91 2.13 2.932 (3) 147
N1—H2⋯O3ii 0.91 2.02 2.911 (3) 164
N1—H3⋯O5v 0.91 2.04 2.947 (3) 176
Symmetry codes: (ii) [-x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]; (iv) [-x, y, -z+{\script{1\over 2}}]; (v) [x-{\script{1\over 2}}, y-{\script{1\over 2}}, z].

Space group C2/c was chosen on the basis of the systematic absences and successful refinement of the structure. No unusual problems occurred during the refinement. H atoms were refined as riding on their carrier atoms, with C—H = 0.99 Å and N—H = 0.91 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(N).

Data collection: SMART (Bruker, 1997[Bruker (1997). SMART, SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1997[Bruker (1997). SMART, SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: DIAMOND (Brandenburg, 2001[Brandenburg, K. (2001). DIAMOND. Release 2.1e. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information


Comment top

The title compound, β-[H3N(CH2)3NH3][V4O10], (I), was prepared during a more general survey of the hydrothermal chemistry of vanadium in the presence of organic templating agents and HF (Aldous et al., 2006). Specifically, it arose from an attempt to prepare a structural analogue of an interesting polar material, [H3N(CH2)2NH3][VOF4(H2O)] (Stephens & Lightfoot, 2005). An α-polymorph of the same composition has been reported previously (Riou & Ferey, 1995). The different polymorphs arise from quite similar hydrothermal reactions, both employing HF, but the α-polymorph also included SiO2 in the reaction mixture and the synthesis was carried out at a higher temperature of 453 K and a lower pH of 4–5.

The α-form has similar unit-cell parameters to (I) [P21/n, a = 7. 9991 (1), b = 10.001 (1) and c = 15.703 (1) Å, and β = 100.49 (1)° at 298 K]. Although the structural units are the same in each case, the higher symmetry in (I) is perhaps encouraged by the additional symmetry within the organic moiety, which lies on a twofold axis in the β-form (Fig. 1). A projection of the unit cell of (I) along the c axis, together with the corresponding view for the α-form, is shown in Fig. 2.

There are two unique V sites in the structure of (I), atom V1 being five-coordinated by O and atom V2 being four-coordinate. Bond-valence sum analysis (Brown & Altermatt, 1985) shows these sites to be VIV and VV, respectively. The compound exhibits a layered crystal structure comprised of edge-sharing V1O5 square pyramids linked together via corner-sharing V2O4 tetrahedra to form continuous inorganic sheets in the ab plane. These are separated by hydrogen-bonded organic cations along the c axis. Similar structural building units are known in vanadium oxide chemistry (Zavalij & Whittingham, 1999).

The most significant difference in the unit-cell parameters of the two forms is the considerable reduction in the c axis of the β-form. A comparative view perpendicular to the c axis is shown in Fig. 3, and the difference in c dimensions may be explained by the more extensive hydrogen bonding in the β-form (Table 2), whereby each N—H bond acts as a donor. This difference in interlayer hydrogen bonding is cooperative with a different stacking of adjacent vanadium oxide layers, such that the vanadyl bonds of the VO5 pyramids take up a `head-to-head' arrangement in the β-polymorph, in contrast with a `head-to-tail' configuration in the α-polymorph. This leads to a short interlayer O5···O5(Symmetry code?) contact of 2.77 Å in (I), which does not occur in the α-polymorph. We note that polymorphism has also been observed in two closely related compositions incorporating dications of ethylenediamine and piperazine (Zhang et al., 1996).

Experimental top

Vanadium pentoxide (0.1819 g), water (5 ml) and a 48% solution of HF (0.5 ml) were heated in a polypropylene bottle at 373 K for 1 h. To the resulting yellow solution was added ethylene glycol (5 ml). Finally, 1,3-diaminopropane (0.5 ml) was added to give a green solution of pH 10. This was heated in a polypropylene bottle at 373 K for 5 d. The pH remained constant over this time. The final product was isolated as dark-blue crystals, filtered off, washed in water and allowed to dry overnight at room temperature. Elemental analysis confirmed phase purity: found: C 8.34, H 2.21, N 6.41%; (C2H12N2)[V4O10] requires: C 8.19, H 2.75, N 6.37%. Additionally, powder X-ray diffraction of the product at room temperature confirmed that the bulk material was the new β-polymorph, with no indication of the presence of the α-polymorph.

Refinement top

Space group C2/c was chosen on the basis of the systematic absences and successful refinement of the structure. No unusual problems occurred during the refinement. H atoms were refined as riding on their carrier atoms, with C—H = 0.99 Å and N—H = 0.91 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(N). [Please check added text].

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The building unit of compound (I), with displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) −1/2 + x, 1/2 + y, z; (ii) −1/2 − x, 1/2 − y, − z; (iii) −x, 1 − y, −z; (iv) −1 − x, y, 1/2 − z.]
[Figure 2] Fig. 2. Projections of the structures of (a) the α-form and (b) the β-form down [001]. Note the relative positions and conformations of the organic cation.
[Figure 3] Fig. 3. Projections of the structures perpendicular to the c axis. (a) The α-form along [110]. (b) The β-form along [110].
propane-1,3-diammonium tetravanadate top
Crystal data top
C3H12N22+·V4O102F(000) = 864
Mr = 439.91Dx = 2.458 Mg m3
Monoclinic, C2/cMelting point: not measured K
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 7.977 (3) ÅCell parameters from 2076 reflections
b = 10.099 (3) Åθ = 2.8–25.4°
c = 15.210 (5) ŵ = 3.10 mm1
β = 104.075 (11)°T = 93 K
V = 1188.6 (7) Å3Needle, blue
Z = 40.15 × 0.01 × 0.01 mm
Data collection top
Make? Mercury70 (2x2 bin mode) CCD area-detector
diffractometer
1075 independent reflections
Radiation source: Rotating anode997 reflections with I > 2σ(I)
Confocal monochromatorRint = 0.019
Detector resolution: 14.6306 pixels mm-1θmax = 25.3°, θmin = 2.8°
ω scansh = 79
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
k = 1210
Tmin = 0.84, Tmax = 0.97l = 1817
3674 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.059H-atom parameters constrained
S = 1.13 w = 1/[σ2(Fo2) + (0.0213P)2 + 5.2306P]
where P = (Fo2 + 2Fc2)/3
1075 reflections(Δ/σ)max = 0.001
87 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.36 e Å3
Crystal data top
C3H12N22+·V4O102V = 1188.6 (7) Å3
Mr = 439.91Z = 4
Monoclinic, C2/cMo Kα radiation
a = 7.977 (3) ŵ = 3.10 mm1
b = 10.099 (3) ÅT = 93 K
c = 15.210 (5) Å0.15 × 0.01 × 0.01 mm
β = 104.075 (11)°
Data collection top
Make? Mercury70 (2x2 bin mode) CCD area-detector
diffractometer
1075 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
997 reflections with I > 2σ(I)
Tmin = 0.84, Tmax = 0.97Rint = 0.019
3674 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.059H-atom parameters constrained
S = 1.13Δρmax = 0.37 e Å3
1075 reflectionsΔρmin = 0.36 e Å3
87 parameters
Special details top

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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
V10.01338 (6)0.19883 (5)0.02763 (3)0.00494 (15)
V20.14358 (6)0.50790 (4)0.05120 (3)0.00451 (14)
O10.0177 (2)0.17039 (19)0.13290 (13)0.0094 (4)
O20.1638 (2)0.12379 (19)0.00601 (13)0.0081 (4)
O30.1929 (2)0.13628 (19)0.04983 (13)0.0071 (4)
O40.0055 (2)0.37790 (19)0.01054 (13)0.0067 (4)
O50.0656 (3)0.5388 (2)0.15692 (14)0.0106 (4)
N10.2888 (3)0.2339 (2)0.22273 (17)0.0107 (5)
H10.18930.19100.24980.016*
H20.27320.27910.17360.016*
H30.37540.17380.20480.016*
C10.3355 (4)0.3290 (3)0.2886 (2)0.0112 (6)
H40.23920.39240.30890.013*
H50.34910.27910.34250.013*
C20.50000.4059 (4)0.25000.0131 (9)
H60.52130.46410.29850.016*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
V10.0043 (2)0.0035 (3)0.0071 (3)0.00007 (18)0.00145 (18)0.00048 (19)
V20.0042 (2)0.0039 (3)0.0054 (3)0.00008 (18)0.00114 (17)0.00049 (18)
O10.0113 (10)0.0088 (10)0.0080 (10)0.0005 (8)0.0023 (8)0.0009 (8)
O20.0067 (9)0.0044 (9)0.0142 (11)0.0010 (8)0.0047 (8)0.0026 (8)
O30.0071 (9)0.0051 (10)0.0091 (10)0.0027 (8)0.0018 (7)0.0002 (8)
O40.0063 (9)0.0042 (10)0.0102 (10)0.0000 (8)0.0034 (8)0.0005 (8)
O50.0127 (10)0.0090 (10)0.0094 (10)0.0008 (9)0.0013 (8)0.0003 (8)
N10.0085 (11)0.0121 (13)0.0120 (13)0.0004 (10)0.0037 (9)0.0002 (10)
C10.0108 (14)0.0108 (15)0.0122 (15)0.0035 (12)0.0030 (11)0.0021 (12)
C20.019 (2)0.005 (2)0.017 (2)0.0000.0073 (18)0.000
Geometric parameters (Å, º) top
V1—O11.635 (2)O3—V2ii1.9516 (19)
V1—O21.705 (2)O4—V2iii1.9821 (19)
V1—O31.737 (2)N1—C11.500 (4)
V1—O41.838 (2)N1—H10.9100
V2—O51.607 (2)N1—H20.9100
V2—O2i1.921 (2)N1—H30.9100
V2—O3ii1.952 (2)C1—C21.515 (4)
V2—O41.969 (2)C1—H40.9900
V2—O4iii1.982 (2)C1—H50.9900
V2—V2iii3.0714 (12)C2—C1v1.515 (4)
O2—V2iv1.921 (2)C2—H60.9900
O1—V1—O2109.06 (10)V1—O2—V2iv146.14 (12)
O1—V1—O3112.96 (10)V1—O3—V2ii135.83 (11)
O2—V1—O3107.04 (10)V1—O4—V2122.34 (10)
O1—V1—O4109.46 (9)V1—O4—V2iii135.52 (10)
O2—V1—O4108.05 (9)V2—O4—V2iii102.03 (9)
O3—V1—O4110.13 (9)C1—N1—H1109.5
O5—V2—O2i108.71 (10)C1—N1—H2109.5
O5—V2—O3ii104.51 (9)H1—N1—H2109.5
O2i—V2—O3ii88.66 (9)C1—N1—H3109.5
O5—V2—O4109.11 (9)H1—N1—H3109.5
O2i—V2—O4141.76 (9)H2—N1—H3109.5
O3ii—V2—O487.26 (8)N1—C1—C2113.7 (2)
O5—V2—O4iii103.68 (9)N1—C1—H4108.8
O2i—V2—O4iii87.95 (8)C2—C1—H4108.8
O3ii—V2—O4iii151.18 (8)N1—C1—H5108.8
O4—V2—O4iii77.97 (9)C2—C1—H5108.8
O5—V2—V2iii111.26 (8)H4—C1—H5107.7
O2i—V2—V2iii118.72 (6)C1v—C2—C1118.3 (4)
O3ii—V2—V2iii122.32 (6)C1v—C2—H6107.7
O4—V2—V2iii39.14 (6)C1—C2—H6107.7
O4iii—V2—V2iii38.83 (6)
Symmetry codes: (i) x1/2, y+1/2, z; (ii) x1/2, y+1/2, z; (iii) x, y+1, z; (iv) x+1/2, y1/2, z; (v) x1, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1vi0.912.132.932 (3)147
N1—H2···O3ii0.912.022.911 (3)164
N1—H3···O5vii0.912.042.947 (3)176
Symmetry codes: (ii) x1/2, y+1/2, z; (vi) x, y, z+1/2; (vii) x1/2, y1/2, z.

Experimental details

Crystal data
Chemical formulaC3H12N22+·V4O102
Mr439.91
Crystal system, space groupMonoclinic, C2/c
Temperature (K)93
a, b, c (Å)7.977 (3), 10.099 (3), 15.210 (5)
β (°) 104.075 (11)
V3)1188.6 (7)
Z4
Radiation typeMo Kα
µ (mm1)3.10
Crystal size (mm)0.15 × 0.01 × 0.01
Data collection
DiffractometerMake? Mercury70 (2x2 bin mode) CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.84, 0.97
No. of measured, independent and
observed [I > 2σ(I)] reflections
3674, 1075, 997
Rint0.019
(sin θ/λ)max1)0.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.059, 1.13
No. of reflections1075
No. of parameters87
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.37, 0.36

Computer programs: SMART (Bruker, 1997), SMART, SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2001), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top
V1—O11.635 (2)V2—O2i1.921 (2)
V1—O21.705 (2)V2—O3ii1.952 (2)
V1—O31.737 (2)V2—O41.969 (2)
V1—O41.838 (2)V2—O4iii1.982 (2)
V2—O51.607 (2)
Symmetry codes: (i) x1/2, y+1/2, z; (ii) x1/2, y+1/2, z; (iii) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1iv0.912.132.932 (3)147
N1—H2···O3ii0.912.022.911 (3)164
N1—H3···O5v0.912.042.947 (3)176
Symmetry codes: (ii) x1/2, y+1/2, z; (iv) x, y, z+1/2; (v) x1/2, y1/2, z.
 

Acknowledgements

The authors thank Professor Alex Slawin for assistance in data collection, and the University of St Andrews for funding.

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