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

Stephens, N.F.; Lightfoot, P.

doi:10.1107/S0108270106040777

metal-organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 62| Part 11| November 2006| Pages m566-m568

doi:10.1107/S0108270106040777

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

Nicholas F. Stephens ^a and Philip Lightfoot ^a ^*

^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 ). 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 syn–syn rather than a syn–anti 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 V^IVO₅ square pyramids linked together via corner-sharing with V^VO₄ 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), 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 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) [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) is perhaps encouraged by the additional symmetry within the organic dication, 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 V^IV and V^V, 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 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), 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 ).

Figure 1
The asymmetric unit of compound (I)

, 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
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
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]
M_r = 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
D_x = 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 ) T_min = 0.84, T_max = 0.97
3674 measured reflections
1075 independent reflections
997 reflections with I > 2σ(I)
R_int = 0.019
θ_max = 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(F_o²) + (0.0213P)² + 5.2306P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.37 e Å⁻³
Δρ_min = −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	D⋯A	D—H⋯A
N1—H1⋯O1^iv	0.91	2.13	2.932 (3)	147
N1—H2⋯O3ⁱⁱ	0.91	2.02	2.911 (3)	164
N1—H3⋯O5^v	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 U_iso(H) = 1.2U_eq(C) or 1.5U_eq(N).

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S0108270106040777/sk3063sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270106040777/sk3063Isup2.hkl

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 V^IV and V^V, 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.

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

	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.]
	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.
	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⁺·V₄O₁₀²⁻	F(000) = 864
M_r = 439.91	D_x = 2.458 Mg m⁻³
Monoclinic, C2/c	Melting point: not measured K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 7.977 (3) Å	Cell parameters from 2076 reflections
b = 10.099 (3) Å	θ = 2.8–25.4°
c = 15.210 (5) Å	µ = 3.10 mm⁻¹
β = 104.075 (11)°	T = 93 K
V = 1188.6 (7) Å³	Needle, blue
Z = 4	0.15 × 0.01 × 0.01 mm

Data collection top

Make? Mercury70 (2x2 bin mode) CCD area-detector diffractometer	1075 independent reflections
Radiation source: Rotating anode	997 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.019
Detector resolution: 14.6306 pixels mm^-1	θ_max = 25.3°, θ_min = 2.8°
ω scans	h = −7→9
Absorption correction: multi-scan (SADABS; Bruker, 1997)	k = −12→10
T_min = 0.84, T_max = 0.97	l = −18→17
3674 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.059	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0213P)² + 5.2306P] where P = (F_o² + 2F_c²)/3
1075 reflections	(Δ/σ)_max = 0.001
87 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₃H₁₂N₂²⁺·V₄O₁₀²⁻	V = 1188.6 (7) Å³
M_r = 439.91	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 7.977 (3) Å	µ = 3.10 mm⁻¹
b = 10.099 (3) Å	T = 93 K
c = 15.210 (5) Å	0.15 × 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)
T_min = 0.84, T_max = 0.97	R_int = 0.019
3674 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.059	H-atom parameters constrained
S = 1.13	Δρ_max = 0.37 e Å⁻³
1075 reflections	Δρ_min = −0.36 e Å⁻³
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

	x	y	z	U_iso*/U_eq
V1	−0.01338 (6)	0.19883 (5)	0.02763 (3)	0.00494 (15)
V2	−0.14358 (6)	0.50790 (4)	0.05120 (3)	0.00451 (14)
O1	−0.0177 (2)	0.17039 (19)	0.13290 (13)	0.0094 (4)
O2	0.1638 (2)	0.12379 (19)	0.00601 (13)	0.0081 (4)
O3	−0.1929 (2)	0.13628 (19)	−0.04983 (13)	0.0071 (4)
O4	0.0055 (2)	0.37790 (19)	0.01054 (13)	0.0067 (4)
O5	−0.0656 (3)	0.5388 (2)	0.15692 (14)	0.0106 (4)
N1	−0.2888 (3)	0.2339 (2)	0.22273 (17)	0.0107 (5)
H1	−0.1893	0.1910	0.2498	0.016*
H2	−0.2732	0.2791	0.1736	0.016*
H3	−0.3754	0.1738	0.2048	0.016*
C1	−0.3355 (4)	0.3290 (3)	0.2886 (2)	0.0112 (6)
H4	−0.2392	0.3924	0.3089	0.013*
H5	−0.3491	0.2791	0.3425	0.013*
C2	−0.5000	0.4059 (4)	0.2500	0.0131 (9)
H6	−0.5213	0.4641	0.2985	0.016*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
V1	0.0043 (2)	0.0035 (3)	0.0071 (3)	0.00007 (18)	0.00145 (18)	0.00048 (19)
V2	0.0042 (2)	0.0039 (3)	0.0054 (3)	−0.00008 (18)	0.00114 (17)	−0.00049 (18)
O1	0.0113 (10)	0.0088 (10)	0.0080 (10)	0.0005 (8)	0.0023 (8)	0.0009 (8)
O2	0.0067 (9)	0.0044 (9)	0.0142 (11)	0.0010 (8)	0.0047 (8)	0.0026 (8)
O3	0.0071 (9)	0.0051 (10)	0.0091 (10)	−0.0027 (8)	0.0018 (7)	−0.0002 (8)
O4	0.0063 (9)	0.0042 (10)	0.0102 (10)	0.0000 (8)	0.0034 (8)	0.0005 (8)
O5	0.0127 (10)	0.0090 (10)	0.0094 (10)	−0.0008 (9)	0.0013 (8)	−0.0003 (8)
N1	0.0085 (11)	0.0121 (13)	0.0120 (13)	−0.0004 (10)	0.0037 (9)	0.0002 (10)
C1	0.0108 (14)	0.0108 (15)	0.0122 (15)	−0.0035 (12)	0.0030 (11)	−0.0021 (12)
C2	0.019 (2)	0.005 (2)	0.017 (2)	0.000	0.0073 (18)	0.000

Geometric parameters (Å, º) top

V1—O1	1.635 (2)	O3—V2ⁱⁱ	1.9516 (19)
V1—O2	1.705 (2)	O4—V2ⁱⁱⁱ	1.9821 (19)
V1—O3	1.737 (2)	N1—C1	1.500 (4)
V1—O4	1.838 (2)	N1—H1	0.9100
V2—O5	1.607 (2)	N1—H2	0.9100
V2—O2ⁱ	1.921 (2)	N1—H3	0.9100
V2—O3ⁱⁱ	1.952 (2)	C1—C2	1.515 (4)
V2—O4	1.969 (2)	C1—H4	0.9900
V2—O4ⁱⁱⁱ	1.982 (2)	C1—H5	0.9900
V2—V2ⁱⁱⁱ	3.0714 (12)	C2—C1^v	1.515 (4)
O2—V2^iv	1.921 (2)	C2—H6	0.9900

O1—V1—O2	109.06 (10)	V1—O2—V2^iv	146.14 (12)
O1—V1—O3	112.96 (10)	V1—O3—V2ⁱⁱ	135.83 (11)
O2—V1—O3	107.04 (10)	V1—O4—V2	122.34 (10)
O1—V1—O4	109.46 (9)	V1—O4—V2ⁱⁱⁱ	135.52 (10)
O2—V1—O4	108.05 (9)	V2—O4—V2ⁱⁱⁱ	102.03 (9)
O3—V1—O4	110.13 (9)	C1—N1—H1	109.5
O5—V2—O2ⁱ	108.71 (10)	C1—N1—H2	109.5
O5—V2—O3ⁱⁱ	104.51 (9)	H1—N1—H2	109.5
O2ⁱ—V2—O3ⁱⁱ	88.66 (9)	C1—N1—H3	109.5
O5—V2—O4	109.11 (9)	H1—N1—H3	109.5
O2ⁱ—V2—O4	141.76 (9)	H2—N1—H3	109.5
O3ⁱⁱ—V2—O4	87.26 (8)	N1—C1—C2	113.7 (2)
O5—V2—O4ⁱⁱⁱ	103.68 (9)	N1—C1—H4	108.8
O2ⁱ—V2—O4ⁱⁱⁱ	87.95 (8)	C2—C1—H4	108.8
O3ⁱⁱ—V2—O4ⁱⁱⁱ	151.18 (8)	N1—C1—H5	108.8
O4—V2—O4ⁱⁱⁱ	77.97 (9)	C2—C1—H5	108.8
O5—V2—V2ⁱⁱⁱ	111.26 (8)	H4—C1—H5	107.7
O2ⁱ—V2—V2ⁱⁱⁱ	118.72 (6)	C1^v—C2—C1	118.3 (4)
O3ⁱⁱ—V2—V2ⁱⁱⁱ	122.32 (6)	C1^v—C2—H6	107.7
O4—V2—V2ⁱⁱⁱ	39.14 (6)	C1—C2—H6	107.7
O4ⁱⁱⁱ—V2—V2ⁱⁱⁱ	38.83 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^vi	0.91	2.13	2.932 (3)	147
N1—H2···O3ⁱⁱ	0.91	2.02	2.911 (3)	164
N1—H3···O5^vii	0.91	2.04	2.947 (3)	176

Symmetry codes: (ii) −x−1/2, −y+1/2, −z; (vi) −x, y, −z+1/2; (vii) x−1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₃H₁₂N₂²⁺·V₄O₁₀²⁻
M_r	439.91
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	93
a, b, c (Å)	7.977 (3), 10.099 (3), 15.210 (5)
β (°)	104.075 (11)
V (Å³)	1188.6 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.10
Crystal size (mm)	0.15 × 0.01 × 0.01

Data collection
Diffractometer	Make? Mercury70 (2x2 bin mode) CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.84, 0.97
No. of measured, independent and observed [I > 2σ(I)] reflections	3674, 1075, 997
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.059, 1.13
No. of reflections	1075
No. of parameters	87
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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—O1	1.635 (2)	V2—O2ⁱ	1.921 (2)
V1—O2	1.705 (2)	V2—O3ⁱⁱ	1.952 (2)
V1—O3	1.737 (2)	V2—O4	1.969 (2)
V1—O4	1.838 (2)	V2—O4ⁱⁱⁱ	1.982 (2)
V2—O5	1.607 (2)

Symmetry codes: (i) x−1/2, y+1/2, z; (ii) −x−1/2, −y+1/2, −z; (iii) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^iv	0.91	2.13	2.932 (3)	147
N1—H2···O3ⁱⁱ	0.91	2.02	2.911 (3)	164
N1—H3···O5^v	0.91	2.04	2.947 (3)	176

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

Acknowledgements

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

References

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Volume 62| Part 11| November 2006| Pages m566-m568

doi:10.1107/S0108270106040777

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