catena-[1,3-Di­ammonio­propane di-μ₂-hydro­xo-di-μ₄-phosphato-trioxotrivanadium dihydrate]: a redetermination at 180 (2) K

The crystal structure of the title compound, (C₃H₁₂N₂)[V₃O₃(OH)₂(PO₄)₂]·2H₂O, has been reported by Soghomonian et al. [Chem. Mater. (1993), 5, 1690–1691]. We present here a redetermination of greatly improved precision and at a low temperature of 180 (2) K. The H atoms connected to oxy­gen have been successfully located and the coordination environments of the two crystallographically independent vanadium centres have been properly elucidated. Large channels, running along the a direction, contain water mol­ecules and 1,3-di­ammonio­propane cations that are strongly hydrogen bonded to the anionic framework through N⁺—H...O and O—H...O interactions. One vanadyl (V=O) bond and the central –CH₂– group of 1,3-di­ammonio­propane are located on a mirror plane.

Key indicators

• Single-crystal X-ray study
• T = 180 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.029
• wR factor = 0.073
• Data-to-parameter ratio = 13.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

Large crystals of the title compound, (I), H₃N(CH₂)₃NH₃[(VO)₃(OH)₂(PO₄)₂]·(H₂O)₂, were obtained in quantitative yields during our syntheses of novel hybrid materials containing vanadium centres. The crystal structure of (I) was originally reported by Soghomonian et al. (1993), and found to contain vanadium centres showing penta- (square-pyramidal geometry, VO₅) and hexacoordination geometries (distorted VO₆ octahedra). A very closely related crystal structure containing mixed IV and V oxidation states for the vanadium centres has also been reported by Loiseau & Ferey (1994). The unusual very long V—O bonds to water molecules reported for the VO₆ octahedra [2.363 (5) and 2.355 Å, respectively] and the unavailability of three-dimensional crystal coordinates for (I) motivated us to reinvestigate the crystal structure at low t emperature.

The compound contains two crystallographically unique vanadium centres, each coordinated to five O atoms in a geometry which is best described as a square pyramid (Figs. 1 and 2, and Table 1). The basal planes are formed by three phosphate ions and a µ₂-OH group with the V—O bonds ranging between 1.95 and 2.02 Å (Table 1). The apical position of each square pyramid is occupied by a V═O bond with the corresponding bond distances being, as expected, much smaller than for the single bonds. Bridges between consecutive V centres are established by the phosphate and the µ₂-OH groups, with the V1—OH and V2—OH bond distances being comparable to the distances reported in the first crystal determination (Soghomonian et al., 1993), but slightly shorter, as was also expected. The µ₂-OH groups are also involved in hydrogen bonding, with O7 acting as a bifurcated acceptor as shown in Fig. 2 (Table 2). Although our calculated distance between V1 and the O atom from the crystallization water molecule [2.3203 (19) Å] is also comparable to that reported by Soghomonian at al. (1993) and Loiseau & Ferey (1994), we believe that the spatial separation between the V and the O centres is very large for a typical dative coordinative bond to take place.

The open three-dimensional anionic framework is templated by 1,3-diaminopropane which appears in the crystal structure as 1,3-diammoniopropane cations. These ions, along with the water molecules, are involved in the complex and extensive hydrogen-bonding network present in the crystal structure (Figs. 2 and 3, and Table 2), and occupying the large channels which run in the a direction (Figs. 3 and 4).

S2. Experimental

All chemicals were obtained from commercial sources and were used as received. A mixture contaning V₂O₅ (0.40 g, Aldrich, 99.6% purity), H₃PO₄ (0.43 g, Merck, minimum 85%), YCl₃·6H₂O (0.54 g, Aldrich, 99.9% purity), adipic acid [HO₂C(CH₂)₄CO₂H, 0.95 g, Aldrich, 99% purity] and 1,3-diaminopropape (C₃H₁₀N₂, 0.32 g, Fluka, 99% purity) in ca 16 ml of distilled water was stirred thoroughly for 15 min at ambient temperature. The suspension was transferred to a Parr stainless steel Teflon-lined reaction vessel (40 ml, 70% full), which was placed inside an oven at 433 K. The reaction took place under autogeneous pressure and static conditions over a period of 7 d, after which the vessel was slowly cooled to ambient temperature before opening. The dark green crystalline product was formed by large crystals of the title compound, which were collected by vacuum filtration and then air-dried.

S3. Refinement

H atoms bound to C atoms were placed in calculated positions and allowed to ride during subsequent refinement, with U_iso(H) = xU_eq(C), where x = 1.2 for –CH₂ and x = 1.5 for –CH₃ groups. Water and –OH H atoms were located in difference Fourier maps and refined with independent isotropic displacement parameters. The O—H bond for the hydroxyl group was restrained to 0.82 (3) Å, and the O—H and H···H distances for the water were also restrained in order to ensure a reasonable geometry for these molecules.

Computing details

Data collection: COLLECT (Nonius 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare at al., 1994); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The asymmetric unit of (I), showing the labelling scheme for all atoms. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres.
	Fig. 2. View in detail of the N^+—H···O and O—H···O hydrogen bonds (dashed light blue lines). For hydrogen-bonding details, see Table 2.
	Fig. 3. Perspective view of (I) along the a (top) and b (bottom) directions, showing the N^+—H···O and O—H···O hydrogen-bonding network (light blue dashed lines). The anionic three-dimensional inorganic framework is represented with white-filled bonds.
	Fig. 4. Polyhedral representation of the crystal structure of (I) along the a (top) and b (bottom) directions. V centres are represented as brown square pyramids, while the phosphate ions are drawn as blue tetrahedra. Water molecules and 1,3-diammoniopropane cations are drawn in ball-and-stick mode.

catena-[1,3-Diammoniopropane di-µ₂-hydroxo-di-µ₄-phosphato-trioxotrivanadium dihydrate]

Crystal data

(C3H12N2)[V3O3(OH)2(PO4)2]·2H2O	F(000) = 1076
Mr = 536.95	Dx = 2.354 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 14014 reflections
a = 10.464 (2) Å	θ = 1.0–27.5°
b = 17.142 (3) Å	µ = 2.11 mm^−1
c = 8.4481 (17) Å	T = 180 K
V = 1515.4 (5) Å^3	Block, green
Z = 4	0.25 × 0.18 × 0.12 mm

Data collection

Nonius KappaCCD diffractometer	1789 independent reflections
Radiation source: fine-focus sealed tube	1568 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
Thin–slice ω and ϕ scans	θmax = 27.5°, θmin = 3.9°
Absorption correction: multi-scan (SORTAV; Blessing 1995)	h = −11→13
Tmin = 0.621, Tmax = 0.786	k = −22→22
12781 measured reflections	l = −10→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.037P)^2 + 1.8P] where P = (Fo^2 + 2Fc^2)/3
1789 reflections	(Δ/σ)max = 0.001
131 parameters	Δρmax = 0.49 e Å^−3
4 restraints	Δρmin = −0.69 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
V1	0.85891 (4)	0.43838 (2)	0.22045 (4)	0.01011 (12)
V2	0.71662 (5)	0.2500	0.32863 (6)	0.01018 (14)
P1	1.12872 (5)	0.41284 (3)	0.02562 (7)	0.00845 (14)
O1	0.71501 (17)	0.41030 (12)	0.0194 (2)	0.0200 (4)
O2	0.84236 (17)	0.32603 (10)	0.2543 (2)	0.0178 (4)
O5	0.83722 (14)	0.54707 (9)	0.13259 (19)	0.0129 (3)
O6	0.98260 (14)	0.41388 (9)	0.04843 (18)	0.0123 (3)
O8	0.67482 (15)	0.32784 (9)	0.49053 (18)	0.0135 (3)
O3	0.69461 (15)	0.45521 (9)	0.33579 (19)	0.0135 (3)
O7	0.6002 (2)	0.2500	0.2062 (3)	0.0248 (6)
O4	0.95592 (16)	0.45951 (10)	0.36269 (19)	0.0168 (4)
C1	0.0357 (2)	0.67795 (13)	0.3337 (3)	0.0157 (5)
H1A	0.0453	0.6798	0.4502	0.019*
H1B	−0.0568	0.6779	0.3090	0.019*
N1	0.09459 (19)	0.60504 (11)	0.2723 (2)	0.0151 (4)
H1C	0.0875	0.6038	0.1649	0.023*
H1D	0.0537	0.5630	0.3144	0.023*
H1E	0.1786	0.6037	0.2998	0.023*
C2	0.0975 (3)	0.7500	0.2612 (4)	0.0166 (7)
H2A	0.1904	0.7500	0.2830	0.020*
H2B	0.0849	0.7500	0.1450	0.020*
H2	0.646 (3)	0.412 (2)	0.058 (5)	0.057 (13)*
H1	0.715 (5)	0.442 (3)	−0.048 (6)	0.16 (3)*
H10	0.901 (3)	0.310 (2)	0.219 (5)	0.075 (16)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.0099 (2)	0.0092 (2)	0.0113 (2)	−0.00052 (13)	0.00033 (14)	0.00049 (14)
V2	0.0106 (3)	0.0073 (3)	0.0126 (3)	0.000	0.00002 (19)	0.000
P1	0.0083 (3)	0.0057 (3)	0.0114 (3)	0.0003 (2)	−0.00059 (19)	0.0000 (2)
O1	0.0164 (9)	0.0251 (10)	0.0186 (9)	−0.0024 (8)	0.0006 (7)	0.0003 (8)
O2	0.0181 (9)	0.0090 (8)	0.0264 (10)	0.0003 (7)	0.0088 (7)	0.0004 (7)
O5	0.0139 (8)	0.0097 (8)	0.0152 (8)	0.0018 (6)	0.0029 (6)	0.0018 (6)
O6	0.0110 (8)	0.0126 (8)	0.0133 (8)	−0.0004 (6)	0.0016 (6)	−0.0005 (6)
O8	0.0189 (8)	0.0063 (7)	0.0153 (8)	0.0018 (6)	0.0024 (6)	−0.0001 (6)
O3	0.0131 (8)	0.0102 (8)	0.0171 (8)	0.0002 (6)	0.0045 (6)	0.0025 (6)
O7	0.0205 (13)	0.0323 (16)	0.0217 (13)	0.000	−0.0062 (10)	0.000
O4	0.0175 (8)	0.0176 (8)	0.0152 (8)	−0.0016 (7)	−0.0009 (6)	0.0009 (7)
C1	0.0168 (11)	0.0097 (10)	0.0207 (12)	0.0002 (9)	0.0003 (9)	−0.0020 (9)
N1	0.0163 (10)	0.0101 (10)	0.0190 (10)	0.0008 (8)	−0.0028 (8)	0.0000 (8)
C2	0.0199 (16)	0.0121 (16)	0.0177 (16)	0.000	0.0010 (14)	0.000

Geometric parameters (Å, º)

V1—O4	1.6142 (16)	O1—H1	0.79 (3)
V1—O2	1.9548 (18)	O2—H10	0.74 (3)
V1—O6	1.9908 (16)	C1—N1	1.487 (3)
V1—O3	1.9972 (16)	C1—C2	1.523 (3)
V1—O5	2.0184 (16)	C1—H1A	0.9900
V2—O7	1.598 (3)	C1—H1B	0.9900
V2—O2	1.9554 (18)	N1—H1C	0.9100
V2—O8	1.9602 (16)	N1—H1D	0.9100
P1—O3^i	1.5407 (16)	N1—H1E	0.9100
P1—O8^i	1.5409 (17)	C2—C1^iii	1.523 (3)
P1—O6	1.5413 (16)	C2—H2A	0.9900
P1—O5^ii	1.5446 (16)	C2—H2B	0.9900
O1—H2	0.79 (3)
O4—V1—O2	99.66 (9)	O6—P1—O5^ii	109.39 (9)
O4—V1—O6	100.48 (8)	V1—O1—H2	106 (3)
O2—V1—O6	87.52 (7)	V1—O1—H1	113 (5)
O4—V1—O3	98.38 (8)	H2—O1—H1	106 (3)
O2—V1—O3	89.69 (7)	V1—O2—V2	139.75 (10)
O6—V1—O3	161.14 (7)	V1—O2—H10	103 (3)
O4—V1—O5	97.90 (8)	V2—O2—H10	117 (4)
O2—V1—O5	162.43 (8)	P1^ii—O5—V1	134.66 (10)
O6—V1—O5	89.96 (6)	P1—O6—V1	137.62 (10)
O3—V1—O5	87.09 (6)	P1^v—O8—V2	130.67 (10)
O4—V1—O1	178.33 (8)	P1^v—O3—V1	133.47 (10)
O2—V1—O1	81.10 (8)	N1—C1—C2	111.4 (2)
O6—V1—O1	81.02 (7)	N1—C1—H1A	109.3
O3—V1—O1	80.12 (7)	C2—C1—H1A	109.3
O5—V1—O1	81.33 (7)	N1—C1—H1B	109.3
O7—V2—O2	107.77 (9)	C2—C1—H1B	109.3
O7—V2—O2^iv	107.77 (9)	H1A—C1—H1B	108.0
O2—V2—O2^iv	83.59 (11)	C1—N1—H1C	109.5
O7—V2—O8	106.35 (8)	C1—N1—H1D	109.5
O2—V2—O8	85.44 (7)	H1C—N1—H1D	109.5
O2^iv—V2—O8	145.87 (8)	C1—N1—H1E	109.5
O7—V2—O8^iv	106.35 (8)	H1C—N1—H1E	109.5
O2—V2—O8^iv	145.87 (8)	H1D—N1—H1E	109.5
O2^iv—V2—O8^iv	85.44 (7)	C1^iii—C2—C1	108.4 (3)
O8—V2—O8^iv	85.80 (10)	C1^iii—C2—H2A	110.0
O3^i—P1—O8^i	111.90 (9)	C1—C2—H2A	110.0
O3^i—P1—O6	110.09 (9)	C1^iii—C2—H2B	110.0
O8^i—P1—O6	109.43 (9)	C1—C2—H2B	110.0
O3^i—P1—O5^ii	110.16 (9)	H2A—C2—H2B	108.4
O8^i—P1—O5^ii	105.77 (9)
O4—V1—O2—V2	108.84 (16)	O5^ii—P1—O6—V1	−134.12 (14)
O6—V1—O2—V2	−150.94 (16)	O4—V1—O6—P1	−1.48 (16)
O3—V1—O2—V2	10.39 (16)	O2—V1—O6—P1	−100.85 (15)
O5—V1—O2—V2	−68.9 (3)	O3—V1—O6—P1	177.40 (15)
O1—V1—O2—V2	−69.65 (16)	O5—V1—O6—P1	96.54 (15)
O7—V2—O2—V1	64.99 (18)	O1—V1—O6—P1	177.77 (15)
O2^iv—V2—O2—V1	171.63 (10)	O7—V2—O8—P1^v	−48.79 (15)
O8—V2—O2—V1	−40.74 (16)	O2—V2—O8—P1^v	58.40 (14)
O8^iv—V2—O2—V1	−116.34 (16)	O2^iv—V2—O8—P1^v	129.90 (14)
O4—V1—O5—P1^ii	115.45 (14)	O8^iv—V2—O8—P1^v	−154.61 (9)
O2—V1—O5—P1^ii	−66.8 (3)	O4—V1—O3—P1^v	−67.15 (15)
O6—V1—O5—P1^ii	14.87 (14)	O2—V1—O3—P1^v	32.56 (14)
O3—V1—O5—P1^ii	−146.49 (14)	O6—V1—O3—P1^v	114.0 (2)
O1—V1—O5—P1^ii	−66.05 (14)	O5—V1—O3—P1^v	−164.71 (14)
O3^i—P1—O6—V1	−12.94 (17)	O1—V1—O3—P1^v	113.58 (14)
O8^i—P1—O6—V1	110.43 (14)	N1—C1—C2—C1^iii	−178.05 (15)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O6^vi	0.91	1.97	2.846 (3)	161
N1—H1D···O4^vii	0.91	2.09	2.985 (3)	168
N1—H1E···O5^v	0.91	2.01	2.842 (3)	152
O1—H2···O4^v	0.79 (3)	2.25 (3)	3.009 (3)	161 (4)
O1—H1···O3^viii	0.79 (3)	2.23 (4)	2.935 (3)	150 (6)
O2—H10···O7^i	0.74 (3)	2.41 (3)	3.015 (3)	140 (4)

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