The crystal structure of the title compound, (C
3H
12N
2)[V
3O
3(OH)
2(PO
4)
2]·2H
2O, 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 –CH
2– group of 1,3-diammoniopropane are located on a mirror plane.
Supporting information
CCDC reference: 209892
Key indicators
- Single-crystal X-ray study
- T = 180 K
- Mean (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
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.
H atoms bound to C atoms were placed in calculated positions and allowed to ride during subsequent refinement, with Uiso(H) = xUeq(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.
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.
catena-[1,3-Diammoniopropane di-µ
2-hydroxo-di-µ
4-phosphato-trioxotrivanadium dihydrate]
top
Crystal data top
(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) Å3 | Block, green |
Z = 4 | 0.25 × 0.18 × 0.12 mm |
Data collection top
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 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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.073 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.037P)2 + 1.8P] where P = (Fo2 + 2Fc2)/3 |
1789 reflections | (Δ/σ)max = 0.001 |
131 parameters | Δρmax = 0.49 e Å−3 |
4 restraints | Δρmin = −0.69 e Å−3 |
Crystal data top
(C3H12N2)[V3O3(OH)2(PO4)2]·2H2O | V = 1515.4 (5) Å3 |
Mr = 536.95 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 10.464 (2) Å | µ = 2.11 mm−1 |
b = 17.142 (3) Å | T = 180 K |
c = 8.4481 (17) Å | 0.25 × 0.18 × 0.12 mm |
Data collection top
Nonius KappaCCD diffractometer | 1789 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing 1995) | 1568 reflections with I > 2σ(I) |
Tmin = 0.621, Tmax = 0.786 | Rint = 0.064 |
12781 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.029 | 4 restraints |
wR(F2) = 0.073 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.49 e Å−3 |
1789 reflections | Δρmin = −0.69 e Å−3 |
131 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 | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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—O3i | 1.5407 (16) | N1—H1E | 0.9100 |
P1—O8i | 1.5409 (17) | C2—C1iii | 1.523 (3) |
P1—O6 | 1.5413 (16) | C2—H2A | 0.9900 |
P1—O5ii | 1.5446 (16) | C2—H2B | 0.9900 |
O1—H2 | 0.79 (3) | | |
| | | |
O4—V1—O2 | 99.66 (9) | O6—P1—O5ii | 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) | P1ii—O5—V1 | 134.66 (10) |
O6—V1—O5 | 89.96 (6) | P1—O6—V1 | 137.62 (10) |
O3—V1—O5 | 87.09 (6) | P1v—O8—V2 | 130.67 (10) |
O4—V1—O1 | 178.33 (8) | P1v—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—O2iv | 107.77 (9) | H1A—C1—H1B | 108.0 |
O2—V2—O2iv | 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 |
O2iv—V2—O8 | 145.87 (8) | C1—N1—H1E | 109.5 |
O7—V2—O8iv | 106.35 (8) | H1C—N1—H1E | 109.5 |
O2—V2—O8iv | 145.87 (8) | H1D—N1—H1E | 109.5 |
O2iv—V2—O8iv | 85.44 (7) | C1iii—C2—C1 | 108.4 (3) |
O8—V2—O8iv | 85.80 (10) | C1iii—C2—H2A | 110.0 |
O3i—P1—O8i | 111.90 (9) | C1—C2—H2A | 110.0 |
O3i—P1—O6 | 110.09 (9) | C1iii—C2—H2B | 110.0 |
O8i—P1—O6 | 109.43 (9) | C1—C2—H2B | 110.0 |
O3i—P1—O5ii | 110.16 (9) | H2A—C2—H2B | 108.4 |
O8i—P1—O5ii | 105.77 (9) | | |
| | | |
O4—V1—O2—V2 | 108.84 (16) | O5ii—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) |
O2iv—V2—O2—V1 | 171.63 (10) | O7—V2—O8—P1v | −48.79 (15) |
O8—V2—O2—V1 | −40.74 (16) | O2—V2—O8—P1v | 58.40 (14) |
O8iv—V2—O2—V1 | −116.34 (16) | O2iv—V2—O8—P1v | 129.90 (14) |
O4—V1—O5—P1ii | 115.45 (14) | O8iv—V2—O8—P1v | −154.61 (9) |
O2—V1—O5—P1ii | −66.8 (3) | O4—V1—O3—P1v | −67.15 (15) |
O6—V1—O5—P1ii | 14.87 (14) | O2—V1—O3—P1v | 32.56 (14) |
O3—V1—O5—P1ii | −146.49 (14) | O6—V1—O3—P1v | 114.0 (2) |
O1—V1—O5—P1ii | −66.05 (14) | O5—V1—O3—P1v | −164.71 (14) |
O3i—P1—O6—V1 | −12.94 (17) | O1—V1—O3—P1v | 113.58 (14) |
O8i—P1—O6—V1 | 110.43 (14) | N1—C1—C2—C1iii | −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) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···O6vi | 0.91 | 1.97 | 2.846 (3) | 161 |
N1—H1D···O4vii | 0.91 | 2.09 | 2.985 (3) | 168 |
N1—H1E···O5v | 0.91 | 2.01 | 2.842 (3) | 152 |
O1—H2···O4v | 0.79 (3) | 2.25 (3) | 3.009 (3) | 161 (4) |
O1—H1···O3viii | 0.79 (3) | 2.23 (4) | 2.935 (3) | 150 (6) |
O2—H10···O7i | 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. |
Experimental details
Crystal data |
Chemical formula | (C3H12N2)[V3O3(OH)2(PO4)2]·2H2O |
Mr | 536.95 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 180 |
a, b, c (Å) | 10.464 (2), 17.142 (3), 8.4481 (17) |
V (Å3) | 1515.4 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.11 |
Crystal size (mm) | 0.25 × 0.18 × 0.12 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing 1995) |
Tmin, Tmax | 0.621, 0.786 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12781, 1789, 1568 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.073, 1.03 |
No. of reflections | 1789 |
No. of parameters | 131 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.49, −0.69 |
Selected geometric parameters (Å, º) topV1—O4 | 1.6142 (16) | V2—O2 | 1.9554 (18) |
V1—O2 | 1.9548 (18) | V2—O8 | 1.9602 (16) |
V1—O6 | 1.9908 (16) | P1—O3i | 1.5407 (16) |
V1—O3 | 1.9972 (16) | P1—O8i | 1.5409 (17) |
V1—O5 | 2.0184 (16) | P1—O6 | 1.5413 (16) |
V2—O7 | 1.598 (3) | P1—O5ii | 1.5446 (16) |
| | | |
O4—V1—O2 | 99.66 (9) | O3—V1—O1 | 80.12 (7) |
O4—V1—O6 | 100.48 (8) | O5—V1—O1 | 81.33 (7) |
O2—V1—O6 | 87.52 (7) | O7—V2—O2 | 107.77 (9) |
O4—V1—O3 | 98.38 (8) | O7—V2—O2iii | 107.77 (9) |
O2—V1—O3 | 89.69 (7) | O2—V2—O2iii | 83.59 (11) |
O6—V1—O3 | 161.14 (7) | O7—V2—O8 | 106.35 (8) |
O4—V1—O5 | 97.90 (8) | O2—V2—O8 | 85.44 (7) |
O2—V1—O5 | 162.43 (8) | O2iii—V2—O8 | 145.87 (8) |
O6—V1—O5 | 89.96 (6) | O7—V2—O8iii | 106.35 (8) |
O3—V1—O5 | 87.09 (6) | O2—V2—O8iii | 145.87 (8) |
O4—V1—O1 | 178.33 (8) | O2iii—V2—O8iii | 85.44 (7) |
O2—V1—O1 | 81.10 (8) | O8—V2—O8iii | 85.80 (10) |
O6—V1—O1 | 81.02 (7) | | |
Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) −x+2, −y+1, −z; (iii) x, −y+1/2, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···O6iv | 0.91 | 1.97 | 2.846 (3) | 161 |
N1—H1D···O4v | 0.91 | 2.09 | 2.985 (3) | 168 |
N1—H1E···O5vi | 0.91 | 2.01 | 2.842 (3) | 152 |
O1—H2···O4vi | 0.79 (3) | 2.25 (3) | 3.009 (3) | 161 (4) |
O1—H1···O3vii | 0.79 (3) | 2.23 (4) | 2.935 (3) | 150 (6) |
O2—H10···O7i | 0.74 (3) | 2.41 (3) | 3.015 (3) | 140 (4) |
Symmetry codes: (i) x+1/2, y, −z+1/2; (iv) −x+1, −y+1, −z; (v) x−1, y, z; (vi) x−1/2, y, −z+1/2; (vii) −x+3/2, −y+1, z−1/2. |
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).