Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103002683/fg1684sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103002683/fg1684Isup2.hkl |
CCDC reference: 207995
NH4VO3 and dabco (1,4-diazabicyclo[2,2,2]octane)were purchased from ABCR and Aldrich, respectively, and used as received. All other chemicals used were from commercial sources and of reagent grade quality. In a typical experiment, a mixture of NH4VO3 (0.117 g, 1.00 mmol), H3PO4 (0.40 ml, 6.88 mmol), ZnCl2 (0.267 g, 1.96 mmol), C6H12N2 (dabco; 0.120 g, 1.07 mmol), H3BO3 (0.130 g, 2.10 mmol) and H2O (2.00 ml, 111 mmol) was added to a 5 ml Teflon-lined stainless steel autoclave and heated under autogenous pressure (453 K, 3 d). The initial pH of the solution was approximately 2.5, and after completion of the reaction the pH value had decreased to 2.0. After temperature quenching, the reaction mixture was left to stand undisturbed at room temperature. During this period of crystallization, the viscosity of the liquid increased markedly. After 7–14 d, block-shaped pale-blue crystals of (I) appeared. A scanning electron microscope (SEM, Jeol 820) equipped for energy dispersive analysis of X-ray spectra (EDS, LINK AN 10000) was used for determining the elemental atomic ratios between the elements V and P in (I). The result was a V:P ratio of 1:5.98. The analyses were performed on the same crystals that were used for single-crystal X-ray diffraction. It has been understood that the anionic borophosphate complex can only be formed under synthetic conditions where divalent metal ions such as Zn2+ and Mg2+ are present in the reaction mixture. However, none of these ions could be detected in the EDS analysis of (I). In the case of Co2+, the EDS analysis showed a partial incorporation just above the detection limit. This indicates that a partial substitution of the VO2+ site for other divalent cations is possible.
All H atoms, except H27A and H27B, were constrained to idealized geometries, with C—H distances of 0.97 Å, N—H distances of 0.91 Å and O—H distances of 0.82 Å Is this added text OK?. All H atoms were assigned isotropic displacement parameters of 1.2Ueq(C,N) and 1.5Ueq(O).
Data collection: IPDS (Stoe & Cie, 1997); cell refinement: IPDS; data reduction: IPDS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON99 (Spek, 2003) and DIAMOND (Brandenburg, 2001).
(N2C6H14)2[VO(PO4H)5B2O]·H2O·H3PO4 | F(000) = 1908 |
Mr = 928.84 | Dx = 1.906 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5000 reflections |
a = 13.4882 (15) Å | θ = 2.3–28.0° |
b = 12.2569 (13) Å | µ = 0.71 mm−1 |
c = 19.6281 (18) Å | T = 293 K |
β = 94.113 (12)° | Block-shaped, pale blue |
V = 3236.6 (6) Å3 | 0.19 × 0.12 × 0.10 mm |
Z = 4 |
Stoe IPDS diffractometer | 7428 independent reflections |
Radiation source: fine-focus sealed tube | 6006 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
Detector resolution: 6.67 pixels mm-1 | θmax = 27.9°, θmin = 2.3° |
ϕ oscillation scans | h = −17→17 |
Absorption correction: numerical X-SHAPE and X-RED; Stoe & Cie, 1997) | k = −16→16 |
Tmin = 0.879, Tmax = 0.938 | l = −24→23 |
30473 measured reflections |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0701P)2 + 0.9891P] where P = (Fo2 + 2Fc2)/3 |
7428 reflections | (Δ/σ)max = 0.001 |
483 parameters | Δρmax = 0.81 e Å−3 |
0 restraints | Δρmin = −0.66 e Å−3 |
(N2C6H14)2[VO(PO4H)5B2O]·H2O·H3PO4 | V = 3236.6 (6) Å3 |
Mr = 928.84 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.4882 (15) Å | µ = 0.71 mm−1 |
b = 12.2569 (13) Å | T = 293 K |
c = 19.6281 (18) Å | 0.19 × 0.12 × 0.10 mm |
β = 94.113 (12)° |
Stoe IPDS diffractometer | 7428 independent reflections |
Absorption correction: numerical X-SHAPE and X-RED; Stoe & Cie, 1997) | 6006 reflections with I > 2σ(I) |
Tmin = 0.879, Tmax = 0.938 | Rint = 0.039 |
30473 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.81 e Å−3 |
7428 reflections | Δρmin = −0.66 e Å−3 |
483 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. |
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. |
x | y | z | Uiso*/Ueq | ||
V1 | 0.71828 (3) | 0.78670 (3) | 0.16028 (2) | 0.01453 (10) | |
P1 | 0.74382 (4) | 0.96597 (5) | −0.08808 (3) | 0.01678 (13) | |
P2 | 0.94315 (4) | 0.86147 (5) | 0.12056 (3) | 0.01900 (14) | |
P3 | 0.68651 (4) | 1.04620 (5) | 0.14519 (3) | 0.01593 (13) | |
P4 | 0.52714 (4) | 0.78683 (5) | 0.05567 (3) | 0.01727 (13) | |
P5 | 0.78963 (5) | 0.61096 (5) | 0.04647 (3) | 0.01956 (14) | |
P6 | 0.23020 (4) | 0.63720 (5) | 0.13206 (3) | 0.01714 (13) | |
O1 | 0.82104 (13) | 0.96239 (14) | −0.14012 (10) | 0.0235 (4) | |
O2 | 0.78353 (13) | 1.01609 (13) | −0.01967 (9) | 0.0208 (4) | |
O3 | 0.70998 (14) | 0.84849 (15) | −0.07304 (10) | 0.0254 (4) | |
O4 | 0.65465 (15) | 1.03185 (18) | −0.11871 (11) | 0.0329 (5) | |
H41 | 0.6168 | 1.0449 | −0.0889 | 0.049* | |
O5 | 0.90059 (12) | 0.92684 (15) | 0.05752 (10) | 0.0230 (4) | |
O6 | 1.00231 (13) | 0.76595 (16) | 0.09603 (12) | 0.0322 (5) | |
O7 | 0.86254 (12) | 0.83116 (16) | 0.16704 (10) | 0.0249 (4) | |
O8 | 1.01490 (14) | 0.93903 (17) | 0.16472 (11) | 0.0302 (4) | |
H81 | 1.0656 | 0.9493 | 0.1450 | 0.045* | |
O9 | 0.70167 (13) | 1.14126 (13) | 0.19431 (9) | 0.0210 (4) | |
O10 | 0.77572 (13) | 1.04328 (13) | 0.09928 (10) | 0.0216 (4) | |
O11 | 0.67750 (13) | 0.93840 (14) | 0.18215 (10) | 0.0229 (4) | |
O12 | 0.58899 (14) | 1.07296 (16) | 0.10113 (11) | 0.0294 (4) | |
H121 | 0.5669 | 1.0170 | 0.0828 | 0.044* | |
O13 | 0.57789 (13) | 0.75713 (16) | 0.12460 (10) | 0.0262 (4) | |
O14 | 0.59685 (13) | 0.76145 (17) | −0.00221 (10) | 0.0275 (4) | |
O15 | 0.48945 (14) | 0.90274 (16) | 0.05260 (12) | 0.0317 (5) | |
O16 | 0.44099 (14) | 0.70462 (17) | 0.03714 (10) | 0.0304 (4) | |
H161 | 0.4129 | 0.6896 | 0.0716 | 0.046* | |
O17 | 0.76581 (16) | 0.69934 (15) | −0.00856 (10) | 0.0305 (4) | |
O18 | 0.74692 (18) | 0.50114 (16) | 0.02499 (12) | 0.0409 (6) | |
O19 | 0.75430 (16) | 0.64764 (14) | 0.11394 (10) | 0.0300 (4) | |
O20 | 0.90470 (15) | 0.59582 (19) | 0.05141 (13) | 0.0414 (6) | |
H201 | 0.9317 | 0.6547 | 0.0600 | 0.062* | |
O21 | 0.72902 (12) | 0.86664 (13) | 0.05172 (9) | 0.0175 (3) | |
O22 | 0.71480 (14) | 0.73386 (15) | 0.23475 (10) | 0.0242 (4) | |
O23 | 0.34197 (12) | 0.64073 (15) | 0.13645 (11) | 0.0264 (4) | |
O24 | 0.19049 (17) | 0.5908 (3) | 0.19777 (13) | 0.0604 (9) | |
H24 | 0.2310 | 0.6023 | 0.2301 | 0.091* | |
O25 | 0.18085 (19) | 0.5662 (3) | 0.07675 (14) | 0.0564 (8) | |
H25 | 0.2155 | 0.5640 | 0.0441 | 0.085* | |
O26 | 0.19260 (17) | 0.7542 (2) | 0.1237 (2) | 0.0764 (11) | |
H26 | 0.1364 | 0.7538 | 0.1047 | 0.115* | |
O27 | 0.80419 (19) | 0.49715 (19) | 0.21476 (13) | 0.0406 (6) | |
H27A | 0.805 (3) | 0.506 (4) | 0.257 (3) | 0.061* | |
H27B | 0.787 (3) | 0.556 (4) | 0.194 (2) | 0.061* | |
N1 | 0.57059 (14) | 0.30495 (16) | 0.18197 (11) | 0.0183 (4) | |
H1 | 0.6080 | 0.2438 | 0.1898 | 0.022* | |
N2 | 0.46899 (16) | 0.47310 (17) | 0.16013 (12) | 0.0245 (5) | |
H2 | 0.4320 | 0.5345 | 0.1524 | 0.029* | |
C1 | 0.40085 (18) | 0.3763 (2) | 0.16156 (16) | 0.0267 (6) | |
H1A | 0.3568 | 0.3745 | 0.1203 | 0.032* | |
H1B | 0.3606 | 0.3814 | 0.2005 | 0.032* | |
C2 | 0.6077 (2) | 0.3651 (2) | 0.12248 (15) | 0.0268 (6) | |
H2A | 0.6103 | 0.3163 | 0.0838 | 0.032* | |
H2B | 0.6742 | 0.3925 | 0.1342 | 0.032* | |
C3 | 0.46439 (19) | 0.2723 (2) | 0.16676 (17) | 0.0278 (6) | |
H3A | 0.4429 | 0.2257 | 0.2029 | 0.033* | |
H3B | 0.4572 | 0.2322 | 0.1241 | 0.033* | |
C4 | 0.5790 (2) | 0.3747 (2) | 0.24460 (15) | 0.0302 (6) | |
H4A | 0.6484 | 0.3860 | 0.2594 | 0.036* | |
H4B | 0.5467 | 0.3394 | 0.2813 | 0.036* | |
C5 | 0.5290 (2) | 0.4839 (2) | 0.22713 (17) | 0.0321 (6) | |
H5A | 0.4862 | 0.5043 | 0.2627 | 0.039* | |
H5B | 0.5790 | 0.5403 | 0.2240 | 0.039* | |
C6 | 0.5376 (2) | 0.4598 (2) | 0.10401 (17) | 0.0337 (7) | |
H6A | 0.5754 | 0.5262 | 0.0988 | 0.040* | |
H6B | 0.4997 | 0.4448 | 0.0612 | 0.040* | |
N3 | −0.05811 (18) | 0.71573 (19) | 0.35649 (13) | 0.0298 (5) | |
H3 | −0.1059 | 0.6633 | 0.3566 | 0.036* | |
N4 | 0.07089 (18) | 0.8594 (2) | 0.35558 (16) | 0.0378 (6) | |
H4 | 0.1184 | 0.9120 | 0.3553 | 0.045* | |
B1 | 0.79514 (19) | 0.9607 (2) | 0.04696 (14) | 0.0164 (5) | |
B2 | 0.70014 (19) | 0.7974 (2) | −0.00588 (14) | 0.0163 (5) | |
C7 | 0.0040 (3) | 0.6962 (2) | 0.29747 (18) | 0.0404 (8) | |
H7A | −0.0361 | 0.7045 | 0.2548 | 0.049* | |
H7B | 0.0307 | 0.6226 | 0.2995 | 0.049* | |
C8 | −0.1073 (2) | 0.8252 (3) | 0.34921 (17) | 0.0345 (6) | |
H8A | −0.1439 | 0.8402 | 0.3890 | 0.041* | |
H8B | −0.1539 | 0.8258 | 0.3092 | 0.041* | |
C9 | 0.0881 (2) | 0.7787 (3) | 0.3015 (2) | 0.0414 (8) | |
H9A | 0.1510 | 0.7418 | 0.3119 | 0.050* | |
H9B | 0.0909 | 0.8154 | 0.2579 | 0.050* | |
C10 | 0.0051 (3) | 0.7097 (3) | 0.42208 (18) | 0.0422 (8) | |
H10A | 0.0411 | 0.6412 | 0.4249 | 0.051* | |
H10B | −0.0360 | 0.7143 | 0.4605 | 0.051* | |
C11 | 0.0780 (3) | 0.8053 (4) | 0.4234 (2) | 0.0577 (11) | |
H11A | 0.0621 | 0.8571 | 0.4584 | 0.069* | |
H11B | 0.1452 | 0.7791 | 0.4340 | 0.069* | |
C12 | −0.0287 (2) | 0.9114 (3) | 0.3423 (2) | 0.0499 (10) | |
H12A | −0.0347 | 0.9422 | 0.2967 | 0.060* | |
H12B | −0.0368 | 0.9697 | 0.3749 | 0.060* |
U11 | U22 | U33 | U12 | U13 | U23 | |
V1 | 0.01776 (19) | 0.01314 (17) | 0.0130 (2) | 0.00111 (13) | 0.00357 (14) | 0.00006 (13) |
P1 | 0.0153 (3) | 0.0202 (3) | 0.0152 (3) | 0.0021 (2) | 0.0032 (2) | 0.0048 (2) |
P2 | 0.0126 (3) | 0.0221 (3) | 0.0223 (4) | 0.0029 (2) | 0.0009 (2) | 0.0011 (2) |
P3 | 0.0168 (3) | 0.0135 (3) | 0.0178 (3) | 0.0022 (2) | 0.0031 (2) | −0.0031 (2) |
P4 | 0.0130 (3) | 0.0221 (3) | 0.0171 (3) | −0.0029 (2) | 0.0038 (2) | −0.0009 (2) |
P5 | 0.0259 (3) | 0.0148 (3) | 0.0188 (4) | 0.0029 (2) | 0.0074 (2) | −0.0030 (2) |
P6 | 0.0130 (3) | 0.0200 (3) | 0.0188 (3) | 0.0009 (2) | 0.0038 (2) | −0.0014 (2) |
O1 | 0.0230 (9) | 0.0248 (9) | 0.0239 (11) | −0.0006 (7) | 0.0102 (7) | 0.0015 (7) |
O2 | 0.0286 (9) | 0.0169 (8) | 0.0167 (9) | −0.0029 (7) | 0.0004 (7) | 0.0045 (6) |
O3 | 0.0354 (10) | 0.0247 (9) | 0.0159 (10) | −0.0107 (7) | 0.0009 (7) | 0.0037 (7) |
O4 | 0.0281 (10) | 0.0471 (12) | 0.0235 (11) | 0.0175 (9) | 0.0018 (8) | 0.0080 (9) |
O5 | 0.0161 (8) | 0.0313 (9) | 0.0221 (10) | 0.0043 (7) | 0.0047 (6) | 0.0065 (7) |
O6 | 0.0177 (9) | 0.0276 (10) | 0.0512 (14) | 0.0088 (7) | 0.0028 (8) | −0.0028 (9) |
O7 | 0.0171 (8) | 0.0348 (10) | 0.0224 (11) | −0.0012 (7) | 0.0002 (7) | 0.0076 (8) |
O8 | 0.0205 (9) | 0.0423 (11) | 0.0280 (12) | −0.0088 (8) | 0.0036 (7) | −0.0063 (9) |
O9 | 0.0269 (9) | 0.0165 (8) | 0.0195 (10) | 0.0049 (6) | −0.0008 (7) | −0.0052 (6) |
O10 | 0.0244 (9) | 0.0179 (8) | 0.0234 (10) | −0.0026 (6) | 0.0085 (7) | −0.0041 (7) |
O11 | 0.0301 (9) | 0.0160 (8) | 0.0239 (10) | 0.0032 (7) | 0.0106 (7) | −0.0002 (7) |
O12 | 0.0255 (9) | 0.0250 (9) | 0.0363 (12) | 0.0045 (7) | −0.0081 (8) | −0.0065 (8) |
O13 | 0.0223 (9) | 0.0333 (10) | 0.0225 (11) | −0.0093 (7) | −0.0011 (7) | 0.0057 (7) |
O14 | 0.0182 (8) | 0.0427 (11) | 0.0226 (11) | −0.0101 (8) | 0.0075 (7) | −0.0088 (8) |
O15 | 0.0216 (9) | 0.0275 (10) | 0.0458 (14) | 0.0054 (7) | 0.0002 (8) | −0.0011 (9) |
O16 | 0.0236 (9) | 0.0428 (11) | 0.0253 (11) | −0.0187 (8) | 0.0059 (7) | −0.0040 (8) |
O17 | 0.0448 (12) | 0.0275 (10) | 0.0204 (11) | 0.0144 (8) | 0.0091 (8) | −0.0001 (7) |
O18 | 0.0613 (14) | 0.0228 (10) | 0.0424 (14) | −0.0152 (9) | 0.0309 (11) | −0.0145 (9) |
O19 | 0.0566 (13) | 0.0168 (8) | 0.0179 (11) | 0.0090 (8) | 0.0120 (8) | −0.0007 (7) |
O20 | 0.0279 (10) | 0.0380 (12) | 0.0580 (16) | 0.0110 (9) | 0.0000 (10) | −0.0174 (11) |
O21 | 0.0200 (8) | 0.0172 (8) | 0.0155 (9) | −0.0035 (6) | 0.0025 (6) | 0.0010 (6) |
O22 | 0.0322 (10) | 0.0243 (9) | 0.0167 (10) | 0.0024 (7) | 0.0070 (7) | 0.0019 (7) |
O23 | 0.0142 (8) | 0.0298 (10) | 0.0358 (12) | 0.0052 (7) | 0.0065 (7) | 0.0094 (8) |
O24 | 0.0326 (12) | 0.125 (3) | 0.0235 (14) | −0.0378 (14) | −0.0002 (9) | 0.0155 (14) |
O25 | 0.0429 (13) | 0.085 (2) | 0.0431 (17) | −0.0204 (13) | 0.0183 (11) | −0.0418 (14) |
O26 | 0.0212 (11) | 0.0244 (11) | 0.182 (4) | 0.0070 (9) | −0.0037 (16) | 0.0134 (16) |
O27 | 0.0602 (15) | 0.0323 (11) | 0.0291 (13) | 0.0194 (10) | 0.0019 (10) | 0.0007 (9) |
N1 | 0.0184 (9) | 0.0166 (9) | 0.0197 (11) | 0.0050 (7) | 0.0009 (7) | −0.0004 (7) |
N2 | 0.0205 (10) | 0.0193 (10) | 0.0344 (14) | 0.0060 (8) | 0.0075 (9) | 0.0030 (9) |
C1 | 0.0171 (11) | 0.0249 (12) | 0.0382 (17) | 0.0009 (9) | 0.0027 (10) | 0.0020 (11) |
C2 | 0.0262 (13) | 0.0319 (14) | 0.0237 (15) | 0.0068 (10) | 0.0118 (10) | 0.0024 (10) |
C3 | 0.0190 (12) | 0.0209 (12) | 0.0433 (18) | −0.0019 (9) | 0.0012 (11) | −0.0010 (11) |
C4 | 0.0380 (15) | 0.0307 (14) | 0.0215 (16) | 0.0036 (11) | −0.0015 (11) | −0.0072 (11) |
C5 | 0.0291 (14) | 0.0274 (13) | 0.0401 (18) | 0.0036 (11) | 0.0052 (12) | −0.0138 (12) |
C6 | 0.0351 (15) | 0.0320 (14) | 0.0357 (18) | 0.0082 (12) | 0.0155 (12) | 0.0137 (12) |
N3 | 0.0333 (12) | 0.0299 (12) | 0.0271 (14) | −0.0146 (9) | 0.0088 (10) | −0.0036 (9) |
N4 | 0.0233 (11) | 0.0228 (11) | 0.068 (2) | −0.0050 (9) | 0.0106 (11) | −0.0034 (11) |
B1 | 0.0175 (12) | 0.0160 (11) | 0.0162 (14) | −0.0004 (9) | 0.0035 (9) | 0.0005 (9) |
B2 | 0.0157 (11) | 0.0197 (12) | 0.0139 (14) | 0.0009 (9) | 0.0041 (9) | 0.0008 (9) |
C7 | 0.058 (2) | 0.0294 (15) | 0.037 (2) | −0.0068 (13) | 0.0237 (15) | −0.0078 (12) |
C8 | 0.0234 (13) | 0.0421 (16) | 0.0381 (19) | 0.0021 (12) | 0.0033 (11) | 0.0001 (13) |
C9 | 0.0385 (17) | 0.0365 (16) | 0.052 (2) | 0.0041 (13) | 0.0246 (15) | 0.0046 (14) |
C10 | 0.060 (2) | 0.0374 (17) | 0.0287 (19) | −0.0018 (15) | −0.0016 (14) | 0.0057 (13) |
C11 | 0.052 (2) | 0.070 (3) | 0.048 (3) | −0.0164 (19) | −0.0158 (17) | −0.0132 (19) |
C12 | 0.0315 (16) | 0.0265 (15) | 0.094 (3) | 0.0082 (12) | 0.0169 (17) | −0.0003 (16) |
V1—O22 | 1.6026 (19) | O27—H27B | 0.85 (5) |
V1—O11 | 1.9944 (17) | N1—C4 | 1.495 (3) |
V1—O13 | 2.0043 (18) | N1—C3 | 1.497 (3) |
V1—O19 | 2.0079 (18) | N1—C2 | 1.497 (3) |
V1—O7 | 2.0159 (17) | N1—H1 | 0.9100 |
V1—O21 | 2.3592 (17) | N2—C6 | 1.498 (3) |
P1—O1 | 1.5107 (18) | N2—C5 | 1.500 (4) |
P1—O4 | 1.5350 (19) | N2—C1 | 1.502 (3) |
P1—O2 | 1.5376 (19) | N2—H2 | 0.9100 |
P1—O3 | 1.5454 (18) | C1—C3 | 1.536 (4) |
P2—O6 | 1.5147 (19) | C1—H1A | 0.9700 |
P2—O7 | 1.5149 (18) | C1—H1B | 0.9700 |
P2—O5 | 1.5493 (19) | C2—C6 | 1.523 (4) |
P2—O8 | 1.572 (2) | C2—H2A | 0.9700 |
P3—O11 | 1.5164 (18) | C2—H2B | 0.9700 |
P3—O9 | 1.5168 (17) | C3—H3A | 0.9700 |
P3—O10 | 1.5546 (18) | C3—H3B | 0.9700 |
P3—O12 | 1.5564 (19) | C4—C5 | 1.527 (4) |
P4—O15 | 1.509 (2) | C4—H4A | 0.9700 |
P4—O13 | 1.516 (2) | C4—H4B | 0.9700 |
P4—O14 | 1.5570 (19) | C5—H5A | 0.9700 |
P4—O16 | 1.5612 (18) | C5—H5B | 0.9700 |
P5—O19 | 1.5077 (19) | C6—H6A | 0.9700 |
P5—O18 | 1.512 (2) | C6—H6B | 0.9700 |
P5—O17 | 1.547 (2) | N3—C10 | 1.494 (4) |
P5—O20 | 1.559 (2) | N3—C7 | 1.497 (4) |
P6—O23 | 1.5045 (18) | N3—C8 | 1.499 (4) |
P6—O25 | 1.509 (2) | N3—H3 | 0.9100 |
P6—O26 | 1.526 (2) | N4—C9 | 1.482 (4) |
P6—O24 | 1.540 (2) | N4—C11 | 1.483 (5) |
O2—B1 | 1.472 (3) | N4—C12 | 1.492 (4) |
O3—B2 | 1.474 (3) | N4—H4 | 0.9100 |
O4—H41 | 0.8200 | C7—C9 | 1.518 (4) |
O5—B1 | 1.482 (3) | C7—H7A | 0.9700 |
O8—H81 | 0.8200 | C7—H7B | 0.9700 |
O10—B1 | 1.478 (3) | C8—C12 | 1.510 (4) |
O12—H121 | 0.8200 | C8—H8A | 0.9700 |
O14—B2 | 1.468 (3) | C8—H8B | 0.9700 |
O16—H161 | 0.8200 | C9—H9A | 0.9700 |
O17—B2 | 1.497 (3) | C9—H9B | 0.9700 |
O20—H201 | 0.8200 | C10—C11 | 1.528 (5) |
O21—B2 | 1.444 (3) | C10—H10A | 0.9700 |
O21—B1 | 1.465 (3) | C10—H10B | 0.9700 |
O24—H24 | 0.8200 | C11—H11A | 0.9700 |
O25—H25 | 0.8200 | C11—H11B | 0.9700 |
O26—H26 | 0.8200 | C12—H12A | 0.9700 |
O27—H27A | 0.83 (5) | C12—H12B | 0.9700 |
O22—V1—O11 | 98.85 (9) | N1—C2—C6 | 108.9 (2) |
O22—V1—O13 | 99.03 (9) | N1—C2—H2A | 109.9 |
O11—V1—O13 | 88.60 (8) | C6—C2—H2A | 109.9 |
O22—V1—O19 | 95.39 (9) | N1—C2—H2B | 109.9 |
O11—V1—O19 | 165.53 (8) | C6—C2—H2B | 109.9 |
O13—V1—O19 | 86.65 (9) | H2A—C2—H2B | 108.3 |
O22—V1—O7 | 98.07 (9) | N1—C3—C1 | 108.2 (2) |
O11—V1—O7 | 90.78 (8) | N1—C3—H3A | 110.1 |
O13—V1—O7 | 162.78 (8) | C1—C3—H3A | 110.1 |
O19—V1—O7 | 89.74 (9) | N1—C3—H3B | 110.1 |
O22—V1—O21 | 178.02 (8) | C1—C3—H3B | 110.1 |
O11—V1—O21 | 80.97 (7) | H3A—C3—H3B | 108.4 |
O13—V1—O21 | 82.95 (7) | N1—C4—C5 | 108.1 (2) |
O19—V1—O21 | 84.88 (7) | N1—C4—H4A | 110.1 |
O7—V1—O21 | 79.96 (7) | C5—C4—H4A | 110.1 |
O1—P1—O4 | 108.02 (11) | N1—C4—H4B | 110.1 |
O1—P1—O2 | 112.84 (10) | C5—C4—H4B | 110.1 |
O4—P1—O2 | 110.24 (11) | H4A—C4—H4B | 108.4 |
O1—P1—O3 | 109.24 (11) | N2—C5—C4 | 108.7 (2) |
O4—P1—O3 | 109.33 (12) | N2—C5—H5A | 109.9 |
O2—P1—O3 | 107.13 (10) | C4—C5—H5A | 109.9 |
O6—P2—O7 | 114.78 (12) | N2—C5—H5B | 109.9 |
O6—P2—O5 | 108.62 (12) | C4—C5—H5B | 109.9 |
O7—P2—O5 | 111.53 (10) | H5A—C5—H5B | 108.3 |
O6—P2—O8 | 108.97 (11) | N2—C6—C2 | 108.3 (2) |
O7—P2—O8 | 104.85 (11) | N2—C6—H6A | 110.0 |
O5—P2—O8 | 107.80 (11) | C2—C6—H6A | 110.0 |
O11—P3—O9 | 112.14 (10) | N2—C6—H6B | 110.0 |
O11—P3—O10 | 110.44 (10) | C2—C6—H6B | 110.0 |
O9—P3—O10 | 108.14 (10) | H6A—C6—H6B | 108.4 |
O11—P3—O12 | 110.85 (11) | C10—N3—C7 | 110.0 (3) |
O9—P3—O12 | 105.14 (10) | C10—N3—C8 | 110.4 (2) |
O10—P3—O12 | 109.96 (12) | C7—N3—C8 | 109.8 (2) |
O15—P4—O13 | 113.01 (12) | C10—N3—H3 | 108.9 |
O15—P4—O14 | 112.23 (12) | C7—N3—H3 | 108.9 |
O13—P4—O14 | 110.21 (11) | C8—N3—H3 | 108.9 |
O15—P4—O16 | 110.82 (12) | C9—N4—C11 | 110.0 (3) |
O13—P4—O16 | 109.50 (11) | C9—N4—C12 | 110.2 (3) |
O14—P4—O16 | 100.34 (10) | C11—N4—C12 | 110.3 (3) |
O19—P5—O18 | 111.86 (12) | C9—N4—H4 | 108.8 |
O19—P5—O17 | 109.97 (10) | C11—N4—H4 | 108.8 |
O18—P5—O17 | 111.88 (13) | C12—N4—H4 | 108.8 |
O19—P5—O20 | 110.90 (13) | O21—B1—O2 | 113.1 (2) |
O18—P5—O20 | 105.60 (13) | O21—B1—O10 | 110.82 (19) |
O17—P5—O20 | 106.42 (13) | O2—B1—O10 | 106.80 (19) |
O23—P6—O25 | 116.51 (13) | O21—B1—O5 | 110.66 (19) |
O23—P6—O26 | 107.65 (12) | O2—B1—O5 | 107.07 (19) |
O25—P6—O26 | 109.8 (2) | O10—B1—O5 | 108.1 (2) |
O23—P6—O24 | 111.71 (12) | O21—B2—O14 | 109.98 (19) |
O25—P6—O24 | 103.17 (16) | O21—B2—O3 | 114.5 (2) |
O26—P6—O24 | 107.7 (2) | O14—B2—O3 | 108.5 (2) |
B1—O2—P1 | 126.88 (15) | O21—B2—O17 | 111.9 (2) |
B2—O3—P1 | 127.82 (17) | O14—B2—O17 | 109.1 (2) |
P1—O4—H41 | 109.5 | O3—B2—O17 | 102.60 (19) |
B1—O5—P2 | 123.62 (16) | N3—C7—C9 | 108.1 (2) |
P2—O7—V1 | 139.26 (12) | N3—C7—H7A | 110.1 |
P2—O8—H81 | 109.5 | C9—C7—H7A | 110.1 |
B1—O10—P3 | 126.97 (15) | N3—C7—H7B | 110.1 |
P3—O11—V1 | 132.57 (11) | C9—C7—H7B | 110.1 |
P3—O12—H121 | 109.5 | H7A—C7—H7B | 108.4 |
P4—O13—V1 | 128.55 (11) | N3—C8—C12 | 109.0 (2) |
B2—O14—P4 | 126.92 (17) | N3—C8—H8A | 109.9 |
P4—O16—H161 | 109.5 | C12—C8—H8A | 109.9 |
B2—O17—P5 | 129.18 (17) | N3—C8—H8B | 109.9 |
P5—O19—V1 | 138.85 (12) | C12—C8—H8B | 109.9 |
P5—O20—H201 | 109.5 | H8A—C8—H8B | 108.3 |
B2—O21—B1 | 122.93 (19) | N4—C9—C7 | 109.1 (2) |
B2—O21—V1 | 115.63 (14) | N4—C9—H9A | 109.9 |
B1—O21—V1 | 117.49 (14) | C7—C9—H9A | 109.9 |
P6—O24—H24 | 109.5 | N4—C9—H9B | 109.9 |
P6—O25—H25 | 109.5 | C7—C9—H9B | 109.9 |
P6—O26—H26 | 109.5 | H9A—C9—H9B | 108.3 |
H27A—O27—H27B | 111 (4) | N3—C10—C11 | 107.6 (3) |
C4—N1—C3 | 109.4 (2) | N3—C10—H10A | 110.2 |
C4—N1—C2 | 110.5 (2) | C11—C10—H10A | 110.2 |
C3—N1—C2 | 110.2 (2) | N3—C10—H10B | 110.2 |
C4—N1—H1 | 108.9 | C11—C10—H10B | 110.2 |
C3—N1—H1 | 108.9 | H10A—C10—H10B | 108.5 |
C2—N1—H1 | 108.9 | N4—C11—C10 | 109.1 (3) |
C6—N2—C5 | 109.3 (2) | N4—C11—H11A | 109.9 |
C6—N2—C1 | 109.8 (2) | C10—C11—H11A | 109.9 |
C5—N2—C1 | 110.2 (2) | N4—C11—H11B | 109.9 |
C6—N2—H2 | 109.1 | C10—C11—H11B | 109.9 |
C5—N2—H2 | 109.1 | H11A—C11—H11B | 108.3 |
C1—N2—H2 | 109.1 | N4—C12—C8 | 108.4 (3) |
N2—C1—C3 | 108.5 (2) | N4—C12—H12A | 110.0 |
N2—C1—H1A | 110.0 | C8—C12—H12A | 110.0 |
C3—C1—H1A | 110.0 | N4—C12—H12B | 110.0 |
N2—C1—H1B | 110.0 | C8—C12—H12B | 110.0 |
C3—C1—H1B | 110.0 | H12A—C12—H12B | 108.4 |
H1A—C1—H1B | 108.4 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O9i | 0.91 | 1.78 | 2.674 (3) | 167 |
N3—H3···O1ii | 0.91 | 1.83 | 2.728 (3) | 167 |
N2—H2···O23 | 0.91 | 1.79 | 2.694 (3) | 171 |
N4—H4···O27iii | 0.91 | 2.07 | 2.816 (4) | 139 |
O16—H161···O23 | 0.82 | 1.75 | 2.563 (3) | 170 |
O24—H24···O9iv | 0.82 | 1.75 | 2.558 (3) | 169 |
O25—H25···O18v | 0.82 | 1.68 | 2.428 (4) | 150 |
O26—H26···O6vi | 0.82 | 1.81 | 2.589 (3) | 158 |
O27—H27A···O1vii | 0.84 (6) | 2.05 (6) | 2.884 (3) | 174 (3) |
O27—H27B···O19 | 0.85 (5) | 1.96 (4) | 2.753 (3) | 155 (4) |
O27—H27B···O22 | 0.85 (5) | 2.54 (5) | 3.177 (3) | 132 (3) |
O4—H41···O15viii | 0.82 | 1.77 | 2.543 (3) | 158 |
O8—H81···O1ix | 0.82 | 1.88 | 2.597 (3) | 145 |
O12—H121···O15 | 0.82 | 1.82 | 2.623 (3) | 165 |
O20—H201···O6 | 0.82 | 1.78 | 2.585 (3) | 166 |
Symmetry codes: (i) x, y−1, z; (ii) x−1, −y+3/2, z+1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+1, y−1/2, −z+1/2; (v) −x+1, −y+1, −z; (vi) x−1, y, z; (vii) x, −y+3/2, z+1/2; (viii) −x+1, −y+2, −z; (ix) −x+2, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | (N2C6H14)2[VO(PO4H)5B2O]·H2O·H3PO4 |
Mr | 928.84 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 13.4882 (15), 12.2569 (13), 19.6281 (18) |
β (°) | 94.113 (12) |
V (Å3) | 3236.6 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.71 |
Crystal size (mm) | 0.19 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Stoe IPDS diffractometer |
Absorption correction | Numerical X-SHAPE and X-RED; Stoe & Cie, 1997) |
Tmin, Tmax | 0.879, 0.938 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 30473, 7428, 6006 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.659 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.113, 1.10 |
No. of reflections | 7428 |
No. of parameters | 483 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.81, −0.66 |
Computer programs: IPDS (Stoe & Cie, 1997), IPDS, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON99 (Spek, 2003) and DIAMOND (Brandenburg, 2001).
V1—O22 | 1.6026 (19) | P4—O13 | 1.516 (2) |
V1—O11 | 1.9944 (17) | P4—O14 | 1.5570 (19) |
V1—O13 | 2.0043 (18) | P4—O16 | 1.5612 (18) |
V1—O19 | 2.0079 (18) | P5—O19 | 1.5077 (19) |
V1—O7 | 2.0159 (17) | P5—O18 | 1.512 (2) |
V1—O21 | 2.3592 (17) | P5—O17 | 1.547 (2) |
P1—O1 | 1.5107 (18) | P5—O20 | 1.559 (2) |
P1—O4 | 1.5350 (19) | P6—O23 | 1.5045 (18) |
P1—O2 | 1.5376 (19) | P6—O25 | 1.509 (2) |
P1—O3 | 1.5454 (18) | P6—O26 | 1.526 (2) |
P2—O6 | 1.5147 (19) | P6—O24 | 1.540 (2) |
P2—O7 | 1.5149 (18) | O2—B1 | 1.472 (3) |
P2—O5 | 1.5493 (19) | O3—B2 | 1.474 (3) |
P2—O8 | 1.572 (2) | O5—B1 | 1.482 (3) |
P3—O11 | 1.5164 (18) | O10—B1 | 1.478 (3) |
P3—O9 | 1.5168 (17) | O14—B2 | 1.468 (3) |
P3—O10 | 1.5546 (18) | O17—B2 | 1.497 (3) |
P3—O12 | 1.5564 (19) | O21—B2 | 1.444 (3) |
P4—O15 | 1.509 (2) | O21—B1 | 1.465 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O9i | 0.91 | 1.78 | 2.674 (3) | 167 |
N3—H3···O1ii | 0.91 | 1.83 | 2.728 (3) | 167 |
N2—H2···O23 | 0.91 | 1.79 | 2.694 (3) | 171 |
N4—H4···O27iii | 0.91 | 2.07 | 2.816 (4) | 139 |
O16—H161···O23 | 0.82 | 1.75 | 2.563 (3) | 170 |
O24—H24···O9iv | 0.82 | 1.75 | 2.558 (3) | 169 |
O25—H25···O18v | 0.82 | 1.68 | 2.428 (4) | 150 |
O26—H26···O6vi | 0.82 | 1.81 | 2.589 (3) | 158 |
O27—H27A···O1vii | 0.84 (6) | 2.05 (6) | 2.884 (3) | 174 (3) |
O27—H27B···O19 | 0.85 (5) | 1.96 (4) | 2.753 (3) | 155 (4) |
O27—H27B···O22 | 0.85 (5) | 2.54 (5) | 3.177 (3) | 132 (3) |
O4—H41···O15viii | 0.82 | 1.77 | 2.543 (3) | 158 |
O8—H81···O1ix | 0.82 | 1.88 | 2.597 (3) | 145 |
O12—H121···O15 | 0.82 | 1.82 | 2.623 (3) | 165 |
O20—H201···O6 | 0.82 | 1.78 | 2.585 (3) | 166 |
Symmetry codes: (i) x, y−1, z; (ii) x−1, −y+3/2, z+1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+1, y−1/2, −z+1/2; (v) −x+1, −y+1, −z; (vi) x−1, y, z; (vii) x, −y+3/2, z+1/2; (viii) −x+1, −y+2, −z; (ix) −x+2, −y+2, −z. |
Borophosphates with anionic [BxPyOz]p- frameworks or isolated clusters represent a rather broad class of compounds that have received much attention recently (Kniep et al., 1999; Cheetham et al., 1999; Bontchev et al., 1999b). In particular, several cluster compounds containing V have been synthesized and structurally characterized (Bontchev et al., 1999b; Bontchev et al., 2000a; Bontchev et al., 2000b). The clusters are mostly anionic species, built up of tetrahedral PO4 units in combination with triangular BO3 or tetrahedral BO4 units. Most of these vanadium borophosphate clusters contain several V atoms in each cluster unit. Our work has focused on the synthesis of metal borophosphates that exhibit structure-dependent magnetic properties (Kritikos et al., 2001). The title borophosphate, (N2C6H14)2[VO(PO3OH)5B2O]·H3PO4·H2O, (I), containing one VO2+ unit, is one of few borophosphate compounds containing a single VO2+ centre within the borophosphate anion. Hence, to the best of our knowledge, the only described example of a borophosphate cluster containing a single V atom is the anion [VO(PO3OH)4(B3O3OH)]4−, which is present in (N2C6H14)2[VO(PO3OH)4(B3O3OH)]·4H2O (Bontchev et al., 1999a Is this the correct reference? The original CIF simply stated 1999). Although the two cluster anions have the same charge, they exhibit different P:B ratios; 5:3 for (I) and 4:3 for the Bontchev cluster. \sch
The geometry of the molecular anionic unit [VO(PO3OH)5B2O]4− in (I) (Fig. 1) is, however, rather similar to the Bontchev anionic cluster. The V atom is hexacoordinated, with one short terminal V═O bond, one elongated V—O contact to an O atom that is only bonded to the B atoms, and four intermediate-range V—O bonds where the O atoms belong to the cluster phosphate groups. All five P atoms in the borophosphate anion exhibit tetrahedral coordination. One of the two terminal P—O bonds in each tetrahedron is significantly elongated due to protonation [1.535 (2)–1.572 (2) Å].
All H-atom positions were unequivocally revealed in difference maps and show that atoms O4, O8, O12, O16 and O20 in the phosphate groups are protonated. Bond-valence sum (BVS) calculations (Brown & Altermatt, 1985; Brese & O'Keeffe, 1991) were also made and are in accord with the protonation pattern obtained from the difference maps.
The solid state structure of (I) is rather complex. The asymmetric unit consists of a borophosphate [VO(PO3OH)5B2O]4− anion that is charge-balanced by two crystallographically independent (N2C6H14)2+ cations, and two solvated molecules, H3PO4 and H2O. These molecular species are connected to each other through a network of homonuclear O—H···O and heteronuclear N—H···O hydrogen bonds. In particular, intermolecular pair-wise interactions, of which some are charge assisted, exist between the following units [dabco is bis(1,4-diaza[2.2.2]octane) and VBPO is the vanadium borophosphate]: dabco-VBPO cluster, VBPO cluster-VBPO cluster, H3PO4—VBPO cluster, dabco-H3PO4 and dabco-H2O. Intramolecular O12···O15 [2.623 (3) Å] and O20···O6 [2.585 (3) Å] hydrogen bonds, classified as self (S) patterns, are present within the VBPO cluster (Fig. 2).
Looking at larger structural units reveals that several hydrogen-bond patterns can be distinguished. Some of the hydrogen bonds that propagate from the borophosphate anion in the asymmetric unit of (I) are shown in Fig. 2. A number of rings, (R), or chains of rings, (R)[C] (Bernstein et al., 1995), are present in the structure. In particular, several rings emanate from the H3PO4 molecule. Particularly noteworthy is the very short O25···O18v distance [2.428 (4) Å; symmetry code: (v) 1 − x, 1 − y, z], indicating the presence of a very strong hydrogen bond between H3PO4 and VBPO units.
Table 2. Short N—H···O and O—H···O contacts (Å, °)