Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108007956/av3143sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108007956/av3143Isup2.hkl |
CCDC reference: 690174
Ni(thiourea)4Cl2 (0.69 g, 1.6 mmol) was added to a mixture of an aqueous solution (20 ml) of anhydrous sodium carbonate (0.16 g, 1.5 mmol) and 1-oxo-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane-4-carboxylic acid (0.61 g, 3.2 mmol) with stirring at room temperature for 20 min. After filtration, slow evaporation of the filtrate for three weeks at room temperature provided crystals of (I).
All water H atoms were found in a difference Fourier map and were fixed during refinement at O—H distances of 0.85 Å, with Uiso(H) = 1.2Ueq(O). The H atoms of the C—H and N—H groups were treated as riding, with C—H = 0.97 Å and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C,N).
Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).
[Ni(H2O)6](C6H10N2O6PS)2·6H2O | Z = 1 |
Mr = 813.28 | F(000) = 426 |
Triclinic, P1 | Dx = 1.710 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.2701 (12) Å | Cell parameters from 2700 reflections |
b = 6.4816 (12) Å | θ = 3.1–26.4° |
c = 19.616 (4) Å | µ = 0.95 mm−1 |
α = 95.807 (3)° | T = 294 K |
β = 93.091 (3)° | Block, green |
γ = 93.760 (3)° | 0.28 × 0.24 × 0.22 mm |
V = 789.9 (3) Å3 |
Bruker SMART CCD area-detector diffractometer | 2789 independent reflections |
Radiation source: fine-focus sealed tube | 2482 reflections with I > 2σ |
Graphite monochromator | Rint = 0.018 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→7 |
Tmin = 0.765, Tmax = 0.818 | k = −7→7 |
4055 measured reflections | l = −22→23 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0402P)2 + 0.6065P] where P = (Fo2 + 2Fc2)/3 |
2789 reflections | (Δ/σ)max < 0.001 |
205 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.49 e Å−3 |
[Ni(H2O)6](C6H10N2O6PS)2·6H2O | γ = 93.760 (3)° |
Mr = 813.28 | V = 789.9 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.2701 (12) Å | Mo Kα radiation |
b = 6.4816 (12) Å | µ = 0.95 mm−1 |
c = 19.616 (4) Å | T = 294 K |
α = 95.807 (3)° | 0.28 × 0.24 × 0.22 mm |
β = 93.091 (3)° |
Bruker SMART CCD area-detector diffractometer | 2789 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2482 reflections with I > 2σ |
Tmin = 0.765, Tmax = 0.818 | Rint = 0.018 |
4055 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.49 e Å−3 |
2789 reflections | Δρmin = −0.49 e Å−3 |
205 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | ||
Ni1 | 0.5000 | 0.5000 | 0.5000 | 0.02462 (13) | |
P1 | 0.64559 (9) | −0.08749 (10) | 0.30461 (3) | 0.02290 (16) | |
S1 | 0.41441 (10) | 0.32226 (9) | 0.11184 (3) | 0.03093 (17) | |
C1 | 0.5881 (3) | −0.0897 (4) | 0.17245 (11) | 0.0215 (5) | |
H1E | 0.6004 | −0.2384 | 0.1644 | 0.026* | |
H1F | 0.6431 | −0.0263 | 0.1336 | 0.026* | |
C2 | 0.2682 (4) | −0.1298 (4) | 0.24308 (11) | 0.0273 (5) | |
H2E | 0.1210 | −0.0954 | 0.2475 | 0.033* | |
H2F | 0.2705 | −0.2801 | 0.2389 | 0.033* | |
C3 | 0.3530 (3) | −0.0470 (3) | 0.17813 (11) | 0.0214 (5) | |
C4 | 0.2195 (4) | −0.1605 (3) | 0.11498 (11) | 0.0227 (5) | |
C5 | 0.3200 (4) | 0.1877 (4) | 0.18258 (12) | 0.0279 (5) | |
H5A | 0.3926 | 0.2541 | 0.2248 | 0.033* | |
H5B | 0.1683 | 0.2058 | 0.1856 | 0.033* | |
C6 | 0.2075 (4) | 0.2744 (4) | 0.04664 (12) | 0.0251 (5) | |
N1 | 0.0039 (3) | 0.2580 (3) | 0.05896 (11) | 0.0322 (5) | |
H1C | −0.0919 | 0.2418 | 0.0254 | 0.039* | |
H1D | −0.0338 | 0.2633 | 0.1006 | 0.039* | |
N2 | 0.2711 (3) | 0.2671 (3) | −0.01556 (10) | 0.0318 (5) | |
H2C | 0.1785 | 0.2511 | −0.0500 | 0.038* | |
H2D | 0.4056 | 0.2783 | −0.0222 | 0.038* | |
O1 | 0.4141 (3) | 0.4878 (3) | 0.39677 (9) | 0.0368 (4) | |
H1A | 0.2805 | 0.4779 | 0.3860 | 0.044* | |
H1B | 0.4947 | 0.5483 | 0.3701 | 0.044* | |
O2 | 0.6239 (3) | 0.2199 (3) | 0.48119 (10) | 0.0449 (5) | |
H2A | 0.6409 | 0.1684 | 0.4403 | 0.054* | |
H2B | 0.6924 | 0.1687 | 0.5129 | 0.054* | |
O3 | 0.7910 (3) | 0.6462 (3) | 0.48574 (11) | 0.0497 (5) | |
H3A | 0.8787 | 0.6006 | 0.4577 | 0.060* | |
H3B | 0.8214 | 0.7665 | 0.5069 | 0.060* | |
O4 | 0.7617 (3) | 0.0529 (3) | 0.36138 (9) | 0.0345 (4) | |
O5 | 0.6648 (3) | −0.3155 (3) | 0.30392 (9) | 0.0366 (4) | |
O6 | 0.7158 (2) | −0.0076 (2) | 0.23479 (8) | 0.0242 (4) | |
O7 | 0.3974 (3) | −0.0411 (3) | 0.30427 (8) | 0.0274 (4) | |
O8 | 0.3045 (3) | −0.1790 (3) | 0.05863 (8) | 0.0290 (4) | |
O9 | 0.0299 (3) | −0.2200 (3) | 0.12484 (9) | 0.0335 (4) | |
O10 | −0.1238 (3) | 0.4457 (3) | 0.18989 (11) | 0.0498 (5) | |
H10A | −0.1771 | 0.4740 | 0.2283 | 0.060* | |
H10B | −0.0471 | 0.5451 | 0.1756 | 0.060* | |
O11 | 0.8514 (3) | 0.0065 (3) | 0.57508 (9) | 0.0372 (4) | |
H11A | 0.7599 | −0.0050 | 0.6054 | 0.045* | |
H11B | 0.9823 | 0.0070 | 0.5895 | 0.045* | |
O12 | 0.9792 (4) | 0.4581 (4) | 0.36201 (14) | 0.0675 (7) | |
H12A | 0.9180 | 0.5374 | 0.3357 | 0.081* | |
H12B | 0.9151 | 0.3382 | 0.3617 | 0.081* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0262 (2) | 0.0255 (2) | 0.0222 (2) | 0.00081 (17) | 0.00170 (17) | 0.00310 (17) |
P1 | 0.0195 (3) | 0.0325 (3) | 0.0169 (3) | 0.0038 (2) | −0.0031 (2) | 0.0045 (2) |
S1 | 0.0334 (3) | 0.0281 (3) | 0.0296 (3) | −0.0028 (3) | −0.0151 (3) | 0.0069 (3) |
C1 | 0.0207 (11) | 0.0267 (12) | 0.0162 (11) | 0.0012 (9) | −0.0031 (9) | 0.0003 (9) |
C2 | 0.0201 (11) | 0.0432 (14) | 0.0182 (11) | −0.0004 (10) | −0.0034 (9) | 0.0047 (10) |
C3 | 0.0194 (11) | 0.0275 (12) | 0.0167 (11) | 0.0022 (9) | −0.0036 (9) | 0.0016 (9) |
C4 | 0.0235 (12) | 0.0234 (11) | 0.0209 (12) | 0.0050 (9) | −0.0068 (9) | 0.0036 (9) |
C5 | 0.0338 (13) | 0.0310 (13) | 0.0185 (11) | 0.0107 (10) | −0.0068 (10) | −0.0005 (10) |
C6 | 0.0290 (13) | 0.0228 (12) | 0.0225 (12) | 0.0034 (9) | −0.0090 (10) | 0.0023 (9) |
N1 | 0.0289 (11) | 0.0464 (13) | 0.0204 (10) | 0.0033 (9) | −0.0053 (8) | 0.0028 (9) |
N2 | 0.0239 (11) | 0.0468 (13) | 0.0238 (11) | 0.0020 (9) | −0.0060 (8) | 0.0031 (9) |
O1 | 0.0321 (10) | 0.0533 (12) | 0.0253 (9) | −0.0031 (8) | −0.0009 (8) | 0.0108 (8) |
O2 | 0.0714 (14) | 0.0403 (11) | 0.0260 (10) | 0.0245 (10) | 0.0026 (9) | 0.0051 (8) |
O3 | 0.0438 (12) | 0.0558 (13) | 0.0448 (12) | −0.0170 (10) | 0.0158 (9) | −0.0114 (10) |
O4 | 0.0288 (9) | 0.0503 (11) | 0.0221 (9) | 0.0042 (8) | −0.0072 (7) | −0.0028 (8) |
O5 | 0.0396 (11) | 0.0364 (10) | 0.0363 (10) | 0.0093 (8) | −0.0007 (8) | 0.0131 (8) |
O6 | 0.0189 (8) | 0.0347 (9) | 0.0183 (8) | −0.0016 (7) | −0.0035 (6) | 0.0043 (7) |
O7 | 0.0211 (8) | 0.0450 (10) | 0.0160 (8) | 0.0049 (7) | −0.0018 (6) | 0.0020 (7) |
O8 | 0.0260 (9) | 0.0409 (10) | 0.0190 (8) | 0.0023 (7) | −0.0021 (7) | −0.0010 (7) |
O9 | 0.0215 (9) | 0.0517 (11) | 0.0258 (9) | −0.0040 (8) | −0.0048 (7) | 0.0040 (8) |
O10 | 0.0473 (12) | 0.0615 (14) | 0.0422 (12) | 0.0111 (10) | 0.0096 (10) | 0.0057 (10) |
O11 | 0.0254 (9) | 0.0547 (12) | 0.0316 (10) | 0.0040 (8) | −0.0027 (8) | 0.0072 (9) |
O12 | 0.0414 (13) | 0.0567 (14) | 0.106 (2) | −0.0055 (10) | −0.0184 (13) | 0.0355 (14) |
Ni1—O2i | 2.0286 (18) | C4—O8 | 1.251 (3) |
Ni1—O1 | 2.0595 (17) | C4—O9 | 1.256 (3) |
Ni1—O2 | 2.0286 (18) | C5—H5A | 0.9699 |
Ni1—O3i | 2.0463 (19) | C5—H5B | 0.9700 |
Ni1—O3 | 2.0463 (19) | C6—N1 | 1.312 (3) |
Ni1—O1i | 2.0595 (17) | C6—N2 | 1.301 (3) |
P1—O4 | 1.4896 (18) | N1—H1C | 0.8600 |
P1—O5 | 1.4893 (19) | N1—H1D | 0.8600 |
P1—O6 | 1.5862 (16) | N2—H2C | 0.8600 |
P1—O7 | 1.6042 (17) | N2—H2D | 0.8600 |
S1—C6 | 1.761 (2) | O1—H1A | 0.8495 |
S1—C5 | 1.817 (3) | O1—H1B | 0.8529 |
C1—O6 | 1.458 (3) | O2—H2A | 0.8524 |
C1—C3 | 1.525 (3) | O2—H2B | 0.8450 |
C1—H1E | 0.9700 | O3—H3A | 0.8440 |
C1—H1F | 0.9700 | O3—H3B | 0.8507 |
C2—O7 | 1.457 (3) | O10—H10A | 0.8485 |
C2—C3 | 1.539 (3) | O10—H10B | 0.8579 |
C2—H2E | 0.9700 | O11—H11A | 0.8536 |
C2—H2F | 0.9700 | O11—H11B | 0.8536 |
C3—C5 | 1.543 (3) | O12—H12A | 0.8580 |
C3—C4 | 1.549 (3) | O12—H12B | 0.8501 |
O2i—Ni1—O2 | 180.0 | C2—C3—C5 | 107.77 (19) |
O2i—Ni1—O3i | 89.98 (9) | C1—C3—C4 | 109.43 (18) |
O2—Ni1—O3i | 90.02 (9) | C2—C3—C4 | 108.18 (18) |
O2i—Ni1—O3 | 90.02 (9) | C5—C3—C4 | 109.38 (18) |
O2—Ni1—O3 | 89.98 (9) | O8—C4—O9 | 125.5 (2) |
O3i—Ni1—O3 | 180.0 | O8—C4—C3 | 118.3 (2) |
O2i—Ni1—O1 | 91.52 (7) | O9—C4—C3 | 116.1 (2) |
O2—Ni1—O1 | 88.48 (8) | C3—C5—S1 | 115.87 (16) |
O3i—Ni1—O1 | 89.11 (8) | C3—C5—H5A | 108.3 |
O3—Ni1—O1 | 90.89 (8) | S1—C5—H5A | 108.3 |
O2i—Ni1—O1i | 88.48 (8) | C3—C5—H5B | 108.4 |
O2—Ni1—O1i | 91.52 (7) | S1—C5—H5B | 108.3 |
O3i—Ni1—O1i | 90.89 (8) | H5A—C5—H5B | 107.4 |
O3—Ni1—O1i | 89.11 (8) | N2—C6—N1 | 121.9 (2) |
O1—Ni1—O1i | 180.0 | N2—C6—S1 | 114.78 (18) |
O5—P1—O4 | 118.18 (11) | N1—C6—S1 | 123.27 (18) |
O5—P1—O6 | 111.08 (10) | C6—N1—H1C | 120.0 |
O4—P1—O6 | 106.96 (10) | C6—N1—H1D | 120.0 |
O5—P1—O7 | 109.23 (10) | H1C—N1—H1D | 120.0 |
O4—P1—O7 | 107.75 (10) | C6—N2—H2C | 120.0 |
O6—P1—O7 | 102.45 (9) | C6—N2—H2D | 120.0 |
C6—S1—C5 | 105.13 (12) | H2C—N2—H2D | 120.0 |
O6—C1—C3 | 111.29 (17) | Ni1—O1—H1A | 115.9 |
O6—C1—H1E | 109.3 | Ni1—O1—H1B | 120.4 |
C3—C1—H1E | 109.4 | H1A—O1—H1B | 116.9 |
O6—C1—H1F | 109.4 | Ni1—O2—H2A | 121.0 |
C3—C1—H1F | 109.4 | Ni1—O2—H2B | 120.1 |
H1E—C1—H1F | 108.0 | H2A—O2—H2B | 116.6 |
O7—C2—C3 | 111.13 (18) | Ni1—O3—H3A | 124.8 |
O7—C2—H2E | 109.4 | Ni1—O3—H3B | 117.7 |
C3—C2—H2E | 109.5 | H3A—O3—H3B | 117.3 |
O7—C2—H2F | 109.4 | C1—O6—P1 | 116.99 (13) |
C3—C2—H2F | 109.4 | C2—O7—P1 | 115.02 (14) |
H2E—C2—H2F | 108.0 | H10A—O10—H10B | 115.5 |
C1—C3—C2 | 110.17 (18) | H11A—O11—H11B | 115.6 |
C1—C3—C5 | 111.83 (19) | H12A—O12—H12B | 114.2 |
O6—C1—C3—C2 | −54.0 (2) | C2—C3—C5—S1 | 178.64 (15) |
O6—C1—C3—C5 | 65.8 (2) | C4—C3—C5—S1 | −64.0 (2) |
O6—C1—C3—C4 | −172.86 (17) | C6—S1—C5—C3 | 82.51 (19) |
O7—C2—C3—C1 | 56.1 (2) | C5—S1—C6—N2 | −149.09 (19) |
O7—C2—C3—C5 | −66.2 (2) | C5—S1—C6—N1 | 34.3 (2) |
O7—C2—C3—C4 | 175.65 (18) | C3—C1—O6—P1 | 57.0 (2) |
C1—C3—C4—O8 | −33.4 (3) | O5—P1—O6—C1 | 63.31 (17) |
C2—C3—C4—O8 | −153.4 (2) | O4—P1—O6—C1 | −166.40 (15) |
C5—C3—C4—O8 | 89.4 (2) | O7—P1—O6—C1 | −53.21 (16) |
C1—C3—C4—O9 | 149.0 (2) | C3—C2—O7—P1 | −59.6 (2) |
C2—C3—C4—O9 | 29.0 (3) | O5—P1—O7—C2 | −63.65 (18) |
C5—C3—C4—O9 | −88.1 (2) | O4—P1—O7—C2 | 166.80 (16) |
C1—C3—C5—S1 | 57.4 (2) | O6—P1—O7—C2 | 54.19 (17) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···O8ii | 0.86 | 2.05 | 2.911 (3) | 174 |
N1—H1D···O10 | 0.86 | 2.14 | 2.904 (3) | 149 |
N2—H2C···O9ii | 0.86 | 1.90 | 2.758 (3) | 179 |
N2—H2D···O8iii | 0.86 | 2.10 | 2.910 (3) | 156 |
O1—H1A···O12iv | 0.85 | 1.91 | 2.764 (3) | 180 |
O1—H1B···O5v | 0.85 | 1.96 | 2.816 (3) | 176 |
O2—H2A···O4 | 0.85 | 1.87 | 2.696 (3) | 163 |
O2—H2B···O11 | 0.85 | 1.96 | 2.798 (3) | 170 |
O3—H3A···O12 | 0.84 | 2.15 | 2.944 (4) | 156 |
O3—H3B···O11v | 0.85 | 1.94 | 2.767 (3) | 164 |
O10—H10A···O5vi | 0.85 | 2.23 | 3.007 (3) | 152 |
O10—H10B···O9v | 0.86 | 1.95 | 2.770 (3) | 159 |
O11—H11A···O7vii | 0.85 | 2.08 | 2.902 (2) | 162 |
O11—H11B···O4viii | 0.85 | 1.91 | 2.735 (2) | 162 |
O12—H12A···O5v | 0.86 | 2.01 | 2.795 (3) | 152 |
O12—H12B···O4 | 0.85 | 2.03 | 2.877 (3) | 180 |
Symmetry codes: (ii) −x, −y, −z; (iii) −x+1, −y, −z; (iv) x−1, y, z; (v) x, y+1, z; (vi) x−1, y+1, z; (vii) −x+1, −y, −z+1; (viii) −x+2, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ni(H2O)6](C6H10N2O6PS)2·6H2O |
Mr | 813.28 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 6.2701 (12), 6.4816 (12), 19.616 (4) |
α, β, γ (°) | 95.807 (3), 93.091 (3), 93.760 (3) |
V (Å3) | 789.9 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.95 |
Crystal size (mm) | 0.28 × 0.24 × 0.22 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.765, 0.818 |
No. of measured, independent and observed (I > 2σ) reflections | 4055, 2789, 2482 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.084, 1.05 |
No. of reflections | 2789 |
No. of parameters | 205 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49, −0.49 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXTL (Bruker, 2001).
P1—O4 | 1.4896 (18) | C4—O8 | 1.251 (3) |
P1—O5 | 1.4893 (19) | C4—O9 | 1.256 (3) |
P1—O6 | 1.5862 (16) | C6—N1 | 1.312 (3) |
P1—O7 | 1.6042 (17) | C6—N2 | 1.301 (3) |
O5—P1—O4 | 118.18 (11) | O4—P1—O7 | 107.75 (10) |
O5—P1—O6 | 111.08 (10) | O6—P1—O7 | 102.45 (9) |
O4—P1—O6 | 106.96 (10) | O8—C4—O9 | 125.5 (2) |
O5—P1—O7 | 109.23 (10) | N2—C6—N1 | 121.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···O8i | 0.86 | 2.05 | 2.911 (3) | 174.3 |
N1—H1D···O10 | 0.86 | 2.14 | 2.904 (3) | 148.6 |
N2—H2C···O9i | 0.86 | 1.90 | 2.758 (3) | 178.6 |
N2—H2D···O8ii | 0.86 | 2.10 | 2.910 (3) | 155.6 |
O1—H1A···O12iii | 0.85 | 1.91 | 2.764 (3) | 179.5 |
O1—H1B···O5iv | 0.85 | 1.96 | 2.816 (3) | 176.2 |
O2—H2A···O4 | 0.85 | 1.87 | 2.696 (3) | 162.9 |
O2—H2B···O11 | 0.85 | 1.96 | 2.798 (3) | 170.0 |
O3—H3A···O12 | 0.84 | 2.15 | 2.944 (4) | 156.3 |
O3—H3B···O11iv | 0.85 | 1.94 | 2.767 (3) | 164.2 |
O10—H10A···O5v | 0.85 | 2.23 | 3.007 (3) | 152.4 |
O10—H10B···O9iv | 0.86 | 1.95 | 2.770 (3) | 159.4 |
O11—H11A···O7vi | 0.85 | 2.08 | 2.902 (2) | 161.8 |
O11—H11B···O4vii | 0.85 | 1.91 | 2.735 (2) | 162.4 |
O12—H12A···O5iv | 0.86 | 2.01 | 2.795 (3) | 152.3 |
O12—H12B···O4 | 0.85 | 2.03 | 2.877 (3) | 179.7 |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z; (iii) x−1, y, z; (iv) x, y+1, z; (v) x−1, y+1, z; (vi) −x+1, −y, −z+1; (vii) −x+2, −y, −z+1. |
This study was initiated as an exploration of a complex containing both a proton donor and a proton acceptor, formed via reaction of a carboxylate with a caged phosphate ester, OP(OCH2)3CCOO-, with Ni(thiourea)4Cl2, because there are currently two main strategies in crystal engineering, based on the use of either co-coordinative bonds or weaker intermolecular interactions (Burrows et al., 2000). The reaction of the coordinated thiourea with the caged phosphate ester unexpectedly produced a polyfunctional anion, 2-N-isothiouronium-S-ylmethyl-2-carboxy-1,3-propandiyl phosphate, where the structure of the bicyclic OP(OCH2)3C cage is opened. Intermolecular interactions between the N-isothiouronium cation and the carboxylate anion, between the 1,3-propandiyl phosphate and water molecules, and so on, result in a wide variety of hydrogen-bond patterns. In addition, intermolecular interactions between the hexaaquanickel(II) cation and non-coordinated water molecules also create a number of interesting water chains and hydrogen-bonded ring graph sets. We describe here the interesting structure of the title compound, (I), with rich O—H···O intra- and interlayer hydrogen-bonding and N—H···O dimer hydrogen-bond patterns, leading to a three-dimensional supramolecular network.
The asymmetric unit of (I) comprises one-half of an Ni atom with three coordinated water molecules, one complete 2-N-isothiouronium-S-ylmethyl-2-carboxy-1,3-propandiyl phosphate anion and three non-coordinated water molecules, and is shown in Fig. 1 in a symmetry-expanded view, which displays the full coordination of the hexaaquanickel(II) cation and the phosphate ester anion. Selected geometric parameters are given in Table 1.
The hexaaquanickel(II) cation of (I) has a distorted octahedral environment. The interactions of the coordinated water molecules and atoms O11 and O12 form network architectures of interesting topology. In the crystallographic b direction, atoms H3B and H2B coordinate to O11v and O11, respectively [symmetry codes: (v) x, y+1, z]. Similarly, atoms H3A and H1A connect to O12 and O12iv, respectively, in the crystallographic a direction [symmetry codes: (iv) x-1, y, z]. Each of them results in the formation of a 12-membered hydrogen-bonded R42(12) ring graph set (Bernstein et al., 1995), which links two hexaaquanickel(II) cations together. These distinct hydrogen-bonding interactions (Fig. 2) are together responsible for the formation of a 20-membered hydrogen-bonded R84(20) ring graph set with two chains of five water molecules. In this way, the hexaaquanickel(II) cations are interconnected together and a two-dimensional supramolecular network of the structure parallel to the ab plane (Fig. 2) is formed.
The 2-N-isothiouronium-S-ylmethyl-2-carboxy-1,3-propandiyl phosphate anion contains a phosphate ester anion, a carboxylate anion and a N-isothiouronium cation. The deprotonated carboxylate group O8/C4/O9 lies on the equatorial site of atom C2 of the chair six-membered ring and its two C—O bonds are equivalent. The N-isothiouronium cation N1/C6/N2 is connected with the methyl group on the axial site of atom C2 via S1 atom and its N—C—N bond is also in a conjugated system (Table 1). In the present structure, there is an intermolecular dimer hydrogen-bonded D22(8) graph set interaction between the O atoms of the carboxylate group and the N—H bonds of the N-isothiouronium cation (Fig. 3). Interactions between N2—H2D and O8iii [symmetry codes: (iii) -x+1, -y, -z] result in the connectivity of these D22(8) graph sets to form two C(6) graph sets along the crystallographic a direction. N1—H1D and the water molecules O10 and O9v are also engaged in the connectivity with the phosphate ester anion. They are responsible for the formation of a hydrogen-bonded C22(10) graph set in the crystallographic b direction. Thus, another two-dimensional layer network of the phosphate ester anion parallel to ab plane is formed.
The structure of (I) as a whole consists of these two distinct types of layers, which are stacked alternately in the [001] direction. The connectivity between the neighbouring layers is mainly completed via the hydrogen-bond interactions between the O atoms of the P—O bond and water molecules. The P1 atom has a distorted tetrahedral environment. The P1—O bonds are longer than corresponding ones in C12H9N2+.OP(OCH2)3CCOO-.OP(OCH2)3CCOOH.H2O (Wang, et al., 2007) and in O=P(OCH2)3CCH2OH (Guo & Zang, 2007), where P=O distances are in the range 1.446 (3)–1.4573 (15) Å, while P—O single bond distances cover the range 1.535 (4)–1.5667 (15) Å. This indicates that the ring stretch of the present phosphate ester anion is smaller than that of the caged phosphate ester. The O4—P1—O5 bond share a negative charge, so atoms O4 and O5 can act as efficient H-atom acceptors. Thus, for atoms O4 and O5 there are three hydrogen-bond interactions, respectively (Table 2). Interestingly, atom H11A is involved in an unexpected intermolecular O11—H11A···O7vii hydrogen bond [symmetry codes: (vii) -x+1, -y, -z+1], where the O atom of C2—O7—P1 group acts as acceptor. The water molecules (atoms O10, O11 and O12) act as both proton donor and proton acceptor to link the phosphate ester anion to the Ni atoms via coordinated water molecules. The whole three-dimensional structure is maintained and stabilized by the presence of these intra- and interlayer hydrogen bonds (Table 2).