Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104023704/sk1775sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104023704/sk1775Isup2.hkl |
CCDC reference: 256997
Compound (I), [{Ba3(Cl2CP2O6H)2(H2O)4}·H2O]n, was crystallized by the gel method using Na2Cl2C(PO3H)2·4H2O (0.014 mmol, 5.0 mg) and Ba(NO3)2 (0.017 mmol, 4.5 mg). These compounds were dissolved in water (0.8 ml, pH 4), tetramethoxysilane (TMOS, 0.2 ml) was added, and the solution was then shaken until homogenous. After gel formation, acetone (1.0 ml) was placed above the gel as precipitant. Needle-shaped crystals of (I) formed in and above the gel, and they were purified for characterization under the microscope. Analysis found: C 2.45, H 0.71, Ba 41.7%; calculated for C2H12O17Ba3Cl4P4: C 2.44, H 1.23, Ba 41.8%.
H atoms were located in Fourier difference maps with O—H distances ~0.85 Å, and a riding model was used, with Uiso(H) = 1.5Ueq(O).
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXL97.
[Ba3(CHCl2O6P2)2(H2O)4]·H2O | F(000) = 1824 |
Mr = 985.82 | Dx = 3.089 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 24802 reflections |
a = 11.4147 (3) Å | θ = 2.8–26.0° |
b = 12.9907 (4) Å | µ = 6.40 mm−1 |
c = 14.2937 (5) Å | T = 120 K |
β = 90.290 (2)° | Needle, colourless |
V = 2119.51 (11) Å3 | 0.25 × 0.10 × 0.10 mm |
Z = 4 |
Nonius KappaCCD area-detector diffractometer | 4133 independent reflections |
Radiation source: fine-focus sealed tube | 3746 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
type of scans | θmax = 26.0°, θmin = 2.8° |
Absorption correction: multi-scan (XPREP in SHELXTL; Bruker, 1998) | h = −14→14 |
Tmin = 0.277, Tmax = 0.528 | k = −16→16 |
24802 measured reflections | l = −17→17 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.057 | w = 1/[σ2(Fo2) + (0.0176P)2 + 7.3351P] where P = (Fo2 + 2Fc2)/3 |
S = 1.13 | (Δ/σ)max < 0.001 |
4133 reflections | Δρmax = 0.72 e Å−3 |
272 parameters | Δρmin = −0.82 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00049 (6) |
[Ba3(CHCl2O6P2)2(H2O)4]·H2O | V = 2119.51 (11) Å3 |
Mr = 985.82 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.4147 (3) Å | µ = 6.40 mm−1 |
b = 12.9907 (4) Å | T = 120 K |
c = 14.2937 (5) Å | 0.25 × 0.10 × 0.10 mm |
β = 90.290 (2)° |
Nonius KappaCCD area-detector diffractometer | 4133 independent reflections |
Absorption correction: multi-scan (XPREP in SHELXTL; Bruker, 1998) | 3746 reflections with I > 2σ(I) |
Tmin = 0.277, Tmax = 0.528 | Rint = 0.054 |
24802 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.057 | H-atom parameters constrained |
S = 1.13 | Δρmax = 0.72 e Å−3 |
4133 reflections | Δρmin = −0.82 e Å−3 |
272 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 | ||
Ba1 | −0.11188 (2) | 0.130025 (18) | 0.514612 (18) | 0.01125 (8) | |
Ba2 | 0.01823 (2) | 0.368685 (18) | 0.337945 (18) | 0.01007 (8) | |
Ba3 | 0.18538 (2) | 0.335076 (19) | 0.618552 (18) | 0.01152 (8) | |
Cl1 | 0.37361 (10) | 0.29439 (8) | 0.44452 (8) | 0.0164 (2) | |
Cl2 | 0.42071 (9) | 0.10881 (8) | 0.34054 (8) | 0.0170 (2) | |
Cl3 | −0.29801 (10) | 0.02586 (8) | 0.21423 (8) | 0.0176 (2) | |
Cl4 | −0.31975 (9) | 0.23672 (8) | 0.14453 (8) | 0.0169 (2) | |
C1 | 0.3323 (4) | 0.1619 (3) | 0.4317 (3) | 0.0112 (9) | |
C2 | −0.2255 (4) | 0.1262 (3) | 0.1515 (3) | 0.0107 (9) | |
P1 | 0.17709 (10) | 0.15788 (8) | 0.39167 (8) | 0.0095 (2) | |
P2 | 0.36085 (10) | 0.09218 (8) | 0.54189 (8) | 0.0113 (2) | |
P3 | −0.09084 (9) | 0.16235 (8) | 0.21712 (8) | 0.0092 (2) | |
P4 | −0.19793 (10) | 0.08175 (8) | 0.03015 (8) | 0.0104 (2) | |
O11 | 0.1063 (3) | 0.2156 (2) | 0.4649 (2) | 0.0125 (6) | |
O12 | 0.1739 (3) | 0.2140 (2) | 0.2988 (2) | 0.0116 (6) | |
O13 | 0.1489 (3) | 0.0443 (2) | 0.3865 (2) | 0.0133 (6) | |
O21 | 0.2836 (3) | 0.1401 (2) | 0.6136 (2) | 0.0138 (7) | |
O22 | 0.4910 (3) | 0.1158 (2) | 0.5684 (2) | 0.0157 (7) | |
H22 | 0.5413 | 0.0776 | 0.5422 | 0.023* | |
O23 | 0.3426 (3) | −0.0208 (2) | 0.5212 (2) | 0.0137 (6) | |
O31 | −0.1235 (3) | 0.1839 (2) | 0.3177 (2) | 0.0152 (7) | |
O32 | −0.0154 (3) | 0.0674 (2) | 0.2047 (2) | 0.0148 (6) | |
O33 | −0.0406 (3) | 0.2576 (2) | 0.1700 (2) | 0.0122 (6) | |
O41 | −0.1186 (3) | 0.1609 (2) | −0.0118 (2) | 0.0142 (6) | |
O42 | −0.3229 (3) | 0.0864 (2) | −0.0170 (2) | 0.0165 (7) | |
H42 | −0.3296 | 0.1460 | −0.0412 | 0.025* | |
O43 | −0.1556 (3) | −0.0275 (2) | 0.0307 (2) | 0.0141 (6) | |
O1 | 0.0753 (3) | 0.0380 (2) | 0.6134 (2) | 0.0166 (7) | |
H1A | 0.1367 | 0.0747 | 0.6188 | 0.025* | |
H1B | 0.0785 | −0.0087 | 0.6550 | 0.025* | |
O2 | −0.3309 (3) | 0.2321 (3) | 0.3960 (3) | 0.0269 (8) | |
H2A | −0.2767 | 0.2065 | 0.3637 | 0.040* | |
H2B | −0.3614 | 0.1843 | 0.4285 | 0.040* | |
O3 | −0.1996 (3) | 0.4634 (2) | 0.2859 (2) | 0.0160 (7) | |
H3A | −0.1721 | 0.4848 | 0.2343 | 0.024* | |
H3B | −0.2583 | 0.4253 | 0.2736 | 0.024* | |
O4 | 0.4180 (3) | 0.4077 (3) | 0.6269 (3) | 0.0279 (8) | |
H4A | 0.4286 | 0.4689 | 0.6464 | 0.042* | |
H4B | 0.4796 | 0.3878 | 0.6002 | 0.042* | |
O5 | 0.4422 (3) | 0.6004 (3) | 0.7230 (3) | 0.0292 (8) | |
H5A | 0.4343 | 0.6495 | 0.6842 | 0.044* | |
H5B | 0.4824 | 0.6219 | 0.7689 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ba1 | 0.01566 (15) | 0.00770 (13) | 0.01037 (15) | −0.00007 (9) | −0.00102 (10) | 0.00007 (10) |
Ba2 | 0.01298 (14) | 0.00725 (13) | 0.00998 (14) | 0.00006 (9) | −0.00127 (10) | 0.00002 (10) |
Ba3 | 0.01581 (15) | 0.00977 (13) | 0.00899 (14) | 0.00212 (10) | 0.00093 (10) | 0.00020 (10) |
Cl1 | 0.0178 (6) | 0.0119 (5) | 0.0196 (6) | −0.0031 (4) | 0.0012 (4) | −0.0018 (4) |
Cl2 | 0.0151 (5) | 0.0208 (5) | 0.0151 (6) | 0.0027 (4) | 0.0038 (4) | −0.0037 (5) |
Cl3 | 0.0180 (6) | 0.0184 (5) | 0.0164 (6) | −0.0071 (4) | 0.0014 (4) | 0.0037 (4) |
Cl4 | 0.0156 (5) | 0.0166 (5) | 0.0185 (6) | 0.0062 (4) | −0.0005 (4) | −0.0015 (4) |
C1 | 0.012 (2) | 0.0103 (19) | 0.011 (2) | 0.0004 (17) | 0.0031 (17) | −0.0050 (17) |
C2 | 0.009 (2) | 0.0079 (19) | 0.015 (2) | −0.0001 (16) | −0.0014 (17) | 0.0032 (17) |
P1 | 0.0105 (5) | 0.0095 (5) | 0.0086 (5) | 0.0005 (4) | −0.0006 (4) | 0.0009 (4) |
P2 | 0.0116 (5) | 0.0111 (5) | 0.0111 (6) | 0.0021 (4) | −0.0023 (4) | −0.0003 (4) |
P3 | 0.0111 (5) | 0.0077 (5) | 0.0087 (5) | −0.0005 (4) | −0.0014 (4) | 0.0001 (4) |
P4 | 0.0128 (6) | 0.0089 (5) | 0.0096 (6) | −0.0015 (4) | −0.0016 (4) | −0.0004 (4) |
O11 | 0.0122 (15) | 0.0139 (15) | 0.0113 (15) | 0.0041 (12) | 0.0001 (12) | −0.0013 (13) |
O12 | 0.0136 (15) | 0.0126 (14) | 0.0086 (15) | 0.0000 (12) | −0.0011 (12) | 0.0012 (12) |
O13 | 0.0198 (17) | 0.0099 (15) | 0.0101 (16) | −0.0008 (12) | −0.0048 (12) | 0.0013 (12) |
O21 | 0.0140 (16) | 0.0123 (15) | 0.0152 (17) | 0.0033 (12) | −0.0006 (13) | 0.0011 (13) |
O22 | 0.0110 (16) | 0.0159 (15) | 0.0200 (18) | 0.0025 (12) | −0.0047 (13) | −0.0038 (13) |
O23 | 0.0132 (16) | 0.0127 (15) | 0.0151 (16) | 0.0030 (12) | −0.0020 (12) | −0.0013 (13) |
O31 | 0.0174 (17) | 0.0167 (16) | 0.0115 (16) | −0.0024 (13) | −0.0007 (13) | 0.0020 (13) |
O32 | 0.0145 (15) | 0.0087 (14) | 0.0211 (17) | 0.0010 (12) | −0.0044 (13) | −0.0040 (13) |
O33 | 0.0162 (16) | 0.0112 (15) | 0.0091 (16) | −0.0014 (12) | −0.0020 (12) | 0.0009 (12) |
O41 | 0.0191 (17) | 0.0115 (14) | 0.0119 (16) | −0.0035 (12) | 0.0025 (13) | −0.0014 (13) |
O42 | 0.0181 (17) | 0.0157 (16) | 0.0156 (17) | −0.0034 (13) | −0.0069 (13) | 0.0008 (13) |
O43 | 0.0213 (17) | 0.0077 (14) | 0.0132 (16) | 0.0011 (12) | −0.0021 (13) | −0.0022 (12) |
O1 | 0.0177 (17) | 0.0125 (15) | 0.0195 (17) | 0.0000 (13) | −0.0009 (13) | 0.0041 (13) |
O2 | 0.0249 (19) | 0.0231 (18) | 0.033 (2) | −0.0077 (15) | 0.0123 (15) | −0.0078 (16) |
O3 | 0.0151 (16) | 0.0183 (16) | 0.0145 (17) | −0.0037 (13) | −0.0020 (13) | 0.0034 (13) |
O4 | 0.0245 (19) | 0.032 (2) | 0.028 (2) | 0.0000 (16) | 0.0010 (15) | −0.0098 (17) |
O5 | 0.032 (2) | 0.0274 (19) | 0.029 (2) | 0.0001 (16) | −0.0025 (16) | −0.0001 (17) |
Ba1—O13i | 2.704 (3) | C1—P2 | 1.844 (5) |
Ba1—O41ii | 2.743 (3) | C1—P1 | 1.860 (4) |
Ba1—O33ii | 2.776 (3) | C2—P3 | 1.857 (4) |
Ba1—O1 | 2.821 (3) | C2—P4 | 1.857 (5) |
Ba1—O11 | 2.822 (3) | P1—O13 | 1.512 (3) |
Ba1—O1i | 2.880 (3) | P1—O12 | 1.514 (3) |
Ba1—O31 | 2.902 (3) | P1—O11 | 1.523 (3) |
Ba1—O23i | 3.032 (3) | P2—O21 | 1.492 (3) |
Ba1—O2 | 3.292 (4) | P2—O23 | 1.512 (3) |
Ba2—O32iii | 2.653 (3) | P2—O22 | 1.562 (3) |
Ba2—O41ii | 2.689 (3) | P3—O31 | 1.514 (3) |
Ba2—O12 | 2.742 (3) | P3—O32 | 1.515 (3) |
Ba2—O43iii | 2.788 (3) | P3—O33 | 1.522 (3) |
Ba2—O3 | 2.869 (3) | P4—O41 | 1.498 (3) |
Ba2—O11 | 2.871 (3) | P4—O43 | 1.500 (3) |
Ba2—O33 | 2.878 (3) | P4—O42 | 1.575 (3) |
Ba2—O31 | 2.909 (3) | O22—H22 | 0.8473 |
Ba3—O12ii | 2.658 (3) | O42—H42 | 0.8521 |
Ba3—O21 | 2.772 (3) | O1—H1A | 0.8500 |
Ba3—O43iii | 2.801 (3) | O1—H1B | 0.8500 |
Ba3—O4 | 2.820 (4) | O2—H2A | 0.8416 |
Ba3—O11 | 2.833 (3) | O2—H2B | 0.8516 |
Ba3—O32ii | 2.898 (3) | O3—H3A | 0.8500 |
Ba3—O33ii | 2.943 (3) | O3—H3B | 0.8506 |
Ba3—O3iv | 2.957 (3) | O4—H4A | 0.8514 |
Cl1—C1 | 1.793 (4) | O4—H4B | 0.8425 |
Cl2—C1 | 1.791 (4) | O5—H5A | 0.8499 |
Cl3—C2 | 1.788 (4) | O5—H5B | 0.8468 |
Cl4—C2 | 1.796 (4) | ||
O13i—Ba1—O41ii | 153.75 (9) | O32ii—Ba3—O3iv | 57.21 (8) |
O13i—Ba1—O33ii | 93.93 (9) | O33ii—Ba3—O3iv | 107.03 (8) |
O41ii—Ba1—O33ii | 66.25 (9) | Cl2—C1—Cl1 | 107.2 (2) |
O13i—Ba1—O1 | 60.24 (9) | Cl2—C1—P2 | 109.5 (2) |
O41ii—Ba1—O1 | 120.60 (9) | Cl1—C1—P2 | 109.8 (2) |
O33ii—Ba1—O1 | 66.69 (9) | Cl2—C1—P1 | 107.7 (2) |
O13i—Ba1—O11 | 127.03 (9) | Cl1—C1—P1 | 107.9 (2) |
O41ii—Ba1—O11 | 66.38 (9) | P2—C1—P1 | 114.4 (2) |
O33ii—Ba1—O11 | 74.84 (9) | Cl3—C2—Cl4 | 109.4 (2) |
O1—Ba1—O11 | 68.01 (9) | Cl3—C2—P3 | 108.4 (2) |
O13i—Ba1—O1i | 73.79 (9) | Cl4—C2—P3 | 108.7 (2) |
O41ii—Ba1—O1i | 131.84 (9) | Cl3—C2—P4 | 108.8 (2) |
O33ii—Ba1—O1i | 149.77 (9) | Cl4—C2—P4 | 107.5 (2) |
O1—Ba1—O1i | 83.39 (10) | P3—C2—P4 | 114.0 (2) |
O11—Ba1—O1i | 90.46 (9) | O13—P1—O12 | 114.99 (17) |
O13i—Ba1—O31 | 134.61 (9) | O13—P1—O11 | 113.63 (18) |
O41ii—Ba1—O31 | 68.08 (9) | O12—P1—O11 | 110.79 (17) |
O33ii—Ba1—O31 | 131.34 (9) | O13—P1—C1 | 104.15 (18) |
O1—Ba1—O31 | 128.19 (9) | O12—P1—C1 | 105.98 (18) |
O11—Ba1—O31 | 72.37 (8) | O11—P1—C1 | 106.39 (18) |
O1i—Ba1—O31 | 64.71 (9) | O21—P2—O23 | 117.27 (18) |
O13i—Ba1—O23i | 63.79 (8) | O21—P2—O22 | 108.44 (18) |
O41ii—Ba1—O23i | 114.60 (8) | O23—P2—O22 | 111.63 (17) |
O33ii—Ba1—O23i | 129.19 (8) | O21—P2—C1 | 106.25 (18) |
O1—Ba1—O23i | 122.76 (8) | O23—P2—C1 | 106.63 (18) |
O11—Ba1—O23i | 155.34 (8) | O22—P2—C1 | 105.89 (19) |
O1i—Ba1—O23i | 70.53 (8) | O31—P3—O32 | 113.86 (18) |
O31—Ba1—O23i | 85.05 (8) | O31—P3—O33 | 111.47 (17) |
O13i—Ba1—O2 | 119.09 (9) | O32—P3—O33 | 113.17 (17) |
O41ii—Ba1—O2 | 60.63 (9) | O31—P3—C2 | 108.61 (19) |
O33ii—Ba1—O2 | 114.75 (8) | O32—P3—C2 | 101.84 (18) |
O1—Ba1—O2 | 178.54 (9) | O33—P3—C2 | 107.13 (17) |
O11—Ba1—O2 | 112.36 (8) | O41—P4—O43 | 117.15 (18) |
O1i—Ba1—O2 | 95.18 (8) | O41—P4—O42 | 110.50 (18) |
O31—Ba1—O2 | 51.14 (9) | O43—P4—O42 | 109.22 (17) |
O23i—Ba1—O2 | 56.30 (8) | O41—P4—C2 | 105.44 (18) |
O32iii—Ba2—O41ii | 108.42 (9) | O43—P4—C2 | 110.26 (18) |
O32iii—Ba2—O12 | 132.35 (9) | O42—P4—C2 | 103.33 (18) |
O41ii—Ba2—O12 | 115.95 (9) | P1—O11—Ba1 | 116.80 (15) |
O32iii—Ba2—O43iii | 71.97 (9) | P1—O11—Ba3 | 129.39 (16) |
O41ii—Ba2—O43iii | 81.84 (9) | Ba1—O11—Ba3 | 107.39 (10) |
O12—Ba2—O43iii | 97.42 (9) | P1—O11—Ba2 | 95.27 (14) |
O32iii—Ba2—O3 | 60.88 (9) | Ba1—O11—Ba2 | 97.20 (9) |
O41ii—Ba2—O3 | 76.24 (9) | Ba3—O11—Ba2 | 102.70 (9) |
O12—Ba2—O3 | 145.39 (9) | P1—O12—Ba3v | 137.15 (17) |
O43iii—Ba2—O3 | 116.80 (9) | P1—O12—Ba2 | 100.77 (14) |
O32iii—Ba2—O11 | 145.42 (9) | Ba3v—O12—Ba2 | 114.12 (10) |
O41ii—Ba2—O11 | 66.37 (9) | P1—O13—Ba1i | 145.65 (17) |
O12—Ba2—O11 | 52.84 (8) | P2—O21—Ba3 | 129.72 (17) |
O43iii—Ba2—O11 | 73.45 (8) | P2—O22—H22 | 115.0 |
O3—Ba2—O11 | 139.58 (9) | P2—O23—Ba1i | 127.31 (16) |
O32iii—Ba2—O33 | 107.09 (9) | P3—O31—Ba1 | 150.05 (17) |
O41ii—Ba2—O33 | 117.43 (9) | P3—O31—Ba2 | 96.14 (14) |
O12—Ba2—O33 | 67.09 (8) | Ba1—O31—Ba2 | 94.59 (9) |
O43iii—Ba2—O33 | 158.82 (9) | P3—O32—Ba2vi | 144.34 (17) |
O3—Ba2—O33 | 78.51 (8) | P3—O32—Ba3v | 98.36 (14) |
O11—Ba2—O33 | 105.04 (8) | Ba2vi—O32—Ba3v | 109.66 (10) |
O32iii—Ba2—O31 | 140.73 (9) | P3—O33—Ba1v | 132.21 (16) |
O41ii—Ba2—O31 | 68.67 (9) | P3—O33—Ba2 | 97.17 (13) |
O12—Ba2—O31 | 74.66 (9) | Ba1v—O33—Ba2 | 118.01 (10) |
O43iii—Ba2—O31 | 140.96 (8) | P3—O33—Ba3v | 96.38 (13) |
O3—Ba2—O31 | 81.21 (9) | Ba1v—O33—Ba3v | 105.62 (9) |
O11—Ba2—O31 | 71.58 (8) | Ba2—O33—Ba3v | 102.27 (9) |
O33—Ba2—O31 | 51.39 (8) | P4—O41—Ba2v | 125.22 (16) |
O12ii—Ba3—O21 | 80.06 (9) | P4—O41—Ba1v | 129.87 (17) |
O12ii—Ba3—O43iii | 152.20 (9) | Ba2v—O41—Ba1v | 103.62 (10) |
O21—Ba3—O43iii | 127.65 (9) | P4—O42—H42 | 106.8 |
O12ii—Ba3—O4 | 95.18 (10) | P4—O43—Ba2vi | 129.88 (17) |
O21—Ba3—O4 | 85.74 (10) | P4—O43—Ba3vi | 124.17 (16) |
O43iii—Ba3—O4 | 85.98 (10) | Ba2vi—O43—Ba3vi | 105.70 (9) |
O12ii—Ba3—O11 | 127.08 (9) | Ba1—O1—Ba1i | 96.61 (10) |
O21—Ba3—O11 | 66.86 (8) | Ba1—O1—H1A | 115.4 |
O43iii—Ba3—O11 | 73.84 (8) | Ba1i—O1—H1A | 111.1 |
O4—Ba3—O11 | 120.82 (9) | Ba1—O1—H1B | 133.0 |
O12ii—Ba3—O32ii | 69.49 (9) | Ba1i—O1—H1B | 84.2 |
O21—Ba3—O32ii | 136.97 (9) | H1A—O1—H1B | 107.7 |
O43iii—Ba3—O32ii | 87.24 (9) | Ba1—O2—H2A | 64.3 |
O4—Ba3—O32ii | 125.61 (9) | Ba1—O2—H2B | 74.8 |
O11—Ba3—O32ii | 108.62 (8) | H2A—O2—H2B | 108.3 |
O12ii—Ba3—O33ii | 67.18 (8) | Ba2—O3—Ba3iv | 102.39 (9) |
O21—Ba3—O33ii | 89.30 (9) | Ba2—O3—H3A | 92.4 |
O43iii—Ba3—O33ii | 110.34 (8) | Ba3iv—O3—H3A | 95.3 |
O4—Ba3—O33ii | 162.28 (9) | Ba2—O3—H3B | 119.0 |
O11—Ba3—O33ii | 72.14 (8) | Ba3iv—O3—H3B | 130.7 |
O32ii—Ba3—O33ii | 51.45 (8) | H3A—O3—H3B | 107.7 |
O12ii—Ba3—O3iv | 76.55 (9) | Ba3—O4—H4A | 117.3 |
O21—Ba3—O3iv | 143.11 (9) | Ba3—O4—H4B | 131.8 |
O43iii—Ba3—O3iv | 78.09 (8) | H4A—O4—H4B | 108.5 |
O4—Ba3—O3iv | 68.59 (9) | H5A—O5—H5B | 108.2 |
O11—Ba3—O3iv | 149.26 (8) |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, −y+1/2, z+1/2; (iii) −x, y+1/2, −z+1/2; (iv) −x, −y+1, −z+1; (v) x, −y+1/2, z−1/2; (vi) −x, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O22—H22···O23vii | 0.85 | 1.77 | 2.606 (4) | 169 |
O42—H42···O2v | 0.85 | 1.82 | 2.667 (4) | 173 |
O1—H1A···O21 | 0.85 | 1.88 | 2.722 (4) | 170 |
O1—H1B···O32i | 0.85 | 2.27 | 3.020 (4) | 148 |
O2—H2A···O31 | 0.84 | 1.89 | 2.697 (5) | 159 |
O2—H2B···O23i | 0.85 | 2.25 | 2.992 (5) | 146 |
O3—H3A···O13iii | 0.85 | 1.91 | 2.744 (4) | 166 |
O3—H3B···O5iv | 0.85 | 2.13 | 2.893 (5) | 150 |
O4—H4A···O5 | 0.85 | 2.03 | 2.868 (5) | 166 |
O5—H5A···O2iv | 0.85 | 2.25 | 3.037 (5) | 154 |
O5—H5B···O22viii | 0.85 | 2.35 | 3.081 (5) | 146 |
Symmetry codes: (i) −x, −y, −z+1; (iii) −x, y+1/2, −z+1/2; (iv) −x, −y+1, −z+1; (v) x, −y+1/2, z−1/2; (vii) −x+1, −y, −z+1; (viii) −x+1, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Ba3(CHCl2O6P2)2(H2O)4]·H2O |
Mr | 985.82 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 11.4147 (3), 12.9907 (4), 14.2937 (5) |
β (°) | 90.290 (2) |
V (Å3) | 2119.51 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 6.40 |
Crystal size (mm) | 0.25 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (XPREP in SHELXTL; Bruker, 1998) |
Tmin, Tmax | 0.277, 0.528 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24802, 4133, 3746 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.057, 1.13 |
No. of reflections | 4133 |
No. of parameters | 272 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.72, −0.82 |
Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), DENZO and SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL (Bruker, 1998), SHELXL97.
Ba1—O13i | 2.704 (3) | Ba3—O43iii | 2.801 (3) |
Ba1—O41ii | 2.743 (3) | Ba3—O4 | 2.820 (4) |
Ba1—O33ii | 2.776 (3) | Ba3—O11 | 2.833 (3) |
Ba1—O1 | 2.821 (3) | Ba3—O32ii | 2.898 (3) |
Ba1—O11 | 2.822 (3) | Ba3—O33ii | 2.943 (3) |
Ba1—O1i | 2.880 (3) | Ba3—O3iv | 2.957 (3) |
Ba1—O31 | 2.902 (3) | P1—O13 | 1.512 (3) |
Ba1—O23i | 3.032 (3) | P1—O12 | 1.514 (3) |
Ba1—O2 | 3.292 (4) | P1—O11 | 1.523 (3) |
Ba2—O32iii | 2.653 (3) | P2—O21 | 1.492 (3) |
Ba2—O41ii | 2.689 (3) | P2—O23 | 1.512 (3) |
Ba2—O12 | 2.742 (3) | P2—O22 | 1.562 (3) |
Ba2—O43iii | 2.788 (3) | P3—O31 | 1.514 (3) |
Ba2—O3 | 2.869 (3) | P3—O32 | 1.515 (3) |
Ba2—O11 | 2.871 (3) | P3—O33 | 1.522 (3) |
Ba2—O33 | 2.878 (3) | P4—O41 | 1.498 (3) |
Ba2—O31 | 2.909 (3) | P4—O43 | 1.500 (3) |
Ba3—O12ii | 2.658 (3) | P4—O42 | 1.575 (3) |
Ba3—O21 | 2.772 (3) | ||
P2—C1—P1 | 114.4 (2) | O22—P2—C1 | 105.89 (19) |
P3—C2—P4 | 114.0 (2) | O31—P3—C2 | 108.61 (19) |
O13—P1—C1 | 104.15 (18) | O32—P3—C2 | 101.84 (18) |
O12—P1—C1 | 105.98 (18) | O33—P3—C2 | 107.13 (17) |
O11—P1—C1 | 106.39 (18) | O41—P4—C2 | 105.44 (18) |
O21—P2—C1 | 106.25 (18) | O43—P4—C2 | 110.26 (18) |
O23—P2—C1 | 106.63 (18) | O42—P4—C2 | 103.33 (18) |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, −y+1/2, z+1/2; (iii) −x, y+1/2, −z+1/2; (iv) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O22—H22···O23v | 0.85 | 1.77 | 2.606 (4) | 169 |
O42—H42···O2vi | 0.85 | 1.82 | 2.667 (4) | 173 |
O1—H1A···O21 | 0.85 | 1.88 | 2.722 (4) | 170 |
O1—H1B···O32i | 0.85 | 2.27 | 3.020 (4) | 148 |
O2—H2A···O31 | 0.84 | 1.89 | 2.697 (5) | 159 |
O2—H2B···O23i | 0.85 | 2.25 | 2.992 (5) | 146 |
O3—H3A···O13iii | 0.85 | 1.91 | 2.744 (4) | 166 |
O3—H3B···O5iv | 0.85 | 2.13 | 2.893 (5) | 150 |
O4—H4A···O5 | 0.85 | 2.03 | 2.868 (5) | 166 |
O5—H5A···O2iv | 0.85 | 2.25 | 3.037 (5) | 154 |
O5—H5B···O22vii | 0.85 | 2.35 | 3.081 (5) | 146 |
Symmetry codes: (i) −x, −y, −z+1; (iii) −x, y+1/2, −z+1/2; (iv) −x, −y+1, −z+1; (v) −x+1, −y, −z+1; (vi) x, −y+1/2, z−1/2; (vii) −x+1, y+1/2, −z+3/2. |
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Due to the chemical applications of metal bisphosphonates in, for example, ion exchange, sorption and catalysis, research on the chemistry of metal phosphonates has recently focused on the properties of solid materials. The effectiveness of these materials is related to the degree of porosity, and their structures consist of chains, layers or pillared layers. The dimensionality is dependent on the number of donor atoms of the ligand, but also on the length of the organic group between the phosphonate groups and on the degree of protonation of the phosphonate group (Clearfield, 1998; Zhang & Clearfield, 1997; Alberti et al., 1996; Snover et al., 1996; Serre & Férey, 2002). Bisphosphonates also have pharmaceutical applications (Fleisch, 1995; Fleisch et al., 1969; Kanis & McCloskey, 1990; Bijvoet et al., 1995), and one of the best-documented methylene bisphosphonate derivatives in these applications is clodronate, (dichloromethylene)bisphosphonate (Major et al., 2000). Clodronate has six possible O-donor atoms and it also forms polymeric structures that can be utilized in chemical applications.
The previously reported crystal structures of Ca and Sr complexes of clodronate, [M{Cl2C(PO3H)2}(H2O)5] (M is Ca or Sr), revealed that clodronate itself acts only as a bidentate chelating ligand, forming monomeric compounds (Nardelli et al., 1983; Kontturi et al., 2004a). On the other hand, our results show that both clodronate and its partial ester derivative also produce polymers (Kontturi et al., 2002, 2004b). The title novel Ba complex of clodronate, [{Ba3(Cl2CP2O6H)2(H2O)4}·H2O]n, (I), is also a polymer, but its composition differs from the polymeric Ca complexes of clodronate described earlier (Kontturi et al., 2004b). Its preparation and crystal structure are reported here. \sch
Compound (I) is a polymer, the asymmetric unit consisting of three independent Ba2+ atoms, two chelating and bridging Cl2CP2O6H3− ligands and four aqua ligands (Fig. 1). Five O atoms of both Cl2CP2O6H3− ligands are coordinated to Ba atoms, forming four- and six-membered chelate rings and acting as monoatomic bridges between the metal atoms. Two O atoms (O11 and O33) are coordinated simultaneously to all three Ba atoms, the P—O distances being 1.523 (3) and 1.522 (3) Å. The other coordinated O atoms have P—O distances of 1.492 (3)–1.515 (3) Å, and the P—O distances of the remaining, protonated, O atoms are 1.562 (3) and 1.575 (3) Å. The other bond distances and angles of the Cl2CP2O6H3− ligand are all typical (Nardelli et al., 1983; Kontturi et al., 2002, 2004a,b).
Of the three Ba atoms in (I), Ba1 is nine-coordinated, while Ba2 and Ba3 are eight-coordinated. The coordination spheres of all Ba atoms consist of four Cl2CP2O6H3− ligands, the remaining coordination sites being occupied by aqua ligands. The Ba—O bond distances range from 2.653 (3) to 3.292 (4) Å (Table 1). The layers of (I) are parallel to the (100) plane, and they are packed via intermolecular hydrogen bonds, the O···O/Cl distances being 2.606 (4)–3.541 (4) Å (138–173°). The packing diagram (Fig. 2) shows pores between the layers in the direction of the b axis. These pores are filled with lattice water molecules.