Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802005809/om6084sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802005809/om6084Isup2.hkl |
CCDC reference: 185747
Warfarin sodium clathrate was obtained from Sigma Chemical Co. (St Louis, MO). Single crystals were prepared from warfarin sodium clathrate and 2-propanol (Hiskey & Melnitchenko, 1965). Every precaution was taken to exclude water from the system during crystallization. The compound was dried in a vacuum oven at about 418 K for about 200 min to remove the surface moisture. 2-Propanol was dried by first refluxing with calcium oxide (200 g l-1) in a round-bottomed flask for several hours. The distillate was further dried using 3 Å molecular sieves (Perrin & Armarego, 1988). Then, 90 mg of anhydrous warfarin sodium clathrate was dissolved in 9 ml of 2-propanol during refluxing. When the solid had dissolved, refluxing was stopped and the flask was allowed to stand undisturbed under a drying tube to exclude moisture. After a few days, as 2-propanol slowly evaporated, crystals of warfarin sodium 2-propanol solvate appeared.
The 2-propanol molecule was found to be disordered. It was refined with 20 restraints to force similar bond lengths and angles to maintain chemically reasonable values. In addition to the disorder of 2-propanol, a number of peaks were found in the difference Fourier map in the region of C5A–C8A. These peaks suggest a possible rotation around the C1A—C2A bond. Attempts to model any chemically reasonable disorder in this region failed.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Bruker, 1997); software used to prepare material for publication: SHELXTL/PC.
2Na+·2C38H30O8−·C3H8O | F(000) = 1512 |
Mr = 720.69 | Dx = 1.311 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 15.393 (2) Å | Cell parameters from 3390 reflections |
b = 11.2392 (17) Å | θ = 1.4–25.1° |
c = 22.124 (3) Å | µ = 0.11 mm−1 |
β = 107.424 (3)° | T = 173 K |
V = 3651.9 (9) Å3 | Irregular plate, colorless |
Z = 4 | 0.40 × 0.23 × 0.11 mm |
Bruker CCD area-detector diffractometer | 6472 independent reflections |
Radiation source: normal-focus sealed tube | 3895 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.060 |
ϕ and ω scans | θmax = 25.1°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −18→18 |
Tmin = 0.970, Tmax = 0.988 | k = −13→13 |
26991 measured reflections | l = −26→26 |
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)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.225 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0999P)2 + 5.7631P] where P = (Fo2 + 2Fc2)/3 |
6472 reflections | (Δ/σ)max = 0.010 |
487 parameters | Δρmax = 0.95 e Å−3 |
20 restraints | Δρmin = −0.48 e Å−3 |
2Na+·2C38H30O8−·C3H8O | V = 3651.9 (9) Å3 |
Mr = 720.69 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.393 (2) Å | µ = 0.11 mm−1 |
b = 11.2392 (17) Å | T = 173 K |
c = 22.124 (3) Å | 0.40 × 0.23 × 0.11 mm |
β = 107.424 (3)° |
Bruker CCD area-detector diffractometer | 6472 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 3895 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 0.988 | Rint = 0.060 |
26991 measured reflections |
R[F2 > 2σ(F2)] = 0.069 | 20 restraints |
wR(F2) = 0.225 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.95 e Å−3 |
6472 reflections | Δρmin = −0.48 e Å−3 |
487 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 | Occ. (<1) | |
Na1 | 0.28289 (10) | 0.48410 (14) | 0.21456 (9) | 0.0496 (5) | |
Na2 | 0.19189 (10) | 0.76079 (13) | 0.20748 (8) | 0.0425 (4) | |
O1A | 0.4218 (2) | 0.4289 (3) | 0.26762 (16) | 0.0539 (8) | |
O2A | 0.6052 (2) | 0.1870 (3) | 0.37154 (15) | 0.0563 (9) | |
O3A | 0.67354 (18) | 0.1725 (2) | 0.29947 (16) | 0.0499 (8) | |
O4A | 0.7297 (2) | 0.4382 (2) | 0.26860 (16) | 0.0528 (8) | |
C1A | 0.5533 (3) | 0.3356 (4) | 0.21103 (19) | 0.0431 (10) | |
H1AA | 0.6059 | 0.2890 | 0.2057 | 0.052* | |
C2A | 0.5481 (2) | 0.3066 (3) | 0.27707 (17) | 0.0309 (8) | |
C3A | 0.4815 (3) | 0.3588 (3) | 0.2996 (2) | 0.0383 (9) | |
C4A | 0.4819 (3) | 0.3279 (4) | 0.3638 (2) | 0.0525 (13) | |
C5A | 0.4266 (4) | 0.3773 (6) | 0.3954 (3) | 0.0776 (17) | |
H5AA | 0.3848 | 0.4374 | 0.3747 | 0.093* | |
C6A | 0.4287 (5) | 0.3447 (7) | 0.4544 (3) | 0.093 (2) | |
H6AA | 0.3917 | 0.3847 | 0.4755 | 0.112* | |
C7A | 0.4858 (4) | 0.2517 (7) | 0.4846 (3) | 0.0827 (19) | |
H7AA | 0.4832 | 0.2262 | 0.5250 | 0.099* | |
C8A | 0.5448 (5) | 0.1958 (6) | 0.4586 (3) | 0.087 (2) | |
H8AA | 0.5839 | 0.1332 | 0.4794 | 0.104* | |
C9A | 0.5431 (4) | 0.2399 (5) | 0.3968 (2) | 0.0555 (13) | |
C10A | 0.6102 (3) | 0.2235 (3) | 0.3131 (2) | 0.0370 (9) | |
C11A | 0.4689 (3) | 0.2898 (4) | 0.16047 (19) | 0.0416 (10) | |
C12A | 0.4604 (3) | 0.1683 (4) | 0.1495 (2) | 0.0559 (12) | |
H12A | 0.5071 | 0.1162 | 0.1727 | 0.067* | |
C13A | 0.3841 (4) | 0.1221 (5) | 0.1045 (2) | 0.0676 (15) | |
H13A | 0.3787 | 0.0386 | 0.0979 | 0.081* | |
C14A | 0.3164 (4) | 0.1961 (5) | 0.0695 (2) | 0.0676 (15) | |
H14A | 0.2644 | 0.1639 | 0.0390 | 0.081* | |
C15A | 0.3246 (3) | 0.3162 (5) | 0.0789 (2) | 0.0629 (14) | |
H15A | 0.2787 | 0.3679 | 0.0544 | 0.075* | |
C16A | 0.3999 (3) | 0.3634 (4) | 0.1244 (2) | 0.0512 (11) | |
H16A | 0.4043 | 0.4470 | 0.1309 | 0.061* | |
C17A | 0.5746 (3) | 0.4650 (4) | 0.2028 (2) | 0.0501 (11) | |
H17A | 0.5660 | 0.4800 | 0.1573 | 0.060* | |
H17B | 0.5302 | 0.5150 | 0.2157 | 0.060* | |
C18A | 0.6683 (3) | 0.5037 (4) | 0.2395 (2) | 0.0426 (10) | |
C19A | 0.6822 (4) | 0.6363 (4) | 0.2399 (3) | 0.0665 (14) | |
H19A | 0.7462 | 0.6535 | 0.2441 | 0.100* | |
H19B | 0.6662 | 0.6714 | 0.2757 | 0.100* | |
H19C | 0.6435 | 0.6703 | 0.2002 | 0.100* | |
O1B | 0.17373 (19) | 0.5785 (2) | 0.24931 (16) | 0.0520 (8) | |
O2B | 0.03431 (19) | 0.4232 (3) | 0.36036 (14) | 0.0473 (7) | |
O3B | −0.06410 (18) | 0.3416 (3) | 0.27758 (14) | 0.0452 (7) | |
O4B | 0.1739 (2) | 0.3400 (3) | 0.17109 (17) | 0.0589 (9) | |
C1B | 0.0110 (3) | 0.4410 (4) | 0.1850 (2) | 0.0414 (10) | |
H1BA | 0.0503 | 0.4885 | 0.1653 | 0.050* | |
C2B | 0.0500 (2) | 0.4597 (3) | 0.2557 (2) | 0.0373 (9) | |
C3B | 0.1285 (3) | 0.5284 (3) | 0.2815 (2) | 0.0409 (10) | |
C4B | 0.1596 (3) | 0.5416 (3) | 0.3513 (2) | 0.0469 (11) | |
C5B | 0.2384 (3) | 0.6060 (4) | 0.3833 (3) | 0.0646 (15) | |
H5BA | 0.2744 | 0.6416 | 0.3600 | 0.078* | |
C6B | 0.2637 (4) | 0.6175 (5) | 0.4484 (3) | 0.0786 (19) | |
H6BA | 0.3179 | 0.6593 | 0.4696 | 0.094* | |
C7B | 0.2108 (4) | 0.5689 (5) | 0.4831 (3) | 0.0776 (18) | |
H7BA | 0.2275 | 0.5802 | 0.5277 | 0.093* | |
C8B | 0.1343 (4) | 0.5044 (4) | 0.4531 (2) | 0.0619 (13) | |
H8BA | 0.0983 | 0.4698 | 0.4766 | 0.074* | |
C9B | 0.1103 (3) | 0.4904 (4) | 0.3877 (2) | 0.0476 (11) | |
C10B | 0.0033 (3) | 0.4055 (4) | 0.2948 (2) | 0.0393 (10) | |
C11B | −0.0849 (3) | 0.4929 (4) | 0.15855 (19) | 0.0402 (9) | |
C12B | −0.0953 (3) | 0.6152 (4) | 0.1560 (2) | 0.0571 (12) | |
H12B | −0.0437 | 0.6648 | 0.1730 | 0.069* | |
C13B | −0.1800 (4) | 0.6664 (5) | 0.1291 (3) | 0.0746 (17) | |
H13B | −0.1858 | 0.7506 | 0.1275 | 0.090* | |
C14B | −0.2558 (3) | 0.5962 (6) | 0.1047 (3) | 0.0693 (15) | |
H14B | −0.3136 | 0.6315 | 0.0855 | 0.083* | |
C15B | −0.2467 (3) | 0.4744 (5) | 0.1084 (2) | 0.0660 (14) | |
H15B | −0.2988 | 0.4252 | 0.0926 | 0.079* | |
C16B | −0.1621 (3) | 0.4233 (4) | 0.1349 (2) | 0.0542 (12) | |
H16B | −0.1568 | 0.3391 | 0.1370 | 0.065* | |
C17B | 0.0177 (3) | 0.3122 (4) | 0.1642 (2) | 0.0475 (11) | |
H17C | 0.0001 | 0.2590 | 0.1943 | 0.057* | |
H17D | −0.0274 | 0.3008 | 0.1221 | 0.057* | |
C18B | 0.1090 (3) | 0.2740 (4) | 0.1604 (2) | 0.0482 (11) | |
C19B | 0.1155 (3) | 0.1475 (4) | 0.1394 (3) | 0.0701 (15) | |
H19D | 0.1685 | 0.1395 | 0.1239 | 0.105* | |
H19E | 0.0601 | 0.1272 | 0.1054 | 0.105* | |
H19F | 0.1220 | 0.0936 | 0.1753 | 0.105* | |
O1S | 0.1022 (3) | 0.7687 (4) | 0.10006 (17) | 0.0797 (12) | 0.667 (13) |
H1SA | 0.0547 | 0.7924 | 0.1076 | 0.120* | 0.667 (13) |
C1S | 0.0783 (6) | 0.7120 (9) | 0.0392 (5) | 0.067 (3) | 0.667 (13) |
H1SB | 0.0816 | 0.7726 | 0.0069 | 0.101* | 0.667 (13) |
C2S | 0.1500 (13) | 0.619 (3) | 0.0426 (14) | 0.090 (3) | 0.667 (13) |
H2SA | 0.1474 | 0.5583 | 0.0738 | 0.136* | 0.667 (13) |
H2SB | 0.2103 | 0.6565 | 0.0552 | 0.136* | 0.667 (13) |
H2SC | 0.1391 | 0.5818 | 0.0009 | 0.136* | 0.667 (13) |
C3S | −0.0168 (7) | 0.6638 (12) | 0.0214 (6) | 0.076 (3) | 0.667 (13) |
H3SA | −0.0210 | 0.6030 | 0.0522 | 0.114* | 0.667 (13) |
H3SB | −0.0320 | 0.6284 | −0.0209 | 0.114* | 0.667 (13) |
H3SC | −0.0594 | 0.7285 | 0.0215 | 0.114* | 0.667 (13) |
O1S' | 0.1022 (3) | 0.7687 (4) | 0.10006 (17) | 0.0797 (12) | 0.333 (13) |
H1SD | 0.0696 | 0.8275 | 0.0843 | 0.120* | 0.333 (13) |
C1S' | 0.0726 (14) | 0.6670 (16) | 0.0605 (8) | 0.067 (3) | 0.333 (13) |
H1SC | 0.0546 | 0.6014 | 0.0849 | 0.101* | 0.333 (13) |
C2S' | 0.151 (3) | 0.628 (6) | 0.038 (3) | 0.090 (3) | 0.333 (13) |
H2SD | 0.1644 | 0.6905 | 0.0107 | 0.136* | 0.333 (13) |
H2SE | 0.1355 | 0.5544 | 0.0137 | 0.136* | 0.333 (13) |
H2SF | 0.2051 | 0.6155 | 0.0744 | 0.136* | 0.333 (13) |
C3S' | −0.0085 (17) | 0.709 (2) | 0.0081 (11) | 0.076 (3) | 0.333 (13) |
H3SD | −0.0558 | 0.7371 | 0.0261 | 0.114* | 0.333 (13) |
H3SE | −0.0324 | 0.6438 | −0.0214 | 0.114* | 0.333 (13) |
H3SF | 0.0098 | 0.7750 | −0.0147 | 0.114* | 0.333 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Na1 | 0.0321 (8) | 0.0326 (9) | 0.0875 (13) | 0.0005 (7) | 0.0231 (8) | 0.0061 (8) |
Na2 | 0.0311 (8) | 0.0289 (8) | 0.0685 (11) | 0.0007 (6) | 0.0165 (7) | −0.0022 (7) |
O1A | 0.0395 (17) | 0.0399 (17) | 0.082 (2) | 0.0108 (14) | 0.0175 (16) | −0.0092 (16) |
O2A | 0.0509 (19) | 0.0496 (19) | 0.060 (2) | −0.0091 (15) | 0.0038 (16) | 0.0101 (16) |
O3A | 0.0307 (15) | 0.0303 (15) | 0.091 (2) | 0.0018 (12) | 0.0212 (15) | −0.0036 (15) |
O4A | 0.0406 (17) | 0.0299 (15) | 0.086 (2) | 0.0039 (13) | 0.0164 (16) | 0.0090 (15) |
C1A | 0.046 (2) | 0.040 (2) | 0.045 (2) | −0.0049 (19) | 0.0161 (19) | 0.0008 (19) |
C2A | 0.0272 (19) | 0.0273 (19) | 0.040 (2) | −0.0022 (15) | 0.0125 (16) | −0.0016 (16) |
C3A | 0.030 (2) | 0.029 (2) | 0.057 (3) | −0.0021 (17) | 0.0143 (19) | −0.0115 (19) |
C4A | 0.051 (3) | 0.060 (3) | 0.064 (3) | −0.029 (2) | 0.044 (2) | −0.033 (3) |
C5A | 0.082 (4) | 0.078 (4) | 0.086 (4) | −0.010 (3) | 0.043 (3) | −0.020 (3) |
C6A | 0.104 (5) | 0.101 (5) | 0.084 (5) | −0.016 (4) | 0.043 (4) | −0.007 (4) |
C7A | 0.076 (4) | 0.117 (6) | 0.062 (4) | −0.041 (4) | 0.031 (3) | −0.011 (4) |
C8A | 0.087 (4) | 0.098 (5) | 0.068 (4) | −0.043 (4) | 0.015 (3) | −0.016 (3) |
C9A | 0.065 (3) | 0.061 (3) | 0.041 (3) | −0.034 (3) | 0.015 (2) | −0.004 (2) |
C10A | 0.028 (2) | 0.029 (2) | 0.054 (3) | −0.0075 (16) | 0.0125 (18) | 0.0017 (18) |
C11A | 0.045 (2) | 0.044 (2) | 0.038 (2) | −0.0060 (19) | 0.0159 (19) | −0.0010 (18) |
C12A | 0.064 (3) | 0.046 (3) | 0.052 (3) | −0.008 (2) | 0.009 (2) | −0.001 (2) |
C13A | 0.083 (4) | 0.052 (3) | 0.063 (3) | −0.017 (3) | 0.016 (3) | −0.016 (3) |
C14A | 0.057 (3) | 0.080 (4) | 0.058 (3) | −0.012 (3) | 0.004 (3) | −0.023 (3) |
C15A | 0.058 (3) | 0.072 (4) | 0.055 (3) | 0.010 (3) | 0.010 (2) | −0.012 (3) |
C16A | 0.053 (3) | 0.051 (3) | 0.050 (3) | 0.001 (2) | 0.016 (2) | −0.010 (2) |
C17A | 0.053 (3) | 0.045 (3) | 0.054 (3) | −0.002 (2) | 0.020 (2) | 0.009 (2) |
C18A | 0.037 (2) | 0.042 (2) | 0.053 (3) | −0.004 (2) | 0.019 (2) | 0.003 (2) |
C19A | 0.069 (3) | 0.040 (3) | 0.086 (4) | 0.006 (2) | 0.016 (3) | 0.010 (3) |
O1B | 0.0362 (16) | 0.0323 (16) | 0.094 (2) | −0.0027 (13) | 0.0294 (16) | 0.0045 (15) |
O2B | 0.0440 (17) | 0.0441 (17) | 0.0516 (18) | −0.0019 (14) | 0.0112 (14) | 0.0047 (14) |
O3B | 0.0336 (15) | 0.0443 (17) | 0.0593 (18) | −0.0079 (13) | 0.0161 (13) | 0.0086 (14) |
O4B | 0.0401 (17) | 0.0387 (17) | 0.103 (3) | −0.0028 (14) | 0.0298 (17) | −0.0034 (17) |
C1B | 0.035 (2) | 0.035 (2) | 0.057 (3) | −0.0030 (17) | 0.0192 (19) | 0.0021 (19) |
C2B | 0.027 (2) | 0.031 (2) | 0.055 (3) | 0.0014 (16) | 0.0140 (18) | 0.0050 (18) |
C3B | 0.030 (2) | 0.024 (2) | 0.071 (3) | 0.0051 (16) | 0.019 (2) | 0.0031 (19) |
C4B | 0.034 (2) | 0.025 (2) | 0.074 (3) | 0.0082 (17) | 0.005 (2) | −0.004 (2) |
C5B | 0.039 (3) | 0.034 (2) | 0.104 (4) | 0.002 (2) | −0.003 (3) | −0.007 (3) |
C6B | 0.058 (3) | 0.048 (3) | 0.099 (5) | 0.006 (3) | −0.023 (3) | −0.021 (3) |
C7B | 0.082 (4) | 0.049 (3) | 0.083 (4) | 0.015 (3) | −0.003 (3) | −0.011 (3) |
C8B | 0.067 (3) | 0.048 (3) | 0.060 (3) | 0.014 (3) | 0.003 (3) | 0.000 (2) |
C9B | 0.042 (2) | 0.035 (2) | 0.058 (3) | 0.007 (2) | 0.003 (2) | 0.000 (2) |
C10B | 0.031 (2) | 0.035 (2) | 0.051 (3) | 0.0053 (18) | 0.0095 (18) | 0.0060 (18) |
C11B | 0.038 (2) | 0.041 (2) | 0.043 (2) | −0.0002 (18) | 0.0152 (18) | 0.0044 (19) |
C12B | 0.045 (3) | 0.046 (3) | 0.081 (3) | −0.001 (2) | 0.022 (2) | 0.012 (2) |
C13B | 0.055 (3) | 0.056 (3) | 0.116 (5) | 0.014 (3) | 0.031 (3) | 0.032 (3) |
C14B | 0.043 (3) | 0.089 (4) | 0.071 (4) | 0.014 (3) | 0.011 (2) | 0.020 (3) |
C15B | 0.042 (3) | 0.082 (4) | 0.069 (3) | 0.001 (3) | 0.009 (2) | −0.012 (3) |
C16B | 0.040 (3) | 0.051 (3) | 0.070 (3) | −0.002 (2) | 0.015 (2) | −0.008 (2) |
C17B | 0.040 (2) | 0.045 (3) | 0.059 (3) | −0.0020 (19) | 0.017 (2) | −0.001 (2) |
C18B | 0.041 (2) | 0.041 (2) | 0.063 (3) | 0.001 (2) | 0.015 (2) | 0.003 (2) |
C19B | 0.052 (3) | 0.042 (3) | 0.115 (5) | 0.001 (2) | 0.022 (3) | −0.014 (3) |
O1S | 0.072 (3) | 0.103 (3) | 0.062 (2) | 0.020 (2) | 0.0153 (19) | −0.022 (2) |
C1S | 0.079 (5) | 0.062 (7) | 0.063 (6) | −0.010 (5) | 0.025 (5) | −0.009 (5) |
C2S | 0.095 (5) | 0.096 (6) | 0.091 (6) | −0.004 (4) | 0.044 (4) | −0.029 (5) |
C3S | 0.089 (5) | 0.076 (10) | 0.066 (6) | −0.007 (6) | 0.027 (5) | 0.002 (5) |
O1S' | 0.072 (3) | 0.103 (3) | 0.062 (2) | 0.020 (2) | 0.0153 (19) | −0.022 (2) |
C1S' | 0.079 (5) | 0.062 (7) | 0.063 (6) | −0.010 (5) | 0.025 (5) | −0.009 (5) |
C2S' | 0.095 (5) | 0.096 (6) | 0.091 (6) | −0.004 (4) | 0.044 (4) | −0.029 (5) |
C3S' | 0.089 (5) | 0.076 (10) | 0.066 (6) | −0.007 (6) | 0.027 (5) | 0.002 (5) |
Na1—O1A | 2.198 (3) | O4B—C18B | 1.209 (5) |
Na1—O3Ai | 2.271 (3) | C1B—C2B | 1.513 (6) |
Na1—O1B | 2.305 (3) | C1B—C11B | 1.530 (6) |
Na1—O4B | 2.323 (3) | C1B—C17B | 1.531 (6) |
Na1—Na2 | 3.395 (2) | C1B—H1BA | 1.0000 |
Na2—O3Bii | 2.279 (3) | C2B—C3B | 1.404 (6) |
Na2—O1B | 2.299 (3) | C2B—C10B | 1.418 (6) |
Na2—O4Ai | 2.309 (3) | C3B—C4B | 1.481 (6) |
Na2—O3Ai | 2.343 (3) | C4B—C9B | 1.386 (7) |
O1A—C3A | 1.256 (5) | C4B—C5B | 1.408 (6) |
O2A—C9A | 1.378 (6) | C5B—C6B | 1.379 (8) |
O2A—C10A | 1.380 (5) | C5B—H5BA | 0.9500 |
O3A—C10A | 1.244 (5) | C6B—C7B | 1.389 (9) |
O3A—Na1iii | 2.271 (3) | C6B—H6BA | 0.9500 |
O3A—Na2iii | 2.343 (3) | C7B—C8B | 1.373 (8) |
O4A—C18A | 1.219 (5) | C7B—H7BA | 0.9500 |
O4A—Na2iii | 2.309 (3) | C8B—C9B | 1.389 (7) |
C1A—C17A | 1.513 (6) | C8B—H8BA | 0.9500 |
C1A—C2A | 1.522 (5) | C11B—C12B | 1.384 (6) |
C1A—C11A | 1.528 (6) | C11B—C16B | 1.388 (6) |
C1A—H1AA | 1.0000 | C12B—C13B | 1.387 (7) |
C2A—C3A | 1.397 (5) | C12B—H12B | 0.9500 |
C2A—C10A | 1.402 (5) | C13B—C14B | 1.377 (8) |
C3A—C4A | 1.460 (6) | C13B—H13B | 0.9500 |
C4A—C5A | 1.370 (7) | C14B—C15B | 1.376 (8) |
C4A—C9A | 1.409 (7) | C14B—H14B | 0.9500 |
C5A—C6A | 1.348 (8) | C15B—C16B | 1.383 (7) |
C5A—H5AA | 0.9500 | C15B—H15B | 0.9500 |
C6A—C7A | 1.399 (9) | C16B—H16B | 0.9500 |
C6A—H6AA | 0.9500 | C17B—C18B | 1.496 (6) |
C7A—C8A | 1.366 (9) | C17B—H17C | 0.9900 |
C7A—H7AA | 0.9500 | C17B—H17D | 0.9900 |
C8A—C9A | 1.447 (8) | C18B—C19B | 1.509 (6) |
C8A—H8AA | 0.9500 | C19B—H19D | 0.9800 |
C11A—C12A | 1.385 (6) | C19B—H19E | 0.9800 |
C11A—C16A | 1.394 (6) | C19B—H19F | 0.9800 |
C12A—C13A | 1.392 (7) | O1S—C1S | 1.434 (8) |
C12A—H12A | 0.9500 | O1S—H1SA | 0.8400 |
C13A—C14A | 1.377 (8) | C1S—C3S | 1.498 (11) |
C13A—H13A | 0.9500 | C1S—C2S | 1.506 (15) |
C14A—C15A | 1.367 (7) | C1S—H1SB | 1.0000 |
C14A—H14A | 0.9500 | C2S—H2SA | 0.9800 |
C15A—C16A | 1.392 (6) | C2S—H2SB | 0.9800 |
C15A—H15A | 0.9500 | C2S—H2SC | 0.9800 |
C16A—H16A | 0.9500 | C3S—H3SA | 0.9800 |
C17A—C18A | 1.491 (6) | C3S—H3SB | 0.9800 |
C17A—H17A | 0.9900 | C3S—H3SC | 0.9800 |
C17A—H17B | 0.9900 | C1S'—C3S' | 1.505 (16) |
C18A—C19A | 1.505 (6) | C1S'—C2S' | 1.507 (18) |
C19A—H19A | 0.9800 | C1S'—H1SC | 1.0000 |
C19A—H19B | 0.9800 | C2S'—H2SD | 0.9800 |
C19A—H19C | 0.9800 | C2S'—H2SE | 0.9800 |
O1B—C3B | 1.268 (5) | C2S'—H2SF | 0.9800 |
O2B—C9B | 1.372 (5) | C3S'—H3SD | 0.9800 |
O2B—C10B | 1.398 (5) | C3S'—H3SE | 0.9800 |
O3B—C10B | 1.224 (5) | C3S'—H3SF | 0.9800 |
O3B—Na2iv | 2.279 (3) | ||
O1A—Na1—O3Ai | 93.22 (12) | C3B—O1B—Na1 | 124.2 (2) |
O1A—Na1—O1B | 129.90 (15) | Na2—O1B—Na1 | 95.01 (12) |
O3Ai—Na1—O1B | 83.74 (11) | C9B—O2B—C10B | 121.2 (3) |
O1A—Na1—O4B | 119.39 (13) | C10B—O3B—Na2iv | 151.1 (3) |
O3Ai—Na1—O4B | 143.13 (14) | C18B—O4B—Na1 | 163.8 (3) |
O1B—Na1—O4B | 87.19 (11) | C2B—C1B—C11B | 112.4 (3) |
O1A—Na1—Na2 | 127.23 (10) | C2B—C1B—C17B | 113.6 (3) |
O3Ai—Na1—Na2 | 43.45 (8) | C11B—C1B—C17B | 112.9 (3) |
O1B—Na1—Na2 | 42.43 (8) | C2B—C1B—H1BA | 105.7 |
O4B—Na1—Na2 | 112.51 (9) | C11B—C1B—H1BA | 105.7 |
O3Bii—Na2—O1B | 94.74 (12) | C17B—C1B—H1BA | 105.7 |
O3Bii—Na2—O4Ai | 92.14 (11) | C3B—C2B—C10B | 121.3 (4) |
O1B—Na2—O4Ai | 142.70 (14) | C3B—C2B—C1B | 121.6 (4) |
O3Bii—Na2—O3Ai | 175.43 (14) | C10B—C2B—C1B | 117.1 (3) |
O1B—Na2—O3Ai | 82.27 (11) | O1B—C3B—C2B | 124.5 (4) |
O4Ai—Na2—O3Ai | 88.20 (11) | O1B—C3B—C4B | 118.8 (4) |
O3Bii—Na2—Na1 | 136.11 (10) | C2B—C3B—C4B | 116.7 (4) |
O1B—Na2—Na1 | 42.56 (8) | C9B—C4B—C5B | 117.4 (5) |
O4Ai—Na2—Na1 | 126.88 (9) | C9B—C4B—C3B | 120.2 (4) |
O3Ai—Na2—Na1 | 41.80 (8) | C5B—C4B—C3B | 122.4 (5) |
C3A—O1A—Na1 | 155.3 (3) | C6B—C5B—C4B | 120.3 (6) |
C9A—O2A—C10A | 119.5 (3) | C6B—C5B—H5BA | 119.9 |
C10A—O3A—Na1iii | 138.4 (2) | C4B—C5B—H5BA | 119.9 |
C10A—O3A—Na2iii | 126.4 (2) | C5B—C6B—C7B | 120.8 (5) |
Na1iii—O3A—Na2iii | 94.75 (11) | C5B—C6B—H6BA | 119.6 |
C18A—O4A—Na2iii | 155.8 (3) | C7B—C6B—H6BA | 119.6 |
C17A—C1A—C2A | 113.3 (3) | C8B—C7B—C6B | 120.0 (6) |
C17A—C1A—C11A | 113.8 (4) | C8B—C7B—H7BA | 120.0 |
C2A—C1A—C11A | 110.7 (3) | C6B—C7B—H7BA | 120.0 |
C17A—C1A—H1AA | 106.1 | C7B—C8B—C9B | 119.1 (6) |
C2A—C1A—H1AA | 106.1 | C7B—C8B—H8BA | 120.5 |
C11A—C1A—H1AA | 106.1 | C9B—C8B—H8BA | 120.5 |
C3A—C2A—C10A | 121.6 (4) | O2B—C9B—C4B | 121.0 (4) |
C3A—C2A—C1A | 120.5 (3) | O2B—C9B—C8B | 116.6 (4) |
C10A—C2A—C1A | 117.8 (3) | C4B—C9B—C8B | 122.4 (4) |
O1A—C3A—C2A | 123.6 (4) | O3B—C10B—O2B | 113.7 (4) |
O1A—C3A—C4A | 119.1 (4) | O3B—C10B—C2B | 126.7 (4) |
C2A—C3A—C4A | 117.3 (4) | O2B—C10B—C2B | 119.6 (4) |
C5A—C4A—C9A | 116.2 (5) | C12B—C11B—C16B | 118.0 (4) |
C5A—C4A—C3A | 125.2 (5) | C12B—C11B—C1B | 118.7 (4) |
C9A—C4A—C3A | 118.6 (4) | C16B—C11B—C1B | 123.3 (4) |
C6A—C5A—C4A | 123.0 (7) | C11B—C12B—C13B | 120.8 (5) |
C6A—C5A—H5AA | 118.5 | C11B—C12B—H12B | 119.6 |
C4A—C5A—H5AA | 118.5 | C13B—C12B—H12B | 119.6 |
C5A—C6A—C7A | 119.7 (7) | C14B—C13B—C12B | 120.5 (5) |
C5A—C6A—H6AA | 120.2 | C14B—C13B—H13B | 119.7 |
C7A—C6A—H6AA | 120.2 | C12B—C13B—H13B | 119.7 |
C8A—C7A—C6A | 123.0 (6) | C15B—C14B—C13B | 119.2 (5) |
C8A—C7A—H7AA | 118.5 | C15B—C14B—H14B | 120.4 |
C6A—C7A—H7AA | 118.5 | C13B—C14B—H14B | 120.4 |
C7A—C8A—C9A | 114.5 (7) | C14B—C15B—C16B | 120.3 (5) |
C7A—C8A—H8AA | 122.8 | C14B—C15B—H15B | 119.9 |
C9A—C8A—H8AA | 122.8 | C16B—C15B—H15B | 119.9 |
O2A—C9A—C4A | 122.0 (4) | C15B—C16B—C11B | 121.1 (5) |
O2A—C9A—C8A | 114.6 (5) | C15B—C16B—H16B | 119.4 |
C4A—C9A—C8A | 123.4 (5) | C11B—C16B—H16B | 119.4 |
O3A—C10A—O2A | 111.0 (4) | C18B—C17B—C1B | 115.9 (4) |
O3A—C10A—C2A | 128.3 (4) | C18B—C17B—H17C | 108.3 |
O2A—C10A—C2A | 120.8 (4) | C1B—C17B—H17C | 108.3 |
C12A—C11A—C16A | 118.0 (4) | C18B—C17B—H17D | 108.3 |
C12A—C11A—C1A | 118.4 (4) | C1B—C17B—H17D | 108.3 |
C16A—C11A—C1A | 123.6 (4) | H17C—C17B—H17D | 107.4 |
C11A—C12A—C13A | 120.5 (5) | O4B—C18B—C17B | 123.3 (4) |
C11A—C12A—H12A | 119.7 | O4B—C18B—C19B | 120.7 (4) |
C13A—C12A—H12A | 119.7 | C17B—C18B—C19B | 115.9 (4) |
C14A—C13A—C12A | 120.8 (5) | C18B—C19B—H19D | 109.5 |
C14A—C13A—H13A | 119.6 | C18B—C19B—H19E | 109.5 |
C12A—C13A—H13A | 119.6 | H19D—C19B—H19E | 109.5 |
C15A—C14A—C13A | 119.3 (5) | C18B—C19B—H19F | 109.5 |
C15A—C14A—H14A | 120.3 | H19D—C19B—H19F | 109.5 |
C13A—C14A—H14A | 120.3 | H19E—C19B—H19F | 109.5 |
C14A—C15A—C16A | 120.4 (5) | O1S—C1S—C3S | 111.3 (8) |
C14A—C15A—H15A | 119.8 | O1S—C1S—C2S | 106.5 (11) |
C16A—C15A—H15A | 119.8 | C3S—C1S—C2S | 114.0 (15) |
C15A—C16A—C11A | 121.0 (4) | O1S—C1S—H1SB | 108.3 |
C15A—C16A—H16A | 119.5 | C3S—C1S—H1SB | 108.3 |
C11A—C16A—H16A | 119.5 | C2S—C1S—H1SB | 108.3 |
C18A—C17A—C1A | 115.1 (4) | C3S'—C1S'—C2S' | 113 (2) |
C18A—C17A—H17A | 108.5 | C3S'—C1S'—H1SC | 110.4 |
C1A—C17A—H17A | 108.5 | C2S'—C1S'—H1SC | 110.4 |
C18A—C17A—H17B | 108.5 | C1S'—C2S'—H2SD | 109.5 |
C1A—C17A—H17B | 108.5 | C1S'—C2S'—H2SE | 109.5 |
H17A—C17A—H17B | 107.5 | H2SD—C2S'—H2SE | 109.5 |
O4A—C18A—C17A | 125.6 (4) | C1S'—C2S'—H2SF | 109.5 |
O4A—C18A—C19A | 120.5 (4) | H2SD—C2S'—H2SF | 109.5 |
C17A—C18A—C19A | 113.9 (4) | H2SE—C2S'—H2SF | 109.5 |
C18A—C19A—H19A | 109.5 | C1S'—C3S'—H3SD | 109.5 |
C18A—C19A—H19B | 109.5 | C1S'—C3S'—H3SE | 109.5 |
H19A—C19A—H19B | 109.5 | H3SD—C3S'—H3SE | 109.5 |
C18A—C19A—H19C | 109.5 | C1S'—C3S'—H3SF | 109.5 |
H19A—C19A—H19C | 109.5 | H3SD—C3S'—H3SF | 109.5 |
H19B—C19A—H19C | 109.5 | H3SE—C3S'—H3SF | 109.5 |
C3B—O1B—Na2 | 140.8 (3) | ||
O1A—Na1—Na2—O3Bii | −128.41 (18) | O3Bii—Na2—O1B—C3B | −13.5 (5) |
O3Ai—Na1—Na2—O3Bii | −174.0 (2) | O4Ai—Na2—O1B—C3B | 86.3 (5) |
O1B—Na1—Na2—O3Bii | −17.13 (18) | O3Ai—Na2—O1B—C3B | 163.0 (5) |
O4B—Na1—Na2—O3Bii | 40.7 (2) | Na1—Na2—O1B—C3B | 178.3 (5) |
O1A—Na1—Na2—O1B | −111.3 (2) | O3Bii—Na2—O1B—Na1 | 168.17 (12) |
O3Ai—Na1—Na2—O1B | −156.89 (19) | O4Ai—Na2—O1B—Na1 | −92.0 (2) |
O4B—Na1—Na2—O1B | 57.86 (16) | O3Ai—Na2—O1B—Na1 | −15.31 (13) |
O1A—Na1—Na2—O4Ai | 19.5 (2) | O1A—Na1—O1B—C3B | −74.0 (4) |
O3Ai—Na1—Na2—O4Ai | −26.10 (18) | O3Ai—Na1—O1B—C3B | −163.0 (4) |
O1B—Na1—Na2—O4Ai | 130.78 (19) | O4B—Na1—O1B—C3B | 52.8 (3) |
O4B—Na1—Na2—O4Ai | −171.36 (16) | Na2—Na1—O1B—C3B | −178.7 (4) |
O1A—Na1—Na2—O3Ai | 45.62 (18) | O1A—Na1—O1B—Na2 | 104.73 (17) |
O1B—Na1—Na2—O3Ai | 156.89 (19) | O3Ai—Na1—O1B—Na2 | 15.76 (13) |
O4B—Na1—Na2—O3Ai | −145.25 (18) | O4B—Na1—O1B—Na2 | −128.45 (14) |
O3Ai—Na1—O1A—C3A | 174.8 (7) | O1A—Na1—O4B—C18B | 108.0 (11) |
O1B—Na1—O1A—C3A | 90.2 (7) | O3Ai—Na1—O4B—C18B | −102.9 (12) |
O4B—Na1—O1A—C3A | −23.2 (8) | O1B—Na1—O4B—C18B | −27.2 (11) |
Na2—Na1—O1A—C3A | 145.3 (6) | Na2—Na1—O4B—C18B | −62.1 (12) |
C17A—C1A—C2A—C3A | 63.5 (5) | C11B—C1B—C2B—C3B | −117.3 (4) |
C11A—C1A—C2A—C3A | −65.8 (5) | C17B—C1B—C2B—C3B | 113.0 (4) |
C17A—C1A—C2A—C10A | −118.6 (4) | C11B—C1B—C2B—C10B | 62.3 (5) |
C11A—C1A—C2A—C10A | 112.1 (4) | C17B—C1B—C2B—C10B | −67.4 (5) |
Na1—O1A—C3A—C2A | 111.1 (7) | Na2—O1B—C3B—C2B | 98.9 (5) |
Na1—O1A—C3A—C4A | −68.1 (8) | Na1—O1B—C3B—C2B | −83.1 (4) |
C10A—C2A—C3A—O1A | −176.2 (4) | Na2—O1B—C3B—C4B | −81.4 (5) |
C1A—C2A—C3A—O1A | 1.7 (6) | Na1—O1B—C3B—C4B | 96.6 (4) |
C10A—C2A—C3A—C4A | 3.0 (5) | C10B—C2B—C3B—O1B | 179.4 (4) |
C1A—C2A—C3A—C4A | −179.1 (3) | C1B—C2B—C3B—O1B | −1.0 (6) |
O1A—C3A—C4A—C5A | −6.1 (6) | C10B—C2B—C3B—C4B | −0.2 (5) |
C2A—C3A—C4A—C5A | 174.6 (4) | C1B—C2B—C3B—C4B | 179.3 (3) |
O1A—C3A—C4A—C9A | 173.5 (4) | O1B—C3B—C4B—C9B | 178.4 (4) |
C2A—C3A—C4A—C9A | −5.8 (5) | C2B—C3B—C4B—C9B | −1.9 (5) |
C9A—C4A—C5A—C6A | −0.5 (8) | O1B—C3B—C4B—C5B | −1.1 (6) |
C3A—C4A—C5A—C6A | 179.2 (5) | C2B—C3B—C4B—C5B | 178.6 (4) |
C4A—C5A—C6A—C7A | −3.7 (10) | C9B—C4B—C5B—C6B | −0.7 (6) |
C5A—C6A—C7A—C8A | 4.3 (10) | C3B—C4B—C5B—C6B | 178.8 (4) |
C6A—C7A—C8A—C9A | −0.6 (8) | C4B—C5B—C6B—C7B | −1.7 (7) |
C10A—O2A—C9A—C4A | 2.2 (6) | C5B—C6B—C7B—C8B | 2.6 (8) |
C10A—O2A—C9A—C8A | −179.1 (4) | C6B—C7B—C8B—C9B | −1.0 (7) |
C5A—C4A—C9A—O2A | −177.0 (4) | C10B—O2B—C9B—C4B | −0.9 (6) |
C3A—C4A—C9A—O2A | 3.3 (6) | C10B—O2B—C9B—C8B | 178.8 (4) |
C5A—C4A—C9A—C8A | 4.4 (7) | C5B—C4B—C9B—O2B | −178.0 (4) |
C3A—C4A—C9A—C8A | −175.3 (4) | C3B—C4B—C9B—O2B | 2.5 (6) |
C7A—C8A—C9A—O2A | 177.5 (4) | C5B—C4B—C9B—C8B | 2.4 (6) |
C7A—C8A—C9A—C4A | −3.8 (7) | C3B—C4B—C9B—C8B | −177.1 (4) |
Na1iii—O3A—C10A—O2A | 59.4 (5) | C7B—C8B—C9B—O2B | 178.8 (4) |
Na2iii—O3A—C10A—O2A | −111.3 (3) | C7B—C8B—C9B—C4B | −1.6 (7) |
Na1iii—O3A—C10A—C2A | −119.9 (4) | Na2iv—O3B—C10B—O2B | 24.2 (7) |
Na2iii—O3A—C10A—C2A | 69.4 (5) | Na2iv—O3B—C10B—C2B | −156.0 (4) |
C9A—O2A—C10A—O3A | 175.5 (3) | C9B—O2B—C10B—O3B | 178.6 (3) |
C9A—O2A—C10A—C2A | −5.1 (5) | C9B—O2B—C10B—C2B | −1.3 (5) |
C3A—C2A—C10A—O3A | −178.3 (4) | C3B—C2B—C10B—O3B | −178.0 (4) |
C1A—C2A—C10A—O3A | 3.8 (6) | C1B—C2B—C10B—O3B | 2.4 (6) |
C3A—C2A—C10A—O2A | 2.4 (5) | C3B—C2B—C10B—O2B | 1.8 (6) |
C1A—C2A—C10A—O2A | −175.5 (3) | C1B—C2B—C10B—O2B | −177.7 (3) |
C17A—C1A—C11A—C12A | 157.9 (4) | C2B—C1B—C11B—C12B | 70.2 (5) |
C2A—C1A—C11A—C12A | −73.1 (5) | C17B—C1B—C11B—C12B | −159.7 (4) |
C17A—C1A—C11A—C16A | −21.8 (6) | C2B—C1B—C11B—C16B | −112.0 (5) |
C2A—C1A—C11A—C16A | 107.3 (4) | C17B—C1B—C11B—C16B | 18.1 (6) |
C16A—C11A—C12A—C13A | −1.3 (7) | C16B—C11B—C12B—C13B | −1.7 (7) |
C1A—C11A—C12A—C13A | 179.1 (4) | C1B—C11B—C12B—C13B | 176.2 (5) |
C11A—C12A—C13A—C14A | 1.0 (8) | C11B—C12B—C13B—C14B | 0.5 (8) |
C12A—C13A—C14A—C15A | 0.2 (8) | C12B—C13B—C14B—C15B | 1.2 (9) |
C13A—C14A—C15A—C16A | −1.2 (8) | C13B—C14B—C15B—C16B | −1.6 (8) |
C14A—C15A—C16A—C11A | 0.9 (7) | C14B—C15B—C16B—C11B | 0.3 (8) |
C12A—C11A—C16A—C15A | 0.3 (7) | C12B—C11B—C16B—C15B | 1.3 (7) |
C1A—C11A—C16A—C15A | 180.0 (4) | C1B—C11B—C16B—C15B | −176.5 (4) |
C2A—C1A—C17A—C18A | 68.3 (5) | C2B—C1B—C17B—C18B | −78.5 (5) |
C11A—C1A—C17A—C18A | −164.0 (4) | C11B—C1B—C17B—C18B | 152.1 (4) |
Na2iii—O4A—C18A—C17A | 24.3 (10) | Na1—O4B—C18B—C17B | 41.1 (14) |
Na2iii—O4A—C18A—C19A | −157.6 (6) | Na1—O4B—C18B—C19B | −141.6 (9) |
C1A—C17A—C18A—O4A | 8.6 (7) | C1B—C17B—C18B—O4B | −2.0 (7) |
C1A—C17A—C18A—C19A | −169.6 (4) | C1B—C17B—C18B—C19B | −179.5 (4) |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1S—H1SA···O2Bii | 0.84 | 2.26 | 3.049 (5) | 156 |
O1S—H1SA···O3Bii | 0.84 | 2.56 | 3.049 (4) | 118 |
Symmetry code: (ii) −x, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | 2Na+·2C38H30O8−·C3H8O |
Mr | 720.69 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 15.393 (2), 11.2392 (17), 22.124 (3) |
β (°) | 107.424 (3) |
V (Å3) | 3651.9 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.40 × 0.23 × 0.11 |
Data collection | |
Diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.970, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26991, 6472, 3895 |
Rint | 0.060 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.225, 1.04 |
No. of reflections | 6472 |
No. of parameters | 487 |
No. of restraints | 20 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.95, −0.48 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Bruker, 1997), SHELXTL/PC.
D—H···A | D—H | H···A | D···A | D—H···A |
O1S—H1SA···O2Bi | 0.84 | 2.26 | 3.049 (5) | 155.9 |
O1S—H1SA···O3Bi | 0.84 | 2.56 | 3.049 (4) | 118.1 |
Symmetry code: (i) −x, y+1/2, −z+1/2. |
Warfarin sodium is a pharmaceutical anticoagulant that acts by inhibiting the synthesis of vitamin K-dependent coagulation factors (Majerus et al., 1996). The parent compound is warfarin, which exists in two enantiomeric forms. Its sodium derivative can be purified by crystallization from 2-propanol as a warfarin sodium 2-propanol complex (Schoreder & Link, 1963). Previously, it has been found that (-)-(S)-warfarin [Valente et al., 1975; Cambridge Structural Database (CSD; Allen & Kennard, 1993) reference code WARFAR10] and racemic warfarin (Bravic et al., 1973; CSD reference code WARFIN) crystallized from acetone and methanol, respectively, as an intramolecular cyclic hemiketal which was formed by reaction between the side-chain keto function and the phenolic hydroxyl at the 4-position of the coumarin ring system. These structures do not contain warfarin molecules themselves, but instead consist of covalently cyclized molecules of warfarin, which may be described as (2S,4S)-2,3H-2-methyl-4-phenyl-5-oxobenzopyrano[3,4-e]dihydropyran-2-ol. The results of the present work, however, show that warfarin sodium crystallizes from 2-propanol as a solvate, in which the asymmetric unit contains two molecules of warfarin sodium (one each of the R and S enantiomer) and one molecule of 2-propanol. Although the unit-cell parameters and the space group have previously been reported (Hiskey & Melnitchenko, 1965; CSD reference code ZZZKXG), the single-crystal structure has hitherto not been completely solved. Few reports of the physical properties of this compound have been published (Hiskey & Melnitchenko, 1965; Gao & Maurin, 2001). In the present study, the complete crystal structure of warfarin sodium 2-propanol solvate is solved and described for the first time.
Currently, the warfarin sodium 2-propanol adduct is commercially available as a pharmaceutical and described as a clathrate (Haleblian, 1975). Clathrates are crystalline molecular inclusion adducts consisting of two distinct components, a relatively rigid host and a quite mobile guest. Within clathrates the guest molecules lie trapped in closed, three-dimensional cavities or cages formed by the crystalline structure of the host (Andreeti, 1984; Mandelcorn, 1959). The term `clathrate' was introduced by Powell (1948) from the Latin word clathratus, which means enclosed by the bars of a grating. The term `clathration' is used instead of 'solvation' when there is no specific, chemical interaction between the solvent and solute (Lipkowski, 1996). In the crystal structure of warfarin sodium 2-propanol solvate in the present work, the guest molecules of 2-propanol are not enclosed in a cage-like structure of the host molecules of warfarin sodium. Indeed, the 2-propanol molecule is strongly coordinated to the sodium atom of warfarin sodium with one molecule of 2-propanol to two molecules of warfarin sodium in the asymmetric unit. Hence, the crystal structure solved in the present work is a solvate, but not a clathrate.