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The crystal structure of the title compound, R-(Na+·C19H15O4-S-(Na+·C19H15O4-)·C3H8O, the 2-propanol sol­vate of the sodium salt of 4-hydroxy-3-(3-oxo-1-phenyl­butyl)-2H-1-benzo­pyran-2-one, i.e. bis­(sodium 2-oxo-3-(3-oxo-1-phenyl­butyl)-2H-1-benzo­pyran-4-olate) 2-propanol solvate, is composed of infinite sheets in the ab plane, separated only by van der Waals contacts. The hydroxy­coumarin fragments display rotational rigid-body motion. The 2-propanol mol­ecule is rotationally disordered and was modeled as two components. Each of the two sodium ions is associated with four O atoms that form a distorted tetrahedron bridging the two warfarin anions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802005809/om6084sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802005809/om6084Isup2.hkl
Contains datablock I

CCDC reference: 185747

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.007 Å
  • R factor = 0.069
  • wR factor = 0.225
  • Data-to-parameter ratio = 13.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
DIFMX_01 Alert C The maximum difference density is > 0.1*ZMAX*0.75 _refine_diff_density_max given = 0.954 Test value = 0.825 DIFMX_02 Alert C The minimum difference density is > 0.1*ZMAX*0.75 The relevant atom site should be identified. General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C41 H38 Na2 O9 Atom count from _chemical_formula_moiety:C79 H68 Na2 O17
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check

Comment top

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.

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The atomic numbering scheme of warfarin sodium 2-propanol solvate in this work. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Warfarin sodium 2-propanol solvate, 3 × 3 × 3 unit cells, looking down the b axis showing molecular sheets in the ab plane. Individual sheets are separated only by van der Waals contacts.
2-propanol solvate of the sodium salt of 4-hydroxy-3-(3-oxo-1-phenylbutyl)-2H-1-benzopyran-2-one top
Crystal data top
2Na+·2C38H30O8·C3H8OF(000) = 1512
Mr = 720.69Dx = 1.311 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 15.393 (2) ÅCell parameters from 3390 reflections
b = 11.2392 (17) Åθ = 1.4–25.1°
c = 22.124 (3) ŵ = 0.11 mm1
β = 107.424 (3)°T = 173 K
V = 3651.9 (9) Å3Irregular plate, colorless
Z = 40.40 × 0.23 × 0.11 mm
Data collection top
Bruker CCD area-detector
diffractometer
6472 independent reflections
Radiation source: normal-focus sealed tube3895 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.060
ϕ and ω scansθmax = 25.1°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
h = 1818
Tmin = 0.970, Tmax = 0.988k = 1313
26991 measured reflectionsl = 2626
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.069Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.225H-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 parametersΔρmax = 0.95 e Å3
20 restraintsΔρmin = 0.48 e Å3
Crystal data top
2Na+·2C38H30O8·C3H8OV = 3651.9 (9) Å3
Mr = 720.69Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.393 (2) ŵ = 0.11 mm1
b = 11.2392 (17) ÅT = 173 K
c = 22.124 (3) Å0.40 × 0.23 × 0.11 mm
β = 107.424 (3)°
Data collection top
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 = 0.988Rint = 0.060
26991 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.06920 restraints
wR(F2) = 0.225H-atom parameters constrained
S = 1.04Δρmax = 0.95 e Å3
6472 reflectionsΔρmin = 0.48 e Å3
487 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Na10.28289 (10)0.48410 (14)0.21456 (9)0.0496 (5)
Na20.19189 (10)0.76079 (13)0.20748 (8)0.0425 (4)
O1A0.4218 (2)0.4289 (3)0.26762 (16)0.0539 (8)
O2A0.6052 (2)0.1870 (3)0.37154 (15)0.0563 (9)
O3A0.67354 (18)0.1725 (2)0.29947 (16)0.0499 (8)
O4A0.7297 (2)0.4382 (2)0.26860 (16)0.0528 (8)
C1A0.5533 (3)0.3356 (4)0.21103 (19)0.0431 (10)
H1AA0.60590.28900.20570.052*
C2A0.5481 (2)0.3066 (3)0.27707 (17)0.0309 (8)
C3A0.4815 (3)0.3588 (3)0.2996 (2)0.0383 (9)
C4A0.4819 (3)0.3279 (4)0.3638 (2)0.0525 (13)
C5A0.4266 (4)0.3773 (6)0.3954 (3)0.0776 (17)
H5AA0.38480.43740.37470.093*
C6A0.4287 (5)0.3447 (7)0.4544 (3)0.093 (2)
H6AA0.39170.38470.47550.112*
C7A0.4858 (4)0.2517 (7)0.4846 (3)0.0827 (19)
H7AA0.48320.22620.52500.099*
C8A0.5448 (5)0.1958 (6)0.4586 (3)0.087 (2)
H8AA0.58390.13320.47940.104*
C9A0.5431 (4)0.2399 (5)0.3968 (2)0.0555 (13)
C10A0.6102 (3)0.2235 (3)0.3131 (2)0.0370 (9)
C11A0.4689 (3)0.2898 (4)0.16047 (19)0.0416 (10)
C12A0.4604 (3)0.1683 (4)0.1495 (2)0.0559 (12)
H12A0.50710.11620.17270.067*
C13A0.3841 (4)0.1221 (5)0.1045 (2)0.0676 (15)
H13A0.37870.03860.09790.081*
C14A0.3164 (4)0.1961 (5)0.0695 (2)0.0676 (15)
H14A0.26440.16390.03900.081*
C15A0.3246 (3)0.3162 (5)0.0789 (2)0.0629 (14)
H15A0.27870.36790.05440.075*
C16A0.3999 (3)0.3634 (4)0.1244 (2)0.0512 (11)
H16A0.40430.44700.13090.061*
C17A0.5746 (3)0.4650 (4)0.2028 (2)0.0501 (11)
H17A0.56600.48000.15730.060*
H17B0.53020.51500.21570.060*
C18A0.6683 (3)0.5037 (4)0.2395 (2)0.0426 (10)
C19A0.6822 (4)0.6363 (4)0.2399 (3)0.0665 (14)
H19A0.74620.65350.24410.100*
H19B0.66620.67140.27570.100*
H19C0.64350.67030.20020.100*
O1B0.17373 (19)0.5785 (2)0.24931 (16)0.0520 (8)
O2B0.03431 (19)0.4232 (3)0.36036 (14)0.0473 (7)
O3B0.06410 (18)0.3416 (3)0.27758 (14)0.0452 (7)
O4B0.1739 (2)0.3400 (3)0.17109 (17)0.0589 (9)
C1B0.0110 (3)0.4410 (4)0.1850 (2)0.0414 (10)
H1BA0.05030.48850.16530.050*
C2B0.0500 (2)0.4597 (3)0.2557 (2)0.0373 (9)
C3B0.1285 (3)0.5284 (3)0.2815 (2)0.0409 (10)
C4B0.1596 (3)0.5416 (3)0.3513 (2)0.0469 (11)
C5B0.2384 (3)0.6060 (4)0.3833 (3)0.0646 (15)
H5BA0.27440.64160.36000.078*
C6B0.2637 (4)0.6175 (5)0.4484 (3)0.0786 (19)
H6BA0.31790.65930.46960.094*
C7B0.2108 (4)0.5689 (5)0.4831 (3)0.0776 (18)
H7BA0.22750.58020.52770.093*
C8B0.1343 (4)0.5044 (4)0.4531 (2)0.0619 (13)
H8BA0.09830.46980.47660.074*
C9B0.1103 (3)0.4904 (4)0.3877 (2)0.0476 (11)
C10B0.0033 (3)0.4055 (4)0.2948 (2)0.0393 (10)
C11B0.0849 (3)0.4929 (4)0.15855 (19)0.0402 (9)
C12B0.0953 (3)0.6152 (4)0.1560 (2)0.0571 (12)
H12B0.04370.66480.17300.069*
C13B0.1800 (4)0.6664 (5)0.1291 (3)0.0746 (17)
H13B0.18580.75060.12750.090*
C14B0.2558 (3)0.5962 (6)0.1047 (3)0.0693 (15)
H14B0.31360.63150.08550.083*
C15B0.2467 (3)0.4744 (5)0.1084 (2)0.0660 (14)
H15B0.29880.42520.09260.079*
C16B0.1621 (3)0.4233 (4)0.1349 (2)0.0542 (12)
H16B0.15680.33910.13700.065*
C17B0.0177 (3)0.3122 (4)0.1642 (2)0.0475 (11)
H17C0.00010.25900.19430.057*
H17D0.02740.30080.12210.057*
C18B0.1090 (3)0.2740 (4)0.1604 (2)0.0482 (11)
C19B0.1155 (3)0.1475 (4)0.1394 (3)0.0701 (15)
H19D0.16850.13950.12390.105*
H19E0.06010.12720.10540.105*
H19F0.12200.09360.17530.105*
O1S0.1022 (3)0.7687 (4)0.10006 (17)0.0797 (12)0.667 (13)
H1SA0.05470.79240.10760.120*0.667 (13)
C1S0.0783 (6)0.7120 (9)0.0392 (5)0.067 (3)0.667 (13)
H1SB0.08160.77260.00690.101*0.667 (13)
C2S0.1500 (13)0.619 (3)0.0426 (14)0.090 (3)0.667 (13)
H2SA0.14740.55830.07380.136*0.667 (13)
H2SB0.21030.65650.05520.136*0.667 (13)
H2SC0.13910.58180.00090.136*0.667 (13)
C3S0.0168 (7)0.6638 (12)0.0214 (6)0.076 (3)0.667 (13)
H3SA0.02100.60300.05220.114*0.667 (13)
H3SB0.03200.62840.02090.114*0.667 (13)
H3SC0.05940.72850.02150.114*0.667 (13)
O1S'0.1022 (3)0.7687 (4)0.10006 (17)0.0797 (12)0.333 (13)
H1SD0.06960.82750.08430.120*0.333 (13)
C1S'0.0726 (14)0.6670 (16)0.0605 (8)0.067 (3)0.333 (13)
H1SC0.05460.60140.08490.101*0.333 (13)
C2S'0.151 (3)0.628 (6)0.038 (3)0.090 (3)0.333 (13)
H2SD0.16440.69050.01070.136*0.333 (13)
H2SE0.13550.55440.01370.136*0.333 (13)
H2SF0.20510.61550.07440.136*0.333 (13)
C3S'0.0085 (17)0.709 (2)0.0081 (11)0.076 (3)0.333 (13)
H3SD0.05580.73710.02610.114*0.333 (13)
H3SE0.03240.64380.02140.114*0.333 (13)
H3SF0.00980.77500.01470.114*0.333 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Na10.0321 (8)0.0326 (9)0.0875 (13)0.0005 (7)0.0231 (8)0.0061 (8)
Na20.0311 (8)0.0289 (8)0.0685 (11)0.0007 (6)0.0165 (7)0.0022 (7)
O1A0.0395 (17)0.0399 (17)0.082 (2)0.0108 (14)0.0175 (16)0.0092 (16)
O2A0.0509 (19)0.0496 (19)0.060 (2)0.0091 (15)0.0038 (16)0.0101 (16)
O3A0.0307 (15)0.0303 (15)0.091 (2)0.0018 (12)0.0212 (15)0.0036 (15)
O4A0.0406 (17)0.0299 (15)0.086 (2)0.0039 (13)0.0164 (16)0.0090 (15)
C1A0.046 (2)0.040 (2)0.045 (2)0.0049 (19)0.0161 (19)0.0008 (19)
C2A0.0272 (19)0.0273 (19)0.040 (2)0.0022 (15)0.0125 (16)0.0016 (16)
C3A0.030 (2)0.029 (2)0.057 (3)0.0021 (17)0.0143 (19)0.0115 (19)
C4A0.051 (3)0.060 (3)0.064 (3)0.029 (2)0.044 (2)0.033 (3)
C5A0.082 (4)0.078 (4)0.086 (4)0.010 (3)0.043 (3)0.020 (3)
C6A0.104 (5)0.101 (5)0.084 (5)0.016 (4)0.043 (4)0.007 (4)
C7A0.076 (4)0.117 (6)0.062 (4)0.041 (4)0.031 (3)0.011 (4)
C8A0.087 (4)0.098 (5)0.068 (4)0.043 (4)0.015 (3)0.016 (3)
C9A0.065 (3)0.061 (3)0.041 (3)0.034 (3)0.015 (2)0.004 (2)
C10A0.028 (2)0.029 (2)0.054 (3)0.0075 (16)0.0125 (18)0.0017 (18)
C11A0.045 (2)0.044 (2)0.038 (2)0.0060 (19)0.0159 (19)0.0010 (18)
C12A0.064 (3)0.046 (3)0.052 (3)0.008 (2)0.009 (2)0.001 (2)
C13A0.083 (4)0.052 (3)0.063 (3)0.017 (3)0.016 (3)0.016 (3)
C14A0.057 (3)0.080 (4)0.058 (3)0.012 (3)0.004 (3)0.023 (3)
C15A0.058 (3)0.072 (4)0.055 (3)0.010 (3)0.010 (2)0.012 (3)
C16A0.053 (3)0.051 (3)0.050 (3)0.001 (2)0.016 (2)0.010 (2)
C17A0.053 (3)0.045 (3)0.054 (3)0.002 (2)0.020 (2)0.009 (2)
C18A0.037 (2)0.042 (2)0.053 (3)0.004 (2)0.019 (2)0.003 (2)
C19A0.069 (3)0.040 (3)0.086 (4)0.006 (2)0.016 (3)0.010 (3)
O1B0.0362 (16)0.0323 (16)0.094 (2)0.0027 (13)0.0294 (16)0.0045 (15)
O2B0.0440 (17)0.0441 (17)0.0516 (18)0.0019 (14)0.0112 (14)0.0047 (14)
O3B0.0336 (15)0.0443 (17)0.0593 (18)0.0079 (13)0.0161 (13)0.0086 (14)
O4B0.0401 (17)0.0387 (17)0.103 (3)0.0028 (14)0.0298 (17)0.0034 (17)
C1B0.035 (2)0.035 (2)0.057 (3)0.0030 (17)0.0192 (19)0.0021 (19)
C2B0.027 (2)0.031 (2)0.055 (3)0.0014 (16)0.0140 (18)0.0050 (18)
C3B0.030 (2)0.024 (2)0.071 (3)0.0051 (16)0.019 (2)0.0031 (19)
C4B0.034 (2)0.025 (2)0.074 (3)0.0082 (17)0.005 (2)0.004 (2)
C5B0.039 (3)0.034 (2)0.104 (4)0.002 (2)0.003 (3)0.007 (3)
C6B0.058 (3)0.048 (3)0.099 (5)0.006 (3)0.023 (3)0.021 (3)
C7B0.082 (4)0.049 (3)0.083 (4)0.015 (3)0.003 (3)0.011 (3)
C8B0.067 (3)0.048 (3)0.060 (3)0.014 (3)0.003 (3)0.000 (2)
C9B0.042 (2)0.035 (2)0.058 (3)0.007 (2)0.003 (2)0.000 (2)
C10B0.031 (2)0.035 (2)0.051 (3)0.0053 (18)0.0095 (18)0.0060 (18)
C11B0.038 (2)0.041 (2)0.043 (2)0.0002 (18)0.0152 (18)0.0044 (19)
C12B0.045 (3)0.046 (3)0.081 (3)0.001 (2)0.022 (2)0.012 (2)
C13B0.055 (3)0.056 (3)0.116 (5)0.014 (3)0.031 (3)0.032 (3)
C14B0.043 (3)0.089 (4)0.071 (4)0.014 (3)0.011 (2)0.020 (3)
C15B0.042 (3)0.082 (4)0.069 (3)0.001 (3)0.009 (2)0.012 (3)
C16B0.040 (3)0.051 (3)0.070 (3)0.002 (2)0.015 (2)0.008 (2)
C17B0.040 (2)0.045 (3)0.059 (3)0.0020 (19)0.017 (2)0.001 (2)
C18B0.041 (2)0.041 (2)0.063 (3)0.001 (2)0.015 (2)0.003 (2)
C19B0.052 (3)0.042 (3)0.115 (5)0.001 (2)0.022 (3)0.014 (3)
O1S0.072 (3)0.103 (3)0.062 (2)0.020 (2)0.0153 (19)0.022 (2)
C1S0.079 (5)0.062 (7)0.063 (6)0.010 (5)0.025 (5)0.009 (5)
C2S0.095 (5)0.096 (6)0.091 (6)0.004 (4)0.044 (4)0.029 (5)
C3S0.089 (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)
Geometric parameters (Å, º) top
Na1—O1A2.198 (3)O4B—C18B1.209 (5)
Na1—O3Ai2.271 (3)C1B—C2B1.513 (6)
Na1—O1B2.305 (3)C1B—C11B1.530 (6)
Na1—O4B2.323 (3)C1B—C17B1.531 (6)
Na1—Na23.395 (2)C1B—H1BA1.0000
Na2—O3Bii2.279 (3)C2B—C3B1.404 (6)
Na2—O1B2.299 (3)C2B—C10B1.418 (6)
Na2—O4Ai2.309 (3)C3B—C4B1.481 (6)
Na2—O3Ai2.343 (3)C4B—C9B1.386 (7)
O1A—C3A1.256 (5)C4B—C5B1.408 (6)
O2A—C9A1.378 (6)C5B—C6B1.379 (8)
O2A—C10A1.380 (5)C5B—H5BA0.9500
O3A—C10A1.244 (5)C6B—C7B1.389 (9)
O3A—Na1iii2.271 (3)C6B—H6BA0.9500
O3A—Na2iii2.343 (3)C7B—C8B1.373 (8)
O4A—C18A1.219 (5)C7B—H7BA0.9500
O4A—Na2iii2.309 (3)C8B—C9B1.389 (7)
C1A—C17A1.513 (6)C8B—H8BA0.9500
C1A—C2A1.522 (5)C11B—C12B1.384 (6)
C1A—C11A1.528 (6)C11B—C16B1.388 (6)
C1A—H1AA1.0000C12B—C13B1.387 (7)
C2A—C3A1.397 (5)C12B—H12B0.9500
C2A—C10A1.402 (5)C13B—C14B1.377 (8)
C3A—C4A1.460 (6)C13B—H13B0.9500
C4A—C5A1.370 (7)C14B—C15B1.376 (8)
C4A—C9A1.409 (7)C14B—H14B0.9500
C5A—C6A1.348 (8)C15B—C16B1.383 (7)
C5A—H5AA0.9500C15B—H15B0.9500
C6A—C7A1.399 (9)C16B—H16B0.9500
C6A—H6AA0.9500C17B—C18B1.496 (6)
C7A—C8A1.366 (9)C17B—H17C0.9900
C7A—H7AA0.9500C17B—H17D0.9900
C8A—C9A1.447 (8)C18B—C19B1.509 (6)
C8A—H8AA0.9500C19B—H19D0.9800
C11A—C12A1.385 (6)C19B—H19E0.9800
C11A—C16A1.394 (6)C19B—H19F0.9800
C12A—C13A1.392 (7)O1S—C1S1.434 (8)
C12A—H12A0.9500O1S—H1SA0.8400
C13A—C14A1.377 (8)C1S—C3S1.498 (11)
C13A—H13A0.9500C1S—C2S1.506 (15)
C14A—C15A1.367 (7)C1S—H1SB1.0000
C14A—H14A0.9500C2S—H2SA0.9800
C15A—C16A1.392 (6)C2S—H2SB0.9800
C15A—H15A0.9500C2S—H2SC0.9800
C16A—H16A0.9500C3S—H3SA0.9800
C17A—C18A1.491 (6)C3S—H3SB0.9800
C17A—H17A0.9900C3S—H3SC0.9800
C17A—H17B0.9900C1S'—C3S'1.505 (16)
C18A—C19A1.505 (6)C1S'—C2S'1.507 (18)
C19A—H19A0.9800C1S'—H1SC1.0000
C19A—H19B0.9800C2S'—H2SD0.9800
C19A—H19C0.9800C2S'—H2SE0.9800
O1B—C3B1.268 (5)C2S'—H2SF0.9800
O2B—C9B1.372 (5)C3S'—H3SD0.9800
O2B—C10B1.398 (5)C3S'—H3SE0.9800
O3B—C10B1.224 (5)C3S'—H3SF0.9800
O3B—Na2iv2.279 (3)
O1A—Na1—O3Ai93.22 (12)C3B—O1B—Na1124.2 (2)
O1A—Na1—O1B129.90 (15)Na2—O1B—Na195.01 (12)
O3Ai—Na1—O1B83.74 (11)C9B—O2B—C10B121.2 (3)
O1A—Na1—O4B119.39 (13)C10B—O3B—Na2iv151.1 (3)
O3Ai—Na1—O4B143.13 (14)C18B—O4B—Na1163.8 (3)
O1B—Na1—O4B87.19 (11)C2B—C1B—C11B112.4 (3)
O1A—Na1—Na2127.23 (10)C2B—C1B—C17B113.6 (3)
O3Ai—Na1—Na243.45 (8)C11B—C1B—C17B112.9 (3)
O1B—Na1—Na242.43 (8)C2B—C1B—H1BA105.7
O4B—Na1—Na2112.51 (9)C11B—C1B—H1BA105.7
O3Bii—Na2—O1B94.74 (12)C17B—C1B—H1BA105.7
O3Bii—Na2—O4Ai92.14 (11)C3B—C2B—C10B121.3 (4)
O1B—Na2—O4Ai142.70 (14)C3B—C2B—C1B121.6 (4)
O3Bii—Na2—O3Ai175.43 (14)C10B—C2B—C1B117.1 (3)
O1B—Na2—O3Ai82.27 (11)O1B—C3B—C2B124.5 (4)
O4Ai—Na2—O3Ai88.20 (11)O1B—C3B—C4B118.8 (4)
O3Bii—Na2—Na1136.11 (10)C2B—C3B—C4B116.7 (4)
O1B—Na2—Na142.56 (8)C9B—C4B—C5B117.4 (5)
O4Ai—Na2—Na1126.88 (9)C9B—C4B—C3B120.2 (4)
O3Ai—Na2—Na141.80 (8)C5B—C4B—C3B122.4 (5)
C3A—O1A—Na1155.3 (3)C6B—C5B—C4B120.3 (6)
C9A—O2A—C10A119.5 (3)C6B—C5B—H5BA119.9
C10A—O3A—Na1iii138.4 (2)C4B—C5B—H5BA119.9
C10A—O3A—Na2iii126.4 (2)C5B—C6B—C7B120.8 (5)
Na1iii—O3A—Na2iii94.75 (11)C5B—C6B—H6BA119.6
C18A—O4A—Na2iii155.8 (3)C7B—C6B—H6BA119.6
C17A—C1A—C2A113.3 (3)C8B—C7B—C6B120.0 (6)
C17A—C1A—C11A113.8 (4)C8B—C7B—H7BA120.0
C2A—C1A—C11A110.7 (3)C6B—C7B—H7BA120.0
C17A—C1A—H1AA106.1C7B—C8B—C9B119.1 (6)
C2A—C1A—H1AA106.1C7B—C8B—H8BA120.5
C11A—C1A—H1AA106.1C9B—C8B—H8BA120.5
C3A—C2A—C10A121.6 (4)O2B—C9B—C4B121.0 (4)
C3A—C2A—C1A120.5 (3)O2B—C9B—C8B116.6 (4)
C10A—C2A—C1A117.8 (3)C4B—C9B—C8B122.4 (4)
O1A—C3A—C2A123.6 (4)O3B—C10B—O2B113.7 (4)
O1A—C3A—C4A119.1 (4)O3B—C10B—C2B126.7 (4)
C2A—C3A—C4A117.3 (4)O2B—C10B—C2B119.6 (4)
C5A—C4A—C9A116.2 (5)C12B—C11B—C16B118.0 (4)
C5A—C4A—C3A125.2 (5)C12B—C11B—C1B118.7 (4)
C9A—C4A—C3A118.6 (4)C16B—C11B—C1B123.3 (4)
C6A—C5A—C4A123.0 (7)C11B—C12B—C13B120.8 (5)
C6A—C5A—H5AA118.5C11B—C12B—H12B119.6
C4A—C5A—H5AA118.5C13B—C12B—H12B119.6
C5A—C6A—C7A119.7 (7)C14B—C13B—C12B120.5 (5)
C5A—C6A—H6AA120.2C14B—C13B—H13B119.7
C7A—C6A—H6AA120.2C12B—C13B—H13B119.7
C8A—C7A—C6A123.0 (6)C15B—C14B—C13B119.2 (5)
C8A—C7A—H7AA118.5C15B—C14B—H14B120.4
C6A—C7A—H7AA118.5C13B—C14B—H14B120.4
C7A—C8A—C9A114.5 (7)C14B—C15B—C16B120.3 (5)
C7A—C8A—H8AA122.8C14B—C15B—H15B119.9
C9A—C8A—H8AA122.8C16B—C15B—H15B119.9
O2A—C9A—C4A122.0 (4)C15B—C16B—C11B121.1 (5)
O2A—C9A—C8A114.6 (5)C15B—C16B—H16B119.4
C4A—C9A—C8A123.4 (5)C11B—C16B—H16B119.4
O3A—C10A—O2A111.0 (4)C18B—C17B—C1B115.9 (4)
O3A—C10A—C2A128.3 (4)C18B—C17B—H17C108.3
O2A—C10A—C2A120.8 (4)C1B—C17B—H17C108.3
C12A—C11A—C16A118.0 (4)C18B—C17B—H17D108.3
C12A—C11A—C1A118.4 (4)C1B—C17B—H17D108.3
C16A—C11A—C1A123.6 (4)H17C—C17B—H17D107.4
C11A—C12A—C13A120.5 (5)O4B—C18B—C17B123.3 (4)
C11A—C12A—H12A119.7O4B—C18B—C19B120.7 (4)
C13A—C12A—H12A119.7C17B—C18B—C19B115.9 (4)
C14A—C13A—C12A120.8 (5)C18B—C19B—H19D109.5
C14A—C13A—H13A119.6C18B—C19B—H19E109.5
C12A—C13A—H13A119.6H19D—C19B—H19E109.5
C15A—C14A—C13A119.3 (5)C18B—C19B—H19F109.5
C15A—C14A—H14A120.3H19D—C19B—H19F109.5
C13A—C14A—H14A120.3H19E—C19B—H19F109.5
C14A—C15A—C16A120.4 (5)O1S—C1S—C3S111.3 (8)
C14A—C15A—H15A119.8O1S—C1S—C2S106.5 (11)
C16A—C15A—H15A119.8C3S—C1S—C2S114.0 (15)
C15A—C16A—C11A121.0 (4)O1S—C1S—H1SB108.3
C15A—C16A—H16A119.5C3S—C1S—H1SB108.3
C11A—C16A—H16A119.5C2S—C1S—H1SB108.3
C18A—C17A—C1A115.1 (4)C3S'—C1S'—C2S'113 (2)
C18A—C17A—H17A108.5C3S'—C1S'—H1SC110.4
C1A—C17A—H17A108.5C2S'—C1S'—H1SC110.4
C18A—C17A—H17B108.5C1S'—C2S'—H2SD109.5
C1A—C17A—H17B108.5C1S'—C2S'—H2SE109.5
H17A—C17A—H17B107.5H2SD—C2S'—H2SE109.5
O4A—C18A—C17A125.6 (4)C1S'—C2S'—H2SF109.5
O4A—C18A—C19A120.5 (4)H2SD—C2S'—H2SF109.5
C17A—C18A—C19A113.9 (4)H2SE—C2S'—H2SF109.5
C18A—C19A—H19A109.5C1S'—C3S'—H3SD109.5
C18A—C19A—H19B109.5C1S'—C3S'—H3SE109.5
H19A—C19A—H19B109.5H3SD—C3S'—H3SE109.5
C18A—C19A—H19C109.5C1S'—C3S'—H3SF109.5
H19A—C19A—H19C109.5H3SD—C3S'—H3SF109.5
H19B—C19A—H19C109.5H3SE—C3S'—H3SF109.5
C3B—O1B—Na2140.8 (3)
O1A—Na1—Na2—O3Bii128.41 (18)O3Bii—Na2—O1B—C3B13.5 (5)
O3Ai—Na1—Na2—O3Bii174.0 (2)O4Ai—Na2—O1B—C3B86.3 (5)
O1B—Na1—Na2—O3Bii17.13 (18)O3Ai—Na2—O1B—C3B163.0 (5)
O4B—Na1—Na2—O3Bii40.7 (2)Na1—Na2—O1B—C3B178.3 (5)
O1A—Na1—Na2—O1B111.3 (2)O3Bii—Na2—O1B—Na1168.17 (12)
O3Ai—Na1—Na2—O1B156.89 (19)O4Ai—Na2—O1B—Na192.0 (2)
O4B—Na1—Na2—O1B57.86 (16)O3Ai—Na2—O1B—Na115.31 (13)
O1A—Na1—Na2—O4Ai19.5 (2)O1A—Na1—O1B—C3B74.0 (4)
O3Ai—Na1—Na2—O4Ai26.10 (18)O3Ai—Na1—O1B—C3B163.0 (4)
O1B—Na1—Na2—O4Ai130.78 (19)O4B—Na1—O1B—C3B52.8 (3)
O4B—Na1—Na2—O4Ai171.36 (16)Na2—Na1—O1B—C3B178.7 (4)
O1A—Na1—Na2—O3Ai45.62 (18)O1A—Na1—O1B—Na2104.73 (17)
O1B—Na1—Na2—O3Ai156.89 (19)O3Ai—Na1—O1B—Na215.76 (13)
O4B—Na1—Na2—O3Ai145.25 (18)O4B—Na1—O1B—Na2128.45 (14)
O3Ai—Na1—O1A—C3A174.8 (7)O1A—Na1—O4B—C18B108.0 (11)
O1B—Na1—O1A—C3A90.2 (7)O3Ai—Na1—O4B—C18B102.9 (12)
O4B—Na1—O1A—C3A23.2 (8)O1B—Na1—O4B—C18B27.2 (11)
Na2—Na1—O1A—C3A145.3 (6)Na2—Na1—O4B—C18B62.1 (12)
C17A—C1A—C2A—C3A63.5 (5)C11B—C1B—C2B—C3B117.3 (4)
C11A—C1A—C2A—C3A65.8 (5)C17B—C1B—C2B—C3B113.0 (4)
C17A—C1A—C2A—C10A118.6 (4)C11B—C1B—C2B—C10B62.3 (5)
C11A—C1A—C2A—C10A112.1 (4)C17B—C1B—C2B—C10B67.4 (5)
Na1—O1A—C3A—C2A111.1 (7)Na2—O1B—C3B—C2B98.9 (5)
Na1—O1A—C3A—C4A68.1 (8)Na1—O1B—C3B—C2B83.1 (4)
C10A—C2A—C3A—O1A176.2 (4)Na2—O1B—C3B—C4B81.4 (5)
C1A—C2A—C3A—O1A1.7 (6)Na1—O1B—C3B—C4B96.6 (4)
C10A—C2A—C3A—C4A3.0 (5)C10B—C2B—C3B—O1B179.4 (4)
C1A—C2A—C3A—C4A179.1 (3)C1B—C2B—C3B—O1B1.0 (6)
O1A—C3A—C4A—C5A6.1 (6)C10B—C2B—C3B—C4B0.2 (5)
C2A—C3A—C4A—C5A174.6 (4)C1B—C2B—C3B—C4B179.3 (3)
O1A—C3A—C4A—C9A173.5 (4)O1B—C3B—C4B—C9B178.4 (4)
C2A—C3A—C4A—C9A5.8 (5)C2B—C3B—C4B—C9B1.9 (5)
C9A—C4A—C5A—C6A0.5 (8)O1B—C3B—C4B—C5B1.1 (6)
C3A—C4A—C5A—C6A179.2 (5)C2B—C3B—C4B—C5B178.6 (4)
C4A—C5A—C6A—C7A3.7 (10)C9B—C4B—C5B—C6B0.7 (6)
C5A—C6A—C7A—C8A4.3 (10)C3B—C4B—C5B—C6B178.8 (4)
C6A—C7A—C8A—C9A0.6 (8)C4B—C5B—C6B—C7B1.7 (7)
C10A—O2A—C9A—C4A2.2 (6)C5B—C6B—C7B—C8B2.6 (8)
C10A—O2A—C9A—C8A179.1 (4)C6B—C7B—C8B—C9B1.0 (7)
C5A—C4A—C9A—O2A177.0 (4)C10B—O2B—C9B—C4B0.9 (6)
C3A—C4A—C9A—O2A3.3 (6)C10B—O2B—C9B—C8B178.8 (4)
C5A—C4A—C9A—C8A4.4 (7)C5B—C4B—C9B—O2B178.0 (4)
C3A—C4A—C9A—C8A175.3 (4)C3B—C4B—C9B—O2B2.5 (6)
C7A—C8A—C9A—O2A177.5 (4)C5B—C4B—C9B—C8B2.4 (6)
C7A—C8A—C9A—C4A3.8 (7)C3B—C4B—C9B—C8B177.1 (4)
Na1iii—O3A—C10A—O2A59.4 (5)C7B—C8B—C9B—O2B178.8 (4)
Na2iii—O3A—C10A—O2A111.3 (3)C7B—C8B—C9B—C4B1.6 (7)
Na1iii—O3A—C10A—C2A119.9 (4)Na2iv—O3B—C10B—O2B24.2 (7)
Na2iii—O3A—C10A—C2A69.4 (5)Na2iv—O3B—C10B—C2B156.0 (4)
C9A—O2A—C10A—O3A175.5 (3)C9B—O2B—C10B—O3B178.6 (3)
C9A—O2A—C10A—C2A5.1 (5)C9B—O2B—C10B—C2B1.3 (5)
C3A—C2A—C10A—O3A178.3 (4)C3B—C2B—C10B—O3B178.0 (4)
C1A—C2A—C10A—O3A3.8 (6)C1B—C2B—C10B—O3B2.4 (6)
C3A—C2A—C10A—O2A2.4 (5)C3B—C2B—C10B—O2B1.8 (6)
C1A—C2A—C10A—O2A175.5 (3)C1B—C2B—C10B—O2B177.7 (3)
C17A—C1A—C11A—C12A157.9 (4)C2B—C1B—C11B—C12B70.2 (5)
C2A—C1A—C11A—C12A73.1 (5)C17B—C1B—C11B—C12B159.7 (4)
C17A—C1A—C11A—C16A21.8 (6)C2B—C1B—C11B—C16B112.0 (5)
C2A—C1A—C11A—C16A107.3 (4)C17B—C1B—C11B—C16B18.1 (6)
C16A—C11A—C12A—C13A1.3 (7)C16B—C11B—C12B—C13B1.7 (7)
C1A—C11A—C12A—C13A179.1 (4)C1B—C11B—C12B—C13B176.2 (5)
C11A—C12A—C13A—C14A1.0 (8)C11B—C12B—C13B—C14B0.5 (8)
C12A—C13A—C14A—C15A0.2 (8)C12B—C13B—C14B—C15B1.2 (9)
C13A—C14A—C15A—C16A1.2 (8)C13B—C14B—C15B—C16B1.6 (8)
C14A—C15A—C16A—C11A0.9 (7)C14B—C15B—C16B—C11B0.3 (8)
C12A—C11A—C16A—C15A0.3 (7)C12B—C11B—C16B—C15B1.3 (7)
C1A—C11A—C16A—C15A180.0 (4)C1B—C11B—C16B—C15B176.5 (4)
C2A—C1A—C17A—C18A68.3 (5)C2B—C1B—C17B—C18B78.5 (5)
C11A—C1A—C17A—C18A164.0 (4)C11B—C1B—C17B—C18B152.1 (4)
Na2iii—O4A—C18A—C17A24.3 (10)Na1—O4B—C18B—C17B41.1 (14)
Na2iii—O4A—C18A—C19A157.6 (6)Na1—O4B—C18B—C19B141.6 (9)
C1A—C17A—C18A—O4A8.6 (7)C1B—C17B—C18B—O4B2.0 (7)
C1A—C17A—C18A—C19A169.6 (4)C1B—C17B—C18B—C19B179.5 (4)
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x, y+1/2, z+1/2; (iii) x+1, y1/2, z+1/2; (iv) x, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1S—H1SA···O2Bii0.842.263.049 (5)156
O1S—H1SA···O3Bii0.842.563.049 (4)118
Symmetry code: (ii) x, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula2Na+·2C38H30O8·C3H8O
Mr720.69
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)15.393 (2), 11.2392 (17), 22.124 (3)
β (°) 107.424 (3)
V3)3651.9 (9)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.40 × 0.23 × 0.11
Data collection
DiffractometerBruker CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2000)
Tmin, Tmax0.970, 0.988
No. of measured, independent and
observed [I > 2σ(I)] reflections
26991, 6472, 3895
Rint0.060
(sin θ/λ)max1)0.597
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.069, 0.225, 1.04
No. of reflections6472
No. of parameters487
No. of restraints20
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1S—H1SA···O2Bi0.842.263.049 (5)155.9
O1S—H1SA···O3Bi0.842.563.049 (4)118.1
Symmetry code: (i) x, y+1/2, z+1/2.
 

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