Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025068/pk2025sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025068/pk2025Isup2.hkl |
CCDC reference: 651534
Key indicators
- Single-crystal X-ray study
- T = 90 K
- Mean (C-C) = 0.004 Å
- R factor = 0.034
- wR factor = 0.095
- Data-to-parameter ratio = 25.6
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT220_ALERT_2_A Large Non-Solvent C Ueq(max)/Ueq(min) ... 5.18 Ratio
Author Response: ... This problem is caused by large thermal motion in an isopropyl group and could not be resolved by splitting the position. |
PLAT222_ALERT_3_A Large Non-Solvent H Ueq(max)/Ueq(min) ... 6.47 Ratio
Author Response: ... This problem is due the H atoms associated with the above carbon atom. |
Alert level C STRVA01_ALERT_4_C Flack test results are ambiguous. From the CIF: _refine_ls_abs_structure_Flack 0.390 From the CIF: _refine_ls_abs_structure_Flack_su 0.070 PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.14 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C1
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 30.51 From the CIF: _reflns_number_total 6014 Count of symmetry unique reflns 3330 Completeness (_total/calc) 180.60% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 2684 Fraction of Friedel pairs measured 0.806 Are heavy atom types Z>Si present yes PLAT033_ALERT_2_G Flack Parameter Value Deviates 2 * su from zero. 0.39 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
2 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Theoretical and conformational studies on related molecules, together with the crystal structure of a sulfonylphosphonate, are reported by Olivato et al. (2001).
For related literature, see: Allen (2002); Hadd et al. (2001); Meadows & Gervay-Hague (2006); Meadows et al. (2005, 2007).
In the synthesis of (diisopropoxy-phosphorylmethanesulfonylmethyl)-phosphonic acid diisopropyl ester (I), to commercially available diisopropyl bromomethylphosphonate (Lancaster) (5.3 g, 20 mmol) in 15 ml of DMF were added potassium thioacetate (3.7 g, 30 mmol) and tetrabutylammonium iodide (370 mg) in sequence. The reaction mixture was heated to 358 K and stirred for 2 h. The solution was cooled and partitioned between water and ethyl acetate. The ethyl acetate layer was collected and dried over sodium sulfate and then evaporated to dryness. To the crude oil was added acetonitrile (15 ml), 3 M NaOH (7.4 ml) and methanol (7.4 ml) and the solution was stirred for 30 min. After 30 min, an additional 1 equiv of diisopropyl bromomethylphosphonate (4.5 g) was added to the mixture at room temperature and stirred overnight. The reaction mixture was then partitioned between water and ethyl acetate. The ethyl acetate layer was collected, dried over sodium sulfate, and evaporated to dryness. The crude oil was oxidized using oxone (24.9 g, 40 mmol) in methanol/water (ca 100 ml, 1:1) overnight to give a crude solid after diethyl ether/bicarbonate extraction. Recrystallization from diethyl ether/ hexane (1:1) provided 4.98 g of compound (I) as colorless, needle-like crystals (80% yield).
The methyl H atoms were constrained to an ideal geometry with C—H distances of 0.98 \%A and Uĩso~(H) = 1.5U~eq~(C), and each group was allowed to rotate freely about its C—C bond. Other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances in the range 0.99–1.00 \%A and Uĩso~(H) = 1.2U~eq~(C). The refined value of the Flack parameter (0.37 (7)) indicated a degree of inversion twinning.
As part of our research into enzymes that are involved in the metastatic potential of tumor cells, a number of potential disulfone inhibitors for HIV-integrase have been identified (Meadows et al., 2005, Meadows & Gervay-Hague, 2006, Meadows et al., 2007). The monosulfone reagent reported here was envisioned and synthesized by a modification of the disulfone reaction (Hadd, et al., 2001).
Molecule (I), has an approximate twofold axis that passes through the central sulfur (Fig. 1). There are no short intermolecular contacts in the packing. As expected, the P=O distances are longer than the S=O distances. A quasi-gauche conformation is indicated by the torsion angles O=P—C—S (-41.65 (14)]° for O2—P1—C2—S1 and -41.75 (14)° for O6—P2—C3—S1) and two of the P—C—S=O angles (-41.92 (13)° for P1—C2—S1—O4 and -42.06 (13)° for P2—C3—S—O5). This conformation is in keeping with the result of a HF/6–31G** calculation on a similar molecule (Olivato, et al., 2001) that is the only other reported structure of a neutral sulfonylphosphonate in the Cambridge Structural Database (v. 5.28, Allen, 2002). The authors suggested that this conformation and the observed intramolecular P···O=S < S···O=P distances reflect a better electron- donating ability of the sulfonyl oxygen lone pair than the phosphoryl oxygen lone pair. In agreement with the previously reported structure, in (I) the P···O=S distances are 3.3094 (14) Å and 3.3082 (15) Å while the S···O=P distances are 3.1593 (16)Å and 3.1616 (15) Å.
Theoretical and conformational studies on related molecules, together with the crystal structure of a sulfonylphosphonate, are reported by Olivato et al. (2001).
For related literature, see: Allen (2002); Hadd et al. (2001); Meadows & Gervay-Hague (2006); Meadows et al. (2005, 2007).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Sheldrick, 1994); software used to prepare material for publication: SHELXL97.
Fig. 1. A view of (I). Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms have been omitted for clarity. |
C14H32O8P2S | Dx = 1.312 Mg m−3 |
Mr = 422.40 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pna21 | Cell parameters from 994 reflections |
a = 9.8124 (9) Å | θ = 2.3–20.0° |
b = 8.3298 (8) Å | µ = 0.34 mm−1 |
c = 26.160 (3) Å | T = 90 K |
V = 2138.2 (4) Å3 | Needle, colorless |
Z = 4 | 0.47 × 0.13 × 0.08 mm |
F(000) = 904 |
Bruker SMART 1000 diffractometer | 6014 independent reflections |
Radiation source: fine-focus sealed tube | 5398 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
Detector resolution: 8.3 pixels mm-1 | θmax = 30.5°, θmin = 1.6° |
ω scans | h = −13→13 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2005) | k = −11→11 |
Tmin = 0.858, Tmax = 0.974 | l = −36→31 |
20017 measured reflections |
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)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.095 | w = 1/[σ2(Fo2) + (0.0555P)2 + 0.3326P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
6014 reflections | Δρmax = 0.50 e Å−3 |
235 parameters | Δρmin = −0.24 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 2547 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.39 (7) |
C14H32O8P2S | V = 2138.2 (4) Å3 |
Mr = 422.40 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 9.8124 (9) Å | µ = 0.34 mm−1 |
b = 8.3298 (8) Å | T = 90 K |
c = 26.160 (3) Å | 0.47 × 0.13 × 0.08 mm |
Bruker SMART 1000 diffractometer | 6014 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2005) | 5398 reflections with I > 2σ(I) |
Tmin = 0.858, Tmax = 0.974 | Rint = 0.029 |
20017 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.095 | Δρmax = 0.50 e Å−3 |
S = 1.09 | Δρmin = −0.24 e Å−3 |
6014 reflections | Absolute structure: Flack (1983), 2547 Friedel pairs |
235 parameters | Absolute structure parameter: 0.39 (7) |
1 restraint |
Experimental. 1H (400 MHz, CDCl3) δ 4.83 (m, 1H), 4.09 (d, J=16 Hz, 1H), 1.37 (q, 6H). 13C (100 MHz, CDCl3) δ 72.89 (d, J=6 Hz), 51.46 (d, J= 137 Hz), 24.29, J=4 Hz), 23.89 (d, J=5 Hz). LRMS (ESI) m/z calcd for C14H32O8P2S (M + H)+ is 423.13 and for (M + Na)+ is 445.13, found (M + H)+ 423.00 and (M + Na)+ 445.13. Anal. Calcd for C14H32O8P2S: C, 39.81; H, 7.64. Found: C, 39.88; H, 7. |
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 | ||
S1 | 0.88344 (5) | 0.34367 (4) | 0.84454 (2) | 0.01515 (8) | |
P1 | 0.89600 (5) | 0.11641 (6) | 0.933576 (18) | 0.01557 (10) | |
P2 | 0.87014 (4) | 0.11416 (6) | 0.756060 (18) | 0.01532 (10) | |
O1 | 0.80358 (14) | −0.01724 (16) | 0.95810 (6) | 0.0205 (3) | |
O2 | 1.02766 (13) | 0.05791 (16) | 0.91381 (6) | 0.0192 (3) | |
O3 | 0.90314 (15) | 0.24746 (18) | 0.97675 (7) | 0.0195 (3) | |
O4 | 0.98063 (14) | 0.43243 (17) | 0.87483 (6) | 0.0205 (3) | |
O5 | 0.78672 (14) | 0.43246 (16) | 0.81398 (6) | 0.0199 (3) | |
O6 | 0.73851 (13) | 0.05654 (16) | 0.77615 (6) | 0.0190 (3) | |
O7 | 0.96206 (14) | −0.02005 (16) | 0.73148 (6) | 0.0201 (3) | |
O8 | 0.86268 (14) | 0.24438 (17) | 0.71228 (7) | 0.0201 (4) | |
C1 | 1.0218 (3) | 0.2557 (3) | 1.01095 (12) | 0.0353 (7) | |
H1 | 1.1065 | 0.2353 | 0.9907 | 0.042* | |
C2 | 0.79050 (17) | 0.2140 (2) | 0.88622 (8) | 0.0166 (3) | |
H2A | 0.7442 | 0.1309 | 0.8655 | 0.020* | |
H2B | 0.7193 | 0.2773 | 0.9039 | 0.020* | |
C3 | 0.97566 (17) | 0.2129 (2) | 0.80333 (7) | 0.0159 (3) | |
H3A | 1.0217 | 0.1302 | 0.8243 | 0.019* | |
H3B | 1.0471 | 0.2755 | 0.7855 | 0.019* | |
C4 | 1.0252 (3) | 0.4245 (4) | 1.03118 (14) | 0.0535 (9) | |
H4A | 0.9419 | 0.4455 | 1.0508 | 0.080* | |
H4B | 1.0309 | 0.5001 | 1.0026 | 0.080* | |
H4C | 1.1048 | 0.4380 | 1.0534 | 0.080* | |
C5 | 1.0094 (5) | 0.1308 (5) | 1.05165 (14) | 0.0823 (15) | |
H5A | 1.0128 | 0.0239 | 1.0361 | 0.123* | |
H5B | 0.9225 | 0.1443 | 1.0696 | 0.123* | |
H5C | 1.0847 | 0.1423 | 1.0760 | 0.123* | |
C6 | 0.8124 (2) | −0.1874 (2) | 0.94238 (8) | 0.0228 (4) | |
H6 | 0.9097 | −0.2167 | 0.9358 | 0.027* | |
C7 | 0.7587 (3) | −0.2831 (4) | 0.98725 (11) | 0.0453 (7) | |
H7A | 0.6638 | −0.2529 | 0.9939 | 0.068* | |
H7B | 0.8141 | −0.2604 | 1.0176 | 0.068* | |
H7C | 0.7635 | −0.3980 | 0.9793 | 0.068* | |
C8 | 0.7292 (2) | −0.2133 (3) | 0.89447 (9) | 0.0260 (4) | |
H8A | 0.7708 | −0.1546 | 0.8660 | 0.039* | |
H8B | 0.6362 | −0.1740 | 0.9000 | 0.039* | |
H8C | 0.7266 | −0.3281 | 0.8864 | 0.039* | |
C9 | 0.9539 (2) | −0.1899 (2) | 0.74786 (8) | 0.0217 (4) | |
H9 | 0.8568 | −0.2196 | 0.7545 | 0.026* | |
C10 | 1.0364 (2) | −0.2130 (3) | 0.79563 (9) | 0.0245 (4) | |
H10A | 0.9948 | −0.1524 | 0.8237 | 0.037* | |
H10B | 1.1295 | −0.1745 | 0.7899 | 0.037* | |
H10C | 1.0386 | −0.3273 | 0.8045 | 0.037* | |
C11 | 1.0085 (3) | −0.2872 (4) | 0.70366 (10) | 0.0430 (7) | |
H11A | 1.1050 | −0.2616 | 0.6984 | 0.064* | |
H11B | 0.9570 | −0.2613 | 0.6726 | 0.064* | |
H11C | 0.9989 | −0.4018 | 0.7113 | 0.064* | |
C12 | 0.7431 (2) | 0.2542 (3) | 0.67915 (11) | 0.0321 (6) | |
H12 | 0.6593 | 0.2357 | 0.7001 | 0.039* | |
C13 | 0.7408 (3) | 0.4223 (4) | 0.65881 (13) | 0.0499 (8) | |
H13A | 0.8210 | 0.4400 | 0.6372 | 0.075* | |
H13B | 0.7418 | 0.4984 | 0.6874 | 0.075* | |
H13C | 0.6580 | 0.4384 | 0.6385 | 0.075* | |
C14 | 0.7511 (5) | 0.1291 (4) | 0.63869 (15) | 0.0702 (11) | |
H14A | 0.7596 | 0.0231 | 0.6546 | 0.105* | |
H14B | 0.8307 | 0.1493 | 0.6170 | 0.105* | |
H14C | 0.6683 | 0.1324 | 0.6178 | 0.105* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.01363 (16) | 0.01357 (15) | 0.01826 (17) | 0.00011 (15) | −0.00119 (14) | 0.0008 (2) |
P1 | 0.0158 (2) | 0.0165 (2) | 0.0145 (2) | −0.00028 (15) | −0.00081 (17) | −0.0002 (2) |
P2 | 0.0149 (2) | 0.0155 (2) | 0.0155 (2) | 0.00026 (15) | −0.00078 (16) | 0.0012 (2) |
O1 | 0.0239 (7) | 0.0181 (6) | 0.0196 (7) | −0.0029 (5) | 0.0008 (5) | 0.0016 (6) |
O2 | 0.0178 (6) | 0.0198 (6) | 0.0200 (7) | 0.0023 (5) | −0.0006 (5) | −0.0001 (5) |
O3 | 0.0218 (7) | 0.0205 (9) | 0.0162 (9) | −0.0012 (5) | −0.0019 (6) | −0.0039 (5) |
O4 | 0.0186 (6) | 0.0177 (6) | 0.0253 (8) | −0.0032 (5) | −0.0019 (5) | −0.0031 (6) |
O5 | 0.0184 (6) | 0.0170 (6) | 0.0241 (8) | 0.0036 (5) | −0.0023 (5) | 0.0037 (6) |
O6 | 0.0181 (6) | 0.0200 (6) | 0.0191 (7) | −0.0016 (5) | −0.0009 (5) | 0.0003 (5) |
O7 | 0.0219 (7) | 0.0165 (6) | 0.0218 (7) | 0.0024 (5) | 0.0024 (5) | 0.0006 (5) |
O8 | 0.0200 (7) | 0.0215 (9) | 0.0189 (10) | −0.0004 (5) | −0.0019 (5) | 0.0043 (5) |
C1 | 0.0282 (11) | 0.0524 (18) | 0.0253 (15) | 0.0067 (10) | −0.0087 (9) | −0.0158 (11) |
C2 | 0.0129 (7) | 0.0175 (8) | 0.0196 (10) | 0.0009 (6) | −0.0003 (6) | 0.0007 (7) |
C3 | 0.0130 (7) | 0.0180 (7) | 0.0167 (9) | 0.0001 (6) | −0.0006 (6) | 0.0008 (7) |
C4 | 0.0459 (16) | 0.061 (2) | 0.053 (2) | −0.0150 (14) | −0.0063 (14) | −0.0313 (17) |
C5 | 0.141 (4) | 0.069 (3) | 0.037 (2) | 0.023 (3) | −0.043 (2) | 0.0053 (17) |
C6 | 0.0265 (9) | 0.0161 (9) | 0.0259 (11) | 0.0002 (7) | −0.0040 (7) | 0.0022 (7) |
C7 | 0.075 (2) | 0.0267 (12) | 0.0344 (16) | −0.0088 (13) | −0.0016 (14) | 0.0128 (12) |
C8 | 0.0320 (10) | 0.0199 (9) | 0.0261 (12) | −0.0022 (8) | −0.0045 (8) | −0.0003 (9) |
C9 | 0.0235 (9) | 0.0156 (8) | 0.0260 (11) | −0.0011 (6) | −0.0029 (7) | 0.0001 (7) |
C10 | 0.0288 (10) | 0.0184 (9) | 0.0262 (12) | 0.0001 (8) | −0.0046 (8) | 0.0029 (9) |
C11 | 0.075 (2) | 0.0239 (11) | 0.0304 (16) | 0.0092 (12) | −0.0089 (13) | −0.0082 (11) |
C12 | 0.0284 (11) | 0.0445 (16) | 0.0234 (15) | −0.0037 (9) | −0.0100 (9) | 0.0141 (10) |
C13 | 0.0465 (16) | 0.0557 (19) | 0.0474 (19) | 0.0145 (13) | −0.0021 (13) | 0.0302 (15) |
C14 | 0.108 (3) | 0.062 (2) | 0.041 (2) | −0.023 (2) | −0.033 (2) | 0.0001 (17) |
S1—O4 | 1.4435 (15) | C5—H5C | 0.9800 |
S1—O5 | 1.4446 (14) | C6—C8 | 1.511 (3) |
S1—C3 | 1.780 (2) | C6—C7 | 1.514 (3) |
S1—C2 | 1.785 (2) | C6—H6 | 1.0000 |
P1—O2 | 1.4744 (14) | C7—H7A | 0.9800 |
P1—O3 | 1.5722 (17) | C7—H7B | 0.9800 |
P1—O1 | 1.5727 (14) | C7—H7C | 0.9800 |
P1—C2 | 1.808 (2) | C8—H8A | 0.9800 |
P2—O6 | 1.4747 (14) | C8—H8B | 0.9800 |
P2—O7 | 1.5737 (14) | C8—H8C | 0.9800 |
P2—O8 | 1.5791 (18) | C9—C10 | 1.501 (3) |
P2—C3 | 1.811 (2) | C9—C11 | 1.510 (3) |
O1—C6 | 1.478 (2) | C9—H9 | 1.0000 |
O3—C1 | 1.470 (3) | C10—H10A | 0.9800 |
O7—C9 | 1.480 (2) | C10—H10B | 0.9800 |
O8—C12 | 1.461 (3) | C10—H10C | 0.9800 |
C1—C5 | 1.493 (5) | C11—H11A | 0.9800 |
C1—C4 | 1.503 (4) | C11—H11B | 0.9800 |
C1—H1 | 1.0000 | C11—H11C | 0.9800 |
C2—H2A | 0.9900 | C12—C14 | 1.487 (5) |
C2—H2B | 0.9900 | C12—C13 | 1.498 (4) |
C3—H3A | 0.9900 | C12—H12 | 1.0000 |
C3—H3B | 0.9900 | C13—H13A | 0.9800 |
C4—H4A | 0.9800 | C13—H13B | 0.9800 |
C4—H4B | 0.9800 | C13—H13C | 0.9800 |
C4—H4C | 0.9800 | C14—H14A | 0.9800 |
C5—H5A | 0.9800 | C14—H14B | 0.9800 |
C5—H5B | 0.9800 | C14—H14C | 0.9800 |
O4—S1—O5 | 118.40 (7) | O1—C6—C7 | 105.61 (19) |
O4—S1—C3 | 108.06 (8) | C8—C6—C7 | 112.32 (19) |
O5—S1—C3 | 108.18 (9) | O1—C6—H6 | 109.7 |
O4—S1—C2 | 108.19 (9) | C8—C6—H6 | 109.7 |
O5—S1—C2 | 108.19 (9) | C7—C6—H6 | 109.7 |
C3—S1—C2 | 105.04 (7) | C6—C7—H7A | 109.5 |
O2—P1—O3 | 116.25 (8) | C6—C7—H7B | 109.5 |
O2—P1—O1 | 114.48 (8) | H7A—C7—H7B | 109.5 |
O3—P1—O1 | 102.95 (9) | C6—C7—H7C | 109.5 |
O2—P1—C2 | 114.21 (9) | H7A—C7—H7C | 109.5 |
O3—P1—C2 | 101.86 (9) | H7B—C7—H7C | 109.5 |
O1—P1—C2 | 105.53 (8) | C6—C8—H8A | 109.5 |
O6—P2—O7 | 114.61 (8) | C6—C8—H8B | 109.5 |
O6—P2—O8 | 116.19 (8) | H8A—C8—H8B | 109.5 |
O7—P2—O8 | 102.60 (9) | C6—C8—H8C | 109.5 |
O6—P2—C3 | 113.92 (9) | H8A—C8—H8C | 109.5 |
O7—P2—C3 | 105.91 (8) | H8B—C8—H8C | 109.5 |
O8—P2—C3 | 102.10 (9) | O7—C9—C10 | 109.55 (16) |
C6—O1—P1 | 122.11 (13) | O7—C9—C11 | 105.78 (18) |
C1—O3—P1 | 120.32 (15) | C10—C9—C11 | 112.18 (19) |
C9—O7—P2 | 121.98 (13) | O7—C9—H9 | 109.8 |
C12—O8—P2 | 120.39 (14) | C10—C9—H9 | 109.8 |
O3—C1—C5 | 109.7 (3) | C11—C9—H9 | 109.8 |
O3—C1—C4 | 106.0 (2) | C9—C10—H10A | 109.5 |
C5—C1—C4 | 113.7 (3) | C9—C10—H10B | 109.5 |
O3—C1—H1 | 109.1 | H10A—C10—H10B | 109.5 |
C5—C1—H1 | 109.1 | C9—C10—H10C | 109.5 |
C4—C1—H1 | 109.1 | H10A—C10—H10C | 109.5 |
S1—C2—P1 | 113.46 (9) | H10B—C10—H10C | 109.5 |
S1—C2—H2A | 108.9 | C9—C11—H11A | 109.5 |
P1—C2—H2A | 108.9 | C9—C11—H11B | 109.5 |
S1—C2—H2B | 108.9 | H11A—C11—H11B | 109.5 |
P1—C2—H2B | 108.9 | C9—C11—H11C | 109.5 |
H2A—C2—H2B | 107.7 | H11A—C11—H11C | 109.5 |
S1—C3—P2 | 113.65 (9) | H11B—C11—H11C | 109.5 |
S1—C3—H3A | 108.8 | O8—C12—C14 | 109.9 (2) |
P2—C3—H3A | 108.8 | O8—C12—C13 | 106.0 (2) |
S1—C3—H3B | 108.8 | C14—C12—C13 | 113.7 (3) |
P2—C3—H3B | 108.8 | O8—C12—H12 | 109.0 |
H3A—C3—H3B | 107.7 | C14—C12—H12 | 109.0 |
C1—C4—H4A | 109.5 | C13—C12—H12 | 109.0 |
C1—C4—H4B | 109.5 | C12—C13—H13A | 109.5 |
H4A—C4—H4B | 109.5 | C12—C13—H13B | 109.5 |
C1—C4—H4C | 109.5 | H13A—C13—H13B | 109.5 |
H4A—C4—H4C | 109.5 | C12—C13—H13C | 109.5 |
H4B—C4—H4C | 109.5 | H13A—C13—H13C | 109.5 |
C1—C5—H5A | 109.5 | H13B—C13—H13C | 109.5 |
C1—C5—H5B | 109.5 | C12—C14—H14A | 109.5 |
H5A—C5—H5B | 109.5 | C12—C14—H14B | 109.5 |
C1—C5—H5C | 109.5 | H14A—C14—H14B | 109.5 |
H5A—C5—H5C | 109.5 | C12—C14—H14C | 109.5 |
H5B—C5—H5C | 109.5 | H14A—C14—H14C | 109.5 |
O1—C6—C8 | 109.63 (16) | H14B—C14—H14C | 109.5 |
O2—P1—O1—C6 | −27.16 (17) | C3—S1—C2—P1 | 73.30 (14) |
O3—P1—O1—C6 | −154.28 (14) | O2—P1—C2—S1 | −41.65 (14) |
C2—P1—O1—C6 | 99.30 (15) | O3—P1—C2—S1 | 84.50 (12) |
O2—P1—O3—C1 | −27.2 (2) | O1—P1—C2—S1 | −168.27 (10) |
O1—P1—O3—C1 | 98.8 (2) | O4—S1—C3—P2 | −171.38 (10) |
C2—P1—O3—C1 | −152.02 (19) | O5—S1—C3—P2 | −42.06 (13) |
O6—P2—O7—C9 | −27.84 (17) | C2—S1—C3—P2 | 73.30 (13) |
O8—P2—O7—C9 | −154.70 (14) | O6—P2—C3—S1 | −41.75 (14) |
C3—P2—O7—C9 | 98.62 (15) | O7—P2—C3—S1 | −168.63 (10) |
O6—P2—O8—C12 | −25.8 (2) | O8—P2—C3—S1 | 84.33 (12) |
O7—P2—O8—C12 | 100.08 (19) | P1—O1—C6—C8 | −82.50 (19) |
C3—P2—O8—C12 | −150.33 (19) | P1—O1—C6—C7 | 156.28 (17) |
P1—O3—C1—C5 | −79.7 (3) | P2—O7—C9—C10 | −81.56 (19) |
P1—O3—C1—C4 | 157.1 (2) | P2—O7—C9—C11 | 157.34 (16) |
O4—S1—C2—P1 | −41.92 (13) | P2—O8—C12—C14 | −80.1 (3) |
O5—S1—C2—P1 | −171.33 (10) | P2—O8—C12—C13 | 156.62 (19) |
Experimental details
Crystal data | |
Chemical formula | C14H32O8P2S |
Mr | 422.40 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 90 |
a, b, c (Å) | 9.8124 (9), 8.3298 (8), 26.160 (3) |
V (Å3) | 2138.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.34 |
Crystal size (mm) | 0.47 × 0.13 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART 1000 |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2005) |
Tmin, Tmax | 0.858, 0.974 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20017, 6014, 5398 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.714 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.095, 1.09 |
No. of reflections | 6014 |
No. of parameters | 235 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.24 |
Absolute structure | Flack (1983), 2547 Friedel pairs |
Absolute structure parameter | 0.39 (7) |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2004), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL (Sheldrick, 1994), SHELXL97.
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As part of our research into enzymes that are involved in the metastatic potential of tumor cells, a number of potential disulfone inhibitors for HIV-integrase have been identified (Meadows et al., 2005, Meadows & Gervay-Hague, 2006, Meadows et al., 2007). The monosulfone reagent reported here was envisioned and synthesized by a modification of the disulfone reaction (Hadd, et al., 2001).
Molecule (I), has an approximate twofold axis that passes through the central sulfur (Fig. 1). There are no short intermolecular contacts in the packing. As expected, the P=O distances are longer than the S=O distances. A quasi-gauche conformation is indicated by the torsion angles O=P—C—S (-41.65 (14)]° for O2—P1—C2—S1 and -41.75 (14)° for O6—P2—C3—S1) and two of the P—C—S=O angles (-41.92 (13)° for P1—C2—S1—O4 and -42.06 (13)° for P2—C3—S—O5). This conformation is in keeping with the result of a HF/6–31G** calculation on a similar molecule (Olivato, et al., 2001) that is the only other reported structure of a neutral sulfonylphosphonate in the Cambridge Structural Database (v. 5.28, Allen, 2002). The authors suggested that this conformation and the observed intramolecular P···O=S < S···O=P distances reflect a better electron- donating ability of the sulfonyl oxygen lone pair than the phosphoryl oxygen lone pair. In agreement with the previously reported structure, in (I) the P···O=S distances are 3.3094 (14) Å and 3.3082 (15) Å while the S···O=P distances are 3.1593 (16)Å and 3.1616 (15) Å.