Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108022439/sq3155sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108022439/sq3155IIsup2.hkl |
CCDC reference: 703726
The anhydride precursor, (I), to the title compound, (II), was synthesized by the photochemical [2+2] cycloaddition of maleic anhydride and 3-sulfolene in acetone at room temperature following the directions of Bloomfield (1975). The initial product, (I), was hydrolyzed to (II), probably during crystallization. Colourless plates of (II) suitable for X-ray crystallographic determination were formed in a solution in acetone.
In order to compare the structure of (II) with those of other molecules in the Cambridge Structural Database, PREQUEST and ACTIVATE (Cambridge Crystallographic Data Centre, 1994) were used to format the CIF file for the Database. The Database (Version 5.29; Allen, 2002) was then searched using CONQUEST (Bruno et al., 2002) for other fused sulfolane–cyclobutane structures. Torsion angles in the sulfolane ring and the dihedral angle in the cyclobutane ring were calculated using VISTA (Cambridge Crystallographic Data Centre, 1994). The pseudorotation angle for the sulfolane rings was calculated and the conformation assigned using the definitions of Altona & Sundaralingam (1972). The cyclobutane puckering angle was calculated using the definition of Allen et al. (2005).
Because they participate in a hydrogen bond, the positions of atoms H8A, H9A, H8B and H9B were refined, with Uiso(H) = 1.2Ueq(O). Idealized positions for other H atoms were calculated at 0.93 Å from bonded C atoms with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2003); cell refinement: SMART (Bruker, 2003); data reduction: SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
C8H10O6S | F(000) = 976 |
Mr = 234.22 | Dx = 1.725 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2YBC | Cell parameters from 7020 reflections |
a = 18.497 (3) Å | θ = 2.6–28.5° |
b = 6.1203 (8) Å | µ = 0.37 mm−1 |
c = 17.188 (2) Å | T = 103 K |
β = 112.051 (2)° | Plate, colourless |
V = 1803.4 (4) Å3 | 0.36 × 0.11 × 0.05 mm |
Z = 8 |
Bruker SMART area-detector diffractometer | 4458 independent reflections |
Radiation source: fine-focus sealed tube | 3212 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
ϕ and ω scans | θmax = 28.5°, θmin = 1.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −22→24 |
Tmin = 0.877, Tmax = 0.982 | k = −8→8 |
13348 measured reflections | l = −21→23 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.128 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0653P)2 + 0.9231P] where P = (Fo2 + 2Fc2)/3 |
4458 reflections | (Δ/σ)max = 0.003 |
283 parameters | Δρmax = 0.71 e Å−3 |
0 restraints | Δρmin = −0.66 e Å−3 |
C8H10O6S | V = 1803.4 (4) Å3 |
Mr = 234.22 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 18.497 (3) Å | µ = 0.37 mm−1 |
b = 6.1203 (8) Å | T = 103 K |
c = 17.188 (2) Å | 0.36 × 0.11 × 0.05 mm |
β = 112.051 (2)° |
Bruker SMART area-detector diffractometer | 4458 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 3212 reflections with I > 2σ(I) |
Tmin = 0.877, Tmax = 0.982 | Rint = 0.061 |
13348 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.128 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.71 e Å−3 |
4458 reflections | Δρmin = −0.66 e Å−3 |
283 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 | ||
S3A | 0.01497 (4) | 1.49593 (10) | 0.16292 (4) | 0.01167 (16) | |
O8'A | 0.26140 (11) | 1.1014 (3) | 0.08573 (12) | 0.0159 (4) | |
O8A | 0.15180 (12) | 1.0505 (3) | −0.02607 (13) | 0.0158 (4) | |
H8A | 0.178 (2) | 1.020 (6) | −0.045 (3) | 0.024* | |
O9A | 0.28435 (12) | 0.8652 (3) | 0.24110 (13) | 0.0157 (4) | |
H9A | 0.333 (2) | 0.850 (5) | 0.261 (2) | 0.024* | |
O9'A | 0.31369 (11) | 1.2103 (3) | 0.27950 (13) | 0.0182 (4) | |
O3'A | 0.01234 (12) | 1.6898 (3) | 0.11450 (13) | 0.0176 (4) | |
O3A | −0.04201 (11) | 1.4798 (3) | 0.20243 (12) | 0.0149 (4) | |
C8A | 0.19202 (15) | 1.0738 (4) | 0.05513 (17) | 0.0114 (5) | |
C7A | 0.13990 (15) | 1.0654 (4) | 0.10401 (16) | 0.0117 (5) | |
H7A | 0.1062 | 0.9322 | 0.0922 | 0.014* | |
C1A | 0.09365 (15) | 1.2828 (4) | 0.09409 (16) | 0.0114 (5) | |
H1A | 0.0940 | 1.3766 | 0.0466 | 0.014* | |
C2A | 0.01411 (15) | 1.2637 (4) | 0.10080 (17) | 0.0128 (5) | |
H2AB | 0.0094 | 1.1265 | 0.1290 | 0.015* | |
H2AA | −0.0287 | 1.2716 | 0.0450 | 0.015* | |
C9A | 0.26570 (16) | 1.0740 (4) | 0.24309 (17) | 0.0131 (5) | |
C6A | 0.18050 (15) | 1.1170 (4) | 0.19870 (16) | 0.0111 (5) | |
H6A | 0.1514 | 1.0426 | 0.2298 | 0.013* | |
C5A | 0.15317 (15) | 1.3561 (4) | 0.18249 (16) | 0.0114 (5) | |
H5A | 0.1946 | 1.4540 | 0.1779 | 0.014* | |
C4A | 0.11201 (15) | 1.4576 (4) | 0.23652 (17) | 0.0130 (5) | |
H4AB | 0.1362 | 1.5985 | 0.2610 | 0.016* | |
H4AA | 0.1132 | 1.3577 | 0.2823 | 0.016* | |
S3B | 0.51397 (4) | 0.93365 (10) | 0.35877 (4) | 0.01193 (16) | |
O9'B | 0.74535 (12) | 1.4373 (3) | 0.59529 (13) | 0.0183 (4) | |
O9B | 0.63679 (12) | 1.4509 (3) | 0.62175 (13) | 0.0179 (4) | |
H9B | 0.659 (2) | 1.546 (6) | 0.654 (2) | 0.027* | |
O8'B | 0.81850 (11) | 1.0853 (3) | 0.49683 (12) | 0.0148 (4) | |
O8B | 0.80328 (12) | 0.9807 (3) | 0.61416 (12) | 0.0177 (4) | |
H8B | 0.857 (2) | 1.001 (6) | 0.636 (2) | 0.027* | |
O3'B | 0.52791 (12) | 0.7951 (3) | 0.43049 (12) | 0.0169 (4) | |
O3B | 0.44779 (11) | 0.8819 (3) | 0.28326 (12) | 0.0161 (4) | |
C9B | 0.68095 (16) | 1.3668 (4) | 0.58417 (16) | 0.0118 (5) | |
C6B | 0.64044 (15) | 1.1858 (4) | 0.52582 (16) | 0.0112 (5) | |
H6B | 0.6036 | 1.1057 | 0.5458 | 0.013* | |
C5B | 0.59881 (15) | 1.2688 (4) | 0.43346 (16) | 0.0120 (5) | |
H5B | 0.6093 | 1.4267 | 0.4270 | 0.014* | |
C4B | 0.51285 (15) | 1.2103 (4) | 0.38998 (17) | 0.0135 (5) | |
H4BB | 0.4872 | 1.3054 | 0.3407 | 0.016* | |
H4BA | 0.4851 | 1.2248 | 0.4290 | 0.016* | |
C8B | 0.77664 (16) | 1.0385 (4) | 0.53359 (17) | 0.0118 (5) | |
C7B | 0.68967 (15) | 1.0255 (4) | 0.49514 (16) | 0.0107 (5) | |
H7B | 0.6724 | 0.8718 | 0.4977 | 0.013* | |
C1B | 0.65147 (15) | 1.1133 (4) | 0.40507 (16) | 0.0111 (5) | |
H1B | 0.6890 | 1.1950 | 0.3865 | 0.013* | |
C2B | 0.60066 (15) | 0.9543 (4) | 0.33825 (17) | 0.0128 (5) | |
H2BB | 0.6264 | 0.8102 | 0.3437 | 0.015* | |
H2BA | 0.5896 | 1.0120 | 0.2811 | 0.015* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S3A | 0.0106 (3) | 0.0135 (3) | 0.0105 (3) | 0.0019 (2) | 0.0036 (2) | 0.0003 (2) |
O8'A | 0.0146 (10) | 0.0181 (9) | 0.0153 (10) | −0.0014 (8) | 0.0059 (8) | −0.0005 (8) |
O8A | 0.0175 (11) | 0.0208 (10) | 0.0110 (10) | 0.0047 (8) | 0.0077 (8) | −0.0008 (8) |
O9A | 0.0129 (10) | 0.0141 (9) | 0.0180 (11) | 0.0040 (8) | 0.0033 (8) | 0.0005 (8) |
O9'A | 0.0150 (10) | 0.0196 (10) | 0.0179 (11) | 0.0003 (8) | 0.0036 (8) | −0.0071 (8) |
O3'A | 0.0211 (11) | 0.0138 (9) | 0.0178 (11) | 0.0025 (8) | 0.0073 (9) | 0.0039 (8) |
O3A | 0.0107 (9) | 0.0224 (10) | 0.0134 (10) | 0.0026 (7) | 0.0067 (8) | 0.0002 (8) |
C8A | 0.0141 (14) | 0.0090 (11) | 0.0108 (13) | 0.0008 (10) | 0.0044 (11) | 0.0000 (9) |
C7A | 0.0127 (13) | 0.0133 (12) | 0.0095 (13) | 0.0013 (10) | 0.0046 (11) | −0.0020 (10) |
C1A | 0.0124 (13) | 0.0119 (11) | 0.0101 (13) | 0.0010 (10) | 0.0045 (10) | −0.0008 (10) |
C2A | 0.0118 (13) | 0.0154 (12) | 0.0099 (13) | 0.0001 (10) | 0.0026 (10) | −0.0027 (10) |
C9A | 0.0164 (14) | 0.0148 (12) | 0.0095 (13) | 0.0001 (11) | 0.0065 (11) | −0.0003 (10) |
C6A | 0.0128 (13) | 0.0117 (12) | 0.0101 (13) | 0.0001 (10) | 0.0057 (11) | 0.0014 (9) |
C5A | 0.0093 (13) | 0.0134 (12) | 0.0094 (13) | 0.0006 (10) | 0.0012 (10) | −0.0002 (10) |
C4A | 0.0118 (13) | 0.0141 (12) | 0.0099 (13) | 0.0015 (10) | 0.0003 (11) | −0.0028 (10) |
S3B | 0.0100 (3) | 0.0132 (3) | 0.0121 (3) | −0.0004 (2) | 0.0036 (3) | −0.0023 (2) |
O9'B | 0.0186 (11) | 0.0227 (10) | 0.0155 (10) | −0.0083 (8) | 0.0085 (9) | −0.0057 (8) |
O9B | 0.0163 (11) | 0.0184 (10) | 0.0205 (11) | −0.0026 (8) | 0.0086 (9) | −0.0093 (8) |
O8'B | 0.0145 (10) | 0.0161 (9) | 0.0149 (10) | 0.0001 (8) | 0.0066 (8) | 0.0005 (7) |
O8B | 0.0110 (10) | 0.0281 (11) | 0.0120 (10) | 0.0002 (8) | 0.0018 (8) | 0.0038 (8) |
O3'B | 0.0190 (11) | 0.0161 (9) | 0.0162 (10) | −0.0020 (8) | 0.0074 (8) | 0.0021 (8) |
O3B | 0.0101 (10) | 0.0212 (10) | 0.0155 (10) | −0.0008 (8) | 0.0030 (8) | −0.0064 (8) |
C9B | 0.0146 (14) | 0.0120 (12) | 0.0079 (12) | 0.0005 (10) | 0.0031 (11) | 0.0017 (9) |
C6B | 0.0129 (13) | 0.0105 (11) | 0.0104 (13) | −0.0004 (10) | 0.0045 (10) | −0.0019 (9) |
C5B | 0.0138 (13) | 0.0109 (11) | 0.0098 (13) | 0.0011 (10) | 0.0028 (11) | 0.0003 (9) |
C4B | 0.0123 (13) | 0.0140 (12) | 0.0134 (14) | 0.0034 (10) | 0.0038 (11) | −0.0025 (10) |
C8B | 0.0130 (13) | 0.0101 (12) | 0.0111 (13) | 0.0004 (9) | 0.0033 (11) | −0.0013 (9) |
C7B | 0.0091 (12) | 0.0129 (12) | 0.0100 (13) | 0.0004 (9) | 0.0034 (10) | 0.0001 (9) |
C1B | 0.0125 (13) | 0.0114 (12) | 0.0100 (13) | −0.0014 (9) | 0.0049 (11) | −0.0010 (9) |
C2B | 0.0123 (13) | 0.0156 (13) | 0.0114 (13) | 0.0015 (10) | 0.0054 (11) | −0.0007 (10) |
S3A—O3'A | 1.440 (2) | S3B—O3'B | 1.438 (2) |
S3A—O3A | 1.456 (2) | S3B—O3B | 1.446 (2) |
S3A—C2A | 1.774 (3) | S3B—C2B | 1.771 (3) |
S3A—C4A | 1.781 (3) | S3B—C4B | 1.779 (3) |
O8'A—C8A | 1.202 (3) | O9'B—C9B | 1.213 (3) |
O8A—C8A | 1.320 (3) | O9B—C9B | 1.321 (3) |
O8A—H8A | 0.69 (4) | O9B—H9B | 0.80 (4) |
O9A—C9A | 1.327 (3) | O8'B—C8B | 1.203 (3) |
O9A—H9A | 0.84 (4) | O8B—C8B | 1.332 (3) |
O9'A—C9A | 1.208 (3) | O8B—H8B | 0.94 (4) |
C8A—C7A | 1.499 (4) | C9B—C6B | 1.493 (3) |
C7A—C6A | 1.548 (4) | C6B—C7B | 1.559 (4) |
C7A—C1A | 1.556 (4) | C6B—C5B | 1.566 (4) |
C7A—H7A | 1.0000 | C6B—H6B | 1.0000 |
C1A—C2A | 1.523 (4) | C5B—C4B | 1.524 (4) |
C1A—C5A | 1.570 (4) | C5B—C1B | 1.565 (4) |
C1A—H1A | 1.0000 | C5B—H5B | 1.0000 |
C2A—H2AB | 0.9900 | C4B—H4BB | 0.9900 |
C2A—H2AA | 0.9900 | C4B—H4BA | 0.9900 |
C9A—C6A | 1.494 (4) | C8B—C7B | 1.494 (4) |
C6A—C5A | 1.539 (3) | C7B—C1B | 1.537 (4) |
C6A—H6A | 1.0000 | C7B—H7B | 1.0000 |
C5A—C4A | 1.536 (4) | C1B—C2B | 1.529 (4) |
C5A—H5A | 1.0000 | C1B—H1B | 1.0000 |
C4A—H4AB | 0.9900 | C2B—H2BB | 0.9900 |
C4A—H4AA | 0.9900 | C2B—H2BA | 0.9900 |
O3'A—S3A—O3A | 116.91 (12) | O3'B—S3B—O3B | 117.35 (12) |
O3'A—S3A—C2A | 108.76 (13) | O3'B—S3B—C2B | 109.18 (12) |
O3A—S3A—C2A | 112.45 (12) | O3B—S3B—C2B | 111.20 (12) |
O3'A—S3A—C4A | 108.99 (13) | O3'B—S3B—C4B | 108.76 (13) |
O3A—S3A—C4A | 111.88 (13) | O3B—S3B—C4B | 112.17 (12) |
C2A—S3A—C4A | 95.79 (12) | C2B—S3B—C4B | 96.09 (13) |
C8A—O8A—H8A | 108 (3) | C9B—O9B—H9B | 111 (3) |
C9A—O9A—H9A | 110 (2) | C8B—O8B—H8B | 108 (2) |
O8'A—C8A—O8A | 124.3 (3) | O9'B—C9B—O9B | 122.4 (2) |
O8'A—C8A—C7A | 124.4 (2) | O9'B—C9B—C6B | 125.8 (3) |
O8A—C8A—C7A | 111.3 (2) | O9B—C9B—C6B | 111.8 (2) |
C8A—C7A—C6A | 115.0 (2) | C9B—C6B—C7B | 119.0 (2) |
C8A—C7A—C1A | 110.6 (2) | C9B—C6B—C5B | 111.8 (2) |
C6A—C7A—C1A | 88.29 (19) | C7B—C6B—C5B | 89.35 (19) |
C8A—C7A—H7A | 113.5 | C9B—C6B—H6B | 111.6 |
C6A—C7A—H7A | 113.5 | C7B—C6B—H6B | 111.6 |
C1A—C7A—H7A | 113.5 | C5B—C6B—H6B | 111.6 |
C2A—C1A—C7A | 115.7 (2) | C4B—C5B—C1B | 111.2 (2) |
C2A—C1A—C5A | 107.2 (2) | C4B—C5B—C6B | 116.5 (2) |
C7A—C1A—C5A | 88.94 (19) | C1B—C5B—C6B | 89.54 (19) |
C2A—C1A—H1A | 114.1 | C4B—C5B—H5B | 112.5 |
C7A—C1A—H1A | 114.1 | C1B—C5B—H5B | 112.5 |
C5A—C1A—H1A | 114.1 | C6B—C5B—H5B | 112.5 |
C1A—C2A—S3A | 101.16 (17) | C5B—C4B—S3B | 104.09 (17) |
C1A—C2A—H2AB | 111.5 | C5B—C4B—H4BB | 110.9 |
S3A—C2A—H2AB | 111.5 | S3B—C4B—H4BB | 110.9 |
C1A—C2A—H2AA | 111.5 | C5B—C4B—H4BA | 110.9 |
S3A—C2A—H2AA | 111.5 | S3B—C4B—H4BA | 110.9 |
H2AB—C2A—H2AA | 109.4 | H4BB—C4B—H4BA | 109.0 |
O9'A—C9A—O9A | 122.1 (3) | O8'B—C8B—O8B | 123.3 (2) |
O9'A—C9A—C6A | 124.9 (2) | O8'B—C8B—C7B | 125.3 (2) |
O9A—C9A—C6A | 113.0 (2) | O8B—C8B—C7B | 111.2 (2) |
C9A—C6A—C5A | 118.2 (2) | C8B—C7B—C1B | 116.0 (2) |
C9A—C6A—C7A | 120.2 (2) | C8B—C7B—C6B | 119.0 (2) |
C5A—C6A—C7A | 90.42 (19) | C1B—C7B—C6B | 90.85 (19) |
C9A—C6A—H6A | 108.9 | C8B—C7B—H7B | 109.9 |
C5A—C6A—H6A | 108.9 | C1B—C7B—H7B | 109.9 |
C7A—C6A—H6A | 108.9 | C6B—C7B—H7B | 109.9 |
C4A—C5A—C6A | 118.6 (2) | C2B—C1B—C7B | 117.0 (2) |
C4A—C5A—C1A | 112.0 (2) | C2B—C1B—C5B | 110.0 (2) |
C6A—C5A—C1A | 88.09 (19) | C7B—C1B—C5B | 90.17 (19) |
C4A—C5A—H5A | 112.0 | C2B—C1B—H1B | 112.6 |
C6A—C5A—H5A | 112.0 | C7B—C1B—H1B | 112.6 |
C1A—C5A—H5A | 112.0 | C5B—C1B—H1B | 112.6 |
C5A—C4A—S3A | 102.71 (17) | C1B—C2B—S3B | 104.06 (18) |
C5A—C4A—H4AB | 111.2 | C1B—C2B—H2BB | 110.9 |
S3A—C4A—H4AB | 111.2 | S3B—C2B—H2BB | 110.9 |
C5A—C4A—H4AA | 111.2 | C1B—C2B—H2BA | 110.9 |
S3A—C4A—H4AA | 111.2 | S3B—C2B—H2BA | 110.9 |
H4AB—C4A—H4AA | 109.1 | H2BB—C2B—H2BA | 109.0 |
O8'A—C8A—C7A—C6A | 5.6 (4) | O9'B—C9B—C6B—C7B | 19.1 (4) |
O8A—C8A—C7A—C6A | −173.5 (2) | O9B—C9B—C6B—C7B | −163.2 (2) |
O8'A—C8A—C7A—C1A | 103.6 (3) | O9'B—C9B—C6B—C5B | −82.9 (3) |
O8A—C8A—C7A—C1A | −75.4 (3) | O9B—C9B—C6B—C5B | 94.8 (3) |
C8A—C7A—C1A—C2A | 150.7 (2) | C9B—C6B—C5B—C4B | −127.5 (2) |
C6A—C7A—C1A—C2A | −93.2 (2) | C7B—C6B—C5B—C4B | 111.3 (2) |
C8A—C7A—C1A—C5A | −100.7 (2) | C9B—C6B—C5B—C1B | 118.9 (2) |
C6A—C7A—C1A—C5A | 15.4 (2) | C7B—C6B—C5B—C1B | −2.20 (19) |
C7A—C1A—C2A—S3A | 137.78 (19) | C1B—C5B—C4B—S3B | 21.8 (3) |
C5A—C1A—C2A—S3A | 40.5 (2) | C6B—C5B—C4B—S3B | −78.8 (2) |
O3'A—S3A—C2A—C1A | 68.18 (19) | O3'B—S3B—C4B—C5B | 78.8 (2) |
O3A—S3A—C2A—C1A | −160.72 (16) | O3B—S3B—C4B—C5B | −149.72 (17) |
C4A—S3A—C2A—C1A | −44.15 (19) | C2B—S3B—C4B—C5B | −33.9 (2) |
O9'A—C9A—C6A—C5A | 12.8 (4) | O8'B—C8B—C7B—C1B | −9.8 (4) |
O9A—C9A—C6A—C5A | −169.2 (2) | O8B—C8B—C7B—C1B | 173.3 (2) |
O9'A—C9A—C6A—C7A | 121.5 (3) | O8'B—C8B—C7B—C6B | −116.6 (3) |
O9A—C9A—C6A—C7A | −60.4 (3) | O8B—C8B—C7B—C6B | 66.4 (3) |
C8A—C7A—C6A—C9A | −27.1 (3) | C9B—C6B—C7B—C8B | 8.1 (4) |
C1A—C7A—C6A—C9A | −139.1 (2) | C5B—C6B—C7B—C8B | 122.9 (2) |
C8A—C7A—C6A—C5A | 96.3 (2) | C9B—C6B—C7B—C1B | −112.5 (2) |
C1A—C7A—C6A—C5A | −15.7 (2) | C5B—C6B—C7B—C1B | 2.24 (19) |
C9A—C6A—C5A—C4A | −105.3 (3) | C8B—C7B—C1B—C2B | 121.9 (3) |
C7A—C6A—C5A—C4A | 129.6 (2) | C6B—C7B—C1B—C2B | −114.9 (2) |
C9A—C6A—C5A—C1A | 140.6 (2) | C8B—C7B—C1B—C5B | −125.4 (2) |
C7A—C6A—C5A—C1A | 15.6 (2) | C6B—C7B—C1B—C5B | −2.24 (19) |
C2A—C1A—C5A—C4A | −19.1 (3) | C4B—C5B—C1B—C2B | 2.8 (3) |
C7A—C1A—C5A—C4A | −135.7 (2) | C6B—C5B—C1B—C2B | 121.2 (2) |
C2A—C1A—C5A—C6A | 101.1 (2) | C4B—C5B—C1B—C7B | −116.1 (2) |
C7A—C1A—C5A—C6A | −15.5 (2) | C6B—C5B—C1B—C7B | 2.23 (19) |
C6A—C5A—C4A—S3A | −112.2 (2) | C7B—C1B—C2B—S3B | 74.7 (2) |
C1A—C5A—C4A—S3A | −11.9 (2) | C5B—C1B—C2B—S3B | −26.2 (2) |
O3'A—S3A—C4A—C5A | −79.33 (18) | O3'B—S3B—C2B—C1B | −76.75 (19) |
O3A—S3A—C4A—C5A | 149.83 (16) | O3B—S3B—C2B—C1B | 152.21 (16) |
C2A—S3A—C4A—C5A | 32.81 (19) | C4B—S3B—C2B—C1B | 35.56 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O8A—H8A···O9′Bi | 0.69 (4) | 1.99 (4) | 2.686 (3) | 178 (5) |
O9A—H9A···O3B | 0.84 (4) | 2.02 (4) | 2.834 (3) | 163 (3) |
O9B—H9B···O9′Aii | 0.80 (4) | 1.83 (4) | 2.618 (3) | 166 (4) |
O8B—H8B···O3Aiii | 0.94 (4) | 1.78 (4) | 2.700 (3) | 165 (3) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, −y+3, −z+1; (iii) x+1, −y+5/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C8H10O6S |
Mr | 234.22 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 103 |
a, b, c (Å) | 18.497 (3), 6.1203 (8), 17.188 (2) |
β (°) | 112.051 (2) |
V (Å3) | 1803.4 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.37 |
Crystal size (mm) | 0.36 × 0.11 × 0.05 |
Data collection | |
Diffractometer | Bruker SMART area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.877, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13348, 4458, 3212 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.671 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.128, 1.05 |
No. of reflections | 4458 |
No. of parameters | 283 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.71, −0.66 |
Computer programs: SMART (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006).
S3A—O3'A | 1.440 (2) | S3B—O3'B | 1.438 (2) |
S3A—O3A | 1.456 (2) | S3B—O3B | 1.446 (2) |
S3A—C2A | 1.774 (3) | S3B—C2B | 1.771 (3) |
S3A—C4A | 1.781 (3) | S3B—C4B | 1.779 (3) |
C1A—C2A | 1.523 (4) | C5B—C4B | 1.524 (4) |
C1A—C5A | 1.570 (4) | C5B—C1B | 1.565 (4) |
C5A—C4A | 1.536 (4) | C1B—C2B | 1.529 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O8A—H8A···O9'Bi | 0.69 (4) | 1.99 (4) | 2.686 (3) | 178 (5) |
O9A—H9A···O3B | 0.84 (4) | 2.02 (4) | 2.834 (3) | 163 (3) |
O9B—H9B···O9'Aii | 0.80 (4) | 1.83 (4) | 2.618 (3) | 166 (4) |
O8B—H8B···O3Aiii | 0.94 (4) | 1.78 (4) | 2.700 (3) | 165 (3) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, −y+3, −z+1; (iii) x+1, −y+5/2, z+1/2. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
The photochemical addition of 3-sulfolene to maleic anhydride and its derivatives was first reported by Shaikhrazieva et al. (1971, 1972). A few years later the anhydride product, (I), the Bloomfield adduct, was patented by Monsanto as a chemical regulator of plant growth or development (Bloomfield, 1975). The various adducts formed by the addition of an alkene to 3-sulfolene have found considerable use in synthesis (Aitken et al., 1999). The structure of (I) was determined at BP Research Centre, Sunbury-on-Thames, in 1982 by Smith (2003; see also Cadogan et al., 1982) and the exo configuration was established by single-crystal X-ray diffraction; unfortunately the crystallographic data were never published and are no longer available. Although the geometry of (I) could be predicted on mechanistic grounds, we deemed it worthwhile to determine it with certainty using X-ray crystallography. However, during the crystallization process, or at some other point, the anhydride ring was opened by water so that the structure actually determined was the title dicarboxylic acid, (II). The opening of the anhydride would not change the configuration of the substituents on the central cyclobutane ring.
The X-ray crystal structure determination of (II) reveals two molecules, A and B, in the asymmetric unit. In both molecules, the geometry of the substituents on the central cyclobutane ring is cis–anti–cis. As shown in Fig. 1, each molecule has a chair-like structure, with the cyclobutane ring as the seat, the carboxylic acid groups the legs, the sulfolane ring the back and the sulfone group the headrest. The two molecules differ in the orientation of the sulfone group. In molecule A the headrest is tilted back, away from the cyclobutane ring, while in molecule B the headrest is tilted forward toward the cyclobutane ring, and the distance between O3'B and the plane of the cyclobutane ring is 2.96 Å. Other interatomic distances are shown in Table 1.
In the ac plane, chains of alternating A and B molecules are linked headrest-to-legs by hydrogen bonds between the –OH group of the carboxylic acid and one O atom of the sulfone group (Fig. 2). Along the b axis, hydrogen bonds between the carboxyl groups join molecule A to B and molecule B to A. Details of the hydrogen-bonding scheme are given in Table 2.
The two molecules in the asymmetric unit of this structure exhibit two different low-energy conformations of the cyclobutane ring that are possible for this bicyclic compound. Cyclobutane in the gas phase has a ring puckering angle of 28° (Egawa et al., 1987). Presumably, puckering relieves torsional strain (Allen, 1984), but the solid-state structures of substituted cyclobutanes exhibit a wide range of puckering angles (Powell et al., 1997; Allen et al., 2005). For instance, in the structure of (II), molecule A is similar to an unsubstituted cyclobutane with a puckering angle of 22°, but the cyclobutane ring of molecule B is almost planar (puckering angle 3°). Despite these differences in ring puckering, the average C—C distances and C—C—C angles in the two cyclobutane rings are the same within the uncertainty of measurement (Table 1), and agree closely with those from a study (Allen, 1984) of puckered and planar cyclobutane derivatives in the Cambridge Structural Database.
Cyclopentane and substituted cyclopentane rings are non-planar, with two low-energy conformations, the twist (half-chair, symmetry C2) and the envelope (symmetry Cs) (Han & Kang, 1996; Riddell et al., 1997). The various possible conformations are described by an imaginary pseudorotation process in which each atom in the ring in turn is displaced out of the plane, becoming the tip of the flap of the envelope. Envelope and twist conformations alternate every 18°. Traversing the complete pseudorotation cycle of 360° returns the ring to its original conformation. In actual cyclopentane structures, conformations intermediate between pure envelope and pure twist are observed. The calculated phase angle of pseudorotation (Altona & Sundaralingam, 1972) is useful to describe these intermediate conformations. For the sulfolane ring of molecule A, the pseudorotation angle is 246°, closest to pure twist at 252°, with S exo (away from the cyclobutane ring) and C2 endo. In contrast, molecule B exhibits the envelope conformation (pseudorotation angle 86°, closest to envelope at 90°), with S at the tip of the flap, endo with respect to the cyclobutane ring.
Because of the two very different conformations exhibited in this structure, it is interesting to compare the conformations of other bicyclic and tricylic compounds containing fused sulfolane and cyclobutane rings in the Cambridge Structural Database (CSD; Version 5.29; Allen, 2002). These comparisons are shown in Table 3. The first diagram defines the torsion angles and shows that τ2 is zero for the pure envelope conformation. The succeeding diagrams show the twist conformation for molecule A, the envelope conformation for molecule B, and the structural diagrams of the comparison molecules. Among the five molecules with saturated cyclobutane rings, the puckering angle varies from 3 to 35°, with molecule A of (II) and DIGNOW (Williams et al., 1985) having the largest angle of puckering. DIGNOW and DIGNIQ (Williams et al., 1985) are tricyclic compounds with a cyclohexane ring fused to the cyclobutane ring; in DIGNIQ the cyclohexane ring is cis to the cyclobutane ring, while in DIGNOW it is trans. The constraints imposed by the cyclohexane ring in these two structures may explain the moderate puckering of the cyclobutane ring in DIGNIQ and the large puckering in DIGNOW. No such constraints apply for molecule A, yet its puckering angle is relatively high.
Among the six sulfolane rings fused to cyclobutane, the preferred conformation is the envelope, with the S atom at the tip of the flap and endo to the cyclobutane ring, as in molecule B, but tricyclic DIGNOW has the envelope conformation with C4 endo. There are only two examples of the twist conformation, both with the S atom and adjacent C atom out of the plane, namely tricyclic DIGNIQ and molecule A of (II). Molecule A is unusual in several respects, having a relatively high puckering of the cyclobutane ring compared with the other bicyclic compounds, and is the only molecule in this bicyclic group with a twist conformation. The two molecules in (II) thus demonstrate the wide range of conformational variability possible in this bicyclic compound.