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The title compounds, C13H15N3O5S and C11H10N2O4S2, respectively, both contain a phenylsulfonyl group connected, through a methylene bridge, to either a substituted nitroimidazole or nitro-1,3-thiazole ring. In the imidazole-containing molecule, the nitro and sulfonyl groups are trans relative to the sulfonyl-methyl bond, while in the thiazole-containing molecule, these substituents are cis. The stabilizing interactions within the crystals are also different between the two compounds.
Supporting information
CCDC references: 193436; 193437
2-(4-Benzenesulfonylmethyl-2-methyl-5-nitroimidazol-1-yl)ethanol, (I), was
prepared by the vicarious nucleophilic substitution of hydrogen (VNS) method
(Makosza & Kwast, 1987) from 2-(2-methyl-5-nitroimidazol-1-yl)ethanol with
chloromethyl phenyl sulfone. 4-Benzenesulfonylmethyl-2-methyl-5-nitrothiazole,
(II), was prepared from 4-chloromethyl-2-methyl-5-nitrothiazole and sodium
benzenesulfinate via an SRN1 reaction (Gellis et al., 1997).
Suitable crystals of (I) and (II) were grown by slow evaporation from
chloroform solutions at room temperature.
Most of the H atoms, particularly the H atoms of the hydroxyethyl group of (I),
were found through the final difference Fourier map. They were introduced in
calculated positions, but were constrained to their parent atom during the
refinement. Disordered H atoms were detected on atom C11 in (II).
For both compounds, data collection: KappaCCD Reference Manual (Nonius, 1998); cell refinement: KappaCCD Reference; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
(I) 2-(4-benzenesulfonylmethyl-2-methyl-5-nitro-imidazol-1-yl)-ethanol
top
Crystal data top
C13H15N3O5S | F(000) = 680 |
Mr = 325.34 | Dx = 1.484 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2911 reflections |
a = 12.5976 (3) Å | θ = 2.4–26.4° |
b = 7.7874 (3) Å | µ = 0.25 mm−1 |
c = 14.8929 (5) Å | T = 293 K |
β = 94.427 (2)° | Prism, colorless |
V = 1456.67 (8) Å3 | 0.6 × 0.5 × 0.4 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD diffractometer | 2509 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.045 |
Graphite monochromator | θmax = 26.4°, θmin = 2.4° |
ϕ scans | h = 0→14 |
2911 measured reflections | k = 0→9 |
2726 independent reflections | l = −18→18 |
Refinement top
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0359P)2 + 0.6408P] where P = (Fo2 + 2Fc2)/3 |
2726 reflections | (Δ/σ)max < 0.001 |
201 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
Crystal data top
C13H15N3O5S | V = 1456.67 (8) Å3 |
Mr = 325.34 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.5976 (3) Å | µ = 0.25 mm−1 |
b = 7.7874 (3) Å | T = 293 K |
c = 14.8929 (5) Å | 0.6 × 0.5 × 0.4 mm |
β = 94.427 (2)° | |
Data collection top
Nonius KappaCCD diffractometer | 2509 reflections with I > 2σ(I) |
2911 measured reflections | Rint = 0.045 |
2726 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.22 e Å−3 |
2726 reflections | Δρmin = −0.28 e Å−3 |
201 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 | x | y | z | Uiso*/Ueq | |
S1 | 0.21423 (4) | 0.02005 (6) | 0.10308 (3) | 0.05482 (19) | |
O1 | 0.14467 (15) | −0.10385 (19) | 0.05876 (12) | 0.0865 (6) | |
O2 | 0.32604 (12) | −0.0151 (2) | 0.11349 (11) | 0.0763 (5) | |
O3 | 0.15023 (17) | 0.6036 (2) | 0.28117 (17) | 0.1074 (7) | |
O4 | 0.06922 (12) | 0.3935 (2) | 0.21328 (12) | 0.0743 (5) | |
O5 | 0.45589 (12) | 0.80584 (17) | 0.33634 (13) | 0.0762 (5) | |
H5B | 0.4093 | 0.8795 | 0.3350 | 0.114* | |
N1 | 0.32903 (10) | 0.10909 (16) | 0.31418 (9) | 0.0388 (3) | |
N2 | 0.31723 (11) | 0.38808 (16) | 0.34262 (8) | 0.0392 (3) | |
N3 | 0.14515 (13) | 0.4535 (2) | 0.25888 (11) | 0.0540 (4) | |
C1 | 0.19509 (13) | 0.2181 (2) | 0.04813 (11) | 0.0461 (4) | |
C2 | 0.10579 (15) | 0.2396 (3) | −0.01101 (12) | 0.0520 (4) | |
H2 | 0.0578 | 0.1499 | −0.0221 | 0.062* | |
C3 | 0.08906 (17) | 0.3957 (3) | −0.05324 (13) | 0.0602 (5) | |
H3 | 0.0304 | 0.4108 | −0.0943 | 0.072* | |
C4 | 0.15864 (19) | 0.5290 (3) | −0.03497 (15) | 0.0656 (6) | |
H4 | 0.1457 | 0.6349 | −0.0626 | 0.079* | |
C5 | 0.24722 (18) | 0.5075 (3) | 0.02373 (15) | 0.0634 (5) | |
H5 | 0.2936 | 0.5990 | 0.0357 | 0.076* | |
C6 | 0.26790 (14) | 0.3511 (3) | 0.06516 (12) | 0.0527 (4) | |
H6 | 0.3289 | 0.3349 | 0.1035 | 0.063* | |
C7 | 0.16892 (14) | 0.0505 (2) | 0.21300 (13) | 0.0491 (4) | |
H7A | 0.0972 | 0.0966 | 0.2071 | 0.059* | |
H7B | 0.1663 | −0.0600 | 0.2429 | 0.059* | |
C8 | 0.23837 (12) | 0.1683 (2) | 0.26970 (10) | 0.0374 (3) | |
C9 | 0.37456 (12) | 0.2425 (2) | 0.35730 (10) | 0.0377 (3) | |
C10 | 0.22990 (12) | 0.3413 (2) | 0.28604 (10) | 0.0386 (3) | |
C11 | 0.47418 (15) | 0.2306 (2) | 0.41651 (12) | 0.0519 (4) | |
H11A | 0.5009 | 0.1152 | 0.4158 | 0.078* | |
H11B | 0.4601 | 0.2613 | 0.4769 | 0.078* | |
H11C | 0.5262 | 0.3077 | 0.3952 | 0.078* | |
C12 | 0.35328 (16) | 0.5592 (2) | 0.37392 (12) | 0.0510 (4) | |
H12A | 0.3999 | 0.5475 | 0.4285 | 0.061* | |
H12B | 0.2922 | 0.6273 | 0.3879 | 0.061* | |
C13 | 0.41195 (17) | 0.6501 (2) | 0.30297 (14) | 0.0555 (5) | |
H13A | 0.4684 | 0.5766 | 0.2843 | 0.067* | |
H13B | 0.3632 | 0.6729 | 0.2507 | 0.067* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0532 (3) | 0.0423 (3) | 0.0657 (3) | 0.01013 (18) | −0.0171 (2) | −0.01797 (19) |
O1 | 0.1042 (13) | 0.0465 (8) | 0.1007 (12) | −0.0015 (8) | −0.0432 (10) | −0.0254 (8) |
O2 | 0.0625 (9) | 0.0831 (11) | 0.0809 (10) | 0.0370 (8) | −0.0100 (7) | −0.0232 (8) |
O3 | 0.1008 (14) | 0.0509 (10) | 0.164 (2) | 0.0333 (9) | −0.0323 (13) | −0.0187 (11) |
O4 | 0.0509 (8) | 0.0752 (10) | 0.0934 (11) | 0.0187 (7) | −0.0154 (7) | 0.0023 (8) |
O5 | 0.0624 (9) | 0.0306 (6) | 0.1301 (14) | −0.0031 (6) | −0.0278 (9) | 0.0022 (7) |
N1 | 0.0364 (7) | 0.0323 (6) | 0.0470 (7) | −0.0025 (5) | −0.0023 (5) | 0.0057 (5) |
N2 | 0.0457 (7) | 0.0336 (7) | 0.0384 (6) | −0.0020 (5) | 0.0035 (5) | −0.0010 (5) |
N3 | 0.0510 (9) | 0.0498 (9) | 0.0612 (9) | 0.0154 (7) | 0.0040 (7) | 0.0040 (7) |
C1 | 0.0408 (9) | 0.0523 (10) | 0.0450 (8) | 0.0059 (7) | 0.0017 (7) | −0.0127 (7) |
C2 | 0.0446 (9) | 0.0609 (11) | 0.0495 (9) | 0.0043 (8) | −0.0036 (7) | −0.0098 (8) |
C3 | 0.0574 (11) | 0.0756 (14) | 0.0474 (10) | 0.0159 (10) | 0.0036 (8) | 0.0003 (9) |
C4 | 0.0770 (15) | 0.0629 (13) | 0.0592 (11) | 0.0081 (11) | 0.0192 (10) | 0.0068 (9) |
C5 | 0.0643 (13) | 0.0629 (12) | 0.0648 (12) | −0.0115 (10) | 0.0172 (10) | −0.0032 (10) |
C6 | 0.0430 (9) | 0.0652 (12) | 0.0504 (9) | −0.0016 (8) | 0.0061 (7) | −0.0118 (8) |
C7 | 0.0393 (9) | 0.0403 (9) | 0.0656 (11) | −0.0074 (7) | −0.0087 (7) | 0.0054 (8) |
C8 | 0.0340 (7) | 0.0356 (8) | 0.0424 (8) | −0.0026 (6) | 0.0016 (6) | 0.0061 (6) |
C9 | 0.0383 (8) | 0.0350 (7) | 0.0395 (7) | −0.0043 (6) | 0.0015 (6) | 0.0049 (6) |
C10 | 0.0386 (8) | 0.0376 (8) | 0.0398 (7) | 0.0042 (6) | 0.0042 (6) | 0.0033 (6) |
C11 | 0.0452 (9) | 0.0515 (10) | 0.0567 (10) | −0.0084 (8) | −0.0106 (8) | 0.0038 (8) |
C12 | 0.0676 (12) | 0.0363 (8) | 0.0486 (9) | −0.0016 (8) | 0.0010 (8) | −0.0105 (7) |
C13 | 0.0646 (12) | 0.0317 (8) | 0.0695 (12) | −0.0049 (8) | 0.0005 (9) | 0.0020 (8) |
Geometric parameters (Å, º) top
S1—O1 | 1.4300 (15) | C3—H3 | 0.9300 |
S1—O2 | 1.4314 (15) | C4—C5 | 1.374 (3) |
S1—C1 | 1.7537 (19) | C4—H4 | 0.9300 |
S1—C7 | 1.791 (2) | C5—C6 | 1.381 (3) |
O3—N3 | 1.215 (2) | C5—H5 | 0.9300 |
O4—N3 | 1.222 (2) | C6—H6 | 0.9300 |
O5—C13 | 1.408 (2) | C7—C8 | 1.486 (2) |
O5—H5B | 0.8200 | C7—H7A | 0.9700 |
N1—C9 | 1.328 (2) | C7—H7B | 0.9700 |
N1—C8 | 1.3562 (19) | C8—C10 | 1.374 (2) |
N2—C9 | 1.353 (2) | C9—C11 | 1.480 (2) |
N2—C10 | 1.382 (2) | C11—H11A | 0.9600 |
N2—C12 | 1.472 (2) | C11—H11B | 0.9600 |
N3—C10 | 1.415 (2) | C11—H11C | 0.9600 |
C1—C2 | 1.384 (2) | C12—C13 | 1.511 (3) |
C1—C6 | 1.394 (3) | C12—H12A | 0.9700 |
C2—C3 | 1.377 (3) | C12—H12B | 0.9700 |
C2—H2 | 0.9300 | C13—H13A | 0.9700 |
C3—C4 | 1.373 (3) | C13—H13B | 0.9700 |
| | | |
O1—S1—O2 | 118.94 (10) | C8—C7—H7A | 109.0 |
O1—S1—C1 | 108.70 (9) | S1—C7—H7A | 109.0 |
O2—S1—C1 | 108.49 (10) | C8—C7—H7B | 109.0 |
O1—S1—C7 | 106.50 (11) | S1—C7—H7B | 109.0 |
O2—S1—C7 | 107.86 (9) | H7A—C7—H7B | 107.8 |
C1—S1—C7 | 105.56 (8) | N1—C8—C10 | 108.71 (13) |
C13—O5—H5B | 109.5 | N1—C8—C7 | 120.29 (14) |
C9—N1—C8 | 106.62 (13) | C10—C8—C7 | 130.98 (15) |
C9—N2—C10 | 105.50 (12) | N1—C9—N2 | 111.85 (13) |
C9—N2—C12 | 124.03 (14) | N1—C9—C11 | 123.64 (15) |
C10—N2—C12 | 130.06 (14) | N2—C9—C11 | 124.48 (15) |
O3—N3—O4 | 122.80 (17) | C8—C10—N2 | 107.30 (13) |
O3—N3—C10 | 119.58 (17) | C8—C10—N3 | 128.49 (15) |
O4—N3—C10 | 117.62 (16) | N2—C10—N3 | 123.98 (15) |
C2—C1—C6 | 121.13 (18) | C9—C11—H11A | 109.5 |
C2—C1—S1 | 118.62 (15) | C9—C11—H11B | 109.5 |
C6—C1—S1 | 120.25 (14) | H11A—C11—H11B | 109.5 |
C3—C2—C1 | 119.04 (19) | C9—C11—H11C | 109.5 |
C3—C2—H2 | 120.5 | H11A—C11—H11C | 109.5 |
C1—C2—H2 | 120.5 | H11B—C11—H11C | 109.5 |
C4—C3—C2 | 120.29 (19) | N2—C12—C13 | 110.99 (14) |
C4—C3—H3 | 119.9 | N2—C12—H12A | 109.4 |
C2—C3—H3 | 119.9 | C13—C12—H12A | 109.4 |
C3—C4—C5 | 120.6 (2) | N2—C12—H12B | 109.4 |
C3—C4—H4 | 119.7 | C13—C12—H12B | 109.4 |
C5—C4—H4 | 119.7 | H12A—C12—H12B | 108.0 |
C4—C5—C6 | 120.5 (2) | O5—C13—C12 | 110.91 (17) |
C4—C5—H5 | 119.7 | O5—C13—H13A | 109.5 |
C6—C5—H5 | 119.7 | C12—C13—H13A | 109.5 |
C5—C6—C1 | 118.38 (18) | O5—C13—H13B | 109.5 |
C5—C6—H6 | 120.8 | C12—C13—H13B | 109.5 |
C1—C6—H6 | 120.8 | H13A—C13—H13B | 108.0 |
C8—C7—S1 | 112.71 (12) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5B···N1i | 0.82 | 2.07 | 2.8562 (19) | 162 |
Symmetry code: (i) x, y+1, z. |
(II) 4-benzenesulfonylmethyl-2-methyl-5-nitro-thiazole
top
Crystal data top
C11H10N2O4S2 | F(000) = 616 |
Mr = 298.34 | Dx = 1.543 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2911 reflections |
a = 11.1646 (4) Å | θ = 2.4–26.4° |
b = 8.8148 (2) Å | µ = 0.43 mm−1 |
c = 13.0731 (4) Å | T = 293 K |
β = 93.542 (2)° | Prism, colorless |
V = 1284.11 (7) Å3 | 0.5 × 0.4 × 0.4 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD diffractometer | 2413 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.034 |
Graphite monochromator | θmax = 26.4°, θmin = 2.4° |
ϕ scans | h = 0→13 |
2739 measured reflections | k = 0→10 |
2562 independent reflections | l = −16→16 |
Refinement top
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.16 | w = 1/[σ2(Fo2) + (0.0394P)2 + 0.5975P] where P = (Fo2 + 2Fc2)/3 |
2562 reflections | (Δ/σ)max < 0.001 |
172 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
C11H10N2O4S2 | V = 1284.11 (7) Å3 |
Mr = 298.34 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.1646 (4) Å | µ = 0.43 mm−1 |
b = 8.8148 (2) Å | T = 293 K |
c = 13.0731 (4) Å | 0.5 × 0.4 × 0.4 mm |
β = 93.542 (2)° | |
Data collection top
Nonius KappaCCD diffractometer | 2413 reflections with I > 2σ(I) |
2739 measured reflections | Rint = 0.034 |
2562 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.16 | Δρmax = 0.22 e Å−3 |
2562 reflections | Δρmin = −0.27 e Å−3 |
172 parameters | |
Special details top
Geometry. All standard uncertainties (except dihedral angles between l.s. planes) are
estimated using the full covariance matrix. The standard uncertainties in cell
dimensions are are used in calculating the standard uncertainties of bond
distances, angles and torsion angles. Angles between l.s. planes have standard
uncertainties calculated from atomic positional standard uncertainties; the
errors in cell dimensions are not used in this case. |
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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
S1 | 0.25806 (4) | 0.40727 (6) | 0.44835 (4) | 0.04078 (16) | |
S2 | 0.62052 (4) | 0.45893 (5) | 0.24580 (4) | 0.04230 (16) | |
O1 | 0.36588 (13) | 0.35967 (19) | 0.50528 (12) | 0.0578 (4) | |
O2 | 0.14641 (13) | 0.33404 (18) | 0.46719 (13) | 0.0582 (4) | |
O3 | 0.61385 (15) | 0.13746 (18) | 0.26099 (17) | 0.0698 (5) | |
O4 | 0.43483 (14) | 0.11085 (16) | 0.31285 (15) | 0.0614 (4) | |
N1 | 0.41650 (13) | 0.58423 (17) | 0.26909 (12) | 0.0381 (3) | |
N2 | 0.51753 (15) | 0.18878 (18) | 0.28407 (13) | 0.0449 (4) | |
C1 | 0.24032 (16) | 0.6046 (2) | 0.46387 (14) | 0.0389 (4) | |
C2 | 0.12568 (18) | 0.6654 (2) | 0.45680 (15) | 0.0456 (4) | |
C3 | 0.1118 (2) | 0.8210 (3) | 0.46669 (17) | 0.0581 (6) | |
C4 | 0.2102 (3) | 0.9130 (3) | 0.48087 (18) | 0.0644 (6) | |
C5 | 0.3244 (2) | 0.8512 (3) | 0.48763 (18) | 0.0636 (6) | |
C6 | 0.34097 (19) | 0.6964 (3) | 0.48004 (16) | 0.0512 (5) | |
C7 | 0.27910 (15) | 0.3814 (2) | 0.31408 (15) | 0.0393 (4) | |
C8 | 0.40000 (15) | 0.4334 (2) | 0.28634 (13) | 0.0342 (4) | |
C9 | 0.52758 (16) | 0.6140 (2) | 0.24900 (15) | 0.0383 (4) | |
C10 | 0.50176 (15) | 0.3492 (2) | 0.27680 (14) | 0.0360 (4) | |
C11 | 0.5744 (2) | 0.7693 (2) | 0.23484 (19) | 0.0538 (5) | |
H11A | 0.6579 | 0.7649 | 0.2212 | 0.065* | 0.50 |
H11B | 0.5649 | 0.8276 | 0.2958 | 0.065* | 0.50 |
H11C | 0.5302 | 0.8163 | 0.1780 | 0.065* | 0.50 |
H11D | 0.6322 | 0.7964 | 0.2935 | 0.065* | 0.50 |
H11E | 0.5039 | 0.8344 | 0.2397 | 0.065* | 0.50 |
H11F | 0.6254 | 0.7742 | 0.1747 | 0.065* | 0.50 |
H14 | 0.0564 | 0.6018 | 0.4449 | 0.055* | |
H18 | 0.0329 | 0.8648 | 0.4639 | 0.070* | |
H13 | 0.1995 | 1.0207 | 0.4865 | 0.077* | |
H19 | 0.3924 | 0.9175 | 0.4974 | 0.076* | |
H16 | 0.4206 | 0.6550 | 0.4857 | 0.061* | |
H12A | 0.2186 | 0.4387 | 0.2757 | 0.047* | |
H12B | 0.2697 | 0.2756 | 0.2982 | 0.047* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0297 (2) | 0.0425 (3) | 0.0509 (3) | 0.00182 (17) | 0.00777 (18) | 0.00746 (19) |
S2 | 0.0320 (2) | 0.0356 (3) | 0.0602 (3) | 0.00028 (17) | 0.00986 (19) | 0.0010 (2) |
O1 | 0.0442 (8) | 0.0716 (10) | 0.0569 (9) | 0.0158 (7) | −0.0022 (6) | 0.0143 (8) |
O2 | 0.0424 (8) | 0.0527 (9) | 0.0820 (11) | −0.0071 (7) | 0.0231 (7) | 0.0079 (8) |
O3 | 0.0548 (9) | 0.0392 (8) | 0.1177 (15) | 0.0143 (7) | 0.0237 (9) | −0.0041 (9) |
O4 | 0.0551 (9) | 0.0339 (7) | 0.0959 (12) | −0.0077 (7) | 0.0105 (8) | 0.0059 (7) |
N1 | 0.0357 (8) | 0.0302 (7) | 0.0489 (9) | 0.0017 (6) | 0.0055 (6) | 0.0006 (6) |
N2 | 0.0444 (9) | 0.0306 (8) | 0.0599 (10) | 0.0010 (7) | 0.0043 (7) | −0.0019 (7) |
C1 | 0.0345 (9) | 0.0449 (10) | 0.0376 (9) | −0.0001 (7) | 0.0050 (7) | 0.0004 (7) |
C2 | 0.0384 (10) | 0.0514 (12) | 0.0477 (11) | 0.0048 (8) | 0.0071 (8) | −0.0006 (9) |
C3 | 0.0653 (14) | 0.0553 (13) | 0.0544 (13) | 0.0169 (11) | 0.0101 (10) | −0.0001 (10) |
C4 | 0.0952 (19) | 0.0470 (12) | 0.0520 (13) | 0.0033 (13) | 0.0117 (12) | −0.0001 (10) |
C5 | 0.0751 (16) | 0.0596 (14) | 0.0563 (13) | −0.0254 (12) | 0.0049 (11) | −0.0061 (11) |
C6 | 0.0406 (10) | 0.0616 (13) | 0.0512 (11) | −0.0094 (9) | 0.0014 (8) | −0.0049 (10) |
C7 | 0.0294 (8) | 0.0360 (9) | 0.0524 (11) | −0.0025 (7) | 0.0033 (7) | −0.0024 (8) |
C8 | 0.0319 (8) | 0.0319 (9) | 0.0389 (9) | −0.0010 (7) | 0.0023 (7) | −0.0013 (7) |
C9 | 0.0374 (9) | 0.0314 (9) | 0.0464 (10) | −0.0005 (7) | 0.0041 (7) | 0.0007 (7) |
C10 | 0.0342 (9) | 0.0293 (9) | 0.0450 (10) | 0.0005 (7) | 0.0053 (7) | −0.0010 (7) |
C11 | 0.0530 (12) | 0.0327 (10) | 0.0763 (15) | −0.0063 (9) | 0.0094 (10) | 0.0043 (9) |
Geometric parameters (Å, º) top
S1—O2 | 1.4384 (14) | C4—C5 | 1.384 (4) |
S1—O1 | 1.4383 (15) | C4—H13 | 0.96 |
S1—C1 | 1.764 (2) | C5—C6 | 1.382 (3) |
S1—C7 | 1.800 (2) | C5—H19 | 0.96 |
S2—C10 | 1.7103 (18) | C6—H16 | 0.96 |
S2—C9 | 1.7184 (18) | C7—C8 | 1.491 (2) |
O3—N2 | 1.222 (2) | C7—H12A | 0.96 |
O4—N2 | 1.228 (2) | C7—H12B | 0.96 |
N1—C9 | 1.310 (2) | C8—C10 | 1.369 (2) |
N1—C8 | 1.363 (2) | C9—C11 | 1.481 (3) |
N2—C10 | 1.427 (2) | C11—H11A | 0.96 |
C1—C2 | 1.385 (3) | C11—H11B | 0.96 |
C1—C6 | 1.390 (3) | C11—H11C | 0.96 |
C2—C3 | 1.388 (3) | C11—H11D | 1.00 |
C2—H14 | 0.96 | C11—H11E | 0.98 |
C3—C4 | 1.369 (4) | C11—H11F | 1.00 |
C3—H18 | 0.96 | | |
| | | |
O2—S1—O1 | 119.14 (10) | C11—C9—S2 | 120.94 (14) |
O2—S1—C1 | 108.55 (9) | C8—C10—N2 | 129.10 (16) |
O1—S1—C1 | 108.94 (10) | C8—C10—S2 | 112.00 (13) |
O2—S1—C7 | 106.07 (9) | N2—C10—S2 | 118.81 (13) |
O1—S1—C7 | 108.19 (9) | C1—C2—H14 | 121.1 |
C1—S1—C7 | 105.05 (9) | C3—C2—H14 | 119.9 |
C10—S2—C9 | 88.06 (8) | C4—C3—H18 | 119.6 |
C9—N1—C8 | 111.60 (15) | C2—C3—H18 | 120.1 |
O3—N2—O4 | 123.94 (17) | C3—C4—H13 | 119.5 |
O3—N2—C10 | 117.22 (16) | C5—C4—H13 | 120.2 |
O4—N2—C10 | 118.84 (16) | C6—C5—H19 | 120.2 |
C2—C1—C6 | 121.3 (2) | C4—C5—H19 | 119.1 |
C2—C1—S1 | 118.93 (15) | C5—C6—H16 | 119.8 |
C6—C1—S1 | 119.73 (15) | C1—C6—H16 | 121.8 |
C1—C2—C3 | 119.0 (2) | C8—C7—H12A | 109.2 |
C4—C3—C2 | 120.3 (2) | S1—C7—H12A | 108.3 |
C3—C4—C5 | 120.3 (2) | C8—C7—H12B | 109.5 |
C6—C5—C4 | 120.7 (2) | S1—C7—H12B | 108.4 |
C5—C6—C1 | 118.4 (2) | C9—C11—H11A | 109.9 |
C8—C7—S1 | 111.89 (13) | C9—C11—H11B | 109.5 |
N1—C8—C10 | 113.11 (15) | C9—C11—H11C | 109.1 |
N1—C8—C7 | 118.28 (15) | C9—C11—H11D | 109.9 |
C10—C8—C7 | 128.60 (16) | C9—C11—H11E | 104.0 |
N1—C9—C11 | 123.78 (17) | C9—C11—H11F | 111.2 |
N1—C9—S2 | 115.21 (13) | | |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C13H15N3O5S | C11H10N2O4S2 |
Mr | 325.34 | 298.34 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/n |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 12.5976 (3), 7.7874 (3), 14.8929 (5) | 11.1646 (4), 8.8148 (2), 13.0731 (4) |
β (°) | 94.427 (2) | 93.542 (2) |
V (Å3) | 1456.67 (8) | 1284.11 (7) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.25 | 0.43 |
Crystal size (mm) | 0.6 × 0.5 × 0.4 | 0.5 × 0.4 × 0.4 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2911, 2726, 2509 | 2739, 2562, 2413 |
Rint | 0.045 | 0.034 |
(sin θ/λ)max (Å−1) | 0.625 | 0.625 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.113, 1.07 | 0.036, 0.097, 1.16 |
No. of reflections | 2726 | 2562 |
No. of parameters | 201 | 172 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.28 | 0.22, −0.27 |
Selected geometric parameters (Å, º) for (I) topS1—O1 | 1.4300 (15) | N1—C8 | 1.3562 (19) |
S1—O2 | 1.4314 (15) | N2—C9 | 1.353 (2) |
S1—C1 | 1.7537 (19) | N2—C10 | 1.382 (2) |
S1—C7 | 1.791 (2) | N2—C12 | 1.472 (2) |
O5—C13 | 1.408 (2) | C8—C10 | 1.374 (2) |
N1—C9 | 1.328 (2) | C12—C13 | 1.511 (3) |
| | | |
O1—S1—O2 | 118.94 (10) | N1—C8—C10 | 108.71 (13) |
C1—S1—C7 | 105.56 (8) | N1—C9—N2 | 111.85 (13) |
C9—N1—C8 | 106.62 (13) | C8—C10—N2 | 107.30 (13) |
C9—N2—C10 | 105.50 (12) | N2—C12—C13 | 110.99 (14) |
C8—C7—S1 | 112.71 (12) | O5—C13—C12 | 110.91 (17) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5B···N1i | 0.82 | 2.07 | 2.8562 (19) | 162 |
Symmetry code: (i) x, y+1, z. |
Selected geometric parameters (Å, º) for (II) topS1—O2 | 1.4384 (14) | S2—C9 | 1.7184 (18) |
S1—O1 | 1.4383 (15) | N1—C9 | 1.310 (2) |
S1—C1 | 1.764 (2) | N1—C8 | 1.363 (2) |
S1—C7 | 1.800 (2) | C8—C10 | 1.369 (2) |
S2—C10 | 1.7103 (18) | | |
| | | |
C1—S1—C7 | 105.05 (9) | N1—C8—C10 | 113.11 (15) |
C10—S2—C9 | 88.06 (8) | N1—C9—S2 | 115.21 (13) |
C9—N1—C8 | 111.60 (15) | C8—C10—S2 | 112.00 (13) |
C8—C7—S1 | 111.89 (13) | | |
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5-Nitroimidazoles and 5-nitrothiazoles are useful compounds with regard to their biological activities (Nair & Nagarajan, 1983; Kawashima et al., 2001; Andreani et al., 2001). We previously showed that sulfones are relevant synthons in the preparation of new 4-substituted-5-nitroheterocycles (Crozet et al., 2002). In this paper, we describe the X-ray structures of 2-(4-benzenesulfonylmethyl-2-methyl-5-nitroimidazol-1-yl)ethanol, (I) and 4-benzenesulfonylmethyl-2-methyl-5-nitrothiazole, (II), which are, to our knowledge, the first examples of benzenesulfonylmethyl–nitro heterocyclic compounds structurally characterized by single-crystal X-ray diffraction.
In both (I) and (II), the nitro group is almost coplanar with the heterocyclic ring; the angles between NO2 and the mean five-membered-ring plane are 4.2 (3) and 6.7 (1)° for (I) and (II), respectively. The distances and angles involving the various heteroatoms (Tables 1 and 3) are comparable to those observed in other phenylsulfonyl compounds containing a heterocycle (De Bondt et al., 1993; Govindamasamy et al., 1998; SethuSankar et al., 2002).
Comparison of the structures of (I) and (II) reveals a difference in the relative position of the six- and five-membered rings relative to each other. In (I), the phenyl is oriented in the same direction as the nitro group on the imidazole ring, while, in (II), it is oriented in the same direction as the C11 methyl group (Figs. 1 and 2). Looking at this another way,, in (I), the nitro and sulfonyl substituents are trans relative to one another, while in (II), they are cis, with the O atoms pointing in the same direction; the dihedral angles between the planes defined by NO2 and SO2 are 157.1 (2) and 47.6 (2)° in (I) and (II), respectively. To complement this description, for each molecule, we defined the bisector of the NO2 and SO2 planes, translated these vectors to a common origin and calculated the angle between them; the values are 134.52 and 40.88% for (I) and (II), respectively, and could be considered as convenient descriptors of the relative orientation of such groups in flexible systems similar to the title compounds. This difference in conformation between the two structures is probably due to the presence of the hydroxyethyl group on the imidazole ring in (I). Indeed, the hydroxyl group is oriented trans relatively to the heterocycle; the torsion angle N2—C12—C13—O5 is -173.9 (2)°. This involves the hydroxyl group in a hydrogen bond with atom N1i of a molecule of an adjacent cell [symmetry code: (I) x, y + 1, z]; the H5b···N1i distance is 2.07 Å and the O5—H5b···N1i angle is 161.9° (Table 2). This hydrogen bond organizes the molecules of (I) within the crystal into an infinite molecular chain parallel to the b axis. Finally, the closed conformation adopted by (I) tends to position the two rings in such a way that they can accommodate a weak C—H···π interaction; the distance between the centroid of the imidazole ring and atom H6 on C6 is 3.26 Å and the C6—H6···centroid angle is 117.6°, which are in the range observed for classical C—H···π interactions (Takahashi et al., 2000).
In compound (II), only an intermolecular C—H···π interaction can be found, between the thiazole ring and the phenyl ring of a molecule of an adjacent cell; the distance between atom H11f on C11 and the centroid of the plane C1ii/C2ii/C3ii/C4ii/C5ii/C6ii is 2.95 Å [symmetry code: (ii) x + 1/2, -y + 3/2, z - 1/2], whereas the C11—H11f···centroid angle is 165.3°. A careful look at the packing of the molecules also shows that both compounds are not stabilized in the same way within the crystal. For (I), we can observe two intermolecular π–π stackings involving the aromatic cycles; the distance between the centroids of the imidazole ring and the centroid of a phenyl ring of a symmetry-related molecule (symmetry code: x, -y + 1/2, z + 1/2) is 3.481 (1) Å and the dihedral between the planes is 6.01°; the distance between the centroid of the phenyl ring and the centroid of the phenyl ring of a molecule in an adjacent cell (symmetry code: -x, 1 - y, -z) is 4.872 (1) Å, with a dihedral of 0.03° between the two planes. In compound (II), no such clear interactions can be found; the shortest distances between the various rings of symmetry-related molecules range from 4.336 (1) to 5.253 (1) Å, with dihedral angles ranging from 17.4 to 21.6°.