Molecules of the title compounds, C15H14N2O4S·H2O and C15H13BrN2O4S·H2O, adopt an E configuration about the azomethine C=N double bond. In both molecules, the two benzene rings and the azomethine group are practically coplanar, as a result of intramolecular hydrogen bonds involving the hydroxy O atom and azomethine N atom. The angular disposition of the bonds about the S atom deviates significantly from that of a regular tetrahedron. In the crystal structures, both compounds form two-dimensional layers parallel to the (100) plane.
Supporting information
CCDC references: 278576; 278577
Schiff bases (I) and (II) were prepared by condensation of salicylic acid and 5-bromosalicylic aldehyde with N-acetyl-4-amino-benzenesulfonamide in boiling ethanol. Please give brief details of quantities used, times etc.
Hydroxyl H atoms and all water H atoms were found in difference maps at an intermediate stage of the refinement and were refined subject to an O—H restraint of 0.84 (4). Please check added value. All other H atoms were placed in idealized positions, with C—H(aromatic) = 0.93 Å, C—H(methyl) = 0.96 Å and N—H = 0.86 Å, and included in the refinement in the riding-model approximation, with Uiso(aromatic H) = 1.2Ueq(C), Uiso(methyl H) = 1.2Ueq(C) and Uiso(H) = 1.2Ueq(N).
For both compounds, data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.
(I)
N-acetyl-4-[(2-hydroxybenzylidene)amino]benzensulfonamide monohydrate
top
Crystal data top
C15H14N2O4S·H2O | Dx = 1.440 Mg m−3 |
Mr = 336.37 | Melting point: 70 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 25.486 (3) Å | Cell parameters from 4944 reflections |
b = 4.8964 (13) Å | θ = 3.3–28.3° |
c = 12.605 (3) Å | µ = 0.24 mm−1 |
β = 99.44 (3)° | T = 298 K |
V = 1551.7 (6) Å3 | Prism, yellow |
Z = 4 | 0.26 × 0.13 × 0.11 mm |
F(000) = 704 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2696 independent reflections |
Radiation source: fine-focus sealed tube | 1966 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
ω scans | θmax = 25.0°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −30→30 |
Tmin = 0.951, Tmax = 0.974 | k = −5→5 |
11981 measured reflections | l = −14→14 |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0529P)2 + 0.2401P] where P = (Fo2 + 2Fc2)/3 |
2696 reflections | (Δ/σ)max = 0.008 |
221 parameters | Δρmax = 0.22 e Å−3 |
2 restraints | Δρmin = −0.30 e Å−3 |
Crystal data top
C15H14N2O4S·H2O | V = 1551.7 (6) Å3 |
Mr = 336.37 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 25.486 (3) Å | µ = 0.24 mm−1 |
b = 4.8964 (13) Å | T = 298 K |
c = 12.605 (3) Å | 0.26 × 0.13 × 0.11 mm |
β = 99.44 (3)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2696 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1966 reflections with I > 2σ(I) |
Tmin = 0.951, Tmax = 0.974 | Rint = 0.057 |
11981 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.054 | 2 restraints |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.22 e Å−3 |
2696 reflections | Δρmin = −0.30 e Å−3 |
221 parameters | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | 0.15532 (3) | −0.33677 (14) | 0.23105 (6) | 0.0325 (2) | |
O1 | 0.35445 (12) | 0.7099 (6) | −0.0325 (2) | 0.0720 (11) | |
O2 | 0.14403 (8) | −0.5389 (4) | 0.14932 (15) | 0.0398 (7) | |
O3 | 0.16811 (8) | −0.4167 (4) | 0.34146 (15) | 0.0438 (7) | |
O4 | 0.08421 (8) | −0.0877 (4) | 0.04497 (15) | 0.0458 (7) | |
N1 | 0.31495 (10) | 0.4534 (5) | 0.11955 (19) | 0.0392 (8) | |
N2 | 0.10248 (9) | −0.1393 (5) | 0.22636 (17) | 0.0337 (8) | |
C1 | 0.38486 (13) | 0.8492 (7) | 0.0478 (3) | 0.0495 (11) | |
C2 | 0.42074 (15) | 1.0414 (8) | 0.0218 (3) | 0.0656 (16) | |
C3 | 0.45174 (14) | 1.1902 (8) | 0.1016 (4) | 0.0652 (14) | |
C4 | 0.44727 (13) | 1.1529 (7) | 0.2082 (3) | 0.0573 (14) | |
C5 | 0.41209 (12) | 0.9623 (7) | 0.2345 (3) | 0.0478 (11) | |
C6 | 0.38048 (11) | 0.8057 (6) | 0.1563 (2) | 0.0386 (10) | |
C7 | 0.34400 (12) | 0.6067 (6) | 0.1871 (2) | 0.0390 (10) | |
C8 | 0.27932 (11) | 0.2586 (6) | 0.1521 (2) | 0.0338 (9) | |
C9 | 0.24816 (11) | 0.1121 (6) | 0.0713 (2) | 0.0360 (9) | |
C10 | 0.21137 (11) | −0.0757 (6) | 0.0935 (2) | 0.0354 (9) | |
C11 | 0.20579 (10) | −0.1199 (5) | 0.2001 (2) | 0.0289 (8) | |
C12 | 0.23733 (12) | 0.0206 (6) | 0.2825 (2) | 0.0393 (10) | |
C13 | 0.27392 (12) | 0.2066 (6) | 0.2586 (2) | 0.0425 (10) | |
C14 | 0.07392 (11) | −0.0311 (6) | 0.1338 (2) | 0.0350 (10) | |
C15 | 0.02959 (12) | 0.1546 (7) | 0.1503 (3) | 0.0486 (11) | |
O1W | 0.08574 (14) | 0.0800 (6) | 0.4180 (2) | 0.0719 (12) | |
H1O | 0.3377 (18) | 0.596 (9) | −0.002 (4) | 0.099 (17)* | |
H2A | 0.42390 | 1.07010 | −0.04990 | 0.0790* | |
H2B | 0.09200 | −0.10130 | 0.28620 | 0.0400* | |
H3A | 0.47590 | 1.31700 | 0.08320 | 0.0780* | |
H4A | 0.46780 | 1.25560 | 0.26160 | 0.0690* | |
H5A | 0.40920 | 0.93680 | 0.30650 | 0.0570* | |
H7A | 0.34150 | 0.58930 | 0.25960 | 0.0470* | |
H9A | 0.25220 | 0.14160 | 0.00020 | 0.0430* | |
H10A | 0.19060 | −0.17160 | 0.03830 | 0.0420* | |
H12A | 0.23370 | −0.01130 | 0.35370 | 0.0470* | |
H13A | 0.29530 | 0.29900 | 0.31400 | 0.0510* | |
H15A | 0.02930 | 0.31110 | 0.10430 | 0.0730* | |
H15B | 0.03460 | 0.21300 | 0.22400 | 0.0730* | |
H15C | −0.00360 | 0.05940 | 0.13320 | 0.0730* | |
H1W | 0.095 (2) | −0.045 (7) | 0.463 (3) | 0.12 (2)* | |
H2W | 0.0917 (19) | 0.239 (5) | 0.443 (4) | 0.114 (18)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0391 (4) | 0.0310 (4) | 0.0275 (4) | 0.0002 (3) | 0.0056 (3) | 0.0028 (3) |
O1 | 0.089 (2) | 0.085 (2) | 0.0454 (15) | −0.0307 (17) | 0.0213 (14) | −0.0025 (14) |
O2 | 0.0475 (13) | 0.0295 (10) | 0.0417 (12) | −0.0016 (9) | 0.0054 (9) | −0.0065 (9) |
O3 | 0.0525 (13) | 0.0496 (12) | 0.0290 (11) | 0.0000 (11) | 0.0062 (9) | 0.0133 (9) |
O4 | 0.0569 (14) | 0.0521 (13) | 0.0279 (11) | 0.0072 (11) | 0.0054 (10) | 0.0001 (10) |
N1 | 0.0376 (14) | 0.0401 (14) | 0.0419 (15) | −0.0021 (12) | 0.0122 (11) | 0.0009 (12) |
N2 | 0.0378 (13) | 0.0394 (14) | 0.0261 (12) | 0.0026 (11) | 0.0114 (10) | 0.0003 (11) |
C1 | 0.052 (2) | 0.0466 (19) | 0.053 (2) | −0.0018 (17) | 0.0179 (16) | 0.0007 (17) |
C2 | 0.068 (3) | 0.066 (2) | 0.070 (3) | −0.007 (2) | 0.033 (2) | 0.010 (2) |
C3 | 0.049 (2) | 0.051 (2) | 0.100 (3) | −0.0098 (19) | 0.025 (2) | 0.008 (2) |
C4 | 0.044 (2) | 0.046 (2) | 0.081 (3) | −0.0034 (18) | 0.0074 (18) | 0.001 (2) |
C5 | 0.0429 (19) | 0.0454 (19) | 0.055 (2) | 0.0006 (16) | 0.0079 (16) | 0.0018 (16) |
C6 | 0.0355 (16) | 0.0341 (17) | 0.0475 (19) | 0.0031 (14) | 0.0107 (14) | 0.0033 (14) |
C7 | 0.0395 (17) | 0.0405 (18) | 0.0380 (17) | 0.0040 (15) | 0.0097 (14) | 0.0043 (14) |
C8 | 0.0342 (16) | 0.0350 (16) | 0.0341 (17) | 0.0033 (13) | 0.0110 (13) | 0.0018 (13) |
C9 | 0.0420 (17) | 0.0402 (17) | 0.0269 (15) | 0.0025 (15) | 0.0092 (13) | 0.0003 (13) |
C10 | 0.0392 (17) | 0.0387 (17) | 0.0279 (15) | −0.0003 (14) | 0.0044 (13) | −0.0036 (12) |
C11 | 0.0293 (14) | 0.0286 (15) | 0.0289 (15) | 0.0044 (12) | 0.0055 (12) | −0.0004 (12) |
C12 | 0.0482 (19) | 0.0453 (18) | 0.0242 (16) | −0.0050 (15) | 0.0057 (13) | −0.0001 (13) |
C13 | 0.0464 (18) | 0.0501 (19) | 0.0301 (17) | −0.0135 (16) | 0.0033 (14) | −0.0049 (14) |
C14 | 0.0352 (16) | 0.0327 (16) | 0.0364 (18) | −0.0022 (14) | 0.0042 (13) | 0.0011 (13) |
C15 | 0.0409 (18) | 0.054 (2) | 0.052 (2) | 0.0087 (17) | 0.0112 (15) | −0.0012 (17) |
O1W | 0.133 (3) | 0.0493 (17) | 0.0335 (14) | 0.0079 (18) | 0.0140 (15) | −0.0050 (13) |
Geometric parameters (Å, º) top
S1—O2 | 1.424 (2) | C8—C9 | 1.385 (4) |
S1—O3 | 1.431 (2) | C8—C13 | 1.395 (4) |
S1—N2 | 1.651 (3) | C9—C10 | 1.374 (4) |
S1—C11 | 1.760 (3) | C10—C11 | 1.391 (4) |
O1—C1 | 1.354 (5) | C11—C12 | 1.387 (4) |
O4—C14 | 1.223 (3) | C12—C13 | 1.372 (4) |
O1—H1O | 0.83 (5) | C14—C15 | 1.491 (4) |
O1W—H1W | 0.84 (4) | C2—H2A | 0.9300 |
O1W—H2W | 0.84 (3) | C3—H3A | 0.9300 |
N1—C8 | 1.423 (4) | C4—H4A | 0.9300 |
N1—C7 | 1.277 (4) | C5—H5A | 0.9300 |
N2—C14 | 1.376 (3) | C7—H7A | 0.9300 |
N2—H2B | 0.8600 | C9—H9A | 0.9300 |
C1—C6 | 1.407 (4) | C10—H10A | 0.9300 |
C1—C2 | 1.388 (5) | C12—H12A | 0.9300 |
C2—C3 | 1.381 (6) | C13—H13A | 0.9300 |
C3—C4 | 1.379 (6) | C15—H15C | 0.9600 |
C4—C5 | 1.372 (5) | C15—H15A | 0.9600 |
C5—C6 | 1.396 (4) | C15—H15B | 0.9600 |
C6—C7 | 1.443 (4) | | |
| | | |
O1···N1 | 2.626 (4) | C10···O4 | 3.199 (4) |
O1W···O4i | 2.897 (4) | C10···O2viii | 3.278 (4) |
O1W···O4ii | 2.960 (4) | C11···O4 | 3.386 (3) |
O1W···N2 | 2.740 (4) | C11···O2viii | 3.263 (3) |
O1W···O2i | 3.054 (3) | C12···O3viii | 3.418 (4) |
O2···O4 | 2.877 (3) | C14···O2viii | 2.987 (4) |
O2···C10iii | 3.278 (4) | C15···O2viii | 3.282 (4) |
O2···C14iii | 2.987 (4) | C4···H4Aix | 2.8900 |
O2···C15iii | 3.282 (4) | C7···H13A | 2.6500 |
O2···O1Wiv | 3.054 (3) | C7···H1O | 2.36 (5) |
O2···C11iii | 3.263 (3) | C13···H7A | 2.5400 |
O3···C10i | 3.188 (3) | C14···H2Wv | 2.90 (4) |
O3···C9i | 3.396 (3) | H1O···N1 | 1.86 (5) |
O3···C12iii | 3.418 (4) | H1O···C7 | 2.36 (5) |
O4···O2 | 2.877 (3) | H1W···O4i | 2.11 (4) |
O4···O1Wiv | 2.897 (4) | H1W···H2B | 2.2300 |
O4···C10 | 3.199 (4) | H1W···O2i | 2.51 (4) |
O4···O1Wv | 2.960 (4) | H2B···H2W | 2.5900 |
O4···C11 | 3.386 (3) | H2B···H15B | 2.1800 |
O1···H7Avi | 2.7700 | H2B···H1W | 2.2300 |
O1···H5Avi | 2.7400 | H2B···O1W | 1.9100 |
O1W···H15B | 2.6600 | H2W···C14ii | 2.90 (4) |
O1W···H2B | 1.9100 | H2W···H2B | 2.5900 |
O2···H10A | 2.6700 | H2W···O4ii | 2.16 (4) |
O2···H2Wiv | 2.89 (5) | H2W···O2i | 2.89 (5) |
O2···H1Wiv | 2.51 (4) | H4A···C4x | 2.8900 |
O3···H10Ai | 2.4900 | H5A···H7A | 2.4300 |
O3···H9Ai | 2.9000 | H5A···O1xi | 2.7400 |
O3···H12A | 2.5800 | H7A···C13 | 2.5400 |
O4···H15Cvii | 2.7900 | H7A···H13A | 2.0400 |
O4···H10A | 2.7600 | H7A···O1xi | 2.7700 |
O4···H1Wiv | 2.11 (4) | H7A···H5A | 2.4300 |
O4···H2Wv | 2.16 (4) | H9A···H12Av | 2.5700 |
N1···O1 | 2.626 (4) | H9A···O3iv | 2.9000 |
N2···O1W | 2.740 (4) | H10A···O4 | 2.7600 |
N1···H1O | 1.86 (5) | H10A···O2 | 2.6700 |
C4···C7viii | 3.421 (5) | H10A···O3iv | 2.4900 |
C6···C8viii | 3.395 (4) | H12A···O3 | 2.5800 |
C7···C8viii | 3.586 (4) | H12A···H9Aii | 2.5700 |
C7···C4iii | 3.421 (5) | H13A···H7A | 2.0400 |
C8···C7iii | 3.586 (4) | H13A···C7 | 2.6500 |
C8···C6iii | 3.395 (4) | H15B···O1W | 2.6600 |
C9···O3iv | 3.396 (3) | H15B···H2B | 2.1800 |
C10···O3iv | 3.188 (3) | H15C···O4vii | 2.7900 |
| | | |
O2—S1—O3 | 120.03 (12) | C10—C11—C12 | 120.5 (2) |
O2—S1—N2 | 108.32 (13) | C11—C12—C13 | 119.7 (2) |
O2—S1—C11 | 109.11 (13) | C8—C13—C12 | 120.7 (3) |
O3—S1—N2 | 104.44 (12) | O4—C14—C15 | 123.2 (3) |
O3—S1—C11 | 108.81 (13) | N2—C14—C15 | 115.1 (2) |
N2—S1—C11 | 105.08 (13) | O4—C14—N2 | 121.7 (3) |
C1—O1—H1O | 105 (3) | C1—C2—H2A | 120.00 |
H1W—O1W—H2W | 114 (4) | C3—C2—H2A | 120.00 |
C7—N1—C8 | 122.0 (2) | C4—C3—H3A | 120.00 |
S1—N2—C14 | 124.81 (19) | C2—C3—H3A | 120.00 |
S1—N2—H2B | 118.00 | C3—C4—H4A | 120.00 |
C14—N2—H2B | 118.00 | C5—C4—H4A | 120.00 |
O1—C1—C2 | 118.9 (3) | C6—C5—H5A | 119.00 |
O1—C1—C6 | 121.6 (3) | C4—C5—H5A | 119.00 |
C2—C1—C6 | 119.5 (3) | N1—C7—H7A | 118.00 |
C1—C2—C3 | 120.4 (4) | C6—C7—H7A | 118.00 |
C2—C3—C4 | 120.7 (4) | C10—C9—H9A | 119.00 |
C3—C4—C5 | 119.2 (3) | C8—C9—H9A | 119.00 |
C4—C5—C6 | 121.8 (3) | C9—C10—H10A | 121.00 |
C1—C6—C7 | 121.4 (3) | C11—C10—H10A | 121.00 |
C1—C6—C5 | 118.4 (3) | C13—C12—H12A | 120.00 |
C5—C6—C7 | 120.2 (3) | C11—C12—H12A | 120.00 |
N1—C7—C6 | 123.1 (2) | C8—C13—H13A | 120.00 |
N1—C8—C13 | 124.6 (2) | C12—C13—H13A | 120.00 |
N1—C8—C9 | 116.8 (2) | C14—C15—H15B | 109.00 |
C9—C8—C13 | 118.6 (3) | C14—C15—H15C | 109.00 |
C8—C9—C10 | 121.7 (2) | C14—C15—H15A | 109.00 |
C9—C10—C11 | 118.8 (2) | H15A—C15—H15C | 109.00 |
S1—C11—C10 | 120.1 (2) | H15B—C15—H15C | 110.00 |
S1—C11—C12 | 119.2 (2) | H15A—C15—H15B | 109.00 |
| | | |
O2—S1—N2—C14 | −46.0 (3) | O1—C1—C2—C3 | 179.0 (3) |
O3—S1—N2—C14 | −175.0 (2) | C1—C2—C3—C4 | −0.7 (6) |
C11—S1—N2—C14 | 70.5 (3) | C2—C3—C4—C5 | 1.0 (5) |
O2—S1—C11—C10 | 29.0 (3) | C3—C4—C5—C6 | −0.3 (5) |
O2—S1—C11—C12 | −155.5 (2) | C4—C5—C6—C1 | −0.7 (5) |
O3—S1—C11—C10 | 161.7 (2) | C4—C5—C6—C7 | 179.9 (3) |
O3—S1—C11—C12 | −22.8 (3) | C1—C6—C7—N1 | 2.2 (5) |
N2—S1—C11—C10 | −87.0 (2) | C5—C6—C7—N1 | −178.4 (3) |
N2—S1—C11—C12 | 88.5 (2) | N1—C8—C9—C10 | −178.2 (3) |
C7—N1—C8—C13 | −2.8 (5) | C13—C8—C9—C10 | 1.9 (4) |
C7—N1—C8—C9 | 177.3 (3) | C9—C8—C13—C12 | −2.1 (4) |
C8—N1—C7—C6 | 180.0 (3) | N1—C8—C13—C12 | 178.0 (3) |
S1—N2—C14—C15 | −176.6 (2) | C8—C9—C10—C11 | −0.5 (4) |
S1—N2—C14—O4 | 4.3 (4) | C9—C10—C11—S1 | 174.6 (2) |
C6—C1—C2—C3 | −0.4 (5) | C9—C10—C11—C12 | −0.9 (4) |
O1—C1—C6—C5 | −178.2 (3) | C10—C11—C12—C13 | 0.7 (4) |
O1—C1—C6—C7 | 1.2 (5) | S1—C11—C12—C13 | −174.8 (2) |
C2—C1—C6—C5 | 1.1 (5) | C11—C12—C13—C8 | 0.8 (4) |
C2—C1—C6—C7 | −179.6 (3) | | |
Symmetry codes: (i) x, −y−1/2, z+1/2; (ii) x, −y+1/2, z+1/2; (iii) x, y−1, z; (iv) x, −y−1/2, z−1/2; (v) x, −y+1/2, z−1/2; (vi) x, −y+3/2, z−1/2; (vii) −x, −y, −z; (viii) x, y+1, z; (ix) −x+1, y−1/2, −z+1/2; (x) −x+1, y+1/2, −z+1/2; (xi) x, −y+3/2, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···N1 | 0.83 (5) | 1.86 (5) | 2.626 (4) | 152 (4) |
O1W—H1W···O2i | 0.84 (4) | 2.51 (4) | 3.054 (3) | 124 (3) |
O1W—H1W···O4i | 0.84 (4) | 2.11 (4) | 2.897 (4) | 155 (5) |
N2—H2B···O1W | 0.86 | 1.91 | 2.740 (4) | 161 |
O1W—H2W···O4ii | 0.84 (3) | 2.16 (4) | 2.960 (4) | 157 (4) |
C10—H10A···O3iv | 0.93 | 2.49 | 3.188 (3) | 132 |
Symmetry codes: (i) x, −y−1/2, z+1/2; (ii) x, −y+1/2, z+1/2; (iv) x, −y−1/2, z−1/2. |
(II)
N-acetyl-4-[(5-bromo-2-hydroxybenzylidene)amino]benzenesulfonamide monohydrate
top
Crystal data top
C15H13BrN2O4S·H2O | Dx = 1.665 Mg m−3 |
Mr = 415.26 | Melting point: 70 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 26.858 (3) Å | Cell parameters from 8514 reflections |
b = 4.855 (2) Å | θ = 5.6–28.1° |
c = 12.708 (3) Å | µ = 2.64 mm−1 |
β = 91.428 (12)° | T = 298 K |
V = 1656.6 (8) Å3 | Prism, yellow |
Z = 4 | 0.24 × 0.23 × 0.11 mm |
F(000) = 840 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2893 independent reflections |
Radiation source: fine-focus sealed tube | 2446 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ω scans | θmax = 25.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −31→31 |
Tmin = 0.549, Tmax = 0.748 | k = −5→5 |
13900 measured reflections | l = −15→15 |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0482P)2 + 0.6173P] where P = (Fo2 + 2Fc2)/3 |
2892 reflections | (Δ/σ)max = 0.043 |
230 parameters | Δρmax = 0.57 e Å−3 |
3 restraints | Δρmin = −0.42 e Å−3 |
Crystal data top
C15H13BrN2O4S·H2O | V = 1656.6 (8) Å3 |
Mr = 415.26 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 26.858 (3) Å | µ = 2.64 mm−1 |
b = 4.855 (2) Å | T = 298 K |
c = 12.708 (3) Å | 0.24 × 0.23 × 0.11 mm |
β = 91.428 (12)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2893 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2446 reflections with I > 2σ(I) |
Tmin = 0.549, Tmax = 0.748 | Rint = 0.029 |
13900 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.033 | 3 restraints |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.57 e Å−3 |
2892 reflections | Δρmin = −0.42 e Å−3 |
230 parameters | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | |
Br1 | 0.47099 (1) | 1.29676 (7) | 0.15738 (3) | 0.0556 (1) | |
S1 | 0.14546 (2) | −0.34321 (13) | 0.18633 (5) | 0.0320 (2) | |
O1 | 0.32605 (10) | 0.7229 (6) | −0.13812 (18) | 0.0628 (9) | |
O2 | 0.13449 (7) | −0.5499 (4) | 0.10915 (15) | 0.0405 (6) | |
O3 | 0.15782 (8) | −0.4214 (4) | 0.29244 (14) | 0.0455 (7) | |
O4 | 0.07830 (8) | −0.0952 (4) | 0.02204 (14) | 0.0449 (7) | |
N1 | 0.29484 (8) | 0.4434 (5) | 0.02450 (18) | 0.0390 (8) | |
N2 | 0.09620 (8) | −0.1432 (4) | 0.19689 (16) | 0.0334 (7) | |
C1 | 0.35791 (11) | 0.8469 (6) | −0.0701 (2) | 0.0447 (10) | |
C2 | 0.39047 (12) | 1.0434 (8) | −0.1072 (2) | 0.0561 (11) | |
C3 | 0.42407 (12) | 1.1739 (7) | −0.0414 (3) | 0.0522 (11) | |
C4 | 0.42497 (10) | 1.1137 (6) | 0.0653 (2) | 0.0407 (9) | |
C5 | 0.39244 (10) | 0.9239 (6) | 0.1048 (2) | 0.0405 (9) | |
C6 | 0.35874 (10) | 0.7855 (6) | 0.0385 (2) | 0.0369 (9) | |
C7 | 0.32536 (10) | 0.5827 (6) | 0.0818 (2) | 0.0400 (9) | |
C8 | 0.26186 (10) | 0.2481 (5) | 0.0683 (2) | 0.0343 (8) | |
C9 | 0.23230 (10) | 0.0988 (6) | −0.0017 (2) | 0.0365 (8) | |
C10 | 0.19769 (10) | −0.0880 (6) | 0.0327 (2) | 0.0339 (8) | |
C11 | 0.19272 (10) | −0.1271 (5) | 0.1398 (2) | 0.0311 (8) | |
C12 | 0.22245 (10) | 0.0159 (6) | 0.2114 (2) | 0.0391 (9) | |
C13 | 0.25674 (11) | 0.2017 (6) | 0.1764 (2) | 0.0438 (10) | |
C14 | 0.06909 (10) | −0.0369 (6) | 0.1121 (2) | 0.0354 (9) | |
C15 | 0.02741 (11) | 0.1511 (7) | 0.1413 (3) | 0.0492 (11) | |
O1W | 0.08098 (12) | 0.0825 (6) | 0.39187 (18) | 0.0708 (12) | |
H1 | 0.3132 (15) | 0.595 (7) | −0.105 (3) | 0.088 (15)* | |
H2B | 0.08670 | −0.10220 | 0.25910 | 0.0400* | |
H2C | 0.38950 | 1.08780 | −0.17850 | 0.0670* | |
H3B | 0.44620 | 1.30210 | −0.06820 | 0.0630* | |
H5A | 0.39290 | 0.88730 | 0.17670 | 0.0490* | |
H7A | 0.32620 | 0.55290 | 0.15410 | 0.0480* | |
H9A | 0.23590 | 0.12500 | −0.07360 | 0.0440* | |
H10A | 0.17800 | −0.18640 | −0.01530 | 0.0410* | |
H12A | 0.21920 | −0.01380 | 0.28320 | 0.0470* | |
H13A | 0.27670 | 0.29760 | 0.22470 | 0.0530* | |
H15A | 0.02710 | 0.30900 | 0.09590 | 0.0740* | |
H15B | 0.03220 | 0.20980 | 0.21300 | 0.0740* | |
H15C | −0.00370 | 0.05500 | 0.13390 | 0.0740* | |
H1W | 0.091 (2) | −0.031 (10) | 0.439 (3) | 0.14 (2)* | |
H2W | 0.0948 (18) | 0.231 (7) | 0.411 (4) | 0.109 (19)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0437 (2) | 0.0604 (2) | 0.0625 (2) | −0.0123 (2) | −0.0051 (2) | −0.0019 (2) |
S1 | 0.0386 (4) | 0.0297 (4) | 0.0274 (3) | −0.0014 (3) | −0.0019 (3) | 0.0034 (3) |
O1 | 0.0694 (16) | 0.0821 (18) | 0.0369 (13) | −0.0314 (14) | 0.0001 (11) | 0.0003 (12) |
O2 | 0.0492 (12) | 0.0301 (10) | 0.0420 (11) | −0.0017 (9) | −0.0034 (9) | −0.0033 (8) |
O3 | 0.0548 (13) | 0.0487 (12) | 0.0327 (11) | 0.0005 (10) | −0.0050 (9) | 0.0133 (9) |
O4 | 0.0561 (13) | 0.0518 (12) | 0.0266 (11) | 0.0085 (10) | −0.0048 (9) | −0.0023 (9) |
N1 | 0.0373 (13) | 0.0395 (13) | 0.0403 (13) | −0.0034 (11) | 0.0025 (10) | 0.0012 (11) |
N2 | 0.0371 (12) | 0.0390 (13) | 0.0243 (11) | −0.0003 (10) | 0.0026 (9) | 0.0005 (9) |
C1 | 0.0441 (17) | 0.0512 (19) | 0.0389 (17) | −0.0065 (14) | 0.0050 (13) | −0.0011 (14) |
C2 | 0.062 (2) | 0.070 (2) | 0.0368 (17) | −0.0190 (18) | 0.0086 (15) | 0.0045 (16) |
C3 | 0.0493 (19) | 0.056 (2) | 0.052 (2) | −0.0150 (15) | 0.0127 (15) | 0.0028 (15) |
C4 | 0.0319 (15) | 0.0401 (16) | 0.0502 (18) | −0.0016 (12) | 0.0030 (13) | −0.0016 (13) |
C5 | 0.0383 (16) | 0.0426 (16) | 0.0405 (16) | 0.0003 (13) | −0.0024 (12) | 0.0038 (13) |
C6 | 0.0344 (15) | 0.0364 (15) | 0.0401 (16) | 0.0010 (12) | 0.0035 (12) | 0.0023 (12) |
C7 | 0.0403 (16) | 0.0408 (16) | 0.0390 (16) | 0.0000 (13) | 0.0011 (13) | 0.0050 (13) |
C8 | 0.0319 (14) | 0.0341 (14) | 0.0369 (15) | 0.0004 (11) | 0.0016 (12) | 0.0025 (11) |
C9 | 0.0412 (15) | 0.0410 (15) | 0.0273 (14) | 0.0011 (13) | 0.0009 (12) | 0.0030 (12) |
C10 | 0.0390 (15) | 0.0363 (14) | 0.0261 (14) | −0.0020 (12) | −0.0024 (11) | −0.0027 (11) |
C11 | 0.0325 (14) | 0.0289 (13) | 0.0319 (14) | 0.0022 (11) | −0.0014 (11) | 0.0005 (11) |
C12 | 0.0446 (16) | 0.0473 (17) | 0.0251 (14) | −0.0077 (13) | −0.0028 (12) | 0.0023 (12) |
C13 | 0.0455 (17) | 0.0516 (18) | 0.0340 (16) | −0.0121 (14) | −0.0047 (13) | −0.0041 (13) |
C14 | 0.0361 (15) | 0.0320 (15) | 0.0379 (16) | −0.0039 (12) | −0.0031 (12) | 0.0016 (12) |
C15 | 0.0385 (17) | 0.055 (2) | 0.0541 (19) | 0.0079 (14) | 0.0014 (14) | −0.0007 (16) |
O1W | 0.130 (3) | 0.0482 (15) | 0.0336 (13) | 0.0043 (17) | −0.0068 (14) | −0.0043 (12) |
Geometric parameters (Å, º) top
Br1—C4 | 1.901 (3) | C6—C7 | 1.449 (4) |
S1—O2 | 1.429 (2) | C8—C9 | 1.383 (4) |
S1—O3 | 1.432 (2) | C8—C13 | 1.402 (4) |
S1—N2 | 1.649 (2) | C9—C10 | 1.378 (4) |
S1—C11 | 1.760 (3) | C10—C11 | 1.384 (4) |
O1—C1 | 1.344 (4) | C11—C12 | 1.383 (4) |
O4—C14 | 1.211 (3) | C12—C13 | 1.371 (4) |
O1—H1 | 0.83 (4) | C14—C15 | 1.498 (4) |
O1W—H2W | 0.84 (4) | C2—H2C | 0.9300 |
O1W—H1W | 0.85 (4) | C3—H3B | 0.9300 |
N1—C7 | 1.277 (4) | C5—H5A | 0.9300 |
N1—C8 | 1.421 (3) | C7—H7A | 0.9300 |
N2—C14 | 1.385 (3) | C9—H9A | 0.9300 |
N2—H2B | 0.8600 | C10—H10A | 0.9300 |
C1—C6 | 1.412 (4) | C12—H12A | 0.9300 |
C1—C2 | 1.385 (5) | C13—H13A | 0.9300 |
C2—C3 | 1.370 (5) | C15—H15C | 0.9600 |
C3—C4 | 1.387 (5) | C15—H15A | 0.9600 |
C4—C5 | 1.373 (4) | C15—H15B | 0.9600 |
C5—C6 | 1.394 (4) | | |
| | | |
Br1···Br1i | 3.6986 (16) | C7···C4vii | 3.523 (4) |
Br1···Br1ii | 3.6986 (16) | C8···C6vii | 3.465 (4) |
Br1···H3Biii | 3.1900 | C9···O3viii | 3.366 (4) |
Br1···H2Civ | 3.1100 | C10···O2ix | 3.276 (4) |
O1···N1 | 2.627 (4) | C10···O3viii | 3.211 (3) |
O1W···O2v | 3.085 (3) | C10···O4 | 3.206 (4) |
O1W···O4v | 2.889 (4) | C11···O2ix | 3.228 (3) |
O1W···O4vi | 2.991 (4) | C11···O4 | 3.388 (4) |
O1W···N2 | 2.749 (3) | C12···O3ix | 3.410 (4) |
O2···N2vii | 3.264 (3) | C12···O2ix | 3.400 (4) |
O2···C10vii | 3.276 (4) | C14···O2ix | 2.946 (4) |
O2···C12vii | 3.400 (4) | C15···O2ix | 3.256 (4) |
O2···C14vii | 2.946 (4) | C7···H13A | 2.6500 |
O2···C15vii | 3.256 (4) | C7···H1 | 2.39 (4) |
O2···O4vii | 3.229 (3) | C13···H7A | 2.5500 |
O2···O1Wviii | 3.085 (3) | C14···H2Wx | 3.05 (5) |
O2···O4 | 2.880 (3) | H1···N1 | 1.88 (4) |
O2···C11vii | 3.228 (3) | H1···C7 | 2.39 (4) |
O3···C12vii | 3.410 (4) | H1W···H2B | 2.3100 |
O3···C10v | 3.211 (3) | H1W···O4v | 2.13 (5) |
O3···C9v | 3.366 (4) | H1W···O2v | 2.46 (4) |
O4···C10 | 3.206 (4) | H2B···H1W | 2.3100 |
O4···O2ix | 3.229 (3) | H2B···H2W | 2.5200 |
O4···O1Wviii | 2.889 (4) | H2B···O1W | 1.9200 |
O4···C11 | 3.388 (4) | H2B···H15B | 2.1800 |
O4···O2 | 2.880 (3) | H2C···Br1xiii | 3.1100 |
O4···O1Wx | 2.991 (4) | H2W···C14vi | 3.05 (5) |
O1···H7Axi | 2.8600 | H2W···O3ix | 2.85 (4) |
O1W···H2B | 1.9200 | H2W···H2B | 2.5200 |
O1W···H15B | 2.6700 | H2W···O2v | 2.85 (5) |
O2···H1Wviii | 2.46 (4) | H2W···O4vi | 2.31 (4) |
O2···H10A | 2.6600 | H3B···Br1iii | 3.1900 |
O2···H2Wviii | 2.85 (5) | H5A···H7A | 2.4300 |
O3···H12A | 2.5800 | H7A···H5A | 2.4300 |
O3···H9Av | 2.8500 | H7A···C13 | 2.5500 |
O3···H2Wvii | 2.85 (4) | H7A···H13A | 2.0400 |
O3···H10Av | 2.5400 | H7A···O1xiv | 2.8600 |
O4···H1Wviii | 2.13 (5) | H9A···O3viii | 2.8500 |
O4···H15Cxii | 2.7900 | H10A···O2 | 2.6600 |
O4···H10A | 2.7700 | H10A···O4 | 2.7700 |
O4···H2Wx | 2.31 (4) | H10A···O3viii | 2.5400 |
N1···O1 | 2.627 (4) | H12A···O3 | 2.5800 |
N2···O2ix | 3.264 (3) | H13A···C7 | 2.6500 |
N2···O1W | 2.749 (3) | H13A···H7A | 2.0400 |
N1···H1 | 1.88 (4) | H15B···H2B | 2.1800 |
C4···C7ix | 3.523 (4) | H15B···O1W | 2.6700 |
C6···C8ix | 3.465 (4) | H15C···O4xii | 2.7900 |
| | | |
O2—S1—O3 | 119.95 (12) | C10—C11—C12 | 120.7 (2) |
O2—S1—N2 | 108.50 (11) | S1—C11—C12 | 119.2 (2) |
O2—S1—C11 | 109.03 (12) | S1—C11—C10 | 120.0 (2) |
O3—S1—N2 | 104.31 (11) | C11—C12—C13 | 119.9 (2) |
O3—S1—C11 | 108.79 (12) | C8—C13—C12 | 120.4 (2) |
N2—S1—C11 | 105.25 (11) | O4—C14—C15 | 123.2 (3) |
C1—O1—H1 | 106 (3) | N2—C14—C15 | 114.6 (2) |
H1W—O1W—H2W | 103 (5) | O4—C14—N2 | 122.2 (3) |
C7—N1—C8 | 121.9 (2) | C3—C2—H2C | 119.00 |
S1—N2—C14 | 124.28 (18) | C1—C2—H2C | 119.00 |
C14—N2—H2B | 118.00 | C2—C3—H3B | 120.00 |
S1—N2—H2B | 118.00 | C4—C3—H3B | 120.00 |
O1—C1—C6 | 121.9 (3) | C6—C5—H5A | 120.00 |
C2—C1—C6 | 118.9 (3) | C4—C5—H5A | 120.00 |
O1—C1—C2 | 119.2 (2) | N1—C7—H7A | 119.00 |
C1—C2—C3 | 121.5 (3) | C6—C7—H7A | 119.00 |
C2—C3—C4 | 119.6 (3) | C10—C9—H9A | 119.00 |
C3—C4—C5 | 120.2 (3) | C8—C9—H9A | 119.00 |
Br1—C4—C5 | 119.90 (19) | C9—C10—H10A | 120.00 |
Br1—C4—C3 | 119.9 (2) | C11—C10—H10A | 121.00 |
C4—C5—C6 | 120.8 (2) | C13—C12—H12A | 120.00 |
C1—C6—C5 | 118.9 (3) | C11—C12—H12A | 120.00 |
C1—C6—C7 | 121.3 (2) | C8—C13—H13A | 120.00 |
C5—C6—C7 | 119.8 (2) | C12—C13—H13A | 120.00 |
N1—C7—C6 | 122.5 (2) | C14—C15—H15B | 109.00 |
N1—C8—C13 | 124.6 (2) | C14—C15—H15C | 109.00 |
C9—C8—C13 | 118.5 (2) | C14—C15—H15A | 109.00 |
N1—C8—C9 | 116.8 (2) | H15A—C15—H15C | 110.00 |
C8—C9—C10 | 121.5 (2) | H15B—C15—H15C | 109.00 |
C9—C10—C11 | 119.0 (2) | H15A—C15—H15B | 109.00 |
| | | |
O2—S1—N2—C14 | −45.8 (2) | C1—C2—C3—C4 | −1.5 (5) |
O3—S1—N2—C14 | −174.7 (2) | C2—C3—C4—C5 | 0.1 (5) |
C11—S1—N2—C14 | 70.8 (2) | C2—C3—C4—Br1 | −179.3 (3) |
O2—S1—C11—C10 | 28.6 (3) | Br1—C4—C5—C6 | −179.4 (2) |
O2—S1—C11—C12 | −155.6 (2) | C3—C4—C5—C6 | 1.2 (4) |
O3—S1—C11—C10 | 161.1 (2) | C4—C5—C6—C1 | −1.1 (4) |
O3—S1—C11—C12 | −23.1 (3) | C4—C5—C6—C7 | 179.0 (3) |
N2—S1—C11—C10 | −87.6 (2) | C1—C6—C7—N1 | 2.3 (4) |
N2—S1—C11—C12 | 88.2 (2) | C5—C6—C7—N1 | −177.7 (3) |
C7—N1—C8—C13 | 4.6 (4) | N1—C8—C9—C10 | −177.4 (3) |
C8—N1—C7—C6 | −179.1 (2) | C13—C8—C9—C10 | 1.3 (4) |
C7—N1—C8—C9 | −176.7 (3) | C9—C8—C13—C12 | −1.2 (4) |
S1—N2—C14—O4 | 3.8 (4) | N1—C8—C13—C12 | 177.5 (3) |
S1—N2—C14—C15 | −177.1 (2) | C8—C9—C10—C11 | −0.3 (4) |
O1—C1—C6—C5 | −179.4 (3) | C9—C10—C11—S1 | 174.9 (2) |
O1—C1—C2—C3 | −179.3 (3) | C9—C10—C11—C12 | −0.9 (4) |
O1—C1—C6—C7 | 0.6 (4) | C10—C11—C12—C13 | 1.0 (4) |
C2—C1—C6—C5 | −0.2 (4) | S1—C11—C12—C13 | −174.8 (2) |
C2—C1—C6—C7 | 179.7 (3) | C11—C12—C13—C8 | 0.1 (4) |
C6—C1—C2—C3 | 1.6 (5) | | |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+1, −y+3, −z; (iv) x, −y+5/2, z+1/2; (v) x, −y−1/2, z+1/2; (vi) x, −y+1/2, z+1/2; (vii) x, y−1, z; (viii) x, −y−1/2, z−1/2; (ix) x, y+1, z; (x) x, −y+1/2, z−1/2; (xi) x, −y+3/2, z−1/2; (xii) −x, −y, −z; (xiii) x, −y+5/2, z−1/2; (xiv) x, −y+3/2, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.83 (4) | 1.88 (4) | 2.627 (4) | 149 (3) |
O1W—H1W···O2v | 0.85 (4) | 2.46 (4) | 3.085 (3) | 130 (4) |
O1W—H1W···O4v | 0.85 (4) | 2.13 (5) | 2.889 (4) | 148 (5) |
N2—H2B···O1W | 0.86 | 1.92 | 2.749 (3) | 161 |
O1W—H2W···O4vi | 0.84 (4) | 2.31 (4) | 2.991 (4) | 138 (4) |
C10—H10A···O3viii | 0.93 | 2.54 | 3.211 (3) | 129 |
C12—H12A···O3 | 0.93 | 2.58 | 2.945 (4) | 104 |
Symmetry codes: (v) x, −y−1/2, z+1/2; (vi) x, −y+1/2, z+1/2; (viii) x, −y−1/2, z−1/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C15H14N2O4S·H2O | C15H13BrN2O4S·H2O |
Mr | 336.37 | 415.26 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 25.486 (3), 4.8964 (13), 12.605 (3) | 26.858 (3), 4.855 (2), 12.708 (3) |
β (°) | 99.44 (3) | 91.428 (12) |
V (Å3) | 1551.7 (6) | 1656.6 (8) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.24 | 2.64 |
Crystal size (mm) | 0.26 × 0.13 × 0.11 | 0.24 × 0.23 × 0.11 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.951, 0.974 | 0.549, 0.748 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11981, 2696, 1966 | 13900, 2893, 2446 |
Rint | 0.057 | 0.029 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.113, 1.06 | 0.033, 0.085, 1.03 |
No. of reflections | 2696 | 2892 |
No. of parameters | 221 | 230 |
No. of restraints | 2 | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.30 | 0.57, −0.42 |
Selected geometric parameters (Å, º) for (I) topS1—O2 | 1.424 (2) | O4—C14 | 1.223 (3) |
S1—O3 | 1.431 (2) | N1—C8 | 1.423 (4) |
S1—N2 | 1.651 (3) | N1—C7 | 1.277 (4) |
S1—C11 | 1.760 (3) | N2—C14 | 1.376 (3) |
O1—C1 | 1.354 (5) | | |
| | | |
O2—S1—O3 | 120.03 (12) | O1—C1—C6 | 121.6 (3) |
O2—S1—N2 | 108.32 (13) | N1—C7—C6 | 123.1 (2) |
O2—S1—C11 | 109.11 (13) | N1—C8—C13 | 124.6 (2) |
O3—S1—N2 | 104.44 (12) | N1—C8—C9 | 116.8 (2) |
O3—S1—C11 | 108.81 (13) | S1—C11—C10 | 120.1 (2) |
N2—S1—C11 | 105.08 (13) | S1—C11—C12 | 119.2 (2) |
C7—N1—C8 | 122.0 (2) | O4—C14—C15 | 123.2 (3) |
S1—N2—C14 | 124.81 (19) | N2—C14—C15 | 115.1 (2) |
O1—C1—C2 | 118.9 (3) | O4—C14—N2 | 121.7 (3) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···N1 | 0.83 (5) | 1.86 (5) | 2.626 (4) | 152 (4) |
O1W—H1W···O2i | 0.84 (4) | 2.51 (4) | 3.054 (3) | 124 (3) |
O1W—H1W···O4i | 0.84 (4) | 2.11 (4) | 2.897 (4) | 155 (5) |
N2—H2B···O1W | 0.86 | 1.91 | 2.740 (4) | 161 |
O1W—H2W···O4ii | 0.84 (3) | 2.16 (4) | 2.960 (4) | 157 (4) |
C10—H10A···O3iii | 0.93 | 2.49 | 3.188 (3) | 132 |
Symmetry codes: (i) x, −y−1/2, z+1/2; (ii) x, −y+1/2, z+1/2; (iii) x, −y−1/2, z−1/2. |
Selected geometric parameters (Å, º) for (II) topBr1—C4 | 1.901 (3) | O1—C1 | 1.344 (4) |
S1—O2 | 1.429 (2) | O4—C14 | 1.211 (3) |
S1—O3 | 1.432 (2) | N1—C7 | 1.277 (4) |
S1—N2 | 1.649 (2) | N1—C8 | 1.421 (3) |
S1—C11 | 1.760 (3) | N2—C14 | 1.385 (3) |
| | | |
O2—S1—O3 | 119.95 (12) | Br1—C4—C5 | 119.90 (19) |
O2—S1—N2 | 108.50 (11) | Br1—C4—C3 | 119.9 (2) |
O2—S1—C11 | 109.03 (12) | N1—C7—C6 | 122.5 (2) |
O3—S1—N2 | 104.31 (11) | N1—C8—C13 | 124.6 (2) |
O3—S1—C11 | 108.79 (12) | N1—C8—C9 | 116.8 (2) |
N2—S1—C11 | 105.25 (11) | S1—C11—C12 | 119.2 (2) |
C7—N1—C8 | 121.9 (2) | S1—C11—C10 | 120.0 (2) |
S1—N2—C14 | 124.28 (18) | O4—C14—C15 | 123.2 (3) |
O1—C1—C6 | 121.9 (3) | N2—C14—C15 | 114.6 (2) |
O1—C1—C2 | 119.2 (2) | O4—C14—N2 | 122.2 (3) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.83 (4) | 1.88 (4) | 2.627 (4) | 149 (3) |
O1W—H1W···O2i | 0.85 (4) | 2.46 (4) | 3.085 (3) | 130 (4) |
O1W—H1W···O4i | 0.85 (4) | 2.13 (5) | 2.889 (4) | 148 (5) |
N2—H2B···O1W | 0.86 | 1.92 | 2.749 (3) | 161 |
O1W—H2W···O4ii | 0.84 (4) | 2.31 (4) | 2.991 (4) | 138 (4) |
C10—H10A···O3iii | 0.93 | 2.54 | 3.211 (3) | 129 |
C12—H12A···O3 | 0.93 | 2.58 | 2.945 (4) | 104 |
Symmetry codes: (i) x, −y−1/2, z+1/2; (ii) x, −y+1/2, z+1/2; (iii) x, −y−1/2, z−1/2. |
The sulfonamides constitute an important class of antimicrobial agents which exert antibacterial action by inhibiting the enzyme dihydropteroate synthase competitively towards the substrate p-aminobenzoate (PAB). This enzyme catalyses the formation of dihydropteroate from PAB and hydroxymethyldihydropteridine pyrophosphate (Brown, 1971), so its inhibition leads to bacteriostasis. It is known that N-acetyl-4-aminobenzenesulfonamide belongs to the class of sulfonamide drugs with short-term action and it is widely applied in medical practice for the treatment of diseases caused by various coccal infections. The presence of the amino group in this compound leads to condensation with aldehydes and ketones, thus enlarging the number of functional groups and changing its chemical and medicobiological properties. Detailed study of the structural features of inhibitors in relation to their biological activity is an important step towards the deduction of the interaction mechanisms of enzyme inhibition and provides useful knowledge for the design of the most suitable molecules according to the stereo-electronic requirements of the inhibitory interaction. Therefore, we report here the crystal structures of N-acetyl-4-[(2-hydroxybenzylidene)amino]benzenesulfonamide monohydrate, (I), and N-acetyl-4-[(5-bromo-2-hydroxybenzylidene)amino]benzenesulfonamide, (II).
The numbering schemes and views of the molecules of (I) and (II) are shown in Figs. 1 and 2, respectively. Both (I) and (II) adopt an E configuration about the azomethine C═N double bond, with torsion angles of 180.0 (3) and 179.1 (2)°, respectively. The differences in the bond lengths and angles in (I) and (II) are within three times the combined values of their s.u.s. The S1—C11 distance of 1.760 (3) Å in (I) and (II) is a normal single-bond value and matches well with those observed in other sulfonamides (Singh et al., 1984; Abramenko & Sergienko, 2002). The S—N bond distances in (I) and (II) have a considerable amount of double-bond character. The S—O distances are similar to those found in analogous structures. These distances do not vary significantly in the sulfonamide structures, despite the differing intermolecular interaction patterns observed. The bond lengths and angles in the benzene rings have characteristic values. The angular disposition of the bonds about atom S1 deviates significantly from that of a regular tetrahedron, with the largest angle being O2—S1—O3 [120.0 (1)°] and the smallest being O3—S1—N2 [104.4 (1)°] in (I), and 120.0 (1) and 104.3 (1)°, respectively, in (II). These distortions of S bond angles may be caused by S1—O2···Cg (π-ring) interactions (Spek, 2003), where Cg is the centroid of the C8–C13 aromatic ring at symmetry position (x, y − 1, z) in (I) and that at (x, y + 1, z) in (II). The O2···Cg and S2···Cg separations for (I) are 3.142 and 3.137 Å, respectively, and for (II) are 3.802 and 3.804 Å, respectively, and the angles between the O2—Cg vectors and the normals to the C8–C13 phenyl rings are 8.3 and 9.06°, respectively, for (I) and (II).
The sulfonamide and acetyl moieties are capable of a variety of conformational states by means of rotations about the S1—N2 and N2—C14 bonds. The dihedral angles describing these conformations are 70.5 (3) and −176.6 (2)° in (I), and 70.9 (2) and −177.1 (1)° in (II). Fig 3 shows a superimposition of the molecules of (I) and (II), with a weighted r.m.s. deviation of 0.066 Å for atoms N1/C1–C13, illustrating the isostructural nature of these compounds.
In (I) and (II), in molecules related by a b-cell translation, short intermolecular contacts exist between carbonyl atom C14 and sulfonyl atom O2, of 2.99 and 2.95 Å, respectively. These molecules are linked by O1W—H1W···O4, O1W—H2W···O4 and O1W—H2W···O2 hydrogen bonds (Tables 2 and 4), which leads to the close approach of atoms O2 and C14 due to the rotation of the sulfonamide and acetyl moieties about the S1—N2 and N2—C14 bonds. In the related structures of 2[4-(acetylaminosulfonyl)phenylcarbamoyl]benzoic acid (phthalylsulfacetamide), (III) (Singh et al., 1984), and p-aminobenzene sulfonacetamide, (IV) (Basak & Mazumdar, 1982), where the water molecule is absent in the crystal packing, the O2—S1—N2—C14 and S1—N2—C14—O4 torsion angles are −53.2 and −61.5°, and 6.8 and 7.2°, respectively, whereas in (I) and (II), these angles are −46.0 (3) and −45.8 (2)°, and 4.3 (4) and 3.8 (4)°, respectively. In (III) and (IV), the above-mentioned intermolecular contacts between the carbonyl C atom and sulfonyl O atoms are 4.69 and 4.39 Å, respectively. A check of the Cambridge Structural Database [Version 5.25 (Allen, 2002); CONQUEST (Bruno et al., 2002)] for close contacts between such atoms has been carried out (R-factor less than 0.075) for compounds containing the benzoylsulfacetamide fragment and in which the given contact ranges from 2.9 to 3.22 Å. Only two such compounds were found, namely 2,8-dimethoxy-5,11-di-p-tosyl-5,6,11,12-tetrahydrodibenzo[b,f]diazocine-6,12-dione (Filipenko et al. 1988) and catena-[[µ3-N-(p-aminophenylsulfonyl)acetamide-O,O',N]silver] (Ghosh et al., 1990), for which the O···C separations are 3.13 and 3.05 Å, respectively. [Please check amended text.]
In the molecules of (I) and (II), the two benzene rings and the azomethine group are practically coplanar, due to intramolecular O1—H···N1 hydrogen bonds. The deviations of atoms N1/C1–C13 from the best-fit plane through them are between 0.043 and −0.042 Å in (I), and 0.098 and 0.096 Å in (II). In the structure of (III), where the above-mentioned intramolecular hydrogen bond is absent, the two benzene rings are rotated by 62.1° with respect to each other.
The molecular packings of (I) and (II) are shown in Figs. 4 and 5, viewed down the b axis. Both compounds and their associated water molecules are arranged in the form of infinite two-dimensional layers parallel to the (100) plane, due to N—H···O, C—H···O and O—H···O hydrogen bonds (Tables 2 and 4). Between the layers there are intermolecular van der Waals interactions.