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The conformation of the N—H bond in the structure of the title compound (3CPMSA), C
7H
8ClNO
2S, is neither
syn nor
anti to the
meta-chloro substituent, in contrast to the
anti conformations observed for the stronger electron-withdrawing
meta-nitro substituted (3NPMSA) and electron-donating
meta-methyl substituted compounds (3MPMSA). The substitution of the Cl atom at the
meta position of
N-(phenyl)-methanesulfonamde (PMSA) changes its space group from
P2
1/
c to
C2/
c compared to the change over from monoclinic
P2
1/
c to orthorhombic
Pccn on
meta-substitution of the electron-donating methyl group in PMSA and from monoclinic
P2
1/
c to triclinic
P, on
meta-substitution of the stronger electron-withdrawing nitro group. The bond parameters in PMSA, 3CPMSA, 3MPMSA and 3NPMSA are similar except for some differences in the S—N—C—C torsion angles. As in other alkyl sulfonanilides, the amide hydrogen is available to a receptor molecule during its biological activity, as it sits alone on one side of the plane of the benzene ring, while the whole methanesulfonyl group is on the opposite side of the plane. The molecules in the title compound are packed into chains in the
b-axis direction
via N—H
O hydrogen bonds [H
O = 2.06, N
O = 2.979 (3) Å and N—H
O 169°].
Supporting information
CCDC reference: 614577
Key indicators
- Single-crystal X-ray study
- T = 299 K
- Mean (C-C) = 0.005 Å
- R factor = 0.064
- wR factor = 0.177
- Data-to-parameter ratio = 14.2
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.94
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.75 mm
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 5
Alert level G
ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be
replaced by the scaled T values. Since the ratio of scaled T's
is identical to the ratio of reported T values, the scaling
does not imply a change to the absorption corrections used in
the study.
Ratio of Tmax expected/reported 0.939
Tmax scaled 0.179 Tmin scaled 0.061
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
3 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
The title compound was prepared according to the literature method (Jayalakshmi
& Gowda, 2004). The purity of the compound was checked by determining its
melting point. It was characterized by recording its infrared and NMR spectra
(Jayalakshmi & Gowda, 2004). Single crystals of the title compound were
obtained from a slow evaporation of its ethanolic solution and used for X-ray
diffraction studied at room temperature.
All H atoms attached to C atoms were fixed geometrically and treated as riding
with C—H = 0.93 Å (CH aromatic) or 0.96 Å (CH3) with Uiso(H)
= 1.2 Ueq. The H atom of the NH group was located in a diffrerence
map and its position refined.
Structure description
top
The stereochemistry of the biologically significant alkyl sulfonanilides,
particularly in the vicinity of the phenyl-N—H portion is of interest in
explaining their biological activity. The latter is thought to be due to the
hydrogen atom of the phenyl N—H portion of the sulfonanilides as it can
align itself, in relation to a receptor site. Therefore the structural studies
of sulfonanilides are of interest. In the present work, the structure of
N-(3-chlorophenyl)-methanesulfonamde (3CPMSA) has been determined to
explore the substituent effects on the structures of sulfonanilides (Gowda
et al., 2007a, b). The conformation of the N—H bond in 3CPMSA
is neither syn nor anti to the meta-chloro substituent
(Fig. 1), in contrast to the anti conformations observed for the
sulfonanilide with the stronger electron withdrawing meta-nitro
substituent (3NPMSA)(Gowda et al., 2007a) and for the compound
with the electron donating meta - methyl substituent (3MPMSA)(Gowda
et al., 2007b). The substitution of Cl atom at the meta
position of N-(phenyl)-methanesulfonamde (PMSA) changes its space group
from P21/c (Klug, 1968) to C 2/c compared to the change over from monoclinic
P21/c to orthorhombic Pccn on meta substitution of electron donating
methyl group in PMSA and from monoclinic P21/c to triclinic P-1, on
meta substitution of stronger electron withdrawing nitro group. The
bond parameters in the 4 compounds, PMSA, 3CPMSA, 3MPMSA and 3NPMSA are
similar except some difference in the torsional angles, S2N5C6C7, S2N5C6C11:
75.5 (2)°,-106.6 (2)° (PMSA); 61.7 (3)°, -120.0 (3)° (3CPMSA);68.1 (4)°,
-114.3 (3)° (3MPMSA); 41.1 (3)°, -140.8 (2)° (3NPMSA), respectively. The data
included for PMSA are the values determined under the present conditions as
the literature values were determined by Klug, 1968. The N—H hydrogen sits
alone on one side of the plane of the phenyl group, while the whole
methanesulfonyl group is on the opposite side of the plane, similar to that
observed in PMSA, 3NPMSA and 3MPMSA. The amide hydrogen is thus available to a
receptor molecule during biological activity. The molecules in the title
compound are packed into chain structure in the direction of b axis
through N—H···O hydrogen bond (Table 1 & Fig. 2).
For related literature, see: Gowda et al. (2007a, 2007b);
Jayalakshmi & Gowda (2004); Klug (1968).
Data collection: CAD-4-PC (Enraf–Nonius, 1996); cell refinement: CAD-4-PC; data reduction: REDU4 (Stoe & Cie, 1987); 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: SHELXL97.
N-(3-Chlorophenyl)methanesulfonamide
top
Crystal data top
C7H8ClNO2S | F(000) = 848 |
Mr = 205.65 | Dx = 1.549 Mg m−3 |
Monoclinic, C2/c | Cu Kα radiation, λ = 1.54180 Å |
Hall symbol: -C 2yc | Cell parameters from 25 reflections |
a = 23.488 (7) Å | θ = 7.9–25.4° |
b = 8.523 (2) Å | µ = 5.73 mm−1 |
c = 9.216 (2) Å | T = 299 K |
β = 107.05 (2)° | Long prism, colourless |
V = 1763.8 (8) Å3 | 0.75 × 0.47 × 0.30 mm |
Z = 8 | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 1486 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.097 |
Graphite monochromator | θmax = 67.0°, θmin = 3.9° |
ω/2θ scans | h = −26→28 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→10 |
Tmin = 0.065, Tmax = 0.191 | l = −10→1 |
1675 measured reflections | 3 standard reflections every 120 min |
1563 independent reflections | intensity decay: 1.2% |
Refinement top
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)] = 0.064 | H-atom parameters constrained |
wR(F2) = 0.177 | w = 1/[σ2(Fo2) + (0.1311P)2 + 1.4214P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.006 |
1563 reflections | Δρmax = 0.40 e Å−3 |
110 parameters | Δρmin = −0.87 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0224 (18) |
Crystal data top
C7H8ClNO2S | V = 1763.8 (8) Å3 |
Mr = 205.65 | Z = 8 |
Monoclinic, C2/c | Cu Kα radiation |
a = 23.488 (7) Å | µ = 5.73 mm−1 |
b = 8.523 (2) Å | T = 299 K |
c = 9.216 (2) Å | 0.75 × 0.47 × 0.30 mm |
β = 107.05 (2)° | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 1486 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.097 |
Tmin = 0.065, Tmax = 0.191 | 3 standard reflections every 120 min |
1675 measured reflections | intensity decay: 1.2% |
1563 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.064 | 0 restraints |
wR(F2) = 0.177 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.40 e Å−3 |
1563 reflections | Δρmin = −0.87 e Å−3 |
110 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 | |
Cl12 | 0.01500 (4) | 0.28125 (12) | 0.56573 (12) | 0.0759 (5) | |
S2 | 0.18925 (3) | 0.58669 (7) | 0.33977 (7) | 0.0419 (4) | |
O3 | 0.16237 (10) | 0.6527 (2) | 0.4463 (2) | 0.0517 (6) | |
O4 | 0.20627 (12) | 0.6889 (3) | 0.2374 (3) | 0.0647 (7) | |
N5 | 0.14299 (11) | 0.4624 (3) | 0.2333 (2) | 0.0480 (7) | |
H5N | 0.1531 | 0.4357 | 0.1457 | 0.058* | |
C1 | 0.25175 (15) | 0.4810 (4) | 0.4443 (4) | 0.0577 (8) | |
H1A | 0.2799 | 0.5516 | 0.5088 | 0.069* | |
H1B | 0.2698 | 0.4298 | 0.3761 | 0.069* | |
H1C | 0.2398 | 0.4038 | 0.5055 | 0.069* | |
C6 | 0.11753 (12) | 0.3372 (3) | 0.2964 (3) | 0.0420 (7) | |
C7 | 0.08190 (12) | 0.3679 (4) | 0.3865 (3) | 0.0451 (7) | |
H7 | 0.0736 | 0.4707 | 0.4074 | 0.054* | |
C8 | 0.05832 (13) | 0.2427 (4) | 0.4464 (3) | 0.0493 (7) | |
C9 | 0.06830 (15) | 0.0902 (4) | 0.4126 (4) | 0.0576 (9) | |
H9 | 0.0522 | 0.0075 | 0.4534 | 0.069* | |
C10 | 0.10249 (15) | 0.0622 (4) | 0.3175 (4) | 0.0618 (9) | |
H10 | 0.1085 | −0.0405 | 0.2912 | 0.074* | |
C11 | 0.12804 (14) | 0.1837 (4) | 0.2603 (4) | 0.0527 (7) | |
H11 | 0.1521 | 0.1633 | 0.1983 | 0.063* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl12 | 0.0730 (7) | 0.0799 (7) | 0.0904 (8) | −0.0152 (4) | 0.0484 (5) | 0.0030 (5) |
S2 | 0.0540 (6) | 0.0361 (5) | 0.0403 (5) | −0.0044 (2) | 0.0215 (3) | −0.0007 (2) |
O3 | 0.0674 (13) | 0.0441 (11) | 0.0497 (11) | 0.0002 (9) | 0.0268 (9) | −0.0063 (8) |
O4 | 0.0914 (18) | 0.0536 (13) | 0.0583 (14) | −0.0144 (12) | 0.0362 (12) | 0.0058 (10) |
N5 | 0.0604 (15) | 0.0514 (14) | 0.0350 (11) | −0.0112 (11) | 0.0181 (10) | −0.0024 (10) |
C1 | 0.0527 (16) | 0.0536 (18) | 0.0658 (18) | 0.0022 (14) | 0.0157 (14) | −0.0049 (14) |
C6 | 0.0422 (13) | 0.0455 (15) | 0.0347 (12) | −0.0080 (11) | 0.0056 (10) | 0.0002 (10) |
C7 | 0.0443 (14) | 0.0451 (14) | 0.0450 (14) | −0.0048 (12) | 0.0118 (11) | −0.0020 (11) |
C8 | 0.0412 (15) | 0.0550 (17) | 0.0509 (15) | −0.0105 (12) | 0.0126 (11) | 0.0017 (12) |
C9 | 0.0519 (17) | 0.0496 (18) | 0.067 (2) | −0.0133 (13) | 0.0103 (14) | 0.0069 (13) |
C10 | 0.0582 (18) | 0.0421 (15) | 0.078 (2) | −0.0052 (13) | 0.0083 (16) | −0.0063 (15) |
C11 | 0.0554 (17) | 0.0473 (15) | 0.0548 (16) | −0.0018 (13) | 0.0150 (13) | −0.0067 (13) |
Geometric parameters (Å, º) top
Cl12—C8 | 1.735 (3) | C6—C7 | 1.366 (4) |
S2—O4 | 1.425 (2) | C6—C11 | 1.390 (4) |
S2—O3 | 1.429 (2) | C7—C8 | 1.389 (4) |
S2—N5 | 1.625 (2) | C7—H7 | 0.9300 |
S2—C1 | 1.751 (3) | C8—C9 | 1.372 (5) |
N5—C6 | 1.428 (4) | C9—C10 | 1.372 (5) |
N5—H5N | 0.9344 | C9—H9 | 0.9300 |
C1—H1A | 0.9600 | C10—C11 | 1.377 (5) |
C1—H1B | 0.9600 | C10—H10 | 0.9300 |
C1—H1C | 0.9600 | C11—H11 | 0.9300 |
| | | |
O4—S2—O3 | 118.70 (14) | C11—C6—N5 | 118.8 (3) |
O4—S2—N5 | 105.47 (13) | C6—C7—C8 | 118.8 (3) |
O3—S2—N5 | 108.64 (13) | C6—C7—H7 | 120.6 |
O4—S2—C1 | 109.04 (17) | C8—C7—H7 | 120.6 |
O3—S2—C1 | 107.00 (15) | C9—C8—C7 | 121.5 (3) |
N5—S2—C1 | 107.54 (15) | C9—C8—Cl12 | 119.6 (2) |
C6—N5—S2 | 121.81 (17) | C7—C8—Cl12 | 118.8 (2) |
C6—N5—H5N | 114.4 | C8—C9—C10 | 118.7 (3) |
S2—N5—H5N | 112.7 | C8—C9—H9 | 120.6 |
S2—C1—H1A | 109.5 | C10—C9—H9 | 120.6 |
S2—C1—H1B | 109.5 | C9—C10—C11 | 121.0 (3) |
H1A—C1—H1B | 109.5 | C9—C10—H10 | 119.5 |
S2—C1—H1C | 109.5 | C11—C10—H10 | 119.5 |
H1A—C1—H1C | 109.5 | C10—C11—C6 | 119.3 (3) |
H1B—C1—H1C | 109.5 | C10—C11—H11 | 120.4 |
C7—C6—C11 | 120.6 (3) | C6—C11—H11 | 120.4 |
C7—C6—N5 | 120.6 (3) | | |
| | | |
O4—S2—N5—C6 | 178.0 (2) | C6—C7—C8—Cl12 | 178.0 (2) |
O3—S2—N5—C6 | −53.7 (3) | C7—C8—C9—C10 | 0.1 (5) |
C1—S2—N5—C6 | 61.7 (3) | Cl12—C8—C9—C10 | 179.7 (2) |
S2—N5—C6—C7 | 62.3 (3) | C8—C9—C10—C11 | 2.0 (5) |
S2—N5—C6—C11 | −119.8 (3) | C9—C10—C11—C6 | −1.8 (5) |
C11—C6—C7—C8 | 2.6 (4) | C7—C6—C11—C10 | −0.5 (4) |
N5—C6—C7—C8 | −179.6 (2) | N5—C6—C11—C10 | −178.4 (3) |
C6—C7—C8—C9 | −2.4 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5N···O3i | 0.93 | 2.06 | 2.979 (3) | 169 |
Symmetry code: (i) x, −y+1, z−1/2. |
Experimental details
Crystal data |
Chemical formula | C7H8ClNO2S |
Mr | 205.65 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 299 |
a, b, c (Å) | 23.488 (7), 8.523 (2), 9.216 (2) |
β (°) | 107.05 (2) |
V (Å3) | 1763.8 (8) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 5.73 |
Crystal size (mm) | 0.75 × 0.47 × 0.30 |
|
Data collection |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.065, 0.191 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1675, 1563, 1486 |
Rint | 0.097 |
(sin θ/λ)max (Å−1) | 0.597 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.064, 0.177, 1.09 |
No. of reflections | 1563 |
No. of parameters | 110 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.40, −0.87 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5N···O3i | 0.93 | 2.06 | 2.979 (3) | 169.1 |
Symmetry code: (i) x, −y+1, z−1/2. |
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The stereochemistry of the biologically significant alkyl sulfonanilides, particularly in the vicinity of the phenyl-N—H portion is of interest in explaining their biological activity. The latter is thought to be due to the hydrogen atom of the phenyl N—H portion of the sulfonanilides as it can align itself, in relation to a receptor site. Therefore the structural studies of sulfonanilides are of interest. In the present work, the structure of N-(3-chlorophenyl)-methanesulfonamde (3CPMSA) has been determined to explore the substituent effects on the structures of sulfonanilides (Gowda et al., 2007a, b). The conformation of the N—H bond in 3CPMSA is neither syn nor anti to the meta-chloro substituent (Fig. 1), in contrast to the anti conformations observed for the sulfonanilide with the stronger electron withdrawing meta-nitro substituent (3NPMSA)(Gowda et al., 2007a) and for the compound with the electron donating meta - methyl substituent (3MPMSA)(Gowda et al., 2007b). The substitution of Cl atom at the meta position of N-(phenyl)-methanesulfonamde (PMSA) changes its space group from P21/c (Klug, 1968) to C 2/c compared to the change over from monoclinic P21/c to orthorhombic Pccn on meta substitution of electron donating methyl group in PMSA and from monoclinic P21/c to triclinic P-1, on meta substitution of stronger electron withdrawing nitro group. The bond parameters in the 4 compounds, PMSA, 3CPMSA, 3MPMSA and 3NPMSA are similar except some difference in the torsional angles, S2N5C6C7, S2N5C6C11: 75.5 (2)°,-106.6 (2)° (PMSA); 61.7 (3)°, -120.0 (3)° (3CPMSA);68.1 (4)°, -114.3 (3)° (3MPMSA); 41.1 (3)°, -140.8 (2)° (3NPMSA), respectively. The data included for PMSA are the values determined under the present conditions as the literature values were determined by Klug, 1968. The N—H hydrogen sits alone on one side of the plane of the phenyl group, while the whole methanesulfonyl group is on the opposite side of the plane, similar to that observed in PMSA, 3NPMSA and 3MPMSA. The amide hydrogen is thus available to a receptor molecule during biological activity. The molecules in the title compound are packed into chain structure in the direction of b axis through N—H···O hydrogen bond (Table 1 & Fig. 2).