Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026438/dn2184sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026438/dn2184Isup2.hkl |
CCDC reference: 614681
Key indicators
- Single-crystal X-ray study
- T = 299 K
- Mean (C-C) = 0.003 Å
- R factor = 0.034
- wR factor = 0.094
- Data-to-parameter ratio = 13.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.91 PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 100 Ang. PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 1000 Deg. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 6 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for S2
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 0.909 Tmax scaled 0.451 Tmin scaled 0.298 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 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.
H atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) or 0.96 Å (CH3) and with Uiso(H) = 1.2Ueq(aromatic) or Uiso(H) = 1.5Ueq(CH3). H atom attached to N was refined using a N—H restraint of 0.85 (1) Å.
The structural studies of sulphonanilides are of interest due to their biological activity as the latter is thought to be due to the amide hydrogen portion of the molecules. In the present work, the structure of N-(3,4-dichlorophenyl)-methanesulfonamde (34DCPMSA) has been determined as part of our study of the substituent effects on the solid state structures of methanesulfonanilides (Gowda et al., 2007a, b, c, d, e, f). The structure of 34DCPMSA (Fig. 1) is similar to those of other methanesulfonanilides(Gowda et al., 2007a,b,c,d,e,f). The conformation of the N—H bond in 34DCPMSA is syn to the meta chloro group in contrast to the anti conformation observed for the meta methyl group in N-(3,4-dimethylphenyl)-methanesulfonamde (34DMPMSA)(Gowda et al., 2007c) and the conformation lying between syn and anti to the meta-chloro substituent in N-(3-chlorophenyl)- methanesulfonamde (3CPMSA)(Gowda et al., 2007b). The substitution of Cl atom at the meta position of N-(phenyl)-methanesulfonamde (PMSA)to produce 3CPMSA changes its space group from monoclinic P21/c (Klug, 1968) to C 2/c (Gowda et al., 2007b). The substitution of an additional chloro group at the para position of 3CPMSA to produce 34DCPMSA changes the space group from monoclinic C 2/c to triclinic P-1 in contrast to change over from orthorhombic Pccn to monoclinic P21 on substitution of an additional methyl group at the para position in N-(3-methylphenyl)-methanesulfonamde to produce 34DMPMSA (Gowda et al., 2007c). The bond parameters in 34DCPMSA are similar to those in PMSA (Klug, 1968), 3CPMSA (Gowda et al., 2007b), 34DMPMSA (Gowda et al., 2007c) and other methanesulpfonanilides (Gowda et al., 2007a, d, e, f), except for some difference in the bond and torsional angles. The amide H atom is nearly in the plane of the dichlorophenyl group, the N atom is 0.110 (3) Å above the plane whereas the S atom is -0.426 (2) Å below the plane. The methyl group is clearly below the plane. The N—H···O hydrogen bonds (Table 1) result in the formation of dimers. The C—H···O interactions among the dimers in turn develop into ribbon like structures (Fig. 2).
For related structures, see: Gowda et al. (2007a,b,c,d,e,f); Klug (1968). For the synthetic procedure, see: Jayalakshmi & Gowda (2004).
Data collection: CAD-4-PC Software (Enraf–Nonius, 1996); cell refinement: CAD-4-PC Software; data reduction: REDU4 (Stoe, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
C7H7Cl2NO2S | Z = 2 |
Mr = 240.10 | F(000) = 244 |
Triclinic, P1 | Dx = 1.681 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.54180 Å |
a = 5.192 (1) Å | Cell parameters from 25 reflections |
b = 8.452 (1) Å | θ = 5.3–27.1° |
c = 11.031 (1) Å | µ = 7.95 mm−1 |
α = 79.72 (1)° | T = 299 K |
β = 89.72 (1)° | Prism, colourless |
γ = 84.89 (1)° | 0.40 × 0.15 × 0.10 mm |
V = 474.38 (12) Å3 |
Enraf–Nonius CAD-4 diffractometer | 1536 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.015 |
Graphite monochromator | θmax = 66.9°, θmin = 4.1° |
ω/2θ scans | h = −6→1 |
Absorption correction: ψ scan (North et al., 1968) | k = −10→10 |
Tmin = 0.328, Tmax = 0.496 | l = −13→13 |
1916 measured reflections | 3 standard reflections every 120 min |
1685 independent reflections | intensity decay: 1.0% |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0543P)2 + 0.2324P] where P = (Fo2 + 2Fc2)/3 |
1685 reflections | (Δ/σ)max < 0.001 |
123 parameters | Δρmax = 0.27 e Å−3 |
1 restraint | Δρmin = −0.33 e Å−3 |
C7H7Cl2NO2S | γ = 84.89 (1)° |
Mr = 240.10 | V = 474.38 (12) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.192 (1) Å | Cu Kα radiation |
b = 8.452 (1) Å | µ = 7.95 mm−1 |
c = 11.031 (1) Å | T = 299 K |
α = 79.72 (1)° | 0.40 × 0.15 × 0.10 mm |
β = 89.72 (1)° |
Enraf–Nonius CAD-4 diffractometer | 1536 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.015 |
Tmin = 0.328, Tmax = 0.496 | 3 standard reflections every 120 min |
1916 measured reflections | intensity decay: 1.0% |
1685 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | 1 restraint |
wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.27 e Å−3 |
1685 reflections | Δρmin = −0.33 e Å−3 |
123 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 | ||
C1 | 0.2536 (6) | 0.2368 (3) | 0.2322 (3) | 0.0596 (7) | |
H1A | 0.3692 | 0.2599 | 0.2931 | 0.089* | |
H1B | 0.3441 | 0.2355 | 0.1562 | 0.089* | |
H1C | 0.1904 | 0.1333 | 0.2601 | 0.089* | |
C6 | 0.2776 (4) | 0.6371 (3) | 0.2260 (2) | 0.0371 (5) | |
C7 | 0.4409 (5) | 0.7364 (3) | 0.1567 (2) | 0.0388 (5) | |
H7 | 0.4471 | 0.7416 | 0.0718 | 0.047* | |
C8 | 0.5949 (4) | 0.8279 (3) | 0.2121 (2) | 0.0378 (5) | |
C9 | 0.5897 (5) | 0.8187 (3) | 0.3392 (2) | 0.0413 (5) | |
C10 | 0.4287 (5) | 0.7178 (3) | 0.4082 (2) | 0.0465 (6) | |
H10 | 0.4258 | 0.7106 | 0.4933 | 0.056* | |
C11 | 0.2715 (5) | 0.6270 (3) | 0.3533 (2) | 0.0443 (5) | |
H11 | 0.1626 | 0.5598 | 0.4008 | 0.053* | |
N5 | 0.1139 (4) | 0.5562 (2) | 0.16041 (18) | 0.0456 (5) | |
O3 | −0.1591 (4) | 0.3621 (2) | 0.10627 (16) | 0.0565 (5) | |
O4 | −0.1291 (4) | 0.3894 (2) | 0.32363 (17) | 0.0547 (5) | |
S2 | −0.00703 (11) | 0.38570 (6) | 0.20856 (5) | 0.03832 (18) | |
Cl12 | 0.79029 (13) | 0.95435 (8) | 0.12089 (6) | 0.0547 (2) | |
Cl13 | 0.77694 (14) | 0.93584 (9) | 0.41041 (7) | 0.0603 (2) | |
H5 | 0.105 (6) | 0.581 (3) | 0.0828 (10) | 0.054 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0588 (16) | 0.0464 (14) | 0.0720 (19) | −0.0034 (12) | 0.0038 (14) | −0.0075 (13) |
C6 | 0.0464 (12) | 0.0306 (10) | 0.0340 (11) | −0.0072 (9) | −0.0007 (9) | −0.0028 (8) |
C7 | 0.0507 (13) | 0.0343 (11) | 0.0302 (11) | −0.0062 (9) | 0.0016 (9) | −0.0010 (9) |
C8 | 0.0433 (12) | 0.0302 (10) | 0.0390 (11) | −0.0074 (9) | 0.0024 (9) | −0.0018 (9) |
C9 | 0.0465 (12) | 0.0375 (12) | 0.0422 (13) | −0.0059 (10) | −0.0019 (10) | −0.0125 (10) |
C10 | 0.0589 (15) | 0.0512 (14) | 0.0311 (11) | −0.0096 (11) | 0.0036 (10) | −0.0094 (10) |
C11 | 0.0553 (14) | 0.0451 (13) | 0.0332 (12) | −0.0159 (11) | 0.0087 (10) | −0.0036 (10) |
N5 | 0.0635 (13) | 0.0435 (11) | 0.0301 (10) | −0.0233 (9) | −0.0029 (9) | 0.0020 (8) |
O3 | 0.0682 (12) | 0.0577 (11) | 0.0448 (10) | −0.0329 (9) | −0.0079 (8) | 0.0010 (8) |
O4 | 0.0618 (11) | 0.0587 (11) | 0.0464 (10) | −0.0213 (9) | 0.0191 (8) | −0.0095 (8) |
S2 | 0.0442 (3) | 0.0374 (3) | 0.0335 (3) | −0.0145 (2) | 0.0033 (2) | −0.0018 (2) |
Cl12 | 0.0603 (4) | 0.0482 (4) | 0.0546 (4) | −0.0244 (3) | 0.0056 (3) | 0.0028 (3) |
Cl13 | 0.0638 (4) | 0.0656 (4) | 0.0600 (4) | −0.0216 (3) | −0.0032 (3) | −0.0260 (3) |
C1—S2 | 1.751 (3) | C8—Cl12 | 1.728 (2) |
C1—H1A | 0.9600 | C9—C10 | 1.377 (4) |
C1—H1B | 0.9600 | C9—Cl13 | 1.732 (2) |
C1—H1C | 0.9600 | C10—C11 | 1.380 (3) |
C6—C7 | 1.378 (3) | C10—H10 | 0.9300 |
C6—C11 | 1.392 (3) | C11—H11 | 0.9300 |
C6—N5 | 1.414 (3) | N5—S2 | 1.624 (2) |
C7—C8 | 1.376 (3) | N5—H5 | 0.844 (10) |
C7—H7 | 0.9300 | O3—S2 | 1.4329 (18) |
C8—C9 | 1.390 (3) | O4—S2 | 1.4201 (18) |
S2—C1—H1A | 109.5 | C8—C9—Cl13 | 120.81 (18) |
S2—C1—H1B | 109.5 | C9—C10—C11 | 121.1 (2) |
H1A—C1—H1B | 109.5 | C9—C10—H10 | 119.4 |
S2—C1—H1C | 109.5 | C11—C10—H10 | 119.4 |
H1A—C1—H1C | 109.5 | C10—C11—C6 | 119.3 (2) |
H1B—C1—H1C | 109.5 | C10—C11—H11 | 120.4 |
C7—C6—C11 | 119.8 (2) | C6—C11—H11 | 120.4 |
C7—C6—N5 | 116.56 (19) | C6—N5—S2 | 127.66 (16) |
C11—C6—N5 | 123.6 (2) | C6—N5—H5 | 119 (2) |
C8—C7—C6 | 120.5 (2) | S2—N5—H5 | 111 (2) |
C8—C7—H7 | 119.7 | O4—S2—O3 | 118.85 (12) |
C6—C7—H7 | 119.7 | O4—S2—N5 | 109.71 (11) |
C7—C8—C9 | 120.1 (2) | O3—S2—N5 | 104.15 (10) |
C7—C8—Cl12 | 118.80 (17) | O4—S2—C1 | 107.99 (14) |
C9—C8—Cl12 | 121.13 (18) | O3—S2—C1 | 108.85 (14) |
C10—C9—C8 | 119.2 (2) | N5—S2—C1 | 106.67 (13) |
C10—C9—Cl13 | 119.97 (18) | ||
C7—C6—N5—S2 | 152.95 (19) | C11—C6—N5—S2 | −30.3 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···O3i | 0.84 (1) | 2.08 (1) | 2.913 (3) | 169 (3) |
C10—H10···O4ii | 0.93 | 2.60 | 3.352 (3) | 138 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C7H7Cl2NO2S |
Mr | 240.10 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 299 |
a, b, c (Å) | 5.192 (1), 8.452 (1), 11.031 (1) |
α, β, γ (°) | 79.72 (1), 89.72 (1), 84.89 (1) |
V (Å3) | 474.38 (12) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 7.95 |
Crystal size (mm) | 0.40 × 0.15 × 0.10 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.328, 0.496 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1916, 1685, 1536 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.094, 1.08 |
No. of reflections | 1685 |
No. of parameters | 123 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.27, −0.33 |
Computer programs: CAD-4-PC Software (Enraf–Nonius, 1996), CAD-4-PC Software, REDU4 (Stoe, 1987), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···O3i | 0.844 (10) | 2.079 (12) | 2.913 (3) | 169 (3) |
C10—H10···O4ii | 0.93 | 2.60 | 3.352 (3) | 138.4 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y+1, −z+1. |
The structural studies of sulphonanilides are of interest due to their biological activity as the latter is thought to be due to the amide hydrogen portion of the molecules. In the present work, the structure of N-(3,4-dichlorophenyl)-methanesulfonamde (34DCPMSA) has been determined as part of our study of the substituent effects on the solid state structures of methanesulfonanilides (Gowda et al., 2007a, b, c, d, e, f). The structure of 34DCPMSA (Fig. 1) is similar to those of other methanesulfonanilides(Gowda et al., 2007a,b,c,d,e,f). The conformation of the N—H bond in 34DCPMSA is syn to the meta chloro group in contrast to the anti conformation observed for the meta methyl group in N-(3,4-dimethylphenyl)-methanesulfonamde (34DMPMSA)(Gowda et al., 2007c) and the conformation lying between syn and anti to the meta-chloro substituent in N-(3-chlorophenyl)- methanesulfonamde (3CPMSA)(Gowda et al., 2007b). The substitution of Cl atom at the meta position of N-(phenyl)-methanesulfonamde (PMSA)to produce 3CPMSA changes its space group from monoclinic P21/c (Klug, 1968) to C 2/c (Gowda et al., 2007b). The substitution of an additional chloro group at the para position of 3CPMSA to produce 34DCPMSA changes the space group from monoclinic C 2/c to triclinic P-1 in contrast to change over from orthorhombic Pccn to monoclinic P21 on substitution of an additional methyl group at the para position in N-(3-methylphenyl)-methanesulfonamde to produce 34DMPMSA (Gowda et al., 2007c). The bond parameters in 34DCPMSA are similar to those in PMSA (Klug, 1968), 3CPMSA (Gowda et al., 2007b), 34DMPMSA (Gowda et al., 2007c) and other methanesulpfonanilides (Gowda et al., 2007a, d, e, f), except for some difference in the bond and torsional angles. The amide H atom is nearly in the plane of the dichlorophenyl group, the N atom is 0.110 (3) Å above the plane whereas the S atom is -0.426 (2) Å below the plane. The methyl group is clearly below the plane. The N—H···O hydrogen bonds (Table 1) result in the formation of dimers. The C—H···O interactions among the dimers in turn develop into ribbon like structures (Fig. 2).