Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807021848/dn2172sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807021848/dn2172Isup2.hkl |
CCDC reference: 651440
Key indicators
- Single-crystal X-ray study
- T = 299 K
- Mean (C-C) = 0.005 Å
- R factor = 0.052
- wR factor = 0.129
- Data-to-parameter ratio = 16.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT230_ALERT_2_C Hirshfeld Test Diff for Cl1 - N1 .. 6.32 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for S1 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.24 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5 PLAT431_ALERT_2_C Short Inter HL..A Contact Cl1 .. O2 .. 3.24 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related structures, see: Gowda et al. (2002, 2005, 2007); Gowda, D'Souza & Kumar (2003); Gowda, Jyothi & Damodara (2003); Gowda, Jyothi, Kozisek & Fuess (2003); Gowda & Shetty (2004); Gowda & Kumar (2003); Minkwitz et al. (1997); Olmstead & Power (1986); George et al. (2000).
The N,N-dichloro-4-chlorobenzenesulfonamide(NNDC4CBSA) was prepared by further chlorination of the sodium salt of N-chloro-4-chlorobenzenesulfonamide (NaNC4CBSA) (Gowda et al., 2003 b). NaNC4CBSA was in turn prepared by the N-chlorination of 4-chlorobenzenesulfonamide (4CBSA)(Gowda et al., 2003 a). 4CBSA was prepared by the chlorosulphonation of chlorobenzene to 4-chlorobenzenesulfonylchloride and subsequent conversion of the latter to 4CBSA (Gowda et al., 2002). Pure chlorine gas was passed through clear solution of 4CBSA in 4M NaOH at 70° C for about 1 hr. The precipitated NaNC4CBSA was filtered, washed, dried and recrystallized from water. Further, pure chlorine gas was bubbled through clear aqueous solution of NaNC4CBSA for about 1 hr. NNDC4CBSA precipitated was filtered, washed, dried and recrystallized from pure acetic acid. Purity of the compound was checked by determining its melting point and by estimating, iodometrically, the amount of active chlorine present in it. The compound was further characterized by recording its infrared and NMR spectra (Gowda et al., 2003 a). Single crystals of NNDC4CBSA were obtained by recrystallization from its water free chloroform or pure acetic acid solution and used for X-ray diffraction studies at room temperature.
All H atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) and with Uiso(H) = 1.2Ueq(C)
The chemistry of N-halo compounds is of interest as they show distinct physical, chemical and biological properties. Many of these compounds exhibit pharmacological, fungicidal and herbicidal activities due to their oxidizing action in aqueous, partial aqueous and non-aqueous media. Thus N-halo arylsulfonamides are of interest in synthetic, mechanistic, analytical and biological chemistry (Gowda et al., 2002, 2005, 2007; Gowda, D'Souza & Kumar, 2003; Gowda, Jyothi & Damodara, 2003; Gowda, Jyothi, Kozisek & Fuess, 2003; Gowda & Shetty, 2004; Gowda & Kumar, 2003). In the present work, the structure of N,N,4-trichlorobenzenesulfonamide (NNDC4MBSA) has been determined to explore the substituent effects on the solid state structures of sulfonamides and N-haloarylsulfonamides (Gowda et al., 2003c; 2007). The structure of NNDC4CBSA (Fig. 1) resembles that of N,N-dichloro-4-methylbenzenesulfonamide (Minkwitz et al., 1997). The structures of arylsulfonamides and N,N-dichloroarylsulfonamides are relatively simple (Minkwitz et al., 1997; Gowda, Jyothi, Kozisek & Fuess, 2003; Gowda et al., 2007), while those of the sodium salts of N-chloroarylsulfonamides are relatively complex (Olmstead & Power, 1986; George et al., 2000). Thus comparison of the first two categories of compounds with the latter is not straight forward. Hence comparison is made between arylsulfonamides and N,N-dichloroarylsulfonamides (Minkwitz et al., 1997; Gowda, Jyothi, Kozisek & Fuess, 2003). The C—S and S—O bond lengths slightly decrease on N-chlorination of arylsulfonamides to N,N-dichloroarylsulfonamides, while S—N bond lengths slightly increase on N-chlorination. The O—S—O, O1—S—C1 and O2—S—C1 bond angles increase on N-chlorination, while O1—S—N, O2—S—N and N—S—C1 bond angles generally decrease on N-chlorination.
For related structures, see: Gowda et al. (2002, 2005, 2007); Gowda, D'Souza & Kumar (2003); Gowda, Jyothi & Damodara (2003); Gowda, Jyothi, Kozisek & Fuess (2003); Gowda & Shetty (2004); Gowda & Kumar (2003); Minkwitz et al. (1997); Olmstead & Power (1986); George et al. (2000).
Data collection: STADI4 (Stoe & Cie, 1996); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2003) and WinGX (Farrugia, 1999).
Fig. 1. ORTEP view of the title compound showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. |
C6H4Cl3NO2S | F(000) = 520 |
Mr = 260.51 | Dx = 1.753 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 30 reflections |
a = 7.028 (2) Å | θ = 16.8–19.9° |
b = 16.059 (3) Å | µ = 1.10 mm−1 |
c = 10.492 (3) Å | T = 299 K |
β = 123.542 (17)° | Prism, colorless |
V = 987.0 (5) Å3 | 0.50 × 0.30 × 0.16 mm |
Z = 4 |
Stoe Stadi-4 four-circle diffractometer | 1463 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.028 |
Graphite monochromator | θmax = 26.1°, θmin = 5.3° |
profile fitted scan 2θ/ω 1/1 | h = −1→8 |
Absorption correction: ψ scan (North et al., 1968) | k = −19→0 |
Tmin = 0.609, Tmax = 0.843 | l = −12→11 |
2909 measured reflections | 3 standard reflections every 180 min |
1893 independent reflections | intensity decay: 18.2% |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0359P)2 + 1.1354P] where P = (Fo2 + 2Fc2)/3 |
1893 reflections | (Δ/σ)max = 0.003 |
118 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.51 e Å−3 |
C6H4Cl3NO2S | V = 987.0 (5) Å3 |
Mr = 260.51 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.028 (2) Å | µ = 1.10 mm−1 |
b = 16.059 (3) Å | T = 299 K |
c = 10.492 (3) Å | 0.50 × 0.30 × 0.16 mm |
β = 123.542 (17)° |
Stoe Stadi-4 four-circle diffractometer | 1463 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.028 |
Tmin = 0.609, Tmax = 0.843 | 3 standard reflections every 180 min |
2909 measured reflections | intensity decay: 18.2% |
1893 independent reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.47 e Å−3 |
1893 reflections | Δρmin = −0.51 e Å−3 |
118 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 | 0.4426 (6) | 0.10921 (19) | 0.7590 (4) | 0.0581 (8) | |
C2 | 0.3401 (6) | 0.1415 (2) | 0.6138 (4) | 0.0586 (8) | |
H2 | 0.3309 | 0.1988 | 0.5986 | 0.07* | |
C3 | 0.2521 (6) | 0.0882 (2) | 0.4923 (4) | 0.0624 (8) | |
H3 | 0.1827 | 0.1087 | 0.3933 | 0.075* | |
C4 | 0.2678 (5) | 0.0029 (2) | 0.5187 (4) | 0.0587 (8) | |
C5 | 0.3736 (7) | −0.0292 (2) | 0.6638 (5) | 0.0681 (9) | |
H5 | 0.3859 | −0.0865 | 0.6791 | 0.082* | |
C6 | 0.4603 (7) | 0.0237 (2) | 0.7850 (4) | 0.0712 (10) | |
H6 | 0.5304 | 0.0029 | 0.8839 | 0.085* | |
N1 | 0.8345 (7) | 0.1993 (2) | 0.9797 (4) | 0.0989 (13) | |
O1 | 0.4435 (7) | 0.25683 (17) | 0.8619 (4) | 0.1012 (10) | |
O2 | 0.5656 (10) | 0.1377 (2) | 1.0389 (4) | 0.1493 (19) | |
S1 | 0.5485 (2) | 0.17781 (6) | 0.91307 (12) | 0.0862 (4) | |
Cl1 | 0.8487 (2) | 0.24204 (7) | 0.83545 (15) | 0.1027 (5) | |
Cl2 | 0.9967 (3) | 0.10945 (9) | 1.04611 (15) | 0.1527 (9) | |
Cl3 | 0.15203 (16) | −0.06413 (7) | 0.36448 (12) | 0.0834 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.084 (2) | 0.0433 (15) | 0.0655 (19) | 0.0008 (15) | 0.0527 (18) | −0.0033 (14) |
C2 | 0.0661 (19) | 0.0439 (16) | 0.068 (2) | 0.0034 (14) | 0.0379 (17) | 0.0018 (14) |
C3 | 0.0604 (19) | 0.0605 (19) | 0.0627 (19) | 0.0019 (15) | 0.0317 (16) | −0.0036 (15) |
C4 | 0.0518 (17) | 0.0589 (18) | 0.076 (2) | −0.0108 (14) | 0.0421 (16) | −0.0190 (16) |
C5 | 0.094 (3) | 0.0426 (16) | 0.090 (3) | −0.0070 (16) | 0.065 (2) | −0.0049 (16) |
C6 | 0.113 (3) | 0.0488 (18) | 0.071 (2) | 0.0012 (18) | 0.063 (2) | 0.0061 (16) |
N1 | 0.124 (3) | 0.0581 (18) | 0.0560 (18) | 0.009 (2) | 0.0132 (19) | −0.0120 (15) |
O1 | 0.150 (3) | 0.0591 (15) | 0.110 (2) | 0.0228 (17) | 0.081 (2) | −0.0109 (15) |
O2 | 0.319 (6) | 0.086 (2) | 0.108 (3) | −0.009 (3) | 0.159 (4) | −0.0083 (19) |
S1 | 0.1578 (11) | 0.0511 (5) | 0.0720 (6) | 0.0065 (6) | 0.0776 (7) | −0.0054 (4) |
Cl1 | 0.1127 (9) | 0.0792 (7) | 0.0955 (8) | −0.0364 (6) | 0.0445 (7) | −0.0213 (6) |
Cl2 | 0.1630 (15) | 0.0953 (9) | 0.0810 (8) | 0.0433 (9) | −0.0073 (9) | −0.0078 (7) |
Cl3 | 0.0699 (6) | 0.0842 (7) | 0.0971 (7) | −0.0202 (5) | 0.0468 (5) | −0.0418 (6) |
C1—C2 | 1.377 (4) | C5—C6 | 1.361 (5) |
C1—C6 | 1.393 (4) | C5—H5 | 0.9300 |
C1—S1 | 1.747 (3) | C6—H6 | 0.9300 |
C2—C3 | 1.367 (5) | N1—Cl1 | 1.714 (5) |
C2—H2 | 0.9300 | N1—Cl2 | 1.729 (4) |
C3—C4 | 1.390 (5) | N1—S1 | 1.759 (5) |
C3—H3 | 0.9300 | O1—S1 | 1.416 (3) |
C4—C5 | 1.373 (5) | O2—S1 | 1.413 (3) |
C4—Cl3 | 1.727 (3) | ||
C2—C1—C6 | 121.6 (3) | C4—C5—H5 | 120.3 |
C2—C1—S1 | 118.8 (2) | C5—C6—C1 | 119.1 (3) |
C6—C1—S1 | 119.6 (3) | C5—C6—H6 | 120.4 |
C3—C2—C1 | 119.1 (3) | C1—C6—H6 | 120.4 |
C3—C2—H2 | 120.4 | Cl1—N1—Cl2 | 110.0 (3) |
C1—C2—H2 | 120.4 | Cl1—N1—S1 | 109.80 (18) |
C2—C3—C4 | 119.1 (3) | Cl2—N1—S1 | 110.5 (2) |
C2—C3—H3 | 120.5 | O2—S1—O1 | 121.3 (2) |
C4—C3—H3 | 120.5 | O2—S1—C1 | 110.49 (19) |
C5—C4—C3 | 121.7 (3) | O1—S1—C1 | 110.38 (18) |
C5—C4—Cl3 | 119.4 (3) | O2—S1—N1 | 103.3 (3) |
C3—C4—Cl3 | 118.9 (3) | O1—S1—N1 | 102.5 (2) |
C6—C5—C4 | 119.4 (3) | C1—S1—N1 | 107.51 (17) |
C6—C5—H5 | 120.3 | ||
C6—C1—C2—C3 | 0.5 (5) | C6—C1—S1—O2 | −21.4 (4) |
S1—C1—C2—C3 | −178.5 (3) | C2—C1—S1—O1 | 20.7 (4) |
C1—C2—C3—C4 | 0.3 (5) | C6—C1—S1—O1 | −158.4 (3) |
C2—C3—C4—C5 | −1.4 (5) | C2—C1—S1—N1 | −90.4 (3) |
C2—C3—C4—Cl3 | 178.9 (2) | C6—C1—S1—N1 | 90.6 (3) |
C3—C4—C5—C6 | 1.8 (5) | Cl1—N1—S1—O2 | 175.7 (2) |
Cl3—C4—C5—C6 | −178.6 (3) | Cl2—N1—S1—O2 | 54.2 (3) |
C4—C5—C6—C1 | −1.0 (6) | Cl1—N1—S1—O1 | −57.5 (2) |
C2—C1—C6—C5 | −0.2 (6) | Cl2—N1—S1—O1 | −179.0 (2) |
S1—C1—C6—C5 | 178.9 (3) | Cl1—N1—S1—C1 | 58.9 (2) |
C2—C1—S1—O2 | 157.6 (4) | Cl2—N1—S1—C1 | −62.7 (2) |
Experimental details
Crystal data | |
Chemical formula | C6H4Cl3NO2S |
Mr | 260.51 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 299 |
a, b, c (Å) | 7.028 (2), 16.059 (3), 10.492 (3) |
β (°) | 123.542 (17) |
V (Å3) | 987.0 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.10 |
Crystal size (mm) | 0.50 × 0.30 × 0.16 |
Data collection | |
Diffractometer | Stoe Stadi-4 four-circle |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.609, 0.843 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2909, 1893, 1463 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.618 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.129, 1.06 |
No. of reflections | 1893 |
No. of parameters | 118 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.47, −0.51 |
Computer programs: STADI4 (Stoe & Cie, 1996), STADI4, X-RED (Stoe & Cie, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97, PLATON (Spek, 2003) and WinGX (Farrugia, 1999).
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The chemistry of N-halo compounds is of interest as they show distinct physical, chemical and biological properties. Many of these compounds exhibit pharmacological, fungicidal and herbicidal activities due to their oxidizing action in aqueous, partial aqueous and non-aqueous media. Thus N-halo arylsulfonamides are of interest in synthetic, mechanistic, analytical and biological chemistry (Gowda et al., 2002, 2005, 2007; Gowda, D'Souza & Kumar, 2003; Gowda, Jyothi & Damodara, 2003; Gowda, Jyothi, Kozisek & Fuess, 2003; Gowda & Shetty, 2004; Gowda & Kumar, 2003). In the present work, the structure of N,N,4-trichlorobenzenesulfonamide (NNDC4MBSA) has been determined to explore the substituent effects on the solid state structures of sulfonamides and N-haloarylsulfonamides (Gowda et al., 2003c; 2007). The structure of NNDC4CBSA (Fig. 1) resembles that of N,N-dichloro-4-methylbenzenesulfonamide (Minkwitz et al., 1997). The structures of arylsulfonamides and N,N-dichloroarylsulfonamides are relatively simple (Minkwitz et al., 1997; Gowda, Jyothi, Kozisek & Fuess, 2003; Gowda et al., 2007), while those of the sodium salts of N-chloroarylsulfonamides are relatively complex (Olmstead & Power, 1986; George et al., 2000). Thus comparison of the first two categories of compounds with the latter is not straight forward. Hence comparison is made between arylsulfonamides and N,N-dichloroarylsulfonamides (Minkwitz et al., 1997; Gowda, Jyothi, Kozisek & Fuess, 2003). The C—S and S—O bond lengths slightly decrease on N-chlorination of arylsulfonamides to N,N-dichloroarylsulfonamides, while S—N bond lengths slightly increase on N-chlorination. The O—S—O, O1—S—C1 and O2—S—C1 bond angles increase on N-chlorination, while O1—S—N, O2—S—N and N—S—C1 bond angles generally decrease on N-chlorination.