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The structure of the title compound (NNDC4CBSA), C6H4Cl3NO2S, resembles that of N,N-dichloro-4-methylbenzene­sulfonamide (NNDC4MBSA). In particular, the structure is relatively simple, unlike those of the sodium salts of N-chloro­aryl­sulfonamides. Furthermore, the S-N distance of 1.759 (5) Å is consistent with the value of 1.735 (5) Å observed with NNDC4MBSA, the value for an S-N single bond. The mol­ecules are packed into zigzag chains in the direction of the a axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807021848/dn2172sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807021848/dn2172Isup2.hkl
Contains datablock I

CCDC reference: 651440

Key indicators

  • Single-crystal X-ray study
  • T = 299 K
  • Mean [sigma](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

Comment top

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.

Related literature top

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).

Experimental top

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.

Refinement top

All H atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) and with Uiso(H) = 1.2Ueq(C)

Structure description top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. ORTEP view of the title compound showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
N,N,4-Trichlorobenzenesulfonamide top
Crystal data top
C6H4Cl3NO2SF(000) = 520
Mr = 260.51Dx = 1.753 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 30 reflections
a = 7.028 (2) Åθ = 16.8–19.9°
b = 16.059 (3) ŵ = 1.10 mm1
c = 10.492 (3) ÅT = 299 K
β = 123.542 (17)°Prism, colorless
V = 987.0 (5) Å30.50 × 0.30 × 0.16 mm
Z = 4
Data collection top
Stoe Stadi-4 four-circle
diffractometer
1463 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.028
Graphite monochromatorθmax = 26.1°, θmin = 5.3°
profile fitted scan 2θ/ω 1/1h = 18
Absorption correction: ψ scan
(North et al., 1968)
k = 190
Tmin = 0.609, Tmax = 0.843l = 1211
2909 measured reflections3 standard reflections every 180 min
1893 independent reflections intensity decay: 18.2%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129H-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 parametersΔρmax = 0.47 e Å3
0 restraintsΔρmin = 0.51 e Å3
Crystal data top
C6H4Cl3NO2SV = 987.0 (5) Å3
Mr = 260.51Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.028 (2) ŵ = 1.10 mm1
b = 16.059 (3) ÅT = 299 K
c = 10.492 (3) Å0.50 × 0.30 × 0.16 mm
β = 123.542 (17)°
Data collection top
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 = 0.8433 standard reflections every 180 min
2909 measured reflections intensity decay: 18.2%
1893 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.129H-atom parameters constrained
S = 1.06Δρmax = 0.47 e Å3
1893 reflectionsΔρmin = 0.51 e Å3
118 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
xyzUiso*/Ueq
C10.4426 (6)0.10921 (19)0.7590 (4)0.0581 (8)
C20.3401 (6)0.1415 (2)0.6138 (4)0.0586 (8)
H20.33090.19880.59860.07*
C30.2521 (6)0.0882 (2)0.4923 (4)0.0624 (8)
H30.18270.10870.39330.075*
C40.2678 (5)0.0029 (2)0.5187 (4)0.0587 (8)
C50.3736 (7)0.0292 (2)0.6638 (5)0.0681 (9)
H50.38590.08650.67910.082*
C60.4603 (7)0.0237 (2)0.7850 (4)0.0712 (10)
H60.53040.00290.88390.085*
N10.8345 (7)0.1993 (2)0.9797 (4)0.0989 (13)
O10.4435 (7)0.25683 (17)0.8619 (4)0.1012 (10)
O20.5656 (10)0.1377 (2)1.0389 (4)0.1493 (19)
S10.5485 (2)0.17781 (6)0.91307 (12)0.0862 (4)
Cl10.8487 (2)0.24204 (7)0.83545 (15)0.1027 (5)
Cl20.9967 (3)0.10945 (9)1.04611 (15)0.1527 (9)
Cl30.15203 (16)0.06413 (7)0.36448 (12)0.0834 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.084 (2)0.0433 (15)0.0655 (19)0.0008 (15)0.0527 (18)0.0033 (14)
C20.0661 (19)0.0439 (16)0.068 (2)0.0034 (14)0.0379 (17)0.0018 (14)
C30.0604 (19)0.0605 (19)0.0627 (19)0.0019 (15)0.0317 (16)0.0036 (15)
C40.0518 (17)0.0589 (18)0.076 (2)0.0108 (14)0.0421 (16)0.0190 (16)
C50.094 (3)0.0426 (16)0.090 (3)0.0070 (16)0.065 (2)0.0049 (16)
C60.113 (3)0.0488 (18)0.071 (2)0.0012 (18)0.063 (2)0.0061 (16)
N10.124 (3)0.0581 (18)0.0560 (18)0.009 (2)0.0132 (19)0.0120 (15)
O10.150 (3)0.0591 (15)0.110 (2)0.0228 (17)0.081 (2)0.0109 (15)
O20.319 (6)0.086 (2)0.108 (3)0.009 (3)0.159 (4)0.0083 (19)
S10.1578 (11)0.0511 (5)0.0720 (6)0.0065 (6)0.0776 (7)0.0054 (4)
Cl10.1127 (9)0.0792 (7)0.0955 (8)0.0364 (6)0.0445 (7)0.0213 (6)
Cl20.1630 (15)0.0953 (9)0.0810 (8)0.0433 (9)0.0073 (9)0.0078 (7)
Cl30.0699 (6)0.0842 (7)0.0971 (7)0.0202 (5)0.0468 (5)0.0418 (6)
Geometric parameters (Å, º) top
C1—C21.377 (4)C5—C61.361 (5)
C1—C61.393 (4)C5—H50.9300
C1—S11.747 (3)C6—H60.9300
C2—C31.367 (5)N1—Cl11.714 (5)
C2—H20.9300N1—Cl21.729 (4)
C3—C41.390 (5)N1—S11.759 (5)
C3—H30.9300O1—S11.416 (3)
C4—C51.373 (5)O2—S11.413 (3)
C4—Cl31.727 (3)
C2—C1—C6121.6 (3)C4—C5—H5120.3
C2—C1—S1118.8 (2)C5—C6—C1119.1 (3)
C6—C1—S1119.6 (3)C5—C6—H6120.4
C3—C2—C1119.1 (3)C1—C6—H6120.4
C3—C2—H2120.4Cl1—N1—Cl2110.0 (3)
C1—C2—H2120.4Cl1—N1—S1109.80 (18)
C2—C3—C4119.1 (3)Cl2—N1—S1110.5 (2)
C2—C3—H3120.5O2—S1—O1121.3 (2)
C4—C3—H3120.5O2—S1—C1110.49 (19)
C5—C4—C3121.7 (3)O1—S1—C1110.38 (18)
C5—C4—Cl3119.4 (3)O2—S1—N1103.3 (3)
C3—C4—Cl3118.9 (3)O1—S1—N1102.5 (2)
C6—C5—C4119.4 (3)C1—S1—N1107.51 (17)
C6—C5—H5120.3
C6—C1—C2—C30.5 (5)C6—C1—S1—O221.4 (4)
S1—C1—C2—C3178.5 (3)C2—C1—S1—O120.7 (4)
C1—C2—C3—C40.3 (5)C6—C1—S1—O1158.4 (3)
C2—C3—C4—C51.4 (5)C2—C1—S1—N190.4 (3)
C2—C3—C4—Cl3178.9 (2)C6—C1—S1—N190.6 (3)
C3—C4—C5—C61.8 (5)Cl1—N1—S1—O2175.7 (2)
Cl3—C4—C5—C6178.6 (3)Cl2—N1—S1—O254.2 (3)
C4—C5—C6—C11.0 (6)Cl1—N1—S1—O157.5 (2)
C2—C1—C6—C50.2 (6)Cl2—N1—S1—O1179.0 (2)
S1—C1—C6—C5178.9 (3)Cl1—N1—S1—C158.9 (2)
C2—C1—S1—O2157.6 (4)Cl2—N1—S1—C162.7 (2)

Experimental details

Crystal data
Chemical formulaC6H4Cl3NO2S
Mr260.51
Crystal system, space groupMonoclinic, P21/c
Temperature (K)299
a, b, c (Å)7.028 (2), 16.059 (3), 10.492 (3)
β (°) 123.542 (17)
V3)987.0 (5)
Z4
Radiation typeMo Kα
µ (mm1)1.10
Crystal size (mm)0.50 × 0.30 × 0.16
Data collection
DiffractometerStoe Stadi-4 four-circle
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.609, 0.843
No. of measured, independent and
observed [I > 2σ(I)] reflections
2909, 1893, 1463
Rint0.028
(sin θ/λ)max1)0.618
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.129, 1.06
No. of reflections1893
No. of parameters118
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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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