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Acta Cryst. (2009). E65, m700    [ doi:10.1107/S1600536809019989 ]

Sodium N-chloro-2-methylbenzenesulfonamidate sesquihydrate

B. T. Gowda, S. Foro and H. Fuess

Abstract top

In the title salt, Na+·C7H7ClNO2S-·1.5H2O, one of the water molecules lies on a twofold axis. The sodium ion shows an O6 octahedral coordination defined by three water O atoms and three sulfonyl O atoms derived from three different anions. The S-N distance of 1.5898 (19) Å is consistent with an S=N double bond. The crystal structure is stabilized by N-H...O and O-H...Cl hydrogen bonds.

Comment top

The chemistry of N-halo-arylsulfonamides is of interest due to their diverse characteristics (Gowda et al., 2005). In the present work, the structure of sodium N-chloro-2-methyl- benzenesulfonamidate (I) has been determined to explore substituent effects on the solid-state structures of N-halo arylsulfonamidates (Gowda et al., 2007a, b, c). The structure of (I), Fig. 1, resembles the sodium salts of N-chloro-4-chloro-benzenesulfonamidate (Gowda et al., 2007a), N-chloro-2-methyl-4-chloro-benzenesulfonamidate (Gowda et al., 2007b), N-bromo-benzenesulfonamidate (Gowda et al., 2007c), and other sodium N-chloro-arylsulfonamidates (George et al., 2000; Olmstead & Power, 1986). The sodium ion shows octahedral coordination defined by three water-O atoms and by three sulfonyl-O atoms derived from three different anions. There is no interaction between the nitrogen and sodium ions in (I). The N1—S1 distance of 1.5898 (19) Å is consistent with a S—N double bond and is in agreement with those observed with related N-chloro arylsulfonamides. In this description, the negative charge on the anion is distributed over the oxygen atoms. With the association described above for the Na+ ion along with N-H···O and O-H···Cl hydrogen bonding, Table 1, the molecular packing comprises layers stacked along the c axis (Fig. 2).

Related literature top

For background to N-halo-arylsulfonamides, see: Gowda et al. (2005). For related structures, see: Gowda et al. (2007a,b,c); George et al. (2000); Olmstead & Power (1986).

Experimental top

The purity of the commmercial sample (TCI Chemicals, Tokyo Kasei) was checked and characterized by recording its infrared and NMR spectra and estimating the amount of active chlorine present in it by the iodometric method (Gowda et al., 2005). The single crystals used in X-ray diffraction studies were grown in a water solution of (I) by slow evaporation at room temperature.

Refinement top

The O-bound H atoms were located in difference map and their positional parameters were refined freely [O—H = 0.77 (3)– 0.83 (3) Å]. The other H atoms were positioned in their idealized geometry using a riding model [C—H = 0.93–0.96 Å]. All H atoms were refined with isotropic displacement parameters set to 1.2 times of the Ueq of the parent atom.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of (I), extended to show the immediate coordination geometry of the sodium cation. Only atoms comprising the asymmetric unit are labelled. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Part of the crystal structure of (I) as viewed down the b axis, showing the O3W—H31···Cl1, O3W—H32···N1 and O4W—H41···N1 hydrogen bonds as dashed lines.
Sodium N-chloro-2-methylbenzenesulfonamidate sesquihydrate top
Crystal data top
Na+·C7H7Cl1N1O2S1–·1.5H2O1F000 = 524
Mr = 509.32Dx = 1.627 Mg m−3
Monoclinic, C2Mo Kα radiation
λ = 0.71073 Å
Hall symbol: C 2yCell parameters from 3049 reflections
a = 11.011 (1) Åθ = 2.6–27.5º
b = 6.6434 (6) ŵ = 0.60 mm−1
c = 14.447 (1) ÅT = 299 K
β = 100.350 (7)ºPlate, colourless
V = 1039.61 (15) Å30.45 × 0.32 × 0.08 mm
Z = 2
Data collection top
Oxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector		1657 independent reflections
Radiation source: fine-focus sealed tube1613 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.018
T = 299 Kθmax = 25.3º
Rotation method data acquisition using ω and φ scansθmin = 2.9º
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2007)		h = −13→12
Tmin = 0.776, Tmax = 0.954k = −7→8
3268 measured reflectionsl = −16→17
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of
independent and constrained refinement
R[F2 > 2σ(F2)] = 0.023  w = 1/[σ2(Fo2) + (0.041P)2 + 0.5427P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.061(Δ/σ)max = 0.017
S = 1.02Δρmax = 0.25 e Å−3
1657 reflectionsΔρmin = −0.16 e Å−3
142 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983), 617 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.02 (6)
Secondary atom site location: difference Fourier map
Crystal data top
Na+·C7H7Cl1N1O2S1–·1.5H2O1V = 1039.61 (15) Å3
Mr = 509.32Z = 2
Monoclinic, C2Mo Kα
a = 11.011 (1) ŵ = 0.60 mm−1
b = 6.6434 (6) ÅT = 299 K
c = 14.447 (1) Å0.45 × 0.32 × 0.08 mm
β = 100.350 (7)º
Data collection top
Oxford Diffraction Xcalibur
diffractometer with a Sapphire CCD detector		1657 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2007)		1613 reflections with I > 2σ(I)
Tmin = 0.776, Tmax = 0.954Rint = 0.018
3268 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.023H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.061Δρmax = 0.25 e Å−3
S = 1.02Δρmin = −0.16 e Å−3
1657 reflectionsAbsolute structure: Flack (1983), 617 Friedel pairs
142 parametersFlack parameter: 0.02 (6)
1 restraint
Special details top

Experimental. Absorption correction: CrysAlis RED, Oxford Diffraction Ltd., 2007 Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
Cl10.38269 (5)0.04628 (9)0.25363 (4)0.03904 (16)
S10.36260 (4)0.41295 (8)0.33507 (3)0.02316 (13)
Na10.14461 (8)0.19582 (15)0.47389 (6)0.0333 (2)
O10.24978 (13)0.3583 (3)0.36677 (10)0.0367 (4)
O20.43766 (13)0.5621 (3)0.39333 (10)0.0320 (4)
O30.29326 (15)0.3727 (3)0.59025 (12)0.0365 (4)
H310.258 (3)0.402 (5)0.6345 (18)0.044*
H320.354 (3)0.324 (5)0.615 (2)0.044*
O40.00000.4675 (4)0.50000.0358 (6)
H41−0.015 (3)0.534 (5)0.4534 (18)0.043*
N10.45553 (16)0.2319 (3)0.32989 (12)0.0286 (4)
C10.31412 (18)0.5172 (3)0.22046 (13)0.0254 (4)
C20.3987 (2)0.5799 (4)0.16471 (15)0.0310 (5)
C30.3489 (3)0.6595 (4)0.07650 (16)0.0442 (6)
H30.40260.70450.03800.053*
C40.2246 (3)0.6740 (5)0.04438 (17)0.0533 (7)
H40.19540.7255−0.01530.064*
C50.1428 (3)0.6125 (5)0.10021 (19)0.0503 (7)
H50.05820.62330.07880.060*
C60.1876 (2)0.5343 (4)0.18857 (16)0.0367 (5)
H60.13280.49300.22680.044*
C70.5365 (2)0.5657 (5)0.19499 (17)0.0410 (6)
H7A0.56000.42700.20400.049*
H7B0.56100.63780.25290.049*
H7C0.57630.62330.14730.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0411 (3)0.0278 (3)0.0496 (3)−0.0037 (2)0.0118 (2)−0.0106 (3)
S10.0232 (2)0.0237 (3)0.0231 (2)−0.0006 (2)0.00549 (16)−0.0007 (2)
Na10.0316 (5)0.0327 (5)0.0374 (4)−0.0053 (4)0.0114 (4)−0.0002 (4)
O10.0316 (8)0.0456 (12)0.0360 (8)−0.0025 (7)0.0143 (6)0.0047 (7)
O20.0343 (8)0.0302 (10)0.0305 (7)−0.0028 (7)0.0034 (6)−0.0084 (6)
O30.0270 (8)0.0421 (12)0.0396 (8)0.0008 (7)0.0040 (6)−0.0010 (7)
O40.0457 (14)0.0257 (14)0.0342 (11)0.0000.0025 (10)0.000
N10.0262 (9)0.0240 (11)0.0342 (9)−0.0005 (7)0.0016 (7)−0.0019 (7)
C10.0296 (10)0.0206 (12)0.0250 (9)−0.0003 (9)0.0024 (7)−0.0009 (8)
C20.0383 (12)0.0250 (14)0.0306 (10)−0.0045 (9)0.0091 (8)−0.0017 (9)
C30.0646 (17)0.0364 (17)0.0332 (11)−0.0040 (13)0.0132 (11)0.0056 (11)
C40.076 (2)0.0450 (18)0.0334 (12)0.0053 (15)−0.0048 (13)0.0079 (12)
C50.0449 (15)0.0508 (18)0.0478 (14)0.0069 (12)−0.0115 (11)−0.0001 (12)
C60.0319 (11)0.0337 (14)0.0432 (11)0.0019 (10)0.0033 (9)0.0007 (11)
C70.0357 (12)0.0449 (17)0.0457 (12)−0.0071 (11)0.0163 (10)0.0029 (12)
Geometric parameters (Å, °) top
Cl1—N11.7491 (19)O3—H310.83 (3)
S1—O11.4454 (15)O3—H320.77 (3)
S1—O21.4571 (16)O4—Na1iv2.480 (2)
S1—N11.5898 (19)O4—H410.80 (3)
S1—C11.785 (2)C1—C61.391 (3)
S1—Na1i3.3517 (10)C1—C21.399 (3)
Na1—O12.3549 (17)C2—C31.397 (3)
Na1—O32.4283 (18)C2—C71.505 (3)
Na1—O2ii2.4319 (16)C3—C41.367 (4)
Na1—O42.480 (2)C3—H30.9300
Na1—O3ii2.483 (2)C4—C51.375 (4)
Na1—O2iii2.5266 (16)C4—H40.9300
Na1—S1ii3.3517 (10)C5—C61.384 (4)
Na1—Na1iv3.4021 (16)C5—H50.9300
Na1—Na1i4.0447 (10)C6—H60.9300
Na1—Na1ii4.0447 (10)C7—H7A0.9600
O2—Na1i2.4319 (16)C7—H7B0.9600
O2—Na1v2.5266 (16)C7—H7C0.9600
O3—Na1i2.483 (2)
O1—S1—O2114.72 (9)O3—Na1—Na1ii88.59 (6)
O1—S1—N1114.96 (10)O2ii—Na1—Na1ii80.53 (5)
O2—S1—N1103.80 (9)O4—Na1—Na1ii158.72 (5)
O1—S1—C1105.10 (9)O3ii—Na1—Na1ii34.12 (4)
O2—S1—C1108.43 (10)O2iii—Na1—Na1ii103.70 (5)
N1—S1—C1109.72 (9)S1ii—Na1—Na1ii58.91 (2)
O1—S1—Na1i74.39 (7)Na1iv—Na1—Na1ii119.16 (2)
N1—S1—Na1i125.01 (7)Na1i—Na1—Na1ii110.42 (4)
C1—S1—Na1i119.92 (8)S1—O1—Na1151.10 (10)
O1—Na1—O383.29 (6)S1—O2—Na1i116.81 (8)
O1—Na1—O2ii169.34 (7)S1—O2—Na1v151.20 (10)
O3—Na1—O2ii86.05 (6)Na1i—O2—Na1v86.63 (5)
O1—Na1—O499.86 (6)Na1—O3—Na1i110.90 (7)
O3—Na1—O485.06 (6)Na1—O3—H31107 (2)
O2ii—Na1—O478.79 (5)Na1i—O3—H31107 (2)
O1—Na1—O3ii87.14 (7)Na1—O3—H32123 (2)
O3—Na1—O3ii118.69 (5)Na1i—O3—H32105 (2)
O2ii—Na1—O3ii98.34 (7)H31—O3—H32103 (3)
O4—Na1—O3ii156.00 (6)Na1iv—O4—Na186.61 (9)
O1—Na1—O2iii111.58 (6)Na1iv—O4—H41119 (2)
O3—Na1—O2iii158.28 (7)Na1—O4—H41108 (2)
O2ii—Na1—O2iii78.57 (6)S1—N1—Cl1109.69 (10)
O4—Na1—O2iii77.02 (5)C6—C1—C2121.0 (2)
O3ii—Na1—O2iii79.06 (6)C6—C1—S1116.98 (16)
O1—Na1—S1ii152.30 (5)C2—C1—S1122.02 (15)
O3—Na1—S1ii79.28 (5)C3—C2—C1116.5 (2)
O2ii—Na1—S1ii22.83 (4)C3—C2—C7119.9 (2)
O4—Na1—S1ii99.90 (4)C1—C2—C7123.7 (2)
O3ii—Na1—S1ii82.61 (5)C4—C3—C2122.7 (2)
O2iii—Na1—S1ii91.68 (5)C4—C3—H3118.6
O1—Na1—Na1iv137.40 (5)C2—C3—H3118.6
O3—Na1—Na1iv112.82 (5)C3—C4—C5120.1 (2)
O2ii—Na1—Na1iv47.85 (4)C3—C4—H4119.9
O4—Na1—Na1iv46.69 (4)C5—C4—H4119.9
O3ii—Na1—Na1iv114.48 (5)C4—C5—C6119.3 (2)
O2iii—Na1—Na1iv45.53 (4)C4—C5—H5120.3
S1ii—Na1—Na1iv69.87 (2)C6—C5—H5120.3
O1—Na1—Na1i54.03 (5)C5—C6—C1120.4 (2)
O3—Na1—Na1i34.99 (5)C5—C6—H6119.8
O2ii—Na1—Na1i115.82 (6)C1—C6—H6119.8
O4—Na1—Na1i74.73 (4)C2—C7—H7A109.5
O3ii—Na1—Na1i126.33 (6)C2—C7—H7B109.5
O2iii—Na1—Na1i144.54 (5)H7A—C7—H7B109.5
S1ii—Na1—Na1i113.86 (3)C2—C7—H7C109.5
Na1iv—Na1—Na1i119.16 (2)H7A—C7—H7C109.5
O1—Na1—Na1ii99.54 (6)H7B—C7—H7C109.5
O2—S1—O1—Na1−71.5 (3)O2ii—Na1—O4—Na1iv−41.12 (4)
N1—S1—O1—Na148.8 (2)O3ii—Na1—O4—Na1iv44.21 (14)
C1—S1—O1—Na1169.5 (2)O2iii—Na1—O4—Na1iv39.58 (4)
Na1i—S1—O1—Na1−73.0 (2)S1ii—Na1—O4—Na1iv−49.86 (2)
O3—Na1—O1—S149.7 (2)Na1i—Na1—O4—Na1iv−162.08 (4)
O2ii—Na1—O1—S151.7 (5)Na1ii—Na1—O4—Na1iv−54.89 (12)
O4—Na1—O1—S1133.4 (2)O1—S1—N1—Cl158.78 (12)
O3ii—Na1—O1—S1−69.7 (2)O2—S1—N1—Cl1−175.11 (9)
O2iii—Na1—O1—S1−146.7 (2)C1—S1—N1—Cl1−59.39 (13)
S1ii—Na1—O1—S1−1.5 (3)Na1i—S1—N1—Cl1146.70 (6)
Na1iv—Na1—O1—S1166.35 (18)O1—S1—C1—C63.1 (2)
Na1i—Na1—O1—S170.6 (2)O2—S1—C1—C6−119.99 (19)
Na1ii—Na1—O1—S1−37.8 (2)N1—S1—C1—C6127.3 (2)
O1—S1—O2—Na1i−2.28 (14)Na1i—S1—C1—C6−77.3 (2)
N1—S1—O2—Na1i−128.55 (10)O1—S1—C1—C2−177.07 (18)
C1—S1—O2—Na1i114.82 (10)O2—S1—C1—C259.8 (2)
O1—S1—O2—Na1v139.18 (19)N1—S1—C1—C2−52.9 (2)
N1—S1—O2—Na1v12.9 (2)Na1i—S1—C1—C2102.50 (18)
C1—S1—O2—Na1v−103.7 (2)C6—C1—C2—C30.0 (3)
Na1i—S1—O2—Na1v141.5 (3)S1—C1—C2—C3−179.79 (19)
O1—Na1—O3—Na1i30.30 (8)C6—C1—C2—C7179.9 (2)
O2ii—Na1—O3—Na1i−149.33 (8)S1—C1—C2—C70.2 (3)
O4—Na1—O3—Na1i−70.26 (7)C1—C2—C3—C4−0.9 (4)
O3ii—Na1—O3—Na1i113.32 (11)C7—C2—C3—C4179.1 (3)
O2iii—Na1—O3—Na1i−104.58 (18)C2—C3—C4—C51.3 (5)
S1ii—Na1—O3—Na1i−171.33 (7)C3—C4—C5—C6−0.6 (5)
Na1iv—Na1—O3—Na1i−108.70 (6)C4—C5—C6—C1−0.3 (5)
Na1ii—Na1—O3—Na1i130.07 (7)C2—C1—C6—C50.6 (4)
O1—Na1—O4—Na1iv149.64 (6)S1—C1—C6—C5−179.6 (2)
O3—Na1—O4—Na1iv−128.06 (5)
Symmetry codes: (i) −x+1/2, y+1/2, −z+1; (ii) −x+1/2, y−1/2, −z+1; (iii) x−1/2, y−1/2, z; (iv) −x, y, −z+1; (v) x+1/2, y+1/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H31···Cl1i0.83 (3)2.62 (3)3.4266 (19)167 (3)
O3—H32···N1vi0.77 (3)2.19 (3)2.951 (3)168 (3)
O4—H41···N1vii0.80 (3)2.19 (3)2.989 (2)176 (3)
Symmetry codes: (i) −x+1/2, y+1/2, −z+1; (vi) −x+1, y, −z+1; (vii) x−1/2, y+1/2, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H31···Cl1i0.83 (3)2.62 (3)3.4266 (19)167 (3)
O3—H32···N1ii0.77 (3)2.19 (3)2.951 (3)168 (3)
O4—H41···N1iii0.80 (3)2.19 (3)2.989 (2)176 (3)
Symmetry codes: (i) −x+1/2, y+1/2, −z+1; (ii) −x+1, y, −z+1; (iii) x−1/2, y+1/2, z.
Acknowledgements top

BTG thanks the Alexander von Humboldt Foundation, Bonn, Germany, for an extension of his research fellowship.

references
References top

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