Sodium N-bromo-4-chloro-2-methyl­benzene­sulfonamidate sesquihydrate

The title compound, Na⁺·C₇H₆BrClNO₂S⁻·1.5H₂O, crystallizes with two cations, two anions and three water mol­ecules in the asymmetric unit; its structure is similar to that of sodium N-bromo­benzene­sulfonamidate and sodium N-bromo-4-chlorobenzene­sulfonamidate. The sodium ion shows octa­hedral coordination by three O atoms of water mol­ecules and by three sulfonyl O atoms of three different N-bromo-4-chloro-2-methyl­benzene­sulfonamide anions. There is no inter­action between the N atoms and sodium ions in the structure. The S—N distance of 1.584 (4) Å is consistent with an S=N double bond. The crystal structure is stabilized by O—H...·N hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 300 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.070
• wR factor = 0.091
• Data-to-parameter ratio = 14.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.95

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.21 Ratio

Alert level G
ABSTM02_ALERT_3_G  The ratio of expected to reported Tmax/Tmin(RR) is > 1.50
            Tmin and Tmax reported:      0.196     0.632
            Tmin and Tmax expected:      0.110     0.666
            RR =      1.875
            Please check that your absorption correction is appropriate.
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          4

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   3 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
   4 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

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S1. Comment

The chemistry of N-halo-arylsulfonamides is of interest due to their diverse characteristics (Usha & Gowda, 2006). In the present work, the structure of sodium N-bromo-2-methyl-4-chloro-benzenesulfonamidate (NaNB2M4CBSA) has been determined to explore the substituent effects on the solid state structures of arylsulfonamides and N-halo arylsulfonamidates (Gowda et al., 2007a, b, c, d). The structure of NaNB2M4CBSA (Fig. 1) resembles those of sodium N-chloro-2-methyl- 4-chloro-benzenesulfonamidate (NaNC2M4CBSA)(Gowda, Srilatha et al., 2007), sodium N-bromo-benzenesulfonamidate (NaNBBSA) (Gowda, Usha et al., 2007) and sodium N-bromo-4-chloro-benzenesulfonamidate (NaNB4CBSA)(Gowda, Kožíšek et al., 2007) and other sodium N-chloro-arylsulfonamidates (George et al., 2000; Gowda, Jyothi et al., 2007). NaNB2M4CBSA crystallizes with two cations, two anions and three water molecules in the asymmetric unit. The sodium ion shows octahedral coordination by three O atoms of water molecules and by three sulfonyl O atoms of three different N-bromo-2-methyl- 4-chloro-benzenesulfonamide anions. There is no interaction between the nitrogen and sodium ions in the molecule. The S—N distances of N1—S1, 1.584 (4) Å is consistent with a S—N double bond and in agreement with those observed with NaNBBSA, NaNB4CBSA and NaNC2M4CBSA. O—H···N hydrogen bonding interactions result in the formation of a polymeric layer structure running parallel to the (0 0 1) plane (Table 1, Fig. 2).

Related literature

For related literature, see: George et al. (2000); Gowda & Usha (2003); Gowda, Jyothi et al. (2007); Gowda, Kožíšek et al. (2007); Gowda, Usha et al. (2007); Gowda, Srilatha et al. (2007); Usha & Gowda (2006).

S2. Experimental

The title compound was prepared according to the literature method (Gowda & Usha, 2003). The purity of the compound was checked by determining its melting point. It was characterized by recording its infrared and NMR spectra (Gowda & Usha, 2003). Single crystals of the title compound were obtained from its aqueous solution and used for X-ray diffraction studies at room temperature.

S3. Refinement

All H atoms attached to C and O atoms were positioned geometrically and treated as riding with C—H = 0.93 Å (aromatic) and C—H = 0.96 Å (methyl). H atoms of water molecules were refined using restraint on O—H bond length 0.85 (3) Å and restraint on their mutual distance 1.45 (4) Å. All H atoms have U_iso(H) = 1.2 U_eq(C).

Regarding the discrepancy with reflection numbers, the number of reflections used in the refinement (2049) differs from the total number of reflections (2231) because of applying resolution shel 0.82 to 3.5 Å.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2002); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2003) and WinGX (Farrugia, 1999).

Figures

	Fig. 1. ORTEP view of the title compound showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Na O interactions are shown as dashed lines. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing diagram of (I) showing hydrogen bonds O3w—H31···N1(i) and O4w—-H41···N1(ii). Symmetry codes: (i) -x, y, -z + 1/2; (ii) x + 1/2, y - 1/2, z. H atoms not involved in hydrogen bonds have been omitted for clarity.

Sodium N-bromo-4-chloro-2-methylbenzenesulfonamidate sesquihydrate

Crystal data

Na^+·C7H6BrClNO2S^−·1.5H2O	F(000) = 1320
Mr = 333.56	Dx = 1.929 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2337 reflections
a = 11.055 (2) Å	θ = 2.5–26.4°
b = 6.7804 (14) Å	µ = 4.06 mm^−1
c = 30.727 (6) Å	T = 300 K
β = 98.84 (3)°	Block, pale yellow
V = 2275.9 (8) Å^3	0.58 × 0.48 × 0.10 mm
Z = 8

Data collection

Oxford Diffraction Xcalibur CCD diffractometer	2066 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
Rotation method data acquisition using ωand φ scans	θmax = 26.4°, θmin = 4.6°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2003) using a multifaceted crystal model (Clark & Reid, 1995)	h = −13→13
Tmin = 0.196, Tmax = 0.632	k = −5→8
6929 measured reflections	l = −38→38
2231 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.070	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.21	w = 1/[σ^2(Fo^2) + (0.0001P)^2 + 21.0707P] where P = (Fo^2 + 2Fc^2)/3
2049 reflections	(Δ/σ)max < 0.001
142 parameters	Δρmax = 0.46 e Å^−3
4 restraints	Δρmin = −0.68 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.6736 (4)	−0.3263 (7)	0.38143 (14)	0.0199 (10)
C2	0.5880 (4)	−0.3838 (7)	0.40799 (15)	0.0236 (11)
C3	0.6320 (5)	−0.4536 (8)	0.45013 (17)	0.0331 (13)
H3	0.5773	−0.4954	0.4684	0.040*
C4	0.7558 (6)	−0.4611 (8)	0.46494 (18)	0.0371 (14)
C5	0.8403 (5)	−0.4086 (9)	0.43893 (19)	0.0399 (14)
H5	0.9237	−0.4177	0.4493	0.048*
C6	0.7983 (5)	−0.3415 (9)	0.39678 (18)	0.0328 (12)
H6	0.8543	−0.3060	0.3785	0.039*
C7	0.4501 (4)	−0.3698 (8)	0.39352 (17)	0.0286 (12)
H7A	0.4086	−0.4212	0.4163	0.043*
H7B	0.4274	−0.4450	0.3671	0.043*
H7C	0.4274	−0.2343	0.3881	0.043*
N1	0.5374 (4)	−0.0524 (6)	0.32821 (13)	0.0242 (9)
O1	0.5613 (3)	−0.3788 (5)	0.30020 (11)	0.0292 (8)
O2	0.7460 (3)	−0.1762 (6)	0.31310 (12)	0.0339 (9)
O3W	0.7076 (3)	−0.1898 (6)	0.20927 (12)	0.0341 (9)
H31	0.6490	−0.1190	0.2001	0.051*
H32	0.7490	−0.2170	0.1886	0.051*
O4W	1.0000	−0.2798 (8)	0.2500	0.0337 (12)
H41	1.0070	−0.3652	0.2695	0.050*
S1	0.63097 (10)	−0.22859 (19)	0.32722 (4)	0.0210 (3)
Cl11	0.80599 (19)	−0.5332 (3)	0.51941 (5)	0.0600 (5)
Br1	0.60784 (5)	0.15106 (9)	0.366127 (17)	0.03129 (16)
Na1	0.85419 (18)	−0.0126 (3)	0.26251 (7)	0.0323 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.023 (2)	0.016 (3)	0.020 (2)	0.000 (2)	−0.0012 (18)	−0.003 (2)
C2	0.028 (2)	0.020 (3)	0.022 (2)	0.000 (2)	0.004 (2)	−0.002 (2)
C3	0.045 (3)	0.029 (3)	0.026 (3)	−0.003 (3)	0.008 (2)	0.004 (2)
C4	0.052 (4)	0.023 (3)	0.030 (3)	0.001 (3)	−0.017 (3)	0.002 (2)
C5	0.030 (3)	0.041 (4)	0.043 (3)	0.007 (3)	−0.011 (3)	0.003 (3)
C6	0.026 (2)	0.032 (3)	0.039 (3)	0.004 (3)	0.002 (2)	0.001 (3)
C7	0.027 (2)	0.030 (3)	0.031 (3)	−0.006 (2)	0.009 (2)	0.004 (2)
N1	0.025 (2)	0.024 (2)	0.0217 (19)	0.0010 (19)	−0.0035 (16)	0.0016 (18)
O1	0.0325 (18)	0.031 (2)	0.0236 (17)	−0.0036 (17)	0.0021 (14)	−0.0051 (15)
O2	0.0286 (18)	0.042 (2)	0.034 (2)	−0.0017 (18)	0.0140 (16)	0.0030 (18)
O3W	0.0277 (18)	0.039 (3)	0.035 (2)	0.0013 (17)	0.0058 (15)	−0.0010 (18)
O4W	0.049 (3)	0.027 (3)	0.024 (2)	0.000	0.001 (2)	0.000
S1	0.0214 (6)	0.0237 (7)	0.0179 (5)	0.0006 (5)	0.0031 (4)	0.0003 (5)
Cl11	0.0932 (13)	0.0454 (11)	0.0324 (8)	−0.0005 (10)	−0.0190 (8)	0.0083 (7)
Br1	0.0338 (3)	0.0274 (3)	0.0330 (3)	−0.0024 (3)	0.0062 (2)	−0.0056 (2)
Na1	0.0316 (11)	0.0338 (12)	0.0330 (11)	−0.0065 (10)	0.0101 (9)	−0.0003 (10)

Geometric parameters (Å, º)

C1—C6	1.390 (6)	N1—Br1	1.894 (4)
C1—C2	1.397 (6)	O1—S1	1.457 (4)
C1—S1	1.788 (5)	O1—Na1^i	2.441 (4)
C2—C3	1.394 (7)	O2—S1	1.449 (3)
C2—C7	1.524 (7)	O2—Na1	2.377 (4)
C3—C4	1.375 (8)	O3W—Na1	2.436 (4)
C3—H3	0.9300	O3W—Na1^i	2.488 (4)
C4—C5	1.366 (8)	O3W—H31	0.8208
C4—Cl11	1.750 (5)	O3W—H32	0.8585
C5—C6	1.384 (8)	O4W—Na1	2.494 (4)
C5—H5	0.9300	O4W—H41	0.8283
C6—H6	0.9300	S1—Na1^i	3.388 (2)
C7—H7A	0.9600	Na1—O1^ii	2.568 (4)
C7—H7B	0.9600	Na1—S1^iii	3.388 (2)
C7—H7C	0.9600	Na1—Na1^iv	3.427 (4)
N1—S1	1.584 (4)	Na1—Na1^i	4.105 (3)
C6—C1—C2	120.4 (4)	C1—S1—Na1^i	120.60 (16)
C6—C1—S1	116.7 (4)	O2—Na1—O3W	81.90 (14)
C2—C1—S1	122.9 (3)	O2—Na1—O1^iii	168.96 (16)
C3—C2—C1	117.8 (4)	O3W—Na1—O1^iii	87.06 (14)
C3—C2—C7	118.9 (4)	O2—Na1—O3W^iii	89.42 (14)
C1—C2—C7	123.3 (4)	O3W—Na1—O3W^iii	118.56 (11)
C4—C3—C2	120.5 (5)	O1^iii—Na1—O3W^iii	96.15 (14)
C4—C3—H3	119.7	O2—Na1—O4W	99.44 (14)
C2—C3—H3	119.7	O3W—Na1—O4W	85.24 (12)
C5—C4—C3	122.1 (5)	O1^iii—Na1—O4W	79.25 (12)
C5—C4—Cl11	119.2 (4)	O3W^iii—Na1—O4W	155.70 (14)
C3—C4—Cl11	118.7 (5)	O2—Na1—O1^ii	111.94 (14)
C4—C5—C6	118.1 (5)	O3W—Na1—O1^ii	158.82 (14)
C4—C5—H5	120.9	O1^iii—Na1—O1^ii	78.58 (14)
C6—C5—H5	120.9	O3W^iii—Na1—O1^ii	78.81 (13)
C5—C6—C1	120.9 (5)	O4W—Na1—O1^ii	76.89 (12)
C5—C6—H6	119.5	O2—Na1—S1^iii	152.84 (12)
C1—C6—H6	119.5	O3W—Na1—S1^iii	81.03 (11)
C2—C7—H7A	109.5	O3W^iii—Na1—S1^iii	80.44 (10)
C2—C7—H7B	109.5	O4W—Na1—S1^iii	100.03 (9)
H7A—C7—H7B	109.5	O1^ii—Na1—S1^iii	90.86 (10)
C2—C7—H7C	109.5	O2—Na1—Na1^iv	137.06 (13)
H7A—C7—H7C	109.5	O3W—Na1—Na1^iv	113.64 (12)
H7B—C7—H7C	109.5	O1^iii—Na1—Na1^iv	48.38 (10)
S1—N1—Br1	110.7 (2)	O3W^iii—Na1—Na1^iv	113.35 (10)
S1—O1—Na1^i	118.48 (19)	O4W—Na1—Na1^iv	46.60 (10)
S1—O1—Na1^v	149.3 (2)	O1^ii—Na1—Na1^iv	45.30 (9)
Na1^i—O1—Na1^v	86.31 (13)	S1^iii—Na1—Na1^iv	69.67 (6)
S1—O2—Na1	149.7 (2)	O2—Na1—Na1^i	54.02 (10)
Na1—O3W—Na1^i	112.95 (15)	O3W—Na1—Na1^i	33.93 (10)
Na1—O3W—H31	110.6	O1^iii—Na1—Na1^i	115.51 (12)
Na1^i—O3W—H31	112.9	O3W^iii—Na1—Na1^i	127.99 (12)
Na1—O3W—H32	103.2	O4W—Na1—Na1^i	74.25 (9)
Na1^i—O3W—H32	106.0	O1^ii—Na1—Na1^i	144.31 (12)
H31—O3W—H32	110.7	S1^iii—Na1—Na1^i	114.39 (9)
Na1^iv—O4W—Na1	86.81 (19)	Na1^iv—Na1—Na1^i	118.57 (6)
Na1^iv—O4W—H41	129.0	O2—Na1—Na1^iii	100.58 (12)
Na1—O4W—H41	112.8	O3W—Na1—Na1^iii	89.16 (13)
O2—S1—O1	114.3 (2)	O1^iii—Na1—Na1^iii	79.46 (10)
O2—S1—N1	115.3 (2)	O3W^iii—Na1—Na1^iii	33.12 (9)
O1—S1—N1	104.4 (2)	O4W—Na1—Na1^iii	158.22 (11)
O2—S1—C1	104.6 (2)	O1^ii—Na1—Na1^iii	103.23 (10)
O1—S1—C1	108.2 (2)	S1^iii—Na1—Na1^iii	58.26 (5)
N1—S1—C1	109.9 (2)	Na1^iv—Na1—Na1^iii	118.57 (6)
O2—S1—Na1^i	75.00 (16)	Na1^i—Na1—Na1^iii	111.37 (10)
N1—S1—Na1^i	123.91 (16)

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x+1/2, y+1/2, z; (iii) −x+3/2, y+1/2, −z+1/2; (iv) −x+2, y, −z+1/2; (v) x−1/2, y−1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3W—H31···N1^vi	0.82	2.16	2.927 (5)	156
O4W—H41···N1^vii	0.83	2.19	3.010 (5)	171

Symmetry codes: (vi) −x+1, y, −z+1/2; (vii) x+1/2, y−1/2, z.