Chlor­amine-B sesquihydrate

In the title compound, sodium N-chloro­benzene­sulfon­amide sesquihydrate, Na⁺·C₆H₅ClNO₂S⁻·1.5H₂O, the sodium ion exhibits octahedral coordination by O atoms from three water mol­ecules and by three sulfonyl O atoms of three different N-­chloro­benzene­sulfon­amide anions. A two-dimensional polymeric layer consists of units, each comprising two face-sharing octahedra which share four corners with four other such units, the layer running parallel to the ab plane. The water mol­ecules participate in hydrogen bonds of the types O—H...O, O—H...N and O—H...Cl.

S1. Comment

The chemistry of N-haloarenesulphonamidates (NHAS) like chloramine-T [N-chloro-p-toluenesulphonamide sodium salt trihydrate, (II)] and chloramine-B [N-chlorobenzenesulphonamide sodium salt hydrate, (I)] has made notable strides in diverse fields over the past century. They are good oxidants, efficient halogenators and versatile analytical and synthetic reagents. Their importance extends to wider scientific fields and technology as evident from their application to waste water treatment, seed and grain protection and the preparation of organic compounds. NHAS are also biologically and medicinally important and are used as antiseptics, disinfectants and fungicides. In industries, they are used in dyeing, bleaching of cellular fabrics and in the production of polymer latexes. \sch

Few crystallographic reports on NHAS compounds have been published except for that on compound (II) (Olmstead & Power, 1986), which investigated the interaction with the sodium ion and reported that the expected Na···N ion interaction was not present. Moreover, the structure revealed the sodium ion coordination as octahedral, formed by one of the sulphonate O atoms, water O atoms and the chlorine atom. These authors concluded that within the molecular anion the negative charge is located on the sulfonyl oxygen rather than on the nitrogen atom. As a part of our work on the solid state and solution studies on the NHAS compounds, we have determined the crystal structure of the title compound (I). It is also of importance to us to determine crystallographically and confirm the number of water molecules of hydration present on this compound.

Our results revealed that (I) is present as a sesqihydrate, in contrast to the trihydrate form found for (II). The bond distances involved in the phenyl ring are normal. The S═O distances in (I) [S1═O1 1.446 (3), S1═O2 1.420 (4) Å] are different from those observed in (II) [1.455 (2) and 1.439 (2) Å]. The N1—Cl1 distance of 1.742 (4) Å is also shorter than in (II). The coordination around the sodium ion is octahedral with all the four available oxygen atoms taking part and with the Na—O distances varying from 2.339 (4) to 2.486 (4) Å. We observe no interaction between the nitrogen and sodium in (I), in agreement with the results of Olmstead & Power (1986) for (II) (see below). Moreover, in (I), the sodium ion is coordinated only by the oxygen atoms from sulfonyl and water: the chlorine does not participate as in (II). As both the sulfonyl O atoms are coordinated to the sodium ions, our results establish that the negative charge is concentrated on the sulfonyl oxygen atoms rather than the nitrogen of the anion, as suggested for (II) by Olmstead & Power (1986).

It is worth mentioning the sodium environment and the lattice formation in the two NHAS compounds (I) and (II). The salt (II) forms dimers but these dimers are connected by the long Na···Cl contacts to form polymeric chains along the crystallographic b axis, whereas in (I) the two-dimensional polymeric structure is formed parallel to the ab plane. The latter situation arises because the octahedral coordination around the sodium ion exclusively involves the sulfonyl and the water oxygen atoms. The two-dimensional polymeric layer (Figure 2) consists of face-sharing octahedra formed by two sodium ions and these twin-octahedra are found to be corner-sharing with other twin-octahedra at four corners.

The chlorine atom does not have any interaction with the sodium ion, suggesting that there is a smaller negative charge on Cl1 in (I) compared with (II). The electron-releasing methyl group in (II) may act to block the movement of charge from the chlorine to the sulfonyl oxygen atoms keeping more negative charge on the chlorine than in (I). We believe that this explains the non-interaction between Cl and Na in the latter structure.

The crystal structure contains O—H···O, O—H···N and O—H···Cl hydrogen bonds involving the water molecules. Since the water H atoms could not be located, only the donor to acceptor distances are given: O1W···O2ⁱ, 3.125 (5) Å; O1W···N1ⁱ, 2.861 (5) Å; O2W···N1ⁱⁱ, 2.897 (5) Å and O1W···Cl1ⁱⁱ, 3.430 (4) Å; symmetry codes: (i) x − 1/2, y − 1/2, z and (ii) x, y − 1, z.

S2. Experimental

The compound was purchased from Fluka and single crystals were obtained by slow evaporation from a saturated solution in distilled water.

S3. Refinement

The hydrogen atoms in the benzene ring were geometrically fixed and allowed to ride on their respective carbon atoms. The H atoms of the water molecule could not be located from difference maps.

Computing details

Data collection: MolEN (Fair, 1990); cell refinement: MolEN; data reduction: MolEN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1983).

Figures

	Fig. 1. Displacement ellipsoid plot of (I) with numbering scheme, showing 50% probability ellipsoids. The H atoms on the water molecules could not be located and are therefore not shown. [symmetry codes: (i) 3/2 − x, y − 1/2, 1 − z; (ii) 2 − x, y, 1 − z; (iii) 3/2 − x, 1/2 + y, 1 − z].
	Fig. 2. The polymeric structure viewed along the b axis, showing the Na—O—Na connectivity along the a axis.

(I)

Crystal data

Na^+·C6H5ClNO2S^−·1.5H2O	Dx = 1.600 Mg m^−3
Mr = 240.63	Melting point = 443–446 K
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
a = 10.450 (3) Å	Cell parameters from 25 reflections
b = 6.623 (3) Å	θ = 8–22°
c = 14.828 (4) Å	µ = 0.61 mm^−1
β = 103.31 (3)°	T = 293 K
V = 998.7 (6) Å^3	Plate, colourless
Z = 4	0.2 × 0.2 × 0.08 mm
F(000) = 492

Data collection

Enraf Nonius CAD-4 diffractometer	902 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.020
Graphite monochromator	θmax = 25.0°, θmin = 2.8°
θ/2θ scans	h = −12→12
Absorption correction: ψ scan MolEN (Fair, 1990)	k = −6→7
Tmin = 0.87, Tmax = 0.98	l = −14→17
1536 measured reflections	3 standard reflections every 100 reflections
963 independent reflections	intensity decay: <2%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2) + (0.028P)^2 + 0.979P] where P = (Fo^2 + 2Fc^2)/3
S = 1.15	(Δ/σ)max = 0.001
963 reflections	Δρmax = 0.23 e Å^−3
123 parameters	Δρmin = −0.24 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (15)

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
Na1	0.86105 (17)	0.4336 (3)	0.53459 (13)	0.0333 (5)
Cl1	0.86652 (15)	1.0831 (2)	0.25532 (10)	0.0498 (4)
S1	0.84388 (10)	0.71690 (18)	0.33379 (7)	0.0240 (3)
O1	0.7159 (3)	0.7688 (6)	0.3488 (3)	0.0383 (9)
O2	0.9183 (3)	0.5806 (7)	0.3993 (2)	0.0345 (8)
N1	0.9393 (4)	0.9058 (6)	0.3382 (3)	0.0305 (9)
C1	0.8179 (5)	0.6095 (8)	0.2217 (3)	0.0345 (12)
C2	0.9222 (6)	0.5627 (14)	0.1851 (4)	0.0566 (18)
H2	1.0056	0.5915	0.2211	0.068*
C3	0.9156 (9)	0.4811 (13)	0.1041 (5)	0.074 (2)
H3	0.9890	0.4673	0.0792	0.088*
C4	0.7888 (12)	0.4146 (15)	0.0565 (5)	0.101 (4)
H4	0.7793	0.3461	0.0006	0.122*
C5	0.6784 (10)	0.4502 (19)	0.0920 (6)	0.100 (3)
H5	0.5954	0.4088	0.0597	0.119*
C6	0.6947 (7)	0.5500 (13)	0.1780 (4)	0.063 (2)
H6	0.6233	0.5743	0.2041	0.076*
O1W	0.6993 (3)	0.2581 (6)	0.4133 (2)	0.0368 (9)
O2W	1.0000	0.1644 (7)	0.5000	0.0341 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0283 (9)	0.0275 (12)	0.0456 (11)	−0.0026 (8)	0.0118 (8)	−0.0014 (10)
Cl1	0.0668 (9)	0.0299 (8)	0.0553 (8)	0.0058 (7)	0.0192 (7)	0.0125 (7)
S1	0.0257 (5)	0.0205 (6)	0.0265 (5)	−0.0005 (5)	0.0077 (4)	0.0008 (5)
O1	0.0334 (18)	0.024 (2)	0.062 (2)	0.0083 (15)	0.0201 (15)	0.0007 (17)
O2	0.0279 (17)	0.042 (2)	0.0332 (17)	−0.0004 (17)	0.0054 (13)	0.0074 (19)
N1	0.033 (2)	0.009 (2)	0.051 (2)	−0.0025 (17)	0.0120 (18)	0.0021 (19)
C1	0.056 (3)	0.016 (3)	0.029 (3)	−0.006 (2)	0.004 (2)	0.003 (2)
C2	0.072 (4)	0.069 (5)	0.034 (3)	−0.001 (4)	0.022 (3)	0.004 (4)
C3	0.128 (7)	0.055 (5)	0.050 (4)	0.014 (5)	0.046 (4)	0.004 (4)
C4	0.201 (11)	0.068 (7)	0.031 (4)	0.031 (8)	0.018 (5)	−0.019 (4)
C5	0.113 (7)	0.099 (8)	0.065 (5)	−0.045 (7)	−0.025 (5)	−0.005 (6)
C6	0.076 (4)	0.054 (5)	0.047 (4)	−0.015 (4)	−0.011 (3)	0.007 (4)
O1W	0.0262 (16)	0.035 (3)	0.050 (2)	−0.0071 (15)	0.0104 (14)	−0.0051 (18)
O2W	0.026 (2)	0.023 (3)	0.054 (3)	0.000	0.011 (2)	0.000

Geometric parameters (Å, º)

Na1—O1^i	2.339 (4)	S1—O2	1.420 (4)
Na1—O2	2.425 (4)	S1—O1	1.446 (3)
Na1—O2^ii	2.486 (4)	S1—N1	1.592 (4)
Na1—O1W	2.459 (4)	S1—C1	1.771 (5)
Na1—O1W^iii	2.416 (4)	C1—C6	1.359 (8)
Na1—O2W	2.428 (4)	C1—C2	1.361 (8)
Na1—Na1^ii	3.295 (3)	C2—C3	1.305 (9)
Na1—Na1^i	4.038 (2)	C3—C4	1.420 (13)
Na1—Na1^iii	4.038 (2)	C4—C5	1.395 (13)
Cl1—N1	1.742 (4)	C5—C6	1.411 (12)
O1^i—Na1—O1W^iii	91.08 (14)	O1W^iii—Na1—Na1^iii	34.40 (8)
O1^i—Na1—O2	172.42 (15)	O2—Na1—Na1^iii	72.41 (11)
O1W^iii—Na1—O2	92.30 (16)	O2W—Na1—Na1^iii	152.29 (10)
O1^i—Na1—O2W	97.92 (14)	O1W—Na1—Na1^iii	86.78 (12)
O1W^iii—Na1—O2W	159.02 (13)	O2^ii—Na1—Na1^iii	101.87 (12)
O2—Na1—O2W	81.17 (13)	Na1^ii—Na1—Na1^iii	114.65 (6)
O1^i—Na1—O1W	91.42 (14)	Na1^i—Na1—Na1^iii	110.17 (9)
O1W^iii—Na1—O1W	117.94 (11)	O2—S1—O1	115.2 (2)
O2—Na1—O1W	81.01 (13)	O2—S1—N1	103.4 (2)
O2W—Na1—O1W	80.91 (12)	O1—S1—N1	113.6 (2)
O1^i—Na1—O2^ii	109.69 (14)	O2—S1—C1	109.2 (3)
O1W^iii—Na1—O2^ii	79.19 (14)	O1—S1—C1	107.0 (2)
O2—Na1—O2^ii	77.63 (14)	N1—S1—C1	108.2 (2)
O2W—Na1—O2^ii	79.94 (13)	S1—O1—Na1^iii	135.4 (2)
O1W—Na1—O2^ii	153.17 (13)	S1—O2—Na1	128.34 (19)
O1^i—Na1—Na1^ii	135.08 (12)	S1—O2—Na1^ii	146.2 (2)
O1W^iii—Na1—Na1^ii	114.41 (9)	Na1—O2—Na1^ii	84.26 (13)
O2—Na1—Na1^ii	48.66 (9)	S1—N1—Cl1	109.5 (2)
O2W—Na1—Na1^ii	47.26 (9)	C6—C1—C2	120.2 (6)
O1W—Na1—Na1^ii	106.20 (11)	C6—C1—S1	119.2 (5)
O2^ii—Na1—Na1^ii	47.08 (9)	C2—C1—S1	120.1 (4)
O1^i—Na1—Na1^i	61.94 (10)	C3—C2—C1	125.7 (7)
O1W^iii—Na1—Na1^i	129.31 (11)	C2—C3—C4	115.6 (7)
O2—Na1—Na1^i	110.85 (13)	C5—C4—C3	121.2 (7)
O2W—Na1—Na1^i	71.39 (9)	C4—C5—C6	118.8 (7)
O1W—Na1—Na1^i	33.72 (10)	C1—C6—C5	118.1 (7)
O2^ii—Na1—Na1^i	147.95 (13)	Na1^i—O1W—Na1	111.87 (14)
Na1^ii—Na1—Na1^i	114.65 (6)	Na1^ii—O2W—Na1	85.48 (18)
O1^i—Na1—Na1^iii	107.16 (12)
O2—S1—O1—Na1^iii	63.3 (4)	O1—S1—C1—C6	−14.7 (6)
N1—S1—O1—Na1^iii	−55.7 (4)	N1—S1—C1—C6	−137.4 (5)
C1—S1—O1—Na1^iii	−175.1 (3)	O2—S1—C1—C2	−60.7 (6)
O1—S1—O2—Na1	−2.1 (4)	O1—S1—C1—C2	174.0 (5)
N1—S1—O2—Na1	122.4 (3)	N1—S1—C1—C2	51.3 (6)
C1—S1—O2—Na1	−122.5 (3)	C6—C1—C2—C3	7.9 (12)
O1—S1—O2—Na1^ii	−164.2 (4)	S1—C1—C2—C3	179.1 (7)
N1—S1—O2—Na1^ii	−39.6 (5)	C1—C2—C3—C4	−8.1 (13)
C1—S1—O2—Na1^ii	75.4 (5)	C2—C3—C4—C5	4.8 (14)
O1^i—Na1—O2—S1	67.4 (14)	C3—C4—C5—C6	−1.5 (16)
O1W^iii—Na1—O2—S1	−49.1 (3)	C2—C1—C6—C5	−3.7 (11)
O2W—Na1—O2—S1	151.0 (3)	S1—C1—C6—C5	−175.0 (7)
O1W—Na1—O2—S1	68.9 (3)	C4—C5—C6—C1	0.9 (14)
O2^ii—Na1—O2—S1	−127.5 (2)	O1^i—Na1—O1W—Na1^i	−27.82 (16)
Na1^ii—Na1—O2—S1	−170.1 (4)	O1W^iii—Na1—O1W—Na1^i	−119.8 (2)
Na1^i—Na1—O2—S1	84.9 (3)	O2—Na1—O1W—Na1^i	152.38 (17)
Na1^iii—Na1—O2—S1	−20.6 (3)	O2W—Na1—O1W—Na1^i	69.97 (14)
O1^i—Na1—O2—Na1^ii	−122.5 (12)	O2^ii—Na1—O1W—Na1^i	114.9 (3)
O1W^iii—Na1—O2—Na1^ii	121.04 (15)	Na1^ii—Na1—O1W—Na1^i	110.32 (12)
O2W—Na1—O2—Na1^ii	−38.92 (11)	Na1^iii—Na1—O1W—Na1^i	−134.93 (14)
O1W—Na1—O2—Na1^ii	−121.02 (14)	O1^i—Na1—O2W—Na1^ii	−147.65 (13)
O2^ii—Na1—O2—Na1^ii	42.64 (19)	O1W^iii—Na1—O2W—Na1^ii	−33.1 (3)
Na1^i—Na1—O2—Na1^ii	−105.04 (10)	O2—Na1—O2W—Na1^ii	39.95 (9)
Na1^iii—Na1—O2—Na1^ii	149.52 (14)	O1W—Na1—O2W—Na1^ii	122.18 (11)
O2—S1—N1—Cl1	176.1 (2)	O2^ii—Na1—O2W—Na1^ii	−38.94 (9)
O1—S1—N1—Cl1	−58.3 (3)	Na1^i—Na1—O2W—Na1^ii	155.57 (9)
C1—S1—N1—Cl1	60.3 (3)	Na1^iii—Na1—O2W—Na1^ii	57.45 (19)
O2—S1—C1—C6	110.6 (5)

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