Sodium N-bromo-2,4-dichloro­benzene­sulfonamidate sesquihydrate

The title compound [systematic name: μ₂-aqua-diaquabis(μ₃-N-bromo-2,4-dichloro­benzene­sulfonamidato)disodium(I)], Na⁺·C₆H₃BrCl₂NO₂S⁻·1.5H₂O, crystallizes with two sodium cations, two N-bromo-2,4-dichloro­benzene­sulfonamidate anions and three water mol­ecules in the asymmetric unit, similar to sodium N-bromo­benzene­sulfon­amidate, sodium N-bromo-4-chloro­benzene­sulfon­amidate and sodium N-bromo-2-methyl-4-chloro­benzene­sulfon­amidate. A crystallographic twofold rotation axis passes through one of the water molecules. There is no inter­action between the nitro­gen atoms and sodium ions. The sodium ion shows octa­hedral coordination by three O atoms of water mol­ecules and by three sulfonyl O atoms of three different N-bromo-2,4-dichloro­benzene­sulfonamidate anions. The S—N distance of 1.590 (6) Å is consistent with an S=N double bond. The Na⁺ ion coordination in the structure gives rise to several hydrogen bonds between water mol­ecules and N or Br atoms.

Key indicators

• Single-crystal X-ray study
• T = 304 K
• Mean [sigma](C-C) = 0.011 Å
• R factor = 0.062
• wR factor = 0.177
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         11
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.37 Ratio

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          5

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

   0 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
   2 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-bromo-arylsulfonamides is of interest due to their diverse characteristics (Usha & Gowda, 2006). In the present work, the structure of sodium N-bromo-2,4-dichloro-benzenesulfonamidate (NaNB24DCBSA) has been determined to explore the substituent effects on the solid state structures of arylsulfonamides and N-halo arylsulfonamidates (Gowda et al., 2007a,b; Gowda, Savitha et al. 2007; Gowda, Usha et al., 2007). The structure of NaNB24DCBSA (Fig. 1) is similar to those of sodium N-chloro-2,4-dichloro-benzenesulfonamidate (NaNC24DCBSA) (Gowda, Savitha et al., 2007), sodium N-bromo-benzenesulfonamidate (NaNBBSA) (Gowda et al., 2007d), sodium N-bromo-4-chloro- benzenesulfonamidate (NaNB4CBSA) (Gowda et al., 2007a) and sodium N-bromo-2-methyl-4-chloro-benzenesulfonamidate (Gowda et al., 2007b). NaNB24DCBSA crystallizes with two sodium cations, two N-bromo-2,4-dichloro-benzenesulfonamidate anions and three water molecules in the asymmetric unit. One of the water molecules is located on a special position. Further, the sodium ion shows octahedral coordination by three O atoms of three different water molecules and by three sulfonyl O atoms of three different N-bromo-2,4-dichloro-benzenesulfonamidate anions. There is no interaction between the nitrogen and sodium ions in the molecule. The S—N distances of N1—S1, 1.590 (6)Å is consistent with a S—N double bond and in agreement with those observed with NaNBBSA, NaNB4CBSA, NaNB2M4CBSA and NaNC24DCBSA. The Na+ ion coordination in the structure gives rise to several hydrogen bonding between water hydrogen, oxygen and nitrogen or bromine atoms in the molecule (Table 1).

Related literature

For related literature, see: Gowda et al. (2007a,b); Gowda, Savitha et al. (2007); Gowda & Usha (2003); Gowda, Usha 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

Crystals of the tittle compound are monoclinic; space group C2/c. The crystal under study was refined as twinned. Non-merohedral twinning was detected and analysed using TWINROTM routine of the WinGX package. 26 percent of total 3121 reflections were found overlapped with rotation matrix (0.853 0.000 - 0.147) (0.000 - 1.000 0.000) (-1.853 0.000 - 0.853) Using this twin matrix a HKLF5 file was generated which was subsequently used in the SHELXL97 refinement of the structure. Fractional contributions of the twin domains were refined to 76 and 24 percent. Benzene H atoms were positioned geometrically and refined using a riding model with C—H = 0.93 Å. H atoms of water molecules (O3w, O4w) were located in a difference map and refined with restraint on bond length O—H = 0.85 (5)Å and on mutual distance of H41, H42 H atoms 2.77 (8) Å. All H atoms have U_iso(H) = 1.2 U_eq(O,C).

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 (Sheldrick, 1997), PLATON (Spek, 2003) and WinGX (Farrugia, 1999).

Figures

Fig. 1. ORTEP view of the title compound showing the atom labelling scheme. H atoms are represented as small spheres of arbitrary radii. Water molecule Ow3 is located on a two fold axis (1/2, 1/2 + y, 1/4). Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) 1 - x, y, 1/2 - z].

Sodium N-bromo-2,4-dichlorobenzenesulfonamidate sesquihydrate

Crystal data

Na^+·C6H3BrCl2NO2S^−·1.5H2O	F(000) = 1384
Mr = 707.96	Dx = 2.067 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2198 reflections
a = 11.1170 (15) Å	θ = 2.5–26.4°
b = 6.780 (1) Å	µ = 4.29 mm^−1
c = 30.567 (4) Å	T = 304 K
β = 99.124 (15)°	Plate, yellow
V = 2274.8 (6) Å^3	0.60 × 0.33 × 0.11 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur CCD diffractometer	2094 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.065
Rotation method data acquisition using ω and phi scans	θmax = 26.0°, θmin = 5.2°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2003; Clark & Reid, 1995)	h = −13→13
Tmin = 0.195, Tmax = 0.627	k = −8→8
3121 measured reflections	l = −36→37
2200 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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.177	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0925P)^2 + 47.8P] where P = (Fo^2 + 2Fc^2)/3
2200 reflections	(Δ/σ)max = 0.002
148 parameters	Δρmax = 1.06 e Å^−3
5 restraints	Δρmin = −1.00 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	0.3275 (6)	0.1809 (9)	0.1192 (2)	0.0183 (12)
C2	0.4084 (7)	0.1212 (10)	0.0912 (2)	0.0219 (13)
C3	0.3665 (8)	0.0504 (11)	0.0492 (2)	0.0319 (17)
H3	0.4213	0.0098	0.031	0.038*
C4	0.2426 (8)	0.0402 (11)	0.0345 (3)	0.0354 (18)
C5	0.1588 (7)	0.0946 (12)	0.0613 (3)	0.0354 (18)
H5	0.0755	0.0843	0.0514	0.042*
C6	0.2028 (6)	0.1643 (11)	0.1032 (3)	0.0279 (16)
H6	0.1475	0.2018	0.1215	0.033*
N1	0.4651 (5)	0.4579 (8)	0.17108 (18)	0.0203 (11)
O1	0.4400 (5)	0.1331 (7)	0.20070 (16)	0.0254 (10)
O2	0.2573 (5)	0.3374 (8)	0.18720 (17)	0.0292 (12)
O3W	0.5	−0.2706 (11)	0.25	0.0289 (15)
H31	0.529 (8)	−0.332 (12)	0.275 (2)	0.035*
O4W	0.7099 (5)	0.3237 (9)	0.20865 (19)	0.0318 (12)
H41	0.745 (8)	0.302 (11)	0.187 (2)	0.038*
H42	0.647 (5)	0.369 (10)	0.196 (3)	0.038*
S1	0.37118 (14)	0.2828 (2)	0.17335 (5)	0.0174 (4)
Na1	0.6445 (3)	−0.0014 (4)	0.23596 (10)	0.0287 (6)
Cl1	0.56406 (16)	0.1333 (3)	0.10764 (7)	0.0358 (5)
Cl2	0.1903 (3)	−0.0354 (3)	−0.01953 (7)	0.0553 (7)
Br1	0.39296 (7)	0.65862 (11)	0.13323 (2)	0.0301 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.019 (3)	0.018 (3)	0.018 (3)	−0.003 (2)	0.001 (2)	0.000 (2)
C2	0.033 (4)	0.019 (3)	0.014 (3)	0.003 (3)	0.006 (3)	0.000 (2)
C3	0.055 (5)	0.018 (3)	0.024 (4)	0.006 (3)	0.010 (3)	−0.008 (3)
C4	0.051 (5)	0.016 (3)	0.033 (4)	−0.004 (3)	−0.010 (4)	−0.003 (3)
C5	0.029 (4)	0.033 (4)	0.038 (4)	−0.005 (3)	−0.012 (3)	−0.003 (3)
C6	0.020 (3)	0.031 (4)	0.032 (4)	−0.004 (3)	−0.001 (3)	0.001 (3)
N1	0.019 (3)	0.019 (3)	0.022 (3)	0.000 (2)	0.003 (2)	0.003 (2)
O1	0.029 (2)	0.024 (2)	0.023 (2)	0.002 (2)	0.001 (2)	0.0059 (19)
O2	0.023 (2)	0.041 (3)	0.027 (3)	0.007 (2)	0.014 (2)	−0.005 (2)
O3W	0.041 (4)	0.025 (4)	0.018 (3)	0	−0.003 (3)	0
O4W	0.022 (3)	0.038 (3)	0.036 (3)	0.002 (2)	0.005 (2)	0.000 (2)
S1	0.0200 (7)	0.0177 (7)	0.0153 (7)	0.0002 (6)	0.0051 (6)	0.0010 (6)
Na1	0.0290 (14)	0.0299 (15)	0.0292 (15)	0.0037 (12)	0.0107 (12)	−0.0006 (12)
Cl1	0.0228 (8)	0.0442 (11)	0.0429 (11)	0.0029 (7)	0.0124 (7)	−0.0097 (9)
Cl2	0.0911 (19)	0.0350 (11)	0.0295 (10)	0.0023 (12)	−0.0216 (11)	−0.0077 (8)
Br1	0.0347 (5)	0.0246 (4)	0.0323 (4)	0.0024 (3)	0.0090 (3)	0.0059 (3)

Geometric parameters (Å, º)

C1—C2	1.397 (9)	O1—Na1	2.526 (6)
C1—C6	1.399 (9)	O2—S1	1.445 (5)
C1—S1	1.788 (7)	O2—Na1^ii	2.363 (5)
C2—C3	1.380 (10)	O3W—Na1	2.513 (6)
C2—Cl1	1.726 (7)	O3W—Na1^i	2.513 (6)
C3—C4	1.381 (12)	O3W—H31	0.88 (5)
C3—H3	0.93	O4W—Na1^iii	2.454 (6)
C4—C5	1.386 (13)	O4W—Na1	2.505 (7)
C4—Cl2	1.739 (8)	O4W—H41	0.82 (5)
C5—C6	1.378 (11)	O4W—H42	0.80 (5)
C5—H5	0.93	Na1—O2^iv	2.363 (5)
C6—H6	0.93	Na1—O4W^v	2.454 (6)
N1—S1	1.590 (6)	Na1—O1^i	2.458 (6)
N1—Br1	1.881 (5)	Na1—Na1^i	3.455 (5)
O1—S1	1.453 (5)	Na1—Na1^iii	4.134 (3)
O1—Na1^i	2.458 (6)	Na1—Na1^v	4.134 (3)
C2—C1—C6	117.4 (6)	N1—S1—C1	109.4 (3)
C2—C1—S1	124.9 (5)	O2^iv—Na1—O4W^v	81.6 (2)
C6—C1—S1	117.7 (5)	O2^iv—Na1—O1^i	167.5 (2)
C3—C2—C1	121.1 (7)	O4W^v—Na1—O1^i	85.9 (2)
C3—C2—Cl1	117.6 (6)	O2^iv—Na1—O4W	89.2 (2)
C1—C2—Cl1	121.4 (5)	O4W^v—Na1—O4W	117.42 (17)
C2—C3—C4	119.5 (7)	O1^i—Na1—O4W	95.9 (2)
C2—C3—H3	120.2	O2^iv—Na1—O3W	100.9 (2)
C4—C3—H3	120.2	O4W^v—Na1—O3W	84.32 (17)
C3—C4—C5	121.5 (7)	O1^i—Na1—O3W	78.48 (17)
C3—C4—Cl2	119.4 (7)	O4W—Na1—O3W	157.4 (2)
C5—C4—Cl2	119.1 (6)	O2^iv—Na1—O1	115.4 (2)
C6—C5—C4	117.9 (7)	O4W^v—Na1—O1	156.8 (2)
C6—C5—H5	121.1	O1^i—Na1—O1	76.8 (2)
C4—C5—H5	121.1	O4W—Na1—O1	80.15 (19)
C5—C6—C1	122.6 (7)	O3W—Na1—O1	77.22 (17)
C5—C6—H6	118.7	O2^iv—Na1—Na1^i	139.86 (18)
C1—C6—H6	118.7	O4W^v—Na1—Na1^i	111.49 (17)
S1—N1—Br1	110.4 (3)	O1^i—Na1—Na1^i	46.95 (13)
S1—O1—Na1^i	118.7 (3)	O4W—Na1—Na1^i	114.39 (14)
S1—O1—Na1	148.6 (3)	O3W—Na1—Na1^i	46.58 (13)
Na1^i—O1—Na1	87.74 (18)	O1—Na1—Na1^i	45.31 (13)
S1—O2—Na1^ii	151.7 (3)	O2^iv—Na1—Na1^iii	99.78 (18)
Na1—O3W—Na1^i	86.8 (3)	O4W^v—Na1—Na1^iii	87.84 (18)
Na1—O3W—H31	109 (6)	O1^i—Na1—Na1^iii	78.90 (14)
Na1^i—O3W—H31	111 (6)	O4W—Na1—Na1^iii	33.14 (13)
Na1^iii—O4W—Na1	112.9 (2)	O3W—Na1—Na1^iii	156.51 (15)
Na1^iii—O4W—H41	106 (6)	O1—Na1—Na1^iii	103.59 (13)
Na1—O4W—H41	108 (5)	Na1^i—Na1—Na1^iii	117.89 (8)
Na1^iii—O4W—H42	125 (6)	O2^iv—Na1—Na1^v	53.92 (15)
Na1—O4W—H42	103 (5)	O4W^v—Na1—Na1^v	33.93 (15)
H41—O4W—H42	100 (10)	O1^i—Na1—Na1^v	114.58 (17)
O2—S1—O1	114.6 (3)	O4W—Na1—Na1^v	127.28 (18)
O2—S1—N1	115.7 (3)	O3W—Na1—Na1^v	74.09 (12)
O1—S1—N1	104.9 (3)	O1—Na1—Na1^v	145.79 (16)
O2—S1—C1	104.4 (3)	Na1^i—Na1—Na1^v	117.89 (8)
O1—S1—C1	107.7 (3)	Na1^iii—Na1—Na1^v	110.17 (13)
C6—C1—C2—C3	0.5 (10)	C6—C1—S1—N1	−127.7 (5)
S1—C1—C2—C3	−177.7 (5)	Na1^iii—O4W—Na1—O2^iv	−109.4 (3)
C6—C1—C2—Cl1	−179.5 (5)	Na1^iii—O4W—Na1—O4W^v	−29.3 (3)
S1—C1—C2—Cl1	2.3 (9)	Na1^iii—O4W—Na1—O1^i	59.1 (2)
C1—C2—C3—C4	0.7 (11)	Na1^iii—O4W—Na1—O3W	133.3 (4)
Cl1—C2—C3—C4	−179.3 (6)	Na1^iii—O4W—Na1—O1	134.6 (3)
C2—C3—C4—C5	−1.8 (12)	Na1^iii—O4W—Na1—Na1^i	104.2 (2)
C2—C3—C4—Cl2	176.3 (5)	Na1^iii—O4W—Na1—Na1^v	−68.1 (3)
C3—C4—C5—C6	1.6 (12)	Na1^i—O3W—Na1—O2^iv	−152.8 (2)
Cl2—C4—C5—C6	−176.5 (6)	Na1^i—O3W—Na1—O4W^v	126.95 (18)
C4—C5—C6—C1	−0.3 (12)	Na1^i—O3W—Na1—O1^i	39.98 (13)
C2—C1—C6—C5	−0.7 (11)	Na1^i—O3W—Na1—O4W	−37.6 (5)
S1—C1—C6—C5	177.6 (6)	Na1^i—O3W—Na1—O1	−38.90 (13)
Na1^ii—O2—S1—O1	73.5 (8)	Na1^i—O3W—Na1—Na1^iii	55.8 (3)
Na1^ii—O2—S1—N1	−48.8 (8)	Na1^i—O3W—Na1—Na1^v	159.94 (14)
Na1^ii—O2—S1—C1	−169.0 (7)	S1—O1—Na1—O2^iv	−74.9 (6)
Na1^i—O1—S1—O2	0.2 (4)	Na1^i—O1—Na1—O2^iv	136.06 (18)
Na1—O1—S1—O2	−143.9 (6)	S1—O1—Na1—O4W^v	150.9 (6)
Na1^i—O1—S1—N1	128.2 (3)	Na1^i—O1—Na1—O4W^v	1.8 (6)
Na1—O1—S1—N1	−16.0 (7)	S1—O1—Na1—O1^i	108.0 (5)
Na1^i—O1—S1—C1	−115.4 (3)	Na1^i—O1—Na1—O1^i	−41.1 (2)
Na1—O1—S1—C1	100.5 (6)	S1—O1—Na1—O4W	9.5 (6)
Br1—N1—S1—O2	−56.7 (4)	Na1^i—O1—Na1—O4W	−139.6 (2)
Br1—N1—S1—O1	176.0 (3)	S1—O1—Na1—O3W	−171.0 (6)
Br1—N1—S1—C1	60.8 (4)	Na1^i—O1—Na1—O3W	39.91 (15)
C2—C1—S1—O2	174.8 (6)	S1—O1—Na1—Na1^i	149.1 (7)
C6—C1—S1—O2	−3.4 (6)	S1—O1—Na1—Na1^iii	33.1 (6)
C2—C1—S1—O1	−63.0 (6)	Na1^i—O1—Na1—Na1^iii	−115.97 (17)
C6—C1—S1—O1	118.8 (6)	S1—O1—Na1—Na1^v	−137.5 (5)
C2—C1—S1—N1	50.5 (7)	Na1^i—O1—Na1—Na1^v	73.5 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4W—H42···N1	0.80 (5)	2.13 (5)	2.925 (8)	169 (8)
O3W—H31···N1^vi	0.88 (5)	2.18 (6)	3.010 (7)	158 (8)
O3W—H31···Br1^vi	0.88 (5)	2.81 (6)	3.6109 (13)	152 (8)
O4W—H41···Br1^iv	0.82 (5)	2.69 (5)	3.493 (6)	165 (8)

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