Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025184/dn2177sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025184/dn2177Isup2.hkl |
CCDC reference: 240005
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.011 Å
- R factor = 0.034
- wR factor = 0.088
- Data-to-parameter ratio = 14.2
checkCIF/PLATON results
No syntax errors found
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 PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.83 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C5 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) . 1.12 Ratio
Alert level G ABSTM02_ALERT_3_G The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.155 0.652 Tmin and Tmax expected: 0.141 0.655 RR = 1.105 Please check that your absorption correction is appropriate. REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 26.02 From the CIF: _reflns_number_total 1880 Count of symmetry unique reflns 1102 Completeness (_total/calc) 170.60% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 778 Fraction of Friedel pairs measured 0.706 Are heavy atom types Z>Si present yes PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K 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 7 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
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.
H atoms of the benzene ring were positioned geometrically and refined using a riding model with C—H = 0.93 Å and with Uiso(H) = 1.2 Ueq(C). H atoms of the water molecules (O3w, O4w) were visible in difference map and were subsequently treated as riding with O—H bond length restrained to 0.85 (1) Å and mutual distance of H atoms 1.35 (1) Å. No restraints were applied for non-hydrogen atoms.
The chemistry of arylsulfonamides and their N-halo compounds is of interest as they show diverse physical, chemical and biological properties. Thus N-halo arylsulfonamides are of interest in synthetic, mechanistic, analytical and biological chemistry (Gowda et al., 2005; Gowda & Shetty, 2004; Usha & Gowda, 2006). In the present work, the structure of sodium N-bromo- benzenesulfonamde (NaNBBSA) has been determined to explore the effects substitution on the solid state structures of sulfonamides and N-halo arylsulfonamides (Gowda et al., 2003; Gowda, Foro et al., 2007; Gowda, Jyothi et al., 2007; Gowda, Kozisek et al., 2007; Gowda, Savitha et al., 2007; Gowda, Srilatha et al., 2007).
The structure of NaNBBSA (Fig. 1) resembles those of sodium N-chloro- arylsulfonamdes (George et al., 2000; Gowda, Foro et al., 2007; Gowda, Jyothi et al., 2007; Gowda, Savitha et al., 2007; Gowda, Srilatha et al., 2007; Olmstead & Power, 1986). NaNBBSA is the parent or unsubstituted N-bromo-arylsulphonamide. The structure confirms that there is no interaction between the nitrogen and sodium atoms. The sodium ion exhibits octahedral coordination by three O atoms from water molecules and by three sulfonyl O atoms of three different N-bromobenzenesulfonamide anions. The S—N distance of 1.578 (4)Å is consistent with a S—N double bond, similar to the distance of 1.582 (5)Å observed with the corresponding N-chloro compound. Packing diagram of the title compound involving hydrogen bonds is shown in Fig.2.
For related literature, see: George et al. (2000); Gowda & Shetty (2004); Gowda & Usha (2003); Gowda et al. (2005); Gowda, Foro et al. (2007); Gowda, Jyothi et al. (2007); Gowda, Kozisek et al. (2007); Gowda, Savitha et al. (2007); Gowda, Srilatha et al. (2007); Gowda et al. (2003); Olmstead & Power (1986); Usha & Gowda (2006).
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).
Na+·C6H5BrNO2S−·1.5H2O | F(000) = 564 |
Mr = 285.10 | Dx = 1.847 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2y | Cell parameters from 2235 reflections |
a = 10.521 (3) Å | θ = 2.5–26.4° |
b = 6.760 (2) Å | µ = 4.24 mm−1 |
c = 14.853 (4) Å | T = 293 K |
β = 103.97 (2)° | Plate, yellow |
V = 1025.1 (5) Å3 | 0.50 × 0.50 × 0.10 mm |
Z = 4 |
Oxford Diffraction Xcalibur diffractometer | 1704 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω and φ scans | θmax = 26.0°, θmin = 4.6° |
Absorption correction: analytical (Clark & Reid, 1995) | h = −12→9 |
Tmin = 0.155, Tmax = 0.652 | k = −8→8 |
2957 measured reflections | l = −18→18 |
1880 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.0547P)2 + 0.3614P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.002 |
1880 reflections | Δρmax = 0.32 e Å−3 |
132 parameters | Δρmin = −0.44 e Å−3 |
5 restraints | Absolute structure: Flack (1983), 778 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.018 (12) |
Na+·C6H5BrNO2S−·1.5H2O | V = 1025.1 (5) Å3 |
Mr = 285.10 | Z = 4 |
Monoclinic, C2 | Mo Kα radiation |
a = 10.521 (3) Å | µ = 4.24 mm−1 |
b = 6.760 (2) Å | T = 293 K |
c = 14.853 (4) Å | 0.50 × 0.50 × 0.10 mm |
β = 103.97 (2)° |
Oxford Diffraction Xcalibur diffractometer | 1880 independent reflections |
Absorption correction: analytical (Clark & Reid, 1995) | 1704 reflections with I > 2σ(I) |
Tmin = 0.155, Tmax = 0.652 | Rint = 0.032 |
2957 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.088 | Δρmax = 0.32 e Å−3 |
S = 1.05 | Δρmin = −0.44 e Å−3 |
1880 reflections | Absolute structure: Flack (1983), 778 Friedel pairs |
132 parameters | Absolute structure parameter: −0.018 (12) |
5 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.8171 (4) | 0.2054 (7) | 0.2212 (3) | 0.0356 (9) | |
C2 | 0.9260 (6) | 0.1722 (13) | 0.1867 (3) | 0.0563 (13) | |
H2 | 1.0085 | 0.2091 | 0.2213 | 0.068* | |
C3 | 0.9128 (10) | 0.0846 (11) | 0.1011 (5) | 0.087 (3) | |
H3 | 0.9862 | 0.0645 | 0.0777 | 0.105* | |
C4 | 0.7953 (12) | 0.0290 (12) | 0.0518 (5) | 0.092 (3) | |
H4 | 0.7869 | −0.0257 | −0.0068 | 0.111* | |
C5 | 0.6873 (11) | 0.0508 (15) | 0.0859 (6) | 0.101 (3) | |
H5 | 0.607 | 0.0026 | 0.0524 | 0.122* | |
C6 | 0.6962 (6) | 0.1473 (11) | 0.1726 (4) | 0.0657 (18) | |
H6 | 0.6222 | 0.1695 | 0.1951 | 0.079* | |
S1 | 0.84086 (9) | 0.31275 (15) | 0.33360 (7) | 0.0271 (2) | |
O1 | 0.9150 (3) | 0.1703 (6) | 0.39966 (19) | 0.0350 (6) | |
O2 | 0.7112 (3) | 0.3566 (6) | 0.3454 (2) | 0.0437 (8) | |
O3W | 0.5 | 0.2619 (7) | 0.5 | 0.0364 (10) | |
H31 | 0.505 (5) | 0.178 (6) | 0.543 (3) | 0.044* | |
O4W | 0.8026 (3) | 0.3538 (5) | 0.5824 (2) | 0.0415 (8) | |
H41 | 0.758 (4) | 0.348 (9) | 0.623 (2) | 0.05* | |
H42 | 0.870 (3) | 0.421 (8) | 0.607 (3) | 0.05* | |
N1 | 0.9361 (4) | 0.4949 (5) | 0.3388 (3) | 0.0347 (8) | |
Br1 | 0.86056 (5) | 0.68675 (6) | 0.24930 (3) | 0.05208 (18) | |
Na1 | 0.63738 (16) | 0.5271 (3) | 0.46276 (12) | 0.0365 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.053 (2) | 0.024 (2) | 0.0294 (19) | 0.002 (2) | 0.0084 (17) | 0.0042 (19) |
C2 | 0.081 (3) | 0.059 (3) | 0.038 (2) | 0.010 (4) | 0.031 (2) | 0.002 (3) |
C3 | 0.154 (8) | 0.060 (4) | 0.062 (4) | 0.024 (5) | 0.053 (5) | −0.006 (4) |
C4 | 0.169 (9) | 0.057 (4) | 0.046 (4) | −0.009 (6) | 0.019 (5) | −0.017 (3) |
C5 | 0.115 (7) | 0.094 (6) | 0.071 (5) | −0.037 (5) | −0.023 (5) | −0.020 (5) |
C6 | 0.072 (3) | 0.078 (5) | 0.041 (3) | −0.022 (3) | 0.001 (2) | −0.009 (3) |
S1 | 0.0296 (4) | 0.0250 (5) | 0.0281 (5) | 0.0014 (4) | 0.0094 (4) | 0.0013 (4) |
O1 | 0.0403 (14) | 0.0319 (15) | 0.0323 (14) | 0.0045 (15) | 0.0078 (11) | 0.0090 (15) |
O2 | 0.0321 (15) | 0.053 (2) | 0.0496 (19) | 0.0076 (15) | 0.0175 (13) | −0.0002 (17) |
O3W | 0.048 (2) | 0.027 (2) | 0.035 (2) | 0 | 0.011 (2) | 0 |
O4W | 0.0332 (14) | 0.042 (2) | 0.048 (2) | 0.0001 (14) | 0.0090 (14) | −0.0032 (15) |
N1 | 0.0377 (18) | 0.0267 (18) | 0.038 (2) | −0.0028 (15) | 0.0053 (15) | 0.0008 (15) |
Br1 | 0.0708 (3) | 0.0315 (2) | 0.0569 (3) | 0.0070 (3) | 0.0214 (2) | 0.0136 (3) |
Na1 | 0.0365 (8) | 0.0316 (9) | 0.0442 (10) | 0.0041 (7) | 0.0156 (7) | −0.0005 (7) |
C1—C6 | 1.360 (7) | S1—N1 | 1.578 (4) |
C1—C2 | 1.382 (7) | O1—Na1i | 2.441 (3) |
C1—S1 | 1.781 (4) | O1—Na1ii | 2.496 (3) |
C2—C3 | 1.379 (9) | O2—Na1 | 2.372 (4) |
C2—H2 | 0.93 | O3W—Na1 | 2.448 (4) |
C3—C4 | 1.330 (12) | O3W—H31 | 0.85 (4) |
C3—H3 | 0.93 | O4W—Na1i | 2.436 (4) |
C4—C5 | 1.359 (13) | O4W—Na1 | 2.461 (4) |
C4—H4 | 0.93 | O4W—H41 | 0.85 (4) |
C5—C6 | 1.427 (12) | O4W—H42 | 0.85 (4) |
C5—H5 | 0.93 | N1—Br1 | 1.890 (4) |
C6—H6 | 0.93 | Na1—Na1iii | 3.335 (3) |
S1—O2 | 1.447 (3) | Na1—Na1iv | 4.123 (2) |
S1—O1 | 1.459 (3) | ||
C6—C1—C2 | 120.6 (5) | S1—N1—Br1 | 110.3 (2) |
C6—C1—S1 | 121.1 (4) | O2—Na1—O4Wiv | 94.90 (14) |
C2—C1—S1 | 118.2 (4) | O2—Na1—O1iv | 171.17 (14) |
C3—C2—C1 | 120.3 (7) | O4Wiv—Na1—O1iv | 89.82 (14) |
C3—C2—H2 | 119.9 | O2—Na1—O3W | 97.26 (13) |
C1—C2—H2 | 119.9 | O4Wiv—Na1—O3W | 158.86 (12) |
C4—C3—C2 | 120.2 (8) | O1iv—Na1—O3W | 80.58 (12) |
C4—C3—H3 | 119.9 | O2—Na1—O4W | 90.00 (13) |
C2—C3—H3 | 119.9 | O4Wiv—Na1—O4W | 116.45 (11) |
C3—C4—C5 | 120.9 (7) | O1iv—Na1—O4W | 81.21 (12) |
C3—C4—H4 | 119.5 | O3W—Na1—O4W | 80.85 (11) |
C5—C4—H4 | 119.5 | O2—Na1—O1v | 110.86 (13) |
C4—C5—C6 | 120.5 (7) | O4Wiv—Na1—O1v | 80.02 (13) |
C4—C5—H5 | 119.8 | O1iv—Na1—O1v | 77.29 (13) |
C6—C5—H5 | 119.8 | O3W—Na1—O1v | 79.51 (11) |
C1—C6—C5 | 117.4 (7) | O4W—Na1—O1v | 152.89 (13) |
C1—C6—H6 | 121.3 | O2—Na1—Na1iii | 135.06 (11) |
C5—C6—H6 | 121.3 | O4Wiv—Na1—Na1iii | 113.23 (9) |
O2—S1—O1 | 114.88 (19) | O1iv—Na1—Na1iii | 48.20 (8) |
O2—S1—N1 | 116.1 (2) | O3W—Na1—Na1iii | 47.07 (8) |
O1—S1—N1 | 104.6 (2) | O4W—Na1—Na1iii | 106.15 (11) |
O2—S1—C1 | 105.9 (2) | O1v—Na1—Na1iii | 46.82 (8) |
O1—S1—C1 | 107.0 (2) | O2—Na1—Na1iv | 109.05 (11) |
N1—S1—C1 | 107.9 (2) | O4Wiv—Na1—Na1iv | 32.85 (8) |
S1—O1—Na1i | 129.23 (17) | O1iv—Na1—Na1iv | 71.44 (10) |
S1—O1—Na1ii | 144.00 (18) | O3W—Na1—Na1iv | 150.70 (10) |
Na1i—O1—Na1ii | 84.98 (12) | O4W—Na1—Na1iv | 86.36 (11) |
S1—O2—Na1 | 132.4 (2) | O1v—Na1—Na1iv | 102.05 (10) |
Na1iii—O3W—Na1 | 85.86 (16) | Na1iii—Na1—Na1iv | 113.52 (6) |
Na1iii—O3W—H31 | 105 (4) | O2—Na1—Na1i | 61.96 (9) |
Na1—O3W—H31 | 137 (4) | O4Wiv—Na1—Na1i | 130.31 (11) |
Na1i—O4W—Na1 | 114.68 (14) | O1iv—Na1—Na1i | 109.38 (11) |
Na1i—O4W—H41 | 112 (4) | O3W—Na1—Na1i | 70.83 (7) |
Na1—O4W—H41 | 97 (4) | O4W—Na1—Na1i | 32.46 (9) |
Na1i—O4W—H42 | 111 (4) | O1v—Na1—Na1i | 147.63 (11) |
Na1—O4W—H42 | 116 (4) | Na1iv—Na1—Na1i | 110.13 (8) |
H41—O4W—H42 | 106 (4) |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1; (ii) x+1/2, y−1/2, z; (iii) −x+1, y, −z+1; (iv) −x+3/2, y+1/2, −z+1; (v) x−1/2, y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3W—H31···N1i | 0.85 (4) | 2.12 (4) | 2.943 (5) | 167 (5) |
O4W—H42···N1vi | 0.85 (4) | 2.07 (2) | 2.878 (5) | 161 (5) |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1; (vi) −x+2, y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | Na+·C6H5BrNO2S−·1.5H2O |
Mr | 285.10 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 293 |
a, b, c (Å) | 10.521 (3), 6.760 (2), 14.853 (4) |
β (°) | 103.97 (2) |
V (Å3) | 1025.1 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.24 |
Crystal size (mm) | 0.50 × 0.50 × 0.10 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur |
Absorption correction | Analytical (Clark & Reid, 1995) |
Tmin, Tmax | 0.155, 0.652 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2957, 1880, 1704 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.088, 1.05 |
No. of reflections | 1880 |
No. of parameters | 132 |
No. of restraints | 5 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.44 |
Absolute structure | Flack (1983), 778 Friedel pairs |
Absolute structure parameter | −0.018 (12) |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), CrysAlis RED (Oxford Diffraction, 2003), CrysAlis RED, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2002), SHELXL97, PLATON (Spek, 2003) and WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O3W—H31···N1i | 0.85 (4) | 2.12 (4) | 2.943 (5) | 167 (5) |
O4W—H42···N1ii | 0.85 (4) | 2.07 (2) | 2.878 (5) | 161 (5) |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1; (ii) −x+2, y, −z+1. |
The chemistry of arylsulfonamides and their N-halo compounds is of interest as they show diverse physical, chemical and biological properties. Thus N-halo arylsulfonamides are of interest in synthetic, mechanistic, analytical and biological chemistry (Gowda et al., 2005; Gowda & Shetty, 2004; Usha & Gowda, 2006). In the present work, the structure of sodium N-bromo- benzenesulfonamde (NaNBBSA) has been determined to explore the effects substitution on the solid state structures of sulfonamides and N-halo arylsulfonamides (Gowda et al., 2003; Gowda, Foro et al., 2007; Gowda, Jyothi et al., 2007; Gowda, Kozisek et al., 2007; Gowda, Savitha et al., 2007; Gowda, Srilatha et al., 2007).
The structure of NaNBBSA (Fig. 1) resembles those of sodium N-chloro- arylsulfonamdes (George et al., 2000; Gowda, Foro et al., 2007; Gowda, Jyothi et al., 2007; Gowda, Savitha et al., 2007; Gowda, Srilatha et al., 2007; Olmstead & Power, 1986). NaNBBSA is the parent or unsubstituted N-bromo-arylsulphonamide. The structure confirms that there is no interaction between the nitrogen and sodium atoms. The sodium ion exhibits octahedral coordination by three O atoms from water molecules and by three sulfonyl O atoms of three different N-bromobenzenesulfonamide anions. The S—N distance of 1.578 (4)Å is consistent with a S—N double bond, similar to the distance of 1.582 (5)Å observed with the corresponding N-chloro compound. Packing diagram of the title compound involving hydrogen bonds is shown in Fig.2.