Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101017930/bm1465sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101017930/bm1465Isup2.hkl |
CCDC reference: 180132
6-Nitro-3-(p-tolylsulfonyl)-1,2,3-benzoxathiazole 2,2-dioxide (3.71 g, 10 mmol), alternatively named N-tosyl-p-nitrobenzoxa sulfamate, prepared according to the method of Andersen & Kociolek (1995) was dissolved in acetonitrile (200 ml). NaN3 (0.65 g, 10 mmol) was dissolved in water (ca 2 ml) and added dropwise into the first solution. The mixture was stirred by means of a magnetic stirrer at room temperature for one hour. The solvent was removed under reduced pressure and the title compound was collected as a yellow solid. The solid was washed with chloroform and recrystallized from THF/water (1/1) to obtain suitable crystals for X-ray analysis.
Water H atoms were found in difference maps and were positionally refined with geometric restraints (O—H 0.82, H···H 1.30 Å) and with Uiso(H) = 1.5 Ueq(C) (Sheldrick, 1997). Other H atoms were placed in calculated positions 0.93 Å from their parent atoms with Uiso(H) = 1.2 Ueq(C).
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick,1997).
Na+·C6H3N2O5S−·H2O | F(000) = 1040 |
Mr = 256.17 | Dx = 1.871 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
a = 13.0610 (7) Å | Cell parameters from 3359 reflections |
b = 6.8155 (4) Å | θ = 3.2–27.5° |
c = 20.7293 (11) Å | µ = 0.42 mm−1 |
β = 99.677 (1)° | T = 298 K |
V = 1819.01 (17) Å3 | Column, yellow |
Z = 8 | 0.55 × 0.16 × 0.11 mm |
Bruker SMART1000 CCD area detector diffractometer | 2096 independent reflections |
Radiation source: fine-focus sealed tube | 1758 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ω scans | θmax = 27.5°, θmin = 2.0° |
Absorption correction: multi-scan SADABS (Bruker, 1999) | h = −16→15 |
Tmin = 0.761, Tmax = 0.949 | k = −8→7 |
6528 measured reflections | l = −26→26 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.085 | w = 1/[σ2(Fo2) + (0.05P)2 + 0.652P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
2096 reflections | Δρmax = 0.26 e Å−3 |
151 parameters | Δρmin = −0.37 e Å−3 |
3 restraints |
Na+·C6H3N2O5S−·H2O | V = 1819.01 (17) Å3 |
Mr = 256.17 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 13.0610 (7) Å | µ = 0.42 mm−1 |
b = 6.8155 (4) Å | T = 298 K |
c = 20.7293 (11) Å | 0.55 × 0.16 × 0.11 mm |
β = 99.677 (1)° |
Bruker SMART1000 CCD area detector diffractometer | 2096 independent reflections |
Absorption correction: multi-scan SADABS (Bruker, 1999) | 1758 reflections with I > 2σ(I) |
Tmin = 0.761, Tmax = 0.949 | Rint = 0.023 |
6528 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 3 restraints |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.26 e Å−3 |
2096 reflections | Δρmin = −0.37 e Å−3 |
151 parameters |
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 | ||
S1 | 0.92560 (3) | 0.19080 (6) | 0.15613 (2) | 0.02760 (13) | |
Na1 | 0.70264 (6) | −0.03018 (10) | 0.23785 (3) | 0.0414 (2) | |
O1W | 0.63443 (9) | 0.28414 (18) | 0.24050 (6) | 0.0342 (3) | |
H1W1 | 0.5972 (14) | 0.342 (3) | 0.2114 (7) | 0.051* | |
H2W1 | 0.6116 (16) | 0.310 (3) | 0.2741 (6) | 0.051* | |
O1 | 1.00939 (10) | 0.32593 (19) | 0.17193 (6) | 0.0422 (3) | |
O2 | 0.84291 (10) | 0.21684 (19) | 0.19272 (6) | 0.0392 (3) | |
O3 | 0.87654 (10) | 0.22657 (17) | 0.07865 (5) | 0.0352 (3) | |
O4 | 0.80116 (11) | −0.3934 (2) | −0.12360 (6) | 0.0473 (3) | |
O5 | 0.78181 (12) | −0.0843 (2) | −0.14476 (6) | 0.0538 (4) | |
N1 | 0.95956 (10) | −0.0322 (2) | 0.15242 (6) | 0.0296 (3) | |
N2 | 0.80933 (11) | −0.2208 (2) | −0.10668 (7) | 0.0363 (3) | |
C1 | 0.92845 (11) | −0.0968 (2) | 0.08939 (7) | 0.0250 (3) | |
C2 | 0.93669 (13) | −0.2855 (2) | 0.06555 (8) | 0.0305 (3) | |
H2 | 0.9683 | −0.3844 | 0.0928 | 0.037* | |
C3 | 0.89724 (12) | −0.3238 (2) | 0.00093 (8) | 0.0321 (4) | |
H3 | 0.9007 | −0.4502 | −0.0155 | 0.039* | |
C4 | 0.85239 (11) | −0.1745 (2) | −0.03979 (7) | 0.0285 (3) | |
C5 | 0.84363 (12) | 0.0177 (2) | −0.01812 (8) | 0.0292 (3) | |
H5 | 0.8140 | 0.1174 | −0.0458 | 0.035* | |
C6 | 0.88135 (11) | 0.0492 (2) | 0.04626 (7) | 0.0256 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0309 (2) | 0.0266 (2) | 0.0252 (2) | 0.00165 (14) | 0.00442 (14) | 0.00046 (14) |
Na1 | 0.0607 (5) | 0.0303 (4) | 0.0351 (4) | 0.0110 (3) | 0.0134 (3) | 0.0036 (3) |
O1W | 0.0378 (6) | 0.0358 (7) | 0.0285 (6) | 0.0107 (5) | 0.0043 (5) | 0.0011 (5) |
O1 | 0.0434 (7) | 0.0390 (7) | 0.0429 (7) | −0.0107 (5) | 0.0035 (6) | 0.0000 (6) |
O2 | 0.0408 (7) | 0.0391 (7) | 0.0403 (7) | 0.0035 (5) | 0.0145 (5) | −0.0063 (5) |
O3 | 0.0498 (7) | 0.0265 (6) | 0.0268 (6) | 0.0116 (5) | −0.0011 (5) | 0.0016 (5) |
O4 | 0.0503 (8) | 0.0527 (9) | 0.0404 (7) | −0.0163 (7) | 0.0115 (6) | −0.0160 (6) |
O5 | 0.0641 (9) | 0.0653 (10) | 0.0276 (6) | 0.0019 (8) | −0.0052 (6) | 0.0035 (6) |
N1 | 0.0360 (7) | 0.0281 (7) | 0.0239 (6) | 0.0069 (6) | 0.0031 (5) | 0.0035 (5) |
N2 | 0.0306 (7) | 0.0504 (9) | 0.0290 (7) | −0.0083 (6) | 0.0080 (6) | −0.0063 (6) |
C1 | 0.0227 (7) | 0.0277 (8) | 0.0252 (7) | 0.0025 (6) | 0.0058 (5) | 0.0038 (6) |
C2 | 0.0344 (8) | 0.0251 (8) | 0.0324 (8) | 0.0059 (6) | 0.0068 (6) | 0.0053 (6) |
C3 | 0.0332 (8) | 0.0275 (8) | 0.0371 (9) | 0.0007 (6) | 0.0100 (7) | −0.0037 (6) |
C4 | 0.0250 (7) | 0.0370 (9) | 0.0240 (7) | −0.0026 (6) | 0.0059 (6) | −0.0017 (6) |
C5 | 0.0274 (7) | 0.0329 (8) | 0.0268 (8) | 0.0034 (6) | 0.0029 (6) | 0.0060 (6) |
C6 | 0.0267 (7) | 0.0237 (7) | 0.0270 (7) | 0.0029 (6) | 0.0058 (6) | 0.0016 (6) |
S1—O1 | 1.4257 (13) | O3—C6 | 1.3893 (18) |
S1—O2 | 1.4312 (12) | N1—C1 | 1.374 (2) |
S1—O3 | 1.6442 (11) | O4—N2 | 1.227 (2) |
S1—N1 | 1.5889 (13) | O5—N2 | 1.234 (2) |
Na1—O1W | 2.3244 (14) | N2—C4 | 1.441 (2) |
Na1—O1Wi | 2.4516 (15) | C1—C6 | 1.408 (2) |
Na1—O1ii | 2.8355 (15) | C1—C2 | 1.388 (2) |
Na1—O2i | 2.3846 (14) | C2—C3 | 1.377 (2) |
Na1—O2 | 2.7644 (15) | C2—H2 | 0.9300 |
Na1—O4iii | 2.4173 (14) | C3—C4 | 1.387 (2) |
Na1—O5iv | 2.5988 (15) | C3—H3 | 0.9300 |
Na1—Na1v | 3.6314 (6) | C4—C5 | 1.396 (2) |
O1W—H1W1 | 0.811 (9) | C5—C6 | 1.360 (2) |
O1W—H2W1 | 0.821 (9) | C5—H5 | 0.9300 |
O1—S1—O2 | 114.62 (8) | Na1v—O1W—H2W1 | 99.4 (16) |
O1—S1—N1 | 114.79 (8) | H1W1—O1W—H2W1 | 105.8 (17) |
O2—S1—N1 | 112.70 (8) | S1—O1—Na1vi | 157.05 (8) |
O1—S1—O3 | 106.66 (7) | S1—O2—Na1v | 134.15 (8) |
O2—S1—O3 | 107.12 (7) | S1—O2—Na1 | 134.90 (7) |
N1—S1—O3 | 99.25 (6) | Na1v—O2—Na1 | 89.39 (4) |
O1W—Na1—O2i | 121.10 (5) | C6—O3—S1 | 107.53 (9) |
O1W—Na1—O4iii | 106.08 (5) | N2—O4—Na1iii | 118.24 (11) |
O2i—Na1—O4iii | 117.99 (6) | N2—O5—Na1vii | 148.51 (12) |
O1W—Na1—O1Wi | 142.73 (5) | C1—N1—S1 | 108.19 (10) |
O2i—Na1—O1Wi | 79.24 (5) | O4—N2—O5 | 122.54 (15) |
O4iii—Na1—O1Wi | 86.70 (5) | O4—N2—C4 | 119.10 (15) |
O1W—Na1—O5iv | 78.16 (5) | O5—N2—C4 | 118.36 (15) |
O2i—Na1—O5iv | 75.66 (5) | N1—C1—C2 | 127.39 (14) |
O4iii—Na1—O5iv | 157.15 (6) | N1—C1—C6 | 113.89 (14) |
O1Wi—Na1—O5iv | 77.71 (5) | C2—C1—C6 | 118.71 (14) |
O1W—Na1—O2 | 74.05 (5) | C3—C2—C1 | 118.89 (14) |
O2i—Na1—O2 | 153.05 (4) | C3—C2—H2 | 120.6 |
O4iii—Na1—O2 | 72.87 (5) | C1—C2—H2 | 120.6 |
O1Wi—Na1—O2 | 76.82 (4) | C2—C3—C4 | 120.24 (15) |
O5iv—Na1—O2 | 87.25 (5) | C2—C3—H3 | 119.9 |
O1W—Na1—O1ii | 90.94 (5) | C4—C3—H3 | 119.9 |
O2i—Na1—O1ii | 75.44 (5) | C3—C4—C5 | 122.79 (15) |
O4iii—Na1—O1ii | 65.37 (5) | C3—C4—N2 | 118.77 (15) |
O1Wi—Na1—O1ii | 125.78 (5) | C5—C4—N2 | 118.39 (14) |
O5iv—Na1—O1ii | 137.47 (5) | C6—C5—C4 | 115.35 (14) |
O2—Na1—O1ii | 129.38 (5) | C6—C5—H5 | 122.3 |
Na1—O1W—Na1v | 98.96 (4) | C4—C5—H5 | 122.3 |
Na1—O1W—H1W1 | 127.9 (15) | C5—C6—O3 | 124.97 (13) |
Na1v—O1W—H1W1 | 106.2 (16) | C5—C6—C1 | 124.00 (15) |
Na1—O1W—H2W1 | 114.2 (14) | O3—C6—C1 | 111.01 (13) |
O1—S1—O3—C6 | 122.54 (11) | O5—N2—C4—C3 | −170.80 (15) |
O2—S1—O3—C6 | −114.28 (11) | O4—N2—C4—C5 | −168.26 (14) |
N1—S1—O3—C6 | 3.06 (11) | O5—N2—C4—C5 | 11.6 (2) |
O1—S1—N1—C1 | −116.69 (11) | C3—C4—C5—C6 | −0.6 (2) |
O2—S1—N1—C1 | 109.63 (11) | N2—C4—C5—C6 | 176.92 (13) |
O3—S1—N1—C1 | −3.42 (12) | C4—C5—C6—O3 | −177.07 (14) |
S1—N1—C1—C2 | −175.71 (13) | C4—C5—C6—C1 | 1.3 (2) |
S1—N1—C1—C6 | 2.82 (16) | S1—O3—C6—C5 | 176.79 (13) |
N1—C1—C2—C3 | 177.54 (15) | S1—O3—C6—C1 | −1.73 (15) |
C6—C1—C2—C3 | −0.9 (2) | N1—C1—C6—C5 | −179.21 (14) |
C1—C2—C3—C4 | 1.6 (2) | C2—C1—C6—C5 | −0.5 (2) |
C2—C3—C4—C5 | −0.8 (2) | N1—C1—C6—O3 | −0.66 (19) |
C2—C3—C4—N2 | −178.32 (14) | C2—C1—C6—O3 | 178.01 (13) |
O4—N2—C4—C3 | 9.4 (2) |
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; (iv) x, −y, z+1/2; (v) −x+3/2, y+1/2, −z+1/2; (vi) x+1/2, y+1/2, z; (vii) x, −y, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···N1viii | 0.81 (1) | 2.17 (1) | 2.9521 (17) | 161 (2) |
O1W—H2W1···N1v | 0.82 (1) | 2.20 (1) | 2.9859 (17) | 161 (2) |
C2—H2···O1ix | 0.93 | 2.57 | 3.475 (2) | 166 |
Symmetry codes: (v) −x+3/2, y+1/2, −z+1/2; (viii) x−1/2, y+1/2, z; (ix) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | Na+·C6H3N2O5S−·H2O |
Mr | 256.17 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 13.0610 (7), 6.8155 (4), 20.7293 (11) |
β (°) | 99.677 (1) |
V (Å3) | 1819.01 (17) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.42 |
Crystal size (mm) | 0.55 × 0.16 × 0.11 |
Data collection | |
Diffractometer | Bruker SMART1000 CCD area detector diffractometer |
Absorption correction | Multi-scan SADABS (Bruker, 1999) |
Tmin, Tmax | 0.761, 0.949 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6528, 2096, 1758 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.085, 1.04 |
No. of reflections | 2096 |
No. of parameters | 151 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.26, −0.37 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick,1997).
S1—O1 | 1.4257 (13) | O3—C6 | 1.3893 (18) |
S1—O2 | 1.4312 (12) | N1—C1 | 1.374 (2) |
S1—O3 | 1.6442 (11) | O4—N2 | 1.227 (2) |
S1—N1 | 1.5889 (13) | O5—N2 | 1.234 (2) |
Na1—O1W | 2.3244 (14) | N2—C4 | 1.441 (2) |
Na1—O1Wi | 2.4516 (15) | C1—C6 | 1.408 (2) |
Na1—O1ii | 2.8355 (15) | C1—C2 | 1.388 (2) |
Na1—O2i | 2.3846 (14) | C2—C3 | 1.377 (2) |
Na1—O2 | 2.7644 (15) | C3—C4 | 1.387 (2) |
Na1—O4iii | 2.4173 (14) | C4—C5 | 1.396 (2) |
Na1—O5iv | 2.5988 (15) | C5—C6 | 1.360 (2) |
Na1—Na1v | 3.6314 (6) |
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; (iv) x, −y, z+1/2; (v) −x+3/2, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···N1vi | 0.811 (9) | 2.173 (12) | 2.9521 (17) | 161 (2) |
O1W—H2W1···N1v | 0.821 (9) | 2.196 (12) | 2.9859 (17) | 161 (2) |
C2—H2···O1vii | 0.93 | 2.57 | 3.475 (2) | 166 |
Symmetry codes: (v) −x+3/2, y+1/2, −z+1/2; (vi) x−1/2, y+1/2, z; (vii) x, y−1, z. |
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Sulfamate derivatives have considerable commercial importance as artificial sweeteners (Spillane et al., 1996; Drew et al., 1998). The structures of acyclic sulfamate (NH2SO3) salts of lithium (Stade et al., 2001), rubidium (Schreuer, 1999a) and caesium (Schreuer, 1999b) were reported recently. However, no structural characterization of the compounds of cyclic sulfamates have yet appeared in the literature, and the structural investigation of the title compound is part of our continuing research on the synthesis of artificial sweeteners and their metal complexes.
A view of the title compound, alternatively named sodium 3H-6-nitro-1,2,3-benzoxathiazole 2,2-dioxidemonohydrate, is shown in Fig. 1. The Na+ cation has seven coordination by three O atoms of sulfamate sulfonyl groups, two O atoms of two sulfamate nitro groups and the O atoms of two water molecules. The geometry around the Na+ centre is best described as a distorted monocapped trigonal prism with approximate C2v symmetry. Each triangular face is defined by one O atom each from a water molecule, a nitro group and a sulfonyl group. The dihedral angle between the two triangular faces is 2.0°. An O atom from a sulfonyl group caps one of the square faces of the trigonal prism unsymmetrically. The structure consists of chains formed by the NaO7 units. The O atoms of the water molecules and sulfonyl groups are bicoordinating and act as bridges between Na+ centers. The nitro group also behaves as a bidentate donor between the cations.
The Na···Na separation is 3.6314 (6) Å. The Na—Owater, Na—Osulfonyl and Na—Onitro distances lie in the ranges 2.3247 (13)–2.4504 (14), 2.3843 (14)–2.8358 (15) and 2.4171 (14)–2.5985 (15) Å, respectively. All metal-oxygen distances are noticably shorter in the title compound than in its potassium analogue (Bekdemir et al., 2001). Although the K+ ions exhibit two different coordination polyhedra, and involve coordination by sulfamate amine N atoms, all the Na+ cations have the same geometry.
A packing diagram with hydrogen bonding scheme is shown in Fig. 2. The phenyl and sulfamate rings are almost planar and lie in a plane with an RMS deviation of 0.0361 Å. The sulfamate ions adopt an antiparallel aligment between the chains and are connected to each other by weak C—H···O interactions [C2···O1 3.475 (2) Å (symmetry code: x,1 + y,z)], and π-π [Cg···Cg 3.6931 (9) Å (symmetry code: -x,-y,2 - z) and Cg···Cg 3.9450 (9) Å (symmetry code:1/2 - x,1/2 - y,2 - z)] interactions. The adjacent polyhedral chains are held together by strong hydrogen bonds. The H atoms of the water molecules form O—H···Namine hydrogen bonds [O1W···N1 2.9538 (17) Å (symmetry code: 1/2 + x,-1/2 + y,z), and 2.9844 (17) Å (symmetry code: 1/2 - x,-1/2 + y,3/2 - z)] with the amine N atom of neighboring sulfamate anions and amine nitrogen atoms accept two hydrogen bonds. The hydrogen bonds as well as the other intramolecular contacts stabilize the crystal structure in the solid state, forming a three-dimensional network.