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The title compound, alternatively named sodium 6-nitro-3H-1,2,3-benzoxa­thia­zole 2,2-dioxide monohydrate, Na+·C6H3­N2O5S·H2O, consists of chains of NaO7 units, with the seven donor-O atoms coming from two water mol­ecules and five p-­nitro­benzoxasulfamate anions. The seven-coordinate geometry around the Na+ ion is described as monocapped trigonal prismatic, but with a large distortion from ideal geometry. Each triangular face is defined by one O atom each from a water mol­ecule, a nitro group and a sulfonyl group. An O atom from a sulfonyl group caps one of the square faces of the trigonal prism in an unsymmetrical fashion. The water mol­ecules and one sulfonyl O atom are involved in bridging adjacent units, as is the nitro group of the anion. The sulfamate ions adopt an antiparallel alignment between the NaO7 units and are connected to each other by C—H...O and π–π interactions. The three-dimensional crystal structure is stabilized by a network of strong O—H...N hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101017930/bm1465sup1.cif
Contains datablocks I, BM1465

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101017930/bm1465Isup2.hkl
Contains datablock I

CCDC reference: 180132

Comment top

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 OH···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.

Experimental top

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.

Refinement top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. View of the title compound showing the coordination around the sodium ions. Displacement ellipsoids are drawn at the 50% probability level. Symmetry codes: (i) 1/2 - x,1/2 + y,3/2 - z; (ii) 1/2 + x,1/2 + y,z; (iii) 1/2 - x,1/2 - y,2 - z; (iv) x,-y,-1/2 + z.
[Figure 2] Fig. 2. A part of packing diagram of the title compound showing the hydrogen bonding. Symmetry codes: (i) 1/2 - x,1/2 + y,3/2 - z; (ii) 1/2 + x,1/2 + y,z; (iii) 1/2 - x,1/2 - y,2 - z; (iv) x,-y,-1/2 + z.
Sodium p-nitrobenzoxasulfamate monohydrate top
Crystal data top
Na+·C6H3N2O5S·H2OF(000) = 1040
Mr = 256.17Dx = 1.871 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71069 Å
a = 13.0610 (7) ÅCell parameters from 3359 reflections
b = 6.8155 (4) Åθ = 3.2–27.5°
c = 20.7293 (11) ŵ = 0.42 mm1
β = 99.677 (1)°T = 298 K
V = 1819.01 (17) Å3Column, yellow
Z = 80.55 × 0.16 × 0.11 mm
Data collection top
Bruker SMART1000 CCD area detector
diffractometer
2096 independent reflections
Radiation source: fine-focus sealed tube1758 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
ω scansθmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan
SADABS (Bruker, 1999)
h = 1615
Tmin = 0.761, Tmax = 0.949k = 87
6528 measured reflectionsl = 2626
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030H 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 reflectionsΔρmax = 0.26 e Å3
151 parametersΔρmin = 0.37 e Å3
3 restraints
Crystal data top
Na+·C6H3N2O5S·H2OV = 1819.01 (17) Å3
Mr = 256.17Z = 8
Monoclinic, C2/cMo Kα radiation
a = 13.0610 (7) ŵ = 0.42 mm1
b = 6.8155 (4) ÅT = 298 K
c = 20.7293 (11) Å0.55 × 0.16 × 0.11 mm
β = 99.677 (1)°
Data collection top
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 = 0.949Rint = 0.023
6528 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0303 restraints
wR(F2) = 0.085H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.26 e Å3
2096 reflectionsΔρmin = 0.37 e Å3
151 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
S10.92560 (3)0.19080 (6)0.15613 (2)0.02760 (13)
Na10.70264 (6)0.03018 (10)0.23785 (3)0.0414 (2)
O1W0.63443 (9)0.28414 (18)0.24050 (6)0.0342 (3)
H1W10.5972 (14)0.342 (3)0.2114 (7)0.051*
H2W10.6116 (16)0.310 (3)0.2741 (6)0.051*
O11.00939 (10)0.32593 (19)0.17193 (6)0.0422 (3)
O20.84291 (10)0.21684 (19)0.19272 (6)0.0392 (3)
O30.87654 (10)0.22657 (17)0.07865 (5)0.0352 (3)
O40.80116 (11)0.3934 (2)0.12360 (6)0.0473 (3)
O50.78181 (12)0.0843 (2)0.14476 (6)0.0538 (4)
N10.95956 (10)0.0322 (2)0.15242 (6)0.0296 (3)
N20.80933 (11)0.2208 (2)0.10668 (7)0.0363 (3)
C10.92845 (11)0.0968 (2)0.08939 (7)0.0250 (3)
C20.93669 (13)0.2855 (2)0.06555 (8)0.0305 (3)
H20.96830.38440.09280.037*
C30.89724 (12)0.3238 (2)0.00093 (8)0.0321 (4)
H30.90070.45020.01550.039*
C40.85239 (11)0.1745 (2)0.03979 (7)0.0285 (3)
C50.84363 (12)0.0177 (2)0.01812 (8)0.0292 (3)
H50.81400.11740.04580.035*
C60.88135 (11)0.0492 (2)0.04626 (7)0.0256 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0309 (2)0.0266 (2)0.0252 (2)0.00165 (14)0.00442 (14)0.00046 (14)
Na10.0607 (5)0.0303 (4)0.0351 (4)0.0110 (3)0.0134 (3)0.0036 (3)
O1W0.0378 (6)0.0358 (7)0.0285 (6)0.0107 (5)0.0043 (5)0.0011 (5)
O10.0434 (7)0.0390 (7)0.0429 (7)0.0107 (5)0.0035 (6)0.0000 (6)
O20.0408 (7)0.0391 (7)0.0403 (7)0.0035 (5)0.0145 (5)0.0063 (5)
O30.0498 (7)0.0265 (6)0.0268 (6)0.0116 (5)0.0011 (5)0.0016 (5)
O40.0503 (8)0.0527 (9)0.0404 (7)0.0163 (7)0.0115 (6)0.0160 (6)
O50.0641 (9)0.0653 (10)0.0276 (6)0.0019 (8)0.0052 (6)0.0035 (6)
N10.0360 (7)0.0281 (7)0.0239 (6)0.0069 (6)0.0031 (5)0.0035 (5)
N20.0306 (7)0.0504 (9)0.0290 (7)0.0083 (6)0.0080 (6)0.0063 (6)
C10.0227 (7)0.0277 (8)0.0252 (7)0.0025 (6)0.0058 (5)0.0038 (6)
C20.0344 (8)0.0251 (8)0.0324 (8)0.0059 (6)0.0068 (6)0.0053 (6)
C30.0332 (8)0.0275 (8)0.0371 (9)0.0007 (6)0.0100 (7)0.0037 (6)
C40.0250 (7)0.0370 (9)0.0240 (7)0.0026 (6)0.0059 (6)0.0017 (6)
C50.0274 (7)0.0329 (8)0.0268 (8)0.0034 (6)0.0029 (6)0.0060 (6)
C60.0267 (7)0.0237 (7)0.0270 (7)0.0029 (6)0.0058 (6)0.0016 (6)
Geometric parameters (Å, º) top
S1—O11.4257 (13)O3—C61.3893 (18)
S1—O21.4312 (12)N1—C11.374 (2)
S1—O31.6442 (11)O4—N21.227 (2)
S1—N11.5889 (13)O5—N21.234 (2)
Na1—O1W2.3244 (14)N2—C41.441 (2)
Na1—O1Wi2.4516 (15)C1—C61.408 (2)
Na1—O1ii2.8355 (15)C1—C21.388 (2)
Na1—O2i2.3846 (14)C2—C31.377 (2)
Na1—O22.7644 (15)C2—H20.9300
Na1—O4iii2.4173 (14)C3—C41.387 (2)
Na1—O5iv2.5988 (15)C3—H30.9300
Na1—Na1v3.6314 (6)C4—C51.396 (2)
O1W—H1W10.811 (9)C5—C61.360 (2)
O1W—H2W10.821 (9)C5—H50.9300
O1—S1—O2114.62 (8)Na1v—O1W—H2W199.4 (16)
O1—S1—N1114.79 (8)H1W1—O1W—H2W1105.8 (17)
O2—S1—N1112.70 (8)S1—O1—Na1vi157.05 (8)
O1—S1—O3106.66 (7)S1—O2—Na1v134.15 (8)
O2—S1—O3107.12 (7)S1—O2—Na1134.90 (7)
N1—S1—O399.25 (6)Na1v—O2—Na189.39 (4)
O1W—Na1—O2i121.10 (5)C6—O3—S1107.53 (9)
O1W—Na1—O4iii106.08 (5)N2—O4—Na1iii118.24 (11)
O2i—Na1—O4iii117.99 (6)N2—O5—Na1vii148.51 (12)
O1W—Na1—O1Wi142.73 (5)C1—N1—S1108.19 (10)
O2i—Na1—O1Wi79.24 (5)O4—N2—O5122.54 (15)
O4iii—Na1—O1Wi86.70 (5)O4—N2—C4119.10 (15)
O1W—Na1—O5iv78.16 (5)O5—N2—C4118.36 (15)
O2i—Na1—O5iv75.66 (5)N1—C1—C2127.39 (14)
O4iii—Na1—O5iv157.15 (6)N1—C1—C6113.89 (14)
O1Wi—Na1—O5iv77.71 (5)C2—C1—C6118.71 (14)
O1W—Na1—O274.05 (5)C3—C2—C1118.89 (14)
O2i—Na1—O2153.05 (4)C3—C2—H2120.6
O4iii—Na1—O272.87 (5)C1—C2—H2120.6
O1Wi—Na1—O276.82 (4)C2—C3—C4120.24 (15)
O5iv—Na1—O287.25 (5)C2—C3—H3119.9
O1W—Na1—O1ii90.94 (5)C4—C3—H3119.9
O2i—Na1—O1ii75.44 (5)C3—C4—C5122.79 (15)
O4iii—Na1—O1ii65.37 (5)C3—C4—N2118.77 (15)
O1Wi—Na1—O1ii125.78 (5)C5—C4—N2118.39 (14)
O5iv—Na1—O1ii137.47 (5)C6—C5—C4115.35 (14)
O2—Na1—O1ii129.38 (5)C6—C5—H5122.3
Na1—O1W—Na1v98.96 (4)C4—C5—H5122.3
Na1—O1W—H1W1127.9 (15)C5—C6—O3124.97 (13)
Na1v—O1W—H1W1106.2 (16)C5—C6—C1124.00 (15)
Na1—O1W—H2W1114.2 (14)O3—C6—C1111.01 (13)
O1—S1—O3—C6122.54 (11)O5—N2—C4—C3170.80 (15)
O2—S1—O3—C6114.28 (11)O4—N2—C4—C5168.26 (14)
N1—S1—O3—C63.06 (11)O5—N2—C4—C511.6 (2)
O1—S1—N1—C1116.69 (11)C3—C4—C5—C60.6 (2)
O2—S1—N1—C1109.63 (11)N2—C4—C5—C6176.92 (13)
O3—S1—N1—C13.42 (12)C4—C5—C6—O3177.07 (14)
S1—N1—C1—C2175.71 (13)C4—C5—C6—C11.3 (2)
S1—N1—C1—C62.82 (16)S1—O3—C6—C5176.79 (13)
N1—C1—C2—C3177.54 (15)S1—O3—C6—C11.73 (15)
C6—C1—C2—C30.9 (2)N1—C1—C6—C5179.21 (14)
C1—C2—C3—C41.6 (2)C2—C1—C6—C50.5 (2)
C2—C3—C4—C50.8 (2)N1—C1—C6—O30.66 (19)
C2—C3—C4—N2178.32 (14)C2—C1—C6—O3178.01 (13)
O4—N2—C4—C39.4 (2)
Symmetry codes: (i) x+3/2, y1/2, z+1/2; (ii) x1/2, y1/2, z; (iii) x+3/2, y1/2, 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, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···N1viii0.81 (1)2.17 (1)2.9521 (17)161 (2)
O1W—H2W1···N1v0.82 (1)2.20 (1)2.9859 (17)161 (2)
C2—H2···O1ix0.932.573.475 (2)166
Symmetry codes: (v) x+3/2, y+1/2, z+1/2; (viii) x1/2, y+1/2, z; (ix) x, y1, z.

Experimental details

Crystal data
Chemical formulaNa+·C6H3N2O5S·H2O
Mr256.17
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)13.0610 (7), 6.8155 (4), 20.7293 (11)
β (°) 99.677 (1)
V3)1819.01 (17)
Z8
Radiation typeMo Kα
µ (mm1)0.42
Crystal size (mm)0.55 × 0.16 × 0.11
Data collection
DiffractometerBruker SMART1000 CCD area detector
diffractometer
Absorption correctionMulti-scan
SADABS (Bruker, 1999)
Tmin, Tmax0.761, 0.949
No. of measured, independent and
observed [I > 2σ(I)] reflections
6528, 2096, 1758
Rint0.023
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.085, 1.04
No. of reflections2096
No. of parameters151
No. of restraints3
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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).

Selected bond lengths (Å) top
S1—O11.4257 (13)O3—C61.3893 (18)
S1—O21.4312 (12)N1—C11.374 (2)
S1—O31.6442 (11)O4—N21.227 (2)
S1—N11.5889 (13)O5—N21.234 (2)
Na1—O1W2.3244 (14)N2—C41.441 (2)
Na1—O1Wi2.4516 (15)C1—C61.408 (2)
Na1—O1ii2.8355 (15)C1—C21.388 (2)
Na1—O2i2.3846 (14)C2—C31.377 (2)
Na1—O22.7644 (15)C3—C41.387 (2)
Na1—O4iii2.4173 (14)C4—C51.396 (2)
Na1—O5iv2.5988 (15)C5—C61.360 (2)
Na1—Na1v3.6314 (6)
Symmetry codes: (i) x+3/2, y1/2, z+1/2; (ii) x1/2, y1/2, z; (iii) x+3/2, y1/2, z; (iv) x, y, z+1/2; (v) x+3/2, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···N1vi0.811 (9)2.173 (12)2.9521 (17)161 (2)
O1W—H2W1···N1v0.821 (9)2.196 (12)2.9859 (17)161 (2)
C2—H2···O1vii0.932.573.475 (2)166
Symmetry codes: (v) x+3/2, y+1/2, z+1/2; (vi) x1/2, y+1/2, z; (vii) x, y1, z.
 

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