Sulfathia­zolium nitrate monohydrate

Banu, A.; Hossain, G.M.G.

doi:10.1107/S1600536806010312

organic compounds

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ISSN: 2056-9890

Volume 62| Part 4| April 2006| Pages o1573-o1574

https://doi.org/10.1107/S1600536806010312

Sulfathiazolium nitrate monohydrate

Afroza Banu ^a and G. M. Golzar Hossain ^a ^*

^aSchool of Chemistry, Cardiff University, Cardiff CF10 3AT, Wales
^*Correspondence e-mail: acsbd@yahoo.com

(Received 16 March 2006; accepted 21 March 2006; online 29 March 2006)

The title compound, C₉H₁₀N₃O₂S₂⁺·NO₃⁻·H₂O, was obtained from a solution of sulfathiazole in dilute nitric acid at room temperature. The crystal structure is stabilized by a network of hydrogen bonds and van der Waals interactions.

Comment

Sulfathiazole has a remarkable solvate-forming ability with interesting structural and conformational properties. Many solvent-containing sulfathiazoles are known and a lot of them have been studied crystallographically (Bingham et al., 2001 ).

Shirotani et al. (1983 ) described three solvates of sulfathiazole and Caira et al. (1994 ) reported the crystal structure of the 1:1 complex of sulfathiazole and cyclodextrin, in which the molecules are hydrogen bonded with each other, forming a layer and these layers are linked by hydrogen bonds with water molecules.

The sulfathiazole molecule in the title complex, (I), is hydrogen bonded with a nitrate ion which is also hydrogen bonded with the water molecule. The sulfathiazole molecule is protonated on its terminal amino group.

The planes of the benzene and thiazole rings are inclined in a gauche conformation about the S12—N11 bond with a dihedral angle of 87.63 (6)°. The crystal structure is stabilized by a network of hydrogen bonds and van der Waals interactions.

Figure 1
View of (I)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms not involved in hydrogen bonding (dashed lines) have been omitted.

Experimental

Solid sulfathiazole (0.255 g; 1 mmol) was dissolved in 1M HNO₃ acid (50 ml) and stirred for 30 minutes, filtered off and the clear solution was left at room temperature for crystallization. Pale-yellow platelike crystals of sulfathiazole nitrate were obtained by slow evaporation of the solution.

Crystal data

C₉H₁₀N₃O₂S₂⁺·NO₃⁻·H₂O
M_r = 336.35
Monoclinic, P2₁/c
a = 12.1917 (2) Å
b = 7.6348 (2) Å
c = 15.3895 (2) Å
β = 107.4664 (14)°
V = 1366.43 (5) Å³
Z = 4
D_x = 1.635 Mg m⁻³
Mo Kα radiation
Cell parameters from 8182 reflections
θ = 2.9–27.5°
μ = 0.42 mm⁻¹
T = 120 (2) K
Plate, pale yellow
0.34 × 0.32 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer
ω scans
Absorption correction: multi-scan (Blessing; 1995 ) T_min = 0.869, T_max = 0.979
17799 measured reflections
3117 independent reflections
2669 reflections with I > 2σ(I)
R_int = 0.081
θ_max = 27.5°
h = −15 → 15
k = −9 → 9
l = −19 → 18

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.106
S = 1.05
3117 reflections
214 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0584P)² + 0.5659P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

S11—C11	1.7362 (17)
S11—C12	1.732 (2)
S12—O11	1.4566 (13)
S12—O12	1.4436 (13)
S12—N11	1.5824 (15)
S12—C14	1.7740 (17)
N11—C11	1.344 (2)
N12—C11	1.335 (2)
N12—C13	1.384 (2)
N13—C17	1.462 (2)
C12—C13	1.335 (3)
C14—C15	1.381 (2)
C14—C19	1.398 (2)
C15—C16	1.392 (2)
C16—C17	1.382 (2)
C17—C18	1.382 (2)
C18—C19	1.384 (3)

C11—S11—C12	90.84 (8)
O11—S12—O12	117.06 (8)
O11—S12—N11	104.67 (8)
O12—S12—N11	114.68 (8)
O11—S12—C14	106.67 (8)
O12—S12—C14	106.87 (8)
N11—S12—C14	106.17 (8)
C11—N11—S12	120.76 (13)
C11—N12—C13	115.14 (15)
N12—C11—N11	119.41 (15)
N12—C11—S11	109.85 (12)
N11—C11—S11	130.74 (14)
C13—C12—S11	111.26 (14)
C12—C13—N12	112.90 (17)
C15—C14—C19	121.33 (15)
C15—C14—S12	120.22 (13)
C19—C14—S12	118.45 (13)
C14—C15—C16	119.52 (15)
C15—C16—C17	118.86 (15)
C16—C17—C18	121.95 (16)
C16—C17—N13	119.15 (15)
C18—C17—N13	118.90 (15)
C17—C18—C19	119.43 (16)
C14—C19—C18	118.90 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N13—H13A⋯O1	0.95 (1)	1.82 (1)	2.765 (2)	177 (2)
O4—H4A⋯O2	0.95 (1)	1.87 (1)	2.8027 (19)	170 (2)
N12—H12A⋯O4ⁱ	0.95 (1)	2.00 (1)	2.9050 (19)	159 (2)
O4—H4B⋯O11ⁱ	0.95 (1)	1.97 (1)	2.8807 (18)	162 (2)
N13—H13C⋯O11ⁱⁱ	0.88 (3)	2.03 (3)	2.907 (2)	176 (2)
N13—H13B⋯O4ⁱⁱⁱ	0.95 (1)	1.91 (1)	2.857 (2)	175 (2)
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z.

C-bound H atoms were included in the riding model approximation with C—H = 0.95 Å, and with U_iso(H) = 1.2U_eq(C). H atoms attached to N and O were located in an electron density map and refined isotropically with the N—H and O—H bond lengths restrained to 0.95 (5) Å.

Data collection: COLLECT (Nonius, 1997–2000 ); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997 ); data reduction: HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK; 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: WinGX publication routines (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806010312/sg2017sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806010312/sg2017Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1997–2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK; 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: WinGX publication routines (Farrugia, 1999).

(I) top

Crystal data top

C₉H₁₀N₃O₂S₂⁺·NO₃⁻·H₂O	F(000) = 696
M_r = 336.35	D_x = 1.635 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8182 reflections
a = 12.1917 (2) Å	θ = 2.9–27.5°
b = 7.6348 (2) Å	µ = 0.42 mm⁻¹
c = 15.3895 (2) Å	T = 120 K
β = 107.466 (1)°	Platelike, pale yellow
V = 1366.43 (5) Å³	0.34 × 0.32 × 0.05 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	3117 independent reflections
Radiation source: fine-focus sealed tube	2669 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.081
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan Blessing (1995)	h = −15→15
T_min = 0.869, T_max = 0.979	k = −9→9
17799 measured reflections	l = −19→18

Refinement top

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0584P)² + 0.5659P] where P = (F_o² + 2F_c²)/3
3117 reflections	(Δ/σ)_max = 0.001
214 parameters	Δρ_max = 0.47 e Å⁻³
5 restraints	Δρ_min = −0.61 e Å⁻³

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

	x	y	z	U_iso*/U_eq
S11	1.03911 (4)	0.33588 (6)	0.62604 (3)	0.02120 (14)
S12	0.80044 (4)	0.12718 (6)	0.62170 (3)	0.01730 (13)
O11	0.70722 (11)	0.07178 (17)	0.65647 (8)	0.0214 (3)
O12	0.90388 (11)	0.02267 (17)	0.64704 (8)	0.0233 (3)
N11	0.81921 (13)	0.32750 (19)	0.64842 (10)	0.0181 (3)
N12	0.91621 (12)	0.5878 (2)	0.64833 (9)	0.0172 (3)
H12A	0.8512 (12)	0.648 (2)	0.6541 (15)	0.028 (6)*
N13	0.61384 (13)	0.1154 (2)	0.21568 (10)	0.0190 (3)
H13A	0.5326 (5)	0.121 (3)	0.2005 (17)	0.039 (7)*
H13B	0.6352 (18)	0.0138 (17)	0.1891 (13)	0.025 (5)*
H13C	0.641 (2)	0.208 (4)	0.1947 (17)	0.041 (7)*
C11	0.91245 (14)	0.4134 (2)	0.64160 (11)	0.0168 (3)
C12	1.09071 (15)	0.5476 (3)	0.62748 (12)	0.0218 (4)
H12	1.1631	0.5768	0.6201	0.026*
C13	1.01555 (15)	0.6644 (2)	0.64025 (12)	0.0203 (4)
H13	1.0289	0.7871	0.6435	0.024*
C14	0.74583 (14)	0.1207 (2)	0.50113 (11)	0.0165 (3)
C15	0.80804 (14)	0.0404 (2)	0.45070 (12)	0.0192 (4)
H15	0.8802	−0.0122	0.4803	0.023*
C16	0.76426 (14)	0.0371 (2)	0.35615 (12)	0.0199 (4)
H16	0.8058	−0.0182	0.3205	0.024*
C17	0.65936 (14)	0.1156 (2)	0.31503 (11)	0.0158 (3)
C18	0.59642 (15)	0.1957 (3)	0.36506 (12)	0.0229 (4)
H18	0.5243	0.2481	0.3351	0.027*
C19	0.63940 (16)	0.1989 (3)	0.45914 (12)	0.0240 (4)
H19	0.5973	0.2534	0.4946	0.029*
O1	0.37657 (11)	0.1342 (2)	0.16636 (9)	0.0291 (3)
O2	0.42291 (11)	0.1643 (2)	0.04127 (9)	0.0319 (4)
O3	0.24360 (11)	0.15191 (19)	0.03616 (9)	0.0283 (3)
N1	0.34639 (13)	0.1506 (2)	0.08093 (10)	0.0206 (3)
O4	0.31305 (11)	0.19590 (17)	−0.14618 (9)	0.0202 (3)
H4A	0.346 (2)	0.198 (3)	−0.0823 (4)	0.047 (7)*
H4B	0.308 (2)	0.3159 (10)	−0.1620 (16)	0.039 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S11	0.0173 (2)	0.0231 (2)	0.0236 (3)	0.00481 (17)	0.00666 (17)	−0.00234 (17)
S12	0.0199 (2)	0.0182 (2)	0.0132 (2)	0.00319 (16)	0.00403 (16)	−0.00013 (15)
O11	0.0271 (7)	0.0204 (6)	0.0189 (6)	−0.0015 (5)	0.0104 (5)	0.0007 (5)
O12	0.0258 (7)	0.0230 (7)	0.0178 (6)	0.0100 (5)	0.0018 (5)	0.0002 (5)
N11	0.0179 (7)	0.0190 (7)	0.0171 (7)	0.0012 (6)	0.0048 (5)	−0.0019 (6)
N12	0.0143 (7)	0.0202 (8)	0.0161 (7)	0.0039 (6)	0.0029 (5)	−0.0001 (6)
N13	0.0157 (7)	0.0260 (8)	0.0149 (7)	0.0007 (6)	0.0038 (6)	0.0015 (6)
C11	0.0152 (8)	0.0218 (9)	0.0115 (8)	0.0040 (7)	0.0013 (6)	−0.0008 (6)
C12	0.0177 (8)	0.0266 (10)	0.0216 (9)	0.0000 (7)	0.0064 (7)	−0.0014 (7)
C13	0.0164 (8)	0.0233 (9)	0.0201 (9)	−0.0010 (7)	0.0036 (7)	0.0000 (7)
C14	0.0185 (8)	0.0176 (8)	0.0128 (8)	0.0008 (6)	0.0037 (6)	0.0000 (6)
C15	0.0150 (8)	0.0236 (9)	0.0176 (8)	0.0046 (7)	0.0027 (6)	0.0006 (7)
C16	0.0181 (8)	0.0246 (9)	0.0183 (8)	0.0044 (7)	0.0077 (6)	−0.0017 (7)
C17	0.0152 (8)	0.0181 (8)	0.0133 (8)	−0.0014 (6)	0.0030 (6)	0.0009 (6)
C18	0.0167 (8)	0.0307 (10)	0.0207 (9)	0.0065 (7)	0.0049 (7)	0.0011 (7)
C19	0.0205 (9)	0.0326 (11)	0.0198 (9)	0.0090 (8)	0.0073 (7)	−0.0011 (7)
O1	0.0212 (7)	0.0483 (9)	0.0166 (7)	0.0021 (6)	0.0041 (5)	0.0039 (6)
O2	0.0167 (6)	0.0584 (10)	0.0217 (7)	−0.0026 (6)	0.0075 (5)	0.0020 (6)
O3	0.0135 (6)	0.0431 (9)	0.0252 (7)	−0.0013 (6)	0.0010 (5)	0.0031 (6)
N1	0.0174 (7)	0.0242 (8)	0.0201 (8)	−0.0004 (6)	0.0053 (6)	0.0008 (6)
O4	0.0189 (6)	0.0212 (7)	0.0205 (6)	−0.0012 (5)	0.0061 (5)	0.0010 (5)

Geometric parameters (Å, º) top

S11—C11	1.7362 (17)	C13—H13	0.9500
S11—C12	1.732 (2)	C14—C15	1.381 (2)
S12—O11	1.4566 (13)	C14—C19	1.398 (2)
S12—O12	1.4436 (13)	C15—C16	1.392 (2)
S12—N11	1.5824 (15)	C15—H15	0.9500
S12—C14	1.7740 (17)	C16—C17	1.382 (2)
N11—C11	1.344 (2)	C16—H16	0.9500
N12—C11	1.335 (2)	C17—C18	1.382 (2)
N12—C13	1.384 (2)	C18—C19	1.384 (3)
N12—H12A	0.945 (5)	C18—H18	0.9500
N13—C17	1.462 (2)	C19—H19	0.9500
N13—H13A	0.948 (5)	N1—O1	1.261 (2)
N13—H13B	0.949 (5)	N1—O2	1.2632 (19)
N13—H13C	0.88 (3)	N1—O3	1.236 (2)
C12—C13	1.335 (3)	O4—H4A	0.945 (5)
C12—H12	0.9500	O4—H4B	0.945 (5)

C11—S11—C12	90.84 (8)	C12—C13—H13	123.6
O11—S12—O12	117.06 (8)	N12—C13—H13	123.6
O11—S12—N11	104.67 (8)	C15—C14—C19	121.33 (15)
O12—S12—N11	114.68 (8)	C15—C14—S12	120.22 (13)
O11—S12—C14	106.67 (8)	C19—C14—S12	118.45 (13)
O12—S12—C14	106.87 (8)	C14—C15—C16	119.52 (15)
N11—S12—C14	106.17 (8)	C14—C15—H15	120.2
C11—N11—S12	120.76 (13)	C16—C15—H15	120.2
C11—N12—C13	115.14 (15)	C15—C16—C17	118.86 (15)
C11—N12—H12A	119.0 (13)	C17—C16—H16	120.6
C13—N12—H12A	125.7 (13)	C15—C16—H16	120.6
C17—N13—H13A	107.3 (15)	C16—C17—C18	121.95 (16)
C17—N13—H13B	112.6 (13)	C16—C17—N13	119.15 (15)
H13A—N13—H13B	109 (2)	C18—C17—N13	118.90 (15)
C17—N13—H13C	108.4 (17)	C17—C18—C19	119.43 (16)
H13A—N13—H13C	110 (2)	C17—C18—H18	120.3
H13B—N13—H13C	109 (2)	C19—C18—H18	120.3
N12—C11—N11	119.41 (15)	C14—C19—C18	118.90 (16)
N12—C11—S11	109.85 (12)	C18—C19—H19	120.5
N11—C11—S11	130.74 (14)	C14—C19—H19	120.5
C13—C12—S11	111.26 (14)	O1—N1—O2	119.04 (15)
C13—C12—H12	124.4	O1—N1—O3	120.80 (15)
S11—C12—H12	124.4	O2—N1—O3	120.16 (15)
C12—C13—N12	112.90 (17)	H4A—O4—H4B	103 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N13—H13A···O1	0.95 (1)	1.82 (1)	2.765 (2)	177 (2)
O4—H4A···O2	0.95 (1)	1.87 (1)	2.8027 (19)	170 (2)
N12—H12A···O4ⁱ	0.95 (1)	2.00 (1)	2.9050 (19)	159 (2)
O4—H4B···O11ⁱ	0.95 (1)	1.97 (1)	2.8807 (18)	162 (2)
N13—H13C···O11ⁱⁱ	0.88 (3)	2.03 (3)	2.907 (2)	176 (2)
N13—H13B···O4ⁱⁱⁱ	0.95 (1)	1.91 (1)	2.857 (2)	175 (2)

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

Acknowledgements

GMGH acknowledges the Ministry of Science and Technology, Bangladesh Secretariat, Dhaka for awarding the Bangabandhu Fellowship.

References

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