2-Nitro-N-(4-pyridinio)benzene­sulfonamidate monohydrate

Hu, L.-B.; Chen, J.; Liu, C.-Z.

doi:10.1107/S1600536808035526

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2277

doi:10.1107/S1600536808035526

Open

access

2-Nitro-N-(4-pyridinio)benzenesulfonamidate monohydrate

Liang-Bin Hu,^a ^* Jian Chen ^b and Chang-Zhong Liu ^c

^aSchool of Food Science, Henan Institute of Science and Technology, Xinxiang 453003, People's Republic of China, ^bCollege of Life Sciences, Nanjing Agricultural University, Nanjing 210095, People's Republic of China, and ^cCollege of Animal Science, Henan Institute of Science and Technology, Xinxiang 453003, People's Republic of China
^*Correspondence e-mail: liangbin_hu@yahoo.cn

(Received 22 October 2008; accepted 30 October 2008; online 8 November 2008)

The title compound, C₁₁H₉N₃O₄S·H₂O, contains both an acid and a base centre and displays a zwitterionic structure. There are two independent molecules and two water molecules in the asymmetric unit. The dihedral angles between the benzene ring and the pyridinium ring are 109.7 (1) and 110.7 (1)°. The dihedral angles between the nitro group and the benzene ring are 116.1 (2) and 116.7 (1)°. The crystal structure is stabilized by N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds.

Related literature

For the uses of organic pyridinium salts, see: Damiano et al. (2007 ). For zwitterionic forms of N-arylbenzenesulfonamides, see: Li et al. (2007 ); Yu & Li (2007 ). For reference geometric data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₁H₉N₃O₄S·H₂O
M_r = 297.29
Monoclinic, P 2₁
a = 8.7206 (17) Å
b = 11.972 (2) Å
c = 12.743 (3) Å
β = 107.65 (3)°
V = 1267.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 113 (2) K
0.14 × 0.10 × 0.04 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.962, T_max = 0.989
10348 measured reflections
4633 independent reflections
3587 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.090
S = 1.03
4633 reflections
385 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.40 e Å⁻³
Absolute structure: Flack (1983 ), 1560 Friedel pairs
Flack parameter: 0.52 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O9	0.913 (10)	1.868 (12)	2.764 (3)	167 (3)
O9—H9A⋯O1	0.864 (10)	2.122 (11)	2.967 (3)	166 (3)
N1—H1A⋯O10ⁱ	0.918 (10)	1.843 (11)	2.757 (3)	174 (4)
O9—H9B⋯N5ⁱⁱ	0.867 (10)	2.043 (11)	2.901 (3)	170 (2)
O9—H9B⋯O6ⁱⁱ	0.867 (10)	2.56 (2)	3.125 (3)	123 (2)
O10—H10A⋯O6ⁱⁱⁱ	0.867 (10)	2.051 (11)	2.914 (3)	174 (4)
O10—H10B⋯N2^iv	0.870 (10)	2.042 (12)	2.902 (3)	170 (3)
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+1]$ ; (ii) x-1, y, z; (iii) $[-x+2, y+{\script{1\over 2}}, -z+1]$ ; (iv) $[-x+1, y+{\script{1\over 2}}, -z+1]$ .

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808035526/hg2431sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808035526/hg2431Isup2.hkl

checkCIF report

Comment top

Organic pyridinium salts have been widely used in the construction of supramolecular architectures (Damiano et al., 2007). As part of our ongoing studies of supramolecular chemistry involving the pyridinium rings (Li et al., 2007), the structure of the title compound was determined by X-ray diffraction. There are two independent molecules and two independent water molecules in the unit cell. In the cations of the title compound the short C—N distance [N2—C1 = 1.367 (3) Å and N5—C12 = 1.365 (3) Å] indicate the slight conjugation of the sulfonamide N with the pyridinium ring (Allen et al., 1987).

The dihedral angles between the benzene ring and the pyridinium ring are 109.7 (1)° and 110.7 (1)° respectively. And the dihedral angles between the nitro group and the benzene ring are 116.1 (2)° and 116.7 (1)° respectively. The crystal structure is stabilized by N—H···O hydrogen bonds.

Related literature top

For the uses of organic pyridinium salts, see: Damiano et al. (2007). For zwitterionic forms of N-arylbenzenesulfonamides, see: Li et al. (2007); Yu & Li (2007). For reference geometric data, see: Allen et al. (1987).

Experimental top

A solution of 2-nitrobenzenesulfonyl chloride (2.2 g, 10 mmol) in CH₂Cl₂ (10 ml) was added dropwise to a suspension of 4-aminopyridine (0.9 g, 10 mmol) in CH₂Cl₂ (10 ml) at room temperature with stirring. The reaction mixture was stirred overnight. The yellow solid obtained was washed with warm water to obtain the title compound in a yield of 55.7%. A colorless single crystal suitable for X-ray analysis was obtained by slow evaporation of an NaOH (10%) solution at room temperature over a period of a week.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. View of the molecule of title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level (arbitrary spheres for the H atoms).

2-Nitro-N-(4-pyridinio)benzenesulfonamidate monohydrate top

Crystal data top

C₁₁H₉N₃O₄S·H₂O	F(000) = 616
M_r = 297.29	D_x = 1.557 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 4439 reflections
a = 8.7206 (17) Å	θ = 2.4–27.5°
b = 11.972 (2) Å	µ = 0.28 mm⁻¹
c = 12.743 (3) Å	T = 113 K
β = 107.65 (3)°	Block, colourless
V = 1267.8 (4) Å³	0.14 × 0.10 × 0.04 mm
Z = 4

Data collection top

Rigaku Saturn diffractometer	4633 independent reflections
Radiation source: rotating anode	3587 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.033
ω scans	θ_max = 27.5°, θ_min = 1.7°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	h = −11→11
T_min = 0.962, T_max = 0.989	k = −12→15
10348 measured reflections	l = −16→16

Refinement top

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)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.090	w = 1/[σ²(F_o²) + (0.0539P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.002
4633 reflections	Δρ_max = 0.22 e Å⁻³
385 parameters	Δρ_min = −0.40 e Å⁻³
9 restraints	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.52 (6)

Crystal data top

C₁₁H₉N₃O₄S·H₂O	V = 1267.8 (4) Å³
M_r = 297.29	Z = 4
Monoclinic, P2₁	Mo Kα radiation
a = 8.7206 (17) Å	µ = 0.28 mm⁻¹
b = 11.972 (2) Å	T = 113 K
c = 12.743 (3) Å	0.14 × 0.10 × 0.04 mm
β = 107.65 (3)°

Data collection top

Rigaku Saturn diffractometer	4633 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	3587 reflections with I > 2σ(I)
T_min = 0.962, T_max = 0.989	R_int = 0.033
10348 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.090	Δρ_max = 0.22 e Å⁻³
S = 1.03	Δρ_min = −0.40 e Å⁻³
4633 reflections	Absolute structure: Flack (1983), with how many Friedel pairs?
385 parameters	Absolute structure parameter: 0.52 (6)
9 restraints

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
S1	0.54299 (7)	0.49945 (5)	0.75574 (5)	0.01423 (14)
S2	1.01577 (7)	0.25356 (5)	0.35546 (5)	0.01307 (14)
O1	0.36887 (19)	0.49815 (17)	0.72910 (14)	0.0177 (4)
O2	0.6116 (2)	0.59540 (15)	0.71745 (16)	0.0187 (4)
O3	0.4219 (3)	0.29003 (18)	0.87441 (18)	0.0318 (5)
O4	0.2777 (2)	0.4008 (2)	0.94108 (18)	0.0326 (5)
O5	0.9524 (2)	0.15286 (15)	0.38857 (15)	0.0165 (4)
O6	1.1904 (2)	0.26159 (18)	0.38501 (16)	0.0182 (4)
O7	1.1373 (3)	0.46983 (18)	0.24125 (19)	0.0334 (5)
O8	1.2807 (2)	0.3638 (2)	0.16880 (18)	0.0371 (6)
N1	1.0324 (3)	0.2999 (2)	0.67719 (19)	0.0185 (5)
N2	0.5920 (2)	0.38299 (18)	0.71702 (19)	0.0146 (5)
N3	0.4050 (3)	0.3727 (2)	0.9245 (2)	0.0217 (5)
N4	0.5077 (3)	0.4240 (2)	0.43389 (18)	0.0179 (5)
N5	0.9564 (2)	0.36491 (18)	0.39696 (18)	0.0141 (5)
N6	1.1564 (3)	0.3888 (2)	0.18846 (19)	0.0230 (6)
C1	0.7414 (3)	0.3615 (2)	0.7078 (2)	0.0132 (5)
C2	0.7644 (3)	0.2549 (2)	0.6690 (2)	0.0167 (5)
H2	0.6813	0.2029	0.6537	0.020*
C3	0.9100 (3)	0.2265 (2)	0.6532 (2)	0.0188 (6)
H3	0.9231	0.1563	0.6259	0.023*
C4	1.0168 (3)	0.4019 (2)	0.7153 (2)	0.0179 (6)
H4	1.1030	0.4513	0.7304	0.021*
C5	0.8752 (3)	0.4350 (2)	0.7325 (2)	0.0169 (6)
H5	0.8672	0.5058	0.7604	0.020*
C6	0.6158 (3)	0.5053 (3)	0.9027 (2)	0.0148 (5)
C7	0.7441 (3)	0.5753 (2)	0.9531 (2)	0.0189 (6)
H7	0.7936	0.6156	0.9100	0.023*
C8	0.7996 (3)	0.5858 (2)	1.0674 (2)	0.0240 (6)
H8	0.8857	0.6329	1.0999	0.029*
C9	0.7271 (3)	0.5264 (3)	1.1326 (2)	0.0245 (7)
H9	0.7656	0.5325	1.2089	0.029*
C10	0.5978 (3)	0.4582 (2)	1.0843 (2)	0.0208 (6)
H10	0.5469	0.4197	1.1277	0.025*
C11	0.5441 (3)	0.4472 (2)	0.9712 (2)	0.0162 (6)
C12	0.8049 (3)	0.3782 (2)	0.4049 (2)	0.0120 (5)
C13	0.7734 (3)	0.4806 (2)	0.4510 (2)	0.0163 (6)
H13	0.8534	0.5347	0.4722	0.020*
C14	0.6264 (3)	0.4998 (2)	0.4642 (2)	0.0181 (5)
H14	0.6078	0.5669	0.4949	0.022*
C15	0.5302 (3)	0.3265 (2)	0.3884 (2)	0.0165 (5)
H15	0.4464	0.2752	0.3672	0.020*
C16	0.6767 (3)	0.3014 (2)	0.3725 (2)	0.0136 (5)
H16	0.6905	0.2339	0.3405	0.016*
C17	0.9459 (3)	0.2526 (2)	0.2084 (2)	0.0145 (5)
C18	0.8167 (3)	0.1850 (2)	0.1552 (2)	0.0179 (6)
H18	0.7672	0.1423	0.1967	0.021*
C19	0.7603 (3)	0.1799 (2)	0.0417 (2)	0.0229 (6)
H19	0.6723	0.1349	0.0080	0.027*
C20	0.8324 (3)	0.2406 (3)	−0.0223 (2)	0.0245 (7)
H20	0.7933	0.2365	−0.0987	0.029*
C21	0.9631 (3)	0.3074 (2)	0.0276 (2)	0.0195 (6)
H21	1.0141	0.3476	−0.0146	0.023*
C22	1.0173 (3)	0.3137 (2)	0.1415 (2)	0.0157 (6)
O9	0.2408 (2)	0.50194 (18)	0.48520 (16)	0.0183 (4)
O10	0.6923 (2)	0.74683 (18)	0.37557 (18)	0.0203 (4)
H1A	1.127 (3)	0.280 (3)	0.665 (3)	0.054 (11)*
H4A	0.411 (2)	0.441 (2)	0.444 (2)	0.021 (8)*
H9A	0.260 (3)	0.500 (3)	0.5558 (8)	0.047 (11)*
H9B	0.160 (2)	0.460 (2)	0.4517 (18)	0.024 (9)*
H10A	0.719 (4)	0.751 (4)	0.4468 (8)	0.11 (2)*
H10B	0.601 (2)	0.780 (3)	0.346 (2)	0.034 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0127 (3)	0.0152 (3)	0.0156 (3)	0.0016 (3)	0.0055 (2)	0.0026 (3)
S2	0.0098 (3)	0.0162 (3)	0.0138 (3)	0.0013 (3)	0.0044 (2)	0.0012 (3)
O1	0.0119 (8)	0.0220 (10)	0.0201 (10)	0.0049 (9)	0.0064 (7)	0.0009 (9)
O2	0.0242 (10)	0.0133 (9)	0.0209 (11)	0.0000 (8)	0.0102 (9)	0.0042 (8)
O3	0.0376 (12)	0.0285 (12)	0.0288 (13)	−0.0115 (10)	0.0095 (10)	−0.0019 (10)
O4	0.0157 (9)	0.0515 (15)	0.0329 (13)	−0.0051 (10)	0.0109 (9)	0.0064 (12)
O5	0.0194 (10)	0.0153 (9)	0.0158 (10)	0.0043 (8)	0.0067 (8)	0.0053 (8)
O6	0.0099 (8)	0.0269 (11)	0.0190 (10)	0.0008 (9)	0.0061 (7)	0.0016 (9)
O7	0.0378 (13)	0.0292 (13)	0.0329 (13)	−0.0111 (10)	0.0101 (11)	−0.0060 (10)
O8	0.0180 (10)	0.0689 (18)	0.0274 (13)	−0.0077 (11)	0.0114 (10)	0.0055 (12)
N1	0.0135 (11)	0.0249 (12)	0.0184 (12)	0.0064 (10)	0.0067 (9)	0.0022 (10)
N2	0.0116 (10)	0.0147 (11)	0.0196 (12)	0.0000 (9)	0.0078 (9)	−0.0001 (9)
N3	0.0209 (12)	0.0263 (14)	0.0176 (13)	−0.0040 (11)	0.0057 (10)	0.0071 (10)
N4	0.0148 (11)	0.0224 (13)	0.0179 (12)	0.0020 (10)	0.0072 (9)	0.0009 (10)
N5	0.0108 (10)	0.0177 (11)	0.0144 (11)	−0.0028 (9)	0.0046 (9)	−0.0035 (9)
N6	0.0193 (12)	0.0354 (15)	0.0146 (12)	−0.0067 (11)	0.0054 (10)	0.0064 (11)
C1	0.0123 (11)	0.0178 (13)	0.0100 (13)	0.0024 (10)	0.0042 (10)	0.0041 (10)
C2	0.0166 (11)	0.0179 (12)	0.0164 (13)	−0.0044 (12)	0.0062 (10)	0.0015 (12)
C3	0.0177 (13)	0.0173 (14)	0.0217 (15)	0.0033 (11)	0.0062 (11)	−0.0025 (11)
C4	0.0133 (12)	0.0214 (14)	0.0181 (14)	−0.0009 (11)	0.0035 (10)	0.0014 (12)
C5	0.0145 (12)	0.0147 (13)	0.0211 (15)	0.0009 (11)	0.0048 (11)	−0.0006 (11)
C6	0.0151 (12)	0.0134 (13)	0.0166 (13)	0.0032 (12)	0.0059 (10)	0.0000 (12)
C7	0.0206 (13)	0.0143 (13)	0.0224 (15)	−0.0036 (11)	0.0075 (12)	0.0006 (11)
C8	0.0252 (15)	0.0225 (15)	0.0224 (16)	−0.0067 (13)	0.0040 (13)	−0.0035 (12)
C9	0.0255 (14)	0.0278 (16)	0.0184 (15)	0.0041 (13)	0.0038 (12)	−0.0030 (12)
C10	0.0236 (14)	0.0239 (15)	0.0178 (15)	0.0041 (12)	0.0106 (12)	0.0047 (12)
C11	0.0103 (11)	0.0175 (13)	0.0217 (15)	0.0013 (10)	0.0062 (11)	0.0027 (11)
C12	0.0152 (12)	0.0125 (12)	0.0083 (12)	0.0024 (10)	0.0038 (10)	0.0017 (10)
C13	0.0168 (12)	0.0141 (13)	0.0183 (14)	−0.0048 (11)	0.0060 (11)	−0.0026 (11)
C14	0.0225 (13)	0.0147 (12)	0.0186 (13)	−0.0018 (12)	0.0087 (11)	−0.0020 (12)
C15	0.0136 (12)	0.0198 (13)	0.0173 (14)	0.0002 (11)	0.0066 (11)	−0.0031 (11)
C16	0.0093 (11)	0.0150 (12)	0.0173 (14)	−0.0026 (10)	0.0051 (10)	−0.0032 (11)
C17	0.0160 (12)	0.0150 (12)	0.0119 (13)	0.0007 (12)	0.0033 (10)	−0.0004 (11)
C18	0.0193 (13)	0.0163 (14)	0.0198 (15)	−0.0015 (12)	0.0084 (12)	0.0037 (12)
C19	0.0262 (15)	0.0190 (15)	0.0202 (15)	−0.0061 (13)	0.0022 (12)	0.0005 (12)
C20	0.0322 (15)	0.0275 (16)	0.0115 (14)	0.0032 (14)	0.0033 (12)	−0.0006 (13)
C21	0.0193 (13)	0.0221 (15)	0.0205 (15)	0.0031 (12)	0.0110 (12)	0.0049 (12)
C22	0.0118 (11)	0.0181 (14)	0.0172 (14)	0.0001 (11)	0.0045 (11)	0.0019 (11)
O9	0.0157 (9)	0.0210 (10)	0.0194 (11)	0.0003 (9)	0.0072 (8)	−0.0056 (10)
O10	0.0170 (9)	0.0221 (10)	0.0215 (11)	0.0022 (9)	0.0057 (8)	0.0043 (10)

Geometric parameters (Å, º) top

S1—O2	1.4464 (19)	C6—C11	1.403 (3)
S1—O1	1.4521 (17)	C7—C8	1.394 (4)
S1—N2	1.581 (2)	C7—H7	0.9300
S1—C6	1.787 (3)	C8—C9	1.383 (4)
S2—O5	1.4416 (19)	C8—H8	0.9300
S2—O6	1.4568 (17)	C9—C10	1.377 (4)
S2—N5	1.578 (2)	C9—H9	0.9300
S2—C17	1.787 (3)	C10—C11	1.380 (4)
O3—N3	1.211 (3)	C10—H10	0.9300
O4—N3	1.237 (3)	C12—C16	1.409 (3)
O7—N6	1.221 (3)	C12—C13	1.421 (3)
O8—N6	1.221 (3)	C13—C14	1.362 (3)
N1—C4	1.336 (4)	C13—H13	0.9300
N1—C3	1.345 (3)	C14—H14	0.9300
N1—H1A	0.918 (10)	C15—C16	1.385 (3)
N2—C1	1.367 (3)	C15—H15	0.9300
N3—C11	1.478 (3)	C16—H16	0.9300
N4—C14	1.342 (3)	C17—C18	1.386 (4)
N4—C15	1.344 (3)	C17—C22	1.404 (3)
N4—H4A	0.913 (10)	C18—C19	1.380 (4)
N5—C12	1.365 (3)	C18—H18	0.9300
N6—C22	1.482 (3)	C19—C20	1.379 (4)
C1—C2	1.405 (4)	C19—H19	0.9300
C1—C5	1.419 (4)	C20—C21	1.380 (4)
C2—C3	1.387 (3)	C20—H20	0.9300
C2—H2	0.9300	C21—C22	1.385 (4)
C3—H3	0.9300	C21—H21	0.9300
C4—C5	1.376 (3)	O9—H9A	0.864 (10)
C4—H4	0.9300	O9—H9B	0.867 (10)
C5—H5	0.9300	O10—H10A	0.867 (10)
C6—C7	1.389 (4)	O10—H10B	0.870 (10)

O2—S1—O1	116.08 (11)	C9—C8—C7	120.3 (3)
O2—S1—N2	114.62 (10)	C9—C8—H8	119.9
O1—S1—N2	106.27 (11)	C7—C8—H8	119.9
O2—S1—C6	105.68 (13)	C10—C9—C8	119.8 (3)
O1—S1—C6	105.03 (11)	C10—C9—H9	120.1
N2—S1—C6	108.55 (13)	C8—C9—H9	120.1
O5—S2—O6	116.29 (11)	C9—C10—C11	119.8 (3)
O5—S2—N5	114.48 (10)	C9—C10—H10	120.1
O6—S2—N5	106.33 (12)	C11—C10—H10	120.1
O5—S2—C17	105.23 (12)	C10—C11—C6	121.9 (3)
O6—S2—C17	105.61 (11)	C10—C11—N3	117.1 (2)
N5—S2—C17	108.33 (12)	C6—C11—N3	121.0 (2)
C4—N1—C3	121.3 (2)	N5—C12—C16	127.0 (2)
C4—N1—H1A	120 (2)	N5—C12—C13	116.4 (2)
C3—N1—H1A	119 (2)	C16—C12—C13	116.6 (2)
C1—N2—S1	123.21 (19)	C14—C13—C12	120.2 (2)
O3—N3—O4	124.9 (3)	C14—C13—H13	119.9
O3—N3—C11	119.3 (2)	C12—C13—H13	119.9
O4—N3—C11	115.9 (2)	N4—C14—C13	121.6 (3)
C14—N4—C15	120.7 (2)	N4—C14—H14	119.2
C14—N4—H4A	118.3 (19)	C13—C14—H14	119.2
C15—N4—H4A	121.0 (19)	N4—C15—C16	120.9 (2)
C12—N5—S2	123.16 (18)	N4—C15—H15	119.6
O7—N6—O8	125.8 (3)	C16—C15—H15	119.6
O7—N6—C22	118.2 (2)	C15—C16—C12	120.0 (2)
O8—N6—C22	115.9 (2)	C15—C16—H16	120.0
N2—C1—C2	116.3 (2)	C12—C16—H16	120.0
N2—C1—C5	127.2 (2)	C18—C17—C22	116.9 (2)
C2—C1—C5	116.5 (2)	C18—C17—S2	119.0 (2)
C3—C2—C1	120.6 (2)	C22—C17—S2	124.1 (2)
C3—C2—H2	119.7	C19—C18—C17	121.1 (2)
C1—C2—H2	119.7	C19—C18—H18	119.4
N1—C3—C2	120.3 (2)	C17—C18—H18	119.4
N1—C3—H3	119.8	C20—C19—C18	121.0 (3)
C2—C3—H3	119.8	C20—C19—H19	119.5
N1—C4—C5	121.1 (3)	C18—C19—H19	119.5
N1—C4—H4	119.5	C19—C20—C21	119.6 (3)
C5—C4—H4	119.5	C19—C20—H20	120.2
C4—C5—C1	120.2 (2)	C21—C20—H20	120.2
C4—C5—H5	119.9	C20—C21—C22	119.1 (3)
C1—C5—H5	119.9	C20—C21—H21	120.4
C7—C6—C11	117.3 (2)	C22—C21—H21	120.4
C7—C6—S1	119.3 (2)	C21—C22—C17	122.3 (2)
C11—C6—S1	123.3 (2)	C21—C22—N6	115.7 (2)
C6—C7—C8	120.9 (3)	C17—C22—N6	122.0 (2)
C6—C7—H7	119.6	H9A—O9—H9B	111.6 (16)
C8—C7—H7	119.6	H10A—O10—H10B	110.7 (16)

O2—S1—N2—C1	36.7 (2)	O4—N3—C11—C10	62.9 (3)
O1—S1—N2—C1	166.3 (2)	O3—N3—C11—C6	64.4 (4)
C6—S1—N2—C1	−81.2 (2)	O4—N3—C11—C6	−116.0 (3)
O5—S2—N5—C12	−36.0 (2)	S2—N5—C12—C16	−4.2 (4)
O6—S2—N5—C12	−165.8 (2)	S2—N5—C12—C13	175.7 (2)
C17—S2—N5—C12	81.0 (2)	N5—C12—C13—C14	−178.5 (2)
S1—N2—C1—C2	−178.07 (19)	C16—C12—C13—C14	1.4 (4)
S1—N2—C1—C5	1.5 (4)	C15—N4—C14—C13	−0.6 (4)
N2—C1—C2—C3	177.8 (2)	C12—C13—C14—N4	−0.4 (4)
C5—C1—C2—C3	−1.9 (4)	C14—N4—C15—C16	0.6 (4)
C4—N1—C3—C2	−0.8 (4)	N4—C15—C16—C12	0.4 (4)
C1—C2—C3—N1	1.4 (4)	N5—C12—C16—C15	178.5 (2)
C3—N1—C4—C5	0.7 (4)	C13—C12—C16—C15	−1.3 (4)
N1—C4—C5—C1	−1.2 (4)	O5—S2—C17—C18	18.6 (2)
N2—C1—C5—C4	−177.8 (3)	O6—S2—C17—C18	142.2 (2)
C2—C1—C5—C4	1.8 (4)	N5—S2—C17—C18	−104.2 (2)
O2—S1—C6—C7	−14.8 (2)	O5—S2—C17—C22	−159.0 (2)
O1—S1—C6—C7	−138.0 (2)	O6—S2—C17—C22	−35.5 (3)
N2—S1—C6—C7	108.6 (2)	N5—S2—C17—C22	78.1 (2)
O2—S1—C6—C11	161.6 (2)	C22—C17—C18—C19	−1.0 (4)
O1—S1—C6—C11	38.3 (3)	S2—C17—C18—C19	−178.8 (2)
N2—S1—C6—C11	−75.0 (2)	C17—C18—C19—C20	1.1 (4)
C11—C6—C7—C8	0.6 (4)	C18—C19—C20—C21	0.1 (4)
S1—C6—C7—C8	177.2 (2)	C19—C20—C21—C22	−1.2 (4)
C6—C7—C8—C9	−0.1 (4)	C20—C21—C22—C17	1.3 (4)
C7—C8—C9—C10	−1.1 (4)	C20—C21—C22—N6	−179.0 (2)
C8—C9—C10—C11	1.7 (4)	C18—C17—C22—C21	−0.2 (4)
C9—C10—C11—C6	−1.2 (4)	S2—C17—C22—C21	177.5 (2)
C9—C10—C11—N3	180.0 (2)	C18—C17—C22—N6	−179.9 (2)
C7—C6—C11—C10	0.0 (4)	S2—C17—C22—N6	−2.2 (4)
S1—C6—C11—C10	−176.4 (2)	O7—N6—C22—C21	116.6 (3)
C7—C6—C11—N3	178.8 (2)	O8—N6—C22—C21	−62.4 (3)
S1—C6—C11—N3	2.4 (4)	O7—N6—C22—C17	−63.7 (4)
O3—N3—C11—C10	−116.7 (3)	O8—N6—C22—C17	117.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O9	0.91 (1)	1.87 (1)	2.764 (3)	167 (3)
O9—H9A···O1	0.86 (1)	2.12 (1)	2.967 (3)	166 (3)
N1—H1A···O10ⁱ	0.92 (1)	1.84 (1)	2.757 (3)	174 (4)
O9—H9B···N5ⁱⁱ	0.87 (1)	2.04 (1)	2.901 (3)	170 (2)
O9—H9B···O6ⁱⁱ	0.87 (1)	2.56 (2)	3.125 (3)	123 (2)
O10—H10A···O6ⁱⁱⁱ	0.87 (1)	2.05 (1)	2.914 (3)	174 (4)
O10—H10B···N2^iv	0.87 (1)	2.04 (1)	2.902 (3)	170 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₁H₉N₃O₄S·H₂O
M_r	297.29
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	113
a, b, c (Å)	8.7206 (17), 11.972 (2), 12.743 (3)
β (°)	107.65 (3)
V (Å³)	1267.8 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.14 × 0.10 × 0.04

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.962, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	10348, 4633, 3587
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.090, 1.03
No. of reflections	4633
No. of parameters	385
No. of restraints	9
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.40
Absolute structure	Flack (1983), with how many Friedel pairs?
Absolute structure parameter	0.52 (6)

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O9	0.913 (10)	1.868 (12)	2.764 (3)	167 (3)
O9—H9A···O1	0.864 (10)	2.122 (11)	2.967 (3)	166 (3)
N1—H1A···O10ⁱ	0.918 (10)	1.843 (11)	2.757 (3)	174 (4)
O9—H9B···N5ⁱⁱ	0.867 (10)	2.043 (11)	2.901 (3)	170 (2)
O9—H9B···O6ⁱⁱ	0.867 (10)	2.56 (2)	3.125 (3)	123 (2)
O10—H10A···O6ⁱⁱⁱ	0.867 (10)	2.051 (11)	2.914 (3)	174 (4)
O10—H10B···N2^iv	0.870 (10)	2.042 (12)	2.902 (3)	170 (3)

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

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Damiano, T., Morton, D. & Nelson, A. (2007). Org. Biomol. Chem. 5, 2735—2752. Web of Science CrossRef Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Li, J.-S., Chen, L.-G., Zhang, Y.-Y., Xu, Y.-J., Deng, Y., Zeng, T. & Huang, P.-M. (2007). J. Chem. Res. pp. 350–352. CrossRef Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yu, H.-J. & Li, J.-S. (2007). Acta Cryst. E63, o3399. CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2277

doi:10.1107/S1600536808035526

Open

access