2-(Hydrazinocarbon­yl)benzene­sulfonamide

In the title compound, C₇H₉N₃O₃S, the chiral conformation of the mol­ecule is determined by an intra­molecular N—H...O hydrogen bond between the sulfonamide and hydrazino­carbonyl groups, with the former group acting as a donor in hydrogen bonding. The crystal structure is stabilized by inter­molecular N—H...O and N—H...N hydrogen bonds and π–π stacking inter­actions between the benzene rings [the inter­planar distance is 3.755 (3) Å].

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.026
• wR factor = 0.071
• Data-to-parameter ratio = 14.0

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S1. Comment

Sulfonamide compounds attract much attention due to their diverse biological activities. Here we report the crystal structure of 2-hydrazinocarbonylbenzenesulfonamide.

The title compound has a basal plane which involves the benzene ring, the S atom and the C7 atom of the carbonyl group with a mean deviation of 0.037 (3) Å. The C, O atoms of the carbonyl group and the two N atoms of the hydrazino group lie in another plane (mean deviation 0.051 (2) Å) with a dihedral angle of 57.5 (2)° to the basal plane.

The intramolecular N1—H1B···O3 hydrogen bond forces the O atom of carbonyl group and the N atom of sulfamoyl group to lie on the same side of the basal plane (Fig. 1) and thus the molecule adopts a chiral conformation. The crystal structure is stabilized by intermolecular hydrogen bonds (Table 1) and π-π stacking interactions between the phenyl rings. (distance of 3.755 (3) Å, Fig. 2).

Related literature

For the crystal structure of an analogouos sulfonamide compound, see: Michaux et al. (2006). For related literature, see: Winum et al. (2005).

S2. Experimental

20 ml of ethanol, 2.16 g of 2-methoxycarbonylbenzenesulfonamide and 1.2 g of 80% hydrazine hydrate were added to a flask and refluxed for 5 h. The mixture was cooled to room temperature and concentrated in vaccuo. The solid residue was recrystallized from ethanol and the title compound was obtained as white crystals. Its melting point and PMR data were consistent with the literature (Winum et al., 2005). Colouress crystals suitable for X-ray analysis were obtained by recrystallization from ethanol at room temperature.

S3. Refinement

The H atoms bonded to N were located in electron-density difference maps; their positional parameters were refined and U_iso(H) = 1.2U_eq(N). Remaining H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å and with U_iso(H) = 1.2 times U_eq(C).

Computing details

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. Molecular structure of the title compound with the displacement ellipsoids drawn at the 35% probability level. The intramolecular hydrogen bond is indicated as dashed line.
	Fig. 2. Crystal packing showing intermolecular hydrogen bonds and π-π stacking interactions. The intermolecular hydrogen bonds are indicated as dashed lines.

2-(hydrazinocarbonyl)benzenesulfonamide

Crystal data

C7H9N3O3S	Dx = 1.622 Mg m^−3
Mr = 215.23	Melting point: 451 K
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.857 (2) Å	Cell parameters from 3162 reflections
b = 11.562 (2) Å	θ = 2.6–27.9°
c = 13.840 (3) Å	µ = 0.35 mm^−1
β = 111.72 (3)°	T = 113 K
V = 1762.6 (6) Å^3	Prism, colourless
Z = 8	0.24 × 0.20 × 0.20 mm
F(000) = 896

Data collection

Rigaku Saturn diffractometer	2057 independent reflections
Radiation source: Rotating anode	1878 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.021
Detector resolution: 7.31 pixels mm^-1	θmax = 27.9°, θmin = 2.6°
ω scans	h = −15→15
Absorption correction: multi-scan (Jacobson, 1998)	k = −15→15
Tmin = 0.902, Tmax = 0.932	l = −18→17
10255 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0332P)^2 + 1.8027P] where P = (Fo^2 + 2Fc^2)/3
2057 reflections	(Δ/σ)max = 0.001
147 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.40 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.24521 (2)	0.16461 (2)	0.24825 (2)	0.01188 (10)
O1	0.31684 (8)	0.08049 (8)	0.32136 (7)	0.0197 (2)
O2	0.21968 (8)	0.27287 (7)	0.28704 (7)	0.01659 (19)
O3	0.09252 (8)	0.32950 (7)	0.05596 (7)	0.0175 (2)
N1	0.31502 (10)	0.19390 (10)	0.17075 (9)	0.0167 (2)
H1A	0.3400 (16)	0.1340 (16)	0.1522 (14)	0.029 (4)*
H1B	0.2715 (16)	0.2362 (16)	0.1226 (14)	0.026 (4)*
N2	−0.06435 (9)	0.36156 (9)	0.10942 (8)	0.0138 (2)
H2A	−0.1060 (16)	0.3347 (14)	0.1388 (14)	0.024 (4)*
N3	−0.07007 (10)	0.48286 (9)	0.09366 (9)	0.0155 (2)
H3A	0.0043 (17)	0.5084 (15)	0.1227 (13)	0.024 (4)*
H3B	−0.0961 (16)	0.4945 (15)	0.0253 (15)	0.026 (4)*
C1	0.10417 (10)	0.10049 (10)	0.17415 (9)	0.0113 (2)
C2	0.00556 (10)	0.16743 (9)	0.11057 (9)	0.0120 (2)
C3	−0.10350 (11)	0.11141 (11)	0.05679 (9)	0.0159 (2)
H3	−0.1706	0.1541	0.0158	0.019*
C4	−0.11318 (11)	−0.00830 (11)	0.06378 (9)	0.0175 (2)
H4	−0.1867	−0.0447	0.0275	0.021*
C5	−0.01455 (12)	−0.07293 (10)	0.12401 (10)	0.0171 (3)
H5	−0.0209	−0.1529	0.1267	0.021*
C6	0.09466 (11)	−0.01826 (10)	0.18084 (9)	0.0142 (2)
H6	0.1608	−0.0613	0.2230	0.017*
C7	0.01711 (10)	0.29415 (10)	0.09073 (9)	0.0131 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.00969 (15)	0.01151 (15)	0.01456 (15)	−0.00050 (9)	0.00463 (11)	−0.00085 (9)
O1	0.0136 (4)	0.0213 (5)	0.0207 (5)	0.0027 (3)	0.0023 (4)	0.0047 (3)
O2	0.0160 (4)	0.0147 (4)	0.0211 (4)	−0.0029 (3)	0.0093 (3)	−0.0061 (3)
O3	0.0174 (4)	0.0154 (4)	0.0237 (5)	0.0035 (3)	0.0125 (4)	0.0056 (3)
N1	0.0150 (5)	0.0162 (5)	0.0225 (5)	−0.0004 (4)	0.0112 (4)	−0.0005 (4)
N2	0.0142 (5)	0.0113 (5)	0.0181 (5)	0.0021 (4)	0.0084 (4)	0.0038 (4)
N3	0.0158 (5)	0.0110 (5)	0.0214 (5)	0.0027 (4)	0.0090 (4)	0.0038 (4)
C1	0.0112 (5)	0.0115 (5)	0.0122 (5)	−0.0008 (4)	0.0054 (4)	−0.0010 (4)
C2	0.0135 (5)	0.0115 (5)	0.0125 (5)	0.0005 (4)	0.0066 (4)	−0.0002 (4)
C3	0.0127 (5)	0.0202 (6)	0.0141 (5)	0.0005 (4)	0.0042 (4)	−0.0012 (4)
C4	0.0155 (6)	0.0202 (6)	0.0183 (6)	−0.0066 (5)	0.0080 (5)	−0.0067 (5)
C5	0.0209 (6)	0.0122 (5)	0.0223 (6)	−0.0042 (4)	0.0129 (5)	−0.0040 (4)
C6	0.0159 (6)	0.0117 (5)	0.0174 (5)	0.0013 (4)	0.0089 (4)	0.0006 (4)
C7	0.0129 (5)	0.0130 (5)	0.0119 (5)	0.0013 (4)	0.0030 (4)	0.0019 (4)

Geometric parameters (Å, º)

S1—O1	1.4335 (10)	C1—C6	1.3836 (16)
S1—O2	1.4378 (9)	C1—C2	1.4067 (16)
S1—N1	1.6148 (11)	C2—C3	1.3903 (17)
S1—C1	1.7687 (13)	C2—C7	1.5063 (15)
O3—C7	1.2314 (15)	C3—C4	1.3953 (17)
N1—H1A	0.831 (19)	C3—H3	0.9300
N1—H1B	0.834 (19)	C4—C5	1.3781 (18)
N2—C7	1.3387 (15)	C4—H4	0.9300
N2—N3	1.4171 (14)	C5—C6	1.3932 (17)
N2—H2A	0.809 (18)	C5—H5	0.9300
N3—H3A	0.874 (19)	C6—H6	0.9300
N3—H3B	0.890 (18)
O1—S1—O2	118.60 (6)	C3—C2—C1	118.14 (11)
O1—S1—N1	107.20 (6)	C3—C2—C7	119.00 (10)
O2—S1—N1	107.21 (6)	C1—C2—C7	122.59 (10)
O1—S1—C1	108.12 (6)	C2—C3—C4	120.60 (11)
O2—S1—C1	107.27 (5)	C2—C3—H3	119.7
N1—S1—C1	108.05 (6)	C4—C3—H3	119.7
S1—N1—H1A	111.1 (12)	C5—C4—C3	120.44 (11)
S1—N1—H1B	109.6 (12)	C5—C4—H4	119.8
H1A—N1—H1B	115.4 (17)	C3—C4—H4	119.8
C7—N2—N3	122.90 (10)	C4—C5—C6	119.92 (11)
C7—N2—H2A	119.5 (12)	C4—C5—H5	120.0
N3—N2—H2A	117.0 (12)	C6—C5—H5	120.0
N2—N3—H3A	106.3 (11)	C1—C6—C5	119.62 (11)
N2—N3—H3B	107.0 (11)	C1—C6—H6	120.2
H3A—N3—H3B	109.4 (15)	C5—C6—H6	120.2
C6—C1—C2	121.22 (11)	O3—C7—N2	124.23 (11)
C6—C1—S1	117.40 (9)	O3—C7—C2	121.48 (10)
C2—C1—S1	121.38 (9)	N2—C7—C2	114.22 (10)
O1—S1—C1—C6	−13.09 (11)	C2—C3—C4—C5	−0.14 (18)
O2—S1—C1—C6	−142.08 (9)	C3—C4—C5—C6	1.91 (18)
N1—S1—C1—C6	102.63 (10)	C2—C1—C6—C5	−0.25 (17)
O1—S1—C1—C2	167.14 (9)	S1—C1—C6—C5	179.98 (9)
O2—S1—C1—C2	38.15 (11)	C4—C5—C6—C1	−1.71 (18)
N1—S1—C1—C2	−77.15 (10)	N3—N2—C7—O3	−1.86 (18)
C6—C1—C2—C3	1.97 (17)	N3—N2—C7—C2	−178.78 (10)
S1—C1—C2—C3	−178.27 (9)	C3—C2—C7—O3	−118.69 (13)
C6—C1—C2—C7	−172.00 (11)	C1—C2—C7—O3	55.23 (16)
S1—C1—C2—C7	7.77 (15)	C3—C2—C7—N2	58.33 (14)
C1—C2—C3—C4	−1.77 (17)	C1—C2—C7—N2	−127.76 (12)
C7—C2—C3—C4	172.42 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O3^i	0.890 (18)	2.333 (18)	2.9424 (14)	125.7 (14)
N3—H3A···O1^ii	0.874 (19)	2.139 (19)	3.0098 (16)	173.9 (15)
N2—H2A···O2^iii	0.809 (18)	2.098 (19)	2.9070 (15)	177.0 (17)
N1—H1B···O3	0.834 (19)	2.251 (19)	2.9731 (16)	145.1 (16)
N1—H1A···N3^iv	0.831 (19)	2.342 (19)	3.1662 (16)	171.6 (17)

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