p-Tosyl­hydrazine: a redetermination from single-crystal data at 100 K

Redetermination of the structure of the title compound, alternatively called 4-methyl­benzene­sulfonohydrazide, C₇H₁₀N₂O₂S, at 100 K reveals that both H atoms of the NH₂ group form inter­molecular N—H...O hydrogen bonds, which together with an N—H...O hydrogen bond from the NH group form a sheet-like structure in the ab plane.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.060
• wR factor = 0.117
• Data-to-parameter ratio = 13.5

checkCIF/PLATON results

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PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.06

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
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   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
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S1. Comment

The structure of the title compound, C₇H₁₀N₂O₂S (Figure 1), has been determined previously by Lightfoot et al. (1993) from powder X-ray diffraction data. However, H atoms could not be located using that technique and the authors assumed the presence of an intramolecular N—H···O hydrogen bond (graph-set motif S(5)). Re-determination of the structure using single-crystal X-ray diffraction reveals that the H atoms of the NH₂ group actually make intermolecular N—H···O hydrogen bonds, with O1 and O2 acting as acceptors (Table 1). The N1—H1···O1 and N2—H2A···O2 hydrogen bonds link the molecules into double chains along the b axis, and these chains are linked via N2—H2B···O2 hydrogen bonds to form a sheet-like structure in the ab planes.

Related literature

For a previous determination of the structure from powder X-ray diffraction data, see: Lightfoot et al. (1993). For synthesis details, see: Friedman et al. (1973).

S2. Experimental

Single crystals of 4-tosylhydrazine (Friedman et al., 1973) were obtained by recrystallization from ethanol.

S3. Refinement

Atoms H2A and H2B of the NH₂ group were located in difference Fourier maps and refined isotropically without restraint. Atom H1 was also located in a difference Fourier map and refined with the N—H distance restrained to be 1.01 (2) Å. All other H atoms were visible in difference Fourier maps but were placed at calculated positions and allowed to ride with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, and with C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL and X-SEED (Barbour, 2001).

Figures

	Fig. 1. Molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level for non-H atoms.
	Fig. 2. N—H···O hydrogen bonds connect the molecules into double chains along the b axis.

4-Methylbenzenesulfonohydrazide

Crystal data

C7H10N2O2S	F(000) = 392
Mr = 186.23	Dx = 1.484 Mg m^−3
Monoclinic, P21/c	Melting point: 382 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.4166 (8) Å	Cell parameters from 5282 reflections
b = 5.6056 (5) Å	θ = 2.3–26.0°
c = 17.9484 (17) Å	µ = 0.35 mm^−1
β = 100.260 (1)°	T = 100 K
V = 833.27 (13) Å^3	Block, colourless
Z = 4	0.30 × 0.18 × 0.10 mm

Data collection

Bruker APEX CCD diffractometer	1641 independent reflections
Radiation source: fine-focus sealed tube	1584 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
φ and ω scans	θmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −10→10
Tmin = 0.903, Tmax = 0.966	k = −6→6
8195 measured reflections	l = −22→22

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.30	w = 1/[σ^2(Fo^2) + (0.0212P)^2 + 1.9226P] where P = (Fo^2 + 2Fc^2)/3
1641 reflections	(Δ/σ)max = 0.001
122 parameters	Δρmax = 0.65 e Å^−3
1 restraint	Δρmin = −0.31 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	0.27606 (8)	0.14178 (13)	0.17916 (4)	0.0144 (2)
O1	0.4359 (2)	0.0492 (4)	0.20362 (12)	0.0207 (5)
O2	0.1440 (2)	−0.0239 (4)	0.16470 (12)	0.0184 (5)
N1	0.2469 (3)	0.3220 (5)	0.24704 (14)	0.0173 (6)
H1	0.346 (3)	0.402 (5)	0.2665 (17)	0.015 (8)*
N2	0.1052 (3)	0.4620 (5)	0.22597 (16)	0.0191 (6)
H2A	0.130 (4)	0.605 (7)	0.215 (2)	0.026 (10)*
H2B	0.056 (4)	0.467 (7)	0.266 (2)	0.027 (10)*
C1	0.2708 (3)	0.3161 (5)	0.09705 (16)	0.0149 (6)
C2	0.3625 (4)	0.5216 (6)	0.10103 (17)	0.0179 (6)
H2	0.4279	0.5681	0.1475	0.021*
C3	0.3581 (4)	0.6590 (6)	0.03662 (17)	0.0204 (7)
H3	0.4215	0.8001	0.0392	0.024*
C4	0.2624 (4)	0.5941 (6)	−0.03207 (17)	0.0182 (6)
C5	0.1721 (4)	0.3860 (6)	−0.03418 (18)	0.0252 (7)
H5	0.1070	0.3383	−0.0806	0.030*
C6	0.1747 (4)	0.2466 (6)	0.02964 (17)	0.0207 (7)
H6	0.1116	0.1053	0.0273	0.025*
C7	0.2553 (4)	0.7451 (7)	−0.10152 (18)	0.0256 (7)
H7A	0.2719	0.6444	−0.1441	0.038*
H7B	0.3400	0.8671	−0.0923	0.038*
H7C	0.1495	0.8225	−0.1136	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0148 (4)	0.0132 (4)	0.0152 (4)	0.0006 (3)	0.0022 (3)	0.0006 (3)
O1	0.0182 (11)	0.0210 (11)	0.0221 (12)	0.0033 (9)	0.0017 (9)	0.0038 (9)
O2	0.0199 (11)	0.0146 (11)	0.0210 (11)	0.0003 (9)	0.0045 (9)	0.0008 (9)
C5	0.0239 (16)	0.0307 (19)	0.0185 (16)	0.0005 (14)	−0.0029 (13)	−0.0018 (14)
C1	0.0130 (13)	0.0165 (15)	0.0148 (14)	0.0025 (11)	0.0017 (11)	0.0025 (12)
N1	0.0162 (12)	0.0191 (14)	0.0159 (12)	−0.0016 (11)	0.0008 (10)	−0.0001 (10)
N2	0.0186 (13)	0.0181 (14)	0.0216 (14)	0.0017 (11)	0.0058 (11)	−0.0009 (12)
C2	0.0168 (14)	0.0209 (16)	0.0155 (14)	−0.0011 (12)	0.0015 (12)	−0.0037 (12)
C6	0.0198 (15)	0.0197 (16)	0.0213 (16)	−0.0022 (13)	−0.0002 (12)	−0.0004 (13)
C3	0.0197 (15)	0.0192 (16)	0.0229 (16)	−0.0009 (13)	0.0053 (12)	0.0015 (13)
C7	0.0247 (17)	0.0330 (19)	0.0193 (16)	0.0039 (15)	0.0042 (13)	0.0066 (14)
C4	0.0171 (14)	0.0201 (16)	0.0182 (15)	0.0070 (12)	0.0054 (12)	0.0022 (12)

Geometric parameters (Å, º)

S1—O1	1.436 (2)	N2—H2A	0.86 (4)
S1—O2	1.436 (2)	N2—H2B	0.89 (4)
S1—N1	1.635 (3)	C2—C3	1.384 (4)
S1—C1	1.762 (3)	C2—H2	0.950
C5—C6	1.384 (4)	C6—H6	0.950
C5—C4	1.389 (5)	C3—C4	1.395 (4)
C5—H5	0.950	C3—H3	0.950
C1—C2	1.381 (4)	C7—C4	1.499 (4)
C1—C6	1.386 (4)	C7—H7A	0.980
N1—N2	1.422 (4)	C7—H7B	0.980
N1—H1	0.96 (2)	C7—H7C	0.980
O1—S1—O2	118.33 (13)	C1—C2—C3	119.3 (3)
O1—S1—N1	104.61 (13)	C1—C2—H2	120.3
O2—S1—N1	108.68 (13)	C3—C2—H2	120.3
O1—S1—C1	109.81 (13)	C5—C6—C1	119.0 (3)
O2—S1—C1	107.70 (13)	C5—C6—H6	120.5
N1—S1—C1	107.22 (14)	C1—C6—H6	120.5
C6—C5—C4	121.6 (3)	C2—C3—C4	121.2 (3)
C6—C5—H5	119.2	C2—C3—H3	119.4
C4—C5—H5	119.2	C4—C3—H3	119.4
C2—C1—C6	120.9 (3)	C4—C7—H7A	109.5
C2—C1—S1	119.2 (2)	C4—C7—H7B	109.5
C6—C1—S1	119.9 (2)	H7A—C7—H7B	109.5
N2—N1—S1	111.91 (19)	C4—C7—H7C	109.5
N2—N1—H1	118 (2)	H7A—C7—H7C	109.5
S1—N1—H1	108.8 (19)	H7B—C7—H7C	109.5
N1—N2—H2A	110 (2)	C5—C4—C3	118.0 (3)
N1—N2—H2B	107 (2)	C5—C4—C7	120.7 (3)
H2A—N2—H2B	109 (3)	C3—C4—C7	121.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.96 (2)	2.00 (2)	2.948 (3)	173 (3)
N2—H2A···O2^ii	0.86 (4)	2.28 (4)	3.122 (4)	167 (3)
N2—H2B···O2^iii	0.89 (4)	2.27 (4)	3.118 (3)	160 (3)

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