Crystal structure of (E)-N′-(3,4-di­fluoro­benzyl­idene)-4-methyl­benzene­sulfono­hydrazide

Wang, Y.; Yan, H.

doi:10.1107/S2056989015016205

organic compounds

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doi:10.1107/S2056989015016205

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Crystal structure of (E)-N′-(3,4-difluorobenzylidene)-4-methylbenzenesulfonohydrazide

Yeming Wang ^a and Hong Yan ^a ^*

^aCollege of Life Science and Bio-engineering, Beijing University of Technology, No. 100 Pingleyuan, Chaoyang District, Beijing 100124, People's Republic of China
^*Correspondence e-mail: hongyan@bjut.edu.cn

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 22 August 2015; accepted 31 August 2015; online 17 September 2015)

In the title compound, C₁₄H₁₂F₂N₂O₂S, the dihedral angle between the aromatic rings is 70.23 (8)° and the S—N—N=C torsion angle is 172.11 (11)°. In the crystal, N—H⋯O hydrogen bonds link the molecules into [100] C(4) chains, with adjacent molecules in the chain related by translational symmetry. The chains are linked by weak C—H⋯F and C—H⋯O interactions, thereby forming a three-dimensional network.

Keywords: crystal structure; sulfonylhydrazone; hydrogen bonding; biological activity.

CCDC reference: 1040450

1. Related literature

For the biological activities of sulfonamides and sulfonylhydrazones, see: El-Sayed et al. (2011 ); de Oliveira et al. (2011 ); Zhao et al. (2011 ).

2. Experimental

2.1. Crystal data

C₁₄H₁₂F₂N₂O₂S
M_r = 310.32
Monoclinic, P 2₁ /c
a = 5.3161 (11) Å
b = 15.388 (3) Å
c = 17.293 (4) Å
β = 97.44 (3)°
V = 1402.8 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 173 K
0.20 × 0.18 × 0.12 mm

2.2. Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009 ) T_min = 0.950, T_max = 0.970
14131 measured reflections
3328 independent reflections
2729 reflections with I > 2σ(I)
R_int = 0.047

2.3. Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.116
S = 1.04
3328 reflections
196 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.89 (1)	2.09 (1)	2.9747 (18)	174 (2)
C1—H1⋯F1ⁱⁱ	0.95	2.47	3.345 (2)	153
C4—H4⋯O2ⁱⁱⁱ	0.95	2.57	3.473 (2)	159
Symmetry codes: (i) x+1, y, z; (ii) -x, -y+1, -z+1; (iii) $[x+1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2009); 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

CCDC reference: 1040450

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S2056989015016205/hb7491sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015016205/hb7491Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015016205/hb7491Isup3.cml

checkCIF report

Experimental top

Synthesis and crystallization top

p-Tosylhydrazine (0.372 g, 2 mmol) was added to a 50 ml refluxing ethanolic solution of 3,4-difluorobenzaldehyde (0.284 g, 2 mmol). The mixture was stirred for 3 h. After cooling, the colorless crystalline solid was isolated by filtration, washed with cold ethanol, and recrystallized from ethanol as colourless prisms.

Refinement top

Results and discussion top

Related literature top

For the biological activities of sulfonamides and sulfonylhydrazones, see: El-Sayed et al. (2011); de Oliveira et al. (2011); Zhao et al. (2011).

Computing details top

Data collection: CrystalClear (Rigaku, 2009); cell refinement: CrystalClear (Rigaku, 2009); data reduction: CrystalClear (Rigaku, 2009); 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. Displacement ellipsoid plot (50% probability level) of the title compound.

(E)-N'-(3,4-Difluorobenzylidene)-4-methylbenzenesulfonohydrazide top

Crystal data top

C₁₄H₁₂F₂N₂O₂S	D_x = 1.469 Mg m⁻³
M_r = 310.32	Melting point: 426 K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.3161 (11) Å	Cell parameters from 3967 reflections
b = 15.388 (3) Å	θ = 1.8–27.9°
c = 17.293 (4) Å	µ = 0.26 mm⁻¹
β = 97.44 (3)°	T = 173 K
V = 1402.8 (5) Å³	Prism, colourless
Z = 4	0.20 × 0.18 × 0.12 mm
F(000) = 640

Data collection top

Rigaku Saturn diffractometer	3328 independent reflections
Radiation source: rotating anode	2729 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.047
ω scans	θ_max = 27.9°, θ_min = 1.8°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009)	h = −6→6
T_min = 0.950, T_max = 0.970	k = −20→19
14131 measured reflections	l = −22→22

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)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.116	w = 1/[σ²(F_o²) + (0.0715P)² + 0.0398P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
3328 reflections	Δρ_max = 0.27 e Å⁻³
196 parameters	Δρ_min = −0.39 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.057 (4)

Crystal data top

C₁₄H₁₂F₂N₂O₂S	V = 1402.8 (5) Å³
M_r = 310.32	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.3161 (11) Å	µ = 0.26 mm⁻¹
b = 15.388 (3) Å	T = 173 K
c = 17.293 (4) Å	0.20 × 0.18 × 0.12 mm
β = 97.44 (3)°

Data collection top

Rigaku Saturn diffractometer	3328 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009)	2729 reflections with I > 2σ(I)
T_min = 0.950, T_max = 0.970	R_int = 0.047
14131 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	1 restraint
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.27 e Å⁻³
3328 reflections	Δρ_min = −0.39 e Å⁻³
196 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

	x	y	z	U_iso*/U_eq
S1	0.17639 (7)	0.83591 (2)	0.34262 (2)	0.02258 (15)
F1	0.15725 (18)	0.45775 (6)	0.58632 (6)	0.0354 (3)
F2	0.52921 (19)	0.43477 (7)	0.70237 (6)	0.0403 (3)
O1	−0.0478 (2)	0.83384 (7)	0.38043 (6)	0.0300 (3)
O2	0.2561 (2)	0.91533 (7)	0.31005 (6)	0.0308 (3)
N1	0.3852 (2)	0.73655 (8)	0.45229 (7)	0.0243 (3)
N2	0.4159 (2)	0.81054 (9)	0.40836 (7)	0.0254 (3)
C1	0.3568 (3)	0.58214 (10)	0.54189 (9)	0.0245 (3)
H1	0.2203	0.5908	0.5014	0.029*
C2	0.3516 (3)	0.51491 (10)	0.59364 (9)	0.0245 (3)
C3	0.5465 (3)	0.50210 (10)	0.65353 (9)	0.0268 (3)
C4	0.7535 (3)	0.55625 (10)	0.66269 (9)	0.0286 (3)
H4	0.8868	0.5476	0.7042	0.034*
C5	0.7641 (3)	0.62404 (10)	0.60986 (9)	0.0257 (3)
H5	0.9075	0.6614	0.6148	0.031*
C6	0.5666 (3)	0.63768 (9)	0.54969 (8)	0.0218 (3)
C7	0.5820 (3)	0.71137 (10)	0.49678 (8)	0.0233 (3)
H7	0.7391	0.7405	0.4956	0.028*
C8	0.1461 (3)	0.75599 (9)	0.26968 (8)	0.0224 (3)
C9	0.3114 (3)	0.75831 (10)	0.21365 (9)	0.0274 (3)
H9	0.4410	0.8011	0.2162	0.033*
C10	0.2849 (3)	0.69783 (11)	0.15446 (9)	0.0323 (4)
H10	0.3983	0.6992	0.1163	0.039*
C11	0.0951 (4)	0.63458 (10)	0.14931 (10)	0.0331 (4)
C12	−0.0658 (3)	0.63306 (11)	0.20640 (10)	0.0315 (4)
H12	−0.1949	0.5901	0.2041	0.038*
C13	−0.0418 (3)	0.69311 (10)	0.26667 (9)	0.0270 (3)
H13	−0.1528	0.6912	0.3055	0.032*
C14	0.0698 (5)	0.56939 (13)	0.08375 (12)	0.0565 (6)
H14A	0.1822	0.5199	0.0982	0.085*
H14B	0.1170	0.5968	0.0365	0.085*
H14C	−0.1062	0.5491	0.0739	0.085*
H2	0.573 (2)	0.8215 (12)	0.3993 (12)	0.043 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0188 (2)	0.0234 (2)	0.0255 (2)	0.00121 (13)	0.00278 (14)	0.00296 (13)
F1	0.0271 (5)	0.0342 (6)	0.0442 (6)	−0.0066 (4)	0.0022 (4)	0.0015 (4)
F2	0.0390 (6)	0.0407 (6)	0.0410 (6)	0.0035 (4)	0.0041 (5)	0.0171 (4)
O1	0.0187 (6)	0.0373 (7)	0.0352 (6)	0.0019 (4)	0.0076 (5)	−0.0028 (5)
O2	0.0332 (7)	0.0237 (6)	0.0354 (6)	−0.0007 (5)	0.0037 (5)	0.0055 (4)
N1	0.0255 (7)	0.0257 (6)	0.0219 (6)	0.0010 (5)	0.0036 (5)	0.0019 (5)
N2	0.0179 (7)	0.0307 (7)	0.0274 (7)	−0.0027 (5)	0.0021 (5)	0.0064 (5)
C1	0.0213 (8)	0.0289 (8)	0.0226 (7)	0.0036 (6)	−0.0003 (6)	−0.0028 (6)
C2	0.0194 (8)	0.0261 (8)	0.0288 (8)	−0.0010 (6)	0.0054 (6)	−0.0034 (6)
C3	0.0288 (8)	0.0275 (8)	0.0250 (7)	0.0057 (6)	0.0068 (6)	0.0033 (6)
C4	0.0246 (8)	0.0355 (9)	0.0247 (7)	0.0060 (6)	−0.0013 (6)	0.0008 (6)
C5	0.0186 (7)	0.0305 (8)	0.0272 (7)	0.0005 (6)	0.0005 (6)	−0.0031 (6)
C6	0.0198 (8)	0.0255 (7)	0.0203 (7)	0.0041 (6)	0.0030 (6)	−0.0032 (5)
C7	0.0202 (8)	0.0283 (8)	0.0217 (7)	−0.0001 (6)	0.0036 (6)	−0.0022 (6)
C8	0.0204 (8)	0.0237 (7)	0.0228 (7)	0.0030 (6)	0.0010 (6)	0.0053 (5)
C9	0.0262 (9)	0.0268 (8)	0.0303 (8)	−0.0011 (6)	0.0075 (6)	0.0064 (6)
C10	0.0424 (10)	0.0314 (9)	0.0253 (8)	0.0008 (7)	0.0126 (7)	0.0057 (6)
C11	0.0471 (11)	0.0255 (8)	0.0263 (8)	0.0016 (7)	0.0036 (7)	0.0040 (6)
C12	0.0333 (9)	0.0257 (8)	0.0350 (9)	−0.0049 (7)	0.0028 (7)	0.0017 (6)
C13	0.0228 (8)	0.0281 (8)	0.0310 (8)	−0.0020 (6)	0.0067 (6)	0.0041 (6)
C14	0.0924 (18)	0.0407 (11)	0.0384 (11)	−0.0107 (11)	0.0163 (11)	−0.0076 (8)

Geometric parameters (Å, º) top

S1—O1	1.4319 (12)	C5—H5	0.9500
S1—O2	1.4324 (11)	C6—C7	1.466 (2)
S1—N2	1.6404 (14)	C7—H7	0.9500
S1—C8	1.7542 (15)	C8—C13	1.387 (2)
F1—C2	1.3502 (18)	C8—C9	1.390 (2)
F2—C3	1.3473 (18)	C9—C10	1.377 (2)
N1—C7	1.2762 (19)	C9—H9	0.9500
N1—N2	1.3901 (17)	C10—C11	1.396 (3)
N2—H2	0.888 (9)	C10—H10	0.9500
C1—C2	1.371 (2)	C11—C12	1.388 (2)
C1—C6	1.398 (2)	C11—C14	1.507 (2)
C1—H1	0.9500	C12—C13	1.386 (2)
C2—C3	1.381 (2)	C12—H12	0.9500
C3—C4	1.373 (2)	C13—H13	0.9500
C4—C5	1.393 (2)	C14—H14A	0.9800
C4—H4	0.9500	C14—H14B	0.9800
C5—C6	1.395 (2)	C14—H14C	0.9800

O1—S1—O2	120.29 (6)	N1—C7—C6	120.22 (13)
O1—S1—N2	107.18 (7)	N1—C7—H7	119.9
O2—S1—N2	103.48 (7)	C6—C7—H7	119.9
O1—S1—C8	107.96 (7)	C13—C8—C9	120.60 (14)
O2—S1—C8	108.65 (7)	C13—C8—S1	120.99 (12)
N2—S1—C8	108.80 (7)	C9—C8—S1	118.40 (11)
C7—N1—N2	115.66 (12)	C10—C9—C8	119.19 (14)
N1—N2—S1	115.99 (10)	C10—C9—H9	120.4
N1—N2—H2	115.6 (13)	C8—C9—H9	120.4
S1—N2—H2	119.9 (13)	C9—C10—C11	121.46 (15)
C2—C1—C6	118.81 (14)	C9—C10—H10	119.3
C2—C1—H1	120.6	C11—C10—H10	119.3
C6—C1—H1	120.6	C12—C11—C10	118.25 (15)
F1—C2—C1	120.70 (14)	C12—C11—C14	121.39 (16)
F1—C2—C3	117.91 (14)	C10—C11—C14	120.36 (16)
C1—C2—C3	121.38 (14)	C13—C12—C11	121.22 (15)
F2—C3—C4	120.86 (14)	C13—C12—H12	119.4
F2—C3—C2	118.32 (14)	C11—C12—H12	119.4
C4—C3—C2	120.81 (14)	C12—C13—C8	119.28 (14)
C3—C4—C5	118.60 (14)	C12—C13—H13	120.4
C3—C4—H4	120.7	C8—C13—H13	120.4
C5—C4—H4	120.7	C11—C14—H14A	109.5
C4—C5—C6	120.77 (14)	C11—C14—H14B	109.5
C4—C5—H5	119.6	H14A—C14—H14B	109.5
C6—C5—H5	119.6	C11—C14—H14C	109.5
C5—C6—C1	119.61 (14)	H14A—C14—H14C	109.5
C5—C6—C7	118.97 (13)	H14B—C14—H14C	109.5
C1—C6—C7	121.40 (13)

C7—N1—N2—S1	172.11 (11)	C5—C6—C7—N1	−165.16 (14)
O1—S1—N2—N1	49.24 (12)	C1—C6—C7—N1	13.7 (2)
O2—S1—N2—N1	177.34 (10)	O1—S1—C8—C13	−12.85 (14)
C8—S1—N2—N1	−67.26 (12)	O2—S1—C8—C13	−144.84 (13)
C6—C1—C2—F1	−177.38 (13)	N2—S1—C8—C13	103.15 (13)
C6—C1—C2—C3	1.0 (2)	O1—S1—C8—C9	165.65 (11)
F1—C2—C3—F2	−1.6 (2)	O2—S1—C8—C9	33.66 (13)
C1—C2—C3—F2	179.95 (13)	N2—S1—C8—C9	−78.36 (13)
F1—C2—C3—C4	177.91 (14)	C13—C8—C9—C10	0.6 (2)
C1—C2—C3—C4	−0.5 (2)	S1—C8—C9—C10	−177.85 (12)
F2—C3—C4—C5	178.96 (13)	C8—C9—C10—C11	0.3 (2)
C2—C3—C4—C5	−0.5 (2)	C9—C10—C11—C12	−1.0 (3)
C3—C4—C5—C6	1.1 (2)	C9—C10—C11—C14	179.77 (16)
C4—C5—C6—C1	−0.6 (2)	C10—C11—C12—C13	0.7 (3)
C4—C5—C6—C7	178.21 (13)	C14—C11—C12—C13	179.94 (17)
C2—C1—C6—C5	−0.4 (2)	C11—C12—C13—C8	0.2 (2)
C2—C1—C6—C7	−179.24 (13)	C9—C8—C13—C12	−0.9 (2)
N2—N1—C7—C6	175.73 (11)	S1—C8—C13—C12	177.54 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.89 (1)	2.09 (1)	2.9747 (18)	174 (2)
C1—H1···F1ⁱⁱ	0.95	2.47	3.345 (2)	153
C4—H4···O2ⁱⁱⁱ	0.95	2.57	3.473 (2)	159

Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z+1; (iii) x+1, −y+3/2, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.888 (9)	2.090 (10)	2.9747 (18)	174.1 (18)
C1—H1···F1ⁱⁱ	0.95	2.47	3.345 (2)	153
C4—H4···O2ⁱⁱⁱ	0.95	2.57	3.473 (2)	159

Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z+1; (iii) x+1, −y+3/2, z+1/2.

Acknowledgements

This work was supported financially by the Key Projects in the National Science & Technology Pillar Program (No. 2012ZX10001007-008-002) and the Doctoral Fund of Innovation of Beijing University of Technology.

References

El-Sayed, N. S., El-Bendary, E. R., El-Ashry, S. M. & El-Kerdawy, M. M. (2011). Eur. J. Med. Chem. 46, 3714–3720. Web of Science CAS PubMed Google Scholar
Oliveira, K. N. de, Costa, P., Santin, J. R., Mazzambani, L., Bürger, C., Mora, C., Nunes, R. J. & de Souza, M. M. (2011). Bioorg. Med. Chem. 19, 4295–4306. PubMed Google Scholar
Rigaku (2009). CrystalClear, Rigaku Inc., Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhao, X., Wu, G., Zhang, Y. & Wang, J. (2011). J. Am. Chem. Soc. 133, 3296–3299. CrossRef CAS PubMed Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of (E)-N′-(3,4-di­fluoro­benzyl­­idene)-4-methyl­benzene­sulfono­hydrazide

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

Crystal structure of (E)-N′-(3,4-difluorobenzylidene)-4-methylbenzenesulfonohydrazide