organic compounds
E)-N′-(3,4-difluorobenzylidene)-4-methylbenzenesulfonohydrazide
of (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
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.
CCDC reference: 1040450
1. Related literature
For the biological activities of et al. (2011); de Oliveira et al. (2011); Zhao et al. (2011).
and sulfonylhydrazones, see: El-Sayed2. Experimental
2.1. Crystal data
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2.3. Refinement
|
Data collection: CrystalClear (Rigaku, 2009); cell 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
10.1107/S2056989015016205/hb7491sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015016205/hb7491Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015016205/hb7491Isup3.cml
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.
Data collection: CrystalClear (Rigaku, 2009); cell
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).C14H12F2N2O2S | Dx = 1.469 Mg m−3 |
Mr = 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 |
Rigaku Saturn diffractometer | 3328 independent reflections |
Radiation source: rotating anode | 2729 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.047 |
ω scans | θmax = 27.9°, θmin = 1.8° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009) | h = −6→6 |
Tmin = 0.950, Tmax = 0.970 | k = −20→19 |
14131 measured reflections | l = −22→22 |
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(Fo2) + (0.0715P)2 + 0.0398P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
3328 reflections | Δρmax = 0.27 e Å−3 |
196 parameters | Δρmin = −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) |
C14H12F2N2O2S | V = 1402.8 (5) Å3 |
Mr = 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)° |
Rigaku Saturn diffractometer | 3328 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009) | 2729 reflections with I > 2σ(I) |
Tmin = 0.950, Tmax = 0.970 | Rint = 0.047 |
14131 measured reflections |
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 | Δρmax = 0.27 e Å−3 |
3328 reflections | Δρmin = −0.39 e Å−3 |
196 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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)* |
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) |
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) |
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. |
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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