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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 2| February 2012| Page o315
doi:10.1107/S160053681105611X

N′-[(1E)-(2,6-Di­fluoro­phen­yl)methyl­­idene]thio­phene-2-carbohydrazide

Amer M. Alanazi,a Adnan A. Kadi,a Ali A. El-Emama and Seik Weng Ngb,c*

aDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia, bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
*Correspondence e-mail: seikweng@um.edu.my

(Received 19 December 2011; accepted 29 December 2011; online 11 January 2012)

In the title compound, C12H8F2N2OS, the thienyl ring is disordered over two positions, with the S atom of the major component [occupancy = 75.03 (18)%] oriented away from an ortho-F atom of the benzene ring. The mol­ecule is nearly planar, the dihedral angle between the thio­phene and benzene rings being 6.19 (18) (in the major component) or 3.5 (6)° (in the minor component). The azomethine C=N double-bond in the mol­ecule is of an E configuration. In the crystal, mol­ecules are linked by pairs of N—H⋯O hydrogen bonds, generating inversion dimers.

Related literature

For a related structure, see: Alanazi et al. (2012[Alanazi, A. M., Lahsasni, S., El-Emam, A. A. & Ng, S. W. (2012). Acta Cryst. E68, o314.]).

[Scheme 1]

Experimental

Crystal data

  • C12H8F2N2OS

  • Mr = 266.26

  • Triclinic, [P \overline 1]

  • a = 6.5032 (3) Å

  • b = 7.7516 (4) Å

  • c = 11.5224 (5) Å

  • α = 95.184 (4)°

  • β = 103.344 (4)°

  • γ = 94.285 (4)°

  • V = 560.11 (5) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.30 mm−1

  • T = 100 K

  • 0.40 × 0.30 × 0.20 mm
Data collection

  • Agilent SuperNova Dual diffractometer with an Atlas detector

  • Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010[Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England.]) Tmin = 0.888, Tmax = 0.942

  • 8250 measured reflections

  • 2594 independent reflections

  • 2174 reflections with I > 2σ(I)

  • Rint = 0.035
Refinement

  • R[F2 > 2σ(F2)] = 0.038

  • wR(F2) = 0.108

  • S = 1.07

  • 2594 reflections

  • 180 parameters

  • 24 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.33 e Å−3

  • Δρmin = −0.28 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1⋯O1i 0.88 (2) 1.97 (2) 2.856 (2) 174 (2)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: CrysAlis PRO (Agilent, 2010[Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681105611X/xu5416sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681105611X/xu5416Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681105611X/xu5416Isup3.cml

checkCIF report


Comment top

2-Thienoylhydrazide forms a large number of Schiff base derivatives with substituted benzaldehydes; among those whose crystal structures have been reported are the 4-chloro and 4-bromo derivatives. The 4-fluoro analog is disordered in respect of the thienyl ring (Alanazi et al., 2012). The azomethine double-bond in the approximately planar C12H8F2N2OS molecule (Scheme I) is of an E configuration (Fig. 1). The thienyl ring is disordered over two positions, with the S atom of the major component (75.03 (18)%) oriented away from an ortho-F atom of the benzene ring. Two molecules are linked across a center-of-inversion by an N–H···O hydrogen bond to generate a dimer (Table 1).

Related literature top

For a related structure, see: Alanazi et al. (2012).

Experimental top

2-Thienoylhydrazide (1.42 g, 0.01 mol) and 2,6-difluorobenzaldehyde (1.42 g, 0.01 mol) dissolved in ethanol (8 ml) was heated for 1 h. The product was collected and recystallized from ethanol to yield the Schiff base in 90% yield, m.p. 453–45548 K.

Refinement top

Carbon-bound H-atoms were placed in calculated positions [C–H 0.95 Å, Uiso(H) 1.2Ueq(C)] and were included in the refinement in the riding model approximation.

The amino H-atom was located in a difference Fourier map, and was refined freely.

The thiophene ring is disordered over two positions in respect of four of the five atoms, with major component being 87.1 (2) %. Pairs of C–C and C–S bond distances were restrained to within 0.0 Å of each other. The temperature factors of C3' was set to those of S1 (as were these pairs: C2' to C1, C1' to C2 and S1' to C3). The anisotropic temperature factors of the disordered atoms were tightly restrained to be nearly isotropic.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C12H8F2N2OS at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The disorder is not shown.
N'-[(1E)-(2,6-Difluorophenyl)methylidene]thiophene- 2-carbohydrazide top
Crystal data top
C12H8F2N2OSZ = 2
Mr = 266.26F(000) = 272
Triclinic, P1Dx = 1.579 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.5032 (3) ÅCell parameters from 3787 reflections
b = 7.7516 (4) Åθ = 2.7–27.5°
c = 11.5224 (5) ŵ = 0.30 mm−1
α = 95.184 (4)°T = 100 K
β = 103.344 (4)°Wedge, colorless
γ = 94.285 (4)°0.40 × 0.30 × 0.20 mm
V = 560.11 (5) Å3
Data collection top
Agilent SuperNova Dual
diffractometer with an Atlas detector		2594 independent reflections
Radiation source: SuperNova (Mo) X-ray Source2174 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.035
Detector resolution: 10.4041 pixels mm-1θmax = 27.6°, θmin = 2.7°
ω scanh = −8→8
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2010)		k = −10→10
Tmin = 0.888, Tmax = 0.942l = −15→14
8250 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0585P)2 + 0.1004P]
where P = (Fo2 + 2Fc2)/3
2594 reflections(Δ/σ)max = 0.001
180 parametersΔρmax = 0.33 e Å−3
24 restraintsΔρmin = −0.28 e Å−3
Crystal data top
C12H8F2N2OSγ = 94.285 (4)°
Mr = 266.26V = 560.11 (5) Å3
Triclinic, P1Z = 2
a = 6.5032 (3) ÅMo Kα radiation
b = 7.7516 (4) ŵ = 0.30 mm−1
c = 11.5224 (5) ÅT = 100 K
α = 95.184 (4)°0.40 × 0.30 × 0.20 mm
β = 103.344 (4)°
Data collection top
Agilent SuperNova Dual
diffractometer with an Atlas detector		2594 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2010)		2174 reflections with I > 2σ(I)
Tmin = 0.888, Tmax = 0.942Rint = 0.035
8250 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03824 restraints
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.33 e Å−3
2594 reflectionsΔρmin = −0.28 e Å−3
180 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
S10.61235 (9)0.40630 (10)0.12814 (6)0.01924 (19)0.7503 (18)
S1'0.9967 (5)0.2911 (5)0.2831 (4)0.0226 (7)0.2497 (18)
F11.02233 (15)0.19692 (13)0.85830 (8)0.0285 (3)
F21.26733 (15)0.14995 (13)0.50356 (8)0.0270 (3)
O10.47384 (17)0.48037 (15)0.34181 (10)0.0228 (3)
N10.7178 (2)0.37086 (17)0.47830 (12)0.0188 (3)
N20.8961 (2)0.28597 (16)0.51113 (11)0.0178 (3)
C10.8196 (10)0.3496 (7)0.0668 (6)0.0214 (8)0.7503 (18)
H1A0.81260.3501−0.01650.026*0.7503 (18)
C20.9871 (9)0.3058 (8)0.1414 (3)0.0199 (7)0.7503 (18)
H21.11270.27250.12050.024*0.7503 (18)
C30.9481 (7)0.3168 (7)0.2667 (5)0.0226 (7)0.7503 (18)
H31.04830.29150.33570.027*0.7503 (18)
C1'0.6702 (15)0.4020 (15)0.1526 (9)0.01924 (19)0.25
H1'0.53500.44360.12770.023*0.2497 (18)
C2'0.801 (3)0.371 (2)0.074 (2)0.0214 (8)0.25
H2'0.78270.3824−0.00920.026*0.2497 (18)
C3'0.983 (3)0.314 (3)0.1659 (13)0.0199 (7)0.25
H3'1.10480.28980.13750.024*0.2497 (18)
C40.7509 (2)0.36777 (19)0.26883 (13)0.0172 (3)
C50.6407 (2)0.40831 (19)0.36486 (13)0.0176 (3)
C70.9443 (2)0.26314 (19)0.62276 (14)0.0176 (3)
H70.85470.30200.67210.021*
C81.1326 (2)0.17935 (19)0.67688 (13)0.0167 (3)
C91.1710 (2)0.1525 (2)0.79783 (13)0.0190 (3)
C101.3490 (3)0.0862 (2)0.86064 (14)0.0225 (4)
H101.36800.07330.94350.027*
C111.4994 (3)0.0391 (2)0.79913 (15)0.0229 (4)
H111.6238−0.00690.84010.027*
C121.4694 (2)0.0587 (2)0.67816 (15)0.0217 (3)
H121.57140.02460.63560.026*
C131.2902 (2)0.1279 (2)0.62060 (14)0.0192 (3)
H10.656 (3)0.409 (3)0.535 (2)0.040 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0198 (4)0.0239 (3)0.0153 (3)0.0069 (3)0.0043 (2)0.0045 (2)
S1'0.0216 (14)0.0257 (11)0.0218 (11)0.0042 (9)0.0074 (10)0.0018 (8)
F10.0271 (5)0.0443 (6)0.0201 (5)0.0167 (5)0.0120 (4)0.0075 (4)
F20.0266 (5)0.0396 (6)0.0208 (5)0.0157 (4)0.0119 (4)0.0080 (4)
O10.0185 (6)0.0310 (6)0.0209 (6)0.0117 (5)0.0054 (5)0.0045 (5)
N10.0168 (6)0.0247 (7)0.0175 (6)0.0095 (5)0.0071 (5)0.0026 (5)
N20.0135 (6)0.0196 (7)0.0208 (7)0.0053 (5)0.0043 (5)0.0026 (5)
C10.0245 (12)0.0234 (14)0.0196 (10)0.0062 (10)0.0103 (8)0.0032 (10)
C20.0207 (8)0.0267 (10)0.0157 (18)0.0046 (7)0.0111 (13)0.0002 (14)
C30.0216 (14)0.0257 (11)0.0218 (11)0.0042 (9)0.0074 (10)0.0018 (8)
C1'0.0198 (4)0.0239 (3)0.0153 (3)0.0069 (3)0.0043 (2)0.0045 (2)
C2'0.0245 (12)0.0234 (14)0.0196 (10)0.0062 (10)0.0103 (8)0.0032 (10)
C3'0.0207 (8)0.0267 (10)0.0157 (18)0.0046 (7)0.0111 (13)0.0002 (14)
C40.0167 (7)0.0182 (7)0.0172 (7)0.0026 (6)0.0050 (6)0.0018 (6)
C50.0168 (7)0.0174 (7)0.0192 (7)0.0029 (6)0.0055 (6)0.0009 (6)
C70.0157 (7)0.0175 (7)0.0210 (7)0.0035 (6)0.0071 (6)0.0014 (6)
C80.0148 (7)0.0153 (7)0.0202 (8)0.0031 (6)0.0041 (6)0.0016 (6)
C90.0187 (7)0.0210 (8)0.0194 (8)0.0056 (6)0.0076 (6)0.0015 (6)
C100.0239 (8)0.0248 (8)0.0184 (8)0.0057 (7)0.0024 (6)0.0047 (6)
C110.0165 (7)0.0216 (8)0.0298 (9)0.0063 (6)0.0018 (7)0.0053 (7)
C120.0172 (7)0.0217 (8)0.0286 (8)0.0060 (6)0.0089 (6)0.0033 (6)
C130.0197 (8)0.0186 (7)0.0205 (8)0.0027 (6)0.0069 (6)0.0032 (6)
Geometric parameters (Å, º) top
S1—C41.7269 (16)C1'—C2'1.40 (2)
S1—C11.727 (6)C1'—H1'0.9500
S1'—C3'1.360 (16)C2'—C3'1.52 (3)
S1'—C41.725 (3)C2'—H2'0.9500
F1—C91.3624 (17)C3'—H3'0.9500
F2—C131.3500 (18)C4—C51.474 (2)
O1—C51.2425 (18)C7—C81.466 (2)
N1—C51.354 (2)C7—H70.9500
N1—N21.3702 (18)C8—C91.395 (2)
N1—H10.88 (2)C8—C131.397 (2)
N2—C71.284 (2)C9—C101.377 (2)
C1—C21.311 (8)C10—C111.385 (2)
C1—H1A0.9500C10—H100.9500
C2—C31.519 (7)C11—C121.386 (2)
C2—H20.9500C11—H110.9500
C3—C41.374 (5)C12—C131.374 (2)
C3—H30.9500C12—H120.9500
C1'—C41.378 (10)
C4—S1—C191.0 (2)C5—C4—S1'127.47 (18)
C3'—S1'—C488.3 (9)C3—C4—S1111.5 (3)
C5—N1—N2123.04 (13)C5—C4—S1114.07 (11)
C5—N1—H1118.9 (14)O1—C5—N1118.90 (13)
N2—N1—H1117.9 (14)O1—C5—C4119.41 (14)
C7—N2—N1113.74 (13)N1—C5—C4121.68 (14)
C2—C1—S1116.3 (5)N2—C7—C8122.42 (14)
C2—C1—H1A121.9N2—C7—H7118.8
S1—C1—H1A121.9C8—C7—H7118.8
C1—C2—C3109.0 (5)C9—C8—C13114.10 (14)
C1—C2—H2125.5C9—C8—C7119.41 (14)
C3—C2—H2125.5C13—C8—C7126.42 (14)
C4—C3—C2112.2 (4)F1—C9—C10117.74 (14)
C4—C3—H3123.9F1—C9—C8117.47 (14)
C2—C3—H3123.9C10—C9—C8124.78 (14)
C4—C1'—C2'115.3 (11)C9—C10—C11117.90 (15)
C4—C1'—H1'122.3C9—C10—H10121.0
C2'—C1'—H1'122.3C11—C10—H10121.0
C1'—C2'—C3'96.1 (16)C10—C11—C12120.42 (15)
C1'—C2'—H2'131.9C10—C11—H11119.8
C3'—C2'—H2'131.9C12—C11—H11119.8
S1'—C3'—C2'129.6 (16)C13—C12—C11119.10 (15)
S1'—C3'—H3'115.2C13—C12—H12120.5
C2'—C3'—H3'115.2C11—C12—H12120.5
C3—C4—C1'103.4 (5)F2—C13—C12117.98 (14)
C3—C4—C5134.2 (3)F2—C13—C8118.33 (14)
C1'—C4—C5121.8 (4)C12—C13—C8123.67 (15)
C1'—C4—S1'110.5 (5)
C5—N1—N2—C7179.73 (14)C3—C4—C5—O1167.6 (3)
C4—S1—C1—C2−0.8 (5)C1'—C4—C5—O1−2.3 (6)
S1—C1—C2—C30.4 (7)S1'—C4—C5—O1172.3 (2)
C1—C2—C3—C40.4 (7)S1—C4—C5—O1−6.89 (19)
C4—C1'—C2'—C3'−1.0 (16)C3—C4—C5—N1−11.6 (4)
C4—S1'—C3'—C2'−4.0 (19)C1'—C4—C5—N1178.5 (5)
C1'—C2'—C3'—S1'4 (2)S1'—C4—C5—N1−6.9 (3)
C2—C3—C4—C1'−4.4 (7)S1—C4—C5—N1173.89 (12)
C2—C3—C4—C5−175.6 (3)N1—N2—C7—C8−178.28 (13)
C2—C3—C4—S1'155 (3)N2—C7—C8—C9−177.48 (14)
C2—C3—C4—S1−1.0 (5)N2—C7—C8—C135.7 (3)
C2'—C1'—C4—C31.9 (12)C13—C8—C9—F1−178.95 (13)
C2'—C1'—C4—C5174.5 (10)C7—C8—C9—F13.9 (2)
C2'—C1'—C4—S1'−0.9 (13)C13—C8—C9—C101.8 (2)
C2'—C1'—C4—S1−157 (4)C7—C8—C9—C10−175.39 (14)
C3'—S1'—C4—C3−19 (3)F1—C9—C10—C11179.29 (14)
C3'—S1'—C4—C1'2.6 (10)C8—C9—C10—C11−1.4 (2)
C3'—S1'—C4—C5−172.6 (9)C9—C10—C11—C120.0 (2)
C3'—S1'—C4—S16.6 (9)C10—C11—C12—C131.0 (2)
C1—S1—C4—C31.0 (3)C11—C12—C13—F2178.28 (14)
C1—S1—C4—C1'23 (3)C11—C12—C13—C8−0.6 (2)
C1—S1—C4—C5176.8 (2)C9—C8—C13—F2−179.60 (13)
C1—S1—C4—S1'−2.4 (3)C7—C8—C13—F2−2.7 (2)
N2—N1—C5—O1177.55 (13)C9—C8—C13—C12−0.7 (2)
N2—N1—C5—C4−3.2 (2)C7—C8—C13—C12176.23 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.88 (2)1.97 (2)2.856 (2)174 (2)
Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formulaC12H8F2N2OS
Mr266.26
Crystal system, space groupTriclinic, P1
Temperature (K)100
a, b, c (Å)6.5032 (3), 7.7516 (4), 11.5224 (5)
α, β, γ (°)95.184 (4), 103.344 (4), 94.285 (4)
V (Å3)560.11 (5)
Z2
Radiation typeMo Kα
µ (mm−1)0.30
Crystal size (mm)0.40 × 0.30 × 0.20
Data collection
DiffractometerAgilent SuperNova Dual
diffractometer with an Atlas detector
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2010)
Tmin, Tmax0.888, 0.942
No. of measured, independent and
observed [I > 2σ(I)] reflections		8250, 2594, 2174
Rint0.035
(sin θ/λ)max (Å−1)0.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.108, 1.07
No. of reflections2594
No. of parameters180
No. of restraints24
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.33, −0.28

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.88 (2)1.97 (2)2.856 (2)174 (2)
Symmetry code: (i) −x+1, −y+1, −z+1.
 

Acknowledgements

We thank the Deanship of Scientific Research and the Research Center of the College of Pharmacy, King Saud University, and the University of Malaya for supporting this study.

References

First citationAgilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England.  Google Scholar
 First citationAlanazi, A. M., Lahsasni, S., El-Emam, A. A. & Ng, S. W. (2012). Acta Cryst. E68, o314.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
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 First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 2| February 2012| Page o315
doi:10.1107/S160053681105611X
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