Crystal structure of 4-fluoro-N-[2-(4-fluoro­benzo­yl)hydra­zine-1-carbono­thio­yl]benzamide

In the title compound, C₁₅H₁₁F₂N₃O₂S, the dihedral angle between the fluoro­benzene rings is 88.43 (10)° and that between the central semithiocarbazide grouping is 47.00 (11)°. The dihedral angle between the amide group and attached fluoro­benzene ring is 50.52 (11)°; the equivalent angle between the carbonyl­thio­amide group and its attached ring is 12.98 (10)°. The major twists in the mol­ecule occur about the C—N—N—C bonds [torsion angle = −138.7 (2)°] and the C_ar—C_ar—C—N (ar = aromatic) bonds [−132.0 (2)°]. An intra­molecular N—H...O hydrogen bond occurs, which generates an S(6) ring. In the crystal, the mol­ecules are linked by N—H...O and N—H...S hydrogen bonds, generating (001) sheets. Weak C—H...O and C—H...F inter­actions are also observed.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.046
• wR factor = 0.099
• Data-to-parameter ratio = 13.9

checkCIF/PLATON results

No syntax errors found



Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.12
            Rint given   0.137
PLAT334_ALERT_2_C Small Average Benzene  C-C Dist. C1     -C6            1.37 Ang.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      5.308 Check

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          3 Why ?
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) .....          3 Why ?

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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Related literature

For further synthetic details and the crystal structures of related thiourea derivatives, see: Yamin & Yusof (2003a,b); Yusof et al. (2003); For a metal complex with a similar ligand, see: Ke et al. (2007).

S1. Experimental

30 ml acetone containing 4-fluorobenzoyl isothiocyanate (1.81 g, 0.01 mol) was mixed with hydrazine (0.16 g, 0.005 mol). The mixture was refluxed for 2 hours. The solution was filtered and left to evaporate at room temperature. The white precipitate obtained after a few days, was washed with water and cold ethanol. Colourless blocks of the title compound were obtained by recrystallization from ethanol solution.

S2. Refinement

After location in the difference map, the H-atoms attached to the C and N atoms were fixed geometrically at ideal positions and allowed to ride on the parent atoms with C—H = 0.93-0.97 Å, N—H = 0.86 Å and with U_iso(H)=1.2U_eq(C or N).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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) and PLATON (Spek, 2009).

Figures

	Fig. 1. : Molecular structure of (I) with 50% probability displacement ellipsoids. The dashes line indicates the intramolecular hydrogen bond.
	Fig. 2. : Unit-cell packing for (I) in the unit cell viewed down a axis. The dashes lines indicate hydrogen bonds.

4-Fluoro-N-[2-(4-fluorobenzoyl)hydrazine-1-carbonothioyl]benzamide

Crystal data

C15H11F2N3O2S	Z = 8
Mr = 335.33	F(000) = 1376
Orthorhombic, Pbca	Dx = 1.520 Mg m^−3
Hall symbol: -P 2ac 2ab	Mo Kα radiation, λ = 0.71073 Å
a = 11.6172 (6) Å	µ = 0.26 mm^−1
b = 8.4086 (5) Å	T = 296 K
c = 30.0002 (16) Å	Block, colorless
V = 2930.6 (3) Å^3	0.50 × 0.12 × 0.08 mm

Data collection

Bruker SMART APEX CCD diffractometer	2886 independent reflections
Radiation source: fine-focus sealed tube	2024 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.137
ω scans	θmax = 26.0°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −14→14
Tmin = 0.883, Tmax = 0.980	k = −10→10
76830 measured reflections	l = −37→37

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.099	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0354P)^2 + 2.0394P] where P = (Fo^2 + 2Fc^2)/3
2886 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.98887 (5)	0.15863 (8)	0.73680 (2)	0.04054 (19)
O1	0.69608 (15)	0.4074 (2)	0.80598 (6)	0.0585 (6)
O2	0.64343 (13)	0.34844 (18)	0.67414 (5)	0.0328 (4)
N1	0.88035 (15)	0.3239 (2)	0.79937 (6)	0.0283 (4)
H1A	0.9472	0.3290	0.8116	0.034*
N2	0.76928 (15)	0.2357 (2)	0.74100 (6)	0.0308 (5)
H2A	0.7137	0.2871	0.7533	0.037*
N3	0.74823 (15)	0.1473 (2)	0.70307 (5)	0.0278 (4)
H3	0.7784	0.0548	0.6995	0.033*
C1	0.7245 (2)	0.5302 (3)	0.88928 (8)	0.0444 (7)
H1	0.6558	0.5469	0.8741	0.053*
C2	0.7347 (2)	0.5802 (3)	0.93299 (8)	0.0511 (7)
H2	0.6738	0.6303	0.9474	0.061*
C3	0.8362 (2)	0.5540 (3)	0.95425 (8)	0.0430 (7)
C4	0.9276 (2)	0.4826 (3)	0.93441 (8)	0.0479 (7)
H4	0.9959	0.4667	0.9500	0.057*
C5	0.9171 (2)	0.4339 (3)	0.89050 (8)	0.0402 (6)
H5	0.9792	0.3861	0.8762	0.048*
C6	0.81520 (19)	0.4557 (3)	0.86779 (7)	0.0300 (5)
C7	0.79209 (19)	0.3964 (3)	0.82191 (7)	0.0315 (5)
C8	0.87407 (18)	0.2428 (3)	0.75895 (7)	0.0258 (5)
C9	0.67935 (17)	0.2104 (3)	0.67201 (7)	0.0254 (5)
C10	0.64585 (18)	0.1018 (3)	0.63505 (7)	0.0263 (5)
C11	0.6553 (2)	0.1549 (3)	0.59144 (7)	0.0383 (6)
H11	0.6838	0.2563	0.5858	0.046*
C12	0.6228 (2)	0.0589 (3)	0.55647 (8)	0.0481 (7)
H12	0.6300	0.0931	0.5271	0.058*
C13	0.5797 (2)	−0.0878 (3)	0.56616 (9)	0.0503 (7)
C15	0.6004 (2)	−0.0473 (3)	0.64350 (8)	0.0360 (6)
H15	0.5929	−0.0828	0.6727	0.043*
F1	0.84583 (15)	0.6012 (2)	0.99733 (5)	0.0681 (5)
F2	0.54797 (19)	−0.1828 (2)	0.53146 (6)	0.0870 (7)
C14	0.5660 (2)	−0.1434 (3)	0.60860 (9)	0.0491 (7)
H14	0.5344	−0.2433	0.6139	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0271 (3)	0.0533 (4)	0.0412 (4)	0.0032 (3)	−0.0018 (3)	−0.0162 (3)
O1	0.0387 (11)	0.0887 (16)	0.0482 (11)	0.0263 (10)	−0.0169 (9)	−0.0332 (11)
O2	0.0344 (9)	0.0280 (9)	0.0359 (9)	0.0044 (8)	−0.0042 (7)	−0.0043 (7)
N1	0.0248 (9)	0.0357 (11)	0.0242 (9)	−0.0003 (8)	−0.0042 (8)	−0.0055 (8)
N2	0.0269 (10)	0.0392 (12)	0.0262 (10)	0.0057 (9)	−0.0042 (8)	−0.0118 (9)
N3	0.0280 (9)	0.0286 (10)	0.0270 (10)	0.0032 (9)	−0.0059 (8)	−0.0073 (8)
C1	0.0390 (15)	0.0567 (18)	0.0374 (14)	0.0123 (13)	−0.0061 (12)	−0.0095 (13)
C2	0.0505 (17)	0.0635 (19)	0.0394 (15)	0.0131 (15)	0.0054 (13)	−0.0154 (14)
C3	0.0531 (17)	0.0494 (17)	0.0265 (13)	−0.0062 (14)	−0.0001 (12)	−0.0112 (12)
C4	0.0389 (14)	0.067 (2)	0.0377 (15)	0.0004 (14)	−0.0096 (12)	−0.0118 (14)
C5	0.0347 (14)	0.0535 (17)	0.0323 (13)	0.0045 (12)	−0.0021 (11)	−0.0116 (12)
C6	0.0316 (13)	0.0303 (13)	0.0280 (12)	−0.0002 (10)	−0.0017 (10)	−0.0027 (11)
C7	0.0300 (12)	0.0332 (14)	0.0314 (13)	0.0042 (10)	−0.0046 (10)	−0.0026 (11)
C8	0.0294 (12)	0.0253 (12)	0.0228 (11)	−0.0025 (10)	−0.0034 (10)	0.0009 (9)
C9	0.0214 (11)	0.0280 (13)	0.0267 (12)	−0.0014 (10)	0.0019 (9)	−0.0010 (10)
C10	0.0233 (11)	0.0289 (13)	0.0267 (12)	0.0027 (10)	−0.0056 (9)	−0.0036 (10)
C11	0.0464 (14)	0.0374 (15)	0.0313 (13)	−0.0068 (13)	−0.0024 (11)	0.0013 (12)
C12	0.0634 (18)	0.0546 (18)	0.0261 (13)	−0.0020 (15)	−0.0060 (12)	−0.0041 (13)
C13	0.0603 (18)	0.0505 (18)	0.0399 (16)	−0.0067 (15)	−0.0182 (13)	−0.0189 (14)
C15	0.0390 (14)	0.0368 (15)	0.0321 (13)	−0.0051 (12)	−0.0082 (11)	0.0020 (11)
F1	0.0741 (11)	0.0980 (14)	0.0322 (8)	−0.0006 (10)	−0.0036 (8)	−0.0258 (9)
F2	0.1324 (18)	0.0781 (14)	0.0506 (11)	−0.0280 (12)	−0.0284 (11)	−0.0258 (10)
C14	0.0589 (18)	0.0370 (16)	0.0514 (17)	−0.0158 (14)	−0.0154 (14)	−0.0037 (13)

Geometric parameters (Å, º)

S1—C8	1.650 (2)	C4—C5	1.385 (3)
O1—C7	1.217 (3)	C4—H4	0.9300
O2—C9	1.235 (3)	C5—C6	1.378 (3)
N1—C7	1.371 (3)	C5—H5	0.9300
N1—C8	1.393 (3)	C6—C7	1.488 (3)
N1—H1A	0.8600	C9—C10	1.488 (3)
N2—C8	1.333 (3)	C10—C15	1.384 (3)
N2—N3	1.381 (2)	C10—C11	1.387 (3)
N2—H2A	0.8600	C11—C12	1.377 (3)
N3—C9	1.338 (3)	C11—H11	0.9300
N3—H3	0.8600	C12—C13	1.362 (4)
C1—C2	1.382 (3)	C12—H12	0.9300
C1—C6	1.385 (3)	C13—F2	1.363 (3)
C1—H1	0.9300	C13—C14	1.366 (4)
C2—C3	1.359 (4)	C15—C14	1.381 (3)
C2—H2	0.9300	C15—H15	0.9300
C3—F1	1.357 (3)	C14—H14	0.9300
C3—C4	1.358 (4)
C7—N1—C8	127.43 (18)	O1—C7—N1	121.7 (2)
C7—N1—H1A	116.3	O1—C7—C6	120.2 (2)
C8—N1—H1A	116.3	N1—C7—C6	118.04 (19)
C8—N2—N3	121.27 (18)	N2—C8—N1	114.95 (18)
C8—N2—H2A	119.4	N2—C8—S1	123.80 (16)
N3—N2—H2A	119.4	N1—C8—S1	121.23 (15)
C9—N3—N2	117.80 (18)	O2—C9—N3	122.6 (2)
C9—N3—H3	121.1	O2—C9—C10	121.8 (2)
N2—N3—H3	121.1	N3—C9—C10	115.58 (19)
C2—C1—C6	121.0 (2)	C15—C10—C11	119.7 (2)
C2—C1—H1	119.5	C15—C10—C9	121.3 (2)
C6—C1—H1	119.5	C11—C10—C9	119.0 (2)
C3—C2—C1	118.0 (2)	C12—C11—C10	120.5 (2)
C3—C2—H2	121.0	C12—C11—H11	119.7
C1—C2—H2	121.0	C10—C11—H11	119.7
F1—C3—C4	118.8 (2)	C13—C12—C11	118.0 (2)
F1—C3—C2	118.1 (2)	C13—C12—H12	121.0
C4—C3—C2	123.0 (2)	C11—C12—H12	121.0
C3—C4—C5	118.6 (2)	C12—C13—F2	117.8 (2)
C3—C4—H4	120.7	C12—C13—C14	123.5 (2)
C5—C4—H4	120.7	F2—C13—C14	118.7 (3)
C6—C5—C4	120.5 (2)	C14—C15—C10	120.1 (2)
C6—C5—H5	119.8	C14—C15—H15	119.9
C4—C5—H5	119.8	C10—C15—H15	119.9
C5—C6—C1	118.9 (2)	C13—C14—C15	118.2 (3)
C5—C6—C7	124.6 (2)	C13—C14—H14	120.9
C1—C6—C7	116.4 (2)	C15—C14—H14	120.9
C8—N2—N3—C9	−138.7 (2)	C7—N1—C8—N2	−0.5 (3)
C6—C1—C2—C3	0.0 (4)	C7—N1—C8—S1	−178.67 (18)
C1—C2—C3—F1	−179.2 (3)	N2—N3—C9—O2	6.9 (3)
C1—C2—C3—C4	0.5 (5)	N2—N3—C9—C10	−171.47 (17)
F1—C3—C4—C5	179.6 (3)	O2—C9—C10—C15	−127.2 (2)
C2—C3—C4—C5	−0.1 (4)	N3—C9—C10—C15	51.2 (3)
C3—C4—C5—C6	−0.9 (4)	O2—C9—C10—C11	49.5 (3)
C4—C5—C6—C1	1.4 (4)	N3—C9—C10—C11	−132.0 (2)
C4—C5—C6—C7	−175.0 (2)	C15—C10—C11—C12	−1.9 (4)
C2—C1—C6—C5	−1.0 (4)	C9—C10—C11—C12	−178.6 (2)
C2—C1—C6—C7	175.7 (3)	C10—C11—C12—C13	1.1 (4)
C8—N1—C7—O1	−6.0 (4)	C11—C12—C13—F2	−179.8 (3)
C8—N1—C7—C6	171.2 (2)	C11—C12—C13—C14	0.7 (4)
C5—C6—C7—O1	172.8 (3)	C11—C10—C15—C14	0.9 (4)
C1—C6—C7—O1	−3.6 (4)	C9—C10—C15—C14	177.6 (2)
C5—C6—C7—N1	−4.4 (4)	C12—C13—C14—C15	−1.7 (4)
C1—C6—C7—N1	179.1 (2)	F2—C13—C14—C15	178.8 (3)
N3—N2—C8—N1	−174.21 (18)	C10—C15—C14—C13	0.8 (4)
N3—N2—C8—S1	3.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	1.89	2.571 (2)	135
N2—H2A···S1^i	0.86	2.84	3.3875 (18)	123
N1—H1A···O2^ii	0.86	2.33	3.165 (2)	165
N3—H3···O2^iii	0.86	2.10	2.942 (2)	166
C4—H4···F1^iv	0.93	2.49	3.409 (3)	169
C5—H5···O2^ii	0.93	2.45	3.345 (3)	160

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