4-(4-Chloro­phen­yl)-1-[2-(2,4-dichloro­phen­oxy)propano­yl]thio­semicarbazide

The title compound, C₁₆H₁₄Cl₃N₃O₂S, is an important inter­mediate for the synthesis of biologically active heterocyclic compounds. The chloro- and dichloro­phenyl rings are oriented at a dihedral angle of 40.41 (3)°. The intra­molecular N—H...O hydrogen bond results in the formation of a nearly planar five-membered ring, which is oriented at dihedral angles of 24.36 (3) and 22.27 (3)° with respect to the chloro- and dichloro­phenyl rings, respectively. In the crystal structure, inter­molecular N—H...O hydrogen bonds link the mol­ecules.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.042
• wR factor = 0.100
• Data-to-parameter ratio = 18.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        200 Deg.

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C9     .....          S

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

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

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S1. Comment

Thiosemicarbazide is interesting because of the formation of complexes with biological activities (Shen et al., 1998). Some substituted thiourea derivatives have shown interesting biological effects, including anti-HIV properties (Mao et al., 1999), and thiourea derivatives have also been successfully screened for various biological actions (Antholine & Taketa, 1982). As a ligand with potential S– and N-atom donors, thiosemicarbazide is interesting because of the structural chemistry of its multifunctional coordination modes (N-monodentate, S-monodentate or N:S-bidentate). In order to investigate further this kind of ligand, we synthesized the title compound, (I), and reported herein its crystal structure.

In the molecule of (I) (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). Rings A (C1—C6) and B (C11—C16) are, of course, planar. The intramolecular N—H···O hydrogen bond (Table 1) results in the formation of a nearly planar five-membered ring; C (N3/C8/C9/O2/H3N). The dihedral angles between them are A/B = 40.41 (3)°, A/C = 24.36 (3)° and B/C = 22.27 (3)°.

In the crystal structure, intermolecular N—H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they seem to be effective in the stabilization of the structure.

Related literature

For related literature, see: Shen et al. (1998); Mao et al. (1999); Antholine & Taketa (1982). For bond-length data, see: Allen et al. (1987).

S2. Experimental

The title compound was prepared by the reaction of 2-(2,4-dichlorophenoxy) propanohydrazide (2.48 g, 20 mmol) and 4-chlorophenyl isothiocyanate (0.84 g, 20 mmol). Single crystals suitable for X-ray analysis were obtained by recrystallization from an aqeous ethanol solution at room temperature (yield; 76%; m.p. 465–466 K).

S3. Refinement

H atoms of NH groups were located in difference syntheses and constrained to ride on their parent atoms, [N—H = 0.8725, 0.9582 and 0.9954 Å and U_iso(H) = 1.5U_eq(N)]. The remaining H atoms were positioned geometrically, with C—H = 0.95 and 1.00 Å for aromatic and methine H atoms, respectively, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: COLLECT (Bruker, 2000); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2007); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.
	Fig. 3. Preparation of the title compound.

4-(4-Chlorophenyl)-1-[2-(2,4-dichlorophenoxy)propanoyl]thiosemicarbazide

Crystal data

C16H14Cl3N3O2S	Z = 2
Mr = 418.71	F(000) = 428
Triclinic, P1	Dx = 1.566 Mg m^−3
Hall symbol: -P 1	Melting point: 465(1) K
a = 7.8930 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.9195 (3) Å	Cell parameters from 11915 reflections
c = 13.3491 (4) Å	θ = 1.0–27.5°
α = 96.514 (2)°	µ = 0.65 mm^−1
β = 98.681 (2)°	T = 120 K
γ = 104.476 (2)°	Block, colorless
V = 888.25 (5) Å^3	0.20 × 0.13 × 0.12 mm

Data collection

Nonius KappaCCD diffractometer	4083 independent reflections
Radiation source: fine-focus sealed tube	3217 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.040
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 1.6°
ϕ scans and ω scans with κ offset	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −11→11
Tmin = 0.881, Tmax = 0.926	l = −17→17
17933 measured reflections

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)] = 0.042	Hydrogen site location: mixed
wR(F^2) = 0.100	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.035P)^2 + 0.9894P] where P = (Fo^2 + 2Fc^2)/3
4083 reflections	(Δ/σ)max < 0.001
227 parameters	Δρmax = 0.59 e Å^−3
0 restraints	Δρmin = −0.47 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
Cl1	1.12353 (7)	1.36448 (7)	0.36324 (5)	0.02892 (15)
Cl2	−0.13947 (8)	0.44813 (8)	0.08375 (5)	0.03269 (16)
Cl3	−0.78798 (10)	0.05093 (8)	−0.06665 (5)	0.04314 (19)
S1	0.24894 (8)	0.84661 (7)	0.21890 (5)	0.02685 (16)
O1	−0.2064 (2)	0.87470 (19)	0.44166 (12)	0.0254 (4)
O2	−0.3218 (2)	0.6062 (2)	0.21131 (12)	0.0322 (4)
N1	0.3706 (2)	1.0769 (2)	0.38554 (14)	0.0210 (4)
H1N	0.3394	1.1144	0.4410	0.031*
N2	0.0791 (2)	0.9544 (2)	0.35479 (15)	0.0225 (4)
H2N	0.0783	1.0127	0.4195	0.034*
N3	−0.0680 (2)	0.8317 (2)	0.30982 (14)	0.0210 (4)
H3N	−0.0763	0.7646	0.2434	0.031*
C1	0.9023 (3)	1.2756 (3)	0.36897 (17)	0.0196 (4)
C2	0.7841 (3)	1.2060 (3)	0.27939 (17)	0.0225 (5)
H2	0.8240	1.2052	0.2157	0.027*
C3	0.6067 (3)	1.1372 (3)	0.28158 (17)	0.0214 (5)
H3	0.5247	1.0901	0.2196	0.026*
C4	0.5497 (3)	1.1377 (2)	0.37567 (17)	0.0185 (4)
C5	0.6708 (3)	1.2093 (3)	0.46567 (17)	0.0203 (5)
H5	0.6316	1.2103	0.5296	0.024*
C6	0.8474 (3)	1.2790 (3)	0.46331 (17)	0.0210 (5)
H6	0.9295	1.3281	0.5248	0.025*
C7	0.2363 (3)	0.9647 (2)	0.32242 (17)	0.0193 (4)
C8	−0.2060 (3)	0.8005 (3)	0.35744 (17)	0.0210 (5)
C9	−0.3661 (3)	0.6672 (3)	0.30407 (17)	0.0246 (5)
H9	−0.4710	0.7097	0.2872	0.030*
C10	−0.4072 (3)	0.5491 (3)	0.37497 (19)	0.0286 (5)
H10A	−0.5123	0.4639	0.3415	0.043*
H10B	−0.4308	0.6000	0.4384	0.043*
H10C	−0.3052	0.5063	0.3913	0.043*
C11	−0.4399 (3)	0.4790 (3)	0.14855 (16)	0.0216 (5)
C12	−0.3656 (3)	0.3914 (3)	0.08300 (17)	0.0217 (5)
C13	−0.4719 (3)	0.2600 (3)	0.01604 (17)	0.0252 (5)
H13	−0.4214	0.2013	−0.0291	0.030*
C14	−0.6526 (3)	0.2161 (3)	0.01616 (18)	0.0265 (5)
C15	−0.7295 (3)	0.3017 (3)	0.07964 (18)	0.0261 (5)
H15	−0.8541	0.2700	0.0784	0.031*
C16	−0.6221 (3)	0.4346 (3)	0.14523 (18)	0.0242 (5)
H16	−0.6740	0.4956	0.1881	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0179 (3)	0.0313 (3)	0.0347 (3)	0.0013 (2)	0.0074 (2)	0.0026 (2)
Cl2	0.0211 (3)	0.0441 (4)	0.0370 (3)	0.0096 (3)	0.0122 (2)	0.0123 (3)
Cl3	0.0487 (4)	0.0326 (4)	0.0340 (4)	−0.0024 (3)	0.0001 (3)	−0.0117 (3)
S1	0.0214 (3)	0.0291 (3)	0.0257 (3)	0.0021 (2)	0.0082 (2)	−0.0078 (2)
O1	0.0244 (9)	0.0259 (9)	0.0214 (8)	0.0002 (7)	0.0080 (7)	−0.0047 (7)
O2	0.0295 (9)	0.0350 (10)	0.0211 (8)	−0.0084 (8)	0.0100 (7)	−0.0089 (7)
N1	0.0181 (9)	0.0234 (10)	0.0197 (9)	0.0016 (8)	0.0080 (7)	−0.0007 (8)
N2	0.0180 (9)	0.0222 (10)	0.0229 (10)	−0.0009 (8)	0.0068 (8)	−0.0043 (8)
N3	0.0164 (9)	0.0226 (10)	0.0198 (9)	−0.0007 (8)	0.0048 (7)	−0.0019 (8)
C1	0.0162 (11)	0.0178 (11)	0.0259 (11)	0.0048 (8)	0.0073 (9)	0.0024 (9)
C2	0.0238 (12)	0.0220 (11)	0.0216 (11)	0.0041 (9)	0.0089 (9)	0.0019 (9)
C3	0.0222 (11)	0.0200 (11)	0.0192 (11)	0.0021 (9)	0.0036 (9)	0.0002 (9)
C4	0.0176 (11)	0.0151 (10)	0.0232 (11)	0.0046 (8)	0.0058 (9)	0.0020 (8)
C5	0.0228 (11)	0.0202 (11)	0.0189 (11)	0.0068 (9)	0.0064 (9)	0.0024 (9)
C6	0.0200 (11)	0.0212 (11)	0.0197 (11)	0.0055 (9)	−0.0003 (9)	0.0004 (9)
C7	0.0194 (11)	0.0177 (11)	0.0209 (11)	0.0050 (9)	0.0044 (9)	0.0023 (8)
C8	0.0201 (11)	0.0227 (11)	0.0192 (11)	0.0036 (9)	0.0054 (9)	0.0022 (9)
C9	0.0238 (12)	0.0270 (12)	0.0192 (11)	0.0011 (10)	0.0064 (9)	−0.0021 (9)
C10	0.0306 (13)	0.0236 (12)	0.0270 (12)	−0.0002 (10)	0.0046 (10)	0.0026 (10)
C11	0.0216 (11)	0.0238 (12)	0.0150 (10)	0.0006 (9)	0.0020 (9)	−0.0007 (9)
C12	0.0195 (11)	0.0289 (12)	0.0191 (11)	0.0075 (9)	0.0065 (9)	0.0069 (9)
C13	0.0327 (13)	0.0253 (12)	0.0194 (11)	0.0098 (10)	0.0093 (10)	0.0007 (9)
C14	0.0326 (13)	0.0220 (12)	0.0203 (11)	0.0036 (10)	0.0004 (10)	−0.0006 (9)
C15	0.0195 (12)	0.0281 (13)	0.0270 (12)	0.0021 (10)	0.0020 (9)	0.0026 (10)
C16	0.0214 (12)	0.0240 (12)	0.0269 (12)	0.0059 (9)	0.0076 (9)	−0.0005 (9)

Geometric parameters (Å, º)

Cl1—C1	1.745 (2)	C3—H3	0.9500
Cl2—C12	1.727 (2)	C4—C5	1.392 (3)
Cl3—C14	1.738 (2)	C5—C6	1.384 (3)
S1—C7	1.671 (2)	C5—H5	0.9500
O1—C8	1.239 (3)	C6—H6	0.9500
O2—C11	1.370 (3)	C8—C9	1.518 (3)
O2—C9	1.423 (3)	C9—C10	1.503 (3)
N1—C7	1.358 (3)	C9—H9	1.0000
N1—C4	1.414 (3)	C10—H10A	0.9800
N1—H1N	0.8725	C10—H10B	0.9800
N2—C7	1.360 (3)	C10—H10C	0.9800
N2—N3	1.382 (3)	C11—C16	1.385 (3)
N2—H2N	0.9582	C11—C12	1.396 (3)
N3—C8	1.329 (3)	C12—C13	1.386 (3)
N3—H3N	0.9954	C13—C14	1.382 (3)
C1—C2	1.375 (3)	C13—H13	0.9500
C1—C6	1.392 (3)	C14—C15	1.382 (3)
C2—C3	1.388 (3)	C15—C16	1.389 (3)
C2—H2	0.9500	C15—H15	0.9500
C3—C4	1.396 (3)	C16—H16	0.9500
C11—O2—C9	119.48 (18)	O1—C8—C9	120.6 (2)
C7—N1—C4	130.11 (18)	N3—C8—C9	116.85 (19)
C7—N1—H1N	113.2	O2—C9—C10	113.9 (2)
C4—N1—H1N	116.6	O2—C9—C8	106.38 (18)
C7—N2—N3	119.54 (18)	C10—C9—C8	109.12 (19)
C7—N2—H2N	119.4	O2—C9—H9	109.1
N3—N2—H2N	118.8	C10—C9—H9	109.1
C8—N3—N2	118.69 (18)	C8—C9—H9	109.1
C8—N3—H3N	117.8	C9—C10—H10A	109.5
N2—N3—H3N	123.5	C9—C10—H10B	109.5
C2—C1—C6	121.1 (2)	H10A—C10—H10B	109.5
C2—C1—Cl1	119.13 (17)	C9—C10—H10C	109.5
C6—C1—Cl1	119.77 (17)	H10A—C10—H10C	109.5
C1—C2—C3	120.3 (2)	H10B—C10—H10C	109.5
C1—C2—H2	119.8	O2—C11—C16	125.2 (2)
C3—C2—H2	119.8	O2—C11—C12	115.4 (2)
C2—C3—C4	119.4 (2)	C16—C11—C12	119.3 (2)
C2—C3—H3	120.3	C13—C12—C11	120.6 (2)
C4—C3—H3	120.3	C13—C12—Cl2	119.42 (17)
C5—C4—C3	119.7 (2)	C11—C12—Cl2	119.93 (18)
C5—C4—N1	116.60 (19)	C14—C13—C12	118.8 (2)
C3—C4—N1	123.6 (2)	C14—C13—H13	120.6
C6—C5—C4	120.9 (2)	C12—C13—H13	120.6
C6—C5—H5	119.6	C13—C14—C15	121.6 (2)
C4—C5—H5	119.6	C13—C14—Cl3	119.52 (18)
C5—C6—C1	118.7 (2)	C15—C14—Cl3	118.85 (19)
C5—C6—H6	120.7	C14—C15—C16	119.1 (2)
C1—C6—H6	120.7	C14—C15—H15	120.5
N1—C7—N2	110.96 (18)	C16—C15—H15	120.5
N1—C7—S1	127.86 (17)	C11—C16—C15	120.5 (2)
N2—C7—S1	121.17 (16)	C11—C16—H16	119.8
O1—C8—N3	122.6 (2)	C15—C16—H16	119.8

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.87	2.02	2.854 (2)	160
N2—H2N···O1^i	0.96	1.99	2.861 (2)	150
N3—H3N···O2	1.00	2.04	2.526 (2)	107

Symmetry code: (i) −x, −y+2, −z+1.