N-(Biphenyl-4-carbon­yl)-N′-(2-chloro­phen­yl)thio­urea

In the title compound, C₂₀H₁₅ClN₂OS, the benzene rings of the biphenyl group are not coplanar, indicated by a dihedral angle of 20.71 (17)°. The mol­ecule maintains its trans–cis configuration with respect to the position of the biphenyl­carbonyl and chloro­benzene groups relative to the thiono S atom across their C—N bonds, respectively. The central carbonyl–thio­urea unit makes dihedral angles with the carbonyl benzene ring and the chloro­benzene fragment of 24.39 (13) and 61.63 (10)°, respectively. There is an intra­molecular N—H...O hydrogen bond in the mol­ecule. The mol­ecules in the structure are packed by weak van der Waals and π–π inter­actions [centroid–centroid distance 3.629 (2) Å].

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.063
• wR factor = 0.131
• Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level C
REFLT03_ALERT_3_C  Reflection count < 95% complete
           From the CIF: _diffrn_reflns_theta_max           26.00
           From the CIF: _diffrn_reflns_theta_full          26.00
           From the CIF: _reflns_number_total               3219
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         3404
           Completeness (_total/calc)             94.57%
PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low ....       0.95
PLAT230_ALERT_2_C Hirshfeld Test Diff for    Cl1    -   C16     ..       6.92 su
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1A    ...          ?

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 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

---

S1. Comment

Many aroylthiourea compounds reported so far are based on a benzene group. The title compound, (I), is also an aroylthiourea derivative but having a biphenyl group (Fig.1). The molecule maintains the trans-cis configuration with respect to the position of the biphenylcarbonyl and chlorobenzene groups about the thiono sulfur atom across their C14—N1 and C14—N2 bonds, respectively. The biphenyl fragment is not planar with C1—C6—C7—C12 and C5—C6—C7—C8 torsion angles of -18.9 (5) and -21.2 (5)° respectively. The bond lengths and angles are in normal ranges (Allen et al., 1987) and close to those observed in (II) (Yusof & Yamin, 2004) and (III) (Shoukat et al., 2007). The benzene C7—C12, the carbonyl-thiourea C13/O1/N1/C14/S1/N2 and the chlorobenzene Cl1/C15—C20 fragments are each planar with maximum deviation of 0.026 (3)Å for N1 atom from the least squares plane of the carbonyl-thiourea moiety. The central carbonyl-thiourea moiety makes dihedral angles with the C7—C12 benzene ring and chlorobenzene fragment of 24.39 (13) and 61.63 (10)°, respectively. There is an N2—H2A···O1 intramolecular hydrogen bond (D—H= 0.863 (12), H···A= 1.882 (18) D···A= 2.619 (4)Å and D—H···A =142 (3)°) formimg a pseudo six-membered ring [C13—N1—C14—N2—H2A···O1]. The crystal packing is stabilized by weak van der Waals and π···π interactions, between the benzene (C7—C12)ⁱ rings ((i): 1 - x, -y, -z) with the distance between the centroids of 3.629 (2) Å.

Related literature

Many N-aroyl-N'(chlorophenyl)thiourea compounds, such as N-benzoyl-N'-(2-chlorophenyl)thiourea (Yusof & Yamin, 2004) and N-pivaloyl-N'-(2-chlorophenyl)thiourea (Shoukat et al., 2007), possess a trans–cis configuration with respect to the position of the carbomoyl and chlorophenyl groups against the thiono S atom about their thiourea C—N bonds, respectively.

For bond-length data, see: Allen et al. (1987).

S2. Experimental

A solution of 2-chloroaniline (0.63 g, 2.5 mmol) in 20 ml acetone was added dropwise to a two-necked round-bottomed flask containing an equimolar solution of biphenylcarbomoylisothiocyanate (0.60 g, 2.5 mmol) in 20 ml of acetone. The mixture was refluxed for about 3 h. The light yellow solution was filtered and allowed to evaporate at room temperature. Some colourless crystals were obtained after five days of evaporation (yield 0.71 g, 85%).

S3. Refinement

H atoms on C were positioned geometrically with C—H 0.93, 0.96 and 0.97 Å, for aromatic, methlylene and methyl H atoms respectively, constrained to ride on their parent atoms with U_iso(H)= 1.2U_eq(C). The hydrogen atom attached to the N atom were located from the difference map and refined isotropically.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Figures

Fig. 1. Molecular structure of compound, (1), with displacement ellipsoid drawn at the 50% probablity level. The dashed line indicates the intramolecular hydrogen bond.

N-(Biphenyl-4-carbonyl)-N'-(2-chlorophenyl)thiourea

Crystal data

C20H15ClN2OS	F(000) = 760
Mr = 366.85	Dx = 1.406 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 993 reflections
a = 9.2448 (14) Å	θ = 1.5–26.0°
b = 7.2284 (11) Å	µ = 0.35 mm^−1
c = 25.934 (4) Å	T = 298 K
β = 90.295 (3)°	Slab, colourless
V = 1733.0 (5) Å^3	0.50 × 0.30 × 0.07 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3219 independent reflections
Radiation source: fine-focus sealed tube	1742 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
Detector resolution: 83.66 pixels mm^-1	θmax = 26.0°, θmin = 1.5°
ω scans	h = −11→10
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −8→8
Tmin = 0.844, Tmax = 0.975	l = −29→31
8945 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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0507P)^2 + 0.1441P] where P = (Fo^2 + 2Fc^2)/3
3219 reflections	(Δ/σ)max < 0.001
234 parameters	Δρmax = 0.17 e Å^−3
2 restraints	Δρmin = −0.17 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	1.27749 (11)	0.44805 (15)	0.13364 (4)	0.0817 (4)
S1	0.88704 (10)	0.09939 (17)	0.21077 (4)	0.0781 (4)
O1	0.9742 (3)	0.1787 (4)	0.04062 (9)	0.0664 (8)
N1	0.8363 (3)	0.1431 (4)	0.11180 (11)	0.0503 (7)
H1A	0.7484 (15)	0.138 (5)	0.1217 (12)	0.071 (12)*
N2	1.0760 (3)	0.1311 (4)	0.13409 (11)	0.0523 (8)
H2A	1.084 (3)	0.143 (4)	0.1011 (4)	0.051 (10)*
C1	0.3650 (4)	0.3033 (5)	−0.12193 (13)	0.0567 (10)
H1B	0.4552	0.2864	−0.1370	0.068*
C2	0.2491 (4)	0.3507 (6)	−0.15248 (14)	0.0695 (11)
H2B	0.2623	0.3679	−0.1877	0.083*
C3	0.1151 (4)	0.3727 (5)	−0.13193 (15)	0.0640 (10)
H3A	0.0369	0.4040	−0.1528	0.077*
C4	0.0972 (4)	0.3481 (5)	−0.08032 (15)	0.0618 (10)
H4A	0.0062	0.3637	−0.0658	0.074*
C5	0.2130 (4)	0.3003 (5)	−0.04933 (13)	0.0548 (9)
H5A	0.1983	0.2811	−0.0143	0.066*
C6	0.3507 (3)	0.2803 (4)	−0.06939 (12)	0.0431 (8)
C7	0.4769 (3)	0.2416 (4)	−0.03535 (12)	0.0426 (8)
C8	0.4740 (4)	0.2821 (4)	0.01696 (13)	0.0502 (9)
H8A	0.3892	0.3289	0.0310	0.060*
C9	0.5914 (4)	0.2560 (5)	0.04891 (13)	0.0512 (9)
H9A	0.5839	0.2819	0.0839	0.061*
C10	0.7212 (3)	0.1910 (4)	0.02908 (12)	0.0441 (8)
C11	0.7267 (4)	0.1514 (5)	−0.02322 (13)	0.0526 (9)
H11A	0.8127	0.1087	−0.0374	0.063*
C12	0.6070 (4)	0.1741 (5)	−0.05464 (13)	0.0515 (9)
H12A	0.6133	0.1438	−0.0894	0.062*
C13	0.8543 (4)	0.1702 (5)	0.06013 (13)	0.0487 (9)
C14	0.9399 (4)	0.1239 (5)	0.15061 (12)	0.0496 (9)
C15	1.2018 (3)	0.1052 (5)	0.16435 (12)	0.0464 (9)
C16	1.3065 (4)	0.2418 (5)	0.16584 (12)	0.0517 (9)
C17	1.4339 (4)	0.2124 (7)	0.19269 (15)	0.0722 (12)
H17A	1.5049	0.3036	0.1934	0.087*
C18	1.4555 (4)	0.0495 (8)	0.21814 (15)	0.0808 (14)
H18A	1.5412	0.0305	0.2364	0.097*
C19	1.3519 (5)	−0.0868 (7)	0.21709 (14)	0.0812 (13)
H19A	1.3671	−0.1973	0.2347	0.097*
C20	1.2259 (4)	−0.0589 (6)	0.18997 (13)	0.0645 (11)
H20A	1.1562	−0.1516	0.1889	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0681 (7)	0.0663 (7)	0.1108 (9)	−0.0126 (6)	0.0092 (6)	0.0044 (7)
S1	0.0552 (6)	0.1315 (11)	0.0477 (6)	−0.0086 (6)	0.0052 (5)	−0.0061 (6)
O1	0.0459 (15)	0.096 (2)	0.0570 (16)	−0.0027 (14)	0.0110 (12)	0.0065 (14)
N1	0.0387 (18)	0.067 (2)	0.0453 (19)	−0.0106 (16)	0.0027 (15)	−0.0040 (15)
N2	0.0409 (18)	0.071 (2)	0.0447 (19)	−0.0087 (15)	0.0037 (15)	0.0036 (17)
C1	0.050 (2)	0.072 (3)	0.048 (2)	−0.0094 (19)	0.0071 (18)	−0.002 (2)
C2	0.067 (3)	0.092 (3)	0.050 (2)	−0.010 (2)	−0.005 (2)	0.006 (2)
C3	0.052 (2)	0.071 (3)	0.069 (3)	−0.004 (2)	−0.008 (2)	0.007 (2)
C4	0.049 (2)	0.067 (3)	0.069 (3)	0.0027 (19)	0.007 (2)	0.001 (2)
C5	0.057 (2)	0.053 (2)	0.055 (2)	−0.0055 (18)	0.010 (2)	0.0032 (19)
C6	0.048 (2)	0.034 (2)	0.048 (2)	−0.0089 (16)	0.0040 (17)	0.0003 (16)
C7	0.049 (2)	0.035 (2)	0.043 (2)	−0.0113 (16)	0.0084 (17)	0.0013 (16)
C8	0.046 (2)	0.052 (2)	0.052 (2)	−0.0012 (17)	0.0104 (18)	−0.0009 (19)
C9	0.055 (2)	0.055 (2)	0.043 (2)	−0.0039 (18)	0.0033 (18)	−0.0032 (18)
C10	0.049 (2)	0.039 (2)	0.043 (2)	−0.0098 (16)	0.0041 (17)	−0.0018 (17)
C11	0.049 (2)	0.055 (2)	0.054 (2)	−0.0022 (18)	0.0115 (18)	−0.0031 (19)
C12	0.053 (2)	0.054 (2)	0.048 (2)	−0.0052 (18)	0.0076 (18)	−0.0029 (18)
C13	0.052 (2)	0.046 (2)	0.048 (2)	−0.0071 (17)	0.0042 (19)	−0.0005 (17)
C14	0.049 (2)	0.051 (2)	0.049 (2)	−0.0133 (17)	0.0039 (18)	−0.0087 (18)
C15	0.040 (2)	0.055 (3)	0.044 (2)	0.0010 (18)	0.0050 (16)	−0.0039 (19)
C16	0.050 (2)	0.056 (2)	0.049 (2)	−0.0038 (19)	0.0036 (18)	−0.0089 (19)
C17	0.048 (3)	0.106 (4)	0.063 (3)	−0.013 (2)	0.004 (2)	−0.013 (3)
C18	0.050 (3)	0.137 (5)	0.056 (3)	0.013 (3)	−0.002 (2)	0.004 (3)
C19	0.069 (3)	0.112 (4)	0.062 (3)	0.016 (3)	0.009 (2)	0.025 (3)
C20	0.063 (3)	0.071 (3)	0.060 (2)	0.001 (2)	0.009 (2)	0.011 (2)

Geometric parameters (Å, º)

Cl1—C16	1.729 (4)	C7—C8	1.388 (4)
S1—C14	1.647 (3)	C7—C12	1.393 (4)
O1—C13	1.222 (3)	C8—C9	1.375 (4)
N1—C13	1.365 (4)	C8—H8A	0.9300
N1—C14	1.393 (4)	C9—C10	1.390 (4)
N1—H1A	0.855 (10)	C9—H9A	0.9300
N2—C14	1.332 (4)	C10—C11	1.387 (4)
N2—C15	1.413 (4)	C10—C13	1.475 (4)
N2—H2A	0.865 (10)	C11—C12	1.381 (4)
C1—C2	1.373 (5)	C11—H11A	0.9300
C1—C6	1.380 (4)	C12—H12A	0.9300
C1—H1B	0.9300	C15—C20	1.378 (5)
C2—C3	1.360 (5)	C15—C16	1.383 (4)
C2—H2B	0.9300	C16—C17	1.382 (5)
C3—C4	1.361 (5)	C17—C18	1.364 (5)
C3—H3A	0.9300	C17—H17A	0.9300
C4—C5	1.379 (4)	C18—C19	1.374 (6)
C4—H4A	0.9300	C18—H18A	0.9300
C5—C6	1.386 (4)	C19—C20	1.373 (5)
C5—H5A	0.9300	C19—H19A	0.9300
C6—C7	1.486 (4)	C20—H20A	0.9300
C13—N1—C14	129.6 (3)	C11—C10—C9	117.9 (3)
C13—N1—H1A	115 (2)	C11—C10—C13	118.5 (3)
C14—N1—H1A	116 (2)	C9—C10—C13	123.5 (3)
C14—N2—C15	126.4 (3)	C12—C11—C10	121.3 (3)
C14—N2—H2A	114 (2)	C12—C11—H11A	119.4
C15—N2—H2A	119 (2)	C10—C11—H11A	119.4
C2—C1—C6	121.4 (3)	C11—C12—C7	121.4 (3)
C2—C1—H1B	119.3	C11—C12—H12A	119.3
C6—C1—H1B	119.3	C7—C12—H12A	119.3
C3—C2—C1	120.8 (4)	O1—C13—N1	121.9 (3)
C3—C2—H2B	119.6	O1—C13—C10	121.6 (3)
C1—C2—H2B	119.6	N1—C13—C10	116.4 (3)
C2—C3—C4	119.0 (3)	N2—C14—N1	114.2 (3)
C2—C3—H3A	120.5	N2—C14—S1	126.5 (3)
C4—C3—H3A	120.5	N1—C14—S1	119.3 (2)
C3—C4—C5	120.5 (3)	C20—C15—C16	119.4 (3)
C3—C4—H4A	119.7	C20—C15—N2	120.8 (3)
C5—C4—H4A	119.7	C16—C15—N2	119.7 (3)
C4—C5—C6	121.3 (3)	C17—C16—C15	119.9 (4)
C4—C5—H5A	119.4	C17—C16—Cl1	120.4 (3)
C6—C5—H5A	119.4	C15—C16—Cl1	119.7 (3)
C1—C6—C5	116.8 (3)	C18—C17—C16	119.9 (4)
C1—C6—C7	122.0 (3)	C18—C17—H17A	120.0
C5—C6—C7	121.1 (3)	C16—C17—H17A	120.0
C8—C7—C12	116.5 (3)	C17—C18—C19	120.6 (4)
C8—C7—C6	121.5 (3)	C17—C18—H18A	119.7
C12—C7—C6	121.9 (3)	C19—C18—H18A	119.7
C9—C8—C7	122.7 (3)	C20—C19—C18	119.7 (4)
C9—C8—H8A	118.6	C20—C19—H19A	120.2
C7—C8—H8A	118.6	C18—C19—H19A	120.2
C8—C9—C10	120.2 (3)	C19—C20—C15	120.5 (4)
C8—C9—H9A	119.9	C19—C20—H20A	119.7
C10—C9—H9A	119.9	C15—C20—H20A	119.7
C6—C1—C2—C3	−1.4 (6)	C14—N1—C13—C10	−178.2 (3)
C1—C2—C3—C4	0.4 (6)	C11—C10—C13—O1	24.0 (5)
C2—C3—C4—C5	−0.5 (6)	C9—C10—C13—O1	−153.1 (3)
C3—C4—C5—C6	1.6 (5)	C11—C10—C13—N1	−156.7 (3)
C2—C1—C6—C5	2.4 (5)	C9—C10—C13—N1	26.2 (5)
C2—C1—C6—C7	−175.8 (3)	C15—N2—C14—N1	−176.2 (3)
C4—C5—C6—C1	−2.5 (5)	C15—N2—C14—S1	5.1 (5)
C4—C5—C6—C7	175.7 (3)	C13—N1—C14—N2	−0.9 (5)
C1—C6—C7—C8	156.9 (3)	C13—N1—C14—S1	177.9 (3)
C5—C6—C7—C8	−21.2 (5)	C14—N2—C15—C20	60.3 (5)
C1—C6—C7—C12	−18.9 (5)	C14—N2—C15—C16	−123.6 (4)
C5—C6—C7—C12	163.0 (3)	C20—C15—C16—C17	0.3 (5)
C12—C7—C8—C9	−0.8 (5)	N2—C15—C16—C17	−175.8 (3)
C6—C7—C8—C9	−176.8 (3)	C20—C15—C16—Cl1	179.8 (2)
C7—C8—C9—C10	1.7 (5)	N2—C15—C16—Cl1	3.7 (4)
C8—C9—C10—C11	−1.0 (5)	C15—C16—C17—C18	−0.7 (5)
C8—C9—C10—C13	176.1 (3)	Cl1—C16—C17—C18	179.8 (3)
C9—C10—C11—C12	−0.5 (5)	C16—C17—C18—C19	0.4 (6)
C13—C10—C11—C12	−177.8 (3)	C17—C18—C19—C20	0.3 (6)
C10—C11—C12—C7	1.4 (5)	C18—C19—C20—C15	−0.8 (6)
C8—C7—C12—C11	−0.7 (5)	C16—C15—C20—C19	0.5 (5)
C6—C7—C12—C11	175.3 (3)	N2—C15—C20—C19	176.5 (3)
C14—N1—C13—O1	1.1 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86 (1)	1.88 (2)	2.619 (4)	142 (3)