N-(4-Methoxy­benzo­yl)-N′-(4-methyl­phen­yl)thio­urea

The mol­ecular structure of the title compound, C₁₆H₁₆N₂O₂S, adopts a trans–cis configuration with respect to the position of the 4-methoxy­benzoyl and 4-methyl­phenyl groups relative to the S atom across the thio­urea C—N bonds. The 4-methyl­phenyl fragment is inclined to the 4-methoxy­benzoyl group by 70.62 (9)°. The mol­ecule is stabilized by inter­molecular N—H...S inter­actions, forming a dimer.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.040
• wR factor = 0.114
• Data-to-parameter ratio = 14.7

checkCIF/PLATON results

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Alert level C
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 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

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S1. Comment

The title compound, (I), is isomeric and isostructural with N-(4-methoxybenzoyl)-N'-o-tolylthiourea (Yusof & Yamin, 2004). The trans–cis configuration with respect to the position of the 4-methoxybenzoyl and 4-methylphenyl groups relative to the S atom across the thiourea C8—N1 and C8—N2 bonds, respectively, is maintained.

The carbonylthiourea (S1/N1/N2/C7/O1/C8), 4-methoxybenzoyl (C1–C6/O2/C15) and 4-methylphenyl (C9–C14/C16) groups are each planar. The maximum deviation is 0.035 (1) Å for atom N1 from the mean plane in the carbonylthiourea group. The dihedral angles between the carbonylthiourea moiety and the 4-methoxyphenyl and 4-methylphenyl fragments of 27.33 (7) and 43.37 (8)°, respectively, are larger compared to those in the N-(4-methoxybenzoyl)-N'-o-tolylthiourea [15.58 (7) and 22.76 (8)°, respectively]. The inclination between the aryl fragments of 70.62 (9)° is larger than that of 7.58 (9)° in N-(4-methoxybenzoyl)-N'-o-tolylthiourea.

There are two intramolecular hydrogen bonds, viz. N2—H2A···O1 and C14—H14···S1 (Table 2), and as a result, two pseudo-six-membered rings (C8—N2—C9—C14—H14···S1 and C7—N1—C8—N2—H2A···O1) are formed. In the crystal structure, molecules are linked by intermolecular interactions, N1–H1A···S1ⁱ [symmetry code: (i) 1 − x, 1 − y, 2 − z], forming a dimer along the bc face.

S2. Experimental

To a stirred acetone solution (75 ml) of anisoyl chloride (2.5 g, 20 mmol) and ammonium thiocyanate (2.1 ml, 20 mmol), p-toulidine (2.8 ml, 20 mmol) was added dropwise. The solution mixture was refluxed for 3 h. The resulting solution was poured into a beaker containing ice cubes. The white precipitate was filtered off and washed with distilled water and cold ethanol, and then dried in a vacuum. Good quality single crystals were obtained by recrystallization from dimethyl sulfoxide.

S3. Refinement

After their location in a difference map, all H atoms were fixed geometrically at ideal positions and allowed to ride on their parent C or N atoms, with C—H = 0.93–0.96 Å and N—H = 0.86 Å, and U_iso(H) = 1.2U_eq(C,N) for CH₂ and NH, and 1.5U_eq(C) for CH₃.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of (I), with the 50% probability displacement ellipsoids. The dashed lines indicate the intramolecular hydrogen-bond contacts.
	Fig. 2. Packing diagram of compound (I), viewed down the a axis. The dashed lines denote N—H···S hydrogen bonds, which form a dimer.

N-(4-Methoxybenzoyl)-N'-(4-methylphenyl)thiourea

Crystal data

C16H16N2O2S	Z = 2
Mr = 300.37	F(000) = 316
Triclinic, P1	Dx = 1.306 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.3676 (9) Å	Cell parameters from 951 reflections
b = 11.4763 (19) Å	θ = 1.6–25.5°
c = 12.447 (2) Å	µ = 0.22 mm^−1
α = 92.505 (3)°	T = 293 K
β = 91.692 (3)°	Block, colourless
γ = 94.138 (3)°	0.45 × 0.39 × 0.30 mm
V = 763.6 (2) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2827 independent reflections
Radiation source: fine-focus sealed tube	2492 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
Detector resolution: 83.66 pixels mm^-1	θmax = 25.5°, θmin = 1.6°
ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −13→13
Tmin = 0.90, Tmax = 0.93	l = −15→15
7554 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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0606P)^2 + 0.149P] where P = (Fo^2 + 2Fc^2)/3
2827 reflections	(Δ/σ)max < 0.001
192 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.16 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.34628 (10)	0.62356 (4)	0.90403 (4)	0.05940 (19)
O1	0.4928 (3)	0.33017 (13)	0.66361 (10)	0.0736 (4)
O2	1.2697 (3)	0.04294 (12)	0.91575 (13)	0.0755 (4)
N1	0.5264 (3)	0.43374 (11)	0.82421 (11)	0.0459 (3)
H1A	0.5934	0.4343	0.8879	0.055*
N2	0.2645 (3)	0.52187 (12)	0.70791 (11)	0.0501 (4)
H2A	0.2857	0.4620	0.6661	0.060*
C1	0.9490 (3)	0.30152 (14)	0.87591 (14)	0.0489 (4)
H1	0.9594	0.3783	0.9037	0.059*
C2	1.1138 (3)	0.22543 (16)	0.91261 (15)	0.0547 (4)
H2	1.2353	0.2509	0.9649	0.066*
C3	1.1004 (3)	0.11053 (15)	0.87219 (15)	0.0540 (4)
C4	0.9219 (4)	0.07293 (16)	0.79354 (16)	0.0605 (5)
H4	0.9125	−0.0038	0.7656	0.073*
C5	0.7577 (4)	0.15083 (16)	0.75692 (15)	0.0591 (5)
H5	0.6382	0.1258	0.7036	0.071*
C6	0.7668 (3)	0.26522 (14)	0.79771 (13)	0.0470 (4)
C7	0.5852 (3)	0.34387 (15)	0.75490 (13)	0.0503 (4)
C8	0.3738 (3)	0.52345 (13)	0.80512 (13)	0.0436 (4)
C9	0.1161 (3)	0.60806 (14)	0.66474 (13)	0.0479 (4)
C10	0.1614 (4)	0.64105 (18)	0.56187 (15)	0.0633 (5)
H10	0.2845	0.6072	0.5227	0.076*
C11	0.0228 (4)	0.72492 (19)	0.51686 (16)	0.0683 (5)
H11	0.0535	0.7462	0.4470	0.082*
C12	−0.1587 (4)	0.77740 (16)	0.57293 (17)	0.0607 (5)
C13	−0.2064 (4)	0.74001 (17)	0.67491 (17)	0.0615 (5)
H13	−0.3326	0.7722	0.7134	0.074*
C14	−0.0711 (3)	0.65599 (16)	0.72124 (15)	0.0555 (4)
H14	−0.1064	0.6321	0.7899	0.067*
C15	1.2704 (5)	−0.07619 (18)	0.8778 (2)	0.0857 (7)
H15A	1.1107	−0.1161	0.8894	0.129*
H15B	1.3984	−0.1133	0.9161	0.129*
H15C	1.3025	−0.0793	0.8023	0.129*
C16	−0.3010 (5)	0.87282 (19)	0.5254 (2)	0.0845 (7)
H16A	−0.2312	0.9477	0.5537	0.127*
H16B	−0.4734	0.8625	0.5437	0.127*
H16C	−0.2887	0.8689	0.4485	0.127*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0841 (4)	0.0489 (3)	0.0469 (3)	0.0265 (2)	−0.0092 (2)	−0.00611 (19)
O1	0.1062 (11)	0.0697 (9)	0.0476 (8)	0.0417 (8)	−0.0169 (7)	−0.0130 (6)
O2	0.0776 (9)	0.0534 (8)	0.0967 (11)	0.0236 (7)	−0.0202 (8)	0.0024 (7)
N1	0.0588 (8)	0.0419 (7)	0.0381 (7)	0.0144 (6)	−0.0033 (6)	0.0004 (5)
N2	0.0624 (9)	0.0470 (8)	0.0421 (7)	0.0160 (7)	−0.0043 (6)	−0.0006 (6)
C1	0.0533 (10)	0.0389 (8)	0.0545 (10)	0.0047 (7)	0.0050 (8)	−0.0015 (7)
C2	0.0508 (10)	0.0508 (10)	0.0621 (11)	0.0058 (8)	−0.0047 (8)	−0.0007 (8)
C3	0.0563 (10)	0.0466 (9)	0.0606 (11)	0.0123 (8)	0.0010 (8)	0.0069 (8)
C4	0.0770 (13)	0.0406 (9)	0.0643 (12)	0.0146 (9)	−0.0062 (10)	−0.0051 (8)
C5	0.0731 (12)	0.0497 (10)	0.0544 (10)	0.0160 (9)	−0.0122 (9)	−0.0077 (8)
C6	0.0566 (10)	0.0435 (9)	0.0418 (8)	0.0108 (7)	0.0033 (7)	0.0005 (7)
C7	0.0636 (10)	0.0458 (9)	0.0424 (9)	0.0131 (8)	−0.0002 (8)	−0.0007 (7)
C8	0.0499 (9)	0.0390 (8)	0.0428 (8)	0.0068 (7)	0.0027 (7)	0.0040 (6)
C9	0.0516 (9)	0.0453 (9)	0.0468 (9)	0.0079 (7)	−0.0070 (7)	0.0027 (7)
C10	0.0678 (12)	0.0759 (13)	0.0487 (10)	0.0221 (10)	−0.0011 (9)	0.0062 (9)
C11	0.0774 (13)	0.0765 (13)	0.0528 (11)	0.0132 (11)	−0.0088 (10)	0.0175 (10)
C12	0.0615 (11)	0.0501 (10)	0.0694 (12)	0.0063 (9)	−0.0235 (9)	0.0040 (9)
C13	0.0540 (10)	0.0615 (11)	0.0697 (12)	0.0157 (9)	−0.0064 (9)	−0.0018 (9)
C14	0.0524 (10)	0.0608 (11)	0.0544 (10)	0.0099 (8)	0.0013 (8)	0.0070 (8)
C15	0.0955 (17)	0.0514 (12)	0.113 (2)	0.0311 (12)	−0.0112 (14)	0.0041 (12)
C16	0.0956 (17)	0.0599 (12)	0.0977 (17)	0.0193 (12)	−0.0393 (14)	0.0069 (11)

Geometric parameters (Å, º)

S1—C8	1.6640 (16)	C5—H5	0.9300
O1—C7	1.225 (2)	C6—C7	1.479 (2)
O2—C3	1.353 (2)	C9—C10	1.375 (3)
O2—C15	1.427 (2)	C9—C14	1.376 (2)
N1—C7	1.376 (2)	C10—C11	1.385 (3)
N1—C8	1.385 (2)	C10—H10	0.9300
N1—H1A	0.8600	C11—C12	1.374 (3)
N2—C8	1.328 (2)	C11—H11	0.9300
N2—C9	1.427 (2)	C12—C13	1.383 (3)
N2—H2A	0.8600	C12—C16	1.511 (3)
C1—C2	1.370 (2)	C13—C14	1.383 (2)
C1—C6	1.388 (2)	C13—H13	0.9300
C1—H1	0.9300	C14—H14	0.9300
C2—C3	1.387 (3)	C15—H15A	0.9600
C2—H2	0.9300	C15—H15B	0.9600
C3—C4	1.382 (3)	C15—H15C	0.9600
C4—C5	1.382 (2)	C16—H16A	0.9600
C4—H4	0.9300	C16—H16B	0.9600
C5—C6	1.384 (2)	C16—H16C	0.9600
N2—C8—N1	116.22 (14)	C10—C9—C14	119.88 (16)
N2—C8—S1	125.97 (12)	C10—C9—N2	117.67 (15)
N1—C8—S1	117.81 (12)	C14—C9—N2	122.44 (15)
C3—O2—C15	118.65 (16)	C9—C10—C11	119.70 (18)
C7—N1—C8	128.64 (14)	C9—C10—H10	120.1
C7—N1—H1A	115.7	C11—C10—H10	120.1
C8—N1—H1A	115.7	C12—C11—C10	121.62 (18)
C8—N2—C9	127.53 (14)	C12—C11—H11	119.2
C8—N2—H2A	116.2	C10—C11—H11	119.2
C9—N2—H2A	116.2	C11—C12—C13	117.56 (17)
C2—C1—C6	120.72 (16)	C11—C12—C16	121.4 (2)
C2—C1—H1	119.6	C13—C12—C16	121.0 (2)
C6—C1—H1	119.6	C12—C13—C14	121.74 (18)
C1—C2—C3	120.32 (17)	C12—C13—H13	119.1
C1—C2—H2	119.8	C14—C13—H13	119.1
C3—C2—H2	119.8	C9—C14—C13	119.41 (17)
O2—C3—C4	125.03 (17)	C9—C14—H14	120.3
O2—C3—C2	115.10 (17)	C13—C14—H14	120.3
C4—C3—C2	119.88 (16)	O2—C15—H15A	109.5
C5—C4—C3	119.16 (17)	O2—C15—H15B	109.5
C5—C4—H4	120.4	H15A—C15—H15B	109.5
C3—C4—H4	120.4	O2—C15—H15C	109.5
C4—C5—C6	121.51 (17)	H15A—C15—H15C	109.5
C4—C5—H5	119.2	H15B—C15—H15C	109.5
C6—C5—H5	119.2	C12—C16—H16A	109.5
C5—C6—C1	118.40 (16)	C12—C16—H16B	109.5
C5—C6—C7	118.67 (16)	H16A—C16—H16B	109.5
C1—C6—C7	122.93 (15)	C12—C16—H16C	109.5
O1—C7—N1	122.01 (15)	H16A—C16—H16C	109.5
O1—C7—C6	122.32 (15)	H16B—C16—H16C	109.5
N1—C7—C6	115.68 (14)
C6—C1—C2—C3	−0.2 (3)	C1—C6—C7—N1	−28.3 (2)
C15—O2—C3—C4	1.0 (3)	C9—N2—C8—N1	−174.53 (15)
C15—O2—C3—C2	−179.32 (19)	C9—N2—C8—S1	4.6 (3)
C1—C2—C3—O2	−178.90 (17)	C7—N1—C8—N2	1.6 (3)
C1—C2—C3—C4	0.8 (3)	C7—N1—C8—S1	−177.65 (14)
O2—C3—C4—C5	179.17 (18)	C8—N2—C9—C10	134.9 (2)
C2—C3—C4—C5	−0.5 (3)	C8—N2—C9—C14	−46.6 (3)
C3—C4—C5—C6	−0.4 (3)	C14—C9—C10—C11	1.8 (3)
C4—C5—C6—C1	1.1 (3)	N2—C9—C10—C11	−179.63 (18)
C4—C5—C6—C7	−179.95 (17)	C9—C10—C11—C12	0.6 (3)
C2—C1—C6—C5	−0.8 (3)	C10—C11—C12—C13	−2.7 (3)
C2—C1—C6—C7	−179.69 (16)	C10—C11—C12—C16	177.1 (2)
C8—N1—C7—O1	−3.4 (3)	C11—C12—C13—C14	2.3 (3)
C8—N1—C7—C6	176.49 (15)	C16—C12—C13—C14	−177.45 (18)
C5—C6—C7—O1	−27.3 (3)	C10—C9—C14—C13	−2.2 (3)
C1—C6—C7—O1	151.62 (19)	N2—C9—C14—C13	179.39 (17)
C5—C6—C7—N1	152.74 (17)	C12—C13—C14—C9	0.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	1.94	2.640 (2)	138
C14—H14···S1	0.93	2.79	3.1980 (19)	108
N1—H1A···S1^i	0.86	2.72	3.5305 (16)	158

Symmetry code: (i) −x+1, −y+1, −z+2.