1-(3-Methoxy­benzoyl)-3,3-diethyl­thiourea

The title compound, C₁₃H₁₈N₂O₂S, crystallizes in the thio­amidic form. The mol­ecules are connected by N—H...S interactions forming dimers with N...S and H...S distances of 3.487 (4) and 2.76 Å, respectively.

S1. Comment

Among organic sulfur compounds, thioureas and its derivatives are of relevant importance. These compounds have been introduced almost in every branch of chemistry and are commercialized as dyes, photographic films, elastomery plastics and textiles (Chynowet, 1955). In chemical research works they have been thoroughly used as intermediates in the synthesis and characterization of organic compounds and in the separation of branched hydrocarbons in organic mixtures (Gabriele, 1995; Rodriguez et al., 1995). In order to continue these studies we have prepared derivatives of acylthioureas (Rodriguez et al., 1995). The crystal structure of 1-(3-methoxybenzoyl)-3,3-diethylthiourea, (I), has been determined to understand better the role of the anions geometry in the reactivity of alkylation reactions with respect to the substitutes present in nitrogen positions 1 and 3. \sch

The title compound crystallizes in the thioamidic form. The S, C2, N1, C1, O1 moiety deviates extensively from planarity. The torsion angles O1—C1—N1—C2 and C1—N1—C2—S are 0.8 (6) and -123.6 (3)°, respectively. The molecule is stabilized in the s-cisoid, s-transoid conformation with respect to the imino C1—N1—C2. The bond distance C2—N2 has a double-bond character but the bonds distances C2—N1 and C1—N1 correspond to a single bond C_sp2—N_sp2. This fact indicates that there is π conjugation only along S—C2—N2 system, but not along O1—C1—N1 and C1—N1—C2 as found in 1-benzoyl-3-n-propylthiourea (Dago et al., 1989) and 1-(4-methoxybenzoyl-3-phenylthiourea (Fajardo et al., 1990). The p atomic orbital of the O2 atom in the methoxy group overlaps with the π system of the phenyl ring, as evidenced by the shortening of the O2—C9 bond distance [1.368 (4) Å]. This also results in the coplanarity of the methoxy group with the phenyl ring C8—C9—O2—C13 = 6.4 (5)°. The diferences in the values of the C10—C9—O2 = 115.5 (3) and C8—C9—O2 = 124.1 (3)° is in agreement with the distortion already observed in anysoles as shown by Domiano et al. (1979). The molecules are held together by N—H···S interactions forming dimers with N1···S and H1···S distances of 3.487 (4) and 2.77 Å, respectively.

S2. Experimental

The compound was prepared by the reaction of diethylamine with 3-methoxybenzoyl isothiocyanate obtained in situ by a method already published (Rodríguez et al., 1995). Recrystallization from ethanol gave suitable crystals for X-ray analysis.

S3. Refinement

H atoms were calculated geometrically and included in the refinement, but were restrained to ride on their parent atoms. The isotropic displacement parameters of the H atoms were fixed to 1.3 times U_eq of their parent atoms. The C6 atom of the terminal methyl group was located from the ΔF map and found to be disordered; it was placed in two positions (C6A and C6B), with 60% and 40% occupancy, respectively. The H atoms of the disordered C6 atom were not located.

Computing details

Data collection: DIF4 (Stoe, 1992a); cell refinement: DIF4; data reduction: REDU4 (Stoe, 1992b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: PLATON (Spek, 1990), PARST (Nardelli, 1983, 1995) and PARSTCIF (Nardelli, 1991).

Figures

Fig. 1. Plot showing the atomic numbering scheme. Displacement ellipsoids are drawn at 50% probability level for non-H atoms.

1-(3-methoxybenzoyl)-3,3-diethylthiourea

Crystal data

C13H18N2O2S	Z = 2
Mr = 266.36	F(000) = 284
Triclinic, P1	Dx = 1.286 Mg m^−3
a = 7.754 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.949 (8) Å	Cell parameters from 25 reflections
c = 11.251 (7) Å	θ = 2–50°
α = 78.48 (6)°	µ = 0.23 mm^−1
β = 70.26 (4)°	T = 293 K
γ = 70.06 (6)°	Prism, colourless
V = 687.6 (8) Å^3	0.61 × 0.57 × 0.34 mm

Data collection

Stoe STADI4 four-circle difractometer diffractometer	1803 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.016
Graphite monochromator	θmax = 25.0°, θmin = 1.9°
w scans	h = −9→1
Absorption correction: ψ scan Empirical absorption correction with EMPIR (Stoe, 1992c). Number of ψ scans used = 12	k = −10→10
Tmin = 0.833, Tmax = 0.924	l = −13→13
3005 measured reflections	2 standard reflections every 60 min
2423 independent reflections	intensity decay: <2.0%

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.184	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.1092P)^2 + 0.4967P] where P = (Fo^2 + 2Fc^2)/3
2423 reflections	(Δ/σ)max < 0.001
163 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.43 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	Occ. (<1)
S	0.74460 (13)	0.16037 (12)	0.60379 (8)	0.0603 (3)
O1	0.8092 (5)	0.3950 (3)	0.2472 (3)	0.0882 (10)
O2	1.3155 (3)	−0.1785 (3)	−0.0247 (2)	0.0604 (8)
N1	0.8533 (4)	0.1483 (3)	0.3549 (2)	0.0443 (8)
N2	0.5269 (4)	0.2641 (3)	0.4479 (2)	0.0505 (9)
C1	0.8991 (5)	0.2545 (4)	0.2497 (3)	0.0503 (10)
C2	0.7000 (4)	0.1961 (3)	0.4634 (3)	0.0410 (9)
C3	0.3654 (5)	0.3419 (5)	0.5520 (3)	0.0582 (11)
C4	0.2317 (7)	0.2453 (7)	0.6192 (4)	0.0861 (18)
C5	0.4813 (7)	0.2587 (9)	0.3325 (5)	0.125 (3)
C6A	0.3688 (12)	0.3895 (11)	0.2816 (8)	0.078 (3)*	0.605 (17)
C7	1.0599 (4)	0.1869 (4)	0.1389 (3)	0.0432 (10)
C8	1.1128 (4)	0.0270 (4)	0.1178 (3)	0.0414 (9)
C9	1.2539 (4)	−0.0253 (4)	0.0073 (3)	0.0470 (10)
C10	1.3400 (5)	0.0800 (5)	−0.0803 (3)	0.0558 (13)
C11	1.2861 (5)	0.2379 (5)	−0.0586 (3)	0.0587 (13)
C12	1.1457 (5)	0.2922 (4)	0.0504 (3)	0.0527 (11)
C13	1.2443 (6)	−0.2940 (5)	0.0660 (4)	0.0667 (14)
C6B	0.3086 (19)	0.3050 (16)	0.3134 (12)	0.080 (5)*	0.395 (17)
H3A	0.29413	0.44363	0.51793	0.0696*
H3B	0.41583	0.36343	0.61267	0.0696*
H4A	0.13007	0.30246	0.68567	0.1297*
H4B	0.30029	0.14536	0.65511	0.1297*
H4C	0.17853	0.22559	0.56028	0.1297*
H5A	0.60230	0.22528	0.26711	0.1501*
H5B	0.42138	0.17446	0.34986	0.1501*
H8	1.05467	−0.04345	0.17676	0.0497*
H10	1.43456	0.04394	−0.15406	0.0667*
H11	1.34455	0.30803	−0.11758	0.0704*
H12	1.10856	0.39908	0.06461	0.0632*
H13A	1.29808	−0.39571	0.03188	0.1008*
H13B	1.10707	−0.26277	0.08597	0.1008*
H13C	1.27942	−0.30194	0.14156	0.1008*
H1	0.92136	0.04965	0.35347	0.0531*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0567 (6)	0.0754 (7)	0.0347 (5)	0.0028 (4)	−0.0141 (4)	−0.0129 (4)
O1	0.106 (2)	0.0427 (15)	0.0649 (17)	0.0050 (15)	0.0091 (16)	−0.0017 (12)
O2	0.0553 (14)	0.0696 (16)	0.0484 (14)	−0.0125 (12)	−0.0008 (11)	−0.0246 (12)
N1	0.0505 (15)	0.0398 (13)	0.0321 (12)	−0.0034 (11)	−0.0062 (11)	−0.0084 (10)
N2	0.0464 (16)	0.0621 (17)	0.0401 (14)	−0.0045 (13)	−0.0122 (12)	−0.0201 (12)
C1	0.058 (2)	0.0440 (18)	0.0396 (16)	−0.0069 (15)	−0.0096 (15)	−0.0066 (13)
C2	0.0472 (17)	0.0370 (15)	0.0351 (15)	−0.0092 (13)	−0.0080 (13)	−0.0082 (12)
C3	0.0452 (18)	0.074 (2)	0.0486 (19)	−0.0014 (16)	−0.0119 (15)	−0.0231 (17)
C4	0.071 (3)	0.118 (4)	0.059 (2)	−0.029 (3)	−0.007 (2)	−0.005 (2)
C5	0.062 (3)	0.223 (7)	0.078 (3)	0.030 (4)	−0.039 (2)	−0.086 (4)
C7	0.0444 (17)	0.0498 (18)	0.0333 (15)	−0.0117 (14)	−0.0124 (13)	−0.0018 (13)
C8	0.0385 (16)	0.0518 (18)	0.0308 (14)	−0.0117 (13)	−0.0086 (12)	−0.0028 (12)
C9	0.0387 (16)	0.065 (2)	0.0360 (15)	−0.0100 (15)	−0.0106 (13)	−0.0119 (14)
C10	0.0409 (17)	0.086 (3)	0.0341 (16)	−0.0186 (17)	−0.0036 (14)	−0.0053 (16)
C11	0.052 (2)	0.080 (3)	0.0445 (18)	−0.0305 (19)	−0.0133 (16)	0.0112 (17)
C12	0.059 (2)	0.057 (2)	0.0450 (18)	−0.0219 (16)	−0.0191 (16)	0.0039 (15)
C13	0.072 (3)	0.060 (2)	0.065 (2)	−0.0117 (19)	−0.015 (2)	−0.0223 (19)

Geometric parameters (Å, º)

S—C2	1.676 (4)	C10—C11	1.377 (6)
O1—C1	1.212 (4)	C11—C12	1.379 (5)
O2—C9	1.368 (4)	C6B—H5B	1.2852
O2—C13	1.415 (5)	C3—H3B	0.9696
N1—C1	1.388 (4)	C3—H3A	0.9704
N1—C2	1.403 (4)	C4—H4A	0.9601
N2—C2	1.327 (5)	C4—H4B	0.9604
N2—C3	1.471 (5)	C4—H4C	0.9599
N2—C5	1.470 (6)	C5—H5A	0.9702
N1—H1	0.8604	C5—H5B	0.9701
C1—C7	1.487 (5)	C8—H8	0.9303
C6B—C5	1.338 (17)	C10—H10	0.9300
C3—C4	1.488 (7)	C11—H11	0.9296
C5—C6A	1.354 (12)	C12—H12	0.9303
C7—C12	1.388 (5)	C13—H13B	0.9600
C7—C8	1.393 (5)	C13—H13C	0.9597
C8—C9	1.388 (5)	C13—H13A	0.9603
C9—C10	1.385 (5)
S···N1^i	3.487 (4)	C7···H13B^iv	3.0765
S···C8^i	3.581 (5)	C8···H13C	2.7804
S···H3B	2.5596	C8···H13B	2.7046
S···H1^i	2.7627	C8···H1	2.5741
S···H8^i	3.1728	C10···H4B^viii	3.0166
O1···N2	2.935 (5)	C11···H13B^iv	3.0956
O1···C5	2.979 (8)	C12···H13B^iv	2.9681
O1···C6A	3.321 (12)	C13···H8	2.5243
O1···C3^ii	3.219 (6)	H1···H8	2.0979
O2···C11^iii	3.368 (6)	H1···C8	2.5741
O2···C5^iv	3.395 (7)	H1···S^i	2.7627
O1···H12	2.5331	H3A···C6A	2.6312
O1···H5A	2.4928	H3A···C6B	2.7781
O1···H11^v	2.8419	H3B···O1^ii	2.6709
O1···H3B^ii	2.6709	H3B···S	2.5596
O2···H5A^iv	2.6683	H4B···C10^ix	3.0166
N1···S^i	3.487 (4)	H4B···H10^ix	2.5699
N2···O1	2.935 (5)	H4C···H5B	2.4887
N1···H8	2.6138	H4C···C5	2.8765
N1···H5A	2.3131	H4C···C6B	2.6544
C1···C5	3.042 (8)	H5A···O1	2.4928
C6B···C4	3.252 (14)	H5A···N1	2.3131
C3···O1^ii	3.219 (6)	H5A···C1	2.3428
C4···C6B	3.252 (14)	H5A···O2^iv	2.6683
C5···O2^iv	3.395 (7)	H5B···H4C	2.4887
C5···O1	2.979 (8)	H5B···C4	2.9780
C5···C1	3.042 (8)	H8···N1	2.6138
C6A···C13^vi	3.437 (10)	H8···C13	2.5243
C6A···O1	3.321 (12)	H8···H1	2.0979
C8···C9^iv	3.579 (6)	H8···S^i	3.1728
C8···S^i	3.581 (5)	H8···H13B	2.2444
C9···C10^iii	3.371 (6)	H8···H13C	2.3864
C9···C8^iv	3.579 (6)	H10···H4B^viii	2.5699
C10···C9^iii	3.371 (6)	H11···O1^v	2.8419
C10···C10^iii	3.323 (6)	H12···O1	2.5331
C11···O2^iii	3.368 (6)	H12···H12^v	2.5963
C13···C6A^vii	3.437 (10)	H13B···C8	2.7046
C1···H5A	2.3428	H13B···C12^iv	2.9681
C6B···H4C	2.6544	H13B···H8	2.2444
C6B···H3A	2.7781	H13B···C7^iv	3.0765
C4···H5B	2.9780	H13B···C11^iv	3.0956
C5···H4C	2.8765	H13C···C6A^vii	2.8779
C6A···H3A	2.6312	H13C···C8	2.7804
C6A···H13C^vi	2.8779	H13C···H8	2.3864
C9—O2—C13	117.8 (3)	H3A—C3—H3B	107.69
C1—N1—C2	122.3 (3)	N2—C3—H3B	108.83
C2—N2—C3	120.2 (3)	C3—C4—H4A	109.49
C2—N2—C5	123.4 (3)	C3—C4—H4B	109.46
C3—N2—C5	116.3 (4)	H4A—C4—H4B	109.44
C1—N1—H1	118.81	H4A—C4—H4C	109.48
C2—N1—H1	118.84	C3—C4—H4C	109.52
O1—C1—N1	121.5 (3)	H4B—C4—H4C	109.44
O1—C1—C7	121.6 (3)	N2—C5—H5B	107.12
N1—C1—C7	116.9 (3)	C6A—C5—H5A	107.10
S—C2—N1	118.6 (3)	N2—C5—H5A	107.11
N1—C2—N2	117.2 (3)	H5A—C5—H5B	106.77
S—C2—N2	124.2 (2)	C6B—C5—H5A	124.55
N2—C3—C4	113.6 (4)	C6A—C5—H5B	107.09
N2—C5—C6B	128.0 (7)	C6B—C5—H5B	65.41
N2—C5—C6A	120.9 (6)	C9—C8—H8	120.60
C8—C7—C12	120.6 (3)	C7—C8—H8	120.60
C1—C7—C8	121.8 (3)	C9—C10—H10	119.87
C1—C7—C12	117.4 (3)	C11—C10—H10	119.87
C7—C8—C9	118.8 (3)	C12—C11—H11	119.91
O2—C9—C10	115.5 (3)	C10—C11—H11	119.93
C8—C9—C10	120.4 (3)	C7—C12—H12	120.10
O2—C9—C8	124.1 (3)	C11—C12—H12	120.10
C9—C10—C11	120.3 (3)	O2—C13—H13B	109.45
C10—C11—C12	120.2 (3)	O2—C13—H13C	109.51
C7—C12—C11	119.8 (3)	O2—C13—H13A	109.44
C5—C6B—H5B	43.34	H13A—C13—H13C	109.48
N2—C3—H3A	108.80	H13B—C13—H13C	109.50
C4—C3—H3A	108.83	H13A—C13—H13B	109.45
C4—C3—H3B	108.89
C13—O2—C9—C8	−6.4 (5)	N1—C1—C7—C8	24.6 (5)
C13—O2—C9—C10	174.8 (4)	O1—C1—C7—C12	20.9 (6)
C2—N1—C1—C7	−177.5 (3)	O1—C1—C7—C8	−153.7 (4)
C1—N1—C2—S	−123.6 (3)	N1—C1—C7—C12	−160.9 (4)
C2—N1—C1—O1	0.8 (6)	C1—C7—C8—C9	174.9 (3)
C1—N1—C2—N2	57.9 (4)	C1—C7—C12—C11	−175.4 (4)
C2—N2—C3—C4	−103.2 (4)	C8—C7—C12—C11	−0.8 (6)
C5—N2—C2—N1	14.4 (5)	C12—C7—C8—C9	0.6 (5)
C2—N2—C5—C6A	−138.2 (6)	C7—C8—C9—C10	−0.1 (5)
C5—N2—C2—S	−164.1 (4)	C7—C8—C9—O2	−178.9 (3)
C5—N2—C3—C4	73.3 (5)	O2—C9—C10—C11	178.8 (4)
C3—N2—C2—N1	−169.5 (3)	C8—C9—C10—C11	−0.1 (6)
C3—N2—C2—S	12.1 (4)	C9—C10—C11—C12	−0.1 (6)
C3—N2—C5—C6A	45.5 (8)	C10—C11—C12—C7	0.6 (6)

Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+3, −y, −z; (iv) −x+2, −y, −z; (v) −x+2, −y+1, −z; (vi) x−1, y+1, z; (vii) x+1, y−1, z; (viii) x+1, y, z−1; (ix) x−1, y, z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S^i	0.86	2.76	3.487 (4)	143
C3—H3B···S	0.97	2.56	3.024 (5)	109
C5—H5A···O1	0.97	2.49	2.979 (8)	111
C5—H5A···N1	0.97	2.31	2.794 (8)	110

Symmetry code: (i) −x+2, −y, −z+1.