3-[4-(3,3-Diethyl­thio­ureidocarbonoyl)­benzoyl]-1,1-diethyl­thio­urea

The title compound, C₁₈H₂₆N₄O₂S₂, lies about a crystallographic inversion centre. The crystal packing shows intermolecular C—H...O and N—H...S interactions, the latter giving rise to the formation of dimers.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.032
• wR factor = 0.090
• Data-to-parameter ratio = 16.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.99

Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     -   C5       =       5.44 su
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C18 H26 N4 O2 S2

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

   0 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
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

The title compound, (I), is another example of our newly synthesized thiourea derivatives which show interesting complexation capacity. The centre of the molecule lies on a crystallographic inversion centre and thus the two thiourea moieties adopt anti position. The planes of the benzoyl ring and the thiourea group N₂CS are almost perpendicular with an angle of 89.0 (1)°. The corresponding torsion angles are N2—C6—C7—C8 = 160.4 (1)°, C6—N2—C5—S1 = 108.3 (1)° and O1—C6—C7—C8 = 154.8 (1)°. Prominent bond lengths are in the expected range, viz. C5—S1 = 1.6660 (13) Å, C6—O1 = 1.2185 (16) Å, C5—N2 = 1.4173 (16) Å and C5—N1 = 1.3214 (17) Å and compare well with the related distances of 1,1-diethyl-3-(4-methylbenzoyl)thiourea (Morales et al., 1997) or N-benzoyl-N'-methyl-N'-phenylthiourea (Shanmuga Sundara Raj et al., 1999). In the crystal structure (Fig. 2), molecules form dimers through strong intermolecular N2—H2···S1(-x + 1, −y, −z + 2) hydrogen bonds with H···S = 2.37 Å and N—H.·S = 171.9°. Additional intermolecular interactions are C2—H2B.·O1(x − 0.5, −y + 0.5, z − 0.5) with H.·O = 2.33 Å and C—H.·O = 151.9°. An intramolecular hydrogen bond is formed by C2—H2A.·N2 with H.·N = 2.30 Å and C—H.·N = 105.3°. All these values are normalized for N—H = 1.03 Å and C—H = 1.08 Å.

S2. Experimental

A solution of 2.5 mmol terephthalyldichlorid in 125 ml acetone was added to 5 mmol KSCN in 25 acetone solution. The mixture was stirred for 30 min at 313 K and the cooled to room temperature. Afterwards a solution of 5 mmol diethylamine in 25 ml acetone was added dropwise and stirring was continued for 2 h. The yellowish precipitate was recrystallized from dichloromethane–ethanol (1:1).

S3. Refinement

The H atom bonded to N2 was refined freely. Other H atoms were placed at calculated positions, riding on their attached C atoms, with isotropic displacement parameters U_iso(H) = 1.2U_eq(C) or 1.5U_eq(CH₃). CH₃ groups were allowed to rotate but not to tip.

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SMART; data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Bruker, 2002); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (A) 1 − x, −y, 3 − z.]
	Fig. 2. Packing diagram, viewed along [100]. Intermolecular hydrogen bonding is indicated by dashed lines.

3-[4-(3,3-Diethylthioureidocarbonoyl)benzoyl]-1,1-diethylthiourea

Crystal data

C18H26N4O2S2	F(000) = 420
Mr = 394.55	Dx = 1.332 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.7980 (7) Å	Cell parameters from 3822 reflections
b = 15.2735 (16) Å	θ = 2.5–28.3°
c = 10.0275 (10) Å	µ = 0.29 mm^−1
β = 109.168 (1)°	T = 173 K
V = 983.43 (17) Å^3	Prism, colourless
Z = 2	0.32 × 0.25 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1991 independent reflections
Radiation source: sealed tube	1821 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ϕ and ω scans	θmax = 26.4°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −8→8
Tmin = 0.890, Tmax = 0.973	k = −19→17
5476 measured reflections	l = −12→12

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)] = 0.032	Hydrogen site location: difference Fourier map
wR(F^2) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0466P)^2 + 0.2868P] where P = (Fo^2 + 2Fc^2)/3
1991 reflections	(Δ/σ)max = 0.001
124 parameters	Δρmax = 0.29 e Å^−3
0 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
S1	0.77404 (6)	0.06233 (2)	0.98444 (4)	0.03319 (14)
O1	0.86306 (15)	0.12206 (6)	1.37451 (10)	0.0304 (2)
N1	0.70776 (16)	0.21277 (7)	1.09557 (11)	0.0224 (2)
N2	0.59341 (17)	0.08783 (7)	1.17977 (11)	0.0230 (2)
H2	0.512 (3)	0.0471 (11)	1.1406 (18)	0.028 (4)*
C1	0.7579 (3)	0.32788 (10)	1.28056 (17)	0.0378 (4)
H1A	0.8584	0.2911	1.3506	0.057*
H1B	0.6813	0.3640	1.3277	0.057*
H1C	0.8320	0.3658	1.2341	0.057*
C2	0.6067 (2)	0.27036 (9)	1.17150 (14)	0.0271 (3)
H2A	0.5292	0.2338	1.2189	0.032*
H2B	0.5046	0.3081	1.1022	0.032*
C3	1.0514 (2)	0.25416 (10)	1.07891 (17)	0.0365 (4)
H3A	1.0919	0.2869	1.1679	0.055*
H3B	1.1179	0.2803	1.0153	0.055*
H3C	1.0961	0.1931	1.0978	0.055*
C4	0.8172 (2)	0.25757 (9)	1.01070 (15)	0.0286 (3)
H4A	0.7720	0.3195	0.9975	0.034*
H4B	0.7784	0.2299	0.9163	0.034*
C5	0.69020 (18)	0.12658 (8)	1.08884 (13)	0.0218 (3)
C6	0.6959 (2)	0.08575 (8)	1.32130 (13)	0.0222 (3)
C7	0.5907 (2)	0.03932 (8)	1.41005 (13)	0.0215 (3)
C8	0.3763 (2)	0.02678 (8)	1.36614 (13)	0.0232 (3)
H8A	0.2919	0.0451	1.2747	0.028*
C9	0.7130 (2)	0.01252 (8)	1.54358 (14)	0.0237 (3)
H9A	0.8594	0.0212	1.5733	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0368 (2)	0.0331 (2)	0.0372 (2)	−0.00868 (14)	0.02230 (18)	−0.01086 (14)
O1	0.0275 (5)	0.0366 (5)	0.0248 (5)	−0.0086 (4)	0.0055 (4)	0.0035 (4)
N1	0.0233 (5)	0.0244 (5)	0.0192 (5)	−0.0031 (4)	0.0065 (4)	0.0023 (4)
N2	0.0258 (6)	0.0236 (5)	0.0205 (5)	−0.0073 (4)	0.0088 (5)	−0.0018 (4)
C1	0.0455 (9)	0.0303 (7)	0.0361 (9)	−0.0035 (6)	0.0111 (7)	−0.0066 (6)
C2	0.0276 (7)	0.0251 (6)	0.0280 (7)	0.0028 (5)	0.0085 (6)	0.0022 (5)
C3	0.0297 (8)	0.0424 (8)	0.0375 (8)	−0.0105 (6)	0.0113 (6)	0.0064 (6)
C4	0.0311 (7)	0.0306 (7)	0.0248 (7)	−0.0061 (5)	0.0099 (6)	0.0074 (5)
C5	0.0191 (6)	0.0269 (6)	0.0185 (6)	−0.0043 (5)	0.0048 (5)	−0.0001 (5)
C6	0.0254 (6)	0.0201 (6)	0.0222 (6)	0.0001 (5)	0.0093 (5)	0.0005 (5)
C7	0.0276 (6)	0.0180 (6)	0.0211 (6)	0.0001 (5)	0.0109 (5)	−0.0010 (5)
C8	0.0266 (6)	0.0231 (6)	0.0195 (6)	0.0013 (5)	0.0069 (5)	0.0009 (5)
C9	0.0243 (6)	0.0233 (6)	0.0244 (6)	−0.0002 (5)	0.0090 (5)	0.0002 (5)

Geometric parameters (Å, º)

S1—C5	1.6660 (13)	C3—C4	1.513 (2)
O1—C6	1.2185 (16)	C3—H3A	0.9800
N1—C5	1.3214 (17)	C3—H3B	0.9800
N1—C4	1.4705 (16)	C3—H3C	0.9800
N1—C2	1.4726 (17)	C4—H4A	0.9900
N2—C6	1.3606 (17)	C4—H4B	0.9900
N2—C5	1.4173 (16)	C6—C7	1.4915 (17)
N2—H2	0.840 (17)	C7—C9	1.3857 (18)
C1—C2	1.512 (2)	C7—C8	1.3905 (18)
C1—H1A	0.9800	C8—C9^i	1.3819 (18)
C1—H1B	0.9800	C8—H8A	0.9500
C1—H1C	0.9800	C9—C8^i	1.3819 (18)
C2—H2A	0.9900	C9—H9A	0.9500
C2—H2B	0.9900
C5—N1—C4	119.24 (11)	H3B—C3—H3C	109.5
C5—N1—C2	124.88 (11)	N1—C4—C3	112.31 (11)
C4—N1—C2	115.58 (10)	N1—C4—H4A	109.1
C6—N2—C5	119.59 (10)	C3—C4—H4A	109.1
C6—N2—H2	120.3 (11)	N1—C4—H4B	109.1
C5—N2—H2	112.5 (11)	C3—C4—H4B	109.1
C2—C1—H1A	109.5	H4A—C4—H4B	107.9
C2—C1—H1B	109.5	N1—C5—N2	115.88 (11)
H1A—C1—H1B	109.5	N1—C5—S1	125.10 (10)
C2—C1—H1C	109.5	N2—C5—S1	119.02 (9)
H1A—C1—H1C	109.5	O1—C6—N2	122.06 (12)
H1B—C1—H1C	109.5	O1—C6—C7	121.05 (12)
N1—C2—C1	113.54 (11)	N2—C6—C7	116.85 (11)
N1—C2—H2A	108.9	C9—C7—C8	119.94 (12)
C1—C2—H2A	108.9	C9—C7—C6	117.64 (11)
N1—C2—H2B	108.9	C8—C7—C6	122.32 (11)
C1—C2—H2B	108.9	C9^i—C8—C7	119.52 (12)
H2A—C2—H2B	107.7	C9^i—C8—H8A	120.2
C4—C3—H3A	109.5	C7—C8—H8A	120.2
C4—C3—H3B	109.5	C8^i—C9—C7	120.53 (12)
H3A—C3—H3B	109.5	C8^i—C9—H9A	119.7
C4—C3—H3C	109.5	C7—C9—H9A	119.7
H3A—C3—H3C	109.5
C5—N1—C2—C1	123.57 (14)	C5—N2—C6—O1	5.64 (19)
C4—N1—C2—C1	−62.86 (15)	C5—N2—C6—C7	−176.43 (11)
C5—N1—C4—C3	−80.55 (15)	O1—C6—C7—C9	−21.67 (18)
C2—N1—C4—C3	105.50 (14)	N2—C6—C7—C9	160.38 (12)
C4—N1—C5—N2	176.47 (10)	O1—C6—C7—C8	154.82 (13)
C2—N1—C5—N2	−10.18 (17)	N2—C6—C7—C8	−23.14 (17)
C4—N1—C5—S1	−2.96 (17)	C9—C7—C8—C9^i	−0.1 (2)
C2—N1—C5—S1	170.40 (9)	C6—C7—C8—C9^i	−176.48 (11)
C6—N2—C5—N1	−71.19 (15)	C8—C7—C9—C8^i	0.1 (2)
C6—N2—C5—S1	108.27 (12)	C6—C7—C9—C8^i	176.64 (11)

Symmetry code: (i) −x+1, −y, −z+3.