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In the title compound, C13H18N2O2S, the 4-meth­oxy­benzoyl fragment is approximately planar [maximum deviation = 0.057 (2) Å] and twisted relative to the thio­amide fragment, forming a dihedral angle of 86.62 (6)°. The two Csp2—Nsp2 bonds in the thio­urea unit differ significantly in length [1.327 (2) and 1.431 (2) Å]. In the crystal, N—H...O hydrogen bonds link the mol­ecules into chains parallel to [010].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811049208/gk2435sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536811049208/gk2435Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536811049208/gk2435Isup3.cml
Supplementary material

CCDC reference: 858483

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.042
  • wR factor = 0.132
  • Data-to-parameter ratio = 15.6

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT934_ALERT_3_B Number of (Iobs-Icalc)/SigmaW .gt. 10 Outliers . 1
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.976 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 31 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 31
Alert level G PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF .... ?
0 ALERT level A = Most likely a serious problem - resolve or explain 1 ALERT level B = A potentially serious problem, consider carefully 3 ALERT level C = Check. Ensure it is not caused by an omission or oversight 1 ALERT level G = General information/check it is not something unexpected 0 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 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

The title compound (I) has been used as a ligand to form stable complexes with Ni and Co (Mohamadou et al., 1994). Compund I and other similar derivatives act as a bidentate (O,S) chelate forming square planar and tetrahedral complexes with NiII and CoIII, respectively.

In the structure of I, the 4-methoxybenzamide moiety [O2/N1/C1/C2/C3/C4/C5/C6/C7/C8/C13] (A) and the thiourea fragment [S1/N1/N2/C8] (B) are essentially planar with maximum deviations from the mean planes 0.057 (2) Å for C13 and -0.031 (2) Å N1. The dihedral angle between the A and B planes is 86.62 (6)°, which is slightly smaller than the analogous dihedral angle [87.99 (11)°] in 1-benzoyl-3-ethyl-3-phenylthiourea (II) (Al-abbasi & Kassim, 2011).

The C=O [1.237 (2) Å] and C=S [1.658 (3) Å] bond lengths are slightly longer than those in II [1.207 (3) and 1.666 (2) Å, respectively].

In the crystal, the molecules are stabilized by intermolecular N1—H1A···O1 hydrogen bonds forming a one-dimensional polymeric network along the b axis (Figure 2).

Related literature top

For structural parameters and chemical properties of 1,1 disubstituted 3-benzoylthioureas, see: Al-abbasi et al. (2010, 2011); Al-abbasi & Kassim (2011); Mohamadou et al. (1994).

Experimental top

A solution of benzoyl chloride (10 mmol) in acetone was added slowly to an equimolar solution of ammonium thiocyanate in acetone. The reaction mixture was stirred at room temperature before adding diethylamine (10 mmol) slowly and the mixture was left stirring at room temperature for 2–3 h. The mixture was poured onto a water-ice, filtered and the residue was recrystallized from ethaaol/acetone solution to give colourless crystals, suitable for X-ray crystallography (yield 85%).

Refinement top

The hydrogen atom positions were calculated geometrically and refined in a riding model approximation with C–H bond lengths in the range 0.93–0.97 Å and N-H= 0.86 Å with Uiso(H) = 1.2Ueq(C, N) for N-H, aromatic C-H and CH2 groups, and Uiso(H) = 1.5Ueq(C) for methyl group.

Structure description top

The title compound (I) has been used as a ligand to form stable complexes with Ni and Co (Mohamadou et al., 1994). Compund I and other similar derivatives act as a bidentate (O,S) chelate forming square planar and tetrahedral complexes with NiII and CoIII, respectively.

In the structure of I, the 4-methoxybenzamide moiety [O2/N1/C1/C2/C3/C4/C5/C6/C7/C8/C13] (A) and the thiourea fragment [S1/N1/N2/C8] (B) are essentially planar with maximum deviations from the mean planes 0.057 (2) Å for C13 and -0.031 (2) Å N1. The dihedral angle between the A and B planes is 86.62 (6)°, which is slightly smaller than the analogous dihedral angle [87.99 (11)°] in 1-benzoyl-3-ethyl-3-phenylthiourea (II) (Al-abbasi & Kassim, 2011).

The C=O [1.237 (2) Å] and C=S [1.658 (3) Å] bond lengths are slightly longer than those in II [1.207 (3) and 1.666 (2) Å, respectively].

In the crystal, the molecules are stabilized by intermolecular N1—H1A···O1 hydrogen bonds forming a one-dimensional polymeric network along the b axis (Figure 2).

For structural parameters and chemical properties of 1,1 disubstituted 3-benzoylthioureas, see: Al-abbasi et al. (2010, 2011); Al-abbasi & Kassim (2011); Mohamadou et al. (1994).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of 1,1-diethyl-3-(4-methoxybenzoyl)thiourea with displacement ellipsods drawn at the 50% probability level.
[Figure 2] Fig. 2. The crystal packing of 1,1-diethyl-3-(4-methoxybenzoyl)thiourea with intermolecular hydrogen bonds shown as dashed lines.
1,1-Diethyl-3-(4-methoxybenzoyl)thiourea top
Crystal data top
C13H18N2O2SDx = 1.314 Mg m3
Mr = 266.35Melting point = 407.15–408.15 K
Orthorhombic, PbcaCu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ac 2abCell parameters from 5648 reflections
a = 12.9024 (5) Åθ = 4.2–71.1°
b = 10.0095 (4) ŵ = 2.11 mm1
c = 20.8585 (11) ÅT = 150 K
V = 2693.8 (2) Å3Plate, colourless
Z = 80.24 × 0.10 × 0.05 mm
F(000) = 1136
Data collection top
Oxford Diffraction Gemini
diffractometer
2548 independent reflections
Radiation source: fine-focus sealed tube2214 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
ω/2θ scansθmax = 71.1°, θmin = 4.2°
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)
h = 1315
Tmin = 0.810, Tmax = 0.900k = 1212
12046 measured reflectionsl = 2325
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132H-atom parameters constrained
S = 1.12 w = 1/[σ2(Fo2) + (0.0835P)2 + 0.6035P]
where P = (Fo2 + 2Fc2)/3
2548 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.43 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
C13H18N2O2SV = 2693.8 (2) Å3
Mr = 266.35Z = 8
Orthorhombic, PbcaCu Kα radiation
a = 12.9024 (5) ŵ = 2.11 mm1
b = 10.0095 (4) ÅT = 150 K
c = 20.8585 (11) Å0.24 × 0.10 × 0.05 mm
Data collection top
Oxford Diffraction Gemini
diffractometer
2548 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)
2214 reflections with I > 2σ(I)
Tmin = 0.810, Tmax = 0.900Rint = 0.030
12046 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.132H-atom parameters constrained
S = 1.12Δρmax = 0.43 e Å3
2548 reflectionsΔρmin = 0.32 e Å3
163 parameters
Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1 K.

Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105 107.

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 (Å2) top
xyzUiso*/Ueq
S10.96773 (4)0.08865 (5)0.60731 (2)0.0302 (2)
O10.72174 (10)0.27396 (13)0.63046 (7)0.0282 (3)
O20.29590 (10)0.00839 (15)0.54492 (7)0.0327 (4)
N10.76759 (11)0.05775 (15)0.63691 (7)0.0210 (3)
H1A0.74950.02460.63320.025*
N20.87609 (11)0.11414 (15)0.72156 (7)0.0215 (3)
C10.52575 (14)0.21406 (19)0.58056 (9)0.0242 (4)
H1B0.54720.30280.58110.029*
C20.42448 (15)0.1834 (2)0.56253 (9)0.0271 (4)
H2A0.37850.25100.55130.033*
C30.39293 (14)0.0509 (2)0.56149 (8)0.0246 (4)
C40.46228 (14)0.05050 (19)0.57806 (9)0.0236 (4)
H4A0.44100.13930.57710.028*
C50.56228 (14)0.01898 (19)0.59584 (8)0.0220 (4)
H5A0.60820.08700.60670.026*
C60.59545 (14)0.11370 (18)0.59775 (8)0.0201 (4)
C70.69945 (13)0.15522 (17)0.62164 (8)0.0202 (4)
C80.86948 (13)0.08980 (16)0.65915 (9)0.0213 (4)
C90.78567 (13)0.11498 (19)0.76513 (9)0.0236 (4)
H9A0.72650.15240.74270.028*
H9B0.80070.17210.80150.028*
C100.75793 (15)0.0231 (2)0.78918 (10)0.0298 (4)
H10A0.69890.01740.81710.045*
H10B0.81560.05990.81230.045*
H10C0.74170.07980.75340.045*
C110.97664 (13)0.14064 (18)0.75210 (9)0.0246 (4)
H11A1.03100.09730.72770.029*
H11B0.97680.10280.79490.029*
C120.99913 (15)0.28917 (19)0.75623 (10)0.0296 (5)
H12A1.06500.30280.77660.044*
H12B0.94590.33220.78080.044*
H12C1.00080.32650.71380.044*
C130.22137 (16)0.1077 (3)0.52797 (11)0.0401 (5)
H13A0.15670.06540.51770.060*
H13B0.24570.15690.49140.060*
H13C0.21160.16760.56340.060*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0251 (3)0.0307 (3)0.0347 (3)0.00535 (18)0.00843 (18)0.00309 (18)
O10.0258 (7)0.0211 (7)0.0378 (8)0.0015 (5)0.0037 (6)0.0012 (5)
O20.0193 (7)0.0438 (9)0.0351 (8)0.0006 (6)0.0042 (5)0.0002 (6)
N10.0196 (7)0.0170 (8)0.0265 (8)0.0021 (5)0.0025 (6)0.0007 (6)
N20.0188 (7)0.0181 (7)0.0275 (8)0.0002 (5)0.0016 (6)0.0003 (6)
C10.0273 (10)0.0215 (10)0.0238 (10)0.0017 (7)0.0004 (7)0.0011 (7)
C20.0255 (9)0.0315 (11)0.0244 (9)0.0085 (8)0.0015 (7)0.0035 (7)
C30.0207 (9)0.0348 (11)0.0184 (9)0.0003 (7)0.0004 (6)0.0014 (7)
C40.0242 (9)0.0227 (9)0.0239 (10)0.0025 (7)0.0016 (7)0.0026 (7)
C50.0209 (9)0.0240 (9)0.0212 (9)0.0018 (7)0.0021 (6)0.0005 (7)
C60.0210 (9)0.0206 (9)0.0187 (8)0.0009 (7)0.0016 (6)0.0006 (6)
C70.0226 (9)0.0184 (9)0.0197 (8)0.0012 (7)0.0022 (6)0.0008 (6)
C80.0194 (9)0.0149 (9)0.0295 (10)0.0000 (6)0.0012 (7)0.0010 (6)
C90.0220 (9)0.0222 (9)0.0265 (10)0.0007 (7)0.0001 (7)0.0027 (7)
C100.0261 (10)0.0314 (11)0.0318 (10)0.0026 (8)0.0028 (8)0.0030 (8)
C110.0204 (9)0.0211 (10)0.0323 (10)0.0008 (7)0.0066 (7)0.0002 (7)
C120.0252 (9)0.0268 (11)0.0367 (11)0.0050 (7)0.0082 (8)0.0024 (8)
C130.0229 (10)0.0591 (15)0.0384 (12)0.0080 (9)0.0058 (8)0.0033 (10)
Geometric parameters (Å, º) top
S1—C81.6663 (18)C5—C61.396 (3)
O1—C71.237 (2)C5—H5A0.9300
O2—C31.367 (2)C6—C71.490 (2)
O2—C131.428 (3)C9—C101.514 (3)
N1—C71.351 (2)C9—H9A0.9700
N1—C81.431 (2)C9—H9B0.9700
N1—H1A0.8600C10—H10A0.9600
N2—C81.327 (2)C10—H10B0.9600
N2—C111.470 (2)C10—H10C0.9600
N2—C91.479 (2)C11—C121.517 (3)
C1—C21.394 (3)C11—H11A0.9700
C1—C61.395 (3)C11—H11B0.9700
C1—H1B0.9300C12—H12A0.9600
C2—C31.387 (3)C12—H12B0.9600
C2—H2A0.9300C12—H12C0.9600
C3—C41.397 (3)C13—H13A0.9600
C4—C51.379 (3)C13—H13B0.9600
C4—H4A0.9300C13—H13C0.9600
C3—O2—C13117.56 (17)N2—C9—C10112.64 (15)
C7—N1—C8120.83 (15)N2—C9—H9A109.1
C7—N1—H1A119.6C10—C9—H9A109.1
C8—N1—H1A119.6N2—C9—H9B109.1
C8—N2—C11121.01 (15)C10—C9—H9B109.1
C8—N2—C9123.58 (14)H9A—C9—H9B107.8
C11—N2—C9115.40 (14)C9—C10—H10A109.5
C2—C1—C6121.00 (17)C9—C10—H10B109.5
C2—C1—H1B119.5H10A—C10—H10B109.5
C6—C1—H1B119.5C9—C10—H10C109.5
C3—C2—C1119.34 (17)H10A—C10—H10C109.5
C3—C2—H2A120.3H10B—C10—H10C109.5
C1—C2—H2A120.3N2—C11—C12111.73 (14)
O2—C3—C2124.80 (17)N2—C11—H11A109.3
O2—C3—C4115.01 (17)C12—C11—H11A109.3
C2—C3—C4120.19 (17)N2—C11—H11B109.3
C5—C4—C3119.97 (18)C12—C11—H11B109.3
C5—C4—H4A120.0H11A—C11—H11B107.9
C3—C4—H4A120.0C11—C12—H12A109.5
C4—C5—C6120.81 (17)C11—C12—H12B109.5
C4—C5—H5A119.6H12A—C12—H12B109.5
C6—C5—H5A119.6C11—C12—H12C109.5
C1—C6—C5118.69 (17)H12A—C12—H12C109.5
C1—C6—C7117.74 (16)H12B—C12—H12C109.5
C5—C6—C7123.43 (16)O2—C13—H13A109.5
O1—C7—N1120.50 (16)O2—C13—H13B109.5
O1—C7—C6121.81 (16)H13A—C13—H13B109.5
N1—C7—C6117.60 (15)O2—C13—H13C109.5
N2—C8—N1114.73 (15)H13A—C13—H13C109.5
N2—C8—S1126.08 (14)H13B—C13—H13C109.5
N1—C8—S1119.16 (13)
C6—C1—C2—C30.2 (3)C1—C6—C7—O15.0 (3)
C13—O2—C3—C20.6 (3)C5—C6—C7—O1170.57 (16)
C13—O2—C3—C4179.54 (17)C1—C6—C7—N1178.57 (16)
C1—C2—C3—O2179.78 (17)C5—C6—C7—N15.9 (2)
C1—C2—C3—C40.3 (3)C11—N2—C8—N1176.34 (14)
O2—C3—C4—C5179.75 (16)C9—N2—C8—N12.8 (2)
C2—C3—C4—C50.3 (3)C11—N2—C8—S11.5 (2)
C3—C4—C5—C60.2 (3)C9—N2—C8—S1179.41 (13)
C2—C1—C6—C50.8 (3)C7—N1—C8—N284.6 (2)
C2—C1—C6—C7175.01 (16)C7—N1—C8—S197.46 (17)
C4—C5—C6—C10.8 (3)C8—N2—C9—C1084.7 (2)
C4—C5—C6—C7174.78 (16)C11—N2—C9—C1094.45 (18)
C8—N1—C7—O14.6 (3)C8—N2—C11—C1294.1 (2)
C8—N1—C7—C6178.96 (15)C9—N2—C11—C1286.69 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.862.052.847 (2)154
Symmetry code: (i) x+3/2, y1/2, z.

Experimental details

Crystal data
Chemical formulaC13H18N2O2S
Mr266.35
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)150
a, b, c (Å)12.9024 (5), 10.0095 (4), 20.8585 (11)
V3)2693.8 (2)
Z8
Radiation typeCu Kα
µ (mm1)2.11
Crystal size (mm)0.24 × 0.10 × 0.05
Data collection
DiffractometerOxford Diffraction Gemini
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2006)
Tmin, Tmax0.810, 0.900
No. of measured, independent and
observed [I > 2σ(I)] reflections
12046, 2548, 2214
Rint0.030
(sin θ/λ)max1)0.614
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.132, 1.12
No. of reflections2548
No. of parameters163
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.43, 0.32

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.862.052.847 (2)154
Symmetry code: (i) x+3/2, y1/2, z.
 

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