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Acta Crystallogr Sect E Struct Rep Online. 2009 March 1; 65(Pt 3): o569.
Published online 2009 February 21. doi:  10.1107/S1600536809005662
PMCID: PMC2968616

3,3′-Dibenzoyl-1,1′-(3,6-dioxaoctane-1,8-di­yl)dithio­urea

Abstract

In the mol­ecule of the title compound, C22H26N4O4S2, the central O—CH2—CH2—O chain adopts a synclinal conformation [torsion angle = 65.0 (2)°]. The crystal structure is stabilized by intra­molecular N—H(...)O=C and inter­molecular N—H(...)O—C hydrogen bonds.

Related literature

For related structures, see: Avşar et al. (2003 [triangle]); Arslan et al. (2004 [triangle]); Du & Du (2008 [triangle]); Ding et al. (2008 [triangle]).

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Object name is e-65-0o569-scheme1.jpg

Experimental

Crystal data

  • C22H26N4O4S2
  • M r = 474.59
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o569-efi1.jpg
  • a = 7.9718 (2) Å
  • b = 9.2177 (3) Å
  • c = 16.4106 (5) Å
  • α = 81.018 (2)°
  • β = 83.364 (2)°
  • γ = 80.450 (2)°
  • V = 1169.60 (6) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.26 mm−1
  • T = 293 K
  • 0.10 × 0.10 × 0.10 mm

Data collection

  • Nonius Kappa CCD diffractometer
  • Absorption correction: none
  • 7989 measured reflections
  • 4211 independent reflections
  • 2737 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.128
  • S = 1.02
  • 4211 reflections
  • 305 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.41 e Å−3
  • Δρmin = −0.50 e Å−3

Data collection: COLLECT (Nonius, 1998 [triangle]); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 [triangle]); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809005662/bh2217sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809005662/bh2217Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Agence Universitaire de la Francophonie for financial support (AUF-PSCI No.6314PS804).

supplementary crystallographic information

Comment

The title compound, C22H26N4O4S2, was characterized by 1H and 13C NMR, solid-state IR and X-ray crystallographic techniques. The X-ray structure determination reveals that the compound crystallizes in the triclinic space group P1 with one molecule in the asymmetric unit. The molecular geometry is illustrated in Fig. 1. The C—S bond lengths of 1.665 (3) Å and 1.659 (2) Å and the C—O bond lengths of 1.220 (3) Å and 1.222 (3) Å are double bonds character and are comparable to those observed for 1-(biphenyl-4-carbonyl)-3-p-tolyl-thiourea [1.647 (3) Å for C—S, 1.217 (3) and 1.224 (3) Å for C—O respectively (Arslan et al., 2004)]. The C—N bond lengths are in the range 1.310 (3)–1.451 (3) Å, and are shorter than the normal single C—N bond length (Avşar et al., 2003). The carbonyl group forms an intramolecular hydrogen bonds with the N2—H2 and the N3—H3 groups, which forms two six-membered rings (C8/N1/C7/O1/H2/N2 and C15/N4/C16/O4/H3/N3) structure (Fig. 2); H2···O1 and the H3···O4 separations are respectively 1.99 (3) Å and 2.01 (3) Å. There is an intermolecular hydrogen bonding between N4—H4 and the O atom of the ethoxy group of a symmetry-related molecule, the H4···O2 (-x + 2, -y, -z + 1) separation being 2.48 (3) Å (Table 1). The structure of the title compound is related to other thiourea derivatives (e.g. Ding et al., 2008; Du & Du, 2008).

Experimental

Benzoyl chloride (7.10 g, 50 mmol) was reacted with potassium thiocyanate (4.86 g, 50 mmol) in CH3OCH3 (50 ml) solution, to give the corresponding benzoyl isothiocyanate after one hour under refluxing. After cooling to room temperature, a solution of 2-(2-(2-aminoethoxy)ethoxy)ethanamine (3.70 g, 25 mmol) in CH3OCH3 (20 ml) was added dropwise to benzoyl isothiocyanate. After three hours under stirring, 200 ml of HCl 1 M was added. A yellow oil was isolated and treated with diethyl ether to give the title compound which is washed with diethyl ether twice. Yield: 55.9%. m.p. 415–419 K. Anal. Calc. for C22H26N4O4S2: C 55.68, H 5.52, N 11.81%. Found: C 55.70, H 5.45, N 11.65%. Selected IR data (cm-1, KBr pellet): 3424, 3218 (ν NH), 1667 (ν C?O), 1160 (ν C?S). 1H-NMR (200 MHz, DMSO-d6, δ, p.p.m.): 3.45 (t, 4H, N—CH2); 3.63 (s, 4H, O—CH2); 3.70 (t, 4H, O—CH2); 7.21–7.92 (m, 10H, C6H5); 11.01 (s, 2H, NH); 11.41 (s, 2H, NH). 13C-NMR (50 MHz, DMSO-d6, δ, p.p.m.): 45.21 (N—CH2); 68.09 (O—CH2); 70.12 (O—CH2); 133.31–127.62 (C6H5); 1168.60 (C?O); 180.81 (C?S). A CH3Cl solution of the title compound was mixed with ethanol (1/1). After several days, colorless block-shaped single crystals suitable for X-ray crystallographic analysis were obtained.

Refinement

H atoms of NH groups were located in a difference map and refined freely. Others H atoms were placed geometrically and refined with a riding model. Uiso(H) for H was calculated as 1.2 Ueq of the carrier atom.

Figures

Fig. 1.
An ORTEP view of the asymmetric unit of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are plotted at the 50% probability level.
Fig. 2.
Molecular representation of the compound showing hydrogen bonds (dashed lines).

Crystal data

C22H26N4O4S2Z = 2
Mr = 474.59F(000) = 500
Triclinic, P1Dx = 1.347 Mg m3
Hall symbol: -P 1Melting point: 415 K
a = 7.9718 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.2177 (3) ÅCell parameters from 4206 reflections
c = 16.4106 (5) Åθ = 1.0–25.4°
α = 81.018 (2)°µ = 0.26 mm1
β = 83.364 (2)°T = 293 K
γ = 80.450 (2)°Prism, yellow
V = 1169.60 (6) Å30.10 × 0.10 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer2737 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.030
graphiteθmax = 25.2°, θmin = 2.3°
ω scansh = −9→9
7989 measured reflectionsk = −11→11
4211 independent reflectionsl = −19→19

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128H atoms treated by a mixture of independent and constrained refinement
S = 1.02w = 1/[σ2(Fo2) + (0.0614P)2 + 0.2609P] where P = (Fo2 + 2Fc2)/3
4211 reflections(Δ/σ)max = 0.008
305 parametersΔρmax = 0.41 e Å3
0 restraintsΔρmin = −0.50 e Å3
0 constraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
S10.37094 (10)0.16706 (9)0.86251 (5)0.0713 (3)
S21.26452 (13)−0.27342 (8)0.52516 (4)0.0790 (3)
O10.7377 (3)0.4586 (2)0.91685 (11)0.0711 (6)
O20.81088 (19)0.39803 (17)0.67050 (9)0.0482 (4)
O31.12041 (19)0.24744 (17)0.60508 (10)0.0472 (4)
O41.2463 (3)0.1608 (2)0.35665 (11)0.0740 (6)
N10.5641 (3)0.2839 (3)0.94678 (14)0.0527 (6)
H10.530 (3)0.224 (3)0.9815 (16)0.049 (8)*
N20.5680 (3)0.3729 (2)0.80784 (13)0.0492 (5)
H20.639 (3)0.422 (3)0.8172 (16)0.056 (8)*
N31.2498 (3)0.0165 (3)0.50822 (13)0.0506 (5)
H31.236 (3)0.099 (3)0.4798 (17)0.063 (9)*
N41.2073 (3)−0.0786 (2)0.39123 (12)0.0465 (5)
H41.190 (3)−0.154 (3)0.3741 (15)0.052 (8)*
C10.7116 (3)0.3433 (3)1.05616 (14)0.0456 (6)
C20.8101 (3)0.4370 (3)1.08034 (16)0.0539 (6)
H2A0.84970.51151.04160.065*
C30.8498 (4)0.4211 (3)1.16088 (18)0.0639 (7)
H3A0.91690.48401.17630.077*
C40.7902 (4)0.3120 (3)1.21864 (18)0.0692 (8)
H4A0.81650.30121.27320.083*
C50.6923 (4)0.2194 (4)1.19573 (19)0.0771 (9)
H50.65130.14641.23500.093*
C60.6537 (4)0.2335 (3)1.11472 (17)0.0649 (8)
H60.58850.16901.09950.078*
C70.6744 (3)0.3674 (3)0.96796 (15)0.0488 (6)
C80.5078 (3)0.2817 (3)0.86956 (15)0.0477 (6)
C90.5275 (3)0.3838 (3)0.72324 (15)0.0537 (6)
H9A0.40950.42930.71890.064*
H9B0.54060.28510.70750.064*
C100.6419 (3)0.4745 (3)0.66582 (15)0.0516 (6)
H10A0.61010.48590.60960.062*
H10B0.63310.57230.68220.062*
C110.9346 (3)0.4733 (3)0.61860 (16)0.0522 (6)
H11A0.92780.57300.63200.063*
H11B0.91330.48040.56100.063*
C121.1067 (3)0.3882 (3)0.63208 (16)0.0506 (6)
H12A1.19360.44260.60140.061*
H12B1.12430.37510.69040.061*
C131.2832 (3)0.1611 (3)0.61572 (16)0.0529 (6)
H13A1.30920.15380.67270.063*
H13B1.37050.20770.57990.063*
C141.2803 (3)0.0091 (3)0.59436 (14)0.0504 (6)
H14A1.3887−0.05290.60450.061*
H14B1.1912−0.03590.62970.061*
C151.2389 (3)−0.1016 (3)0.47501 (14)0.0447 (6)
C161.2118 (3)0.0483 (3)0.33592 (14)0.0454 (6)
C171.1796 (3)0.0433 (2)0.24907 (14)0.0419 (5)
C181.2227 (3)0.1595 (3)0.19018 (15)0.0527 (6)
H181.26840.23610.20620.063*
C191.1984 (3)0.1624 (3)0.10851 (16)0.0610 (7)
H191.22990.23980.06930.073*
C201.1281 (3)0.0520 (3)0.08436 (16)0.0618 (7)
H201.11200.05460.02890.074*
C211.0811 (3)−0.0632 (3)0.14224 (16)0.0605 (7)
H211.0324−0.13780.12600.073*
C221.1069 (3)−0.0672 (3)0.22467 (15)0.0507 (6)
H221.0751−0.14460.26380.061*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0807 (5)0.0781 (5)0.0659 (5)−0.0445 (4)−0.0032 (4)−0.0115 (4)
S20.1467 (8)0.0464 (4)0.0494 (4)−0.0296 (5)−0.0275 (5)0.0059 (3)
O10.0906 (14)0.0822 (14)0.0503 (11)−0.0502 (12)−0.0123 (10)0.0050 (10)
O20.0498 (10)0.0443 (9)0.0461 (9)−0.0077 (8)0.0014 (8)0.0036 (7)
O30.0497 (10)0.0457 (9)0.0501 (10)−0.0119 (8)−0.0053 (7)−0.0140 (8)
O40.1328 (18)0.0430 (11)0.0518 (11)−0.0288 (11)−0.0176 (11)−0.0010 (9)
N10.0584 (14)0.0572 (14)0.0453 (13)−0.0237 (11)0.0023 (11)−0.0054 (11)
N20.0468 (12)0.0626 (14)0.0431 (12)−0.0214 (11)0.0000 (10)−0.0112 (10)
N30.0716 (15)0.0397 (13)0.0409 (12)−0.0077 (11)−0.0081 (10)−0.0055 (10)
N40.0666 (14)0.0372 (12)0.0385 (11)−0.0162 (10)−0.0079 (9)−0.0024 (9)
C10.0450 (13)0.0445 (14)0.0455 (14)−0.0027 (11)−0.0034 (11)−0.0053 (11)
C20.0562 (15)0.0556 (16)0.0514 (15)−0.0127 (13)−0.0023 (12)−0.0093 (12)
C30.0698 (18)0.0677 (18)0.0579 (17)−0.0074 (15)−0.0134 (14)−0.0177 (15)
C40.076 (2)0.078 (2)0.0507 (17)0.0048 (17)−0.0169 (15)−0.0081 (16)
C50.087 (2)0.080 (2)0.0591 (19)−0.0181 (18)−0.0171 (16)0.0192 (16)
C60.0748 (19)0.0598 (17)0.0612 (18)−0.0203 (15)−0.0184 (15)0.0077 (14)
C70.0483 (14)0.0492 (15)0.0496 (15)−0.0124 (12)−0.0012 (12)−0.0062 (12)
C80.0461 (13)0.0507 (15)0.0486 (15)−0.0121 (11)0.0023 (11)−0.0135 (12)
C90.0498 (15)0.0667 (17)0.0491 (15)−0.0132 (13)−0.0048 (12)−0.0167 (13)
C100.0562 (15)0.0521 (15)0.0451 (14)−0.0026 (12)−0.0084 (12)−0.0056 (12)
C110.0639 (16)0.0404 (14)0.0514 (15)−0.0188 (12)0.0041 (12)0.0006 (11)
C120.0578 (15)0.0444 (14)0.0527 (15)−0.0208 (12)0.0023 (12)−0.0082 (12)
C130.0527 (15)0.0607 (16)0.0485 (15)−0.0100 (13)−0.0065 (12)−0.0144 (12)
C140.0612 (16)0.0531 (15)0.0379 (13)−0.0040 (12)−0.0102 (11)−0.0100 (11)
C150.0512 (14)0.0442 (14)0.0399 (13)−0.0115 (11)−0.0051 (11)−0.0044 (11)
C160.0543 (14)0.0392 (14)0.0426 (13)−0.0097 (11)−0.0041 (11)−0.0023 (11)
C170.0440 (13)0.0396 (13)0.0399 (13)−0.0052 (10)−0.0027 (10)−0.0009 (10)
C180.0591 (16)0.0488 (15)0.0492 (15)−0.0153 (12)−0.0033 (12)0.0029 (12)
C190.0667 (18)0.0656 (18)0.0458 (16)−0.0163 (15)−0.0043 (13)0.0132 (13)
C200.0631 (17)0.080 (2)0.0399 (14)−0.0112 (15)−0.0098 (13)0.0033 (14)
C210.0691 (17)0.0629 (17)0.0527 (16)−0.0161 (14)−0.0134 (13)−0.0059 (13)
C220.0572 (15)0.0500 (15)0.0434 (14)−0.0135 (12)−0.0065 (12)0.0052 (11)

Geometric parameters (Å, °)

S1—C81.665 (3)C5—H50.9300
S2—C151.659 (2)C6—H60.9300
O1—C71.220 (3)C9—C101.492 (3)
O2—C101.417 (3)C9—H9A0.9700
O2—C111.424 (3)C9—H9B0.9700
O3—C121.419 (3)C10—H10A0.9700
O3—C131.419 (3)C10—H10B0.9700
O4—C161.222 (3)C11—C121.485 (3)
N1—C71.366 (3)C11—H11A0.9700
N1—C81.396 (3)C11—H11B0.9700
N1—H10.79 (3)C12—H12A0.9700
N2—C81.311 (3)C12—H12B0.9700
N2—C91.446 (3)C13—C141.501 (3)
N2—H20.82 (3)C13—H13A0.9700
N3—C151.310 (3)C13—H13B0.9700
N3—C141.451 (3)C14—H14A0.9700
N3—H30.83 (3)C14—H14B0.9700
N4—C161.367 (3)C16—C171.486 (3)
N4—C151.404 (3)C17—C221.382 (3)
N4—H40.82 (3)C17—C181.386 (3)
C1—C61.382 (3)C18—C191.372 (4)
C1—C21.387 (3)C18—H180.9300
C1—C71.486 (3)C19—C201.369 (4)
C2—C31.375 (4)C19—H190.9300
C2—H2A0.9300C20—C211.380 (4)
C3—C41.376 (4)C20—H200.9300
C3—H3A0.9300C21—C221.386 (4)
C4—C51.366 (4)C21—H210.9300
C4—H4A0.9300C22—H220.9300
C5—C61.381 (4)
C10—O2—C11113.12 (18)H10A—C10—H10B108.5
C12—O3—C13112.15 (18)O2—C11—C12108.43 (19)
C7—N1—C8129.4 (2)O2—C11—H11A110.0
C7—N1—H1117.6 (19)C12—C11—H11A110.0
C8—N1—H1112.9 (19)O2—C11—H11B110.0
C8—N2—C9124.1 (2)C12—C11—H11B110.0
C8—N2—H2117.9 (18)H11A—C11—H11B108.4
C9—N2—H2117.9 (19)O3—C12—C11109.5 (2)
C15—N3—C14122.6 (2)O3—C12—H12A109.8
C15—N3—H3119 (2)C11—C12—H12A109.8
C14—N3—H3118 (2)O3—C12—H12B109.8
C16—N4—C15127.9 (2)C11—C12—H12B109.8
C16—N4—H4118.1 (18)H12A—C12—H12B108.2
C15—N4—H4113.8 (18)O3—C13—C14108.6 (2)
C6—C1—C2118.7 (2)O3—C13—H13A110.0
C6—C1—C7123.7 (2)C14—C13—H13A110.0
C2—C1—C7117.6 (2)O3—C13—H13B110.0
C3—C2—C1120.8 (3)C14—C13—H13B110.0
C3—C2—H2A119.6H13A—C13—H13B108.4
C1—C2—H2A119.6N3—C14—C13111.0 (2)
C2—C3—C4119.8 (3)N3—C14—H14A109.4
C2—C3—H3A120.1C13—C14—H14A109.4
C4—C3—H3A120.1N3—C14—H14B109.4
C5—C4—C3119.9 (3)C13—C14—H14B109.4
C5—C4—H4A120.0H14A—C14—H14B108.0
C3—C4—H4A120.0N3—C15—N4116.7 (2)
C4—C5—C6120.5 (3)N3—C15—S2124.06 (19)
C4—C5—H5119.7N4—C15—S2119.18 (18)
C6—C5—H5119.7O4—C16—N4121.1 (2)
C5—C6—C1120.2 (3)O4—C16—C17121.1 (2)
C5—C6—H6119.9N4—C16—C17117.8 (2)
C1—C6—H6119.9C22—C17—C18119.0 (2)
O1—C7—N1121.3 (2)C22—C17—C16124.1 (2)
O1—C7—C1121.7 (2)C18—C17—C16116.9 (2)
N1—C7—C1117.0 (2)C19—C18—C17120.5 (3)
N2—C8—N1116.1 (2)C19—C18—H18119.8
N2—C8—S1125.2 (2)C17—C18—H18119.8
N1—C8—S1118.66 (18)C20—C19—C18120.4 (2)
N2—C9—C10110.6 (2)C20—C19—H19119.8
N2—C9—H9A109.5C18—C19—H19119.8
C10—C9—H9A109.5C19—C20—C21120.1 (3)
N2—C9—H9B109.5C19—C20—H20120.0
C10—C9—H9B109.5C21—C20—H20120.0
H9A—C9—H9B108.1C20—C21—C22119.7 (3)
O2—C10—C9107.14 (19)C20—C21—H21120.1
O2—C10—H10A110.3C22—C21—H21120.1
C9—C10—H10A110.3C17—C22—C21120.3 (2)
O2—C10—H10B110.3C17—C22—H22119.8
C9—C10—H10B110.3C21—C22—H22119.8
O2—C11—C12—O365.0 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···O10.82 (3)1.99 (3)2.648 (3)136 (2)
N3—H3···O40.83 (3)2.01 (3)2.632 (3)132 (3)
N4—H4···O2i0.82 (3)2.48 (3)3.290 (3)170 (2)

Symmetry codes: (i) −x+2, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2217).

References

  • Arslan, H., Flörke, U. & Külcü, N. (2004). Acta Chim. Slov.51, 787–792.
  • Avşar, G., Arslan, H., Haupt, H.-J. & Külcü, N. (2003). Turk. J. Chem.27, 281–285.
  • Ding, Y.-J., Chang, X.-B., Yang, X.-Q. & Dong, W.-K. (2008). Acta Cryst. E64, o658. [PMC free article] [PubMed]
  • Du, H.-T. & Du, H.-J. (2008). Acta Cryst. E64, o1632–o1633. [PMC free article] [PubMed]
  • Nonius (1998). COLLECT Nonius BV, Delft, The Netherlands.
  • Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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