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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o21.
Published online 2007 December 6. doi:  10.1107/S1600536807061545
PMCID: PMC2914983

Diethyl 5,5′-thio­bis[2-amino-4-(4-fluoro­phen­yl)-1-phenyl-1H-pyrrole-3-carboxyl­ate]

Abstract

In the title compound, C38H32F2N4O4S, the ethyl chain of the ethoxy­carbonyl group displays rotational disorder with site occupancy factors ca 0.6 and 0.4. The S atom lies on a twofold rotation axis. There are both inter- and intra­molecular hydrogen bonds in the crystal structure. An intra­molecular N—H(...)O hydrogen bond forms a six-membered ring, while an inter­molecular N—H(...)F hydrogen bond results in a chain.

Related literature

For related literature, see: Yin & Pidgeon (1997 [triangle]); Herradura et al. (2000 [triangle]); Baumgarten & Tyutyulkov (1998 [triangle]); Barton & Ollis (1979 [triangle]).

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Object name is e-64-00o21-scheme1.jpg

Experimental

Crystal data

  • C38H32F2N4O4S
  • M r = 678.74
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-00o21-efi1.jpg
  • a = 12.158 (3) Å
  • b = 19.160 (4) Å
  • c = 14.958 (3) Å
  • β = 106.944 (4)°
  • V = 3333.0 (13) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.16 mm−1
  • T = 294 (2) K
  • 0.20 × 0.18 × 0.18 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.970, T max = 0.973
  • 8487 measured reflections
  • 2942 independent reflections
  • 1645 reflections with I > 2σ(I)
  • R int = 0.045

Refinement

  • R[F 2 > 2σ(F 2)] = 0.047
  • wR(F 2) = 0.135
  • S = 1.08
  • 2942 reflections
  • 241 parameters
  • 31 restraints
  • H-atom parameters constrained
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 1999 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL (Bruker, 1999 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807061545/at2503sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807061545/at2503Isup2.hkl

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

Acknowledgments

This project was supported by the National Science Found­ation of China (No. 20572057), the Natural Science Foundation of Shandong Province (Y2006B11) and the Doctoral Foundation of Qingdao University of Science and Technology.

supplementary crystallographic information

Comment

Organic sulfides represent important building blocks in organic and medicinal chemistry (Barton et al., 1979) due to their diverse biological and pharmacological properties (Herradura et al., 2000). Because of their synthetic and biological potential, considerable interest has been focused on the synthesis of organic sulfides (Yin et al., 1997). In addition, polysubstituted pyrroles are molecular frameworks having immense importance in material science (Baumgarten et al., 1998). In order to develop new biological activities, we synthesized the title compound, (I) (Fig.1), the structure of which is reported here.

The title compound adopts a V conformation, which contains two parts which are same to each other, and each part comprises three rings, two phenyl rings and one pyrrole ring. In each part, the two phenyl rings are not conjugated with the pyrrole ring, with the dihedral angle of 49.07° and 73.04°, respectively.

All the bond lengths and angles (Table 1) in the title compound are within the normal range. The bond lengths of C7—C8 (1.356 Å) and C9—C10 (1.380 Å) in the pyrrole ring is obviously shorter than C—C (1.52 Å) but are close to normal C?C (1.32 Å), it is indicated that they are both C?C. The bond length of C7—C10 (1.454 Å) is between C—C and C?C.

X-ray analysis reveals that there exists both intermolecular hydrogen and intromolecular hydrogen bonds in the crystal structure (Fig. 2). The intromolecular N2—H2B···O1 hydrogen bond forms a six-membered ring, while the intermolecular N2—H2A···F1 hydrogen bond makes the molecule extended in line.

Experimental

A mixture of 2-(4-fluorophenyl)-2-oxo-N-phenylethanethioamide (3 mmol, 0.819 g), ethyl 2-cyanoacetate (3 mmol, 0.339 g), 10% NaOH solution (0.5 ml), and 15 ml e thanol in a 25 ml flask was stirred for 3 h at room temperature (monitored by TLC). The yellow solid was got by filtering. And then the solid was added to a stirred solution of acetic acid (1 ml) in ethanol (15 ml) at 313 K under MW for 30 min. After cooling to room temperature, the solid product was then got by filtering. The pure product was purified by recrystallization from ethanol (m.p. 498 K).

Refinement

All H atoms were placed in calculated positions, with C—H distances in the range 0.93 - 0.97 Å, and N—H = 0.90 Å and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2 or 1.5Ueq(C,N). The ethyl chain of the ethoxycarbonyl group displays rotational disorder. The site-occupation factors of the disordered atoms C12, C13 and C12', C13' refined to 0.588 (14) and 0.412 (146), respectively.

Figures

Fig. 1.
View of the title compound with 35% probability ellipsoid. Both disordered components are shown.
Fig. 2.
The packing of the title compound viewed along the c axis. Hydrogen bonds are shown as dashed lines.

Crystal data

C38H32F2N4O4SF000 = 1416
Mr = 678.74Dx = 1.353 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1735 reflections
a = 12.158 (3) Åθ = 2.6–21.3º
b = 19.160 (4) ŵ = 0.16 mm1
c = 14.958 (3) ÅT = 294 (2) K
β = 106.944 (4)ºPrism, yellow
V = 3333.0 (13) Å30.20 × 0.18 × 0.18 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer2942 independent reflections
Radiation source: fine-focus sealed tube1645 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.045
T = 294(2) Kθmax = 25.0º
phi and ω scansθmin = 2.1º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −14→8
Tmin = 0.970, Tmax = 0.973k = −22→21
8487 measured reflectionsl = −17→17

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.135  w = 1/[σ2(Fo2) + (0.060P)2] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
2942 reflectionsΔρmax = 0.23 e Å3
241 parametersΔρmin = −0.16 e Å3
31 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

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 (Å2)

xyzUiso*/UeqOcc. (<1)
S10.00000.02157 (5)0.25000.0518 (3)
F10.41195 (19)−0.13211 (10)0.15342 (15)0.1094 (7)
O10.0803 (2)0.21900 (12)−0.06429 (16)0.0943 (8)
O20.1802 (2)0.11943 (13)−0.04003 (15)0.0918 (8)
N1−0.0635 (2)0.13810 (11)0.13685 (14)0.0495 (6)
N2−0.0895 (2)0.23284 (12)0.02943 (17)0.0715 (8)
H2A−0.12840.25750.06140.086*
H2B−0.05210.2595−0.00140.086*
C10.2891 (3)0.04044 (15)0.13523 (18)0.0581 (8)
H10.31280.08670.13780.070*
C20.3696 (3)−0.01205 (18)0.14655 (19)0.0669 (9)
H20.4470−0.00170.15660.080*
C30.3327 (3)−0.08003 (18)0.1426 (2)0.0680 (9)
C40.2211 (3)−0.09736 (16)0.1275 (2)0.0687 (9)
H40.1986−0.14390.12490.082*
C50.1410 (3)−0.04417 (14)0.11607 (17)0.0555 (8)
H50.0638−0.05540.10550.067*
C60.1734 (2)0.02548 (14)0.12005 (16)0.0458 (7)
C70.0855 (2)0.07966 (13)0.11175 (17)0.0460 (7)
C80.0077 (2)0.07882 (13)0.16089 (17)0.0455 (7)
C9−0.0292 (3)0.17553 (14)0.07162 (18)0.0532 (8)
C100.0626 (3)0.14193 (14)0.05373 (18)0.0518 (7)
C110.1072 (3)0.16536 (19)−0.0206 (2)0.0672 (9)
C120.2371 (9)0.1505 (5)−0.1060 (7)0.079 (3)0.588 (14)
H12A0.27210.1950−0.08320.094*0.588 (14)
H12B0.18290.1570−0.16740.094*0.588 (14)
C130.3270 (9)0.0970 (6)−0.1087 (6)0.095 (3)0.588 (14)
H13A0.36980.1129−0.14960.142*0.588 (14)
H13B0.29030.0535−0.13120.142*0.588 (14)
H13C0.37830.0907−0.04690.142*0.588 (14)
C12'0.2111 (9)0.1190 (9)−0.1291 (6)0.080 (4)0.412 (14)
H12C0.16420.1513−0.17430.095*0.412 (14)
H12D0.20470.0727−0.15630.095*0.412 (14)
C13'0.3355 (12)0.1429 (10)−0.0939 (9)0.113 (5)0.412 (14)
H13D0.36710.1462−0.14560.170*0.412 (14)
H13E0.37910.1099−0.04930.170*0.412 (14)
H13F0.33880.1878−0.06480.170*0.412 (14)
C14−0.1757 (3)0.14464 (15)0.14982 (18)0.0524 (7)
C15−0.2597 (3)0.09787 (17)0.1047 (2)0.0688 (9)
H15−0.24250.06210.06900.083*
C16−0.3690 (3)0.1044 (2)0.1128 (2)0.0853 (11)
H16−0.42560.07260.08270.102*
C17−0.3948 (4)0.1564 (3)0.1640 (3)0.0874 (12)
H17−0.46940.16050.16820.105*
C18−0.3129 (4)0.2029 (2)0.2097 (3)0.0886 (12)
H18−0.33160.23840.24520.106*
C19−0.2004 (3)0.19735 (16)0.2033 (2)0.0741 (10)
H19−0.14380.22870.23450.089*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0657 (8)0.0467 (6)0.0470 (6)0.0000.0226 (5)0.000
F10.1062 (17)0.0986 (14)0.1301 (17)0.0439 (14)0.0450 (15)0.0001 (13)
O10.110 (2)0.0893 (16)0.0968 (17)0.0169 (15)0.0499 (16)0.0455 (14)
O20.0972 (19)0.1199 (19)0.0773 (15)0.0303 (16)0.0551 (15)0.0414 (14)
N10.0517 (15)0.0512 (13)0.0475 (13)0.0019 (12)0.0175 (12)0.0028 (11)
N20.091 (2)0.0552 (15)0.0735 (16)0.0113 (15)0.0327 (16)0.0166 (13)
C10.059 (2)0.0615 (18)0.0543 (18)−0.0052 (18)0.0178 (16)−0.0033 (14)
C20.052 (2)0.089 (2)0.061 (2)0.005 (2)0.0178 (17)0.0000 (18)
C30.076 (3)0.070 (2)0.061 (2)0.026 (2)0.0260 (19)−0.0023 (17)
C40.085 (3)0.0581 (19)0.068 (2)0.000 (2)0.031 (2)−0.0103 (16)
C50.059 (2)0.0592 (19)0.0512 (17)−0.0006 (17)0.0206 (15)−0.0082 (14)
C60.0503 (18)0.0531 (17)0.0353 (14)−0.0031 (15)0.0147 (13)−0.0013 (12)
C70.0507 (18)0.0471 (16)0.0380 (14)−0.0035 (14)0.0094 (13)−0.0042 (12)
C80.0503 (18)0.0468 (15)0.0399 (15)0.0003 (14)0.0139 (14)−0.0007 (12)
C90.066 (2)0.0473 (16)0.0453 (16)−0.0019 (16)0.0141 (16)0.0030 (13)
C100.061 (2)0.0505 (16)0.0451 (16)−0.0028 (15)0.0181 (15)0.0061 (13)
C110.063 (2)0.078 (2)0.062 (2)−0.0014 (19)0.0203 (18)0.0137 (18)
C120.086 (6)0.093 (6)0.068 (5)−0.005 (5)0.039 (4)0.013 (4)
C130.098 (6)0.118 (6)0.089 (5)0.016 (5)0.059 (4)0.013 (4)
C12'0.097 (7)0.081 (7)0.073 (6)−0.022 (6)0.044 (5)0.008 (5)
C13'0.101 (8)0.126 (9)0.121 (8)−0.026 (7)0.046 (6)−0.009 (7)
C140.063 (2)0.0549 (17)0.0414 (15)0.0123 (16)0.0187 (15)0.0105 (14)
C150.070 (2)0.078 (2)0.062 (2)−0.007 (2)0.0243 (19)0.0014 (17)
C160.068 (3)0.110 (3)0.079 (3)−0.006 (2)0.025 (2)0.015 (2)
C170.072 (3)0.114 (3)0.083 (3)0.023 (3)0.032 (2)0.036 (2)
C180.105 (3)0.091 (3)0.080 (3)0.050 (3)0.043 (3)0.019 (2)
C190.084 (3)0.072 (2)0.065 (2)0.022 (2)0.020 (2)−0.0003 (17)

Geometric parameters (Å, °)

S1—C81.750 (2)C9—C101.380 (4)
S1—C8i1.750 (2)C10—C111.443 (4)
F1—C31.363 (3)C12—C131.507 (8)
O1—C111.211 (3)C12—H12A0.9700
O2—C111.341 (4)C12—H12B0.9700
O2—C121.484 (6)C13—H13A0.9600
O2—C12'1.485 (8)C13—H13B0.9600
N1—C91.370 (3)C13—H13C0.9600
N1—C81.409 (3)C12'—C13'1.520 (9)
N1—C141.438 (3)C12'—H12C0.9700
N2—C91.368 (3)C12'—H12D0.9700
N2—H2A0.8989C13'—H13D0.9600
N2—H2B0.8954C13'—H13E0.9600
C1—C21.379 (4)C13'—H13F0.9600
C1—C61.388 (4)C14—C191.375 (4)
C1—H10.9300C14—C151.378 (4)
C2—C31.373 (4)C15—C161.375 (4)
C2—H20.9300C15—H150.9300
C3—C41.350 (4)C16—C171.349 (5)
C4—C51.385 (4)C16—H160.9300
C4—H40.9300C17—C181.363 (5)
C5—C61.388 (4)C17—H170.9300
C5—H50.9300C18—C191.403 (5)
C6—C71.469 (4)C18—H180.9300
C7—C81.356 (3)C19—H190.9300
C7—C101.454 (3)
C8—S1—C8i102.35 (16)O2—C12—C13103.1 (6)
C11—O2—C12110.3 (4)O2—C12—H12A111.1
C11—O2—C12'123.7 (6)C13—C12—H12A111.1
C12—O2—C12'28.1 (4)O2—C12—H12B111.1
C9—N1—C8108.2 (2)C13—C12—H12B111.1
C9—N1—C14123.2 (2)H12A—C12—H12B109.1
C8—N1—C14124.8 (2)C12—C13—H13A109.5
C9—N2—H2A118.1C12—C13—H13B109.5
C9—N2—H2B114.3H13A—C13—H13B109.5
H2A—N2—H2B113.4C12—C13—H13C109.5
C2—C1—C6121.2 (3)H13A—C13—H13C109.5
C2—C1—H1119.4H13B—C13—H13C109.5
C6—C1—H1119.4O2—C12'—C13'100.0 (9)
C3—C2—C1118.4 (3)O2—C12'—H12C111.8
C3—C2—H2120.8C13'—C12'—H12C111.8
C1—C2—H2120.8O2—C12'—H12D111.8
C4—C3—F1118.7 (3)C13'—C12'—H12D111.8
C4—C3—C2122.7 (3)H12C—C12'—H12D109.5
F1—C3—C2118.6 (3)C12'—C13'—H13D109.5
C3—C4—C5118.4 (3)C12'—C13'—H13E109.5
C3—C4—H4120.8H13D—C13'—H13E109.5
C5—C4—H4120.8C12'—C13'—H13F109.5
C4—C5—C6121.4 (3)H13D—C13'—H13F109.5
C4—C5—H5119.3H13E—C13'—H13F109.5
C6—C5—H5119.3C19—C14—C15120.4 (3)
C1—C6—C5117.9 (3)C19—C14—N1121.3 (3)
C1—C6—C7123.1 (2)C15—C14—N1118.3 (3)
C5—C6—C7119.0 (3)C16—C15—C14119.7 (3)
C8—C7—C10106.9 (2)C16—C15—H15120.1
C8—C7—C6123.4 (2)C14—C15—H15120.1
C10—C7—C6129.6 (2)C17—C16—C15120.5 (4)
C7—C8—N1109.0 (2)C17—C16—H16119.7
C7—C8—S1128.4 (2)C15—C16—H16119.7
N1—C8—S1122.32 (19)C16—C17—C18120.7 (4)
N2—C9—N1121.0 (3)C16—C17—H17119.6
N2—C9—C10129.8 (3)C18—C17—H17119.6
N1—C9—C10109.0 (2)C17—C18—C19120.0 (3)
C9—C10—C11120.7 (3)C17—C18—H18120.0
C9—C10—C7107.0 (2)C19—C18—H18120.0
C11—C10—C7131.7 (3)C14—C19—C18118.6 (3)
O1—C11—O2122.2 (3)C14—C19—H19120.7
O1—C11—C10125.2 (3)C18—C19—H19120.7
O2—C11—C10112.6 (3)
C6—C1—C2—C3−0.1 (4)N2—C9—C10—C7−173.8 (3)
C1—C2—C3—C40.4 (5)N1—C9—C10—C70.2 (3)
C1—C2—C3—F1179.8 (3)C8—C7—C10—C90.0 (3)
F1—C3—C4—C5−179.6 (2)C6—C7—C10—C9180.0 (3)
C2—C3—C4—C5−0.3 (5)C8—C7—C10—C11−171.0 (3)
C3—C4—C5—C6−0.2 (4)C6—C7—C10—C119.0 (5)
C2—C1—C6—C5−0.4 (4)C12—O2—C11—O111.3 (7)
C2—C1—C6—C7177.2 (2)C12'—O2—C11—O1−16.7 (7)
C4—C5—C6—C10.5 (4)C12—O2—C11—C10−171.2 (6)
C4—C5—C6—C7−177.2 (2)C12'—O2—C11—C10160.8 (6)
C1—C6—C7—C8−129.7 (3)C9—C10—C11—O19.6 (5)
C5—C6—C7—C847.9 (3)C7—C10—C11—O1179.6 (3)
C1—C6—C7—C1050.3 (4)C9—C10—C11—O2−167.8 (3)
C5—C6—C7—C10−132.1 (3)C7—C10—C11—O22.2 (5)
C10—C7—C8—N1−0.2 (3)C11—O2—C12—C13171.9 (9)
C6—C7—C8—N1179.8 (2)C12'—O2—C12—C13−63.9 (13)
C10—C7—C8—S1−173.5 (2)C11—O2—C12'—C13'110.4 (13)
C6—C7—C8—S16.5 (4)C12—O2—C12'—C13'41.5 (12)
C9—N1—C8—C70.4 (3)C9—N1—C14—C19−82.7 (3)
C14—N1—C8—C7159.1 (2)C8—N1—C14—C19121.7 (3)
C9—N1—C8—S1174.16 (19)C9—N1—C14—C1595.3 (3)
C14—N1—C8—S1−27.2 (3)C8—N1—C14—C15−60.3 (3)
C8i—S1—C8—C7128.1 (3)C19—C14—C15—C160.5 (4)
C8i—S1—C8—N1−44.36 (16)N1—C14—C15—C16−177.5 (3)
C8—N1—C9—N2174.3 (2)C14—C15—C16—C170.4 (5)
C14—N1—C9—N215.2 (4)C15—C16—C17—C18−0.8 (5)
C8—N1—C9—C10−0.4 (3)C16—C17—C18—C190.4 (5)
C14—N1—C9—C10−159.5 (2)C15—C14—C19—C18−0.9 (4)
N2—C9—C10—C11−1.6 (5)N1—C14—C19—C18177.0 (3)
N1—C9—C10—C11172.5 (2)C17—C18—C19—C140.4 (5)

Symmetry codes: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···F1ii0.902.493.181 (3)134
N2—H2B···O10.902.232.825 (3)124

Symmetry codes: (ii) x−1/2, y+1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2503).

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