Diethyl 5,5'-thio-bis[2-amino-4-(4-fluoro-phen-yl)-1-phenyl-1H-pyrrole-3-carboxyl-ate].

In the title compound, C(38)H(32)F(2)N(4)O(4)S, the ethyl chain of the ethoxy-carbonyl 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 intra-molecular hydrogen bonds in the crystal structure. An intra-molecular N-H⋯O hydrogen bond forms a six-membered ring, while an inter-molecular N-H⋯F hydrogen bond results in a chain.

Related literature

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

Experimental

Crystal data

C38H32F2N4O4S

M = 678.74

Monoclinic,

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

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

C38H32F2N4O4S	F000 = 1416
Mr = 678.74	Dx = 1.353 Mg m−3
Monoclinic, C2/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1735 reflections
a = 12.158 (3) Å	θ = 2.6–21.3º
b = 19.160 (4) Å	µ = 0.16 mm−1
c = 14.958 (3) Å	T = 294 (2) K
β = 106.944 (4)º	Prism, yellow
V = 3333.0 (13) Å3	0.20 × 0.18 × 0.18 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	2942 independent reflections
Radiation source: fine-focus sealed tube	1645 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.045
T = 294(2) K	θmax = 25.0º
phi and ω scans	θmin = 2.1º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −14→8
Tmin = 0.970, Tmax = 0.973	k = −22→21
8487 measured reflections	l = −17→17

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047	H-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 reflections	Δρmax = 0.23 e Å−3
241 parameters	Δρmin = −0.16 e Å−3
31 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.0000	0.02157 (5)	0.2500	0.0518 (3)
F1	0.41195 (19)	−0.13211 (10)	0.15342 (15)	0.1094 (7)
O1	0.0803 (2)	0.21900 (12)	−0.06429 (16)	0.0943 (8)
O2	0.1802 (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	−0.1284	0.2575	0.0614	0.086*
H2B	−0.0521	0.2595	−0.0014	0.086*
C1	0.2891 (3)	0.04044 (15)	0.13523 (18)	0.0581 (8)
H1	0.3128	0.0867	0.1378	0.070*
C2	0.3696 (3)	−0.01205 (18)	0.14655 (19)	0.0669 (9)
H2	0.4470	−0.0017	0.1566	0.080*
C3	0.3327 (3)	−0.08003 (18)	0.1426 (2)	0.0680 (9)
C4	0.2211 (3)	−0.09736 (16)	0.1275 (2)	0.0687 (9)
H4	0.1986	−0.1439	0.1249	0.082*
C5	0.1410 (3)	−0.04417 (14)	0.11607 (17)	0.0555 (8)
H5	0.0638	−0.0554	0.1055	0.067*
C6	0.1734 (2)	0.02548 (14)	0.12005 (16)	0.0458 (7)
C7	0.0855 (2)	0.07966 (13)	0.11175 (17)	0.0460 (7)
C8	0.0077 (2)	0.07882 (13)	0.16089 (17)	0.0455 (7)
C9	−0.0292 (3)	0.17553 (14)	0.07162 (18)	0.0532 (8)
C10	0.0626 (3)	0.14193 (14)	0.05373 (18)	0.0518 (7)
C11	0.1072 (3)	0.16536 (19)	−0.0206 (2)	0.0672 (9)
C12	0.2371 (9)	0.1505 (5)	−0.1060 (7)	0.079 (3)	0.588 (14)
H12A	0.2721	0.1950	−0.0832	0.094*	0.588 (14)
H12B	0.1829	0.1570	−0.1674	0.094*	0.588 (14)
C13	0.3270 (9)	0.0970 (6)	−0.1087 (6)	0.095 (3)	0.588 (14)
H13A	0.3698	0.1129	−0.1496	0.142*	0.588 (14)
H13B	0.2903	0.0535	−0.1312	0.142*	0.588 (14)
H13C	0.3783	0.0907	−0.0469	0.142*	0.588 (14)
C12'	0.2111 (9)	0.1190 (9)	−0.1291 (6)	0.080 (4)	0.412 (14)
H12C	0.1642	0.1513	−0.1743	0.095*	0.412 (14)
H12D	0.2047	0.0727	−0.1563	0.095*	0.412 (14)
C13'	0.3355 (12)	0.1429 (10)	−0.0939 (9)	0.113 (5)	0.412 (14)
H13D	0.3671	0.1462	−0.1456	0.170*	0.412 (14)
H13E	0.3791	0.1099	−0.0493	0.170*	0.412 (14)
H13F	0.3388	0.1878	−0.0648	0.170*	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	−0.2425	0.0621	0.0690	0.083*
C16	−0.3690 (3)	0.1044 (2)	0.1128 (2)	0.0853 (11)
H16	−0.4256	0.0726	0.0827	0.102*
C17	−0.3948 (4)	0.1564 (3)	0.1640 (3)	0.0874 (12)
H17	−0.4694	0.1605	0.1682	0.105*
C18	−0.3129 (4)	0.2029 (2)	0.2097 (3)	0.0886 (12)
H18	−0.3316	0.2384	0.2452	0.106*
C19	−0.2004 (3)	0.19735 (16)	0.2033 (2)	0.0741 (10)
H19	−0.1438	0.2287	0.2345	0.089*

	U11	U22	U33	U12	U13	U23
S1	0.0657 (8)	0.0467 (6)	0.0470 (6)	0.000	0.0226 (5)	0.000
F1	0.1062 (17)	0.0986 (14)	0.1301 (17)	0.0439 (14)	0.0450 (15)	0.0001 (13)
O1	0.110 (2)	0.0893 (16)	0.0968 (17)	0.0169 (15)	0.0499 (16)	0.0455 (14)
O2	0.0972 (19)	0.1199 (19)	0.0773 (15)	0.0303 (16)	0.0551 (15)	0.0414 (14)
N1	0.0517 (15)	0.0512 (13)	0.0475 (13)	0.0019 (12)	0.0175 (12)	0.0028 (11)
N2	0.091 (2)	0.0552 (15)	0.0735 (16)	0.0113 (15)	0.0327 (16)	0.0166 (13)
C1	0.059 (2)	0.0615 (18)	0.0543 (18)	−0.0052 (18)	0.0178 (16)	−0.0033 (14)
C2	0.052 (2)	0.089 (2)	0.061 (2)	0.005 (2)	0.0178 (17)	0.0000 (18)
C3	0.076 (3)	0.070 (2)	0.061 (2)	0.026 (2)	0.0260 (19)	−0.0023 (17)
C4	0.085 (3)	0.0581 (19)	0.068 (2)	0.000 (2)	0.031 (2)	−0.0103 (16)
C5	0.059 (2)	0.0592 (19)	0.0512 (17)	−0.0006 (17)	0.0206 (15)	−0.0082 (14)
C6	0.0503 (18)	0.0531 (17)	0.0353 (14)	−0.0031 (15)	0.0147 (13)	−0.0013 (12)
C7	0.0507 (18)	0.0471 (16)	0.0380 (14)	−0.0035 (14)	0.0094 (13)	−0.0042 (12)
C8	0.0503 (18)	0.0468 (15)	0.0399 (15)	0.0003 (14)	0.0139 (14)	−0.0007 (12)
C9	0.066 (2)	0.0473 (16)	0.0453 (16)	−0.0019 (16)	0.0141 (16)	0.0030 (13)
C10	0.061 (2)	0.0505 (16)	0.0451 (16)	−0.0028 (15)	0.0181 (15)	0.0061 (13)
C11	0.063 (2)	0.078 (2)	0.062 (2)	−0.0014 (19)	0.0203 (18)	0.0137 (18)
C12	0.086 (6)	0.093 (6)	0.068 (5)	−0.005 (5)	0.039 (4)	0.013 (4)
C13	0.098 (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)
C14	0.063 (2)	0.0549 (17)	0.0414 (15)	0.0123 (16)	0.0187 (15)	0.0105 (14)
C15	0.070 (2)	0.078 (2)	0.062 (2)	−0.007 (2)	0.0243 (19)	0.0014 (17)
C16	0.068 (3)	0.110 (3)	0.079 (3)	−0.006 (2)	0.025 (2)	0.015 (2)
C17	0.072 (3)	0.114 (3)	0.083 (3)	0.023 (3)	0.032 (2)	0.036 (2)
C18	0.105 (3)	0.091 (3)	0.080 (3)	0.050 (3)	0.043 (3)	0.019 (2)
C19	0.084 (3)	0.072 (2)	0.065 (2)	0.022 (2)	0.020 (2)	−0.0003 (17)

S1—C8	1.750 (2)	C9—C10	1.380 (4)
S1—C8i	1.750 (2)	C10—C11	1.443 (4)
F1—C3	1.363 (3)	C12—C13	1.507 (8)
O1—C11	1.211 (3)	C12—H12A	0.9700
O2—C11	1.341 (4)	C12—H12B	0.9700
O2—C12	1.484 (6)	C13—H13A	0.9600
O2—C12'	1.485 (8)	C13—H13B	0.9600
N1—C9	1.370 (3)	C13—H13C	0.9600
N1—C8	1.409 (3)	C12'—C13'	1.520 (9)
N1—C14	1.438 (3)	C12'—H12C	0.9700
N2—C9	1.368 (3)	C12'—H12D	0.9700
N2—H2A	0.8989	C13'—H13D	0.9600
N2—H2B	0.8954	C13'—H13E	0.9600
C1—C2	1.379 (4)	C13'—H13F	0.9600
C1—C6	1.388 (4)	C14—C19	1.375 (4)
C1—H1	0.9300	C14—C15	1.378 (4)
C2—C3	1.373 (4)	C15—C16	1.375 (4)
C2—H2	0.9300	C15—H15	0.9300
C3—C4	1.350 (4)	C16—C17	1.349 (5)
C4—C5	1.385 (4)	C16—H16	0.9300
C4—H4	0.9300	C17—C18	1.363 (5)
C5—C6	1.388 (4)	C17—H17	0.9300
C5—H5	0.9300	C18—C19	1.403 (5)
C6—C7	1.469 (4)	C18—H18	0.9300
C7—C8	1.356 (3)	C19—H19	0.9300
C7—C10	1.454 (3)
C8—S1—C8i	102.35 (16)	O2—C12—C13	103.1 (6)
C11—O2—C12	110.3 (4)	O2—C12—H12A	111.1
C11—O2—C12'	123.7 (6)	C13—C12—H12A	111.1
C12—O2—C12'	28.1 (4)	O2—C12—H12B	111.1
C9—N1—C8	108.2 (2)	C13—C12—H12B	111.1
C9—N1—C14	123.2 (2)	H12A—C12—H12B	109.1
C8—N1—C14	124.8 (2)	C12—C13—H13A	109.5
C9—N2—H2A	118.1	C12—C13—H13B	109.5
C9—N2—H2B	114.3	H13A—C13—H13B	109.5
H2A—N2—H2B	113.4	C12—C13—H13C	109.5
C2—C1—C6	121.2 (3)	H13A—C13—H13C	109.5
C2—C1—H1	119.4	H13B—C13—H13C	109.5
C6—C1—H1	119.4	O2—C12'—C13'	100.0 (9)
C3—C2—C1	118.4 (3)	O2—C12'—H12C	111.8
C3—C2—H2	120.8	C13'—C12'—H12C	111.8
C1—C2—H2	120.8	O2—C12'—H12D	111.8
C4—C3—F1	118.7 (3)	C13'—C12'—H12D	111.8
C4—C3—C2	122.7 (3)	H12C—C12'—H12D	109.5
F1—C3—C2	118.6 (3)	C12'—C13'—H13D	109.5
C3—C4—C5	118.4 (3)	C12'—C13'—H13E	109.5
C3—C4—H4	120.8	H13D—C13'—H13E	109.5
C5—C4—H4	120.8	C12'—C13'—H13F	109.5
C4—C5—C6	121.4 (3)	H13D—C13'—H13F	109.5
C4—C5—H5	119.3	H13E—C13'—H13F	109.5
C6—C5—H5	119.3	C19—C14—C15	120.4 (3)
C1—C6—C5	117.9 (3)	C19—C14—N1	121.3 (3)
C1—C6—C7	123.1 (2)	C15—C14—N1	118.3 (3)
C5—C6—C7	119.0 (3)	C16—C15—C14	119.7 (3)
C8—C7—C10	106.9 (2)	C16—C15—H15	120.1
C8—C7—C6	123.4 (2)	C14—C15—H15	120.1
C10—C7—C6	129.6 (2)	C17—C16—C15	120.5 (4)
C7—C8—N1	109.0 (2)	C17—C16—H16	119.7
C7—C8—S1	128.4 (2)	C15—C16—H16	119.7
N1—C8—S1	122.32 (19)	C16—C17—C18	120.7 (4)
N2—C9—N1	121.0 (3)	C16—C17—H17	119.6
N2—C9—C10	129.8 (3)	C18—C17—H17	119.6
N1—C9—C10	109.0 (2)	C17—C18—C19	120.0 (3)
C9—C10—C11	120.7 (3)	C17—C18—H18	120.0
C9—C10—C7	107.0 (2)	C19—C18—H18	120.0
C11—C10—C7	131.7 (3)	C14—C19—C18	118.6 (3)
O1—C11—O2	122.2 (3)	C14—C19—H19	120.7
O1—C11—C10	125.2 (3)	C18—C19—H19	120.7
O2—C11—C10	112.6 (3)
C6—C1—C2—C3	−0.1 (4)	N2—C9—C10—C7	−173.8 (3)
C1—C2—C3—C4	0.4 (5)	N1—C9—C10—C7	0.2 (3)
C1—C2—C3—F1	179.8 (3)	C8—C7—C10—C9	0.0 (3)
F1—C3—C4—C5	−179.6 (2)	C6—C7—C10—C9	180.0 (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—C11	9.0 (5)
C2—C1—C6—C5	−0.4 (4)	C12—O2—C11—O1	11.3 (7)
C2—C1—C6—C7	177.2 (2)	C12'—O2—C11—O1	−16.7 (7)
C4—C5—C6—C1	0.5 (4)	C12—O2—C11—C10	−171.2 (6)
C4—C5—C6—C7	−177.2 (2)	C12'—O2—C11—C10	160.8 (6)
C1—C6—C7—C8	−129.7 (3)	C9—C10—C11—O1	9.6 (5)
C5—C6—C7—C8	47.9 (3)	C7—C10—C11—O1	179.6 (3)
C1—C6—C7—C10	50.3 (4)	C9—C10—C11—O2	−167.8 (3)
C5—C6—C7—C10	−132.1 (3)	C7—C10—C11—O2	2.2 (5)
C10—C7—C8—N1	−0.2 (3)	C11—O2—C12—C13	171.9 (9)
C6—C7—C8—N1	179.8 (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—S1	6.5 (4)	C12—O2—C12'—C13'	41.5 (12)
C9—N1—C8—C7	0.4 (3)	C9—N1—C14—C19	−82.7 (3)
C14—N1—C8—C7	159.1 (2)	C8—N1—C14—C19	121.7 (3)
C9—N1—C8—S1	174.16 (19)	C9—N1—C14—C15	95.3 (3)
C14—N1—C8—S1	−27.2 (3)	C8—N1—C14—C15	−60.3 (3)
C8i—S1—C8—C7	128.1 (3)	C19—C14—C15—C16	0.5 (4)
C8i—S1—C8—N1	−44.36 (16)	N1—C14—C15—C16	−177.5 (3)
C8—N1—C9—N2	174.3 (2)	C14—C15—C16—C17	0.4 (5)
C14—N1—C9—N2	15.2 (4)	C15—C16—C17—C18	−0.8 (5)
C8—N1—C9—C10	−0.4 (3)	C16—C17—C18—C19	0.4 (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—C18	177.0 (3)
N1—C9—C10—C11	172.5 (2)	C17—C18—C19—C14	0.4 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···F1ii	0.90	2.49	3.181 (3)	134
N2—H2B···O1	0.90	2.23	2.825 (3)	124

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯F1ii	0.90	2.49	3.181 (3)	134
N2—H2B⋯O1	0.90	2.23	2.825 (3)	124

Symmetry code: (ii) .