Diethyl 2,5-bis-[(1E)-(1H-pyrrol-2-yl-methyl-idene)amino]-thio-phene-3,4-dicarboxyl-ate.

In the crystal structure of the title compound, C(20)H(20)N(4)O(4)S, the azomethine group adopt E conformations. The pyrrole units are twisted by 10.31 (4) and 18.90 (5)° with respect to the central thio-phene ring. The three-dimensional network is close packed and involves N-H⋯O, N-H⋯N, C-H⋯N and C-H⋯O hydrogen bonding.

Related literature

For general background, see: Dufresne et al. (2007 ▶, 2011 ▶). For thio­phene azomethines, see: Dufresne et al. (2006 ▶, 2010a ▶,b ▶). For alkene comparison, see: Ruban et al. (1975 ▶); Zobel et al. (1978 ▶).

Experimental

Crystal data

C20H20N4O4S

M = 412.46

Orthorhombic,

a = 16.898 (3) Å

b = 12.643 (3) Å

c = 9.4220 (19) Å

V = 2012.9 (7) Å3

Z = 4

Cu Kα radiation

μ = 1.73 mm−1

T = 150 K

0.10 × 0.03 × 0.03 mm

Data collection

Bruker SMART 6000 diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.841, T max = 0.947

17313 measured reflections

3040 independent reflections

3004 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.064

S = 1.04

3040 reflections

264 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.15 e Å−3

Absolute structure: Flack (1983) ▶, 1275 Friedel pairs

Flack parameter: 0.085 (12)

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: UdMX (Marris, 2004 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811031576/zq2118sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811031576/zq2118Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811031576/zq2118Isup3.cml

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

C20H20N4O4S	Dx = 1.361 Mg m−3
Mr = 412.46	Melting point: 483(2) K
Orthorhombic, Pna21	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2c -2n	Cell parameters from 4515 reflections
a = 16.898 (3) Å	θ = 4.4–70.6°
b = 12.643 (3) Å	µ = 1.73 mm−1
c = 9.4220 (19) Å	T = 150 K
V = 2012.9 (7) Å3	Block, orange
Z = 4	0.10 × 0.03 × 0.03 mm
F(000) = 864

Bruker SMART 6000 diffractometer	3040 independent reflections
Radiation source: Rotating Anode	3004 reflections with I > 2σ(I)
Montel 200 optics	Rint = 0.028
Detector resolution: 5.5 pixels mm-1	θmax = 66.6°, θmin = 4.4°
ω scans	h = −19→19
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −14→14
Tmin = 0.841, Tmax = 0.947	l = −9→10
17313 measured reflections

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)] = 0.024	H-atom parameters constrained
wR(F2) = 0.064	w = 1/[σ2(Fo2) + (0.0475P)2 + 0.2939P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
3040 reflections	Δρmax = 0.19 e Å−3
264 parameters	Δρmin = −0.15 e Å−3
1 restraint	Absolute structure: Flack (1983), 1275 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.085 (12)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
S1	0.025121 (19)	0.93934 (3)	0.61244 (5)	0.01883 (11)
O1	0.19929 (6)	0.77328 (9)	0.93257 (16)	0.0238 (3)
O2	0.08597 (7)	0.76090 (9)	1.05985 (15)	0.0233 (3)
O3	−0.07216 (7)	0.66172 (8)	0.89456 (15)	0.0223 (3)
O4	−0.08363 (6)	0.80055 (8)	1.04346 (14)	0.0199 (3)
N1	0.34790 (7)	0.92360 (10)	0.62911 (19)	0.0211 (3)
H100	0.3404	0.8921	0.7113	0.025*
N2	0.18309 (7)	0.90938 (10)	0.69168 (16)	0.0176 (3)
N3	−0.12532 (7)	0.86607 (10)	0.69517 (18)	0.0186 (3)
N4	−0.29025 (7)	0.83824 (9)	0.63130 (17)	0.0176 (3)
H400	−0.2741	0.7876	0.6885	0.021*
C1	0.41958 (10)	0.94223 (13)	0.5679 (2)	0.0274 (5)
H1	0.4695	0.9235	0.6069	0.033*
C2	0.40779 (9)	0.99277 (13)	0.4398 (2)	0.0255 (4)
H2	0.4476	1.0149	0.3751	0.031*
C3	0.32546 (9)	1.00526 (12)	0.4233 (2)	0.0237 (4)
H3	0.2996	1.0376	0.3449	0.028*
C4	0.28871 (9)	0.96205 (12)	0.54149 (19)	0.0180 (4)
C5	0.20611 (9)	0.95575 (11)	0.5762 (2)	0.0188 (4)
H5	0.1680	0.9858	0.5139	0.023*
C6	0.10367 (9)	0.89476 (11)	0.72176 (19)	0.0171 (3)
C7	0.07559 (9)	0.83597 (11)	0.8356 (2)	0.0173 (3)
C8	−0.00907 (9)	0.82379 (11)	0.83286 (19)	0.0163 (3)
C9	−0.04488 (9)	0.87299 (11)	0.7205 (2)	0.0177 (3)
C10	−0.15923 (9)	0.92361 (11)	0.5995 (2)	0.0177 (3)
H10	−0.1285	0.9729	0.5471	0.021*
C11	−0.24267 (9)	0.91463 (12)	0.57050 (19)	0.0166 (3)
C12	−0.29035 (9)	0.97881 (12)	0.4860 (2)	0.0197 (3)
H12	−0.2734	1.0374	0.4307	0.024*
C13	−0.36866 (10)	0.94050 (11)	0.4980 (2)	0.0206 (4)
H13	−0.4142	0.9688	0.4526	0.025*
C14	−0.36664 (8)	0.85413 (11)	0.5881 (2)	0.0200 (4)
H14	−0.4110	0.8127	0.6154	0.024*
C15	0.12846 (9)	0.78771 (11)	0.9451 (2)	0.0177 (4)
C16	0.12941 (10)	0.71688 (13)	1.1806 (2)	0.0245 (4)
H16A	0.1752	0.6754	1.1459	0.029*
H16B	0.0945	0.6688	1.2350	0.029*
C17	0.15813 (11)	0.80532 (14)	1.2762 (2)	0.0294 (4)
H17A	0.1958	0.8497	1.2243	0.044*
H17B	0.1842	0.7751	1.3599	0.044*
H17C	0.1130	0.8484	1.3064	0.044*
C18	−0.05767 (8)	0.75280 (11)	0.9270 (2)	0.0168 (3)
C19	−0.12474 (10)	0.73187 (13)	1.1459 (2)	0.0250 (4)
H19A	−0.0956	0.6645	1.1578	0.030*
H19B	−0.1789	0.7156	1.1120	0.030*
C20	−0.12819 (12)	0.79079 (15)	1.2846 (2)	0.0325 (4)
H20A	−0.0744	0.8084	1.3153	0.049*
H20B	−0.1536	0.7463	1.3565	0.049*
H20C	−0.1588	0.8560	1.2722	0.049*

	U11	U22	U33	U12	U13	U23
S1	0.01600 (17)	0.02159 (18)	0.0189 (3)	−0.00165 (12)	−0.00024 (17)	0.00547 (15)
O1	0.0191 (6)	0.0282 (6)	0.0243 (8)	0.0010 (4)	−0.0022 (5)	0.0040 (5)
O2	0.0212 (5)	0.0307 (6)	0.0179 (8)	0.0002 (5)	−0.0019 (5)	0.0047 (5)
O3	0.0294 (6)	0.0174 (5)	0.0201 (8)	−0.0038 (4)	0.0021 (5)	−0.0007 (4)
O4	0.0224 (5)	0.0197 (5)	0.0175 (8)	−0.0038 (4)	0.0047 (4)	−0.0006 (4)
N1	0.0192 (6)	0.0238 (6)	0.0204 (10)	0.0005 (5)	0.0019 (6)	0.0054 (6)
N2	0.0163 (6)	0.0179 (6)	0.0186 (10)	−0.0028 (5)	−0.0004 (5)	0.0008 (6)
N3	0.0166 (6)	0.0193 (6)	0.0199 (9)	−0.0007 (5)	0.0006 (5)	−0.0005 (5)
N4	0.0194 (6)	0.0160 (6)	0.0174 (9)	0.0025 (4)	−0.0001 (5)	0.0019 (5)
C1	0.0161 (8)	0.0342 (9)	0.0318 (14)	0.0000 (6)	0.0017 (7)	−0.0003 (8)
C2	0.0209 (8)	0.0331 (9)	0.0226 (12)	−0.0056 (6)	0.0054 (7)	0.0051 (7)
C3	0.0252 (8)	0.0249 (8)	0.0210 (12)	−0.0031 (6)	−0.0020 (7)	0.0045 (7)
C4	0.0172 (8)	0.0167 (7)	0.0201 (11)	−0.0009 (6)	−0.0019 (6)	0.0008 (6)
C5	0.0207 (8)	0.0151 (6)	0.0206 (12)	0.0003 (6)	−0.0008 (6)	0.0004 (6)
C6	0.0164 (8)	0.0145 (7)	0.0202 (10)	−0.0005 (5)	−0.0006 (6)	−0.0022 (6)
C7	0.0183 (8)	0.0142 (7)	0.0193 (10)	−0.0017 (5)	0.0001 (6)	−0.0038 (6)
C8	0.0174 (7)	0.0132 (7)	0.0183 (11)	−0.0003 (5)	0.0007 (6)	−0.0025 (6)
C9	0.0184 (7)	0.0162 (7)	0.0186 (10)	−0.0018 (5)	0.0025 (6)	0.0006 (6)
C10	0.0187 (7)	0.0167 (6)	0.0178 (11)	0.0009 (5)	0.0020 (7)	0.0012 (7)
C11	0.0195 (7)	0.0168 (7)	0.0136 (10)	0.0016 (6)	0.0027 (6)	−0.0008 (5)
C12	0.0220 (8)	0.0181 (7)	0.0190 (11)	0.0017 (6)	0.0007 (6)	0.0041 (6)
C13	0.0202 (8)	0.0196 (7)	0.0220 (11)	0.0030 (6)	−0.0027 (7)	0.0000 (7)
C14	0.0183 (7)	0.0185 (7)	0.0233 (12)	−0.0010 (5)	0.0001 (7)	−0.0011 (7)
C15	0.0191 (8)	0.0148 (7)	0.0190 (11)	−0.0022 (6)	0.0008 (7)	−0.0027 (6)
C16	0.0282 (9)	0.0274 (8)	0.0178 (11)	−0.0007 (6)	−0.0042 (7)	0.0061 (7)
C17	0.0335 (10)	0.0330 (9)	0.0215 (12)	−0.0004 (7)	−0.0028 (8)	0.0002 (8)
C18	0.0143 (7)	0.0174 (7)	0.0187 (11)	0.0008 (5)	−0.0017 (6)	0.0015 (7)
C19	0.0262 (8)	0.0271 (8)	0.0218 (13)	−0.0062 (6)	0.0072 (7)	0.0015 (7)
C20	0.0424 (10)	0.0323 (9)	0.0228 (13)	−0.0036 (7)	0.0076 (9)	−0.0003 (8)

S1—C9	1.7717 (17)	C6—C7	1.389 (2)
S1—C6	1.7721 (17)	C7—C8	1.439 (2)
O1—C15	1.2165 (19)	C7—C15	1.495 (2)
O2—C15	1.342 (2)	C8—C9	1.369 (2)
O2—C16	1.464 (2)	C8—C18	1.506 (2)
O3—C18	1.2164 (19)	C10—C11	1.441 (2)
O4—C18	1.327 (2)	C10—H10	0.9500
O4—C19	1.472 (2)	C11—C12	1.393 (2)
N1—C1	1.362 (2)	C12—C13	1.414 (2)
N1—C4	1.385 (2)	C12—H12	0.9500
N1—H100	0.8800	C13—C14	1.384 (2)
N2—C5	1.296 (2)	C13—H13	0.9500
N2—C6	1.384 (2)	C14—H14	0.9500
N3—C10	1.292 (2)	C16—C17	1.516 (3)
N3—C9	1.383 (2)	C16—H16A	0.9900
N4—C14	1.369 (2)	C16—H16B	0.9900
N4—C11	1.381 (2)	C17—H17A	0.9800
N4—H400	0.8800	C17—H17B	0.9800
C1—C2	1.380 (3)	C17—H17C	0.9800
C1—H1	0.9500	C19—C20	1.505 (3)
C2—C3	1.409 (2)	C19—H19A	0.9900
C2—H2	0.9500	C19—H19B	0.9900
C3—C4	1.387 (3)	C20—H20A	0.9800
C3—H3	0.9500	C20—H20B	0.9800
C4—C5	1.436 (2)	C20—H20C	0.9800
C5—H5	0.9500
C9—S1—C6	90.89 (8)	N4—C11—C10	123.11 (14)
C15—O2—C16	117.02 (13)	C12—C11—C10	128.93 (14)
C18—O4—C19	115.44 (12)	C11—C12—C13	107.25 (14)
C1—N1—C4	109.20 (16)	C11—C12—H12	126.4
C1—N1—H100	125.4	C13—C12—H12	126.4
C4—N1—H100	125.4	C14—C13—C12	107.22 (14)
C5—N2—C6	121.56 (15)	C14—C13—H13	126.4
C10—N3—C9	121.37 (14)	C12—C13—H13	126.4
C14—N4—C11	108.84 (13)	N4—C14—C13	108.77 (13)
C14—N4—H400	125.6	N4—C14—H14	125.6
C11—N4—H400	125.6	C13—C14—H14	125.6
N1—C1—C2	108.79 (16)	O1—C15—O2	124.51 (16)
N1—C1—H1	125.6	O1—C15—C7	125.64 (16)
C2—C1—H1	125.6	O2—C15—C7	109.85 (13)
C1—C2—C3	106.93 (15)	O2—C16—C17	110.00 (14)
C1—C2—H2	126.5	O2—C16—H16A	109.7
C3—C2—H2	126.5	C17—C16—H16A	109.7
C4—C3—C2	108.02 (16)	O2—C16—H16B	109.7
C4—C3—H3	126.0	C17—C16—H16B	109.7
C2—C3—H3	126.0	H16A—C16—H16B	108.2
N1—C4—C3	107.07 (14)	C16—C17—H17A	109.5
N1—C4—C5	123.16 (16)	C16—C17—H17B	109.5
C3—C4—C5	129.77 (16)	H17A—C17—H17B	109.5
N2—C5—C4	120.53 (15)	C16—C17—H17C	109.5
N2—C5—H5	119.7	H17A—C17—H17C	109.5
C4—C5—H5	119.7	H17B—C17—H17C	109.5
N2—C6—C7	124.12 (15)	O3—C18—O4	124.90 (15)
N2—C6—S1	124.39 (13)	O3—C18—C8	121.72 (16)
C7—C6—S1	111.31 (11)	O4—C18—C8	113.35 (12)
C6—C7—C8	112.52 (15)	O4—C19—C20	107.18 (14)
C6—C7—C15	123.18 (14)	O4—C19—H19A	110.3
C8—C7—C15	124.26 (14)	C20—C19—H19A	110.3
C9—C8—C7	113.87 (15)	O4—C19—H19B	110.3
C9—C8—C18	119.05 (14)	C20—C19—H19B	110.3
C7—C8—C18	126.54 (14)	H19A—C19—H19B	108.5
C8—C9—N3	122.62 (15)	C19—C20—H20A	109.5
C8—C9—S1	111.38 (12)	C19—C20—H20B	109.5
N3—C9—S1	125.95 (13)	H20A—C20—H20B	109.5
N3—C10—C11	121.45 (15)	C19—C20—H20C	109.5
N3—C10—H10	119.3	H20A—C20—H20C	109.5
C11—C10—H10	119.3	H20B—C20—H20C	109.5
N4—C11—C12	107.92 (13)
C4—N1—C1—C2	−0.1 (2)	C10—N3—C9—S1	−11.7 (2)
N1—C1—C2—C3	0.1 (2)	C6—S1—C9—C8	1.58 (13)
C1—C2—C3—C4	0.0 (2)	C6—S1—C9—N3	−175.84 (14)
C1—N1—C4—C3	0.08 (19)	C9—N3—C10—C11	178.43 (15)
C1—N1—C4—C5	−179.37 (15)	C14—N4—C11—C12	−0.75 (19)
C2—C3—C4—N1	−0.02 (19)	C14—N4—C11—C10	176.99 (15)
C2—C3—C4—C5	179.37 (16)	N3—C10—C11—N4	−6.6 (3)
C6—N2—C5—C4	−174.69 (14)	N3—C10—C11—C12	170.66 (17)
N1—C4—C5—N2	−2.4 (2)	N4—C11—C12—C13	0.7 (2)
C3—C4—C5—N2	178.28 (16)	C10—C11—C12—C13	−176.88 (17)
C5—N2—C6—C7	172.80 (15)	C11—C12—C13—C14	−0.4 (2)
C5—N2—C6—S1	−1.8 (2)	C11—N4—C14—C13	0.5 (2)
C9—S1—C6—N2	173.29 (13)	C12—C13—C14—N4	−0.1 (2)
C9—S1—C6—C7	−1.94 (12)	C16—O2—C15—O1	3.6 (2)
N2—C6—C7—C8	−173.42 (14)	C16—O2—C15—C7	−177.18 (12)
S1—C6—C7—C8	1.82 (16)	C6—C7—C15—O1	−17.3 (2)
N2—C6—C7—C15	4.4 (2)	C8—C7—C15—O1	160.28 (15)
S1—C6—C7—C15	179.65 (12)	C6—C7—C15—O2	163.54 (14)
C6—C7—C8—C9	−0.63 (19)	C8—C7—C15—O2	−18.9 (2)
C15—C7—C8—C9	−178.43 (14)	C15—O2—C16—C17	87.68 (18)
C6—C7—C8—C18	170.77 (15)	C19—O4—C18—O3	7.5 (2)
C15—C7—C8—C18	−7.0 (2)	C19—O4—C18—C8	−174.19 (13)
C7—C8—C9—N3	176.67 (14)	C9—C8—C18—O3	81.61 (19)
C18—C8—C9—N3	4.6 (2)	C7—C8—C18—O3	−89.4 (2)
C7—C8—C9—S1	−0.86 (17)	C9—C8—C18—O4	−96.74 (18)
C18—C8—C9—S1	−172.96 (11)	C7—C8—C18—O4	92.26 (18)
C10—N3—C9—C8	171.18 (16)	C18—O4—C19—C20	163.89 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H100···O3i	0.88	2.37	3.040 (2)	133
N4—H400···O1ii	0.88	2.47	3.174 (2)	138
N4—H400···N2ii	0.88	2.59	3.2136 (19)	128
C3—H3···N4iii	0.95	2.56	3.441 (2)	155
C13—H13···O3iv	0.95	2.51	3.126 (2)	123

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H100⋯O3i	0.88	2.37	3.040 (2)	133
N4—H400⋯O1ii	0.88	2.47	3.174 (2)	138
N4—H400⋯N2ii	0.88	2.59	3.2136 (19)	128
C3—H3⋯N4iii	0.95	2.56	3.441 (2)	155
C13—H13⋯O3iv	0.95	2.51	3.126 (2)	123

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .