Diethyl 2,5-bis­[(1E)-(1H-pyrrol-2-yl­methyl­idene)amino]­thio­phene-3,4-dicarboxyl­ate

Dufresne, S.; Skene, W.G.

doi:10.1107/S1600536811031576

organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2302

doi:10.1107/S1600536811031576

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Diethyl 2,5-bis[(1E)-(1H-pyrrol-2-ylmethylidene)amino]thiophene-3,4-dicarboxylate

Stéphane Dufresne ^a and W. G. Skene ^a ^*

^aDepartment of Chemistry, University of Montreal, CP 6128, succ. Centre-ville, Montréal, Québec, Canada H3C 3J7
^*Correspondence e-mail: w.skene@umontreal.ca

(Received 28 July 2011; accepted 4 August 2011; online 11 August 2011)

In the crystal structure of the title compound, C₂₀H₂₀N₄O₄S, the azomethine group adopt E conformations. The pyrrole units are twisted by 10.31 (4) and 18.90 (5)° with respect to the central thiophene 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_r = 412.46
Orthorhombic, P n a 2₁
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[F² > 2σ(F²)] = 0.024
wR(F²) = 0.064
S = 1.04
3040 reflections
264 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.15 e Å⁻³
Absolute structure: Flack (1983), 1275 Friedel pairs
Flack parameter: 0.085 (12)

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⋯O3^iv	0.95	2.51	3.126 (2)	123
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (iii) $[-x, -y+2, z-{\script{1\over 2}}]$ ; (iv) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811031576/zq2118sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536811031576/zq2118Isup3.cml

checkCIF report

Comment top

During our on-going research relating to conjugated azomethines (Dufresne et al., 2007; Dufresne & Skene, 2010a,b; Dufresne & Skene, 2011) we prepared the title compound (I), C₂₀H₂₀N₄O₄S. To the best of our knowledge, there are very few reported crystal structures of azomethines consisting of pyrrole and thiophene units together. The molecular structure was confirmed by a X-ray diffraction study (Fig. 1). Neither solvent molecules nor counter-ions were found in the closed-packing of the crystal structure.

A major point of interest is the azomethine bond which adopts the E configuration. The bond lengths for C4—C5, N2—C5 and N2—C6 are 1.429 (3), 1.294 (3) and 1.379 (2) Å, respectively. The related bonds C10—C11, N3—C10 and N3—C9 are 1.434 (3), 1.288 (3) and 1.379 (3) Å, respectively. All bond distances are consistent with those of a similar conjugated compound consisting uniquely of thiophenes with two azomethine bonds (Dufresne et al., 2006). The analogues bond lengths for the all-thiophene counterpart are: 1.441 (4), 1.272 (3) and 1.388 (3) Å. It was found that the three heterocycles of (I) are not perfectly coplanar. This was confirmed by measuring the dihedral angles between the planes described by both terminal pyrroles and the plane described by the central thiophene. The dihedral angle between the N1-pyrrole and thiophene planes is 10.31 (4)°, while that for the thiophene and N4-pyrrole planes is 18.90 (5)°. The measured angles are similar to the all-thiophene analogue whose terminal thiophenes are twisted by 9.04 (4)° and 25.07 (6)° with the central thiophene. The pyrrole N-H is involved in several N—H···O and N—H···N donor-acceptor interactions while C—H···N and C—H···O are also observed (Table 1). All these interactions are responsible for the overall extended three-dimensional crystal network (Fig. 2), while no π-stacking was found.

Related literature top

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 top

In anhydrous toluene (25 mL) was added 1H-pyrrole-2-carbaldehyde to which was subsequently added DABCO, TiCl₄ in toluene at 0 °C and then diethyl 2,5-diaminothiophene-3,4-dicarboxylate was added. The mixture was then refluxed for 30 minutes and the solvent, after which the solvent was removed. Purification by flash chromatography yielded the title product as a red solid. Single crystals were obtained by slow evaporation of an acetone solution of the title compound.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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).

Figures top

	Fig. 1. The molecular structure of the title compound with thermal ellipsoids drawn at 30% probability level.
	Fig. 2. Supramolecular structure showing the intermolecular hydrogen bonding (dashed lines). Symmetry codes: (i) x+1/2, -y+3/2, z; (ii) x-1/2, -y+3/2, z; (iii) -x, -y+2, z-1/2; (iv) -x-1/2, y+1/2, z-1/2.

Diethyl 2,5-bis[(1E)-(1H-pyrrol-2- ylmethylidene)amino]thiophene-3,4-dicarboxylate top

Crystal data top

C₂₀H₂₀N₄O₄S	D_x = 1.361 Mg m⁻³
M_r = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0475P)² + 0.2939P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3040 reflections	Δρ_max = 0.19 e Å⁻³
264 parameters	Δρ_min = −0.15 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1275 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.085 (12)

Crystal data top

C₂₀H₂₀N₄O₄S	V = 2012.9 (7) Å³
M_r = 412.46	Z = 4
Orthorhombic, Pna2₁	Cu Kα radiation
a = 16.898 (3) Å	µ = 1.73 mm⁻¹
b = 12.643 (3) Å	T = 150 K
c = 9.4220 (19) Å	0.10 × 0.03 × 0.03 mm

Data collection top

Bruker SMART 6000 diffractometer	3040 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3004 reflections with I > 2σ(I)
T_min = 0.841, T_max = 0.947	R_int = 0.028
17313 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	H-atom parameters constrained
wR(F²) = 0.064	Δρ_max = 0.19 e Å⁻³
S = 1.04	Δρ_min = −0.15 e Å⁻³
3040 reflections	Absolute structure: Flack (1983), 1275 Friedel pairs
264 parameters	Absolute structure parameter: 0.085 (12)
1 restraint

Special details top

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.

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···O3^iv	0.95	2.51	3.126 (2)	123

Symmetry codes: (i) x+1/2, −y+3/2, z; (ii) x−1/2, −y+3/2, z; (iii) −x, −y+2, z−1/2; (iv) −x−1/2, y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₂₀H₂₀N₄O₄S
M_r	412.46
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	150
a, b, c (Å)	16.898 (3), 12.643 (3), 9.4220 (19)
V (Å³)	2012.9 (7)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	1.73
Crystal size (mm)	0.10 × 0.03 × 0.03

Data collection
Diffractometer	Bruker SMART 6000 diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.841, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	17313, 3040, 3004
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.064, 1.04
No. of reflections	3040
No. of parameters	264
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.15
Absolute structure	Flack (1983), 1275 Friedel pairs
Absolute structure parameter	0.085 (12)

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and ORTEP-3 (Farrugia, 1997), UdMX (Marris, 2004).

Hydrogen-bond geometry (Å, º) top

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···O3^iv	0.95	2.51	3.126 (2)	123

Symmetry codes: (i) x+1/2, −y+3/2, z; (ii) x−1/2, −y+3/2, z; (iii) −x, −y+2, z−1/2; (iv) −x−1/2, y+1/2, z−1/2.

Acknowledgements

The authors acknowledge financial support from the Natural Sciences and Engineering Research Council Canada, the Centre for Self-Assembled Chemical Structures, and the Canada Foundation for Innovation. SD thanks both NSERC and the Université de Montréal for graduate scholarships.

References

Bruker (2003). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dufresne, S., Bourgeaux, M. & Skene, W. G. (2006). Acta Cryst. E62, o5602–o5604. Web of Science CSD CrossRef IUCr Journals Google Scholar
Dufresne, S., Bourgeaux, M. & Skene, W. G. (2007). J. Mater. Chem. 17, 1–13. Web of Science CSD CrossRef Google Scholar
Dufresne, S. & Skene, W. G. (2010a). Acta Cryst. E66, o3027. CrossRef IUCr Journals Google Scholar
Dufresne, S. & Skene, W. G. (2010b). Acta Cryst. E66, o3221. CrossRef IUCr Journals Google Scholar
Dufresne, S. & Skene, W. G. (2011). J. Phys. Org. Chem. DOI 10.1002/poc.1894. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Marris, T. (2004). UdMX. Université de Montréal, Québec, Canada. Google Scholar
Ruban, G. & Zobel, D. (1975). Acta Cryst. B31, 2632–2634. CSD CAS Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zobel, D. & Ruban, G. (1978). Acta Cryst. B34, 1652–1657. CSD CAS Web of Science Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Di­ethyl 2,5-bis­­[(1E)-(1H-pyrrol-2-yl­methyl­­idene)amino]­thio­phene-3,4-di­carboxyl­ate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Diethyl 2,5-bis[(1E)-(1H-pyrrol-2-ylmethylidene)amino]thiophene-3,4-dicarboxylate