Diethyl 2-amino-5-[(E)-(1-methyl-1H-pyrrol-2-yl)methylideneamino]thiophene-3,4-dicarboxylate

Dufresne, S.; Skene, W.G.

doi:10.1107/S1600536810046775

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3221

https://doi.org/10.1107/S1600536810046775

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Diethyl 2-amino-5-[(E)-(1-methyl-1H-pyrrol-2-yl)methylideneamino]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, H3C 3J7, Canada
^*Correspondence e-mail: w.skene@umontreal.ca

(Received 21 October 2010; accepted 11 November 2010; online 20 November 2010)

The structure of the title compound, C₁₆H₁₉N₃O₄S, shows the planes described by the thiophene and the pyrroles are twisted by 17.06 (4)°. Additionally, the structure shows the azomethine bond adopts the E configuration, while the pyrrole is disordered as a heterocycle flip [occupancy ratio 0.729 (5):0.271 (5)]. The three-dimensional network is well packed and involves N–H⋯O hydrogen bonding and π–π stacking [centroid–centroid distance = 4.294 (8) Å].

Related literature

For our on-going research on conjugated azomethines, see: Dufresne & Skene (2008 ). For bond lengths in comparable azomethines, see: Skene et al. (2006 ); Dufresne & Skene (2010 ).

Experimental

Crystal data

C₁₆H₁₉N₃O₄S
M_r = 349.40
Monoclinic, P 2₁ /c
a = 8.8212 (18) Å
b = 9.0799 (18) Å
c = 21.793 (4) Å
β = 97.50 (3)°
V = 1730.6 (6) Å³
Z = 4
Cu Kα radiation
μ = 1.89 mm⁻¹
T = 123 K
0.17 × 0.16 × 0.15 mm

Data collection

Bruker SMART 6000 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick,1996 ) T_min = 0.710, T_max = 0.762
20876 measured reflections
3367 independent reflections
3046 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.116
S = 1.07
3367 reflections
267 parameters
32 restraints
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O3ⁱ	0.88	2.09	2.925 (3)	157
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: https://doi.org/10.1107/S1600536810046775/bh2321sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810046775/bh2321Isup2.hkl

checkCIF report

Comment top

During our on-going research relating to conjugated azomethines (Dufresne & Skene, 2008), we prepared the title compound. The structure is given in figure 1. The pyrrole is disordered. The occupation factor was found to be 73% for the antiperiplanar heterocycle. The salient feature of the resolved structure is assigning the absolute isomer of the azomethine, which is not readily possible by other means. The E isomer was found and the crystal symmetry was P2₁/c. Neither solvent nor counter-ions were found in the structure.

A major point of interest is the azomethine bond. The bond lengths for N2—C4, N2—C5 and C5—C6 are 1.372 (2), 1.292 (2) and 1.424 (2) Å, respectively. These are similar to comparable azomethines (Skene et al., 2006 and Dufresne & Skene, 2010) whose homologue lengths are 1.381 (3), 1.283 (3) and 1.426 (3) Å.

We found that the heterocycles of the title compound are not coplanar, according to angle between the mean planes described by them. The angle between these planes was found to be 17.06 (4)°. This is in contrast to an analogous thiophene-azomethine compound (Skene et al., 2006) whose mean plane angle is 7.25 (11)°.

Figure 2 shows the H-bonding occurring within the lattice. Only one H-bonding was found between N1—H1B···O3ⁱⁱ with an angle of 157.1° and a distance of 2.925 (3) Å between the nitrogen and the oxygen. Hydrogen bonding and π-stacking are the driving forces for the overall assembly. π-stacking was found to take place between the pyrroles as seen in Figure 3.

Related literature top

For our on-going research on conjugated azomethines, see: Dufresne & Skene (2008). For bond lengths in comparable azomethines, see: Skene et al. (2006); Dufresne & Skene (2010).

Experimental top

1-Methyl-2-pyrrole-carboxaldehyde and 2,5-diamino-thiophene-3,4-dicarboxylic acid diethyl ester were mixed in anhydrous 2-propanol with a catalytic amount of TFA and refluxed for 12 h. The reaction was then purified by flash chromatography to afford the title compound as a yellow solid. Single crystals were obtained by slow evaporation of an acetone solution.

Structure description top

For our on-going research on conjugated azomethines, see: Dufresne & Skene (2008). For bond lengths in comparable azomethines, see: Skene et al. (2006); Dufresne & Skene (2010).

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. ORTEP representation of the title molecule with the numbering scheme adopted (Farrugia, 1997). The disorder on the pyrrole unit is represented by prime symbols. Ellipsoids drawn at 30% probability level.
	Fig. 2. Supramolecular structure showing the intermolecular H-bonding giving the structural arrangement. Disorder has been omitted for clarity. Dashed lines indicate hydrogen bonds. [Symmetry codes: (i) 1 - x, -1/2 + y, 1/2 - z; (ii) 1 - x, 1/2 + y, 1/2 - z; (iii) x, 1 + y, z.]
	Fig. 3. The three-dimensional network demonstrating the π-stacking in the lattice. Disorder has been omitted for clarity.

Diethyl 2-amino-5-[(E)-(1-methyl-1H-pyrrol- 2-yl)methylideneamino]thiophene-3,4-dicarboxylate top

Crystal data top

C₁₆H₁₉N₃O₄S	F(000) = 736
M_r = 349.40	D_x = 1.341 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 404(2) K
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54178 Å
a = 8.8212 (18) Å	Cell parameters from 10603 reflections
b = 9.0799 (18) Å	θ = 4.1–71.3°
c = 21.793 (4) Å	µ = 1.89 mm⁻¹
β = 97.50 (3)°	T = 123 K
V = 1730.6 (6) Å³	Block, yellow
Z = 4	0.17 × 0.16 × 0.15 mm

Data collection top

Bruker SMART 6000 diffractometer	3367 independent reflections
Radiation source: Rotating Anode	3046 reflections with I > 2σ(I)
Montel 200 optics monochromator	R_int = 0.034
Detector resolution: 5.5 pixels mm^-1	θ_max = 72.0°, θ_min = 4.1°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick,1996)	k = −11→11
T_min = 0.710, T_max = 0.762	l = −26→25
20876 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0845P)² + 0.153P] where P = (F_o² + 2F_c²)/3
3367 reflections	(Δ/σ)_max < 0.001
267 parameters	Δρ_max = 0.32 e Å⁻³
32 restraints	Δρ_min = −0.54 e Å⁻³
0 constraints

Crystal data top

C₁₆H₁₉N₃O₄S	V = 1730.6 (6) Å³
M_r = 349.40	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 8.8212 (18) Å	µ = 1.89 mm⁻¹
b = 9.0799 (18) Å	T = 123 K
c = 21.793 (4) Å	0.17 × 0.16 × 0.15 mm
β = 97.50 (3)°

Data collection top

Bruker SMART 6000 diffractometer	3367 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick,1996)	3046 reflections with I > 2σ(I)
T_min = 0.710, T_max = 0.762	R_int = 0.034
20876 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	32 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.07	Δρ_max = 0.32 e Å⁻³
3367 reflections	Δρ_min = −0.54 e Å⁻³
267 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.45470 (4)	0.43388 (4)	0.275627 (17)	0.02979 (14)
O1	0.80431 (13)	0.22781 (12)	0.16548 (5)	0.0338 (3)
O2	0.89746 (11)	0.11974 (11)	0.25566 (5)	0.0280 (2)
O3	0.73230 (12)	0.04262 (11)	0.38224 (5)	0.0347 (3)
O4	0.89935 (11)	0.22984 (11)	0.38638 (5)	0.0288 (2)
N1	0.56568 (15)	0.42094 (15)	0.16734 (6)	0.0352 (3)
H1A	0.6308	0.3913	0.1426	0.042*
H1B	0.4906	0.4809	0.1534	0.042*
N2	0.50239 (13)	0.31869 (14)	0.39473 (6)	0.0304 (3)
C1	0.58092 (15)	0.37474 (15)	0.22635 (6)	0.0255 (3)
C2	0.69216 (14)	0.28057 (14)	0.25579 (6)	0.0217 (3)
C3	0.67137 (15)	0.25520 (14)	0.31923 (6)	0.0227 (3)
C4	0.54893 (15)	0.32748 (16)	0.33720 (7)	0.0268 (3)
C5	0.39981 (16)	0.40771 (17)	0.41036 (8)	0.0328 (3)
H5	0.3630	0.4830	0.3820	0.039*
C6	0.33869 (17)	0.39978 (19)	0.46758 (8)	0.0377 (4)
C11	0.80092 (15)	0.20966 (14)	0.22090 (6)	0.0231 (3)
C12	1.01267 (19)	0.04672 (18)	0.22452 (8)	0.0370 (4)
H12A	0.9660	0.0140	0.1830	0.044*
H12B	1.0502	−0.0417	0.2484	0.044*
C13	1.14477 (19)	0.1469 (2)	0.21800 (9)	0.0468 (5)
H13A	1.1091	0.2309	0.1918	0.070*
H13B	1.2228	0.0928	0.1990	0.070*
H13C	1.1887	0.1824	0.2589	0.070*
C14	0.76941 (15)	0.16206 (14)	0.36484 (6)	0.0229 (3)
C15	1.00158 (18)	0.15225 (19)	0.43389 (7)	0.0357 (4)
H15A	0.9401	0.0962	0.4608	0.043*
H15B	1.0642	0.2248	0.4600	0.043*
C16	1.1047 (2)	0.0488 (2)	0.40530 (9)	0.0498 (5)
H16A	1.0429	−0.0259	0.3811	0.075*
H16B	1.1741	0.0005	0.4380	0.075*
H16C	1.1644	0.1040	0.3782	0.075*
N3	0.3667 (7)	0.3033 (4)	0.5110 (3)	0.0300 (10)	0.729 (5)
C7	0.2273 (5)	0.5042 (6)	0.4841 (2)	0.0307 (9)	0.729 (5)
H7	0.1852	0.5864	0.4609	0.037*	0.729 (5)
C8	0.1955 (9)	0.4567 (9)	0.5423 (3)	0.0351 (13)	0.729 (5)
H8	0.1274	0.5019	0.5670	0.042*	0.729 (5)
C9	0.2812 (8)	0.3328 (7)	0.5569 (3)	0.0339 (12)	0.729 (5)
H9	0.2807	0.2761	0.5935	0.041*	0.729 (5)
C10	0.4701 (3)	0.1768 (3)	0.51050 (11)	0.0425 (7)	0.729 (5)
H10A	0.4547	0.1301	0.4696	0.064*	0.729 (5)
H10B	0.4484	0.1055	0.5420	0.064*	0.729 (5)
H10C	0.5763	0.2104	0.5196	0.064*	0.729 (5)
N83	0.2589 (11)	0.4768 (12)	0.5004 (4)	0.0224 (17)	0.271 (5)
C87	0.369 (2)	0.2593 (12)	0.5158 (9)	0.027 (2)	0.271 (5)
H87	0.4264	0.1731	0.5101	0.033*	0.271 (5)
C88	0.290 (2)	0.2937 (17)	0.5684 (7)	0.026 (2)	0.271 (5)
H88	0.2875	0.2365	0.6048	0.031*	0.271 (5)
C89	0.221 (2)	0.426 (2)	0.5544 (8)	0.028 (3)	0.271 (5)
H89	0.1559	0.4746	0.5792	0.033*	0.271 (5)
C90	0.2156 (6)	0.6219 (7)	0.4747 (2)	0.0302 (15)	0.271 (5)
H90A	0.3063	0.6850	0.4773	0.045*	0.271 (5)
H90B	0.1400	0.6666	0.4982	0.045*	0.271 (5)
H90C	0.1713	0.6113	0.4312	0.045*	0.271 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0183 (2)	0.0303 (2)	0.0411 (2)	0.00671 (12)	0.00480 (14)	0.00178 (13)
O1	0.0328 (6)	0.0391 (6)	0.0299 (5)	0.0073 (4)	0.0059 (4)	−0.0022 (4)
O2	0.0241 (5)	0.0257 (5)	0.0357 (5)	0.0080 (4)	0.0101 (4)	0.0037 (4)
O3	0.0277 (5)	0.0292 (5)	0.0458 (6)	−0.0060 (4)	−0.0010 (5)	0.0100 (5)
O4	0.0195 (5)	0.0273 (5)	0.0379 (6)	−0.0020 (4)	−0.0026 (4)	−0.0003 (4)
N1	0.0293 (7)	0.0422 (8)	0.0333 (7)	0.0123 (5)	0.0008 (5)	0.0051 (5)
N2	0.0206 (6)	0.0346 (7)	0.0376 (7)	−0.0001 (5)	0.0096 (5)	−0.0028 (5)
C1	0.0188 (6)	0.0236 (7)	0.0334 (7)	−0.0004 (5)	0.0009 (5)	−0.0015 (5)
C2	0.0170 (6)	0.0183 (6)	0.0296 (7)	−0.0003 (5)	0.0028 (5)	−0.0015 (5)
C3	0.0172 (6)	0.0200 (6)	0.0310 (7)	−0.0017 (5)	0.0037 (5)	−0.0005 (5)
C4	0.0181 (6)	0.0264 (7)	0.0363 (7)	0.0000 (5)	0.0053 (5)	−0.0001 (5)
C5	0.0225 (7)	0.0314 (7)	0.0461 (9)	−0.0030 (5)	0.0107 (6)	−0.0042 (6)
C6	0.0253 (8)	0.0436 (9)	0.0470 (10)	−0.0086 (7)	0.0152 (7)	−0.0144 (8)
C11	0.0198 (6)	0.0196 (6)	0.0298 (7)	−0.0015 (5)	0.0033 (5)	−0.0019 (5)
C12	0.0344 (8)	0.0303 (8)	0.0499 (9)	0.0153 (6)	0.0185 (7)	0.0049 (6)
C13	0.0295 (8)	0.0536 (11)	0.0611 (11)	0.0137 (7)	0.0200 (8)	0.0188 (9)
C14	0.0176 (6)	0.0231 (6)	0.0283 (6)	−0.0012 (5)	0.0045 (5)	−0.0016 (5)
C15	0.0284 (7)	0.0422 (8)	0.0336 (8)	0.0025 (6)	−0.0072 (6)	0.0008 (6)
C16	0.0381 (10)	0.0591 (11)	0.0499 (10)	0.0204 (8)	−0.0031 (8)	0.0037 (8)
N3	0.0230 (11)	0.032 (2)	0.0357 (16)	0.001 (2)	0.0083 (9)	−0.005 (2)
C7	0.0216 (19)	0.030 (3)	0.041 (3)	0.0043 (13)	0.0066 (15)	−0.0019 (16)
C8	0.028 (2)	0.040 (3)	0.041 (3)	−0.0014 (19)	0.015 (2)	−0.012 (2)
C9	0.0328 (18)	0.044 (4)	0.026 (2)	0.000 (3)	0.0054 (17)	0.003 (2)
C10	0.0417 (14)	0.0451 (14)	0.0425 (13)	0.0156 (11)	0.0120 (10)	0.0147 (10)
N83	0.018 (4)	0.019 (4)	0.029 (4)	0.007 (3)	−0.003 (3)	0.007 (3)
C87	0.035 (4)	0.012 (5)	0.036 (4)	−0.003 (4)	0.007 (3)	0.000 (4)
C88	0.032 (4)	0.026 (6)	0.021 (5)	0.008 (4)	0.010 (4)	0.010 (3)
C89	0.031 (7)	0.031 (8)	0.023 (4)	0.000 (5)	0.009 (4)	0.008 (4)
C90	0.030 (3)	0.033 (4)	0.029 (3)	0.008 (2)	0.006 (2)	0.008 (2)

Geometric parameters (Å, º) top

S1—C1	1.7301 (15)	C13—H13b	0.98
S1—C4	1.7703 (15)	C13—H13c	0.98
O1—C11	1.2232 (17)	C15—C16	1.499 (2)
O2—C11	1.3407 (16)	C15—H15a	0.99
O2—C12	1.4537 (17)	C15—H15b	0.99
O3—C14	1.2080 (17)	C16—H16a	0.98
O4—C14	1.3313 (16)	C16—H16b	0.98
O4—C15	1.4622 (17)	C16—H16c	0.98
N1—C1	1.3428 (19)	N3—C9	1.354 (7)
N1—H1a	0.88	N3—C10	1.468 (4)
N1—H1b	0.88	C7—C8	1.402 (7)
N2—C5	1.2918 (19)	C7—H7	0.95
N2—C4	1.3715 (19)	C8—C9	1.369 (5)
C1—C2	1.3933 (18)	C8—H8	0.95
C2—C3	1.4368 (18)	C9—H9	0.95
C2—C11	1.4503 (18)	C10—H10a	0.98
C3—C4	1.3643 (19)	C10—H10b	0.98
C3—C14	1.4923 (18)	C10—H10c	0.98
C5—C6	1.424 (2)	N83—C89	1.346 (15)
C5—H5	0.95	N83—C90	1.463 (8)
C6—N83	1.276 (12)	C87—C88	1.450 (18)
C6—N3	1.290 (5)	C87—H87	0.95
C6—C7	1.445 (5)	C88—C89	1.361 (11)
C6—C87	1.652 (14)	C88—H88	0.95
C12—C13	1.499 (2)	C89—H89	0.95
C12—H12a	0.99	C90—H90a	0.98
C12—H12b	0.99	C90—H90b	0.98
C13—H13a	0.98	C90—H90c	0.98

C1—S1—C4	91.41 (7)	O3—C14—O4	124.09 (13)
C11—O2—C12	116.43 (11)	O3—C14—C3	124.09 (12)
C14—O4—C15	116.74 (11)	O4—C14—C3	111.73 (11)
C1—N1—H1A	120	O4—C15—C16	111.07 (13)
C1—N1—H1B	120	O4—C15—H15A	109.4
H1A—N1—H1B	120	C16—C15—H15A	109.4
C5—N2—C4	120.54 (14)	O4—C15—H15B	109.4
N1—C1—C2	127.53 (13)	C16—C15—H15B	109.4
N1—C1—S1	120.36 (11)	H15A—C15—H15B	108
C2—C1—S1	112.11 (11)	C15—C16—H16A	109.5
C1—C2—C3	111.76 (12)	C15—C16—H16B	109.5
C1—C2—C11	120.36 (12)	H16A—C16—H16B	109.5
C3—C2—C11	127.55 (12)	C15—C16—H16C	109.5
C4—C3—C2	113.85 (12)	H16A—C16—H16C	109.5
C4—C3—C14	119.55 (13)	H16B—C16—H16C	109.5
C2—C3—C14	126.60 (12)	C6—N3—C9	109.6 (4)
C3—C4—N2	125.24 (13)	C6—N3—C10	125.8 (4)
C3—C4—S1	110.85 (11)	C9—N3—C10	124.5 (4)
N2—C4—S1	123.90 (11)	C8—C7—C6	104.3 (4)
N2—C5—C6	123.90 (16)	C8—C7—H7	127.9
N2—C5—H5	118.1	C6—C7—H7	127.9
C6—C5—H5	118.1	C9—C8—C7	107.0 (5)
N83—C6—N3	91.6 (4)	C9—C8—H8	126.5
N83—C6—C5	139.8 (4)	C7—C8—H8	126.5
N3—C6—C5	128.3 (2)	N3—C9—C8	109.6 (5)
N3—C6—C7	109.5 (3)	N3—C9—H9	125.2
C5—C6—C7	122.2 (2)	C8—C9—H9	125.2
N83—C6—C87	97.0 (7)	C6—N83—C89	121.2 (1)
C5—C6—C87	123.2 (6)	C6—N83—C90	114.4 (7)
C7—C6—C87	114.0 (6)	C89—N83—C90	124.4 (1)
O1—C11—O2	122.99 (12)	C88—C87—C6	106.4 (9)
O1—C11—C2	124.12 (13)	C88—C87—H87	126.8
O2—C11—C2	112.89 (11)	C6—C87—H87	126.8
O2—C12—C13	111.53 (14)	C89—C88—C87	104.90 (11)
O2—C12—H12A	109.3	C89—C88—H88	127.5
C13—C12—H12A	109.3	C87—C88—H88	127.5
O2—C12—H12B	109.3	N83—C89—C88	110.30 (13)
C13—C12—H12B	109.3	N83—C89—H89	124.9
H12A—C12—H12B	108	C88—C89—H89	124.9
C12—C13—H13A	109.5	N83—C90—H90A	109.5
C12—C13—H13B	109.5	N83—C90—H90B	109.5
H13A—C13—H13B	109.5	H90A—C90—H90B	109.5
C12—C13—H13C	109.5	N83—C90—H90C	109.5
H13A—C13—H13C	109.5	H90A—C90—H90C	109.5
H13B—C13—H13C	109.5	H90B—C90—H90C	109.5

C4—S1—C1—N1	179.29 (13)	C2—C3—C14—O4	77.00 (16)
C4—S1—C1—C2	−1.27 (11)	C14—O4—C15—C16	86.08 (17)
N1—C1—C2—C3	−179.63 (13)	N83—C6—N3—C9	8.3 (7)
S1—C1—C2—C3	0.98 (14)	C5—C6—N3—C9	−178.0 (4)
N1—C1—C2—C11	−5.7 (2)	C7—C6—N3—C9	0.4 (6)
S1—C1—C2—C11	174.91 (9)	C87—C6—N3—C9	−126 (7)
C1—C2—C3—C4	−0.01 (16)	N83—C6—N3—C10	−174.1 (7)
C11—C2—C3—C4	−173.40 (12)	C5—C6—N3—C10	−0.4 (7)
C1—C2—C3—C14	−179.28 (12)	C7—C6—N3—C10	178.1 (5)
C11—C2—C3—C14	7.3 (2)	C87—C6—N3—C10	52 (6)
C2—C3—C4—N2	178.30 (12)	N83—C6—C7—C8	−23.70 (19)
C14—C3—C4—N2	−2.4 (2)	N3—C6—C7—C8	0.3 (5)
C2—C3—C4—S1	−0.93 (15)	C5—C6—C7—C8	178.9 (4)
C14—C3—C4—S1	178.40 (9)	C87—C6—C7—C8	7.2 (1)
C5—N2—C4—C3	169.49 (14)	C6—C7—C8—C9	−1.0 (7)
C5—N2—C4—S1	−11.4 (2)	C6—N3—C9—C8	−1.1 (8)
C1—S1—C4—C3	1.25 (11)	C10—N3—C9—C8	−178.7 (6)
C1—S1—C4—N2	−177.99 (13)	C7—C8—C9—N3	1.3 (9)
C4—N2—C5—C6	175.94 (14)	N3—C6—N83—C89	−9.00 (14)
N2—C5—C6—N83	166.7 (8)	C5—C6—N83—C89	178.70 (11)
N2—C5—C6—N3	−3.6 (4)	C7—C6—N83—C89	148 (3)
N2—C5—C6—C7	178.1 (3)	C87—C6—N83—C89	−3.40 (15)
N2—C5—C6—C87	−10.9 (9)	N3—C6—N83—C90	170.4 (7)
C12—O2—C11—O1	2.11 (19)	C5—C6—N83—C90	−2.00 (13)
C12—O2—C11—C2	−178.63 (12)	C7—C6—N83—C90	−32.20 (15)
C1—C2—C11—O1	0.9 (2)	C87—C6—N83—C90	176.0 (1)
C3—C2—C11—O1	173.81 (13)	N83—C6—C87—C88	0.70 (15)
C1—C2—C11—O2	−178.33 (11)	N3—C6—C87—C88	47 (6)
C3—C2—C11—O2	−5.44 (19)	C5—C6—C87—C88	179.20 (11)
C11—O2—C12—C13	80.18 (17)	C7—C6—C87—C88	−9.20 (17)
C15—O4—C14—O3	0.2 (2)	C6—C87—C88—C89	2 (2)
C15—O4—C14—C3	176.97 (11)	C6—N83—C89—C88	5 (2)
C4—C3—C14—O3	74.56 (18)	C90—N83—C89—C88	−174.20 (14)
C2—C3—C14—O3	−106.21 (17)	C87—C88—C89—N83	−4 (2)
C4—C3—C14—O4	−102.23 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O3ⁱ	0.88	2.09	2.925 (3)	157

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₉N₃O₄S
M_r	349.40
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	123
a, b, c (Å)	8.8212 (18), 9.0799 (18), 21.793 (4)
β (°)	97.50 (3)
V (Å³)	1730.6 (6)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	1.89
Crystal size (mm)	0.17 × 0.16 × 0.15

Data collection
Diffractometer	Bruker SMART 6000
Absorption correction	Multi-scan (SADABS; Sheldrick,1996)
T_min, T_max	0.710, 0.762
No. of measured, independent and observed [I > 2σ(I)] reflections	20876, 3367, 3046
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.116, 1.07
No. of reflections	3367
No. of parameters	267
No. of restraints	32
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.54

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—H1B···O3ⁱ	0.88	2.094	2.925 (3)	157

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Acknowledgements

NSERC Canada is thanked for DG and RTI grants allowing this work to be performed in addition to CFI for additional equipment funding. SD also thanks NSERC for a graduate scholarship. WGS acknowledges both the Alexander von Humboldt Foundation and the RSC for a JWT Jones Travelling fellowships, allowing the completion of this manuscript.

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. & Skene, W. G. (2008). J. Org. Chem. 73, 3859–3866. Web of Science CSD CrossRef PubMed CAS Google Scholar
Dufresne, S. & Skene, W. G. (2010). Acta Cryst. E66, o3027. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Marris, T. (2004). UdMX. Université de Montréal, Montréal, Québec, Canada. 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
Skene, W. G., Dufresne, S., Trefz, T. & Simard, M. (2006). Acta Cryst. E62, o2382–o2384. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar

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

Di­ethyl 2-amino-5-[(E)-(1-methyl-1H-pyrrol-2-yl)methyl­idene­amino]thiophene-3,4-di­carboxylate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

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organic compounds

Diethyl 2-amino-5-[(E)-(1-methyl-1H-pyrrol-2-yl)methylideneamino]thiophene-3,4-dicarboxylate