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

The structure of the title compound, C(16)H(19)N(3)O(4)S, shows the planes described by the thio-phene 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 = 349.40

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.116

S = 1.07

3367 reflections

267 parameters

32 restraints

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.54 e Å−3

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 datablocks I, global. DOI: 10.1107/S1600536810046775/bh2321sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810046775/bh2321Isup2.hkl

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

C16H19N3O4S	F(000) = 736
Mr = 349.40	Dx = 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

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

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(Fo2) + (0.0845P)2 + 0.153P] where P = (Fo2 + 2Fc2)/3
3367 reflections	(Δ/σ)max < 0.001
267 parameters	Δρmax = 0.32 e Å−3
32 restraints	Δρmin = −0.54 e Å−3
0 constraints

	x	y	z	Uiso*/Ueq	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)

	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)

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)

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

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) .