Hydrogen-bonded network of diethyl 2,5-diamino­thio­phene-3,4-dicarboxyl­ate

The crystal structure of the title compound, C₁₀H₁₄N₂O₄S, has a supra­molecular network involving both inter- and intra­molecular hydrogen bonding. The thio­phene core of the mol­ecule adopts a planar geometry.

Key indicators

• Single-crystal X-ray study
• T = 220 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.042
• wR factor = 0.125
• Data-to-parameter ratio = 14.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.82
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.67 Ratio
PLAT420_ALERT_2_C D-H Without Acceptor       N2     -   H2B    ...          ?

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

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

diethyl 2,5-diaminothiophene-3,4-dicarboxylate

Crystal data

C10H14N2O4S	F(000) = 544
Mr = 258.29	Dx = 1.365 Mg m^−3
Monoclinic, P21/c	Melting point = 428–429 K
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54178 Å
a = 9.5306 (3) Å	Cell parameters from 8976 reflections
b = 8.8206 (3) Å	θ = 4.8–68.3°
c = 15.5518 (5) Å	µ = 2.37 mm^−1
β = 105.963 (1)°	T = 220 K
V = 1256.96 (7) Å^3	Block, colorless
Z = 4	0.32 × 0.28 × 0.15 mm

Data collection

Bruker SMART 6000 diffractometer	2270 independent reflections
Radiation source: Rotating Anode	2032 reflections with I > 2σ(I)
Montel 200 optics monochromator	Rint = 0.055
Detector resolution: 5.5 pixels mm^-1	θmax = 68.3°, θmin = 4.8°
ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −10→10
Tmin = 0.405, Tmax = 0.702	l = −17→15
16465 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0895P)^2 + 0.1856P] where P = (Fo^2 + 2Fc^2)/3
2270 reflections	(Δ/σ)max = 0.012
156 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

Experimental. On completion of the data collection, the first 101 frames were recollected for decay correction analysis using SAINT.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.44693 (5)	0.25668 (5)	0.15560 (3)	0.0394 (2)
O1	0.03919 (14)	−0.04344 (15)	0.10762 (9)	0.0451 (4)
O2	0.02651 (12)	0.06675 (14)	0.23561 (8)	0.0357 (3)
O3	0.26221 (13)	−0.01334 (14)	0.37325 (8)	0.0392 (3)
O4	0.38359 (14)	0.19601 (16)	0.43339 (8)	0.0441 (3)
N1	0.23991 (18)	0.1084 (2)	0.03354 (10)	0.0469 (4)
H1A	0.1630	0.0514	0.0151	0.056*
H1B	0.2838	0.1433	−0.0045	0.056*
N2	0.54748 (17)	0.3193 (2)	0.33018 (11)	0.0512 (5)
H2A	0.5494	0.3112	0.3862	0.061*
H2B	0.6133	0.3732	0.3149	0.061*
C1	0.29108 (18)	0.14254 (19)	0.12110 (11)	0.0335 (4)
C2	0.23954 (17)	0.10016 (17)	0.19235 (10)	0.0298 (4)
C3	0.33000 (17)	0.15861 (18)	0.27735 (10)	0.0301 (4)
C4	0.44253 (19)	0.24820 (18)	0.26684 (12)	0.0352 (4)
C5	0.09533 (17)	0.03121 (17)	0.17386 (11)	0.0307 (4)
C6	0.32620 (17)	0.11865 (19)	0.36730 (11)	0.0328 (4)
C7	−0.11305 (19)	−0.0064 (2)	0.22757 (13)	0.0422 (4)
H7A	−0.1000	−0.1158	0.2375	0.051*
H7B	−0.1793	0.0105	0.1679	0.051*
C8	−0.1728 (3)	0.0632 (4)	0.2970 (2)	0.0794 (9)
H8A	−0.1117	0.0360	0.3558	0.119*
H8B	−0.2712	0.0264	0.2900	0.119*
H8C	−0.1745	0.1726	0.2904	0.119*
C9	0.2495 (2)	−0.0531 (2)	0.46179 (13)	0.0504 (5)
H9A	0.1930	0.0242	0.4829	0.061*
H9B	0.3465	−0.0597	0.5044	0.061*
C10	0.1747 (4)	−0.2015 (3)	0.45402 (16)	0.0758 (8)
H10A	0.0793	−0.1938	0.4112	0.114*
H10B	0.1633	−0.2307	0.5119	0.114*
H10C	0.2323	−0.2773	0.4339	0.114*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0378 (3)	0.0434 (3)	0.0429 (3)	−0.00892 (16)	0.0210 (2)	0.00052 (16)
O1	0.0464 (7)	0.0520 (8)	0.0395 (7)	−0.0161 (6)	0.0161 (6)	−0.0110 (6)
O2	0.0289 (6)	0.0418 (7)	0.0406 (7)	−0.0060 (5)	0.0166 (5)	−0.0051 (5)
O3	0.0451 (7)	0.0423 (7)	0.0312 (6)	−0.0072 (5)	0.0121 (5)	0.0026 (5)
O4	0.0460 (7)	0.0527 (8)	0.0372 (7)	−0.0080 (6)	0.0173 (5)	−0.0129 (6)
N1	0.0516 (9)	0.0599 (10)	0.0332 (8)	−0.0153 (8)	0.0183 (6)	−0.0013 (7)
N2	0.0468 (10)	0.0621 (11)	0.0484 (10)	−0.0243 (8)	0.0192 (7)	−0.0119 (8)
C1	0.0335 (8)	0.0331 (8)	0.0374 (9)	−0.0010 (6)	0.0153 (6)	0.0011 (6)
C2	0.0299 (8)	0.0286 (8)	0.0342 (8)	0.0007 (6)	0.0144 (6)	−0.0005 (6)
C3	0.0290 (8)	0.0300 (8)	0.0347 (9)	0.0007 (6)	0.0142 (6)	−0.0023 (6)
C4	0.0326 (9)	0.0346 (9)	0.0415 (10)	−0.0016 (6)	0.0156 (7)	−0.0024 (6)
C5	0.0317 (8)	0.0298 (8)	0.0329 (8)	0.0003 (6)	0.0125 (6)	0.0025 (6)
C6	0.0277 (8)	0.0386 (9)	0.0348 (9)	0.0024 (6)	0.0129 (6)	−0.0032 (7)
C7	0.0312 (9)	0.0478 (10)	0.0511 (11)	−0.0100 (8)	0.0173 (7)	0.0003 (8)
C8	0.0565 (14)	0.098 (2)	0.105 (2)	−0.0267 (13)	0.0574 (15)	−0.0374 (16)
C9	0.0601 (12)	0.0584 (12)	0.0341 (10)	−0.0131 (9)	0.0152 (8)	0.0050 (8)
C10	0.114 (2)	0.0672 (15)	0.0475 (13)	−0.0355 (15)	0.0249 (13)	0.0065 (11)

Geometric parameters (Å, º)

S1—C4	1.7434 (19)	C2—C3	1.459 (2)
S1—C1	1.7519 (17)	C3—C4	1.378 (2)
O1—C5	1.216 (2)	C3—C6	1.453 (2)
O2—C5	1.3405 (19)	C7—C8	1.485 (3)
O2—C7	1.452 (2)	C7—H7A	0.98
O3—C6	1.329 (2)	C7—H7B	0.98
O3—C9	1.458 (2)	C8—H8A	0.97
O4—C6	1.230 (2)	C8—H8B	0.97
N1—C1	1.348 (2)	C8—H8C	0.97
N1—H1A	0.87	C9—C10	1.480 (3)
N1—H1B	0.87	C9—H9A	0.98
N2—C4	1.350 (2)	C9—H9B	0.98
N2—H2A	0.87	C10—H10A	0.97
N2—H2B	0.87	C10—H10B	0.97
C1—C2	1.381 (2)	C10—H10C	0.97
C2—C5	1.457 (2)
C4—S1—C1	91.69 (8)	O3—C6—C3	114.39 (14)
C5—O2—C7	116.83 (13)	O2—C7—C8	106.21 (16)
C6—O3—C9	115.79 (14)	O2—C7—H7A	110.5
C1—N1—H1A	120	C8—C7—H7A	110.5
C1—N1—H1B	120	O2—C7—H7B	110.5
H1A—N1—H1B	120	C8—C7—H7B	110.5
C4—N2—H2A	120	H7A—C7—H7B	108.7
C4—N2—H2B	120	C7—C8—H8A	109.5
H2A—N2—H2B	120	C7—C8—H8B	109.5
N1—C1—C2	129.79 (16)	H8A—C8—H8B	109.5
N1—C1—S1	118.59 (13)	C7—C8—H8C	109.5
C2—C1—S1	111.62 (12)	H8A—C8—H8C	109.5
C1—C2—C5	118.61 (14)	H8B—C8—H8C	109.5
C1—C2—C3	112.28 (14)	O3—C9—C10	107.40 (17)
C5—C2—C3	128.04 (13)	O3—C9—H9A	110.2
C4—C3—C6	118.68 (15)	C10—C9—H9A	110.2
C4—C3—C2	112.35 (14)	O3—C9—H9B	110.2
C6—C3—C2	128.43 (14)	C10—C9—H9B	110.2
N2—C4—C3	128.66 (17)	H9A—C9—H9B	108.5
N2—C4—S1	119.27 (13)	C9—C10—H10A	109.5
C3—C4—S1	111.98 (13)	C9—C10—H10B	109.5
O1—C5—O2	123.07 (15)	H10A—C10—H10B	109.5
O1—C5—C2	124.38 (15)	C9—C10—H10C	109.5
O2—C5—C2	112.44 (14)	H10A—C10—H10C	109.5
O4—C6—O3	122.35 (15)	H10B—C10—H10C	109.5
O4—C6—C3	123.17 (15)
C4—S1—C1—N1	−179.91 (15)	C1—S1—C4—C3	1.78 (13)
C4—S1—C1—C2	−0.25 (13)	C7—O2—C5—O1	8.8 (2)
N1—C1—C2—C5	−12.5 (3)	C7—O2—C5—C2	−175.00 (14)
S1—C1—C2—C5	167.85 (12)	C1—C2—C5—O1	29.2 (2)
N1—C1—C2—C3	178.35 (17)	C3—C2—C5—O1	−163.64 (17)
S1—C1—C2—C3	−1.27 (18)	C1—C2—C5—O2	−147.00 (15)
C1—C2—C3—C4	2.6 (2)	C3—C2—C5—O2	20.2 (2)
C5—C2—C3—C4	−165.20 (15)	C9—O3—C6—O4	6.7 (2)
C1—C2—C3—C6	−168.76 (16)	C9—O3—C6—C3	−176.82 (15)
C5—C2—C3—C6	23.4 (3)	C4—C3—C6—O4	25.4 (2)
C6—C3—C4—N2	−6.9 (3)	C2—C3—C6—O4	−163.69 (16)
C2—C3—C4—N2	−179.28 (17)	C4—C3—C6—O3	−151.10 (15)
C6—C3—C4—S1	169.53 (12)	C2—C3—C6—O3	19.8 (2)
C2—C3—C4—S1	−2.80 (18)	C5—O2—C7—C8	−174.27 (19)
C1—S1—C4—N2	178.63 (15)	C6—O3—C9—C10	179.40 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.87	2.26	2.827 (2)	123
N1—H1A···O1^i	0.87	2.31	3.002 (2)	137
N1—H1B···O4^ii	0.87	2.09	2.907 (2)	157
N2—H2A···O4	0.87	2.17	2.753 (2)	124

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