(2Z,3E)-2,3-Bis(2-thienylmethylene)­succinic acid methanol hemisolvate

In the title compound, C₁₄H₁₀O₄S₂·0.5CH₃OH, the mol­ecule adopts a gauche conformation around the central C—C bond. Inter­molecular O—H...O hydrogen bonds between carboxyl groups link the mol­ecules into zigzag chains. Between chains, the thio­phene rings form π–π stacking inter­actions with a centroid–centroid distance of 3.98 Å. The methanol solvent mol­ecule forms an O—H...O hydrogen bond to one carboxyl group and is disordered about a crystallographic centre of inversion.

Key indicators

• Single-crystal X-ray study
• T = 290 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in solvent or counterion
• R factor = 0.072
• wR factor = 0.233
• Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       3.30
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      50.00 Perc.
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

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

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

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S1. Comment

Compounds containing the succinyl group are known for their promising biological activities. Succinyl peroxide is used as a germicide and antiseptic. Compounds such as succinylsulfathiazole and succisulfone exhibit antibacterial activity (Windholz, 1976). Amongst heterocyclic systems, thiophene derivatives exhibit diversity in biological applications, namely antibacterial, anti-inflammatory and antifungal activities (Nakanishi et al., 1970). The crystal and molecular structures of thiophene-containing compounds have recently been analyzed in detail (Vasu, 2007).

The title molecule (Fig. 1) is non-planar. It is evident from the torsion angles C10/C7/C6/C5 = 77.3 (4)° and C9/C6/C7/C8 = 73.6 (4)° that the thiophene rings and the carboxyl groups exist in a gauche arrangement. The thiophene bond lengths and bond angles are similar to those in unsubstituted thiophene (Bonham & Momany, 1963). The C6—C7 bond length [1.492 (4) Å] is slightly shorter than a typical single bond, suggesting the possibility of extended conjugation.

The crystal structure contains O—H···O carboxylic acid dimers, which link the molecules into zigzag chains. Between these chains, π-π stacking interactions are formed involving the thiophene ring [S1/C1–C4], with a centroid-centroid distance of 3.98 Å (Fig. 2) [symmetry code: -x + 1, y, -z + 1/2]. The methanol solvent molecule forms an O—H···O hydrogen bond to one carboxylic acid group, and is disordered over two equivalent sites.

Related literature

For related literature, see: Abdel-Wahhab & El-Rayyes (1971); Bonham & Momany (1963); Nakanishi et al. (1970); Vasu (2007); Windholz (1976).

S2. Experimental

The compound was made in accordance with the literature procedure (Abdel-Wahhab & El-Rayyes, 1971) and was recrystallized from methanol.

S3. Refinement

H atoms bound to C atoms were placed in calculated positions with C—H = 0.93–0.96 Å and refined as riding with U_iso(H) = 1.2 or 1.5 U_eq(C). The H atoms of the carboxyl groups were placed so as to form the best hydrogen bond (AFIX 83) with O—H = 0.82 Å, and refined as riding with U_iso(H) = 1.5 U_eq(O). In the case of C9/O1/O3, the hydrogen-bonded dimer is formed about a centre of inversion and the hydroxyl group could be distinguished by the longer C9—O3 bond length. For C8/O2/O4, the hydrogen bonded dimer is formed about a 2-fold rotation axis and the C8—O2 and C8—O4 bonds do not differ significantly, requiring the H atom to be disordered equally over atoms O2 and O4. The methanol molecule forms a hydrogen bond to the C9=O1 group, and atom H50 was placed along the O50···O1 vector with O—H = 0.82 Å and refined as riding with U_iso(H) = 1.5 U_eq(O). The methanol molecule is disordered equally over two equivalent sites related by a centre of inversion, with the C—O distance restrained to be 1.40 (1) Å.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1999) and CAMERON (Pearce et al., 1993); software used to prepare material for publication: PLATON (Spek, 2003).

Figures

	Fig. 1. Molecular structure of the title compound showing displacement ellipsoids at 30% probabilty for non-H atoms. The dashed line indicates an O—H···O hydrogen bond.
	Fig. 2. Partial packing diagram of the title compound showing the π–π stacking interaction between adjacent [S1/C1–C4] rings. The centroids (denoted Cg1) are joined by dotted lines.

(2Z,3E)-2,3-Bis(2-thienylmethylene)succinic acid methanol hemisolvate

Crystal data

C14H10O4S2·0.5CH4O	F(000) = 1336
Mr = 322.36	Dx = 1.349 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 560 reflections
a = 15.042 (7) Å	θ = 1.4–26.4°
b = 13.295 (6) Å	µ = 0.35 mm^−1
c = 16.219 (7) Å	T = 290 K
β = 101.792 (7)°	Block, yellow
V = 3175 (2) Å^3	0.25 × 0.20 × 0.15 mm
Z = 8

Data collection

Bruker SMART CCD area-detector diffractometer	2783 independent reflections
Radiation source: fine-focus sealed tube	2407 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ and ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→17
Tmin = 0.902, Tmax = 0.950	k = −15→15
14721 measured reflections	l = −19→19

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)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.233	H-atom parameters constrained
S = 1.12	w = 1/[σ^2(Fo^2) + (0.1453P)^2 + 4.5426P] where P = (Fo^2 + 2Fc^2)/3
2783 reflections	(Δ/σ)max < 0.001
189 parameters	Δρmax = 1.01 e Å^−3
1 restraint	Δρmin = −0.31 e Å^−3

Special details

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	Occ. (<1)
S1	0.04546 (7)	0.51459 (8)	0.13193 (8)	0.0698 (4)
S2	0.24373 (9)	0.57706 (9)	0.38316 (7)	0.0762 (4)
O1	0.2673 (2)	0.63802 (19)	0.05018 (16)	0.0654 (8)
O2	0.41114 (17)	0.62150 (18)	0.22940 (18)	0.0600 (7)
H2O	0.4661	0.6119	0.2424	0.090*	0.50
O3	0.2015 (2)	0.7757 (2)	0.08846 (18)	0.0820 (10)
H3O	0.2083	0.7946	0.0420	0.123*
O4	0.41109 (17)	0.45447 (18)	0.2387 (2)	0.0704 (9)
H4O	0.4660	0.4646	0.2508	0.106*	0.50
C1	0.1300 (2)	0.4297 (2)	0.1708 (2)	0.0440 (7)
C2	0.0941 (3)	0.3337 (3)	0.1680 (3)	0.0592 (9)
H2	0.1288	0.2768	0.1857	0.071*
C3	0.0010 (3)	0.3306 (3)	0.1359 (3)	0.0698 (11)
H3	−0.0332	0.2718	0.1307	0.084*
C4	−0.0342 (3)	0.4212 (4)	0.1134 (3)	0.0747 (12)
H4	−0.0952	0.4323	0.0903	0.090*
C5	0.2252 (2)	0.4518 (2)	0.19699 (19)	0.0416 (7)
H5	0.2617	0.3959	0.2134	0.050*
C6	0.2700 (2)	0.5393 (2)	0.20167 (19)	0.0402 (7)
C7	0.2259 (2)	0.6395 (2)	0.18277 (19)	0.0402 (7)
C8	0.3698 (2)	0.5376 (2)	0.2245 (2)	0.0456 (8)
C9	0.2323 (2)	0.6863 (2)	0.1019 (2)	0.0482 (8)
C10	0.1832 (2)	0.6901 (2)	0.2356 (2)	0.0437 (7)
H10	0.1527	0.7481	0.2137	0.052*
C11	0.1786 (2)	0.6665 (2)	0.3211 (2)	0.0503 (8)
C12	0.1206 (4)	0.7246 (3)	0.3669 (3)	0.0761 (13)
H12	0.0806	0.7761	0.3455	0.091*
C13	0.1383 (5)	0.6852 (4)	0.4523 (3)	0.0934 (18)
H13	0.1089	0.7096	0.4934	0.112*
C14	0.2006 (4)	0.6106 (4)	0.4678 (3)	0.0879 (16)
H14	0.2182	0.5803	0.5203	0.105*
C50	0.4751 (10)	0.5542 (11)	0.0075 (10)	0.122 (4)*	0.50
H50A	0.4454	0.5847	−0.0445	0.184*	0.50
H50B	0.5201	0.5075	−0.0032	0.184*	0.50
H50C	0.5038	0.6054	0.0456	0.184*	0.50
O50	0.4124 (13)	0.5001 (14)	0.0413 (13)	0.233 (8)*	0.50
H50	0.3689	0.5348	0.0468	0.349*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0508 (6)	0.0504 (6)	0.1032 (9)	0.0079 (4)	0.0038 (5)	0.0053 (5)
S2	0.1012 (9)	0.0771 (8)	0.0530 (7)	−0.0035 (6)	0.0217 (6)	0.0110 (5)
O1	0.101 (2)	0.0519 (15)	0.0530 (14)	0.0236 (14)	0.0386 (14)	0.0142 (11)
O2	0.0514 (14)	0.0375 (13)	0.0911 (19)	−0.0048 (10)	0.0145 (12)	0.0030 (12)
O3	0.138 (3)	0.0505 (16)	0.0713 (18)	0.0392 (17)	0.0534 (18)	0.0279 (13)
O4	0.0459 (14)	0.0369 (13)	0.124 (3)	0.0054 (10)	0.0060 (14)	0.0080 (14)
C1	0.0482 (17)	0.0401 (16)	0.0459 (17)	0.0012 (13)	0.0149 (13)	0.0058 (13)
C2	0.057 (2)	0.0457 (18)	0.075 (2)	−0.0067 (16)	0.0145 (18)	0.0125 (17)
C3	0.058 (2)	0.066 (2)	0.086 (3)	−0.0200 (19)	0.017 (2)	0.007 (2)
C4	0.046 (2)	0.077 (3)	0.099 (3)	−0.0014 (19)	0.009 (2)	0.002 (2)
C5	0.0464 (16)	0.0330 (15)	0.0463 (17)	0.0059 (12)	0.0119 (13)	0.0062 (12)
C6	0.0473 (17)	0.0333 (14)	0.0419 (16)	0.0031 (12)	0.0132 (13)	0.0059 (12)
C7	0.0470 (16)	0.0323 (14)	0.0430 (16)	0.0003 (12)	0.0138 (13)	0.0037 (12)
C8	0.0472 (17)	0.0348 (16)	0.0559 (19)	0.0017 (13)	0.0126 (14)	0.0028 (13)
C9	0.064 (2)	0.0372 (16)	0.0470 (17)	0.0094 (14)	0.0199 (15)	0.0074 (13)
C10	0.0489 (17)	0.0320 (15)	0.0531 (18)	−0.0015 (12)	0.0174 (14)	0.0019 (13)
C11	0.063 (2)	0.0427 (17)	0.0512 (18)	−0.0132 (15)	0.0260 (15)	−0.0065 (14)
C12	0.119 (4)	0.064 (2)	0.059 (2)	−0.038 (2)	0.049 (2)	−0.0141 (19)
C13	0.146 (5)	0.083 (3)	0.067 (3)	−0.033 (4)	0.059 (3)	−0.022 (2)
C14	0.134 (5)	0.084 (3)	0.052 (2)	−0.030 (3)	0.034 (3)	−0.001 (2)

Geometric parameters (Å, º)

S1—C4	1.708 (5)	C5—H5	0.930
S1—C1	1.721 (3)	C6—C8	1.470 (5)
S2—C14	1.693 (5)	C6—C7	1.492 (4)
S2—C11	1.728 (4)	C7—C10	1.351 (4)
O1—C9	1.254 (4)	C7—C9	1.472 (4)
O2—C8	1.272 (4)	C10—C11	1.436 (5)
O2—H2O	0.820	C10—H10	0.930
O3—C9	1.278 (4)	C11—C12	1.475 (6)
O3—H3O	0.820	C12—C13	1.454 (7)
O4—C8	1.266 (4)	C12—H12	0.930
O4—H4O	0.820	C13—C14	1.353 (8)
C1—C2	1.383 (5)	C13—H13	0.930
C1—C5	1.437 (5)	C14—H14	0.930
C2—C3	1.392 (6)	C50—O50	1.384 (9)
C2—H2	0.930	C50—H50A	0.960
C3—C4	1.336 (6)	C50—H50B	0.960
C3—H3	0.930	C50—H50C	0.960
C4—H4	0.930	O50—H50	0.820
C5—C6	1.340 (4)
C4—S1—C1	91.6 (2)	O4—C8—C6	119.8 (3)
C14—S2—C11	91.5 (3)	O2—C8—C6	117.6 (3)
C8—O2—H2O	109.5	O1—C9—O3	123.2 (3)
C9—O3—H3O	109.5	O1—C9—C7	119.5 (3)
C8—O4—H4O	109.5	O3—C9—C7	117.2 (3)
C2—C1—C5	123.8 (3)	C7—C10—C11	128.8 (3)
C2—C1—S1	109.8 (3)	C7—C10—H10	115.6
C5—C1—S1	126.3 (2)	C11—C10—H10	115.6
C1—C2—C3	113.3 (3)	C10—C11—C12	121.5 (3)
C1—C2—H2	123.3	C10—C11—S2	125.4 (3)
C3—C2—H2	123.3	C12—C11—S2	113.0 (3)
C4—C3—C2	112.8 (4)	C13—C12—C11	106.2 (5)
C4—C3—H3	123.6	C13—C12—H12	126.9
C2—C3—H3	123.6	C11—C12—H12	126.9
C3—C4—S1	112.5 (3)	C14—C13—C12	115.2 (4)
C3—C4—H4	123.7	C14—C13—H13	122.4
S1—C4—H4	123.7	C12—C13—H13	122.4
C6—C5—C1	130.8 (3)	C13—C14—S2	114.1 (4)
C6—C5—H5	114.6	C13—C14—H14	122.9
C1—C5—H5	114.6	S2—C14—H14	122.9
C5—C6—C8	118.5 (3)	O50—C50—H50A	109.6
C5—C6—C7	124.5 (3)	O50—C50—H50B	107.3
C8—C6—C7	117.0 (3)	O50—C50—H50C	111.5
C10—C7—C9	118.7 (3)	H50A—C50—H50B	109.5
C10—C7—C6	124.3 (3)	H50A—C50—H50C	109.5
C9—C7—C6	116.9 (3)	H50B—C50—H50C	109.5
O4—C8—O2	122.6 (3)	C50—O50—H50	112.0
C4—S1—C1—C2	0.1 (3)	C5—C6—C8—O2	−179.4 (3)
C4—S1—C1—C5	175.9 (3)	C7—C6—C8—O2	2.3 (4)
C5—C1—C2—C3	−176.4 (3)	C10—C7—C9—O1	−176.1 (3)
S1—C1—C2—C3	−0.5 (4)	C6—C7—C9—O1	5.6 (5)
C1—C2—C3—C4	0.9 (6)	C10—C7—C9—O3	4.1 (5)
C2—C3—C4—S1	−0.8 (6)	C6—C7—C9—O3	−174.1 (3)
C1—S1—C4—C3	0.4 (4)	C9—C7—C10—C11	−171.1 (3)
C2—C1—C5—C6	178.7 (3)	C6—C7—C10—C11	7.0 (5)
S1—C1—C5—C6	3.5 (5)	C7—C10—C11—C12	−173.4 (3)
C1—C5—C6—C8	−175.0 (3)	C7—C10—C11—S2	11.6 (5)
C1—C5—C6—C7	3.1 (5)	C14—S2—C11—C10	175.0 (3)
C5—C6—C7—C10	77.3 (4)	C14—S2—C11—C12	−0.3 (3)
C8—C6—C7—C10	−104.5 (4)	C10—C11—C12—C13	−175.7 (3)
C5—C6—C7—C9	−104.5 (4)	S2—C11—C12—C13	−0.1 (4)
C8—C6—C7—C9	73.6 (4)	C11—C12—C13—C14	0.7 (6)
C5—C6—C8—O4	0.4 (5)	C12—C13—C14—S2	−1.1 (6)
C7—C6—C8—O4	−177.8 (3)	C11—S2—C14—C13	0.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O50—H50···O1	0.82	2.06	2.88 (2)	171
O3—H3O···O1^i	0.82	1.84	2.650 (3)	168
O2—H2O···O2^ii	0.82	1.81	2.620 (5)	167
O4—H4O···O4^ii	0.82	1.83	2.624 (5)	164

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