organic compounds
(±)-trans-6,7-Dimethoxy-1-oxo-3-(2-thienyl)isochroman-4-carboxylic acid
aDepartment of Physics, Faculty of Arts and Sciences, Erciyes University, 38039 Kayseri, Turkey, bFaculty of Chemistry, University of Sofia, 1 James Bourchier Boulevard, 1164 Sofia, Bulgaria, and cDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139 Samsun, Turkey
*Correspondence e-mail: akkurt@erciyes.edu.tr
The title compound, C16H14O6S, was synthesized by the reaction of 6,7-dimethoxyhomophthalic anhydride with thiophene-2-carbaldehyde in the presence of 4-(dimethylamino)pyridine (DMAP) as a basic catalyst. The thiophene ring of the title molecule is disordered over two sites with occupancies of 0.877 (3) and 0.123 (3). The disorder corresponds to an approximate 180° rotation of the thiophene ring with respect to the C—C bond linking it to the rest of the molecule. The six-membered ring of the 3,4-dihydroisochromanone ring system is not planar [puckering parameters QT = 0.571 (2) Å, θ = 115.2 (2)° and φ = 99.1 (2)°]. The benzene ring of the 3,4-dihydroisochromanone ring system makes dihedral angles of 75.0 (2) and 77.2 (5)° with the disordered thiophene rings. Intermolecular O—H⋯O and C—H⋯O hydrogen bonds, as well as C—H⋯π interactions, lead to the observed supramolecular structure.
Related literature
For details of the synthesis of the title compound, see: Bogdanov & Palamareva (2004). For the synthesis of new dihydroisocoumarins, see: Bogdanov et al. (2007a,b). For ring-puckering parameters, see: Cremer & Pople (1975).
Experimental
Crystal data
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Refinement
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Data collection: X-AREA (Stoe & Cie, 2002); cell X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
10.1107/S1600536809018844/im2117sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809018844/im2117Isup2.hkl
Compound (I) was synthesized by the reaction of 6,7-dimethoxyhomophthalic anhydride (1) with thiophene-2-carbaldehyde (2) in the presence of DMAP as a basic catalyst (Bogdanov & Palamareva, 2004). To a mixture of 1 (0.33 g, 1.5 mmol) and 2 (0.15 ml, 1.65 mmol) in dry chloroform (5 ml) DMAP (0.18 g, 1.5 mmol) was added. The mixture was stirred at room temperature for 1 h. At the end of the reaction (monitored by TLC), the reaction mixture was extracted with 10% sodium hydrogen carbonate. The aqueous layer was further acidified (pH = 3) with 10% hydrochloric acid and extracted with ethyl acetate. The organic layer was dried (sodium sulfate), filtered and the solvent was then evaporated under reduced pressure giving (0.49 g, 98%) of a diastereomeric mixture of cis- and trans-(±)-6,7-dimethoxy-1-oxo-3-(thiophen-2-yl)isochroman-4-carboxylic acids, in a 30:70 ratio, favoring the trans diastereomer. Pure trans-diastereomer (I) was obtained by fractional crystallization of the residue from ethyl acetate. The product was characterized by 1H NMR, IR spectra and elemental analysis. Single crystals were obtained by slow evaporation of a chloroform–ethyl acetate (3:1) solution of (I) at room temperature (m.p. 465–467 K). Analysis, calculated for C16H14O6S (334.34): C 57.48, H 4.22, O 28.71, S 9.59 (%); found: C 57.74, H 3.97, O 28.71, S 9.91 (%). IR (KBr) 1693 cm-1 (C═O), 1741 cm-1 (C═O). The 1H NMR spectrum of (I) was obtained on a Bruker DRX-250 spectrometer at 250.13 MHz. Chemical shifts (δ) are expressed in parts per million (p.p.m.). 1H NMR (250 MHz, DMSO-d6) δ = 3.82 (3H, s, –O—CH3), 3.85 (3H, s, –O—CH3), 4.43 (1H, d, J = 3 Hz, H-4), 6.29 (1H, d, J = 3 Hz, H-3), 6.96 (1H, dd, J = 3.6 and 5 Hz, Th—H), 7.08 (1H, s, Ph—H), 7.13 (1H, d, J = 3.5 Hz, Th—H), 7.37 (1H, s, Ph—H), 7.44 (1H, dd, J = 1 and 5 Hz, Th—H).
The H atom of the hydroxyl group was found from a difference Fourier map and refined freely [O6—H6 = 0.864 (3) Å]. H atoms bonded to C atoms were placed at calculated positions with the C—H distances in a range of 0.93–0.98 Å, and were included in the
in the riding-model approximation, with Uiso(H) = 1.2 or 1.5Ueq(C). The ratio of the refined site occupancies for the major and minor components of the disordered thiophene ring is 0.877 (3):0.123 (3). Similarity restraints were applied to the displacement parameters of the disordered atoms, and there were also geometrical restraints.Data collection: X-AREA (Stoe & Cie, 2002); cell
X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).Fig. 1. The title molecule of (I) with the atom-labelling scheme and displacement ellipsoids drawn at the 30% probability level. The minor component of the disorder has been omitted. | |
Fig. 2. Perspective view of the intermolecular hdrogen bonding interactions in the structure of (I). H atoms not involved in hydrogen bonding and the minor component of the disordered thiophene ring have been omitted for clarity. |
C16H14O6S | Z = 2 |
Mr = 334.34 | F(000) = 348 |
Triclinic, P1 | Dx = 1.428 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.3369 (6) Å | Cell parameters from 16761 reflections |
b = 8.4587 (6) Å | θ = 2.6–28.0° |
c = 11.9143 (9) Å | µ = 0.24 mm−1 |
α = 76.441 (6)° | T = 296 K |
β = 81.127 (6)° | Prism, colourless |
γ = 72.958 (6)° | 0.53 × 0.41 × 0.21 mm |
V = 777.6 (1) Å3 |
Stoe IPDS II diffractometer | 3229 independent reflections |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 2663 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.030 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.5°, θmin = 2.6° |
ω scans | h = −10→10 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −10→10 |
Tmin = 0.885, Tmax = 0.952 | l = −14→14 |
8329 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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0514P)2 + 0.2422P] where P = (Fo2 + 2Fc2)/3 |
3229 reflections | (Δ/σ)max < 0.001 |
219 parameters | Δρmax = 0.27 e Å−3 |
13 restraints | Δρmin = −0.31 e Å−3 |
C16H14O6S | γ = 72.958 (6)° |
Mr = 334.34 | V = 777.6 (1) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.3369 (6) Å | Mo Kα radiation |
b = 8.4587 (6) Å | µ = 0.24 mm−1 |
c = 11.9143 (9) Å | T = 296 K |
α = 76.441 (6)° | 0.53 × 0.41 × 0.21 mm |
β = 81.127 (6)° |
Stoe IPDS II diffractometer | 3229 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 2663 reflections with I > 2σ(I) |
Tmin = 0.885, Tmax = 0.952 | Rint = 0.030 |
8329 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 13 restraints |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.27 e Å−3 |
3229 reflections | Δρmin = −0.31 e Å−3 |
219 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1A | 0.17140 (13) | 0.63559 (11) | 0.85712 (7) | 0.0759 (3) | 0.877 (3) |
O1 | 0.5188 (2) | 0.77377 (19) | 0.14713 (12) | 0.0557 (5) | |
O2 | 0.38518 (19) | 0.54308 (18) | 0.12791 (12) | 0.0503 (5) | |
O3 | 0.15691 (17) | 0.32562 (15) | 0.54690 (12) | 0.0445 (4) | |
O4 | 0.13106 (15) | 0.53400 (15) | 0.63275 (10) | 0.0370 (4) | |
O5 | 0.42866 (19) | 0.91589 (18) | 0.62175 (13) | 0.0515 (5) | |
O6 | 0.22136 (17) | 1.01715 (16) | 0.50460 (13) | 0.0451 (4) | |
C1 | 0.33543 (19) | 0.67769 (19) | 0.44799 (14) | 0.0304 (4) | |
C2 | 0.4244 (2) | 0.7526 (2) | 0.35183 (16) | 0.0356 (5) | |
C3 | 0.4377 (2) | 0.7065 (2) | 0.24602 (16) | 0.0384 (5) | |
C4 | 0.3637 (2) | 0.5802 (2) | 0.23513 (15) | 0.0372 (5) | |
C5 | 0.2797 (2) | 0.5039 (2) | 0.33076 (16) | 0.0359 (5) | |
C6 | 0.26476 (19) | 0.55214 (19) | 0.43731 (15) | 0.0311 (5) | |
C7 | 0.6107 (4) | 0.8880 (4) | 0.1547 (2) | 0.0869 (13) | |
C8 | 0.3476 (3) | 0.3914 (3) | 0.12059 (19) | 0.0611 (8) | |
C9 | 0.1816 (2) | 0.4620 (2) | 0.53946 (15) | 0.0330 (5) | |
C10 | 0.1347 (2) | 0.7092 (2) | 0.61942 (15) | 0.0319 (5) | |
C11 | 0.31183 (19) | 0.72133 (19) | 0.56665 (14) | 0.0305 (4) | |
C12 | 0.3300 (2) | 0.8940 (2) | 0.56779 (15) | 0.0339 (5) | |
C13 | 0.0822 (2) | 0.7555 (2) | 0.73510 (16) | 0.0385 (5) | |
C14A | −0.0344 (8) | 0.8941 (8) | 0.7626 (6) | 0.0585 (17) | 0.877 (3) |
C15 | −0.0506 (4) | 0.9063 (4) | 0.8781 (2) | 0.0802 (8) | |
C16 | 0.0534 (4) | 0.7747 (4) | 0.9384 (2) | 0.0802 (8) | |
S1B | −0.0621 (16) | 0.9313 (15) | 0.7433 (10) | 0.058 (3) | 0.123 (3) |
C14B | 0.144 (3) | 0.692 (3) | 0.8422 (15) | 0.0802 (8) | 0.123 (3) |
H5 | 0.23240 | 0.41970 | 0.32480 | 0.0430* | |
H6 | 0.227 (3) | 1.112 (3) | 0.516 (2) | 0.064 (7)* | |
H7A | 0.69670 | 0.83190 | 0.20660 | 0.1050* | |
H7B | 0.53550 | 0.98290 | 0.18340 | 0.1050* | |
H7C | 0.66180 | 0.92640 | 0.07920 | 0.1050* | |
H8A | 0.23190 | 0.39800 | 0.14800 | 0.0730* | |
H2 | 0.47510 | 0.83390 | 0.35870 | 0.0430* | |
H8C | 0.36690 | 0.37790 | 0.04140 | 0.0730* | |
H10 | 0.05270 | 0.78130 | 0.56540 | 0.0380* | |
H11 | 0.39450 | 0.63610 | 0.61480 | 0.0370* | |
H14A | −0.09870 | 0.97510 | 0.70800 | 0.0700* | 0.877 (3) |
H15 | −0.12440 | 0.99480 | 0.90910 | 0.0960* | |
H16 | 0.06060 | 0.76040 | 1.01750 | 0.0960* | |
H8B | 0.41900 | 0.29650 | 0.16740 | 0.0730* | |
H14B | 0.23880 | 0.60080 | 0.85330 | 0.0960* | 0.123 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1A | 0.0947 (6) | 0.0739 (6) | 0.0417 (4) | 0.0110 (4) | −0.0144 (3) | −0.0153 (3) |
O1 | 0.0752 (10) | 0.0589 (9) | 0.0414 (8) | −0.0358 (8) | 0.0138 (7) | −0.0161 (6) |
O2 | 0.0680 (9) | 0.0552 (8) | 0.0366 (7) | −0.0240 (7) | −0.0013 (6) | −0.0192 (6) |
O3 | 0.0519 (7) | 0.0311 (6) | 0.0557 (8) | −0.0171 (6) | 0.0018 (6) | −0.0156 (6) |
O4 | 0.0425 (6) | 0.0332 (6) | 0.0399 (7) | −0.0162 (5) | 0.0033 (5) | −0.0132 (5) |
O5 | 0.0596 (8) | 0.0501 (8) | 0.0586 (9) | −0.0260 (7) | −0.0186 (7) | −0.0145 (7) |
O6 | 0.0488 (7) | 0.0274 (6) | 0.0646 (9) | −0.0079 (5) | −0.0164 (6) | −0.0154 (6) |
C1 | 0.0262 (7) | 0.0273 (7) | 0.0391 (9) | −0.0044 (6) | −0.0033 (6) | −0.0128 (6) |
C2 | 0.0346 (8) | 0.0336 (8) | 0.0430 (9) | −0.0126 (7) | 0.0006 (7) | −0.0144 (7) |
C3 | 0.0391 (9) | 0.0362 (9) | 0.0392 (9) | −0.0089 (7) | 0.0020 (7) | −0.0112 (7) |
C4 | 0.0379 (9) | 0.0384 (9) | 0.0370 (9) | −0.0062 (7) | −0.0049 (7) | −0.0152 (7) |
C5 | 0.0342 (8) | 0.0349 (8) | 0.0437 (10) | −0.0099 (7) | −0.0054 (7) | −0.0157 (7) |
C6 | 0.0264 (7) | 0.0287 (8) | 0.0395 (9) | −0.0046 (6) | −0.0035 (6) | −0.0128 (7) |
C7 | 0.129 (3) | 0.100 (2) | 0.0588 (15) | −0.084 (2) | 0.0344 (16) | −0.0281 (15) |
C8 | 0.0914 (17) | 0.0613 (13) | 0.0447 (12) | −0.0308 (13) | −0.0033 (11) | −0.0266 (10) |
C9 | 0.0298 (8) | 0.0292 (8) | 0.0422 (9) | −0.0064 (6) | −0.0041 (7) | −0.0131 (7) |
C10 | 0.0324 (8) | 0.0282 (8) | 0.0373 (9) | −0.0086 (6) | −0.0015 (7) | −0.0113 (6) |
C11 | 0.0296 (7) | 0.0270 (7) | 0.0365 (9) | −0.0060 (6) | −0.0041 (6) | −0.0108 (6) |
C12 | 0.0349 (8) | 0.0357 (8) | 0.0364 (9) | −0.0137 (7) | 0.0009 (7) | −0.0150 (7) |
C13 | 0.0384 (9) | 0.0389 (9) | 0.0404 (10) | −0.0109 (7) | 0.0015 (7) | −0.0148 (7) |
C14A | 0.066 (3) | 0.053 (3) | 0.047 (3) | 0.001 (2) | −0.0090 (19) | −0.011 (2) |
C15 | 0.1059 (16) | 0.0819 (14) | 0.0539 (11) | −0.0163 (11) | 0.0061 (10) | −0.0355 (10) |
C16 | 0.1059 (16) | 0.0819 (14) | 0.0539 (11) | −0.0163 (11) | 0.0061 (10) | −0.0355 (10) |
S1B | 0.065 (4) | 0.054 (5) | 0.041 (4) | 0.015 (3) | −0.008 (3) | −0.020 (4) |
C14B | 0.1059 (16) | 0.0819 (14) | 0.0539 (11) | −0.0163 (11) | 0.0061 (10) | −0.0355 (10) |
S1A—C13 | 1.702 (2) | C10—C13 | 1.487 (2) |
S1A—C16 | 1.689 (3) | C10—C11 | 1.536 (2) |
S1B—C15 | 1.584 (12) | C11—C12 | 1.515 (2) |
S1B—C13 | 1.628 (13) | C13—C14B | 1.379 (19) |
O1—C7 | 1.423 (4) | C13—C14A | 1.357 (7) |
O1—C3 | 1.354 (2) | C14A—C15 | 1.387 (7) |
O2—C8 | 1.431 (3) | C14B—C16 | 1.47 (2) |
O2—C4 | 1.359 (2) | C15—C16 | 1.326 (4) |
O3—C9 | 1.211 (2) | C2—H2 | 0.9300 |
O4—C9 | 1.344 (2) | C5—H5 | 0.9300 |
O4—C10 | 1.462 (2) | C7—H7A | 0.9600 |
O5—C12 | 1.197 (2) | C7—H7B | 0.9600 |
O6—C12 | 1.327 (2) | C7—H7C | 0.9600 |
O6—H6 | 0.86 (3) | C8—H8A | 0.9600 |
C1—C11 | 1.513 (2) | C8—H8B | 0.9600 |
C1—C2 | 1.392 (2) | C8—H8C | 0.9600 |
C1—C6 | 1.394 (2) | C10—H10 | 0.9800 |
C2—C3 | 1.384 (3) | C11—H11 | 0.9800 |
C3—C4 | 1.419 (2) | C14A—H14A | 0.9300 |
C4—C5 | 1.371 (3) | C14B—H14B | 0.9300 |
C5—C6 | 1.399 (2) | C15—H15 | 0.9300 |
C6—C9 | 1.469 (2) | C16—H16 | 0.9300 |
S1A···O4 | 3.0857 (15) | C3···H11viii | 3.0300 |
S1A···C8i | 3.589 (2) | C4···H11viii | 2.8300 |
S1B···O6ii | 3.308 (12) | C5···H8B | 2.8100 |
S1B···O6 | 3.488 (13) | C5···H11viii | 2.7400 |
S1B···C12 | 3.571 (13) | C5···H8A | 2.6600 |
S1B···C2ii | 3.530 (13) | C6···H10 | 2.7900 |
S1B···C3ii | 3.694 (13) | C6···H11viii | 2.8700 |
S1A···H8Ci | 3.0000 | C7···H2 | 2.5200 |
S1A···H11 | 3.1800 | C8···H5 | 2.5100 |
O1···O2 | 2.581 (2) | C9···H11 | 2.9600 |
O2···O1 | 2.581 (2) | C9···H6iii | 2.95 (2) |
O3···O6iii | 2.6575 (18) | C12···H2 | 2.6900 |
O3···C6iv | 3.350 (2) | H2···O6 | 2.8500 |
O3···O4iv | 3.2369 (19) | H2···C7 | 2.5200 |
O3···C9iv | 3.051 (2) | H2···C12 | 2.6900 |
O4···O3iv | 3.2369 (19) | H2···H7A | 2.3800 |
O4···S1A | 3.0857 (15) | H2···H7B | 2.2400 |
O5···O6v | 3.212 (2) | H2···O5v | 2.5400 |
O5···O5v | 3.138 (2) | H5···O3 | 2.6100 |
O5···C12v | 3.244 (2) | H5···C8 | 2.5100 |
O5···C7v | 3.382 (3) | H5···H8A | 2.1600 |
O6···S1Bii | 3.308 (12) | H5···H8B | 2.4700 |
O6···C2 | 3.150 (2) | H5···O4iv | 2.9200 |
O6···O3vi | 2.6575 (18) | H6···O3vi | 1.84 (2) |
O6···S1B | 3.488 (13) | H6···C9vi | 2.95 (2) |
O6···C13 | 3.385 (2) | H6···H10ii | 2.5000 |
O6···O5v | 3.212 (2) | H7A···C2 | 2.7800 |
O1···H8Cvii | 2.7500 | H7A···H2 | 2.3800 |
O2···H8Cvii | 2.7700 | H7B···C2 | 2.7100 |
O3···H6iii | 1.84 (2) | H7B···H2 | 2.2400 |
O3···H10iv | 2.8100 | H7B···H8Bvi | 2.5200 |
O3···H5 | 2.6100 | H7B···O5v | 2.7400 |
O4···H5iv | 2.9200 | H7C···H15x | 2.5600 |
O5···H2v | 2.5400 | H8A···C5 | 2.6600 |
O5···H7Bv | 2.7400 | H8A···H5 | 2.1600 |
O6···H14Aii | 2.8500 | H8B···C5 | 2.8100 |
O6···H10 | 2.6700 | H8B···H5 | 2.4700 |
O6···H2 | 2.8500 | H8B···H7Biii | 2.5200 |
O6···H10ii | 2.5400 | H8C···S1Aix | 3.0000 |
C1···C1viii | 3.545 (2) | H8C···O1vii | 2.7500 |
C2···S1Bii | 3.530 (13) | H8C···O2vii | 2.7700 |
C2···C9viii | 3.532 (2) | H10···O6 | 2.6700 |
C2···O6 | 3.150 (2) | H10···C6 | 2.7900 |
C3···S1Bii | 3.694 (13) | H10···H14A | 2.5700 |
C6···O3iv | 3.350 (2) | H10···O3iv | 2.8100 |
C7···O5v | 3.382 (3) | H10···O6ii | 2.5400 |
C8···S1Aix | 3.589 (2) | H10···H6ii | 2.5000 |
C9···C9iv | 3.150 (2) | H11···S1A | 3.1800 |
C9···C2viii | 3.532 (2) | H11···C9 | 2.9600 |
C9···O3iv | 3.051 (2) | H11···C1viii | 3.1000 |
C12···O5v | 3.244 (2) | H11···C3viii | 3.0300 |
C12···S1B | 3.571 (13) | H11···C4viii | 2.8300 |
C12···C14A | 3.527 (7) | H11···C5viii | 2.7400 |
C13···O6 | 3.385 (2) | H11···C6viii | 2.8700 |
C14A···C12 | 3.527 (7) | H14A···H10 | 2.5700 |
C1···H11viii | 3.1000 | H14A···O6ii | 2.8500 |
C2···H7B | 2.7100 | H14A···C2ii | 3.0600 |
C2···H14Aii | 3.0600 | H15···H7Cxi | 2.5600 |
C2···H7A | 2.7800 | ||
C13—S1A—C16 | 91.85 (12) | C13—C14A—C15 | 115.2 (5) |
C13—S1B—C15 | 92.3 (7) | C13—C14B—C16 | 117.2 (17) |
C3—O1—C7 | 117.71 (16) | C14A—C15—C16 | 110.8 (4) |
C4—O2—C8 | 116.56 (15) | S1B—C15—C16 | 123.5 (5) |
C9—O4—C10 | 117.75 (13) | S1A—C16—C15 | 113.17 (19) |
C12—O6—H6 | 108.4 (17) | C14B—C16—C15 | 98.8 (9) |
C6—C1—C11 | 116.64 (14) | C1—C2—H2 | 120.00 |
C2—C1—C6 | 119.26 (15) | C3—C2—H2 | 120.00 |
C2—C1—C11 | 124.09 (15) | C4—C5—H5 | 120.00 |
C1—C2—C3 | 120.20 (16) | C6—C5—H5 | 120.00 |
O1—C3—C2 | 124.71 (16) | O1—C7—H7A | 110.00 |
C2—C3—C4 | 120.36 (16) | O1—C7—H7B | 109.00 |
O1—C3—C4 | 114.93 (16) | O1—C7—H7C | 109.00 |
C3—C4—C5 | 119.21 (16) | H7A—C7—H7B | 109.00 |
O2—C4—C5 | 125.01 (16) | H7A—C7—H7C | 109.00 |
O2—C4—C3 | 115.78 (16) | H7B—C7—H7C | 109.00 |
C4—C5—C6 | 120.31 (16) | O2—C8—H8A | 109.00 |
C5—C6—C9 | 118.97 (15) | O2—C8—H8B | 109.00 |
C1—C6—C5 | 120.64 (16) | O2—C8—H8C | 109.00 |
C1—C6—C9 | 120.30 (15) | H8A—C8—H8B | 109.00 |
O4—C9—C6 | 118.04 (14) | H8A—C8—H8C | 109.00 |
O3—C9—O4 | 117.07 (16) | H8B—C8—H8C | 109.00 |
O3—C9—C6 | 124.89 (16) | O4—C10—H10 | 109.00 |
O4—C10—C13 | 107.21 (13) | C11—C10—H10 | 109.00 |
O4—C10—C11 | 107.57 (13) | C13—C10—H10 | 109.00 |
C11—C10—C13 | 115.54 (14) | C1—C11—H11 | 108.00 |
C1—C11—C10 | 106.68 (13) | C10—C11—H11 | 108.00 |
C10—C11—C12 | 109.46 (13) | C12—C11—H11 | 108.00 |
C1—C11—C12 | 115.26 (14) | C13—C14A—H14A | 122.00 |
O6—C12—C11 | 112.16 (15) | C15—C14A—H14A | 122.00 |
O5—C12—C11 | 123.52 (16) | C16—C14B—H14B | 121.00 |
O5—C12—O6 | 124.30 (16) | C13—C14B—H14B | 121.00 |
C10—C13—C14A | 128.5 (3) | C16—C15—H15 | 125.00 |
S1A—C13—C10 | 122.57 (13) | S1B—C15—H15 | 112.00 |
S1A—C13—C14A | 109.0 (3) | C14A—C15—H15 | 125.00 |
S1B—C13—C14B | 107.5 (11) | C14B—C16—H16 | 138.00 |
S1B—C13—C10 | 118.1 (4) | S1A—C16—H16 | 123.00 |
C10—C13—C14B | 133.8 (10) | C15—C16—H16 | 123.00 |
C16—S1A—C13—C14A | −0.8 (4) | O1—C3—C4—C5 | 179.60 (16) |
C13—S1A—C16—C15 | 0.5 (3) | O2—C4—C5—C6 | −179.91 (16) |
C16—S1A—C13—C10 | 177.53 (18) | C3—C4—C5—C6 | 1.1 (3) |
C7—O1—C3—C2 | 6.4 (3) | C4—C5—C6—C1 | −0.3 (3) |
C7—O1—C3—C4 | −173.5 (2) | C4—C5—C6—C9 | −176.89 (16) |
C8—O2—C4—C3 | 165.72 (18) | C5—C6—C9—O4 | −163.86 (15) |
C8—O2—C4—C5 | −13.3 (3) | C5—C6—C9—O3 | 17.3 (3) |
C10—O4—C9—C6 | 10.7 (2) | C1—C6—C9—O4 | 19.5 (2) |
C9—O4—C10—C13 | −177.08 (14) | C1—C6—C9—O3 | −159.38 (18) |
C9—O4—C10—C11 | −52.23 (19) | O4—C10—C11—C12 | −171.59 (13) |
C10—O4—C9—O3 | −170.33 (15) | O4—C10—C13—S1A | 50.92 (19) |
C2—C1—C11—C10 | 144.44 (16) | C13—C10—C11—C1 | −177.25 (14) |
C2—C1—C6—C5 | −1.3 (2) | O4—C10—C11—C1 | 63.07 (16) |
C6—C1—C11—C12 | −158.42 (15) | C11—C10—C13—C14A | 109.1 (4) |
C2—C1—C6—C9 | 175.27 (16) | C13—C10—C11—C12 | −51.91 (19) |
C11—C1—C2—C3 | −179.11 (16) | O4—C10—C13—C14A | −131.1 (4) |
C11—C1—C6—C5 | 179.76 (15) | C11—C10—C13—S1A | −68.96 (19) |
C11—C1—C6—C9 | −3.7 (2) | C1—C11—C12—O5 | −123.00 (19) |
C2—C1—C11—C12 | 22.7 (2) | C1—C11—C12—O6 | 58.6 (2) |
C6—C1—C11—C10 | −36.70 (19) | C10—C11—C12—O5 | 116.78 (19) |
C6—C1—C2—C3 | 2.1 (3) | C10—C11—C12—O6 | −61.66 (18) |
C1—C2—C3—C4 | −1.3 (3) | S1A—C13—C14A—C15 | 1.0 (6) |
C1—C2—C3—O1 | 178.82 (17) | C10—C13—C14A—C15 | −177.2 (3) |
C2—C3—C4—C5 | −0.3 (3) | C13—C14A—C15—C16 | −0.7 (7) |
C2—C3—C4—O2 | −179.43 (16) | C14A—C15—C16—S1A | 0.1 (5) |
O1—C3—C4—O2 | 0.5 (2) |
Symmetry codes: (i) x, y, z+1; (ii) −x, −y+2, −z+1; (iii) x, y−1, z; (iv) −x, −y+1, −z+1; (v) −x+1, −y+2, −z+1; (vi) x, y+1, z; (vii) −x+1, −y+1, −z; (viii) −x+1, −y+1, −z+1; (ix) x, y, z−1; (x) x+1, y, z−1; (xi) x−1, y, z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6···O3vi | 0.86 (3) | 1.84 (2) | 2.658 (2) | 159 (3) |
C2—H2···O5v | 0.93 | 2.54 | 3.465 (2) | 172 |
C10—H10···O6ii | 0.98 | 2.54 | 3.475 (2) | 159 |
C11—H11···Cg4viii | 0.98 | 2.61 | 3.525 (2) | 156 |
Symmetry codes: (ii) −x, −y+2, −z+1; (v) −x+1, −y+2, −z+1; (vi) x, y+1, z; (viii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C16H14O6S |
Mr | 334.34 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 8.3369 (6), 8.4587 (6), 11.9143 (9) |
α, β, γ (°) | 76.441 (6), 81.127 (6), 72.958 (6) |
V (Å3) | 777.6 (1) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.53 × 0.41 × 0.21 |
Data collection | |
Diffractometer | Stoe IPDS II diffractometer |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | 0.885, 0.952 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8329, 3229, 2663 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.113, 1.07 |
No. of reflections | 3229 |
No. of parameters | 219 |
No. of restraints | 13 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.27, −0.31 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6···O3i | 0.86 (3) | 1.84 (2) | 2.658 (2) | 159 (3) |
C2—H2···O5ii | 0.93 | 2.5400 | 3.465 (2) | 172 |
C10—H10···O6iii | 0.98 | 2.5400 | 3.475 (2) | 159 |
C11—H11···Cg4iv | 0.98 | 2.61 | 3.525 (2) | 156 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+2, −z+1; (iii) −x, −y+2, −z+1; (iv) −x+1, −y+1, −z+1. |
Acknowledgements
The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS2 diffractometer (purchased under grant F.279 of the University Research Fund).
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The title compound (I) was obtained as a part of a research project aimed at the synthesis of new dihydroisocoumarins with potential pharmacological activities (Bogdanov et al., 2007a,b). (I) was synthesized by a one-pot reaction of 6,7-dimethoxyhomophthalic anhydride with thiophene-2-carboxaldehyde in the presence of DMAP as a basic catalyst (Bogdanov & Palamareva, 2004). The structure of (I) was determined by spectral methods (1H NMR & IR) and microanalysis. In this paper, we report the X-ray crystallographic study of (I).
In the title molecule, (I), the thiophene ring is disordered over two sites and the major component of the disorder labelled with suffix A is shown in Fig. 1. The disorder corresponds to an approximate 180° rotation with respect to the C10—C13 bond. The six-membered ring (O4/C1/C6/C9–C11) of the 3,4-dihydroisochromanone ring system is not planar, showing the puckering parameters: QT = 0.571 (2) Å, θ = 115.2 (2)° and ϕ = 99.1 (2)° (Cremer & Pople, 1975). The benzene ring (C1–C6) of the 3,4-dihydroisochromanone ring system encloses dihedral angles of 75.0 (2)° and 77.2 (5)° with the thiophene rings A(C13/C14A/C15/C16/S1A) and B (C13/C14B/C15/C16/S1B), respectively.
The crystal structure is realized by intermolecular O—H···O and C—H···O hydrogen bonds and C—H···π interactions (Table 1, Fig. 2).