Literature DB >> 21583225

(±)-trans-6,7-Dimeth-oxy-1-oxo-3-(2-thien-yl)isochroman-4-carboxylic acid.

Mehmet Akkurt, Zeliha Baktır, Milen G Bogdanov, Ivan V Svinyarov, Orhan Büyükgüngör.   

Abstract

The title compound, C(16)H(14)O(6)S, was synthesized by the reaction of 6,7-dimethoxy-homophthalic anhydride with thio-phene-2-carbaldehyde in the presence of 4-(dimethyl-amino)pyridine (DMAP) as a basic catalyst. The thio-phene ring of the title mol-ecule 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 thio-phene ring with respect to the C-C bond linking it to the rest of the mol-ecule. The six-membered ring of the 3,4-dihydro-isochromanone ring system is not planar [puckering parameters Q(T) = 0.571 (2) Å, θ = 115.2 (2)° and ϕ = 99.1 (2)°]. The benzene ring of the 3,4-dihydro-isochromanone ring system makes dihedral angles of 75.0 (2) and 77.2 (5)° with the disordered thio-phene rings. Inter-molecular O-H⋯O and C-H⋯O hydrogen bonds, as well as C-H⋯π inter-actions, lead to the observed supra-molecular structure.

Entities:  

Year:  2009        PMID： 21583225      PMCID： PMC2969835          DOI： 10.1107/S1600536809018844

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


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

C16H14O6S M = 334.34 Triclinic, a = 8.3369 (6) Å b = 8.4587 (6) Å c = 11.9143 (9) Å α = 76.441 (6)° β = 81.127 (6)° γ = 72.958 (6)° V = 777.6 (1) Å3 Z = 2 Mo Kα radiation μ = 0.24 mm−1 T = 296 K 0.53 × 0.41 × 0.21 mm

Data collection

Stoe IPDS II diffractometer Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T min = 0.885, T max = 0.952 8329 measured reflections 3229 independent reflections 2663 reflections with I > 2σ(I) R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.044 wR(F 2) = 0.113 S = 1.07 3229 reflections 219 parameters 13 restraints H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.27 e Å−3 Δρmin = −0.31 e Å−3 Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: 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 ▶). Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809018844/im2117sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536809018844/im2117Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
C16H14O6SZ = 2
Mr = 334.34F(000) = 348
Triclinic, P1Dx = 1.428 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.3369 (6) ÅCell parameters from 16761 reflections
b = 8.4587 (6) Åθ = 2.6–28.0°
c = 11.9143 (9) ŵ = 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 diffractometer3229 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus2663 reflections with I > 2σ(I)
plane graphiteRint = 0.030
Detector resolution: 6.67 pixels mm-1θmax = 26.5°, θmin = 2.6°
ω scansh = −10→10
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)k = −10→10
Tmin = 0.885, Tmax = 0.952l = −14→14
8329 measured reflections
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H atoms treated by a mixture of independent and constrained refinement
S = 1.07w = 1/[σ2(Fo2) + (0.0514P)2 + 0.2422P] where P = (Fo2 + 2Fc2)/3
3229 reflections(Δ/σ)max < 0.001
219 parametersΔρmax = 0.27 e Å−3
13 restraintsΔρmin = −0.31 e Å−3
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.
xyzUiso*/UeqOcc. (<1)
S1A0.17140 (13)0.63559 (11)0.85712 (7)0.0759 (3)0.877 (3)
O10.5188 (2)0.77377 (19)0.14713 (12)0.0557 (5)
O20.38518 (19)0.54308 (18)0.12791 (12)0.0503 (5)
O30.15691 (17)0.32562 (15)0.54690 (12)0.0445 (4)
O40.13106 (15)0.53400 (15)0.63275 (10)0.0370 (4)
O50.42866 (19)0.91589 (18)0.62175 (13)0.0515 (5)
O60.22136 (17)1.01715 (16)0.50460 (13)0.0451 (4)
C10.33543 (19)0.67769 (19)0.44799 (14)0.0304 (4)
C20.4244 (2)0.7526 (2)0.35183 (16)0.0356 (5)
C30.4377 (2)0.7065 (2)0.24602 (16)0.0384 (5)
C40.3637 (2)0.5802 (2)0.23513 (15)0.0372 (5)
C50.2797 (2)0.5039 (2)0.33076 (16)0.0359 (5)
C60.26476 (19)0.55214 (19)0.43731 (15)0.0311 (5)
C70.6107 (4)0.8880 (4)0.1547 (2)0.0869 (13)
C80.3476 (3)0.3914 (3)0.12059 (19)0.0611 (8)
C90.1816 (2)0.4620 (2)0.53946 (15)0.0330 (5)
C100.1347 (2)0.7092 (2)0.61942 (15)0.0319 (5)
C110.31183 (19)0.72133 (19)0.56665 (14)0.0305 (4)
C120.3300 (2)0.8940 (2)0.56779 (15)0.0339 (5)
C130.0822 (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)
C160.0534 (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)
C14B0.144 (3)0.692 (3)0.8422 (15)0.0802 (8)0.123 (3)
H50.232400.419700.324800.0430*
H60.227 (3)1.112 (3)0.516 (2)0.064 (7)*
H7A0.696700.831900.206600.1050*
H7B0.535500.982900.183400.1050*
H7C0.661800.926400.079200.1050*
H8A0.231900.398000.148000.0730*
H20.475100.833900.358700.0430*
H8C0.366900.377900.041400.0730*
H100.052700.781300.565400.0380*
H110.394500.636100.614800.0370*
H14A−0.098700.975100.708000.0700*0.877 (3)
H15−0.124400.994800.909100.0960*
H160.060600.760401.017500.0960*
H8B0.419000.296500.167400.0730*
H14B0.238800.600800.853300.0960*0.123 (3)
U11U22U33U12U13U23
S1A0.0947 (6)0.0739 (6)0.0417 (4)0.0110 (4)−0.0144 (3)−0.0153 (3)
O10.0752 (10)0.0589 (9)0.0414 (8)−0.0358 (8)0.0138 (7)−0.0161 (6)
O20.0680 (9)0.0552 (8)0.0366 (7)−0.0240 (7)−0.0013 (6)−0.0192 (6)
O30.0519 (7)0.0311 (6)0.0557 (8)−0.0171 (6)0.0018 (6)−0.0156 (6)
O40.0425 (6)0.0332 (6)0.0399 (7)−0.0162 (5)0.0033 (5)−0.0132 (5)
O50.0596 (8)0.0501 (8)0.0586 (9)−0.0260 (7)−0.0186 (7)−0.0145 (7)
O60.0488 (7)0.0274 (6)0.0646 (9)−0.0079 (5)−0.0164 (6)−0.0154 (6)
C10.0262 (7)0.0273 (7)0.0391 (9)−0.0044 (6)−0.0033 (6)−0.0128 (6)
C20.0346 (8)0.0336 (8)0.0430 (9)−0.0126 (7)0.0006 (7)−0.0144 (7)
C30.0391 (9)0.0362 (9)0.0392 (9)−0.0089 (7)0.0020 (7)−0.0112 (7)
C40.0379 (9)0.0384 (9)0.0370 (9)−0.0062 (7)−0.0049 (7)−0.0152 (7)
C50.0342 (8)0.0349 (8)0.0437 (10)−0.0099 (7)−0.0054 (7)−0.0157 (7)
C60.0264 (7)0.0287 (8)0.0395 (9)−0.0046 (6)−0.0035 (6)−0.0128 (7)
C70.129 (3)0.100 (2)0.0588 (15)−0.084 (2)0.0344 (16)−0.0281 (15)
C80.0914 (17)0.0613 (13)0.0447 (12)−0.0308 (13)−0.0033 (11)−0.0266 (10)
C90.0298 (8)0.0292 (8)0.0422 (9)−0.0064 (6)−0.0041 (7)−0.0131 (7)
C100.0324 (8)0.0282 (8)0.0373 (9)−0.0086 (6)−0.0015 (7)−0.0113 (6)
C110.0296 (7)0.0270 (7)0.0365 (9)−0.0060 (6)−0.0041 (6)−0.0108 (6)
C120.0349 (8)0.0357 (8)0.0364 (9)−0.0137 (7)0.0009 (7)−0.0150 (7)
C130.0384 (9)0.0389 (9)0.0404 (10)−0.0109 (7)0.0015 (7)−0.0148 (7)
C14A0.066 (3)0.053 (3)0.047 (3)0.001 (2)−0.0090 (19)−0.011 (2)
C150.1059 (16)0.0819 (14)0.0539 (11)−0.0163 (11)0.0061 (10)−0.0355 (10)
C160.1059 (16)0.0819 (14)0.0539 (11)−0.0163 (11)0.0061 (10)−0.0355 (10)
S1B0.065 (4)0.054 (5)0.041 (4)0.015 (3)−0.008 (3)−0.020 (4)
C14B0.1059 (16)0.0819 (14)0.0539 (11)−0.0163 (11)0.0061 (10)−0.0355 (10)
S1A—C131.702 (2)C10—C131.487 (2)
S1A—C161.689 (3)C10—C111.536 (2)
S1B—C151.584 (12)C11—C121.515 (2)
S1B—C131.628 (13)C13—C14B1.379 (19)
O1—C71.423 (4)C13—C14A1.357 (7)
O1—C31.354 (2)C14A—C151.387 (7)
O2—C81.431 (3)C14B—C161.47 (2)
O2—C41.359 (2)C15—C161.326 (4)
O3—C91.211 (2)C2—H20.9300
O4—C91.344 (2)C5—H50.9300
O4—C101.462 (2)C7—H7A0.9600
O5—C121.197 (2)C7—H7B0.9600
O6—C121.327 (2)C7—H7C0.9600
O6—H60.86 (3)C8—H8A0.9600
C1—C111.513 (2)C8—H8B0.9600
C1—C21.392 (2)C8—H8C0.9600
C1—C61.394 (2)C10—H100.9800
C2—C31.384 (3)C11—H110.9800
C3—C41.419 (2)C14A—H14A0.9300
C4—C51.371 (3)C14B—H14B0.9300
C5—C61.399 (2)C15—H150.9300
C6—C91.469 (2)C16—H160.9300
S1A···O43.0857 (15)C3···H11viii3.0300
S1A···C8i3.589 (2)C4···H11viii2.8300
S1B···O6ii3.308 (12)C5···H8B2.8100
S1B···O63.488 (13)C5···H11viii2.7400
S1B···C123.571 (13)C5···H8A2.6600
S1B···C2ii3.530 (13)C6···H102.7900
S1B···C3ii3.694 (13)C6···H11viii2.8700
S1A···H8Ci3.0000C7···H22.5200
S1A···H113.1800C8···H52.5100
O1···O22.581 (2)C9···H112.9600
O2···O12.581 (2)C9···H6iii2.95 (2)
O3···O6iii2.6575 (18)C12···H22.6900
O3···C6iv3.350 (2)H2···O62.8500
O3···O4iv3.2369 (19)H2···C72.5200
O3···C9iv3.051 (2)H2···C122.6900
O4···O3iv3.2369 (19)H2···H7A2.3800
O4···S1A3.0857 (15)H2···H7B2.2400
O5···O6v3.212 (2)H2···O5v2.5400
O5···O5v3.138 (2)H5···O32.6100
O5···C12v3.244 (2)H5···C82.5100
O5···C7v3.382 (3)H5···H8A2.1600
O6···S1Bii3.308 (12)H5···H8B2.4700
O6···C23.150 (2)H5···O4iv2.9200
O6···O3vi2.6575 (18)H6···O3vi1.84 (2)
O6···S1B3.488 (13)H6···C9vi2.95 (2)
O6···C133.385 (2)H6···H10ii2.5000
O6···O5v3.212 (2)H7A···C22.7800
O1···H8Cvii2.7500H7A···H22.3800
O2···H8Cvii2.7700H7B···C22.7100
O3···H6iii1.84 (2)H7B···H22.2400
O3···H10iv2.8100H7B···H8Bvi2.5200
O3···H52.6100H7B···O5v2.7400
O4···H5iv2.9200H7C···H15x2.5600
O5···H2v2.5400H8A···C52.6600
O5···H7Bv2.7400H8A···H52.1600
O6···H14Aii2.8500H8B···C52.8100
O6···H102.6700H8B···H52.4700
O6···H22.8500H8B···H7Biii2.5200
O6···H10ii2.5400H8C···S1Aix3.0000
C1···C1viii3.545 (2)H8C···O1vii2.7500
C2···S1Bii3.530 (13)H8C···O2vii2.7700
C2···C9viii3.532 (2)H10···O62.6700
C2···O63.150 (2)H10···C62.7900
C3···S1Bii3.694 (13)H10···H14A2.5700
C6···O3iv3.350 (2)H10···O3iv2.8100
C7···O5v3.382 (3)H10···O6ii2.5400
C8···S1Aix3.589 (2)H10···H6ii2.5000
C9···C9iv3.150 (2)H11···S1A3.1800
C9···C2viii3.532 (2)H11···C92.9600
C9···O3iv3.051 (2)H11···C1viii3.1000
C12···O5v3.244 (2)H11···C3viii3.0300
C12···S1B3.571 (13)H11···C4viii2.8300
C12···C14A3.527 (7)H11···C5viii2.7400
C13···O63.385 (2)H11···C6viii2.8700
C14A···C123.527 (7)H14A···H102.5700
C1···H11viii3.1000H14A···O6ii2.8500
C2···H7B2.7100H14A···C2ii3.0600
C2···H14Aii3.0600H15···H7Cxi2.5600
C2···H7A2.7800
C13—S1A—C1691.85 (12)C13—C14A—C15115.2 (5)
C13—S1B—C1592.3 (7)C13—C14B—C16117.2 (17)
C3—O1—C7117.71 (16)C14A—C15—C16110.8 (4)
C4—O2—C8116.56 (15)S1B—C15—C16123.5 (5)
C9—O4—C10117.75 (13)S1A—C16—C15113.17 (19)
C12—O6—H6108.4 (17)C14B—C16—C1598.8 (9)
C6—C1—C11116.64 (14)C1—C2—H2120.00
C2—C1—C6119.26 (15)C3—C2—H2120.00
C2—C1—C11124.09 (15)C4—C5—H5120.00
C1—C2—C3120.20 (16)C6—C5—H5120.00
O1—C3—C2124.71 (16)O1—C7—H7A110.00
C2—C3—C4120.36 (16)O1—C7—H7B109.00
O1—C3—C4114.93 (16)O1—C7—H7C109.00
C3—C4—C5119.21 (16)H7A—C7—H7B109.00
O2—C4—C5125.01 (16)H7A—C7—H7C109.00
O2—C4—C3115.78 (16)H7B—C7—H7C109.00
C4—C5—C6120.31 (16)O2—C8—H8A109.00
C5—C6—C9118.97 (15)O2—C8—H8B109.00
C1—C6—C5120.64 (16)O2—C8—H8C109.00
C1—C6—C9120.30 (15)H8A—C8—H8B109.00
O4—C9—C6118.04 (14)H8A—C8—H8C109.00
O3—C9—O4117.07 (16)H8B—C8—H8C109.00
O3—C9—C6124.89 (16)O4—C10—H10109.00
O4—C10—C13107.21 (13)C11—C10—H10109.00
O4—C10—C11107.57 (13)C13—C10—H10109.00
C11—C10—C13115.54 (14)C1—C11—H11108.00
C1—C11—C10106.68 (13)C10—C11—H11108.00
C10—C11—C12109.46 (13)C12—C11—H11108.00
C1—C11—C12115.26 (14)C13—C14A—H14A122.00
O6—C12—C11112.16 (15)C15—C14A—H14A122.00
O5—C12—C11123.52 (16)C16—C14B—H14B121.00
O5—C12—O6124.30 (16)C13—C14B—H14B121.00
C10—C13—C14A128.5 (3)C16—C15—H15125.00
S1A—C13—C10122.57 (13)S1B—C15—H15112.00
S1A—C13—C14A109.0 (3)C14A—C15—H15125.00
S1B—C13—C14B107.5 (11)C14B—C16—H16138.00
S1B—C13—C10118.1 (4)S1A—C16—H16123.00
C10—C13—C14B133.8 (10)C15—C16—H16123.00
C16—S1A—C13—C14A−0.8 (4)O1—C3—C4—C5179.60 (16)
C13—S1A—C16—C150.5 (3)O2—C4—C5—C6−179.91 (16)
C16—S1A—C13—C10177.53 (18)C3—C4—C5—C61.1 (3)
C7—O1—C3—C26.4 (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—C3165.72 (18)C5—C6—C9—O4−163.86 (15)
C8—O2—C4—C5−13.3 (3)C5—C6—C9—O317.3 (3)
C10—O4—C9—C610.7 (2)C1—C6—C9—O419.5 (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—S1A50.92 (19)
C2—C1—C11—C10144.44 (16)C13—C10—C11—C1−177.25 (14)
C2—C1—C6—C5−1.3 (2)O4—C10—C11—C163.07 (16)
C6—C1—C11—C12−158.42 (15)C11—C10—C13—C14A109.1 (4)
C2—C1—C6—C9175.27 (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—C5179.76 (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—C1222.7 (2)C1—C11—C12—O658.6 (2)
C6—C1—C11—C10−36.70 (19)C10—C11—C12—O5116.78 (19)
C6—C1—C2—C32.1 (3)C10—C11—C12—O6−61.66 (18)
C1—C2—C3—C4−1.3 (3)S1A—C13—C14A—C151.0 (6)
C1—C2—C3—O1178.82 (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—S1A0.1 (5)
O1—C3—C4—O20.5 (2)
D—H···AD—HH···AD···AD—H···A
O6—H6···O3vi0.86 (3)1.84 (2)2.658 (2)159 (3)
C2—H2···O5v0.932.543.465 (2)172
C10—H10···O6ii0.982.543.475 (2)159
C11—H11···Cg4viii0.982.613.525 (2)156
Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯AD—HH⋯AD⋯AD—H⋯A
O6—H6⋯O3i0.86 (3)1.84 (2)2.658 (2)159 (3)
C2—H2⋯O5ii0.932.543.465 (2)172
C10—H10⋯O6iii0.982.543.475 (2)159
C11—H11⋯Cg4iv0.982.613.525 (2)156

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) . Cg4 is the centroid of the C1–C6 ring.

  2 in total

1.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

2.  Preliminary evaluation of antimicrobial activity of diastereomeric cis/trans-3-aryl(heteroaryl)-3,4-dihydroisocoumarin-4-carboxylic acids.

Authors:  Milen G Bogdanov; Meglena I Kandinska; Darina B Dimitrova; Blagovesta T Gocheva; Mariana D Palamareva
Journal:  Z Naturforsch C J Biosci       Date:  2007 Jul-Aug
  2 in total

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