Dimethyl 1-(4-methyl­phen­yl)-8-(thio­phen-2-yl)-11-oxatricyclo­[6.2.1.02,7]undeca-2,4,6,9-tetra­ene-9,10-dicarboxy­late

Balakrishnan, B.; Nandakumar, M.; Seshadri, P.R.; Mohanakrishnan, A.K.

doi:10.1107/S1600536813005308

organic compounds

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ISSN: 2056-9890

Volume 69| Part 4| April 2013| Pages o498-o499

doi:10.1107/S1600536813005308

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Dimethyl 1-(4-methylphenyl)-8-(thiophen-2-yl)-11-oxatricyclo[6.2.1.0^2,7]undeca-2,4,6,9-tetraene-9,10-dicarboxylate

B. Balakrishnan,^a Meganathan Nandakumar,^b Pandamangalam R. Seshadri ^c ^* and Arasambattu K. Mohanakrishnan ^b

^aDepartment of Physics, P.T. Lee Chengalvaraya Naicker College of Engineering & Technology, Kancheepuram 631 502, India, ^bDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India, and ^cPostGraduate & Research Department of Physics, Agurchand Manmull Jain College, Chennai 600 114, India
^*Correspondence e-mail: seshadri_pr@yahoo.com

(Received 7 February 2013; accepted 24 February 2013; online 6 March 2013)

The title compound, C₂₅H₂₀O₅S, is the product of a Diels–Alder reaction. The molecule consists of a fused tricyclic system containing two five-membered rings and one six-membered ring. The five-membered rings both show an envelope conformation with the O atom at the flap, whereas the six-membered ring adopts a boat conformation. The thiophene ring is disordered over two sets of sites with an occupancy ratio of 0.53 (1):0.47 (1). The dihedral angles between the 4-methylphenyl ring and the major and minor components of the thiophene ring are 66.3 (1) and 67.9 (1)°, respectively, while the dihedral angle between the disordered thiophenyl components is 3.1 (1)°. The mean plane of the tricyclic ring system makes dihedral angles of 35.8 (1), 30.8 (1) and 32.8 (1)°, respectively, with the 4-methylphenyl ring and the major and minor components of the thiophenyl ring. In the crystal, inversion dimers are formed through pairs of C—H⋯π interactions. In addition, C—H⋯O interactions are observed.

Related literature

For background to Diels–Alder reactions, see: Denmark & Thorarensen (1996 ). For related structures, see: Ohwada et al. (2001 ); Takahashi et al. (2003 ); Fun et al. (2011 ); Gurbanov et al. (2009 ); Balakrishnan et al. (2013 ). For puckering and asymmetry parameters, see: Cremer & Pople (1975 ); Nardelli (1983 ).

Experimental

Crystal data

C₂₅H₂₀O₅S
M_r = 432.47
Triclinic, $[P \overline 1]$
a = 7.5966 (15) Å
b = 10.877 (2) Å
c = 13.515 (3) Å
α = 91.339 (5)°
β = 93.456 (4)°
γ = 100.129 (5)°
V = 1096.6 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
19981 measured reflections
5464 independent reflections
4142 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.129
S = 1.03
5464 reflections
321 parameters
52 restraints
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯O4ⁱ	0.93	2.47	3.378 (1)	165
C17—H17B⋯Cgⁱⁱ	0.96	3.26	3.99 (2)	136
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x+1, y, z.

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813005308/im2420sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813005308/im2420Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813005308/im2420Isup3.cml

checkCIF report

Comment top

The Diels-Alder reaction involves [4 + 2] cycloaddition of a conjucated diene and a dienophile (an alkene or alkyne). The Diels-Alder reaction is among the most powerful C—C bond forming process and one of most widely used and studied transformation in organic chemistry (Denmark & Thorarensen, 1996). The title compound, C₂₅H₂₀O₅S, comprises a fused tricyclic system with one 4-methylphenyl and one thiophenyl group attached to it. The tricyclic system consists of two 5-membered rings and one aromatic ring. In addition, two carboxylate units are attached to the tricyclic system. Geometrical parameters agree well with reported structures (Fun et al., 2011; Gurbanov et al., 2009; Ohwada et al. 2001; Takahashi et al. 2003). The five membered ring C₁\C₂\C₇\C₈\O₁ adopts an envelope conformation with atom O₁ displaced by 0.787 Å from the mean plane of the other ring atoms C₁\C₂\C₇\C₈.The puckering parameters (Cremer & Pople, 1975) and asymmetry parameters (Nardelli, 1983) are q₂ = 0.539 (1) Å, ϕ = 144.8 (1)°, Δ_S(O₁) = 0.006 (1)° and Δ₂(O₁) = 0.325 (1)°.The second five membered ring C₁\ C₂₀\C₂₃\C₈\O₁ also adopts an envelope conformation with O₁ displaced by -0.787 Å from the mean plane of the other ring atoms C₁\ C₂₀\C₂₃\C₈.The puckering parameters (Cremer & Pople, 1975) and asymmetry parameters (Nardelli, 1983) are q₂ = 0.542 (1) Å, ϕ = -37.3 (1)°, Δ_S(O₁) = 0.011 (1)° and Δ₂(O₁) = 0.327 (1)°.The six membered ring C₁/C₂/C₇/C₈/C₂₃/C₂₀ adopts boat conformation with puckering parameter q₂ = 0.9849 (1) Å, θ= 89.9 (8)° and ϕ = 359.2 (8)°.

The thiophene ring is disordered over two sites with occupancy ratio of 0.53 (3): 0.47 (3).The dihedral angle between the rings C₁/C₂/C₇/C₈/O₁ and C₁/C₂₀/C₂₃/C₈/O₁ is 82.15 (1)°. The dihedral angle between the terminal 4-methylphenyl and major and minor components of the thiophene rings are 66.3 (1)° and 67.9 (1)° respectively. The mean plane of the tricyclic system makes dihedral angles of 35.8 (1)°, 30.8 (1)° and 32.8 (1)°, respectively, with the 4-methylphenyl ring and the major and minor components of the thiophenyl group. The carboxylate ligand at the C20 carbon atom is turned out the plane in the positive direction of the five membered ring C20/ C1/ O1/ C8/ C23 (the torsion angle C23—C20—C21—O3= 32.2 (2)°, while that at the C23 carbon atom is turned out of this plane in the negative direction (the torsion angle is C20—C23—C24=O4 = -73.8 (2)°). In the crystal structure centrosymmetric dimers are realised by C—H···π interactions. In addition, intermolecular C—H···O interactions are observed (Table 1).

Related literature top

For background to Diels–Alder reactions, see: Denmark & Thorarensen (1996). For related structures, see: Ohwada et al. (2001); Takahashi et al. (2003); Fun et al. (2011); Gurbanov et al. (2009); Balakrishnan et al. (2013). For puckering and asymmetry parameters, see: Cremer & Pople (1975); Nardelli (1983).

Experimental top

To a stirred solution of 1-(thiophen-2-yl)-3-p-tolylisobenzofuran (2 g, 6.897 mmol) in dry DCM was added DMAD (1.08 g, 7.59 mmol) and the reaction mixture was stirred for 0.5 h at room temperature under nitrogen atmosphere. The solvent was removed and the resulting solid was washed with methanol to give the title compound as a colourless solid. This adduct was crystallized from CHCl₃/CH₃OH (3:1) by slow evaporation method.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. A view of the C—H···π interactions in the crystal structure of the title compound.

Dimethyl 1-(4-methylphenyl)-8-(thiophen-2-yl)-11-oxatricyclo[6.2.1.0^2,7]undeca-2,4,6,9-tetraene-9,10-dicarboxylate top

Crystal data top

C₂₅H₂₀O₅S	V = 1096.6 (4) Å³
M_r = 432.47	Z = 2
Triclinic, P1	F(000) = 452
Hall symbol: -P 1	D_x = 1.310 Mg m⁻³
a = 7.5966 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.877 (2) Å	θ = 1.5–28.5°
c = 13.515 (3) Å	µ = 0.18 mm⁻¹
α = 91.339 (5)°	T = 293 K
β = 93.456 (4)°	Block, colourless
γ = 100.129 (5)°	0.35 × 0.30 × 0.25 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	4142 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.024
Graphite monochromator	θ_max = 28.5°, θ_min = 1.5°
ω and ϕ scans	h = −10→10
19981 measured reflections	k = −14→14
5464 independent reflections	l = −18→18

Refinement top

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0648P)² + 0.1968P] where P = (F_o² + 2F_c²)/3
5464 reflections	(Δ/σ)_max < 0.001
321 parameters	Δρ_max = 0.25 e Å⁻³
52 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₂₅H₂₀O₅S	γ = 100.129 (5)°
M_r = 432.47	V = 1096.6 (4) Å³
Triclinic, P1	Z = 2
a = 7.5966 (15) Å	Mo Kα radiation
b = 10.877 (2) Å	µ = 0.18 mm⁻¹
c = 13.515 (3) Å	T = 293 K
α = 91.339 (5)°	0.35 × 0.30 × 0.25 mm
β = 93.456 (4)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	4142 reflections with I > 2σ(I)
19981 measured reflections	R_int = 0.024
5464 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	52 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.03	Δρ_max = 0.25 e Å⁻³
5464 reflections	Δρ_min = −0.16 e Å⁻³
321 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C17	−0.3508 (4)	−0.3528 (2)	0.05041 (17)	0.1061 (10)
H17A	−0.2958	−0.4245	0.0396	0.159*
H17B	−0.3950	−0.3260	−0.0121	0.159*
H17C	−0.4485	−0.3742	0.0923	0.159*
C16	−0.2140 (3)	−0.24828 (15)	0.09987 (12)	0.0618 (5)
C18	−0.2271 (2)	−0.21039 (15)	0.19687 (12)	0.0577 (4)
H18	−0.3214	−0.2500	0.2319	0.069*
C19	−0.1036 (2)	−0.11537 (14)	0.24304 (11)	0.0484 (3)
H19	−0.1157	−0.0918	0.3085	0.058*
C13	0.03822 (19)	−0.05453 (11)	0.19297 (9)	0.0391 (3)
C14	0.0529 (2)	−0.09272 (14)	0.09555 (10)	0.0520 (4)
H14	0.1476	−0.0537	0.0605	0.062*
C15	−0.0721 (3)	−0.18817 (16)	0.05039 (11)	0.0647 (5)
H15	−0.0601	−0.2125	−0.0149	0.078*
C1	0.15925 (18)	0.05759 (11)	0.24036 (9)	0.0365 (3)
C2	0.34514 (18)	0.10769 (12)	0.20407 (9)	0.0394 (3)
C3	0.4745 (2)	0.05272 (16)	0.16187 (11)	0.0510 (4)
H3	0.4534	−0.0321	0.1446	0.061*
C4	0.6378 (2)	0.12840 (19)	0.14586 (12)	0.0622 (5)
H4	0.7257	0.0938	0.1160	0.075*
C5	0.6713 (2)	0.25310 (19)	0.17340 (13)	0.0608 (4)
H5	0.7816	0.3014	0.1622	0.073*
C6	0.5419 (2)	0.30857 (15)	0.21812 (11)	0.0494 (3)
H6	0.5653	0.3926	0.2381	0.059*
C7	0.37929 (18)	0.23483 (12)	0.23151 (9)	0.0391 (3)
C8	0.21057 (17)	0.25712 (11)	0.28215 (9)	0.0359 (3)
C23	0.21701 (17)	0.18743 (11)	0.38086 (9)	0.0358 (3)
C20	0.18841 (18)	0.06611 (12)	0.35510 (9)	0.0364 (3)
C21	0.23243 (19)	−0.03877 (12)	0.41371 (10)	0.0409 (3)
C22	0.2710 (3)	−0.11567 (19)	0.57314 (13)	0.0660 (5)
H22A	0.2071	−0.1960	0.5492	0.099*
H22B	0.2407	−0.1000	0.6397	0.099*
H22C	0.3975	−0.1145	0.5725	0.099*
C24	0.2738 (2)	0.25025 (12)	0.47907 (10)	0.0413 (3)
C25	0.5151 (3)	0.3704 (2)	0.57359 (15)	0.0837 (7)
H25A	0.4399	0.4267	0.5952	0.126*
H25B	0.6332	0.4162	0.5656	0.126*
H21C	0.5214	0.3081	0.6222	0.126*
C9	0.16129 (19)	0.38335 (12)	0.28373 (10)	0.0409 (3)
O2	0.2780 (2)	−0.12775 (11)	0.37594 (9)	0.0698 (4)
O3	0.22201 (16)	−0.01996 (10)	0.50989 (7)	0.0536 (3)
O4	0.17981 (19)	0.24950 (13)	0.54677 (9)	0.0712 (4)
O5	0.44061 (16)	0.31032 (11)	0.47947 (8)	0.0606 (3)
O1	0.07523 (12)	0.16735 (8)	0.22614 (6)	0.0360 (2)
S1	0.2161 (5)	0.4865 (3)	0.1956 (3)	0.0697 (7)	0.531 (3)
C12	0.0495 (16)	0.4293 (11)	0.3505 (9)	0.093 (5)	0.531 (3)
H12	0.0023	0.3858	0.4041	0.112*	0.531 (3)
C11	0.019 (3)	0.5478 (14)	0.3260 (14)	0.066 (2)	0.531 (3)
H11	−0.0536	0.5916	0.3607	0.079*	0.531 (3)
C10	0.1054 (17)	0.5919 (11)	0.2473 (9)	0.063 (2)	0.531 (3)
H10	0.1048	0.6714	0.2235	0.076*	0.531 (3)
S1'	0.0250 (4)	0.4286 (3)	0.3645 (2)	0.0532 (4)	0.466 (3)
C12'	0.214 (2)	0.4812 (10)	0.2173 (8)	0.071 (4)	0.466 (3)
H12'	0.2990	0.4796	0.1708	0.085*	0.466 (3)
C11'	0.122 (2)	0.5793 (14)	0.2312 (12)	0.082 (3)	0.466 (3)
H11'	0.1272	0.6462	0.1892	0.098*	0.466 (3)
C10'	0.024 (4)	0.5679 (16)	0.3107 (17)	0.063 (3)	0.466 (3)
H10'	−0.0362	0.6289	0.3338	0.076*	0.466 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C17	0.132 (2)	0.0921 (16)	0.0677 (12)	−0.0455 (15)	−0.0117 (13)	−0.0130 (11)
C16	0.0819 (12)	0.0487 (8)	0.0460 (8)	−0.0072 (8)	−0.0117 (8)	0.0001 (6)
C18	0.0628 (10)	0.0538 (9)	0.0509 (8)	−0.0046 (7)	0.0019 (7)	0.0017 (7)
C19	0.0553 (9)	0.0477 (8)	0.0410 (7)	0.0068 (6)	0.0034 (6)	−0.0043 (6)
C13	0.0477 (8)	0.0339 (6)	0.0363 (6)	0.0110 (5)	−0.0027 (5)	−0.0017 (5)
C14	0.0696 (10)	0.0478 (8)	0.0349 (7)	0.0001 (7)	0.0030 (6)	−0.0001 (6)
C15	0.0943 (14)	0.0575 (9)	0.0345 (7)	−0.0049 (9)	−0.0011 (8)	−0.0058 (6)
C1	0.0425 (7)	0.0344 (6)	0.0345 (6)	0.0132 (5)	−0.0005 (5)	−0.0023 (5)
C2	0.0411 (7)	0.0453 (7)	0.0339 (6)	0.0142 (6)	0.0007 (5)	−0.0009 (5)
C3	0.0522 (9)	0.0610 (9)	0.0448 (7)	0.0249 (7)	0.0025 (6)	−0.0059 (6)
C4	0.0465 (9)	0.0950 (14)	0.0521 (9)	0.0301 (9)	0.0098 (7)	0.0011 (9)
C5	0.0393 (8)	0.0861 (12)	0.0565 (9)	0.0080 (8)	0.0061 (7)	0.0083 (8)
C6	0.0434 (8)	0.0558 (8)	0.0473 (8)	0.0050 (6)	−0.0004 (6)	0.0041 (6)
C7	0.0390 (7)	0.0450 (7)	0.0345 (6)	0.0117 (5)	0.0005 (5)	0.0011 (5)
C8	0.0375 (7)	0.0338 (6)	0.0368 (6)	0.0085 (5)	0.0003 (5)	−0.0019 (5)
C23	0.0365 (6)	0.0374 (6)	0.0351 (6)	0.0113 (5)	0.0026 (5)	−0.0010 (5)
C20	0.0383 (7)	0.0374 (6)	0.0344 (6)	0.0100 (5)	0.0016 (5)	−0.0015 (5)
C21	0.0447 (7)	0.0383 (6)	0.0401 (7)	0.0097 (6)	−0.0012 (5)	0.0004 (5)
C22	0.0725 (12)	0.0807 (12)	0.0532 (9)	0.0335 (10)	0.0043 (8)	0.0249 (8)
C24	0.0514 (8)	0.0363 (6)	0.0380 (7)	0.0142 (6)	−0.0005 (6)	−0.0036 (5)
C25	0.0901 (15)	0.0779 (13)	0.0740 (12)	0.0069 (11)	−0.0338 (11)	−0.0254 (10)
C9	0.0450 (8)	0.0343 (6)	0.0446 (7)	0.0122 (6)	−0.0013 (6)	−0.0020 (5)
O2	0.1124 (11)	0.0517 (6)	0.0545 (7)	0.0423 (7)	−0.0019 (7)	−0.0020 (5)
O3	0.0697 (7)	0.0588 (6)	0.0388 (5)	0.0287 (5)	0.0024 (5)	0.0074 (4)
O4	0.0834 (9)	0.0810 (8)	0.0479 (6)	0.0093 (7)	0.0176 (6)	−0.0169 (6)
O5	0.0544 (7)	0.0663 (7)	0.0561 (6)	0.0035 (5)	−0.0083 (5)	−0.0156 (5)
O1	0.0372 (5)	0.0334 (4)	0.0382 (5)	0.0104 (4)	−0.0025 (4)	−0.0017 (3)
S1	0.0928 (13)	0.0521 (9)	0.0734 (13)	0.0312 (9)	0.0184 (10)	0.0206 (9)
C12	0.100 (8)	0.061 (5)	0.118 (8)	0.014 (4)	−0.009 (5)	0.016 (4)
C11	0.068 (4)	0.059 (6)	0.076 (6)	0.031 (5)	−0.001 (4)	−0.012 (4)
C10	0.087 (4)	0.035 (2)	0.072 (5)	0.027 (2)	−0.012 (4)	−0.001 (3)
S1'	0.0557 (7)	0.0439 (8)	0.0641 (7)	0.0204 (6)	0.0050 (6)	−0.0040 (6)
C12'	0.088 (6)	0.059 (6)	0.064 (6)	0.019 (4)	−0.011 (4)	−0.027 (4)
C11'	0.129 (7)	0.050 (5)	0.071 (5)	0.025 (4)	0.018 (4)	0.013 (4)
C10'	0.078 (5)	0.044 (4)	0.075 (6)	0.035 (4)	−0.005 (4)	−0.002 (3)

Geometric parameters (Å, º) top

C17—C16	1.511 (2)	C23—C20	1.3335 (17)
C17—H17A	0.9600	C23—C24	1.4831 (17)
C17—H17B	0.9600	C20—C21	1.4782 (18)
C17—H17C	0.9600	C21—O2	1.1969 (17)
C16—C15	1.377 (3)	C21—O3	1.3204 (17)
C16—C18	1.379 (2)	C22—O3	1.4465 (18)
C18—C19	1.377 (2)	C22—H22A	0.9600
C18—H18	0.9300	C22—H22B	0.9600
C19—C13	1.384 (2)	C22—H22C	0.9600
C19—H19	0.9300	C24—O4	1.1932 (18)
C13—C14	1.3881 (19)	C24—O5	1.3195 (19)
C13—C1	1.4970 (17)	C25—O5	1.453 (2)
C14—C15	1.380 (2)	C25—H25A	0.9600
C14—H14	0.9300	C25—H25B	0.9600
C15—H15	0.9300	C25—H21C	0.9600
C1—O1	1.4606 (14)	C9—C12	1.417 (9)
C1—C2	1.5353 (19)	C9—C12'	1.428 (10)
C1—C20	1.5515 (17)	C9—S1'	1.673 (3)
C2—C3	1.381 (2)	C9—S1	1.676 (3)
C2—C7	1.3984 (19)	S1—C10	1.697 (11)
C3—C4	1.395 (3)	C12—C11	1.392 (14)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.374 (3)	C11—C10	1.338 (7)
C4—H4	0.9300	C11—H11	0.9300
C5—C6	1.399 (2)	C10—H10	0.9300
C5—H5	0.9300	S1'—C10'	1.696 (12)
C6—C7	1.374 (2)	C12'—C11'	1.390 (14)
C6—H6	0.9300	C12'—H12'	0.9300
C7—C8	1.5419 (19)	C11'—C10'	1.337 (7)
C8—O1	1.4498 (15)	C11'—H11'	0.9300
C8—C9	1.4853 (18)	C10'—H10'	0.9300
C8—C23	1.5521 (17)

C16—C17—H17A	109.5	C24—C23—C8	124.05 (11)
C16—C17—H17B	109.5	C23—C20—C21	128.37 (11)
H17A—C17—H17B	109.5	C23—C20—C1	106.33 (11)
C16—C17—H17C	109.5	C21—C20—C1	122.53 (10)
H17A—C17—H17C	109.5	O2—C21—O3	125.26 (13)
H17B—C17—H17C	109.5	O2—C21—C20	122.09 (13)
C15—C16—C18	117.71 (14)	O3—C21—C20	112.60 (11)
C15—C16—C17	121.50 (17)	O3—C22—H22A	109.5
C18—C16—C17	120.79 (18)	O3—C22—H22B	109.5
C19—C18—C16	121.53 (16)	H22A—C22—H22B	109.5
C19—C18—H18	119.2	O3—C22—H22C	109.5
C16—C18—H18	119.2	H22A—C22—H22C	109.5
C18—C19—C13	120.66 (14)	H22B—C22—H22C	109.5
C18—C19—H19	119.7	O4—C24—O5	125.08 (13)
C13—C19—H19	119.7	O4—C24—C23	124.66 (14)
C19—C13—C14	118.14 (13)	O5—C24—C23	110.22 (12)
C19—C13—C1	119.86 (12)	O5—C25—H25A	109.5
C14—C13—C1	121.69 (13)	O5—C25—H25B	109.5
C15—C14—C13	120.44 (15)	H25A—C25—H25B	109.5
C15—C14—H14	119.8	O5—C25—H21C	109.5
C13—C14—H14	119.8	H25A—C25—H21C	109.5
C16—C15—C14	121.52 (15)	H25B—C25—H21C	109.5
C16—C15—H15	119.2	C12—C9—C12'	106.5 (9)
C14—C15—H15	119.2	C12—C9—C8	126.6 (5)
O1—C1—C13	109.03 (10)	C12'—C9—C8	126.9 (6)
O1—C1—C2	99.71 (10)	C12—C9—S1'	3.5 (6)
C13—C1—C2	122.54 (11)	C12'—C9—S1'	109.8 (6)
O1—C1—C20	98.77 (9)	C8—C9—S1'	123.20 (15)
C13—C1—C20	118.47 (11)	C12—C9—S1	110.4 (5)
C2—C1—C20	104.23 (10)	C12'—C9—S1	6.3 (6)
C3—C2—C7	120.66 (14)	C8—C9—S1	122.68 (15)
C3—C2—C1	134.05 (13)	S1'—C9—S1	113.69 (18)
C7—C2—C1	105.03 (11)	C21—O3—C22	116.20 (12)
C2—C3—C4	117.93 (15)	C24—O5—C25	115.45 (14)
C2—C3—H3	121.0	C8—O1—C1	97.66 (9)
C4—C3—H3	121.0	C9—S1—C10	92.5 (5)
C5—C4—C3	121.26 (15)	C11—C12—C9	111.6 (11)
C5—C4—H4	119.4	C11—C12—H12	124.2
C3—C4—H4	119.4	C9—C12—H12	124.2
C4—C5—C6	120.97 (16)	C10—C11—C12	112.9 (12)
C4—C5—H5	119.5	C10—C11—H11	123.6
C6—C5—H5	119.5	C12—C11—H11	123.6
C7—C6—C5	117.80 (15)	C11—C10—S1	112.4 (11)
C7—C6—H6	121.1	C11—C10—H10	123.8
C5—C6—H6	121.1	S1—C10—H10	123.8
C6—C7—C2	121.35 (13)	C9—S1'—C10'	93.2 (6)
C6—C7—C8	133.63 (13)	C11'—C12'—C9	111.2 (12)
C2—C7—C8	104.81 (11)	C11'—C12'—H12'	124.4
O1—C8—C9	111.21 (10)	C9—C12'—H12'	124.4
O1—C8—C7	100.06 (9)	C10'—C11'—C12'	113.4 (14)
C9—C8—C7	120.07 (11)	C10'—C11'—H11'	123.3
O1—C8—C23	98.86 (9)	C12'—C11'—H11'	123.3
C9—C8—C23	118.64 (11)	C11'—C10'—S1'	111.8 (13)
C7—C8—C23	104.50 (10)	C11'—C10'—H10'	124.1
C20—C23—C24	129.51 (12)	S1'—C10'—H10'	124.1
C20—C23—C8	105.73 (10)

C15—C16—C18—C19	0.4 (3)	C2—C1—C20—C21	−92.07 (14)
C17—C16—C18—C19	180.0 (2)	C23—C20—C21—O2	−145.48 (17)
C16—C18—C19—C13	0.1 (3)	C1—C20—C21—O2	13.0 (2)
C18—C19—C13—C14	−0.5 (2)	C23—C20—C21—O3	32.2 (2)
C18—C19—C13—C1	173.23 (14)	C1—C20—C21—O3	−169.33 (12)
C19—C13—C14—C15	0.5 (2)	C20—C23—C24—O4	−73.8 (2)
C1—C13—C14—C15	−173.11 (15)	C8—C23—C24—O4	117.26 (17)
C18—C16—C15—C14	−0.4 (3)	C20—C23—C24—O5	108.36 (17)
C17—C16—C15—C14	−180.0 (2)	C8—C23—C24—O5	−60.61 (16)
C13—C14—C15—C16	−0.1 (3)	O1—C8—C9—C12	84.9 (7)
C19—C13—C1—O1	−81.69 (15)	C7—C8—C9—C12	−158.9 (7)
C14—C13—C1—O1	91.80 (15)	C23—C8—C9—C12	−28.6 (7)
C19—C13—C1—C2	162.74 (13)	O1—C8—C9—C12'	−93.7 (7)
C14—C13—C1—C2	−23.77 (19)	C7—C8—C9—C12'	22.5 (7)
C19—C13—C1—C20	30.06 (18)	C23—C8—C9—C12'	152.7 (7)
C14—C13—C1—C20	−156.45 (13)	O1—C8—C9—S1'	83.85 (18)
O1—C1—C2—C3	−152.34 (15)	C7—C8—C9—S1'	−159.97 (15)
C13—C1—C2—C3	−32.2 (2)	C23—C8—C9—S1'	−29.7 (2)
C20—C1—C2—C3	105.94 (16)	O1—C8—C9—S1	−88.1 (2)
O1—C1—C2—C7	33.71 (12)	C7—C8—C9—S1	28.1 (2)
C13—C1—C2—C7	153.82 (11)	C23—C8—C9—S1	158.34 (19)
C20—C1—C2—C7	−68.00 (12)	O2—C21—O3—C22	0.3 (2)
C7—C2—C3—C4	−1.3 (2)	C20—C21—O3—C22	−177.29 (13)
C1—C2—C3—C4	−174.46 (14)	O4—C24—O5—C25	5.3 (2)
C2—C3—C4—C5	1.6 (2)	C23—C24—O5—C25	−176.88 (14)
C3—C4—C5—C6	−0.3 (3)	C9—C8—O1—C1	−178.92 (11)
C4—C5—C6—C7	−1.4 (2)	C7—C8—O1—C1	53.14 (10)
C5—C6—C7—C2	1.8 (2)	C23—C8—O1—C1	−53.42 (10)
C5—C6—C7—C8	175.54 (14)	C13—C1—O1—C8	176.84 (10)
C3—C2—C7—C6	−0.4 (2)	C2—C1—O1—C8	−53.64 (10)
C1—C2—C7—C6	174.50 (12)	C20—C1—O1—C8	52.55 (11)
C3—C2—C7—C8	−175.79 (12)	C12—C9—S1—C10	2.8 (7)
C1—C2—C7—C8	−0.84 (13)	C12'—C9—S1—C10	−49 (7)
C6—C7—C8—O1	152.90 (14)	C8—C9—S1—C10	176.8 (4)
C2—C7—C8—O1	−32.60 (12)	S1'—C9—S1—C10	4.2 (5)
C6—C7—C8—C9	31.1 (2)	C12'—C9—C12—C11	3.9 (16)
C2—C7—C8—C9	−154.42 (11)	C8—C9—C12—C11	−174.9 (13)
C6—C7—C8—C23	−105.12 (16)	S1'—C9—C12—C11	−160 (11)
C2—C7—C8—C23	69.38 (12)	S1—C9—C12—C11	−1.2 (16)
O1—C8—C23—C20	34.38 (12)	C9—C12—C11—C10	−2 (2)
C9—C8—C23—C20	154.53 (12)	C12—C11—C10—S1	4 (2)
C7—C8—C23—C20	−68.50 (13)	C9—S1—C10—C11	−3.8 (15)
O1—C8—C23—C24	−154.44 (12)	C12—C9—S1'—C10'	20 (10)
C9—C8—C23—C24	−34.28 (18)	C12'—C9—S1'—C10'	3.0 (13)
C7—C8—C23—C24	102.68 (14)	C8—C9—S1'—C10'	−174.9 (11)
C24—C23—C20—C21	−10.6 (2)	S1—C9—S1'—C10'	−2.3 (12)
C8—C23—C20—C21	159.93 (13)	C12—C9—C12'—C11'	−7.9 (14)
C24—C23—C20—C1	−171.81 (13)	C8—C9—C12'—C11'	170.9 (9)
C8—C23—C20—C1	−1.28 (13)	S1'—C9—C12'—C11'	−6.9 (13)
O1—C1—C20—C23	−31.92 (13)	S1—C9—C12'—C11'	122 (7)
C13—C1—C20—C23	−149.24 (12)	C9—C12'—C11'—C10'	8 (2)
C2—C1—C20—C23	70.50 (13)	C12'—C11'—C10'—S1'	−6 (3)
O1—C1—C20—C21	165.50 (12)	C9—S1'—C10'—C11'	2 (2)
C13—C1—C20—C21	48.18 (18)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C2–C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O4ⁱ	0.93	2.47	3.378 (1)	165
C17—H17B···Cgⁱⁱ	0.96	3.26	3.99 (2)	136

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

Experimental details

Crystal data
Chemical formula	C₂₅H₂₀O₅S
M_r	432.47
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.5966 (15), 10.877 (2), 13.515 (3)
α, β, γ (°)	91.339 (5), 93.456 (4), 100.129 (5)
V (Å³)	1096.6 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.35 × 0.30 × 0.25

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	19981, 5464, 4142
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.129, 1.03
No. of reflections	5464
No. of parameters	321
No. of restraints	52
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.16

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C2–C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O4ⁱ	0.93	2.47	3.378 (1)	165
C17—H17B···Cgⁱⁱ	0.96	3.26	3.99 (2)	136

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

Acknowledgements

The authors acknowledge the Technology Business Incubator (TBI), CAS in Crystallography, University of Madras, Chennai 600 025, India, for the data collection.

References

Balakrishnan, B., Nandakumar, M., Seshadri, P. R. & Mohanakrishnan, A. K. (2013). Acta Cryst. E69, o323. CSD CrossRef IUCr Journals Google Scholar
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Volume 69| Part 4| April 2013| Pages o498-o499

doi:10.1107/S1600536813005308

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Di­methyl 1-(4-methyl­phen­yl)-8-(thio­phen-2-yl)-11-oxatri­cyclo­[6.2.1.02,7]undeca-2,4,6,9-tetra­ene-9,10-di­carb­oxy­late

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Dimethyl 1-(4-methylphenyl)-8-(thiophen-2-yl)-11-oxatricyclo[6.2.1.0^2,7]undeca-2,4,6,9-tetraene-9,10-dicarboxylate