Crystal structure of 2-(thio-phen-3-yl)ethyl pyrene-1-carboxyl-ate.

In the title compound, C23H16O2S, the thio-phene group is rotationally disordered into two fractions almost parallel to each other, with occupation factors of 0.523 (7) and 0.477 (7), and subtending dihedral angles of 10.5 (5) and 9.3 (5)°, respectively, to the thio-phene group. The mol-ecules are held together by weak C-H⋯O and C-H⋯π hydrogen bonds, producing a laminar arrangement, which are further connected in a perpendicular fashion by S⋯π contacts [S⋯centroid = 3.539 (8) and 3.497 (8) Å]. In spite of the presence of the entended pyrene group, the structure does not present any parallel π-π stacking inter-actions. The structure was refined as an inversion twin.

Related literature

For optical and electronic properties of pyrene compounds, see: Hrdlovič & Lukáč (2000 ▸); Winnik (1993 ▸); Kim et al. (2008 ▸). For use of pyrenes as sensors, see: Basu & Rajam (2004 ▸); Chmela et al. (2005 ▸). For applications of thio­phenes, see: Perepichka et al. (2005 ▸); Abd-El-Aziz et al. (2013 ▸). For a previous report of meth­oxy­pyrene, see: Morales-Espinoza et al. (2015 ▸). For S⋯π inter­actions, see: Mooibroek et al. (2008 ▸).

Experimental

Crystal data

C23H16O2S

M = 356.42

Orthorhombic,

a = 12.020 (9) Å

b = 7.576 (6) Å

c = 18.521 (14) Å

V = 1687 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.21 mm−1

T = 298 K

0.30 × 0.23 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2012 ▸) T min = ?, T max = ?

11964 measured reflections

3116 independent reflections

2546 reflections with I > 2σ(I)

R int = 0.162

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.148

S = 1.05

3116 reflections

256 parameters

56 restraints

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.16 e Å−3

Absolute structure: Refined as an inversion twin.

Absolute structure parameter: 0.3 (2)

Data collection: APEX2 (Bruker, 2012 ▸); cell refinement: SAINT (Bruker, 2012 ▸); data reduction: SAINT (Bruker, 2012 ▸); program(s) used to solve structure: SHELXS97 (Sheldrick 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: SHELXTL (Sheldrick 2008 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸) and DIAMOND (Brandenburg, 2006 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015020873/bg2569sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015020873/bg2569Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015020873/bg2569Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015020873/bg2569fig1.tif

The mol­ecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. Only the major fraction of the disordered thio­phene has been drawn.

Click here for additional data file.

Cg . DOI: 10.1107/S2056989015020873/bg2569fig2.tif

A partial view of crystal packing of the title compound showing C—H⋯O and C—H⋯Cg inter­actions, drawn as dashed lines. Only H atoms involved in hydrogen bonding have been included for clarity.

Click here for additional data file.

. DOI: 10.1107/S2056989015020873/bg2569fig3.tif

A view of the crystal packing of the title compound, with the hydrogen bonds shown as dashed lines. Only H atoms involved in hydrogen bonding have been included.

Click here for additional data file.

. DOI: 10.1107/S2056989015020873/bg2569fig4.tif

Representation of the S⋯π inter­action (Only major fraction of the disordered thio­phene group). Hydrogen atosm omitted.

CCDC reference: 1435021

Additional supporting information: crystallographic information; 3D view; checkCIF report

C23H16O2S	F(000) = 744
Mr = 356.42	Dx = 1.404 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
a = 12.020 (9) Å	θ = 2.2–25.6°
b = 7.576 (6) Å	µ = 0.21 mm−1
c = 18.521 (14) Å	T = 298 K
V = 1687 (2) Å3	Prism, yellow
Z = 4	0.30 × 0.23 × 0.17 mm

Bruker APEXII CCD diffractometer	2546 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.162
Absorption correction: multi-scan (SADABS; Bruker, 2012)	θmax = 25.6°, θmin = 2.2°
	h = −14→14
11964 measured reflections	k = −9→8
3116 independent reflections	l = −22→22

Refinement on F2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0753P)2 + 0.2852P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.057	(Δ/σ)max < 0.001
wR(F2) = 0.148	Δρmax = 0.19 e Å−3
S = 1.05	Δρmin = −0.16 e Å−3
3116 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
256 parameters	Extinction coefficient: 0.014 (3)
56 restraints	Absolute structure: Refined as an inversion twin.
Hydrogen site location: inferred from neighbouring sites	Absolute structure parameter: 0.3 (2)

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. Refined as a 2-component inversion twin.

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.4023 (3)	0.3325 (5)	0.6430 (2)	0.0658 (10)
O2	0.4120 (3)	0.0607 (4)	0.59746 (17)	0.0510 (8)
C1	0.2701 (3)	0.2387 (6)	0.5549 (2)	0.0420 (10)
C2	0.1998 (4)	0.0944 (7)	0.5482 (3)	0.0500 (11)
H2	0.2155	−0.0085	0.5736	0.060*
C3	0.1074 (3)	0.1005 (6)	0.5046 (3)	0.0492 (11)
H3	0.0598	0.0039	0.5025	0.059*
C3A	0.0849 (3)	0.2482 (6)	0.4641 (2)	0.0440 (10)
C3B	0.1558 (3)	0.3963 (5)	0.4684 (2)	0.0390 (9)
C4	−0.0076 (4)	0.2540 (6)	0.4150 (3)	0.0523 (12)
H4	−0.0551	0.1575	0.4115	0.063*
C5	−0.0260 (4)	0.3965 (8)	0.3746 (3)	0.0552 (12)
H5	−0.0868	0.3972	0.3435	0.066*
C5A	0.0444 (4)	0.5480 (7)	0.3774 (2)	0.0490 (11)
C5B	0.1362 (3)	0.5460 (6)	0.4248 (2)	0.0434 (10)
C6	0.0274 (5)	0.6961 (8)	0.3344 (3)	0.0630 (14)
H6	−0.0342	0.7004	0.3041	0.076*
C7	0.0992 (5)	0.8348 (8)	0.3360 (3)	0.0705 (15)
H7	0.0872	0.9309	0.3057	0.085*
C8	0.1889 (5)	0.8350 (7)	0.3816 (3)	0.0622 (13)
H8	0.2368	0.9312	0.3822	0.075*
C8A	0.2087 (4)	0.6929 (6)	0.4269 (2)	0.0486 (11)
C9	0.2985 (4)	0.6875 (6)	0.4764 (3)	0.0507 (11)
H9	0.3459	0.7843	0.4795	0.061*
C10	0.3174 (4)	0.5475 (6)	0.5188 (3)	0.0485 (10)
H10	0.3766	0.5510	0.5511	0.058*
C10A	0.2495 (3)	0.3931 (6)	0.5161 (2)	0.0408 (9)
C11	0.3678 (4)	0.2211 (6)	0.6034 (3)	0.0477 (10)
C12	0.5016 (4)	0.0193 (6)	0.6460 (3)	0.0521 (11)
H12A	0.4762	0.0247	0.6957	0.063*
H12B	0.5622	0.1027	0.6400	0.063*
C13	0.5397 (4)	−0.1636 (6)	0.6279 (3)	0.0537 (11)
H13A	0.4753	−0.2406	0.6255	0.064*
H13B	0.5739	−0.1623	0.5804	0.064*
C14	0.6204 (3)	−0.2380 (6)	0.6806 (2)	0.0450 (9)
C15	0.7168 (4)	−0.1566 (7)	0.7033 (3)	0.0582 (12)
H15	0.7400	−0.0471	0.6864	0.070*
C16	0.6081 (4)	−0.4007 (7)	0.7125 (3)	0.0553 (11)
H16	0.5479	−0.4733	0.7017	0.066*
S1	0.7874 (4)	−0.2729 (6)	0.7637 (3)	0.0658 (13)	0.523 (7)
C17	0.6862 (17)	−0.450 (3)	0.7596 (15)	0.066 (4)	0.523 (7)
H17	0.6883	−0.5554	0.7854	0.079*	0.523 (7)
S1A	0.7088 (5)	−0.4534 (8)	0.7678 (4)	0.0682 (16)	0.477 (7)
C17A	0.782 (2)	−0.250 (3)	0.7479 (15)	0.071 (5)	0.477 (7)
H17A	0.8515	−0.2173	0.7653	0.085*	0.477 (7)

	U11	U22	U33	U12	U13	U23
O1	0.070 (2)	0.0563 (19)	0.071 (2)	0.0105 (17)	−0.0173 (18)	−0.0139 (18)
O2	0.0506 (16)	0.0516 (16)	0.0507 (16)	0.0079 (14)	−0.0132 (14)	−0.0026 (15)
C1	0.040 (2)	0.047 (2)	0.039 (2)	0.0071 (18)	0.0023 (18)	−0.0015 (18)
C2	0.049 (3)	0.048 (3)	0.053 (3)	0.000 (2)	0.010 (2)	0.005 (2)
C3	0.042 (2)	0.049 (2)	0.056 (3)	−0.0065 (19)	0.001 (2)	−0.002 (2)
C3A	0.038 (2)	0.050 (2)	0.044 (2)	−0.0021 (17)	0.0097 (18)	−0.0046 (19)
C3B	0.0375 (19)	0.043 (2)	0.037 (2)	0.0057 (16)	0.0066 (17)	−0.0062 (17)
C4	0.037 (2)	0.066 (3)	0.054 (3)	−0.006 (2)	0.0048 (19)	−0.007 (2)
C5	0.044 (2)	0.077 (3)	0.044 (2)	0.006 (2)	−0.006 (2)	−0.007 (2)
C5A	0.049 (2)	0.061 (3)	0.037 (2)	0.014 (2)	0.0033 (19)	−0.005 (2)
C5B	0.046 (2)	0.050 (2)	0.0343 (18)	0.0089 (19)	0.0069 (18)	−0.0044 (19)
C6	0.073 (3)	0.070 (3)	0.045 (3)	0.019 (3)	−0.008 (2)	−0.001 (2)
C7	0.103 (4)	0.056 (3)	0.052 (3)	0.018 (3)	−0.005 (3)	0.005 (2)
C8	0.080 (3)	0.049 (3)	0.058 (3)	0.003 (2)	0.007 (3)	0.005 (2)
C8A	0.054 (3)	0.045 (2)	0.046 (2)	0.0068 (19)	0.010 (2)	−0.004 (2)
C9	0.049 (2)	0.043 (2)	0.060 (3)	−0.0017 (19)	0.004 (2)	−0.003 (2)
C10	0.043 (2)	0.048 (3)	0.054 (2)	0.0007 (19)	0.001 (2)	−0.006 (2)
C10A	0.0352 (19)	0.046 (2)	0.041 (2)	0.0034 (17)	0.0052 (17)	−0.0051 (18)
C11	0.046 (2)	0.050 (2)	0.047 (2)	0.0033 (19)	0.001 (2)	0.000 (2)
C12	0.053 (2)	0.053 (2)	0.051 (3)	0.004 (2)	−0.010 (2)	0.002 (2)
C13	0.056 (2)	0.056 (3)	0.049 (2)	0.005 (2)	−0.006 (2)	0.003 (2)
C14	0.0417 (17)	0.0518 (19)	0.041 (2)	0.0043 (14)	0.0039 (16)	0.0031 (16)
C15	0.0474 (19)	0.062 (2)	0.065 (3)	−0.0019 (17)	−0.0052 (19)	0.010 (2)
C16	0.056 (2)	0.055 (2)	0.055 (2)	−0.0008 (17)	−0.002 (2)	0.0091 (18)
S1	0.0549 (17)	0.071 (2)	0.071 (3)	0.0106 (14)	−0.0107 (16)	0.0112 (17)
C17	0.065 (5)	0.070 (5)	0.063 (7)	0.004 (4)	−0.009 (5)	0.011 (5)
S1A	0.069 (3)	0.067 (2)	0.068 (3)	0.0100 (18)	−0.016 (2)	0.0109 (19)
C17A	0.063 (5)	0.073 (5)	0.076 (10)	0.007 (4)	−0.014 (6)	0.012 (6)

O1—C11	1.193 (6)	C8—C8A	1.386 (7)
O2—C11	1.330 (5)	C8—H8	0.9300
O2—C12	1.438 (5)	C8A—C9	1.417 (6)
C1—C2	1.388 (7)	C9—C10	1.339 (7)
C1—C10A	1.395 (6)	C9—H9	0.9300
C1—C11	1.484 (6)	C10—C10A	1.427 (7)
C2—C3	1.373 (6)	C10—H10	0.9300
C2—H2	0.9300	C12—C13	1.498 (7)
C3—C3A	1.375 (7)	C12—H12A	0.9700
C3—H3	0.9300	C12—H12B	0.9700
C3A—C3B	1.411 (6)	C13—C14	1.488 (6)
C3A—C4	1.437 (7)	C13—H13A	0.9700
C3B—C5B	1.412 (6)	C13—H13B	0.9700
C3B—C10A	1.432 (6)	C14—C16	1.375 (6)
C4—C5	1.332 (7)	C14—C15	1.378 (6)
C4—H4	0.9300	C15—C17A	1.341 (19)
C5—C5A	1.427 (7)	C15—S1	1.656 (6)
C5—H5	0.9300	C15—H15	0.9300
C5A—C6	1.391 (7)	C16—C17	1.334 (19)
C5A—C5B	1.409 (6)	C16—S1A	1.635 (6)
C5B—C8A	1.413 (7)	C16—H16	0.9300
C6—C7	1.360 (9)	S1—C17	1.814 (16)
C6—H6	0.9300	C17—H17	0.9300
C7—C8	1.369 (8)	S1A—C17A	1.810 (17)
C7—H7	0.9300	C17A—H17A	0.9300
C11—O2—C12	116.5 (3)	C8A—C9—H9	119.0
C2—C1—C10A	120.4 (4)	C9—C10—C10A	122.1 (4)
C2—C1—C11	117.7 (4)	C9—C10—H10	118.9
C10A—C1—C11	121.9 (4)	C10A—C10—H10	118.9
C3—C2—C1	121.3 (4)	C1—C10A—C10	124.5 (4)
C3—C2—H2	119.4	C1—C10A—C3B	118.2 (4)
C1—C2—H2	119.4	C10—C10A—C3B	117.2 (4)
C2—C3—C3A	120.5 (4)	O1—C11—O2	123.9 (4)
C2—C3—H3	119.7	O1—C11—C1	125.7 (4)
C3A—C3—H3	119.7	O2—C11—C1	110.4 (4)
C3—C3A—C3B	119.9 (4)	O2—C12—C13	106.9 (4)
C3—C3A—C4	121.5 (4)	O2—C12—H12A	110.3
C3B—C3A—C4	118.6 (4)	C13—C12—H12A	110.3
C3A—C3B—C5B	120.4 (4)	O2—C12—H12B	110.3
C3A—C3B—C10A	119.7 (4)	C13—C12—H12B	110.3
C5B—C3B—C10A	119.9 (4)	H12A—C12—H12B	108.6
C5—C4—C3A	120.6 (4)	C14—C13—C12	113.7 (4)
C5—C4—H4	119.7	C14—C13—H13A	108.8
C3A—C4—H4	119.7	C12—C13—H13A	108.8
C4—C5—C5A	122.2 (4)	C14—C13—H13B	108.8
C4—C5—H5	118.9	C12—C13—H13B	108.8
C5A—C5—H5	118.9	H13A—C13—H13B	107.7
C6—C5A—C5B	118.7 (5)	C16—C14—C15	111.2 (4)
C6—C5A—C5	122.7 (5)	C16—C14—C13	123.4 (4)
C5B—C5A—C5	118.6 (4)	C15—C14—C13	125.4 (4)
C5A—C5B—C3B	119.7 (4)	C17A—C15—C14	116.2 (10)
C5A—C5B—C8A	119.5 (4)	C14—C15—S1	113.5 (4)
C3B—C5B—C8A	120.9 (4)	C14—C15—H15	123.3
C7—C6—C5A	121.2 (5)	S1—C15—H15	123.3
C7—C6—H6	119.4	C17—C16—C14	117.1 (10)
C5A—C6—H6	119.4	C14—C16—S1A	114.1 (4)
C6—C7—C8	120.9 (5)	C17—C16—H16	121.4
C6—C7—H7	119.6	C14—C16—H16	121.4
C8—C7—H7	119.6	C15—S1—C17	91.3 (8)
C7—C8—C8A	120.5 (5)	C16—C17—S1	106.9 (14)
C7—C8—H8	119.7	C16—C17—H17	126.5
C8A—C8—H8	119.7	S1—C17—H17	126.5
C8—C8A—C5B	119.2 (4)	C16—S1A—C17A	91.4 (8)
C8—C8A—C9	123.0 (5)	C15—C17A—S1A	106.9 (14)
C5B—C8A—C9	117.8 (4)	C15—C17A—H17A	126.5
C10—C9—C8A	122.0 (4)	S1A—C17A—H17A	126.5
C10—C9—H9	119.0
C10A—C1—C2—C3	−1.3 (6)	C2—C1—C10A—C10	−179.4 (4)
C11—C1—C2—C3	179.7 (4)	C11—C1—C10A—C10	−0.4 (6)
C1—C2—C3—C3A	2.7 (7)	C2—C1—C10A—C3B	−1.4 (6)
C2—C3—C3A—C3B	−1.4 (6)	C11—C1—C10A—C3B	177.6 (4)
C2—C3—C3A—C4	176.4 (4)	C9—C10—C10A—C1	174.9 (4)
C3—C3A—C3B—C5B	177.4 (4)	C9—C10—C10A—C3B	−3.1 (6)
C4—C3A—C3B—C5B	−0.5 (5)	C3A—C3B—C10A—C1	2.7 (5)
C3—C3A—C3B—C10A	−1.3 (6)	C5B—C3B—C10A—C1	−176.0 (4)
C4—C3A—C3B—C10A	−179.2 (4)	C3A—C3B—C10A—C10	−179.2 (4)
C3—C3A—C4—C5	−177.9 (4)	C5B—C3B—C10A—C10	2.1 (5)
C3B—C3A—C4—C5	−0.1 (6)	C12—O2—C11—O1	4.5 (7)
C3A—C4—C5—C5A	0.4 (7)	C12—O2—C11—C1	−174.8 (4)
C4—C5—C5A—C6	178.7 (5)	C2—C1—C11—O1	−140.3 (5)
C4—C5—C5A—C5B	−0.2 (6)	C10A—C1—C11—O1	40.7 (7)
C6—C5A—C5B—C3B	−179.4 (4)	C2—C1—C11—O2	38.9 (5)
C5—C5A—C5B—C3B	−0.4 (6)	C10A—C1—C11—O2	−140.0 (4)
C6—C5A—C5B—C8A	−0.6 (6)	C11—O2—C12—C13	−178.3 (4)
C5—C5A—C5B—C8A	178.3 (4)	O2—C12—C13—C14	−170.9 (4)
C3A—C3B—C5B—C5A	0.8 (5)	C12—C13—C14—C16	128.8 (5)
C10A—C3B—C5B—C5A	179.4 (4)	C12—C13—C14—C15	−52.1 (6)
C3A—C3B—C5B—C8A	−178.0 (4)	C16—C14—C15—C17A	3.1 (17)
C10A—C3B—C5B—C8A	0.7 (6)	C13—C14—C15—C17A	−176.1 (17)
C5B—C5A—C6—C7	2.1 (7)	C16—C14—C15—S1	−1.9 (6)
C5—C5A—C6—C7	−176.8 (5)	C13—C14—C15—S1	178.9 (5)
C5A—C6—C7—C8	−2.0 (8)	C15—C14—C16—C17	1.6 (16)
C6—C7—C8—C8A	0.4 (8)	C13—C14—C16—C17	−179.2 (16)
C7—C8—C8A—C5B	1.0 (7)	C15—C14—C16—S1A	0.1 (6)
C7—C8—C8A—C9	−178.5 (5)	C13—C14—C16—S1A	179.3 (5)
C5A—C5B—C8A—C8	−0.9 (6)	C14—C15—S1—C17	1.3 (11)
C3B—C5B—C8A—C8	177.9 (4)	C14—C16—C17—S1	−1 (2)
C5A—C5B—C8A—C9	178.7 (4)	C15—S1—C17—C16	−0.4 (18)
C3B—C5B—C8A—C9	−2.6 (6)	C14—C16—S1A—C17A	−2.2 (12)
C8—C8A—C9—C10	−178.8 (5)	C14—C15—C17A—S1A	−5 (2)
C5B—C8A—C9—C10	1.7 (6)	C16—S1A—C17A—C15	3.8 (19)
C8A—C9—C10—C10A	1.2 (7)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···O1i	0.93	2.55	3.448 (6)	161
C13—H13B···Cg3ii	0.97	2.86	3.776 (5)	155

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16⋯O1i	0.93	2.55	3.448 (6)	161
C13—H13B⋯Cg3ii	0.97	2.86	3.776 (5)	155

Symmetry codes: (i) ; (ii) .