(E)-2-Methyl-5-(thiophen-2-ylmethyl­idene)cyclopentan-1-one

Asiri, A.M.; Al-Youbi, A.O.; Faidallah, H.M.; Alamry, K.A.; Ng, S.W.

doi:10.1107/S1600536811033708

organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2443

doi:10.1107/S1600536811033708

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(E)-2-Methyl-5-(thiophen-2-ylmethylidene)cyclopentan-1-one

Abdullah M. Asiri,^a,^b Abdulrahman O. Al-Youbi,^a Hassan M. Faidallah,^a Khalid A. Alamry ^a and Seik Weng Ng ^c ^*

^aChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia, ^bCenter of Excellence for Advanced Materials Research, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 18 August 2011; accepted 18 August 2011; online 27 August 2011)

The exocyclic C=C double-bond in the title compound, C₁₁H₁₂OS, has an E configuration. The methyl-bearing C atom in the cyclopentane ring is disordered over two positions with a site-occupation factor of 0.899 (8) for the major occupied site.

Related literature

For the synthesis of 2-(2-thienylidene)cyclopentanone, see: Austin et al. (2007 ); Tsukerman et al. (1964 ).

Experimental

Crystal data

C₁₁H₁₂OS
M_r = 192.27
Monoclinic, P 2₁ /c
a = 12.0667 (5) Å
b = 11.0576 (4) Å
c = 7.3003 (3) Å
β = 100.469 (4)°
V = 957.85 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 100 K
0.25 × 0.15 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.931, T_max = 0.971
4842 measured reflections
2131 independent reflections
1817 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.104
S = 0.99
2131 reflections
122 parameters
9 restraints
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811033708/bt5619sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811033708/bt5619Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811033708/bt5619Isup3.cml

checkCIF report

Comment top

The α-methylene hydrogen of cyclic ketones can be abstracted by a strong base to give a carbanion that reacts with aromatic aldehydes to form a compound having a carbon-carbon double bond. Cyclopentanone has been reacted with thiophene-2-carboxaldehyde to yield 2-(2-thienyl)cyclopentanone (Austin et al., 2007; Tsukerman et al., 1964). In the present study, 2-methylcyclopentanone was used in place of the unsubstituted cyclic ketone to yield C₁₁H₁₂OS (Scheme I); the ketone functionality can be further reacted with, for example, primary amines, to yield other halochromic compounds. The carbon-carbon double-bond i of an E configuration. The cyclopentane ring adopts an envelope-shaped conformation whose flap is represented by the methine carbon (Fig. 1). This atom is disordered over two positions in a 90 (1):10 ratio, i.e., it lies above the plane comprising the other non-H atoms in 90% of the molecules, and below the plane in 10% of the molecules.

Related literature top

For the synthesis of 2-(2-thienylidene)cyclopentanone, see: Austin et al. (2007); Tsukerman et al. (1964).

Experimental top

Thiophene-2-carboxaldehyde (1.10 g, 0.01 mol) in ethanol (20 m) was added to a solution of 2-methylcyclopentanone (0.98 g, 0.01 mol) dissolved in 20% ethanolic potassium hydroxide (20 ml). The mixture was stirred for 6 h. This was then poured into water (200 ml) and set aside for several hours. The precipitated product was collected, washed with water, dried and finallly recrystallized from ethanol to yield faint yellow crystals, 343–343 K.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C₁₁H₁₂OS at the 70% probability level; H atoms are drawn as spheres of arbitrary radius. The disorder in the methine carbon is not shown.

(E)-2-Methyl-5-(thiophen-2-ylmethylidene)cyclopentan-1-one top

Crystal data top

C₁₁H₁₂OS	F(000) = 408
M_r = 192.27	D_x = 1.333 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2335 reflections
a = 12.0667 (5) Å	θ = 2.5–29.2°
b = 11.0576 (4) Å	µ = 0.29 mm⁻¹
c = 7.3003 (3) Å	T = 100 K
β = 100.469 (4)°	Prism, light yellow
V = 957.85 (7) Å³	0.25 × 0.15 × 0.10 mm
Z = 4

Data collection top

Agilent SuperNova Dual diffractometer with Atlas detector	2131 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1817 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.028
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.5°, θ_min = 2.5°
ω scans	h = −12→15
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −10→14
T_min = 0.931, T_max = 0.971	l = −9→9
4842 measured reflections

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) = 0.104	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0433P)² + 0.8843P] where P = (F_o² + 2F_c²)/3
2131 reflections	(Δ/σ)_max = 0.001
122 parameters	Δρ_max = 0.57 e Å⁻³
9 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₁H₁₂OS	V = 957.85 (7) Å³
M_r = 192.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.0667 (5) Å	µ = 0.29 mm⁻¹
b = 11.0576 (4) Å	T = 100 K
c = 7.3003 (3) Å	0.25 × 0.15 × 0.10 mm
β = 100.469 (4)°

Data collection top

Agilent SuperNova Dual diffractometer with Atlas detector	2131 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1817 reflections with I > 2σ(I)
T_min = 0.931, T_max = 0.971	R_int = 0.028
4842 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	9 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 0.99	Δρ_max = 0.57 e Å⁻³
2131 reflections	Δρ_min = −0.31 e Å⁻³
122 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.46249 (4)	0.03090 (4)	0.23692 (6)	0.01813 (15)
O1	0.83453 (11)	0.32223 (13)	0.2085 (2)	0.0294 (4)
C1	0.32149 (16)	0.06255 (19)	0.1851 (3)	0.0207 (4)
H1	0.2639	0.0080	0.2046	0.025*
C2	0.30192 (15)	0.17578 (18)	0.1124 (3)	0.0207 (4)
H2	0.2287	0.2089	0.0749	0.025*
C3	0.40176 (14)	0.23853 (17)	0.0985 (2)	0.0172 (4)
H3	0.4028	0.3183	0.0504	0.021*
C4	0.49807 (15)	0.17173 (16)	0.1624 (2)	0.0162 (4)
C5	0.61209 (15)	0.21367 (17)	0.1727 (3)	0.0170 (4)
H5	0.6195	0.2946	0.1330	0.020*
C6	0.70943 (15)	0.15444 (17)	0.2306 (3)	0.0181 (4)
C7	0.81999 (16)	0.21558 (19)	0.2394 (3)	0.0245 (4)
C8	0.91401 (17)	0.1245 (2)	0.3085 (3)	0.0251 (7)	0.899 (8)
H8	0.9358	0.1353	0.4463	0.030*	0.899 (8)
C8'	0.8943 (7)	0.1127 (8)	0.187 (2)	0.0251 (7)	0.10
H8'	0.8730	0.1011	0.0492	0.030*	0.101 (8)
C9	0.85457 (16)	0.00382 (19)	0.2756 (3)	0.0286 (5)
H9A	0.8895	−0.0559	0.3697	0.034*	0.899 (8)
H9B	0.8595	−0.0275	0.1503	0.034*	0.899 (8)
H9C	0.9009	−0.0091	0.4006	0.034*	0.101 (8)
H9D	0.8609	−0.0687	0.1988	0.034*	0.101 (8)
C10	0.73056 (16)	0.02545 (17)	0.2918 (3)	0.0197 (4)
H10A	0.6799	−0.0303	0.2097	0.024*
H10B	0.7193	0.0143	0.4217	0.024*
C11	1.01808 (16)	0.1430 (2)	0.2272 (3)	0.0321 (5)
H11A	1.0501	0.2228	0.2636	0.048*	0.899 (8)
H11B	0.9989	0.1381	0.0911	0.048*	0.899 (8)
H11C	1.0734	0.0802	0.2738	0.048*	0.899 (8)
H11D	1.0276	0.2304	0.2461	0.048*	0.101 (8)
H11E	1.0528	0.1179	0.1219	0.048*	0.101 (8)
H11F	1.0544	0.1004	0.3400	0.048*	0.101 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0192 (2)	0.0158 (2)	0.0198 (3)	−0.00094 (17)	0.00467 (18)	0.00170 (18)
O1	0.0229 (7)	0.0190 (7)	0.0480 (10)	−0.0013 (6)	0.0112 (7)	0.0039 (7)
C1	0.0185 (9)	0.0236 (10)	0.0199 (9)	−0.0038 (8)	0.0035 (7)	−0.0029 (8)
C2	0.0170 (9)	0.0231 (10)	0.0210 (10)	0.0008 (8)	0.0007 (7)	−0.0021 (8)
C3	0.0192 (9)	0.0165 (9)	0.0151 (9)	−0.0006 (7)	0.0012 (7)	−0.0008 (7)
C4	0.0197 (9)	0.0138 (9)	0.0158 (9)	0.0000 (7)	0.0047 (7)	0.0003 (7)
C5	0.0200 (9)	0.0129 (9)	0.0196 (9)	−0.0007 (7)	0.0081 (7)	0.0008 (7)
C6	0.0191 (9)	0.0159 (9)	0.0205 (9)	−0.0012 (7)	0.0069 (7)	−0.0027 (8)
C7	0.0201 (9)	0.0197 (10)	0.0361 (12)	0.0016 (8)	0.0114 (8)	0.0011 (9)
C8	0.0195 (11)	0.0234 (12)	0.0330 (14)	0.0011 (9)	0.0060 (9)	0.0006 (10)
C8'	0.0195 (11)	0.0234 (12)	0.0330 (14)	0.0011 (9)	0.0060 (9)	0.0006 (10)
C9	0.0195 (9)	0.0220 (10)	0.0413 (13)	0.0022 (8)	−0.0023 (9)	0.0031 (10)
C10	0.0215 (9)	0.0154 (9)	0.0222 (10)	0.0007 (7)	0.0044 (7)	0.0010 (8)
C11	0.0176 (9)	0.0309 (12)	0.0485 (14)	0.0040 (9)	0.0074 (9)	0.0030 (11)

Geometric parameters (Å, º) top

S1—C1	1.7107 (19)	C8—H8	1.0000
S1—C4	1.7293 (18)	C8'—C9	1.487 (9)
O1—C7	1.219 (2)	C8'—C11	1.506 (9)
C1—C2	1.364 (3)	C8'—H8'	1.0000
C1—H1	0.9500	C9—C10	1.541 (3)
C2—C3	1.410 (3)	C9—H9A	0.9900
C2—H2	0.9500	C9—H9B	0.9900
C3—C4	1.384 (3)	C9—H9C	0.9900
C3—H3	0.9500	C9—H9D	0.9900
C4—C5	1.441 (2)	C10—H10A	0.9900
C5—C6	1.344 (3)	C10—H10B	0.9900
C5—H5	0.9500	C11—H11A	0.9800
C6—C7	1.487 (3)	C11—H11B	0.9800
C6—C10	1.503 (3)	C11—H11C	0.9800
C7—C8	1.533 (3)	C11—H11D	0.9800
C7—C8'	1.539 (9)	C11—H11E	0.9800
C8—C11	1.497 (3)	C11—H11F	0.9800
C8—C9	1.513 (3)

C1—S1—C4	92.29 (9)	C7—C8'—H8'	106.8
C2—C1—S1	111.64 (14)	C8'—C9—C10	107.6 (3)
C2—C1—H1	124.2	C8—C9—C10	106.86 (17)
S1—C1—H1	124.2	C8—C9—H9A	110.3
C1—C2—C3	112.96 (17)	C10—C9—H9A	110.3
C1—C2—H2	123.5	C8'—C9—H9B	78.6
C3—C2—H2	123.5	C8—C9—H9B	110.3
C4—C3—C2	112.91 (17)	C10—C9—H9B	110.3
C4—C3—H3	123.5	H9A—C9—H9B	108.6
C2—C3—H3	123.5	C8'—C9—H9C	110.2
C3—C4—C5	125.52 (17)	C10—C9—H9C	110.2
C3—C4—S1	110.19 (13)	C8'—C9—H9D	110.2
C5—C4—S1	124.24 (14)	C10—C9—H9D	110.2
C6—C5—C4	129.13 (17)	H9C—C9—H9D	108.5
C6—C5—H5	115.4	C6—C10—C9	103.84 (15)
C4—C5—H5	115.4	C6—C10—H10A	111.0
C5—C6—C7	121.20 (17)	C9—C10—H10A	111.0
C5—C6—C10	130.35 (17)	C6—C10—H10B	111.0
C7—C6—C10	108.45 (16)	C9—C10—H10B	111.0
O1—C7—C6	126.17 (18)	H10A—C10—H10B	109.0
O1—C7—C8	125.02 (18)	C8—C11—H11A	109.5
C6—C7—C8	108.67 (17)	C8—C11—H11B	109.5
O1—C7—C8'	124.0 (4)	H11A—C11—H11B	109.5
C6—C7—C8'	102.2 (4)	C8—C11—H11C	109.5
C11—C8—C9	117.7 (2)	C8'—C11—H11C	119.9
C11—C8—C7	113.82 (19)	H11A—C11—H11C	109.5
C9—C8—C7	103.08 (16)	H11B—C11—H11C	109.5
C11—C8—H8	107.2	C8'—C11—H11D	109.5
C9—C8—H8	107.2	H11B—C11—H11D	101.3
C7—C8—H8	107.2	C8'—C11—H11E	109.5
C9—C8'—C11	118.8 (8)	H11A—C11—H11E	105.3
C9—C8'—C7	104.0 (6)	H11D—C11—H11E	109.5
C11—C8'—C7	112.9 (7)	C8'—C11—H11F	109.5
C9—C8'—H8'	106.8	H11D—C11—H11F	109.5
C11—C8'—H8'	106.8	H11E—C11—H11F	109.5

C4—S1—C1—C2	0.45 (16)	O1—C7—C8'—C9	172.1 (4)
S1—C1—C2—C3	−0.2 (2)	C6—C7—C8'—C9	−36.9 (9)
C1—C2—C3—C4	−0.2 (2)	C8—C7—C8'—C9	68.5 (8)
C2—C3—C4—C5	−177.31 (17)	O1—C7—C8'—C11	42.1 (12)
C2—C3—C4—S1	0.5 (2)	C6—C7—C8'—C11	−167.0 (7)
C1—S1—C4—C3	−0.56 (15)	C8—C7—C8'—C11	−61.6 (8)
C1—S1—C4—C5	177.32 (16)	C11—C8'—C9—C8	59.1 (9)
C3—C4—C5—C6	−179.18 (19)	C7—C8'—C9—C8	−67.4 (8)
S1—C4—C5—C6	3.3 (3)	C11—C8'—C9—C10	153.4 (7)
C4—C5—C6—C7	−177.08 (18)	C7—C8'—C9—C10	27.0 (9)
C4—C5—C6—C10	3.9 (3)	C11—C8—C9—C8'	−58.8 (6)
C5—C6—C7—O1	4.8 (3)	C7—C8—C9—C8'	67.4 (6)
C10—C6—C7—O1	−176.0 (2)	C11—C8—C9—C10	−155.4 (2)
C5—C6—C7—C8	−179.48 (18)	C7—C8—C9—C10	−29.2 (2)
C10—C6—C7—C8	−0.3 (2)	C5—C6—C10—C9	161.5 (2)
C5—C6—C7—C8'	−145.3 (6)	C7—C6—C10—C9	−17.6 (2)
C10—C6—C7—C8'	33.9 (6)	C8'—C9—C10—C6	−6.5 (7)
O1—C7—C8—C11	−37.2 (3)	C8—C9—C10—C6	29.4 (2)
C6—C7—C8—C11	146.97 (19)	C9—C8—C11—C8'	57.6 (6)
C8'—C7—C8—C11	63.0 (6)	C7—C8—C11—C8'	−63.1 (6)
O1—C7—C8—C9	−165.9 (2)	C9—C8'—C11—C8	−60.2 (9)
C6—C7—C8—C9	18.3 (2)	C7—C8'—C11—C8	61.9 (8)
C8'—C7—C8—C9	−65.7 (5)

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂OS
M_r	192.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	12.0667 (5), 11.0576 (4), 7.3003 (3)
β (°)	100.469 (4)
V (Å³)	957.85 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.25 × 0.15 × 0.10

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.931, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	4842, 2131, 1817
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.104, 0.99
No. of reflections	2131
No. of parameters	122
No. of restraints	9
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.31

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

The authors thank King Abdulaziz University and the University of Malaya for supporting this study.

References

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