(3,5-Dimethyl-1H-pyrrol-2-yl)(phen­yl)methanone

Wang, F.; Peng, S.; Yue, M.; Zhu, R.

doi:10.1107/S2414314616007859

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 5| May 2016| x160785

doi:10.1107/S2414314616007859

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(3,5-Dimethyl-1H-pyrrol-2-yl)(phenyl)methanone

Fengzhen Wang,^a Songsong Peng,^a Mingbo Yue ^a ^* and Ruitao Zhu ^b

^aSchool of Chemistry and Chemical Engineering, Qufu Normal University, Shandong, People's Republic of China, and ^bDepartment of Chemistry, Taiyuan Normal University, Taiyuan, 030031, People's Republic of China
^*Correspondence e-mail: ruitaozhu@126.com

Edited by A. J. Lough, University of Toronto, Canada (Received 2 May 2016; accepted 13 May 2016; online 20 May 2016)

In the title molecule, C₁₃H₁₃NO, the dihedral angle between phenyl and pyrrole rings is 57.2 (1)°. In the crystal, N—H⋯O hydrogen bonds link the molecules, forming chains propagating along the b axis.

Keywords: crystal structure; pyrrole; methanone; hydrogen bond.

CCDC reference: 1479616

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Chemical scheme

Structure description

Pyrrole compounds are important units of many biologically active natural products and pharmaceutical compounds. Their transition metal-mediated synthesis (Gulevich et al., 2013 ) and complexation behaviour with ruthenium has been reported (Lundrigan et al., 2012 ).

The title molecule is shown in Fig. 1. The dihedral angle between the phenyl ring (C8–C13) and the pyrrole ring (N1/C1–C4) is 57.2 (1)°. In the crystal, molecules are linked by N—H⋯O hydrogen bonds (Table 1), forming chains propagating along the b axis (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.08	2.898 (2)	160
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.

Figure 2
Part of the crystal structure, viewed along the b axis, with hydrogen bonds drawn as dashed lines.

Synthesis and crystallization

The title compound was synthesized according to a literature method (Guo et al., 2015 ). All of the reactions were carried out under a purified nitrogen atmosphere using the standard Schlenk techniques. Diethyl ether was distilled from sodium benzophenone under nitrogen. Hexane was dried using sodium potassium alloy and distilled under nitrogen prior to use. All commercial reagents were sublimed, recrystallized or distilled before use. To a solution of 3,5-dimethylpyrrole (0.31 ml, 3.0 mmol) in dry diethyl ether (20 ml), n-butyllithium (2.5 M in hexane, 1.2 mL, 3.0 mmol) was added at 273 K; the reaction mixture was then allowed to warm to room temperature and then stirred for 2 h under a nitrogen atmosphere. To this suspension, 2,6-dimethylaniline (0.18 ml, 1.5 mmol) was added dropwise and stirred for 30 min followed by the addition of benzaldehyde (0.61 ml, 6 mmol). Stirring was continued for 5 h at 303 K and the progress of the reaction was monitored by TLC. The reaction mixture was then cooled to room temperature, quenched with saturated aqueous ammonium chloride solution, filtered over Celite^R and extracted into ethyl acetate. The organic layer was then washed with brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure to get the crude mixture. The product was isolated from the crude mixture by column chromatography on silica gel using an ethyl acetate hexane mixture (1:7) as an eluent and characterized by spectroscopic methods. Colourless crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution of the title compound in an ethyl acetate–hexane mixture (1:7) at room temperature for one week.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₁₃NO
M_r	199.24
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	25.755 (7), 6.5962 (16), 14.503 (4)
β (°)	116.935 (5)
V (Å³)	2196.5 (10)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.23 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007 )
T_min, T_max	0.977, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	5885, 1941, 1254
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.117, 1.01
No. of reflections	1941
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.20
Computer programs: APEX2 and SAINT (Bruker, 2007), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1479616

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S2414314616007859/lh4007sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616007859/lh4007Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616007859/lh4007Isup3.cml

checkCIF report

Refinement details top

Experimental top

The title compound was synthesized according to a literature method (Guo et al., 2015). All of the reactions were carried out under a purified nitrogen atmosphere using the standard Schlenk techniques. Diethyl ether was distilled from sodium benzophenone under nitrogen. Hexane was dried using sodium potassium alloy and distilled under nitrogen prior to use. All commercial reagents were sublimed, recrystallized or distilled before use. To a solution of 3,5-dimethylpyrrole (0.31 ml, 3.0 mmol) in dry diethyl ether (20 ml), n-butyllithium (2.5 M in hexane, 1.2 mL, 3.0 mmol) was added at 273 K; the reaction mixture was then allowed to warm to room temperature and then stirred for 2 h under a nitrogen atmosphere. To this suspension, 2,6-dimethylaniline (0.18 ml, 1.5 mmol) was added dropwise and stirred for 30 min followed by the addition of benzaldehyde (0.61 ml, 6 mmol). Stirring was continued for 5 h at 303 K and the progress of the reaction was monitored by TLC. The reaction mixture was then cooled to room temperature, quenched with saturated aqueous ammonium chloride solution, filtered over Celite^R and extracted into ethyl acetate. The organic layer was then washed with brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure to get the crude mixture. The product was isolated from the crude mixture by column chromatography on silica gel using ethyl acetate hexane mixture (1:7) as an eluent and characterized by spectroscopic methods. Colourless crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution of the title compound in an ethyl acetate–hexane mixture at room temperature for one week.

Structure description top

Pyrrole compounds are important units of many biologically active natural products and pharmaceutical compounds. Their transition metal-mediated synthesis (Gulevich et al., 2013) and complexation behaviour with ruthenium has been reported (Lundrigan et al., 2012).

The title molecule is shown in Fig. 1. The dihedral angle between the phenyl ring (C8–C13) and the pyrrole ring (N1/C1–C4) is 57.2 (1)°. In the crystal, molecules are linked by N—H···O hydrogen bonds (Table 1), forming chains propagating along the b axis (Fig. 2).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure, viewed along the b axis, with hydrogen bonds drawn as dashed lines.

(3,5-Dimethyl-1H-pyrrol-2-yl)(phenyl)methanone top

Crystal data top

C₁₃H₁₃NO	F(000) = 848
M_r = 199.24	D_x = 1.205 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 898 reflections
a = 25.755 (7) Å	θ = 2.8–21.5°
b = 6.5962 (16) Å	µ = 0.08 mm⁻¹
c = 14.503 (4) Å	T = 296 K
β = 116.935 (5)°	Block, colourless
V = 2196.5 (10) Å³	0.30 × 0.23 × 0.20 mm
Z = 8

Data collection top

Bruker SMART APEX CCD diffractometer	1941 independent reflections
Radiation source: fine-focus sealed tube	1254 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
φ and ω scans	θ_max = 25.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −30→30
T_min = 0.977, T_max = 0.985	k = −7→4
5885 measured reflections	l = −13→17

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0389P)² + 1.514P] where P = (F_o² + 2F_c²)/3
1941 reflections	(Δ/σ)_max < 0.001
138 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₃H₁₃NO	V = 2196.5 (10) Å³
M_r = 199.24	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 25.755 (7) Å	µ = 0.08 mm⁻¹
b = 6.5962 (16) Å	T = 296 K
c = 14.503 (4) Å	0.30 × 0.23 × 0.20 mm
β = 116.935 (5)°

Data collection top

Bruker SMART APEX CCD diffractometer	1941 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1254 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.985	R_int = 0.039
5885 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.01	Δρ_max = 0.16 e Å⁻³
1941 reflections	Δρ_min = −0.20 e Å⁻³
138 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
N1	0.19605 (7)	0.2779 (3)	0.08665 (13)	0.0425 (5)
H1	0.2241	0.2467	0.1458	0.051*
O1	0.21736 (6)	0.5700 (2)	0.23331 (12)	0.0638 (5)
C1	0.16027 (8)	0.4441 (3)	0.06853 (16)	0.0398 (5)
C2	0.12220 (9)	0.4446 (3)	−0.03716 (17)	0.0455 (6)
C3	0.13576 (9)	0.2726 (4)	−0.07836 (18)	0.0520 (6)
H3	0.1170	0.2332	−0.1474	0.062*
C4	0.18111 (9)	0.1708 (3)	−0.00092 (18)	0.0450 (5)
C5	0.21193 (10)	−0.0191 (3)	−0.0016 (2)	0.0593 (7)
H5A	0.2525	−0.0062	0.0457	0.089*
H5B	0.2075	−0.0432	−0.0701	0.089*
H5C	0.1957	−0.1306	0.0191	0.089*
C6	0.07803 (10)	0.6011 (4)	−0.10058 (19)	0.0641 (7)
H6A	0.0411	0.5693	−0.1027	0.096*
H6B	0.0741	0.6016	−0.1696	0.096*
H6C	0.0906	0.7324	−0.0700	0.096*
C7	0.17080 (9)	0.5785 (3)	0.15294 (17)	0.0431 (5)
C8	0.12592 (9)	0.7268 (3)	0.14765 (16)	0.0418 (5)
C9	0.14329 (10)	0.9203 (3)	0.18634 (18)	0.0503 (6)
H9	0.1822	0.9577	0.2120	0.060*
C10	0.10339 (12)	1.0572 (4)	0.1870 (2)	0.0623 (7)
H10	0.1151	1.1880	0.2114	0.075*
C11	0.04640 (12)	1.0020 (4)	0.1520 (2)	0.0692 (8)
H11	0.0196	1.0950	0.1533	0.083*
C12	0.02863 (11)	0.8103 (5)	0.1150 (2)	0.0677 (8)
H12	−0.0101	0.7730	0.0922	0.081*
C13	0.06793 (9)	0.6722 (4)	0.11150 (18)	0.0545 (6)
H13	0.0556	0.5430	0.0850	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0375 (10)	0.0438 (11)	0.0401 (10)	0.0007 (8)	0.0121 (8)	0.0039 (9)
O1	0.0453 (9)	0.0663 (11)	0.0542 (11)	0.0107 (8)	0.0001 (8)	−0.0147 (9)
C1	0.0338 (11)	0.0390 (12)	0.0437 (13)	0.0005 (10)	0.0150 (10)	0.0026 (10)
C2	0.0381 (12)	0.0516 (15)	0.0429 (13)	0.0001 (11)	0.0149 (10)	0.0048 (11)
C3	0.0523 (14)	0.0583 (16)	0.0410 (13)	−0.0033 (12)	0.0172 (12)	−0.0034 (11)
C4	0.0459 (13)	0.0429 (13)	0.0480 (14)	−0.0067 (11)	0.0228 (11)	−0.0037 (11)
C5	0.0643 (15)	0.0483 (15)	0.0712 (18)	−0.0002 (12)	0.0359 (14)	−0.0049 (12)
C6	0.0580 (15)	0.0708 (18)	0.0513 (16)	0.0122 (13)	0.0140 (13)	0.0138 (13)
C7	0.0371 (12)	0.0414 (13)	0.0454 (13)	−0.0029 (10)	0.0140 (11)	0.0013 (10)
C8	0.0399 (12)	0.0457 (13)	0.0382 (12)	0.0016 (10)	0.0162 (10)	0.0044 (10)
C9	0.0525 (14)	0.0441 (14)	0.0572 (15)	0.0000 (12)	0.0273 (12)	0.0049 (11)
C10	0.0782 (18)	0.0439 (15)	0.0730 (18)	0.0106 (14)	0.0413 (15)	0.0079 (13)
C11	0.0667 (18)	0.0670 (19)	0.080 (2)	0.0265 (15)	0.0386 (16)	0.0149 (15)
C12	0.0432 (14)	0.084 (2)	0.0740 (19)	0.0088 (14)	0.0246 (14)	0.0075 (16)
C13	0.0431 (13)	0.0582 (16)	0.0572 (16)	−0.0015 (12)	0.0184 (12)	−0.0003 (12)

Geometric parameters (Å, º) top

N1—C4	1.348 (3)	C6—H6B	0.9600
N1—C1	1.379 (3)	C6—H6C	0.9600
N1—H1	0.8600	C7—C8	1.490 (3)
O1—C7	1.238 (2)	C8—C13	1.388 (3)
C1—C2	1.396 (3)	C8—C9	1.384 (3)
C1—C7	1.434 (3)	C9—C10	1.371 (3)
C2—C3	1.399 (3)	C9—H9	0.9300
C2—C6	1.502 (3)	C10—C11	1.367 (3)
C3—C4	1.374 (3)	C10—H10	0.9300
C3—H3	0.9300	C11—C12	1.369 (4)
C4—C5	1.486 (3)	C11—H11	0.9300
C5—H5A	0.9600	C12—C13	1.380 (3)
C5—H5B	0.9600	C12—H12	0.9300
C5—H5C	0.9600	C13—H13	0.9300
C6—H6A	0.9600

C4—N1—C1	110.87 (17)	C2—C6—H6C	109.5
C4—N1—H1	124.6	H6A—C6—H6C	109.5
C1—N1—H1	124.6	H6B—C6—H6C	109.5
N1—C1—C2	106.72 (19)	O1—C7—C1	120.2 (2)
N1—C1—C7	118.50 (18)	O1—C7—C8	118.4 (2)
C2—C1—C7	134.6 (2)	C1—C7—C8	121.32 (18)
C1—C2—C3	106.25 (19)	C13—C8—C9	119.2 (2)
C1—C2—C6	129.4 (2)	C13—C8—C7	121.7 (2)
C3—C2—C6	124.2 (2)	C9—C8—C7	118.95 (19)
C4—C3—C2	109.4 (2)	C10—C9—C8	120.3 (2)
C4—C3—H3	125.3	C10—C9—H9	119.9
C2—C3—H3	125.3	C8—C9—H9	119.9
N1—C4—C3	106.8 (2)	C11—C10—C9	120.3 (3)
N1—C4—C5	121.5 (2)	C11—C10—H10	119.9
C3—C4—C5	131.7 (2)	C9—C10—H10	119.9
C4—C5—H5A	109.5	C10—C11—C12	120.2 (2)
C4—C5—H5B	109.5	C10—C11—H11	119.9
H5A—C5—H5B	109.5	C12—C11—H11	119.9
C4—C5—H5C	109.5	C11—C12—C13	120.3 (2)
H5A—C5—H5C	109.5	C11—C12—H12	119.9
H5B—C5—H5C	109.5	C13—C12—H12	119.9
C2—C6—H6A	109.5	C8—C13—C12	119.8 (2)
C2—C6—H6B	109.5	C8—C13—H13	120.1
H6A—C6—H6B	109.5	C12—C13—H13	120.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.08	2.898 (2)	160

Symmetry code: (i) −x+1/2, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.08	2.898 (2)	159.6

Symmetry code: (i) −x+1/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₃NO
M_r	199.24
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	25.755 (7), 6.5962 (16), 14.503 (4)
β (°)	116.935 (5)
V (Å³)	2196.5 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.23 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.977, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	5885, 1941, 1254
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.117, 1.01
No. of reflections	1941
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.20

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Acknowledgements

The project was supported by the National Natural Science Foundation of China (21003083), the Shandong Provincial Natural Science Foundation (ZR2014BM012) and the National Entrepreneurship Training Programs for Undergraduates (201510446058).

References

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