N-(Pyrrolidin-1-ylcarbothio­yl)benzamide

Al-abbasi, A.A.; Mohamed Tahir, M.I.; Kassim, M.B.

doi:10.1107/S1600536811053694

organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o201

doi:10.1107/S1600536811053694

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N-(Pyrrolidin-1-ylcarbothioyl)benzamide

Aisha A. Al-abbasi,^a Mohamed Ibrahim Mohamed Tahir ^b and Mohammad B. Kassim ^a,^c ^*

^aSchool of Chemical Sciences & Food Technology, Faculty of Science & Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia, ^bDepartment of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia, and ^cFuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Selangor, Malaysia
^*Correspondence e-mail: mbkassim@ukm.my

(Received 5 December 2011; accepted 13 December 2011; online 21 December 2011)

In the title compound, C₁₂H₁₄N₂OS, the pyrrolidine ring adopts an envelope conformation with the C atom at the 3-position as the flap and makes a dihedral angle of 65.80 (9)° with the benzene ring. In the crystal, N—H⋯O hydrogen bonds join c-glide related molecules into chains extended along [001] that are further connected into (100) layers via C—H⋯O interactions.

Related literature

For related compounds, their structural parameters and chemical properties, see: Al-abbasi et al. (2010 , 2011 ); Al-abbasi & Kassim (2011 ); Ngah et al. (2006 ).

Experimental

Crystal data

C₁₂H₁₄N₂OS
M_r = 234.31
Monoclinic, P 2₁ /c
a = 10.3666 (4) Å
b = 14.6008 (5) Å
c = 7.8240 (3) Å
β = 98.446 (4)°
V = 1171.40 (8) Å³
Z = 4
Cu Kα radiation
μ = 2.29 mm⁻¹
T = 150 K
0.13 × 0.06 × 0.03 mm

Data collection

Oxford Diffraction Gemini area-detector diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, England.]$ ) T_min = 0.870, T_max = 0.934
8077 measured reflections
2245 independent reflections
1958 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.098
S = 1.03
2245 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.05	2.8637 (17)	157
C11—H11A⋯O1ⁱⁱ	0.97	2.52	3.339 (2)	142
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL, PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811053694/gk2440sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811053694/gk2440Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811053694/gk2440Isup3.cml

checkCIF report

Comment top

The title compound, I, is a derivative of a previously reported (2S)-1-(benzoylthiocarbamoyl)pyrrolidine-2-carboxylic acid (II) molecule (Ngah et al. 2006). In the crystal structure of I, the five-membered pyrrolidine ring has an envelope conformation with a maximum deviation from the mean plane of 0.238 (2)Å at C11. The benzene ring [C1/C2/C3/C4/C5/C6/C7] and the [(S1/N1/N2/C8/C9/C10] fragment are essentially planar and form dihedral angle of 79.03 (6)°.

The C=S and C=O bond lengths in I [1.6737 (17)Å and 1.2273 (19)Å, respectively] are comparable to those of II [1.662 (5)Å and 1.219 (5)Å]. In addition, the thiourea fragment in both compounds adopted a similar configuration with respect to the benzoyl and pyrrole fragments.

In the crystal, adjacent molecules are linked by N—H···O and C—H···O intermolecular interactions forming a two-dimensional polymeric structure parallel to (1 0 0) (Figure 2).

Related literature top

For related compounds, their structural parameters and chemical properties, see: Al-abbasi et al. (2010, 2011); Al-abbasi & Kassim (2011); Ngah et al. (2006).

Experimental top

The title compound was synthesized according to a previously reported compound (Al-abbasi et al., 2010) with some modifications. A solution of benzoyl chloride (10 mmol) in acetone was added slowly to an equimolar solution of ammonium thiocyanate in acetone. The reaction mixture was stirred at room temperature before adding piperidine (10 mmol) slowly and left stirring at room temperature for 4 h. The mixture was poured onto a water-ice and then filtered. The product was recrystallized to give a colourless crystal, suitable for X-ray crystallography (yield 81%; m.p. 407-408 K).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsods shown at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed down the c-axis with intermolecular hydrogen bonds drawn as dashed lines.

N-(Pyrrolidin-1-ylcarbothioyl)benzamide top

Crystal data top

C₁₂H₁₄N₂OS	F(000) = 496
M_r = 234.31	D_x = 1.329 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 3639 reflections
a = 10.3666 (4) Å	θ = 4–71.2°
b = 14.6008 (5) Å	µ = 2.29 mm⁻¹
c = 7.8240 (3) Å	T = 150 K
β = 98.446 (4)°	Needle, colourless
V = 1171.40 (8) Å³	0.13 × 0.06 × 0.03 mm
Z = 4

Data collection top

Oxford Diffraction Gemini area-detector diffractometer	2245 independent reflections
Radiation source: fine-focus sealed tube	1958 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
Detector resolution: 0 pixels mm^-1	θ_max = 71.2°, θ_min = 4.3°
ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	k = −17→17
T_min = 0.870, T_max = 0.934	l = −9→9
8077 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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0577P)² + 0.4389P] where P = (F_o² + 2F_c²)/3
2245 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₂H₁₄N₂OS	V = 1171.40 (8) Å³
M_r = 234.31	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 10.3666 (4) Å	µ = 2.29 mm⁻¹
b = 14.6008 (5) Å	T = 150 K
c = 7.8240 (3) Å	0.13 × 0.06 × 0.03 mm
β = 98.446 (4)°

Data collection top

Oxford Diffraction Gemini area-detector diffractometer	2245 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	1958 reflections with I > 2σ(I)
T_min = 0.870, T_max = 0.934	R_int = 0.024
8077 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.03	Δρ_max = 0.32 e Å⁻³
2245 reflections	Δρ_min = −0.27 e Å⁻³
145 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1 K.

(Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst., 105, 107.)

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
S1	−0.07552 (4)	0.14802 (3)	0.15309 (5)	0.02646 (15)
O1	0.19040 (11)	0.34576 (8)	0.07829 (14)	0.0257 (3)
N1	0.10339 (13)	0.27023 (9)	0.28912 (17)	0.0225 (3)
H1	0.1201	0.2472	0.3911	0.027*
N2	−0.08955 (12)	0.32949 (10)	0.14768 (16)	0.0221 (3)
C1	0.30423 (16)	0.36102 (11)	0.5288 (2)	0.0258 (4)
H1A	0.2228	0.3603	0.5651	0.031*
C2	0.41496 (17)	0.38288 (13)	0.6445 (2)	0.0313 (4)
H2	0.4074	0.3981	0.7580	0.038*
C3	0.53634 (17)	0.38203 (13)	0.5908 (3)	0.0340 (4)
H3	0.6104	0.3956	0.6690	0.041*
C4	0.54804 (17)	0.36105 (13)	0.4211 (3)	0.0326 (4)
H4	0.6300	0.3601	0.3861	0.039*
C5	0.43831 (16)	0.34158 (12)	0.3035 (2)	0.0288 (4)
H5	0.4459	0.3295	0.1887	0.035*
C6	0.31615 (15)	0.34018 (11)	0.3581 (2)	0.0235 (3)
C7	0.19885 (15)	0.31944 (11)	0.2285 (2)	0.0221 (3)
C8	−0.02146 (15)	0.25496 (11)	0.19383 (19)	0.0215 (3)
C9	−0.22292 (15)	0.32549 (12)	0.0516 (2)	0.0256 (3)
H9A	−0.2807	0.2921	0.1162	0.031*
H9B	−0.2236	0.2965	−0.0600	0.031*
C10	−0.26313 (17)	0.42580 (13)	0.0310 (2)	0.0309 (4)
H10A	−0.3556	0.4330	0.0351	0.037*
H10B	−0.2434	0.4503	−0.0775	0.037*
C11	−0.18200 (16)	0.47345 (12)	0.1844 (2)	0.0283 (4)
H11A	−0.1726	0.5383	0.1621	0.034*
H11B	−0.2210	0.4659	0.2889	0.034*
C12	−0.05187 (16)	0.42453 (11)	0.1987 (2)	0.0257 (4)
H12A	0.0028	0.4511	0.1211	0.031*
H12B	−0.0059	0.4268	0.3159	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0244 (2)	0.0229 (2)	0.0312 (2)	−0.00252 (14)	0.00082 (16)	−0.00183 (14)
O1	0.0254 (6)	0.0300 (6)	0.0211 (6)	−0.0026 (4)	0.0011 (4)	0.0003 (4)
N1	0.0208 (6)	0.0272 (7)	0.0182 (6)	−0.0020 (5)	−0.0012 (5)	0.0017 (5)
N2	0.0204 (6)	0.0237 (7)	0.0214 (7)	−0.0030 (5)	0.0002 (5)	−0.0005 (5)
C1	0.0241 (8)	0.0263 (8)	0.0263 (8)	0.0006 (6)	0.0014 (7)	−0.0012 (6)
C2	0.0325 (9)	0.0311 (9)	0.0277 (9)	0.0002 (7)	−0.0039 (7)	−0.0043 (7)
C3	0.0257 (9)	0.0313 (9)	0.0403 (10)	−0.0018 (7)	−0.0105 (7)	−0.0024 (7)
C4	0.0205 (8)	0.0323 (9)	0.0447 (11)	−0.0021 (7)	0.0038 (7)	−0.0001 (8)
C5	0.0249 (8)	0.0317 (9)	0.0296 (9)	−0.0015 (6)	0.0036 (7)	−0.0018 (7)
C6	0.0220 (8)	0.0224 (8)	0.0250 (8)	−0.0005 (6)	−0.0003 (6)	−0.0002 (6)
C7	0.0207 (7)	0.0218 (8)	0.0233 (8)	0.0010 (6)	0.0016 (6)	−0.0024 (6)
C8	0.0212 (8)	0.0263 (8)	0.0173 (7)	−0.0020 (6)	0.0035 (6)	0.0003 (6)
C9	0.0193 (8)	0.0315 (9)	0.0248 (8)	−0.0027 (6)	−0.0005 (6)	−0.0012 (7)
C10	0.0250 (8)	0.0330 (10)	0.0330 (9)	0.0022 (7)	−0.0012 (7)	0.0016 (7)
C11	0.0283 (8)	0.0261 (9)	0.0299 (8)	0.0004 (6)	0.0027 (7)	0.0012 (7)
C12	0.0261 (8)	0.0219 (8)	0.0281 (8)	−0.0030 (6)	0.0001 (6)	0.0002 (6)

Geometric parameters (Å, º) top

S1—C8	1.6737 (16)	C4—H4	0.9300
O1—C7	1.2275 (19)	C5—C6	1.395 (2)
N1—C7	1.363 (2)	C5—H5	0.9300
N1—C8	1.413 (2)	C6—C7	1.496 (2)
N1—H1	0.8600	C9—C10	1.525 (2)
N2—C8	1.318 (2)	C9—H9A	0.9700
N2—C9	1.4746 (19)	C9—H9B	0.9700
N2—C12	1.480 (2)	C10—C11	1.528 (2)
C1—C2	1.391 (2)	C10—H10A	0.9700
C1—C6	1.392 (2)	C10—H10B	0.9700
C1—H1A	0.9300	C11—C12	1.516 (2)
C2—C3	1.384 (3)	C11—H11A	0.9700
C2—H2	0.9300	C11—H11B	0.9700
C3—C4	1.385 (3)	C12—H12A	0.9700
C3—H3	0.9300	C12—H12B	0.9700
C4—C5	1.384 (2)

C7—N1—C8	123.71 (13)	N2—C8—N1	115.24 (14)
C7—N1—H1	118.1	N2—C8—S1	124.55 (12)
C8—N1—H1	118.1	N1—C8—S1	120.18 (12)
C8—N2—C9	122.08 (14)	N2—C9—C10	103.72 (13)
C8—N2—C12	126.18 (13)	N2—C9—H9A	111.0
C9—N2—C12	111.41 (13)	C10—C9—H9A	111.0
C2—C1—C6	119.56 (16)	N2—C9—H9B	111.0
C2—C1—H1A	120.2	C10—C9—H9B	111.0
C6—C1—H1A	120.2	H9A—C9—H9B	109.0
C3—C2—C1	120.06 (17)	C9—C10—C11	104.10 (13)
C3—C2—H2	120.0	C9—C10—H10A	110.9
C1—C2—H2	120.0	C11—C10—H10A	110.9
C2—C3—C4	120.29 (16)	C9—C10—H10B	110.9
C2—C3—H3	119.9	C11—C10—H10B	110.9
C4—C3—H3	119.9	H10A—C10—H10B	109.0
C5—C4—C3	120.25 (17)	C12—C11—C10	102.97 (14)
C5—C4—H4	119.9	C12—C11—H11A	111.2
C3—C4—H4	119.9	C10—C11—H11A	111.2
C4—C5—C6	119.58 (17)	C12—C11—H11B	111.2
C4—C5—H5	120.2	C10—C11—H11B	111.2
C6—C5—H5	120.2	H11A—C11—H11B	109.1
C1—C6—C5	120.22 (15)	N2—C12—C11	103.01 (13)
C1—C6—C7	121.10 (14)	N2—C12—H12A	111.2
C5—C6—C7	118.64 (15)	C11—C12—H12A	111.2
O1—C7—N1	123.00 (14)	N2—C12—H12B	111.2
O1—C7—C6	121.50 (14)	C11—C12—H12B	111.2
N1—C7—C6	115.49 (14)	H12A—C12—H12B	109.1

C6—C1—C2—C3	−1.3 (3)	C9—N2—C8—N1	−178.38 (13)
C1—C2—C3—C4	1.2 (3)	C12—N2—C8—N1	−5.5 (2)
C2—C3—C4—C5	0.6 (3)	C9—N2—C8—S1	−0.6 (2)
C3—C4—C5—C6	−2.1 (3)	C12—N2—C8—S1	172.25 (12)
C2—C1—C6—C5	−0.3 (3)	C7—N1—C8—N2	−59.7 (2)
C2—C1—C6—C7	−177.91 (15)	C7—N1—C8—S1	122.50 (15)
C4—C5—C6—C1	2.0 (3)	C8—N2—C9—C10	178.74 (14)
C4—C5—C6—C7	179.69 (15)	C12—N2—C9—C10	4.89 (17)
C8—N1—C7—O1	−8.9 (2)	N2—C9—C10—C11	−26.57 (16)
C8—N1—C7—C6	170.83 (14)	C9—C10—C11—C12	38.33 (17)
C1—C6—C7—O1	142.08 (16)	C8—N2—C12—C11	−154.72 (15)
C5—C6—C7—O1	−35.6 (2)	C9—N2—C12—C11	18.82 (17)
C1—C6—C7—N1	−37.7 (2)	C10—C11—C12—N2	−34.56 (16)
C5—C6—C7—N1	144.65 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.05	2.8637 (17)	157
C11—H11A···O1ⁱⁱ	0.97	2.52	3.339 (2)	142
C12—H12A···O1	0.97	2.54	3.035 (2)	112

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄N₂OS
M_r	234.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	10.3666 (4), 14.6008 (5), 7.8240 (3)
β (°)	98.446 (4)
V (Å³)	1171.40 (8)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	2.29
Crystal size (mm)	0.13 × 0.06 × 0.03

Data collection
Diffractometer	Oxford Diffraction Gemini area-detector diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2006)
T_min, T_max	0.870, 0.934
No. of measured, independent and observed [I > 2σ(I)] reflections	8077, 2245, 1958
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.614

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.098, 1.03
No. of reflections	2245
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.27

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.05	2.8637 (17)	157
C11—H11A···O1ⁱⁱ	0.97	2.52	3.339 (2)	142

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x, −y+1, −z.

Acknowledgements

The authors thank Universiti Kebangsaan Malaysia for providing facilities and grants (UKM-OUP-TK-16–73/2011 and UKM-PTS-016–2010) and the Libyan Government for providing a scholarship to AAA.

References

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