N-(4-Chloro­phen­yl)-4-methyl­piperazine-1-carboxamide

Li, Y.-F.; Wang, W.-M.

doi:10.1107/S1600536811034283

organic compounds

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Volume 67| Part 9| September 2011| Page o2453

doi:10.1107/S1600536811034283

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N-(4-Chlorophenyl)-4-methylpiperazine-1-carboxamide

Yu-Feng Li ^a ^* and Wen-Mei Wang ^b

^aMicroscale Science Institute, Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China, and ^bCenter of Forestry Science, Linjiacun Town, Zhucheng 261000, People's Republic of China
^*Correspondence e-mail: liyufeng8111@163.com

(Received 6 August 2011; accepted 21 August 2011; online 27 August 2011)

In the title compound, C₁₂H₁₆ClN₃O, the piperazine ring has a chair conformation. Within this ring, the N-methyl nitrogen atom has a pyramidal geometry and the N-carboxamide nitrogen atom is almost planar (bond-angle sum = 359.8°). In the crystal, the molecules are linked by N—H⋯O hydrogen bonds into C(4) chains propagating in [010].

Related literature

For related structures, see: Arrieta et al. (2007 1); Li (2011a ,b ).

Experimental

Crystal data

C₁₂H₁₆ClN₃O
M_r = 253.73
Orthorhombic, P b c n
a = 24.920 (5) Å
b = 9.5033 (19) Å
c = 11.064 (2) Å
V = 2620.3 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
23785 measured reflections
3006 independent reflections
2077 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.192
S = 1.11
3006 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1ⁱ	0.86	2.26	3.001 (2)	144
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811034283/hb6351sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811034283/hb6351Isup2.hkl

checkCIF report

Related literature top

For related structures, see: Arrieta et al. (20071); Li (2011a,b).

Experimental top

A mixture of 1-methylpiperazine (0.1 mol), and (4-chlorophenyl)carbamic chloride (0.1 mol) was stirred in refluxing ethanol (20 ml) for 4 h to afford the title compound (0.079 mol, yield 79%). Colourless blocks of the title compound were obtained by recrystallization from ethanol at room temperature.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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).

Figures top

Fig. 1. The molecular structure of the title compound showing 30% probability displacement ellipsoids.

N-(4-Chlorophenyl)-4-methylpiperazine-1-carboxamide top

Crystal data top

C₁₂H₁₆ClN₃O	D_x = 1.286 Mg m⁻³
M_r = 253.73	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 2077 reflections
a = 24.920 (5) Å	θ = 3.2–27.4°
b = 9.5033 (19) Å	µ = 0.28 mm⁻¹
c = 11.064 (2) Å	T = 293 K
V = 2620.3 (9) Å³	Block, colorless
Z = 8	0.22 × 0.20 × 0.18 mm
F(000) = 1072

Data collection top

Bruker SMART CCD diffractometer	2077 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.045
Graphite monochromator	θ_max = 27.5°, θ_min = 3.3°
ϕ and ω scans	h = −31→32
23785 measured reflections	k = −12→10
3006 independent reflections	l = −14→14

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.192	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.1054P)² + 0.5647P] where P = (F_o² + 2F_c²)/3
3006 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

C₁₂H₁₆ClN₃O	V = 2620.3 (9) Å³
M_r = 253.73	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 24.920 (5) Å	µ = 0.28 mm⁻¹
b = 9.5033 (19) Å	T = 293 K
c = 11.064 (2) Å	0.22 × 0.20 × 0.18 mm

Data collection top

Bruker SMART CCD diffractometer	2077 reflections with I > 2σ(I)
23785 measured reflections	R_int = 0.045
3006 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.192	H-atom parameters constrained
S = 1.11	Δρ_max = 0.25 e Å⁻³
3006 reflections	Δρ_min = −0.60 e Å⁻³
154 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
Cl1	0.07382 (3)	0.14060 (8)	0.66714 (8)	0.0750 (3)
O1	0.28704 (6)	0.11160 (14)	1.01352 (17)	0.0559 (5)
C6	0.28896 (7)	−0.0180 (2)	1.0143 (2)	0.0424 (5)
C7	0.21110 (7)	−0.0415 (2)	0.88098 (19)	0.0399 (5)
N3	0.25282 (6)	−0.09932 (17)	0.95154 (18)	0.0453 (5)
H3A	0.2558	−0.1894	0.9555	0.054*
C12	0.16012 (8)	−0.0996 (2)	0.8900 (2)	0.0479 (5)
H12A	0.1541	−0.1754	0.9415	0.058*
C11	0.11817 (8)	−0.0447 (3)	0.8224 (2)	0.0516 (6)
H11A	0.0840	−0.0836	0.8282	0.062*
C10	0.12738 (8)	0.0675 (2)	0.7469 (2)	0.0501 (5)
C9	0.17805 (9)	0.1239 (2)	0.7340 (2)	0.0522 (6)
H9A	0.1840	0.1981	0.6809	0.063*
C8	0.21988 (8)	0.0687 (2)	0.8010 (2)	0.0464 (5)
H8A	0.2542	0.1057	0.7925	0.056*
N2	0.32650 (7)	−0.08928 (19)	1.0782 (2)	0.0558 (6)
N1	0.43172 (7)	−0.1934 (2)	1.1165 (2)	0.0605 (6)
C3	0.33749 (9)	−0.2391 (2)	1.0715 (3)	0.0593 (7)
H3B	0.3139	−0.2824	1.0126	0.071*
H3C	0.3306	−0.2822	1.1495	0.071*
C4	0.36406 (10)	−0.0151 (3)	1.1554 (3)	0.0681 (8)
H4A	0.3592	−0.0450	1.2385	0.082*
H4B	0.3572	0.0852	1.1512	0.082*
C5	0.42085 (10)	−0.0446 (3)	1.1162 (3)	0.0719 (8)
H5A	0.4265	−0.0074	1.0356	0.086*
H5B	0.4456	0.0025	1.1705	0.086*
C2	0.39479 (11)	−0.2641 (3)	1.0361 (3)	0.0647 (7)
H2A	0.4021	−0.3643	1.0372	0.078*
H2B	0.4004	−0.2305	0.9542	0.078*
C1	0.48742 (12)	−0.2234 (5)	1.0819 (4)	0.1134 (15)
H1A	0.5114	−0.1767	1.1367	0.170*
H1B	0.4937	−0.1902	1.0012	0.170*
H1C	0.4936	−0.3231	1.0851	0.170*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0629 (4)	0.0773 (5)	0.0846 (6)	0.0211 (3)	−0.0201 (3)	0.0074 (4)
O1	0.0555 (9)	0.0286 (7)	0.0836 (13)	0.0032 (6)	−0.0119 (8)	−0.0023 (7)
C6	0.0424 (10)	0.0319 (9)	0.0529 (13)	0.0009 (7)	−0.0027 (8)	0.0008 (8)
C7	0.0433 (10)	0.0341 (9)	0.0422 (11)	0.0036 (8)	−0.0015 (8)	0.0007 (8)
N3	0.0477 (9)	0.0295 (8)	0.0587 (12)	0.0000 (7)	−0.0117 (8)	0.0055 (7)
C12	0.0493 (11)	0.0431 (11)	0.0514 (13)	−0.0051 (9)	−0.0025 (9)	0.0047 (9)
C11	0.0419 (10)	0.0536 (13)	0.0591 (15)	−0.0025 (9)	−0.0016 (9)	−0.0004 (11)
C10	0.0499 (12)	0.0490 (12)	0.0514 (13)	0.0120 (9)	−0.0052 (9)	−0.0021 (10)
C9	0.0592 (13)	0.0455 (11)	0.0520 (14)	0.0077 (9)	0.0019 (10)	0.0093 (10)
C8	0.0433 (10)	0.0436 (11)	0.0523 (13)	0.0014 (8)	0.0018 (9)	0.0060 (9)
N2	0.0542 (11)	0.0345 (9)	0.0787 (15)	0.0054 (8)	−0.0240 (10)	−0.0057 (9)
N1	0.0428 (10)	0.0548 (12)	0.0838 (16)	0.0033 (8)	−0.0014 (9)	−0.0012 (11)
C3	0.0574 (13)	0.0342 (11)	0.0862 (19)	0.0016 (9)	−0.0252 (12)	0.0045 (11)
C4	0.0611 (13)	0.0508 (14)	0.092 (2)	0.0102 (11)	−0.0304 (13)	−0.0211 (14)
C5	0.0595 (14)	0.0533 (14)	0.103 (2)	−0.0107 (11)	−0.0139 (14)	0.0008 (15)
C2	0.0767 (16)	0.0486 (13)	0.0689 (18)	0.0123 (12)	−0.0063 (13)	−0.0065 (12)
C1	0.0538 (18)	0.113 (3)	0.173 (4)	0.0106 (17)	0.023 (2)	−0.011 (3)

Geometric parameters (Å, º) top

Cl1—C10	1.745 (2)	N2—C3	1.452 (3)
O1—C6	1.232 (2)	N1—C5	1.440 (3)
C6—N2	1.355 (3)	N1—C2	1.446 (3)
C6—N3	1.375 (3)	N1—C1	1.468 (3)
C7—C8	1.388 (3)	C3—C2	1.500 (4)
C7—C12	1.389 (3)	C3—H3B	0.9700
C7—N3	1.411 (2)	C3—H3C	0.9700
N3—H3A	0.8600	C4—C5	1.506 (4)
C12—C11	1.388 (3)	C4—H4A	0.9700
C12—H12A	0.9300	C4—H4B	0.9700
C11—C10	1.374 (3)	C5—H5A	0.9700
C11—H11A	0.9300	C5—H5B	0.9700
C10—C9	1.379 (3)	C2—H2A	0.9700
C9—C8	1.383 (3)	C2—H2B	0.9700
C9—H9A	0.9300	C1—H1A	0.9600
C8—H8A	0.9300	C1—H1B	0.9600
N2—C4	1.450 (3)	C1—H1C	0.9600

O1—C6—N2	122.02 (19)	N2—C3—C2	110.4 (2)
O1—C6—N3	122.22 (18)	N2—C3—H3B	109.6
N2—C6—N3	115.75 (17)	C2—C3—H3B	109.6
C8—C7—C12	119.35 (19)	N2—C3—H3C	109.6
C8—C7—N3	122.00 (17)	C2—C3—H3C	109.6
C12—C7—N3	118.63 (18)	H3B—C3—H3C	108.1
C6—N3—C7	122.87 (16)	N2—C4—C5	110.3 (2)
C6—N3—H3A	118.6	N2—C4—H4A	109.6
C7—N3—H3A	118.6	C5—C4—H4A	109.6
C11—C12—C7	120.0 (2)	N2—C4—H4B	109.6
C11—C12—H12A	120.0	C5—C4—H4B	109.6
C7—C12—H12A	120.0	H4A—C4—H4B	108.1
C10—C11—C12	119.6 (2)	N1—C5—C4	111.0 (2)
C10—C11—H11A	120.2	N1—C5—H5A	109.4
C12—C11—H11A	120.2	C4—C5—H5A	109.4
C11—C10—C9	121.2 (2)	N1—C5—H5B	109.4
C11—C10—Cl1	119.27 (17)	C4—C5—H5B	109.4
C9—C10—Cl1	119.57 (18)	H5A—C5—H5B	108.0
C10—C9—C8	119.2 (2)	N1—C2—C3	111.8 (2)
C10—C9—H9A	120.4	N1—C2—H2A	109.3
C8—C9—H9A	120.4	C3—C2—H2A	109.3
C9—C8—C7	120.6 (2)	N1—C2—H2B	109.3
C9—C8—H8A	119.7	C3—C2—H2B	109.3
C7—C8—H8A	119.7	H2A—C2—H2B	107.9
C6—N2—C4	120.68 (18)	N1—C1—H1A	109.5
C6—N2—C3	126.47 (18)	N1—C1—H1B	109.5
C4—N2—C3	112.64 (17)	H1A—C1—H1B	109.5
C5—N1—C2	109.6 (2)	N1—C1—H1C	109.5
C5—N1—C1	111.6 (2)	H1A—C1—H1C	109.5
C2—N1—C1	110.5 (3)	H1B—C1—H1C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1ⁱ	0.86	2.26	3.001 (2)	144

Symmetry code: (i) −x+1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₆ClN₃O
M_r	253.73
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	24.920 (5), 9.5033 (19), 11.064 (2)
V (Å³)	2620.3 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.22 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	23785, 3006, 2077
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.192, 1.11
No. of reflections	3006
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.60

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1ⁱ	0.86	2.26	3.001 (2)	144

Symmetry code: (i) −x+1/2, y−1/2, z.

References

Arrieta, A., Otaegui, D., Zubia, A., et al. (2007). J. Org. Chem. 72, 4313–4322. CrossRef CAS Google Scholar
Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Li, Y.-F. (2011a). Acta Cryst. E67, o1796. Web of Science CSD CrossRef IUCr Journals Google Scholar
Li, Y.-F. (2011b). Acta Cryst. E67, o1792. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2453

doi:10.1107/S1600536811034283

Open

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