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

Li, Y.-F.

doi:10.1107/S1600536811035331

organic compounds

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Volume 67| Part 10| October 2011| Page o2574

https://doi.org/10.1107/S1600536811035331

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

Yu-Feng Li ^a ^*

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

(Received 23 August 2011; accepted 30 August 2011; online 14 September 2011)

In the title molecule, C₁₃H₁₈ClN₃O, the piperazine ring has a chair conformation. In the crystal, molecules are linked into chains along [100] by N—H⋯O hydrogen bonds.

Related literature

For applications of carboxamide compounds, see: Arrieta et al. (2007 ). For a related structure, see: Li (2011 ).

Experimental

Crystal data

C₁₃H₁₈ClN₃O
M_r = 267.75
Orthorhombic, P b c a
a = 9.5546 (19) Å
b = 10.910 (2) Å
c = 26.477 (5) Å
V = 2760.1 (10) Å³
Z = 8
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 293 K
0.25 × 0.22 × 0.21 mm

Data collection

Bruker SMART CCD diffractometer
24955 measured reflections
3167 independent reflections
1720 reflections with I > 2σ(I)
R_int = 0.079

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.187
S = 1.00
3167 reflections
168 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 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
N3—H3A⋯O1ⁱ	0.82 (3)	2.18 (3)	2.986 (3)	167 (2)
Symmetry code: (i) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

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: https://doi.org/10.1107/S1600536811035331/lh5326sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811035331/lh5326Isup2.hkl

checkCIF report

Comment top

Carboxamide compounds are an important intermediate reagent in organic synthesis (Arrieta et al., 2007). The molecular structure of the title compound is shown in Fig. 1. The piperazine ring (N1/N2/C3-C6) is in a chair conformation. Bond lengths and angles are comparable to those common to a similar structure (Li, 2011).

Related literature top

For applications of carboxamide compounds, see: Arrieta et al. (2007). For a related structure, see: Li (2011).

Experimental top

A mixture of 1-ethylpiperazine (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 (0.065 mol, yield 65%). Colourless blocks were obtained by recrystallization of a solution of the title compound in ethanol at room temperature.

Structure description top

For applications of carboxamide compounds, see: Arrieta et al. (2007). For a related structure, see: Li (2011).

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-ethylpiperazine-1-carboxamide top

Crystal data top

C₁₃H₁₈ClN₃O	F(000) = 1136
M_r = 267.75	D_x = 1.289 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1720 reflections
a = 9.5546 (19) Å	θ = 3.2–27.2°
b = 10.910 (2) Å	µ = 0.27 mm⁻¹
c = 26.477 (5) Å	T = 293 K
V = 2760.1 (10) Å³	Block, colorless
Z = 8	0.25 × 0.22 × 0.21 mm

Data collection top

Bruker SMART CCD diffractometer	1720 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.079
Graphite monochromator	θ_max = 27.5°, θ_min = 3.1°
φ and ω scans	h = −11→12
24955 measured reflections	k = −14→14
3167 independent reflections	l = −34→33

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.061	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.187	w = 1/[σ²(F_o²) + (0.1045P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
3167 reflections	Δρ_max = 0.27 e Å⁻³
168 parameters	Δρ_min = −0.27 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.021 (3)

Crystal data top

C₁₃H₁₈ClN₃O	V = 2760.1 (10) Å³
M_r = 267.75	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.5546 (19) Å	µ = 0.27 mm⁻¹
b = 10.910 (2) Å	T = 293 K
c = 26.477 (5) Å	0.25 × 0.22 × 0.21 mm

Data collection top

Bruker SMART CCD diffractometer	1720 reflections with I > 2σ(I)
24955 measured reflections	R_int = 0.079
3167 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.187	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.27 e Å⁻³
3167 reflections	Δρ_min = −0.27 e Å⁻³
168 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	0.12528 (9)	0.54490 (8)	0.41931 (3)	0.0847 (4)
O1	0.14283 (15)	0.18919 (18)	0.21930 (6)	0.0616 (5)
N3	0.3536 (2)	0.2579 (2)	0.24861 (7)	0.0514 (6)
C8	0.2986 (2)	0.3286 (2)	0.28864 (8)	0.0458 (6)
N2	0.34171 (19)	0.1241 (2)	0.18146 (8)	0.0580 (6)
C13	0.3594 (2)	0.3193 (2)	0.33612 (9)	0.0542 (6)
H13A	0.4350	0.2671	0.3412	0.065*
N1	0.4083 (2)	0.1241 (2)	0.07662 (7)	0.0644 (7)
C11	0.1940 (3)	0.4637 (2)	0.36844 (9)	0.0567 (7)
C12	0.3070 (3)	0.3881 (3)	0.37613 (9)	0.0596 (7)
H12A	0.3482	0.3829	0.4079	0.072*
C10	0.1353 (3)	0.4758 (3)	0.32123 (10)	0.0590 (7)
H10A	0.0605	0.5290	0.3163	0.071*
C7	0.2716 (2)	0.1909 (2)	0.21612 (8)	0.0483 (6)
C9	0.1878 (2)	0.4087 (2)	0.28136 (9)	0.0547 (6)
H9A	0.1486	0.4173	0.2494	0.066*
C6	0.4827 (3)	0.2016 (3)	0.11215 (10)	0.0652 (7)
H6A	0.4382	0.2815	0.1134	0.078*
H6B	0.5782	0.2129	0.1006	0.078*
C4	0.2660 (3)	0.0469 (3)	0.14571 (9)	0.0639 (7)
H4A	0.1702	0.0367	0.1571	0.077*
H4B	0.3094	−0.0334	0.1443	0.077*
C5	0.4841 (2)	0.1467 (3)	0.16426 (9)	0.0612 (7)
H5A	0.5360	0.0703	0.1638	0.073*
H5B	0.5305	0.2023	0.1874	0.073*
C3	0.2667 (3)	0.1030 (3)	0.09430 (10)	0.0707 (8)
H3B	0.2187	0.0490	0.0709	0.085*
H3C	0.2164	0.1802	0.0952	0.085*
C2	0.4049 (4)	0.1795 (4)	0.02561 (12)	0.0997 (12)
H2A	0.3649	0.2610	0.0280	0.120*
H2B	0.3440	0.1308	0.0042	0.120*
C1	0.5445 (4)	0.1884 (5)	0.00140 (12)	0.1227 (16)
H1A	0.5349	0.2248	−0.0314	0.184*
H1B	0.5840	0.1079	−0.0019	0.184*
H1C	0.6048	0.2382	0.0219	0.184*
H3A	0.435 (3)	0.236 (2)	0.2526 (8)	0.053 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0886 (6)	0.0831 (6)	0.0824 (6)	0.0078 (4)	0.0226 (4)	−0.0221 (4)
O1	0.0337 (8)	0.0846 (14)	0.0665 (11)	−0.0008 (8)	0.0028 (7)	−0.0060 (9)
N3	0.0335 (10)	0.0646 (14)	0.0561 (12)	0.0059 (9)	−0.0007 (8)	−0.0081 (10)
C8	0.0382 (11)	0.0471 (14)	0.0521 (13)	−0.0021 (10)	0.0039 (9)	0.0014 (10)
N2	0.0406 (10)	0.0713 (16)	0.0622 (13)	−0.0072 (10)	0.0060 (9)	−0.0169 (11)
C13	0.0484 (13)	0.0530 (16)	0.0613 (15)	0.0056 (11)	−0.0028 (11)	0.0003 (12)
N1	0.0520 (12)	0.0864 (18)	0.0547 (12)	−0.0125 (12)	−0.0010 (9)	−0.0015 (11)
C11	0.0547 (14)	0.0511 (16)	0.0643 (15)	−0.0002 (12)	0.0145 (12)	−0.0034 (12)
C12	0.0600 (15)	0.0637 (18)	0.0552 (14)	−0.0045 (13)	0.0019 (11)	−0.0056 (12)
C10	0.0504 (14)	0.0499 (16)	0.0766 (17)	0.0083 (11)	0.0075 (12)	0.0008 (13)
C7	0.0386 (12)	0.0567 (15)	0.0496 (12)	0.0009 (11)	0.0008 (10)	0.0032 (11)
C9	0.0488 (13)	0.0554 (16)	0.0597 (14)	0.0032 (12)	0.0002 (11)	0.0063 (12)
C6	0.0466 (13)	0.075 (2)	0.0737 (16)	−0.0132 (13)	0.0069 (12)	−0.0094 (15)
C4	0.0510 (14)	0.075 (2)	0.0658 (15)	−0.0186 (13)	0.0059 (12)	−0.0164 (13)
C5	0.0380 (12)	0.084 (2)	0.0618 (15)	0.0002 (12)	−0.0005 (11)	−0.0181 (13)
C3	0.0469 (14)	0.096 (2)	0.0691 (17)	−0.0125 (15)	−0.0036 (12)	−0.0090 (16)
C2	0.083 (2)	0.144 (4)	0.072 (2)	−0.015 (2)	−0.0036 (17)	0.023 (2)
C1	0.097 (3)	0.194 (5)	0.077 (2)	−0.033 (3)	0.0140 (19)	0.021 (2)

Geometric parameters (Å, º) top

Cl1—C11	1.741 (2)	C10—H10A	0.9300
O1—C7	1.233 (3)	C9—H9A	0.9300
N3—C7	1.374 (3)	C6—C5	1.504 (4)
N3—C8	1.413 (3)	C6—H6A	0.9700
N3—H3A	0.82 (3)	C6—H6B	0.9700
C8—C9	1.386 (3)	C4—C3	1.492 (4)
C8—C13	1.389 (3)	C4—H4A	0.9700
N2—C7	1.350 (3)	C4—H4B	0.9700
N2—C5	1.456 (3)	C5—H5A	0.9700
N2—C4	1.458 (3)	C5—H5B	0.9700
C13—C12	1.391 (3)	C3—H3B	0.9700
C13—H13A	0.9300	C3—H3C	0.9700
N1—C3	1.450 (3)	C2—C1	1.482 (5)
N1—C6	1.451 (3)	C2—H2A	0.9700
N1—C2	1.480 (4)	C2—H2B	0.9700
C11—C12	1.374 (4)	C1—H1A	0.9600
C11—C10	1.377 (3)	C1—H1B	0.9600
C12—H12A	0.9300	C1—H1C	0.9600
C10—C9	1.379 (3)

C7—N3—C8	123.20 (19)	N1—C6—H6B	109.3
C7—N3—H3A	117.5 (17)	C5—C6—H6B	109.3
C8—N3—H3A	114.8 (16)	H6A—C6—H6B	108.0
C9—C8—C13	119.4 (2)	N2—C4—C3	110.7 (2)
C9—C8—N3	121.6 (2)	N2—C4—H4A	109.5
C13—C8—N3	118.9 (2)	C3—C4—H4A	109.5
C7—N2—C5	125.8 (2)	N2—C4—H4B	109.5
C7—N2—C4	120.42 (19)	C3—C4—H4B	109.5
C5—N2—C4	111.01 (18)	H4A—C4—H4B	108.1
C8—C13—C12	120.0 (2)	N2—C5—C6	110.24 (19)
C8—C13—H13A	120.0	N2—C5—H5A	109.6
C12—C13—H13A	120.0	C6—C5—H5A	109.6
C3—N1—C6	109.9 (2)	N2—C5—H5B	109.6
C3—N1—C2	109.8 (2)	C6—C5—H5B	109.6
C6—N1—C2	111.4 (2)	H5A—C5—H5B	108.1
C12—C11—C10	120.9 (2)	N1—C3—C4	111.3 (2)
C12—C11—Cl1	119.17 (19)	N1—C3—H3B	109.4
C10—C11—Cl1	120.0 (2)	C4—C3—H3B	109.4
C11—C12—C13	119.6 (2)	N1—C3—H3C	109.4
C11—C12—H12A	120.2	C4—C3—H3C	109.4
C13—C12—H12A	120.2	H3B—C3—H3C	108.0
C11—C10—C9	119.7 (2)	N1—C2—C1	113.7 (3)
C11—C10—H10A	120.1	N1—C2—H2A	108.8
C9—C10—H10A	120.1	C1—C2—H2A	108.8
O1—C7—N2	122.2 (2)	N1—C2—H2B	108.8
O1—C7—N3	122.3 (2)	C1—C2—H2B	108.8
N2—C7—N3	115.43 (19)	H2A—C2—H2B	107.7
C10—C9—C8	120.4 (2)	C2—C1—H1A	109.5
C10—C9—H9A	119.8	C2—C1—H1B	109.5
C8—C9—H9A	119.8	H1A—C1—H1B	109.5
N1—C6—C5	111.5 (2)	C2—C1—H1C	109.5
N1—C6—H6A	109.3	H1A—C1—H1C	109.5
C5—C6—H6A	109.3	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	0.82 (3)	2.18 (3)	2.986 (3)	167 (2)

Symmetry code: (i) x+1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₈ClN₃O
M_r	267.75
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	9.5546 (19), 10.910 (2), 26.477 (5)
V (Å³)	2760.1 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.25 × 0.22 × 0.21

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	24955, 3167, 1720
R_int	0.079
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.187, 1.00
No. of reflections	3167
No. of parameters	168
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.27

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	0.82 (3)	2.18 (3)	2.986 (3)	167 (2)

Symmetry code: (i) x+1/2, y, −z+1/2.

References

Arrieta, A., Otaegui, D., Zubia, A., Cossío, F. P., Díaz-Ortiz, A., Hoz, A., Herrero, A., Prieto, P., Foces-Foces, C., Pizarro, J. L. & Arriortua, M. I. (2007). J. Org. Chem. 72, 4313-4322. Web of Science CSD CrossRef PubMed CAS Google Scholar
Bruker (1997). SMART and SAINT. Bruker AXS, Inc., Madison, Wisconsin, USA. Google Scholar
Li, Y.-F. (2011). Acta Cryst. E67, o2492. 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 10| October 2011| Page o2574

https://doi.org/10.1107/S1600536811035331

Open

access