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

Abstract

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,

• a = 24.920 (5) Å

• b = 9.5033 (19) Å

• c = 11.064 (2) Å

• V = 2620.3 (9) ų

• 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[F ² > 2σ(F ²)] = 0.059

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Experimental

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.

Refinement

H atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H distances = 0.93–0.97 Å; N—H = 0.86Å and with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(C_methyl).

Figures

Fig. 1.

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

Crystal data

C12H16ClN3O	Dx = 1.286 Mg m−3
Mr = 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

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

Refinement

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(Fo2) + (0.1054P)2 + 0.5647P] where P = (Fo2 + 2Fc2)/3
3006 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.60 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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

Symmetry codes: (i) −x+1/2, y−1/2, z.