(2-Chloro-3,5-dinitro­phen­yl)(piperidin-1-yl)methanone

Luo, X.; Huang, Y.-C.; Gao, C.; Yu, L.-T.

doi:10.1107/S1600536811011469

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1066

doi:10.1107/S1600536811011469

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(2-Chloro-3,5-dinitrophenyl)(piperidin-1-yl)methanone

Xun Luo,^a ^* Yun-Chuang Huang,^a Chao Gao ^a and Luo-Ting Yu ^a

^aState Key Laboratory of Biotherapy and Cancer Center, West China Hospital, West China Medical School, Sichuan University, Chengdu 610041, People's Republic of China
^*Correspondence e-mail: yuluot@scu.edu.cn

(Received 14 March 2011; accepted 28 March 2011; online 7 April 2011)

In the title compound, C₁₂H₁₂ClN₃O₅, the piperidine ring adopts a chair conformation. One of the nitro groups is almost coplanar with the aromatic ring [O—N—C—C = −1.4 (2)°], whereas the other one is significantly twisted out of the ring plane [O—N—C—C = 34.7 (2)°]. The crystal packing is stabilized by intermolecular π–π stacking interactions with centroid–centroid distances of 3.579 (3) Å.

Related literature

For the biological activity of benzamide derivatives, see: Christophe et al. (2009 ).

Experimental

Crystal data

C₁₂H₁₂ClN₃O₅
M_r = 313.70
Orthorhombic, P b c a
a = 10.7864 (3) Å
b = 11.1264 (3) Å
c = 21.9775 (5) Å
V = 2637.60 (11) Å³
Z = 8
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 150 K
0.40 × 0.38 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.979, T_max = 1.0
6722 measured reflections
2696 independent reflections
2240 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.077
S = 1.05
2696 reflections
238 parameters
All H-atom parameters refined
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011469/bt5492sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811011469/bt5492Isup2.hkl

checkCIF report

Comment top

Benzamide derivatives are of great importance owing to their antibacterial properties (Christophe et al., 2009). The title compound is one of the key intermediates in our synthetic investigations of antibacterial drugs.

The piperidine ring adopts a chair conformation. As shown in Fig.1, the amide group forms a dihedral angles of 75.96 (5)° and 51.61 (9)° with the benzene ring and the piperidine ring, respectively. The crystal packing is strengthened by intermolecular π–π stacking interaction with centroid–centroid distances of 3.579 (3) Å.

Related literature top

For the biological activity of benzamide derivatives, see: Christophe et al. (2009).

Experimental top

A solution of 3.42 g (12.9 mmol) of 2-chloro-3,5-dinitrobenzoyl chloride in 20 ml of dichloromethane was added to a solution of 1.097 g (12.9 mmol) piperidine with a catalyst of 1.82 g (17.9 mmol) triethylamine. The mixture was stirred for 2 h at room temperature and extracted with water and dichloromethane, then the organic solvent was evaporated and the title compound was recrystallized from ethanol (yield 3.24 g, 80%). Crystals suitable for X-ray analysis were obtained by slow evaporation from a solution of ethyl acetate.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2006); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A packing diagram of the title compound.

(2-Chloro-3,5-dinitrophenyl)(piperidin-1-yl)methanone top

Crystal data top

C₁₂H₁₂ClN₃O₅	F(000) = 1296
M_r = 313.70	D_x = 1.580 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3316 reflections
a = 10.7864 (3) Å	θ = 3.2–29.1°
b = 11.1264 (3) Å	µ = 0.32 mm⁻¹
c = 21.9775 (5) Å	T = 150 K
V = 2637.60 (11) Å³	Block, yellow
Z = 8	0.40 × 0.38 × 0.20 mm

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	2696 independent reflections
Radiation source: fine-focus sealed tube	2240 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 16.0874 pixels mm^-1	θ_max = 26.4°, θ_min = 3.2°
ω scans	h = −13→7
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)	k = −13→13
T_min = 0.979, T_max = 1.0	l = −27→15
6722 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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	All H-atom parameters refined
S = 1.05	w = 1/[σ²(F_o²) + (0.0283P)² + 0.9862P] where P = (F_o² + 2F_c²)/3
2696 reflections	(Δ/σ)_max < 0.001
238 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₂H₁₂ClN₃O₅	V = 2637.60 (11) Å³
M_r = 313.70	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.7864 (3) Å	µ = 0.32 mm⁻¹
b = 11.1264 (3) Å	T = 150 K
c = 21.9775 (5) Å	0.40 × 0.38 × 0.20 mm

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	2696 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)	2240 reflections with I > 2σ(I)
T_min = 0.979, T_max = 1.0	R_int = 0.021
6722 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.077	All H-atom parameters refined
S = 1.05	Δρ_max = 0.25 e Å⁻³
2696 reflections	Δρ_min = −0.24 e Å⁻³
238 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	0.14710 (4)	0.51437 (4)	0.126198 (18)	0.02618 (12)
O1	0.28382 (11)	0.39665 (10)	0.03083 (6)	0.0308 (3)
O2	0.37259 (10)	0.52238 (11)	−0.03080 (6)	0.0297 (3)
O3	0.06436 (13)	0.74355 (12)	−0.14870 (6)	0.0376 (3)
O4	−0.09872 (13)	0.81129 (12)	−0.10265 (6)	0.0409 (4)
O5	−0.18116 (11)	0.60708 (11)	0.10878 (6)	0.0331 (3)
N1	0.28706 (12)	0.49108 (12)	0.00224 (6)	0.0219 (3)
N2	−0.00012 (14)	0.75653 (13)	−0.10356 (7)	0.0269 (3)
N3	−0.05433 (13)	0.73621 (12)	0.15851 (6)	0.0238 (3)
C1	0.10865 (14)	0.58412 (14)	0.05898 (7)	0.0179 (3)
C2	0.17880 (14)	0.57192 (13)	0.00600 (7)	0.0178 (3)
C3	0.14762 (15)	0.63140 (14)	−0.04708 (7)	0.0188 (3)
H3	0.1955 (17)	0.6182 (15)	−0.0830 (8)	0.028 (5)*
C4	0.04113 (15)	0.69969 (13)	−0.04645 (7)	0.0191 (3)
C5	−0.03125 (16)	0.71333 (14)	0.00470 (7)	0.0204 (4)
H5	−0.1055 (16)	0.7566 (15)	0.0036 (7)	0.018 (4)*
C6	0.00352 (14)	0.65690 (13)	0.05846 (7)	0.0177 (3)
C7	−0.08451 (15)	0.66492 (14)	0.11200 (7)	0.0207 (3)
C8	0.05941 (16)	0.80784 (16)	0.16249 (9)	0.0274 (4)
H8A	0.1068 (18)	0.7963 (17)	0.1263 (9)	0.034 (5)*
H8B	0.1111 (17)	0.7754 (16)	0.1984 (9)	0.032 (5)*
C9	0.02738 (18)	0.93938 (16)	0.17196 (8)	0.0274 (4)
H9A	−0.0143 (18)	0.9693 (16)	0.1353 (9)	0.031 (5)*
H9B	0.1038 (18)	0.9841 (16)	0.1769 (8)	0.029 (5)*
C10	−0.05450 (17)	0.95620 (17)	0.22745 (8)	0.0274 (4)
H10A	−0.0069 (16)	0.9325 (15)	0.2639 (8)	0.025 (5)*
H10B	−0.0785 (17)	1.0388 (17)	0.2320 (8)	0.033 (5)*
C11	−0.16990 (17)	0.87786 (17)	0.22253 (9)	0.0306 (4)
H11A	−0.2230 (19)	0.9067 (18)	0.1888 (9)	0.040 (6)*
H11B	−0.2193 (18)	0.8836 (16)	0.2593 (10)	0.041 (6)*
C12	−0.13634 (17)	0.74677 (16)	0.21155 (8)	0.0269 (4)
H12A	−0.2103 (16)	0.7001 (15)	0.2041 (8)	0.022 (4)*
H12B	−0.0908 (17)	0.7123 (15)	0.2473 (9)	0.028 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0277 (2)	0.0334 (2)	0.0174 (2)	0.00122 (18)	−0.00259 (17)	0.00550 (16)
O1	0.0322 (7)	0.0251 (6)	0.0350 (7)	0.0091 (6)	−0.0015 (6)	0.0029 (6)
O2	0.0189 (6)	0.0370 (7)	0.0332 (7)	−0.0013 (5)	0.0053 (5)	−0.0070 (6)
O3	0.0446 (8)	0.0466 (8)	0.0216 (7)	−0.0021 (7)	−0.0007 (6)	0.0093 (6)
O4	0.0399 (8)	0.0395 (8)	0.0434 (8)	0.0123 (7)	−0.0068 (7)	0.0168 (7)
O5	0.0250 (6)	0.0402 (7)	0.0341 (7)	−0.0139 (6)	0.0082 (6)	−0.0182 (6)
N1	0.0188 (7)	0.0246 (7)	0.0222 (7)	0.0011 (6)	−0.0029 (6)	−0.0045 (6)
N2	0.0329 (8)	0.0232 (7)	0.0246 (8)	−0.0050 (7)	−0.0055 (7)	0.0064 (6)
N3	0.0220 (7)	0.0285 (7)	0.0209 (7)	−0.0096 (6)	0.0061 (6)	−0.0079 (6)
C1	0.0199 (7)	0.0175 (8)	0.0162 (7)	−0.0048 (7)	−0.0022 (7)	0.0008 (6)
C2	0.0172 (7)	0.0166 (8)	0.0198 (8)	−0.0012 (7)	−0.0015 (6)	−0.0035 (6)
C3	0.0215 (8)	0.0191 (8)	0.0159 (8)	−0.0049 (7)	0.0011 (7)	−0.0026 (6)
C4	0.0244 (8)	0.0141 (7)	0.0187 (8)	−0.0030 (7)	−0.0036 (7)	0.0014 (6)
C5	0.0203 (8)	0.0154 (8)	0.0256 (9)	0.0010 (7)	−0.0010 (7)	−0.0022 (7)
C6	0.0193 (7)	0.0151 (7)	0.0186 (8)	−0.0038 (6)	0.0001 (7)	−0.0048 (6)
C7	0.0205 (8)	0.0189 (8)	0.0228 (9)	−0.0007 (7)	0.0018 (7)	−0.0032 (7)
C8	0.0225 (9)	0.0332 (10)	0.0266 (10)	−0.0106 (8)	0.0062 (8)	−0.0110 (8)
C9	0.0303 (10)	0.0295 (10)	0.0224 (9)	−0.0119 (8)	0.0016 (8)	−0.0023 (7)
C10	0.0308 (9)	0.0256 (9)	0.0258 (9)	−0.0027 (8)	0.0018 (8)	−0.0077 (8)
C11	0.0261 (9)	0.0381 (11)	0.0277 (10)	−0.0018 (8)	0.0076 (8)	−0.0098 (8)
C12	0.0272 (9)	0.0322 (9)	0.0212 (9)	−0.0100 (8)	0.0084 (8)	−0.0058 (8)

Geometric parameters (Å, º) top

Cl1—C1	1.7196 (16)	C5—H5	0.935 (17)
O1—N1	1.2247 (17)	C5—C6	1.389 (2)
O2—N1	1.2246 (17)	C6—C7	1.515 (2)
O3—N2	1.2200 (19)	C8—H8A	0.95 (2)
O4—N2	1.2260 (19)	C8—H8B	1.032 (19)
O5—C7	1.2273 (19)	C8—C9	1.518 (3)
N1—C2	1.476 (2)	C9—H9A	0.98 (2)
N2—C4	1.474 (2)	C9—H9B	0.97 (2)
N3—C7	1.334 (2)	C9—C10	1.517 (2)
N3—C8	1.466 (2)	C10—H10A	0.987 (18)
N3—C12	1.468 (2)	C10—H10B	0.960 (19)
C1—C2	1.395 (2)	C10—C11	1.523 (2)
C1—C6	1.394 (2)	C11—H11A	0.99 (2)
C2—C3	1.383 (2)	C11—H11B	0.97 (2)
C3—H3	0.954 (18)	C11—C12	1.522 (3)
C3—C4	1.377 (2)	C12—H12A	0.966 (17)
C4—C5	1.377 (2)	C12—H12B	1.004 (19)

O1—N1—C2	118.12 (13)	C6—C1—Cl1	117.75 (12)
O2—N1—O1	124.73 (14)	C6—C1—C2	119.41 (14)
O2—N1—C2	117.11 (13)	C6—C5—H5	119.0 (10)
O3—N2—O4	124.53 (15)	C7—N3—C8	124.97 (14)
O3—N2—C4	118.00 (14)	C7—N3—C12	120.59 (13)
O4—N2—C4	117.45 (15)	C8—N3—C12	114.43 (13)
O5—C7—N3	124.28 (15)	C8—C9—H9A	108.6 (11)
O5—C7—C6	117.18 (14)	C8—C9—H9B	108.5 (10)
N3—C7—C6	118.51 (13)	H8A—C8—H8B	107.6 (15)
N3—C8—H8A	109.0 (11)	C9—C8—H8A	111.5 (12)
N3—C8—H8B	107.9 (10)	C9—C8—H8B	110.8 (10)
N3—C8—C9	109.99 (15)	C9—C10—H10A	108.5 (10)
N3—C12—C11	110.24 (15)	C9—C10—H10B	111.1 (11)
N3—C12—H12A	108.7 (10)	C9—C10—C11	110.37 (15)
N3—C12—H12B	107.2 (10)	H9A—C9—H9B	107.9 (15)
C1—C2—N1	122.34 (14)	C10—C9—C8	111.20 (15)
C1—C6—C7	122.55 (14)	C10—C9—H9A	110.6 (11)
C2—C1—Cl1	122.84 (12)	C10—C9—H9B	110.0 (11)
C2—C3—H3	119.5 (11)	C10—C11—H11A	109.9 (12)
C3—C2—N1	115.90 (14)	C10—C11—H11B	110.6 (11)
C3—C2—C1	121.70 (14)	H10A—C10—H10B	108.1 (15)
C3—C4—N2	118.68 (14)	C11—C10—H10A	109.2 (10)
C4—C3—C2	117.30 (15)	C11—C10—H10B	109.5 (11)
C4—C3—H3	122.9 (11)	C11—C12—H12A	110.2 (10)
C4—C5—H5	121.5 (10)	C11—C12—H12B	111.0 (10)
C4—C5—C6	119.43 (15)	H11A—C11—H11B	106.6 (16)
C5—C4—N2	118.47 (14)	C12—C11—C10	111.42 (15)
C5—C4—C3	122.80 (15)	C12—C11—H11A	109.2 (12)
C5—C6—C1	119.29 (14)	C12—C11—H11B	109.0 (11)
C5—C6—C7	117.69 (14)	H12A—C12—H12B	109.3 (14)

Cl1—C1—C2—N1	4.4 (2)	C2—C3—C4—N2	−175.24 (14)
Cl1—C1—C2—C3	−178.34 (12)	C2—C3—C4—C5	2.1 (2)
Cl1—C1—C6—C5	−179.12 (12)	C3—C4—C5—C6	0.3 (2)
Cl1—C1—C6—C7	−7.17 (19)	C4—C5—C6—C1	−2.2 (2)
O1—N1—C2—C1	34.7 (2)	C4—C5—C6—C7	−174.59 (14)
O1—N1—C2—C3	−142.65 (15)	C5—C6—C7—O5	71.21 (19)
O2—N1—C2—C1	−147.16 (15)	C5—C6—C7—N3	−106.95 (18)
O2—N1—C2—C3	35.45 (19)	C6—C1—C2—N1	−176.46 (13)
O3—N2—C4—C3	−2.2 (2)	C6—C1—C2—C3	0.8 (2)
O3—N2—C4—C5	−179.72 (14)	C7—N3—C8—C9	123.65 (18)
O4—N2—C4—C3	176.04 (14)	C7—N3—C12—C11	−124.47 (17)
O4—N2—C4—C5	−1.4 (2)	C8—N3—C7—O5	−178.63 (17)
N1—C2—C3—C4	174.76 (13)	C8—N3—C7—C6	−0.6 (2)
N2—C4—C5—C6	177.67 (14)	C8—N3—C12—C11	56.3 (2)
N3—C8—C9—C10	55.5 (2)	C8—C9—C10—C11	−55.0 (2)
C1—C2—C3—C4	−2.6 (2)	C9—C10—C11—C12	54.1 (2)
C1—C6—C7—O5	−100.86 (19)	C10—C11—C12—N3	−53.7 (2)
C1—C6—C7—N3	81.0 (2)	C12—N3—C7—O5	2.2 (3)
C2—C1—C6—C5	1.7 (2)	C12—N3—C7—C6	−179.80 (15)
C2—C1—C6—C7	173.67 (14)	C12—N3—C8—C9	−57.1 (2)

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂ClN₃O₅
M_r	313.70
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	150
a, b, c (Å)	10.7864 (3), 11.1264 (3), 21.9775 (5)
V (Å³)	2637.60 (11)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.40 × 0.38 × 0.20

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)
T_min, T_max	0.979, 1.0
No. of measured, independent and observed [I > 2σ(I)] reflections	6722, 2696, 2240
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.077, 1.05
No. of reflections	2696
No. of parameters	238
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.24

Computer programs: CrysAlis PRO (Oxford Diffraction, 2006), CrysAlis PRO (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Acknowledgements

We thank the Analytical and Testing Center of Sichuan University for the X-ray measurements.

References

Christophe, T., Jackson, M., Jeon, H. K., Fenistein, D., Contreras-Dominguez, M., Kim, J., Genovesio, A., Carralot, J. P., Ewann, F., Kim, E. H., Lee, S. Y., Kang, S., Seo, M. J., Park, E. J., Skovierova, H., Pham, H., Riccardi, G., Nam, J. Y., Marsollier, L., Kempf, M., Joly-Guillou, M. L., Oh, T., Shin, W. K., No, Z., Nehrbass, U., Brosch, R., Cole, S. T. & Brodin, P. (2009). PLoS Pathog. 5, 1–10. Web of Science CrossRef Google Scholar
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