Phenyl piperidine-1-carboxyl­ate

Shahwar, D.; Tahir, M.N.; Ahmad, N.; Ullah, S.; Khan, M.A.

doi:10.1107/S1600536809050958

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o21

doi:10.1107/S1600536809050958

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Phenyl piperidine-1-carboxylate

Durre Shahwar,^a M. Nawaz Tahir,^b ^* Naeem Ahmad,^a Saif Ullah ^a and Muhammad Akmal Khan ^a

^aDepartment of Chemistry, Government College University, Lahore, Pakistan, and ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 22 November 2009; accepted 26 November 2009; online 4 December 2009)

In the title compound, C₁₂H₁₅NO₂, the dihedral angle between the benzene ring and the basal plane of the piperidine ring (which is in a chair conformation) is 49.55 (8)°. In the crystal, molecules are linked by C—H⋯O hydrogen bonds and very weak C–H⋯π interactions.

Related literature

For related structures, see: Shahwar et al. (2009a ,b ).

Experimental

Crystal data

C₁₂H₁₅NO₂
M_r = 205.25
Monoclinic, P 2₁
a = 6.2091 (2) Å
b = 7.6881 (3) Å
c = 11.2838 (4) Å
β = 97.211 (2)°
V = 534.39 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.28 × 0.11 × 0.09 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.987, T_max = 0.993
6213 measured reflections
1422 independent reflections
1243 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.088
S = 1.05
1422 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2ⁱ	0.93	2.47	3.342 (2)	157
C5—H5⋯Cg2ⁱⁱ	0.93	2.99	3.632 (2)	128
C10—H10A⋯Cg2ⁱⁱⁱ	0.97	2.97	3.848 (2)	151
Symmetry codes: (i) x-1, y, z; (ii) $[-x, y-{\script{1\over 2}}, -z]$ ; (iii) $[-x, y+{\script{1\over 2}}, -z+1]$ . Cg2 is the centroid of the C1–C6 ring.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809050958/hb5246sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809050958/hb5246Isup2.hkl

checkCIF report

Comment top

We have recently reported the crystal structure of (II) Phenyl N-(2-methylphenyl)carbamate (Shahwar et al., 2009a) and (III) Phenyl N-phenylcarbamate (Shahwar et al., 2009b). The title compound (I, Fig. 1) is in continuation to synthesize various carbamates.

In (I), the benzene ring A (C1—C6) is of course planar. The group B (O1/O2/C7/N1/C8/C12) and C (C8/C9/C11/C12) are also planar with maximum r. m. s. deviations of 0.0127 and 0.0046 Å respectively, from the respective mean square planes. The dihedral angles between A/B, B/C and A/C are 56.37 (5)°, 50.95 (7)° and 49.55 (8)° respectively. The piperidine is in the chair conformation as the apical atoms N1 and C10 are at a distance of -0.6211 (26) and 0.6523 (30) Å respectively, from the basal plane (C8/C9/C11/C12). The molecules are stabilized in the form of polymeric chains (Table 1, Fig. 2). The C–H···π interactions (Table 1) also play a role in stabilizing the molecules.

Related literature top

For related structures, see: Shahwar et al. (2009a,b). Cg2 is the centroid of the C1–C6 ring.

Experimental top

Piperidine (0.01 M, 0.99 ml) and triethylamine (0.012 M, 1.66 ml) were added to 20 ml dichlorometnane in a 50 ml round bottom flask equipped with magnetic stirrer. Phenyl chloroformate (0.01 M, 1.26 ml) was added drop wise with continuous stirring of the contents of the flask. After complete addition the stirring was continued for 30 minutes. Extra dichloromethane was evaporated and then resulting solid was washed with 1M HCL and filtered to get pure product. Recrystallization of the crude product with ethyl acetate affoarded colourless needles of (I).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of (I) with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The partial packing of (I), which shows that molecules are linked in polymeric chains.

Phenyl piperidine-1-carboxylate top

Crystal data top

C₁₂H₁₅NO₂	F(000) = 220
M_r = 205.25	D_x = 1.276 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1422 reflections
a = 6.2091 (2) Å	θ = 3.2–28.3°
b = 7.6881 (3) Å	µ = 0.09 mm⁻¹
c = 11.2838 (4) Å	T = 296 K
β = 97.211 (2)°	Needles, colorless
V = 534.39 (3) Å³	0.28 × 0.11 × 0.09 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD diffractometer	1422 independent reflections
Radiation source: fine-focus sealed tube	1243 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 7.40 pixels mm^-1	θ_max = 28.3°, θ_min = 3.2°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −9→10
T_min = 0.987, T_max = 0.993	l = −15→14
6213 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) = 0.088	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0453P)² + 0.0354P] where P = (F_o² + 2F_c²)/3
1422 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₂H₁₅NO₂	V = 534.39 (3) Å³
M_r = 205.25	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.2091 (2) Å	µ = 0.09 mm⁻¹
b = 7.6881 (3) Å	T = 296 K
c = 11.2838 (4) Å	0.28 × 0.11 × 0.09 mm
β = 97.211 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	1422 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1243 reflections with I > 2σ(I)
T_min = 0.987, T_max = 0.993	R_int = 0.022
6213 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.05	Δρ_max = 0.14 e Å⁻³
1422 reflections	Δρ_min = −0.22 e Å⁻³
136 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
O1	−0.00238 (19)	0.6920 (2)	0.32910 (10)	0.0497 (4)
O2	0.3128 (2)	0.83567 (19)	0.31583 (11)	0.0534 (4)
N1	0.2483 (2)	0.7051 (2)	0.48833 (12)	0.0442 (4)
C1	−0.0639 (3)	0.6857 (2)	0.20515 (14)	0.0395 (5)
C2	−0.2721 (3)	0.7369 (3)	0.16604 (16)	0.0465 (6)
C3	−0.3512 (3)	0.7125 (4)	0.04706 (18)	0.0599 (7)
C4	−0.2238 (4)	0.6384 (3)	−0.03033 (18)	0.0631 (8)
C5	−0.0147 (4)	0.5895 (3)	0.01023 (19)	0.0578 (7)
C6	0.0681 (3)	0.6137 (3)	0.12898 (16)	0.0485 (6)
C7	0.2001 (3)	0.7508 (2)	0.37356 (14)	0.0384 (5)
C8	0.1076 (3)	0.6065 (3)	0.55852 (15)	0.0474 (6)
C9	0.0725 (3)	0.7057 (3)	0.67042 (15)	0.0487 (6)
C10	0.2875 (3)	0.7539 (3)	0.74199 (17)	0.0538 (6)
C11	0.4301 (3)	0.8523 (3)	0.66545 (17)	0.0521 (6)
C12	0.4601 (3)	0.7516 (3)	0.55382 (17)	0.0486 (5)
H2	−0.35844	0.78703	0.21843	0.0558*
H3	−0.49220	0.74669	0.01916	0.0719*
H4	−0.27888	0.62132	−0.10998	0.0757*
H5	0.07179	0.53993	−0.04228	0.0693*
H6	0.21007	0.58190	0.15663	0.0582*
H8A	0.17346	0.49472	0.58031	0.0569*
H8B	−0.03120	0.58559	0.51088	0.0569*
H9A	−0.01098	0.63469	0.71919	0.0584*
H9B	−0.00986	0.81054	0.64855	0.0584*
H10A	0.26113	0.82542	0.80952	0.0646*
H10B	0.36158	0.64910	0.77265	0.0646*
H11A	0.36452	0.96411	0.64339	0.0626*
H11B	0.57069	0.87341	0.71114	0.0626*
H12A	0.54102	0.82153	0.50311	0.0584*
H12B	0.54274	0.64671	0.57525	0.0584*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0416 (7)	0.0749 (9)	0.0328 (6)	−0.0111 (7)	0.0056 (5)	0.0005 (7)
O2	0.0542 (7)	0.0587 (8)	0.0497 (7)	−0.0108 (7)	0.0159 (6)	0.0040 (7)
N1	0.0396 (7)	0.0565 (9)	0.0366 (7)	−0.0128 (7)	0.0047 (6)	−0.0020 (7)
C1	0.0429 (9)	0.0422 (9)	0.0336 (8)	−0.0044 (8)	0.0057 (7)	0.0045 (8)
C2	0.0404 (9)	0.0524 (10)	0.0481 (10)	−0.0005 (9)	0.0106 (8)	0.0029 (9)
C3	0.0429 (10)	0.0806 (16)	0.0539 (11)	0.0016 (10)	−0.0034 (8)	0.0127 (12)
C4	0.0619 (13)	0.0892 (18)	0.0366 (10)	−0.0035 (12)	−0.0003 (9)	0.0017 (10)
C5	0.0645 (12)	0.0676 (13)	0.0425 (10)	0.0097 (10)	0.0120 (9)	−0.0034 (9)
C6	0.0469 (10)	0.0573 (11)	0.0415 (9)	0.0120 (9)	0.0068 (8)	0.0056 (9)
C7	0.0368 (8)	0.0406 (8)	0.0395 (8)	−0.0010 (8)	0.0110 (7)	−0.0063 (8)
C8	0.0497 (10)	0.0552 (10)	0.0366 (9)	−0.0162 (9)	0.0027 (7)	0.0026 (8)
C9	0.0488 (9)	0.0599 (12)	0.0376 (9)	−0.0028 (9)	0.0066 (7)	0.0040 (8)
C10	0.0637 (12)	0.0561 (11)	0.0386 (9)	−0.0001 (10)	−0.0054 (8)	−0.0060 (9)
C11	0.0461 (10)	0.0503 (11)	0.0559 (11)	−0.0050 (9)	−0.0096 (8)	−0.0079 (9)
C12	0.0360 (8)	0.0536 (10)	0.0549 (10)	−0.0043 (8)	0.0002 (7)	−0.0031 (9)

Geometric parameters (Å, º) top

O1—C1	1.4037 (19)	C2—H2	0.9300
O1—C7	1.371 (2)	C3—H3	0.9300
O2—C7	1.206 (2)	C4—H4	0.9300
N1—C7	1.339 (2)	C5—H5	0.9300
N1—C8	1.463 (2)	C6—H6	0.9300
N1—C12	1.470 (2)	C8—H8A	0.9700
C1—C2	1.370 (3)	C8—H8B	0.9700
C1—C6	1.376 (3)	C9—H9A	0.9700
C2—C3	1.383 (3)	C9—H9B	0.9700
C3—C4	1.373 (3)	C10—H10A	0.9700
C4—C5	1.374 (3)	C10—H10B	0.9700
C5—C6	1.386 (3)	C11—H11A	0.9700
C8—C9	1.514 (3)	C11—H11B	0.9700
C9—C10	1.517 (3)	C12—H12A	0.9700
C10—C11	1.515 (3)	C12—H12B	0.9700
C11—C12	1.510 (3)

C1—O1—C7	119.90 (13)	C1—C6—H6	121.00
C7—N1—C8	125.71 (14)	C5—C6—H6	121.00
C7—N1—C12	119.99 (15)	N1—C8—H8A	110.00
C8—N1—C12	114.30 (14)	N1—C8—H8B	110.00
O1—C1—C2	116.02 (15)	C9—C8—H8A	110.00
O1—C1—C6	121.82 (16)	C9—C8—H8B	110.00
C2—C1—C6	121.75 (16)	H8A—C8—H8B	108.00
C1—C2—C3	118.64 (18)	C8—C9—H9A	109.00
C2—C3—C4	120.71 (19)	C8—C9—H9B	109.00
C3—C4—C5	119.83 (19)	C10—C9—H9A	109.00
C4—C5—C6	120.4 (2)	C10—C9—H9B	109.00
C1—C6—C5	118.69 (18)	H9A—C9—H9B	108.00
O1—C7—O2	123.27 (15)	C9—C10—H10A	109.00
O1—C7—N1	110.54 (14)	C9—C10—H10B	109.00
O2—C7—N1	126.16 (16)	C11—C10—H10A	109.00
N1—C8—C9	110.42 (17)	C11—C10—H10B	109.00
C8—C9—C10	110.97 (16)	H10A—C10—H10B	108.00
C9—C10—C11	110.91 (16)	C10—C11—H11A	109.00
C10—C11—C12	111.21 (18)	C10—C11—H11B	109.00
N1—C12—C11	110.36 (15)	C12—C11—H11A	109.00
C1—C2—H2	121.00	C12—C11—H11B	109.00
C3—C2—H2	121.00	H11A—C11—H11B	108.00
C2—C3—H3	120.00	N1—C12—H12A	110.00
C4—C3—H3	120.00	N1—C12—H12B	110.00
C3—C4—H4	120.00	C11—C12—H12A	110.00
C5—C4—H4	120.00	C11—C12—H12B	110.00
C4—C5—H5	120.00	H12A—C12—H12B	108.00
C6—C5—H5	120.00

C7—O1—C1—C2	−139.17 (18)	O1—C1—C2—C3	−171.8 (2)
C7—O1—C1—C6	48.0 (2)	C6—C1—C2—C3	1.0 (3)
C1—O1—C7—O2	18.0 (3)	O1—C1—C6—C5	171.01 (18)
C1—O1—C7—N1	−163.81 (15)	C2—C1—C6—C5	−1.4 (3)
C8—N1—C7—O1	−0.1 (2)	C1—C2—C3—C4	0.0 (4)
C8—N1—C7—O2	178.06 (18)	C2—C3—C4—C5	−0.7 (4)
C12—N1—C7—O1	178.78 (15)	C3—C4—C5—C6	0.3 (4)
C12—N1—C7—O2	−3.1 (3)	C4—C5—C6—C1	0.7 (3)
C7—N1—C8—C9	−124.65 (18)	N1—C8—C9—C10	−54.5 (2)
C12—N1—C8—C9	56.5 (2)	C8—C9—C10—C11	54.4 (2)
C7—N1—C12—C11	124.72 (18)	C9—C10—C11—C12	−54.5 (2)
C8—N1—C12—C11	−56.3 (2)	C10—C11—C12—N1	54.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2ⁱ	0.93	2.47	3.342 (2)	157
C5—H5···Cg2ⁱⁱ	0.93	2.99	3.632 (2)	128
C10—H10A···Cg2ⁱⁱⁱ	0.97	2.97	3.848 (2)	151

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₅NO₂
M_r	205.25
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	6.2091 (2), 7.6881 (3), 11.2838 (4)
β (°)	97.211 (2)
V (Å³)	534.39 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.28 × 0.11 × 0.09

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.987, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	6213, 1422, 1243
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.088, 1.05
No. of reflections	1422
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.22

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2ⁱ	0.93	2.47	3.342 (2)	157
C5—H5···Cg2ⁱⁱ	0.93	2.99	3.632 (2)	128
C10—H10A···Cg2ⁱⁱⁱ	0.97	2.97	3.848 (2)	151

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

Acknowledgements

DS is grateful to Dr I. U. Khan and M. N. Arshad for their assistance with the crystallographic data collection.

References

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