4-Anilino-1-benzyl-piperidine-4-carbo-nitrile.

The title mol-ecule, C(19)H(21)N(3), an important precursor in the synthesis of porphyrin-fentanyl conjugates, has its piperidine ring in the chair conformation, with endocyclic torsion-angle magnitudes in the range 53.26 (8)-60.63 (9)°. The C N group is axial, while the CH(2)Ph and NHPh groups are equatorial. The NH group does not engage in strong hydrogen bonding, but forms an inter-molecular N-H⋯N inter-action.

Related literature

For background literature, see: Barth et al. (2005 ▶); Deguchi et al. (2004 ▶); Henriksen et al. (2005 ▶); Terasaki et al. (2003 ▶); Vicente, (2001 ▶). For a related structure, see: Brine et al. (1994 ▶).

Experimental

Crystal data

C19H21N3

M = 291.39

Monoclinic,

a = 9.7718 (13) Å

b = 10.0415 (14) Å

c = 15.9519 (15) Å

β = 94.532 (9)°

V = 1560.4 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.07 mm−1

T = 90 K

0.37 × 0.25 × 0.23 mm

Data collection

Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler

Absorption correction: none

24180 measured reflections

6842 independent reflections

5189 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.124

S = 1.03

6842 reflections

203 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.49 e Å−3

Δρmin = −0.27 e Å−3

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808009136/om2222sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808009136/om2222Isup2.hkl

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

C19H21N3	F000 = 624
Mr = 291.39	Dx = 1.240 Mg m−3
Monoclinic, P21/n	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5228 reflections
a = 9.7718 (13) Å	θ = 2.5–35.0º
b = 10.0415 (14) Å	µ = 0.07 mm−1
c = 15.9519 (15) Å	T = 90 K
β = 94.532 (9)º	Fragment, colorless
V = 1560.4 (3) Å3	0.37 × 0.25 × 0.23 mm
Z = 4

Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler	5189 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Monochromator: graphite	θmax = 35.0º
T = 90 K	θmin = 2.5º
ω scans with κ offsets	h = −15→15
Absorption correction: none	k = −12→16
24180 measured reflections	l = −25→25
6842 independent reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.044	w = 1/[σ2(Fo2) + (0.0605P)2 + 0.3181P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.124	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.49 e Å−3
6842 reflections	Δρmin = −0.27 e Å−3
203 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0081 (18)
Secondary atom site location: difference Fourier map

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.

	x	y	z	Uiso*/Ueq
N1	0.43216 (7)	0.37118 (8)	0.73394 (4)	0.01247 (13)
N2	0.68233 (8)	0.66885 (8)	0.63306 (4)	0.01659 (14)
H2N	0.6447 (13)	0.7350 (14)	0.6548 (8)	0.020*
N3	0.86941 (8)	0.40176 (9)	0.70892 (5)	0.01981 (15)
C1	0.53227 (8)	0.44146 (9)	0.79097 (4)	0.01280 (14)
H1A	0.6124	0.3830	0.8050	0.015*
H1B	0.4903	0.4628	0.8438	0.015*
C2	0.57970 (8)	0.56932 (9)	0.75123 (5)	0.01372 (14)
H2A	0.6475	0.6144	0.7910	0.016*
H2B	0.5002	0.6298	0.7403	0.016*
C3	0.64507 (8)	0.54198 (8)	0.66810 (5)	0.01146 (13)
C4	0.54095 (8)	0.45965 (9)	0.61165 (5)	0.01336 (14)
H4A	0.4602	0.5158	0.5947	0.016*
H4B	0.5837	0.4328	0.5600	0.016*
C5	0.49370 (8)	0.33556 (9)	0.65622 (5)	0.01364 (15)
H5A	0.4256	0.2869	0.6185	0.016*
H5B	0.5731	0.2759	0.6695	0.016*
C6	0.38149 (8)	0.25204 (9)	0.77503 (5)	0.01443 (14)
H6A	0.4604	0.1982	0.7983	0.017*
H6B	0.3273	0.1971	0.7329	0.017*
C7	0.29300 (8)	0.28909 (9)	0.84504 (5)	0.01256 (14)
C8	0.17137 (8)	0.35979 (9)	0.82626 (5)	0.01463 (15)
H8	0.1458	0.3852	0.7698	0.018*
C9	0.08730 (9)	0.39339 (9)	0.88947 (5)	0.01645 (16)
H9	0.0047	0.4414	0.8760	0.020*
C10	0.12395 (9)	0.35679 (10)	0.97276 (5)	0.01752 (16)
H10	0.0655	0.3777	1.0157	0.021*
C11	0.24640 (10)	0.28969 (9)	0.99214 (5)	0.01758 (16)
H11	0.2730	0.2665	1.0488	0.021*
C12	0.33101 (9)	0.25597 (9)	0.92851 (5)	0.01539 (15)
H12	0.4149	0.2102	0.9423	0.018*
C13	0.74564 (8)	0.68867 (8)	0.55887 (5)	0.01178 (14)
C14	0.80105 (8)	0.58537 (8)	0.51281 (5)	0.01315 (14)
H14	0.7935	0.4957	0.5308	0.016*
C15	0.86740 (8)	0.61438 (9)	0.44045 (5)	0.01405 (14)
H15	0.9037	0.5437	0.4094	0.017*
C16	0.88109 (8)	0.74472 (9)	0.41323 (5)	0.01466 (15)
H16	0.9273	0.7636	0.3644	0.018*
C17	0.82588 (8)	0.84752 (9)	0.45882 (5)	0.01452 (15)
H17	0.8344	0.9371	0.4408	0.017*
C18	0.75859 (8)	0.82007 (9)	0.53034 (5)	0.01298 (14)
H18	0.7208	0.8911	0.5604	0.016*
C19	0.77255 (8)	0.46283 (9)	0.68964 (5)	0.01285 (14)

	U11	U22	U33	U12	U13	U23
N1	0.0132 (3)	0.0145 (3)	0.0100 (2)	−0.0015 (2)	0.0032 (2)	−0.0008 (2)
N2	0.0258 (4)	0.0095 (3)	0.0161 (3)	0.0039 (3)	0.0115 (3)	0.0025 (2)
N3	0.0166 (3)	0.0209 (4)	0.0217 (3)	0.0027 (3)	0.0001 (2)	0.0017 (3)
C1	0.0158 (3)	0.0133 (3)	0.0096 (3)	−0.0012 (3)	0.0027 (2)	0.0001 (3)
C2	0.0178 (3)	0.0127 (3)	0.0113 (3)	0.0002 (3)	0.0056 (2)	−0.0002 (3)
C3	0.0131 (3)	0.0106 (3)	0.0111 (3)	0.0017 (3)	0.0034 (2)	0.0015 (2)
C4	0.0125 (3)	0.0182 (4)	0.0095 (3)	0.0011 (3)	0.0016 (2)	0.0012 (3)
C5	0.0137 (3)	0.0168 (4)	0.0106 (3)	−0.0015 (3)	0.0024 (2)	−0.0024 (3)
C6	0.0155 (3)	0.0131 (3)	0.0152 (3)	−0.0009 (3)	0.0050 (2)	−0.0007 (3)
C7	0.0133 (3)	0.0121 (3)	0.0126 (3)	−0.0022 (3)	0.0032 (2)	−0.0003 (3)
C8	0.0135 (3)	0.0170 (4)	0.0134 (3)	−0.0017 (3)	0.0016 (2)	−0.0013 (3)
C9	0.0132 (3)	0.0178 (4)	0.0187 (3)	−0.0017 (3)	0.0036 (3)	−0.0033 (3)
C10	0.0200 (4)	0.0168 (4)	0.0167 (3)	−0.0048 (3)	0.0080 (3)	−0.0025 (3)
C11	0.0250 (4)	0.0146 (4)	0.0136 (3)	−0.0030 (3)	0.0046 (3)	0.0016 (3)
C12	0.0183 (3)	0.0130 (4)	0.0151 (3)	−0.0003 (3)	0.0024 (3)	0.0021 (3)
C13	0.0125 (3)	0.0117 (3)	0.0114 (3)	0.0011 (3)	0.0027 (2)	0.0014 (2)
C14	0.0157 (3)	0.0109 (3)	0.0134 (3)	0.0010 (3)	0.0042 (2)	0.0012 (3)
C15	0.0148 (3)	0.0150 (4)	0.0128 (3)	0.0007 (3)	0.0038 (2)	−0.0007 (3)
C16	0.0150 (3)	0.0163 (4)	0.0131 (3)	0.0002 (3)	0.0038 (2)	0.0022 (3)
C17	0.0152 (3)	0.0132 (4)	0.0154 (3)	0.0002 (3)	0.0032 (2)	0.0039 (3)
C18	0.0141 (3)	0.0115 (3)	0.0135 (3)	0.0012 (3)	0.0027 (2)	0.0009 (3)
C19	0.0139 (3)	0.0126 (3)	0.0123 (3)	−0.0011 (3)	0.0023 (2)	0.0003 (3)

N1—C1	1.4636 (10)	C7—C12	1.3940 (11)
N1—C5	1.4644 (10)	C7—C8	1.3964 (12)
N1—C6	1.4688 (11)	C8—C9	1.3915 (11)
N2—C13	1.3924 (10)	C8—H8	0.9500
N2—C3	1.4491 (11)	C9—C10	1.3977 (12)
N2—H2N	0.847 (14)	C9—H9	0.9500
N3—C19	1.1492 (11)	C10—C11	1.3867 (13)
C1—C2	1.5203 (12)	C10—H10	0.9500
C1—H1A	0.9900	C11—C12	1.4004 (12)
C1—H1B	0.9900	C11—H11	0.9500
C2—C3	1.5414 (11)	C12—H12	0.9500
C2—H2A	0.9900	C13—C14	1.4042 (11)
C2—H2B	0.9900	C13—C18	1.4047 (12)
C3—C19	1.4946 (11)	C14—C15	1.3986 (11)
C3—C4	1.5443 (11)	C14—H14	0.9500
C4—C5	1.5242 (12)	C15—C16	1.3887 (12)
C4—H4A	0.9900	C15—H15	0.9500
C4—H4B	0.9900	C16—C17	1.3955 (12)
C5—H5A	0.9900	C16—H16	0.9500
C5—H5B	0.9900	C17—C18	1.3888 (11)
C6—C7	1.5119 (11)	C17—H17	0.9500
C6—H6A	0.9900	C18—H18	0.9500
C6—H6B	0.9900
C1—N1—C5	110.18 (6)	C7—C6—H6B	109.4
C1—N1—C6	110.34 (6)	H6A—C6—H6B	108.0
C5—N1—C6	110.76 (7)	C12—C7—C8	118.96 (7)
C13—N2—C3	126.55 (7)	C12—C7—C6	121.47 (7)
C13—N2—H2N	118.2 (9)	C8—C7—C6	119.57 (7)
C3—N2—H2N	113.6 (9)	C9—C8—C7	120.60 (7)
N1—C1—C2	111.03 (6)	C9—C8—H8	119.7
N1—C1—H1A	109.4	C7—C8—H8	119.7
C2—C1—H1A	109.4	C8—C9—C10	120.23 (8)
N1—C1—H1B	109.4	C8—C9—H9	119.9
C2—C1—H1B	109.4	C10—C9—H9	119.9
H1A—C1—H1B	108.0	C11—C10—C9	119.43 (8)
C1—C2—C3	111.66 (7)	C11—C10—H10	120.3
C1—C2—H2A	109.3	C9—C10—H10	120.3
C3—C2—H2A	109.3	C10—C11—C12	120.29 (8)
C1—C2—H2B	109.3	C10—C11—H11	119.9
C3—C2—H2B	109.3	C12—C11—H11	119.9
H2A—C2—H2B	108.0	C7—C12—C11	120.44 (8)
N2—C3—C19	109.02 (7)	C7—C12—H12	119.8
N2—C3—C2	108.01 (7)	C11—C12—H12	119.8
C19—C3—C2	106.94 (6)	N2—C13—C14	123.69 (7)
N2—C3—C4	114.82 (6)	N2—C13—C18	117.84 (7)
C19—C3—C4	110.37 (7)	C14—C13—C18	118.43 (7)
C2—C3—C4	107.35 (6)	C15—C14—C13	120.06 (8)
C5—C4—C3	112.06 (6)	C15—C14—H14	120.0
C5—C4—H4A	109.2	C13—C14—H14	120.0
C3—C4—H4A	109.2	C16—C15—C14	121.12 (8)
C5—C4—H4B	109.2	C16—C15—H15	119.4
C3—C4—H4B	109.2	C14—C15—H15	119.4
H4A—C4—H4B	107.9	C15—C16—C17	118.91 (7)
N1—C5—C4	110.80 (7)	C15—C16—H16	120.5
N1—C5—H5A	109.5	C17—C16—H16	120.5
C4—C5—H5A	109.5	C18—C17—C16	120.59 (8)
N1—C5—H5B	109.5	C18—C17—H17	119.7
C4—C5—H5B	109.5	C16—C17—H17	119.7
H5A—C5—H5B	108.1	C17—C18—C13	120.88 (8)
N1—C6—C7	111.21 (7)	C17—C18—H18	119.6
N1—C6—H6A	109.4	C13—C18—H18	119.6
C7—C6—H6A	109.4	N3—C19—C3	177.73 (8)
N1—C6—H6B	109.4
C5—N1—C1—C2	60.63 (9)	C12—C7—C8—C9	−1.83 (13)
C6—N1—C1—C2	−176.75 (6)	C6—C7—C8—C9	179.10 (8)
N1—C1—C2—C3	−58.68 (9)	C7—C8—C9—C10	0.10 (13)
C13—N2—C3—C19	63.33 (10)	C8—C9—C10—C11	1.61 (14)
C13—N2—C3—C2	179.19 (8)	C9—C10—C11—C12	−1.57 (14)
C13—N2—C3—C4	−61.08 (11)	C8—C7—C12—C11	1.86 (13)
C1—C2—C3—N2	177.84 (6)	C6—C7—C12—C11	−179.09 (8)
C1—C2—C3—C19	−64.94 (8)	C10—C11—C12—C7	−0.17 (14)
C1—C2—C3—C4	53.51 (8)	C3—N2—C13—C14	−9.65 (13)
N2—C3—C4—C5	−173.35 (7)	C3—N2—C13—C18	172.56 (8)
C19—C3—C4—C5	62.96 (8)	N2—C13—C14—C15	−177.68 (8)
C2—C3—C4—C5	−53.26 (8)	C18—C13—C14—C15	0.09 (12)
C1—N1—C5—C4	−59.98 (8)	C13—C14—C15—C16	0.65 (12)
C6—N1—C5—C4	177.65 (6)	C14—C15—C16—C17	−0.77 (12)
C3—C4—C5—N1	57.77 (8)	C15—C16—C17—C18	0.15 (12)
C1—N1—C6—C7	69.20 (8)	C16—C17—C18—C13	0.59 (12)
C5—N1—C6—C7	−168.52 (6)	N2—C13—C18—C17	177.20 (7)
N1—C6—C7—C12	−116.76 (9)	C14—C13—C18—C17	−0.70 (12)
N1—C6—C7—C8	62.28 (10)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···N3i	0.847 (14)	2.756 (13)	3.5044 (12)	148.2 (11)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯N3i	0.847 (14)	2.756 (13)	3.5044 (12)	148.2 (11)

Symmetry code: (i) .