1,1′-[(2,3,5,6-Tetra­methyl-1,4-phenyl­ene)bis(methyl­ene)]di­piperidine

Grace, P.S.; Nirmalram, J.S.; Nayagam, B.R.D.; Schollmeyer, D.

doi:10.1107/S2414314618012373

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 9| September 2018| x181237

https://doi.org/10.1107/S2414314618012373

Open

access

1,1′-[(2,3,5,6-Tetramethyl-1,4-phenylene)bis(methylene)]dipiperidine

P. Selvarathy Grace,^a Jeyaraman Selvaraj Nirmalram,^b B. Ravindran Durai Nayagam ^a ^* and Dieter Schollmeyer ^c

^aDepartment of Chemistry, Popes College affiliated to Manonmaniam Sundaranar University, Tirunelveli, Tamil Nadu 627 012, India, ^bDepartment of Chemistry, Ponnaiyah Ramajayam Institute of Science and Technology, Vallam, Thanjavur 613 403, TamilNadu, India, and ^cUniversity of Mainz, Institut of Organic Chemistry, Duesbergweg 10-14, 55128 Mainz, Germany
^*Correspondence e-mail: bravidurai@gmail.com

Edited by R. J. Butcher, Howard University, USA (Received 21 August 2018; accepted 31 August 2018; online 7 September 2018)

The asymmetric unit of the title compound, C₂₂H₃₆N₂, comprises one half-molecule, the other half being generated by a center of inversion. The piperidine ring adopts a chair conformation, with the exocyclic N—C bond in an equatorial orientation. A short intramolecular C—H⋯N hydrogen bond occurs and forms an S(6) motif. No directional interactions beyond van der Waals contacts are observed between the molecules, which form a wave-like supramolecular architecture.

Keywords: crystal structure; piperidine-substituted durene; intramolecular C—H⋯N hydrogen bond.

CCDC reference: 943697

Structure description

Some piperidine derivatives possess significant biological and medicinal properties including insulin normalization, addiction therapeutics (Kozikowski et al., 1998 ) and local anaesthesia (McElvain & Carney, 1946 ). Here we report the synthesis and crystal structure of a new piperidine-substituted durene.

The asymmetric unit is made up of one half-molecule, the other half being generated by inversion (symmetry code: 1 − x,1 − y,1 − z; see Fig. 1). The piperidine rings adopt a chair conformation with puckering parameters Q = 0.5765 (16) Å, Θ =178.20 (15)° φ = 181 (5)°. The dihedral angle between the phenyl (C8/C9/C11/C8a/C9a/C11a) and piperidine (N1/C2–C6) rings is 73.66 (7)°. The weak intramolecular C12—H12B⋯N1 hydrogen bond (Table 1) forms an S(6) motif. In the crystal, adjacent molecules are aggregated by weak van der Waals interactions, leading to a wave-like supramolecular architecture (Fig. 2) extending along b-axis direction.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12B⋯N1	0.94 (2)	2.59 (2)	3.2204 (18)	124.8 (14)

Figure 1
The molecular structure of the title compound with the atom labelling and displacement ellipsoids drawn at the 50% probability level [symmetry code: (a) 1 − x, 1 − y, 1 − z].

Figure 2
Part of the crystal packing showing the wave-like architecture. View is along the a axis.

Synthesis and crystallization

A mixture of piperidine hydrochloride (0.242 g, 2 mmol) in sodium ethoxide solution and 1,4-bis(bromomethyl)durene (0.320 g, 1 mmol) in ethanol and water (15 ml) were heated at 333 K with continuous stirring for about 4 h. The mixture was kept aside for slow evaporation. After two weeks, colourless block-shaped crystals (m.p. 462 K) suitable for single-crystal X-ray diffraction were formed.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₂H₃₆N₂
M_r	328.53
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	5.6271 (4), 21.1764 (14), 8.2787 (5)
β (°)	105.860 (2)
V (Å³)	948.95 (11)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.07
Crystal size (mm)	0.45 × 0.17 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII
No. of measured, independent and observed [I > 2σ(I)] reflections	6578, 2237, 1779
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.655

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.118, 1.03
No. of reflections	2237
No. of parameters	172
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.16
Computer programs: APEX2 and SAINT (Bruker, 2004 ), SIR2004 (Burla et al., 2005 ), SHELXL2018 (Sheldrick, 2015 ), ORTEPII (Johnson, 1976 ), Mercury (Macrae et al. (2008 ) and POV-RAY for Windows (Cason, 2004 ).

Structural data

CCDC reference: 943697

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314618012373/bv4021sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618012373/bv4021Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618012373/bv4021Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015).

1,1'-[(2,3,5,6-Tetramethyl-1,4-phenylene)bis(methylene)]dipiperidine top

Crystal data top

C₂₂H₃₆N₂	F(000) = 364
M_r = 328.53	D_x = 1.150 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 5.6271 (4) Å	Cell parameters from 1751 reflections
b = 21.1764 (14) Å	θ = 2.7–27.7°
c = 8.2787 (5) Å	µ = 0.07 mm⁻¹
β = 105.860 (2)°	T = 173 K
V = 948.95 (11) Å³	Block, colourless
Z = 2	0.45 × 0.17 × 0.15 mm

Data collection top

Bruker SMART APEXII diffractometer	1779 reflections with I > 2σ(I)
Radiation source: sealed Tube	R_int = 0.027
Graphite monochromator	θ_max = 27.7°, θ_min = 1.9°
CCD scan	h = −7→6
6578 measured reflections	k = −27→16
2237 independent reflections	l = −9→10

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	All H-atom parameters refined
wR(F²) = 0.118	w = 1/[σ²(F_o²) + (0.0555P)² + 0.2324P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2237 reflections	Δρ_max = 0.28 e Å⁻³
172 parameters	Δρ_min = −0.16 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The H atoms were added at positions obtained from difference Fourier maps and refined isotropically.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.48878 (19)	0.63789 (5)	0.20943 (13)	0.0239 (3)
C2	0.4075 (2)	0.59637 (6)	0.06304 (16)	0.0268 (3)
H2A	0.221 (3)	0.6020 (6)	0.0122 (18)	0.029 (3)*
H2B	0.434 (3)	0.5516 (7)	0.1021 (18)	0.029 (3)*
C3	0.5439 (3)	0.61062 (6)	−0.06807 (17)	0.0305 (3)
H3A	0.487 (3)	0.5819 (8)	−0.166 (2)	0.039 (3)*
H3B	0.725 (3)	0.6027 (7)	−0.018 (2)	0.039 (3)*
C4	0.5071 (3)	0.67927 (7)	−0.12320 (19)	0.0363 (3)
H4A	0.331 (3)	0.6873 (8)	−0.179 (2)	0.048 (3)*
H4B	0.605 (3)	0.6902 (8)	−0.201 (2)	0.048 (3)*
C5	0.5808 (3)	0.72219 (7)	0.0303 (2)	0.0380 (4)
H5A	0.765 (3)	0.7182 (8)	0.083 (2)	0.047 (3)*
H5B	0.549 (3)	0.7677 (9)	−0.003 (2)	0.047 (3)*
C6	0.4436 (3)	0.70403 (6)	0.15832 (18)	0.0320 (3)
H6A	0.497 (3)	0.7317 (7)	0.262 (2)	0.037 (3)*
H6B	0.258 (3)	0.7116 (7)	0.1108 (19)	0.037 (3)*
C7	0.3611 (2)	0.62262 (6)	0.33824 (16)	0.0267 (3)
H7A	0.178 (3)	0.6271 (6)	0.2908 (18)	0.028 (2)*
H7B	0.407 (3)	0.6563 (7)	0.4244 (18)	0.028 (2)*
C8	0.4317 (2)	0.55846 (6)	0.41941 (15)	0.0227 (3)
C9	0.2674 (2)	0.50691 (6)	0.38251 (14)	0.0232 (3)
C10	0.0179 (3)	0.51192 (7)	0.25473 (18)	0.0312 (3)
H10A	0.015 (4)	0.4889 (11)	0.152 (3)	0.088 (4)*
H10B	−0.024 (4)	0.5535 (12)	0.220 (3)	0.088 (4)*
H10C	−0.114 (5)	0.4943 (10)	0.296 (3)	0.088 (4)*
C11	0.6640 (2)	0.55124 (6)	0.53631 (15)	0.0231 (3)
C12	0.8452 (3)	0.60566 (7)	0.57599 (18)	0.0307 (3)
H12A	0.882 (3)	0.6199 (8)	0.695 (2)	0.056 (3)*
H12B	0.791 (4)	0.6411 (9)	0.508 (2)	0.056 (3)*
H12C	1.002 (4)	0.5941 (9)	0.561 (2)	0.056 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0289 (5)	0.0205 (5)	0.0239 (5)	0.0011 (4)	0.0102 (4)	0.0009 (4)
C2	0.0328 (7)	0.0242 (6)	0.0244 (6)	−0.0008 (5)	0.0095 (5)	0.0001 (5)
C3	0.0380 (7)	0.0309 (7)	0.0255 (7)	0.0034 (6)	0.0136 (6)	0.0014 (5)
C4	0.0427 (8)	0.0372 (8)	0.0339 (8)	0.0082 (6)	0.0187 (7)	0.0127 (6)
C5	0.0491 (9)	0.0247 (7)	0.0477 (9)	0.0014 (6)	0.0256 (7)	0.0074 (6)
C6	0.0409 (8)	0.0208 (6)	0.0375 (8)	0.0032 (5)	0.0164 (6)	0.0021 (5)
C7	0.0316 (7)	0.0248 (6)	0.0269 (7)	0.0036 (5)	0.0134 (5)	0.0009 (5)
C8	0.0275 (6)	0.0243 (6)	0.0194 (6)	0.0005 (5)	0.0117 (5)	−0.0014 (4)
C9	0.0255 (6)	0.0283 (6)	0.0180 (6)	0.0004 (5)	0.0098 (5)	−0.0016 (5)
C10	0.0286 (7)	0.0359 (7)	0.0274 (7)	−0.0018 (5)	0.0049 (5)	0.0015 (6)
C11	0.0282 (6)	0.0249 (6)	0.0194 (6)	−0.0024 (5)	0.0117 (5)	−0.0036 (4)
C12	0.0337 (7)	0.0290 (7)	0.0294 (7)	−0.0073 (5)	0.0085 (6)	−0.0030 (5)

Geometric parameters (Å, º) top

N1—C6	1.4652 (16)	C6—H6B	1.024 (16)
N1—C2	1.4655 (16)	C7—C8	1.5198 (17)
N1—C7	1.4753 (16)	C7—H7A	1.003 (15)
C2—C3	1.5207 (18)	C7—H7B	0.991 (15)
C2—H2A	1.026 (15)	C8—C11	1.4060 (17)
C2—H2B	1.000 (14)	C8—C9	1.4090 (17)
C3—C4	1.5209 (19)	C9—C11ⁱ	1.4055 (17)
C3—H3A	0.991 (17)	C9—C10	1.5131 (18)
C3—H3B	1.003 (17)	C10—H10A	0.98 (2)
C4—C5	1.525 (2)	C10—H10B	0.94 (2)
C4—H4A	0.987 (18)	C10—H10C	0.97 (2)
C4—H4B	0.984 (18)	C11—C12	1.5143 (17)
C5—C6	1.521 (2)	C12—H12A	0.996 (19)
C5—H5A	1.013 (18)	C12—H12B	0.94 (2)
C5—H5B	1.003 (18)	C12—H12C	0.957 (19)
C6—H6A	1.017 (16)

C6—N1—C2	110.14 (10)	N1—C6—H6B	109.9 (9)
C6—N1—C7	109.74 (10)	C5—C6—H6B	110.6 (9)
C2—N1—C7	111.27 (10)	H6A—C6—H6B	105.6 (12)
N1—C2—C3	111.53 (11)	N1—C7—C8	113.30 (10)
N1—C2—H2A	108.8 (8)	N1—C7—H7A	110.4 (8)
C3—C2—H2A	110.1 (8)	C8—C7—H7A	112.0 (8)
N1—C2—H2B	108.5 (8)	N1—C7—H7B	106.3 (8)
C3—C2—H2B	111.0 (8)	C8—C7—H7B	109.8 (8)
H2A—C2—H2B	106.7 (11)	H7A—C7—H7B	104.5 (11)
C2—C3—C4	110.49 (11)	C11—C8—C9	119.77 (11)
C2—C3—H3A	110.2 (9)	C11—C8—C7	118.88 (11)
C4—C3—H3A	110.8 (9)	C9—C8—C7	121.33 (11)
C2—C3—H3B	109.0 (9)	C11ⁱ—C9—C8	119.79 (11)
C4—C3—H3B	108.9 (9)	C11ⁱ—C9—C10	118.48 (11)
H3A—C3—H3B	107.5 (13)	C8—C9—C10	121.73 (11)
C3—C4—C5	109.63 (12)	C9—C10—H10A	111.6 (14)
C3—C4—H4A	109.9 (10)	C9—C10—H10B	112.8 (15)
C5—C4—H4A	107.2 (10)	H10A—C10—H10B	104.8 (19)
C3—C4—H4B	111.5 (10)	C9—C10—H10C	112.3 (14)
C5—C4—H4B	109.5 (10)	H10A—C10—H10C	106.1 (19)
H4A—C4—H4B	109.0 (14)	H10B—C10—H10C	108.6 (19)
C6—C5—C4	110.83 (12)	C9ⁱ—C11—C8	120.44 (11)
C6—C5—H5A	109.3 (9)	C9ⁱ—C11—C12	118.84 (11)
C4—C5—H5A	109.0 (9)	C8—C11—C12	120.72 (11)
C6—C5—H5B	110.2 (10)	C11—C12—H12A	113.1 (10)
C4—C5—H5B	111.0 (10)	C11—C12—H12B	113.0 (12)
H5A—C5—H5B	106.5 (13)	H12A—C12—H12B	107.0 (15)
N1—C6—C5	111.19 (11)	C11—C12—H12C	111.5 (11)
N1—C6—H6A	108.6 (9)	H12A—C12—H12C	104.8 (15)
C5—C6—H6A	110.8 (9)	H12B—C12—H12C	106.8 (16)

C6—N1—C2—C3	59.72 (14)	N1—C7—C8—C11	74.54 (14)
C7—N1—C2—C3	−178.35 (10)	N1—C7—C8—C9	−106.87 (13)
N1—C2—C3—C4	−57.54 (15)	C11—C8—C9—C11ⁱ	0.46 (18)
C2—C3—C4—C5	53.97 (16)	C7—C8—C9—C11ⁱ	−178.11 (10)
C3—C4—C5—C6	−54.05 (17)	C11—C8—C9—C10	−178.56 (11)
C2—N1—C6—C5	−59.38 (15)	C7—C8—C9—C10	2.87 (18)
C7—N1—C6—C5	177.78 (12)	C9—C8—C11—C9ⁱ	−0.46 (18)
C4—C5—C6—N1	57.25 (16)	C7—C8—C11—C9ⁱ	178.14 (10)
C6—N1—C7—C8	−170.47 (11)	C9—C8—C11—C12	179.05 (11)
C2—N1—C7—C8	67.37 (14)	C7—C8—C11—C12	−2.34 (17)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···N1	0.94 (2)	2.59 (2)	3.2204 (18)	124.8 (14)

References

Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Cason, C. J. (2004). POV-RAY for Windows. Persistence of Vision, Raytracer Pty. Ltd, Victoria, Australia. https://www.povray.org. Google Scholar
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Kozikowski, A. P., Araldi, G. L., Boja, J., Meil, W. M., Johnson, K. M., Flippen-Anderson, J. L., George, C. & Saiah, E. (1998). J. Med. Chem. 41, 1962–1969. Web of Science CSD CrossRef CAS PubMed Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
McElvain, S. M. & Carney, T. P. (1946). J. Am. Chem. Soc. 68, 2592–2600. CrossRef Web of Science Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.