1,4-Bis(piperidin-1-ylcarbon­yl)benzene

Armbrust, L.; Bilyk, A.; Brown, C.L.; Healy, P.C.

doi:10.1107/S1600536807062423

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o31

https://doi.org/10.1107/S1600536807062423

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1,4-Bis(piperidin-1-ylcarbonyl)benzene

Lee Armbrust,^a,^b Alex Bilyk,^b Christopher L. Brown ^a and Peter C. Healy ^c ^*

^aNanoscale Science and Technology Centre, Griffith University, Nathan, Brisbane 4111, Australia, ^bCSIRO Materials and Science Engineering, 37 Graham Road, Highett, Victoria 3190, Australia, and ^cSchool of Science, Griffith University, Nathan, Brisbane 4111, Australia
^*Correspondence e-mail: p.healy@griffith.edu.au

(Received 14 November 2007; accepted 23 November 2007; online 6 December 2007)

The title compound, C₁₈H₂₀N₂O₂, has been synthesized by the reaction of terephthaloyl chloride and 1,2,3,6-tetrahydropyridine. This compound crystallizes as discrete molecular species disposed about a crystallographic centre of symmetry, such that half the molecule constitutes the asymmetric unit. The structure shows an envelope conformation for the dehydropiperidine ring with the amide carbonyl twisted out of the benzene ring plane by 57.3 (2)°.

Related literature

For background literature, see: Pang et al. (2006 ). For related structures, see: Jones et al. (2002 ).

Experimental

Crystal data

C₁₈H₂₀N₂O₂
M_r = 296.36
Monoclinic, P 2₁ /n
a = 9.1255 (19) Å
b = 10.060 (3) Å
c = 8.6941 (16) Å
β = 106.991 (14)°
V = 763.3 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 (2) K
0.35 × 0.30 × 0.15 mm

Data collection

Rigaku AFC-7R diffractometer
Absorption correction: none
1985 measured reflections
1753 independent reflections
1122 reflections with I > 2σ(I)
R_int = 0.022
3 standard reflections every 150 reflections intensity decay: 0.9%

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.124
S = 1.01
1753 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.16 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
C9—H9⋯O1ⁱ	0.9500	2.5100	3.290 (2)	140.00
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: MSC/AFC7 Diffractometer Control (Molecular Structure Corporation, 1999 $[Molecular Structure Corporation (1999). MSC/AFC7 Diffractometer Control. Version 1.02. MSC, The Woodlands, Texas, USA.]$ ); cell refinement: MSC/AFC7 Diffractometer Control; data reduction: TEXSAN (Molecular Structure Corporation, 2001 ); program(s) used to solve structure: TEXSAN; program(s) used to refine structure: TEXSAN, SHELXL97 (Sheldrick, 1997 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: TEXSAN, PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807062423/sj2448sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807062423/sj2448Isup2.hkl

checkCIF report

Comment top

Derivatives of terephthalic acid are widely used in a range of polymer applications (Pang et al., 2006). As part of our work on the synthesis of these compounds for use in new coating technologies, we have synthesized and determined the solid state structure of the title compound (I). This compound crystallizes as discrete molecular species (Fig. 1) disposed about a crystallographic centre of symmetry such that half the molecule consitutes the asymmetric unit of the crystal lattice. The bond lengths and bond angles in (I) are in accord with values for similar structures reported in the literature (Jones et al., 2002). The tertiary nitrogen lies in the C1—C3—C7 plane with the sum of the C—N—C angles 359.3°. The amide plane is twisted out of the plane of the central phenyl ring as reflected in the O1—C1—C8—C10 torsion angle of -57.6 (2)°. C7 approaches coplanarity with amide plane with C7—N1—C1—O1 - 4.3 (2)°. C3 bends out of this plane with C3—N1—C1—C8 = -16.4 (2)° to give an envelope conformation to the dehydropiperidine ring. A weak intermolecular C—H···O interaction is observed between C9—H9 and the carbonyl oxygen (Table 1).

Related literature top

For background literature, see: Pang et al. (2006). For related structures, see: Jones et al. (2002).

Experimental top

1,2,3,6-tetrahydropyridine (494.4 ml, 5.418 mm0l) was added to a solution of terephthaloyl chloride (500 mg, 2.46 mmol) in toluene (50 ml) under an N₂ atmosphere with stirring. The reaction mixture was stirred and heated under reflux for 24 hr. On cooling to room temperature the mixture was washed with aqueous acid (2M HCl) and then aqueous base (2M NaOH) followed by two water washes with the organic layer collected and dried (MgSO₄). Removal of the solvent under vacuum resulted in isolation of a solid white product. Recrystallization from ethanol resulted in the formation of small white crystals (Yield 601 mg, 82.4%).

Structure description top

For background literature, see: Pang et al. (2006). For related structures, see: Jones et al. (2002).

Computing details top

Data collection: MSC/AFC7 Diffractometer Control (Molecular Structure Corporation, 1999); cell refinement: MSC/AFC7 Diffractometer Control; data reduction: TEXSAN (Molecular Structure Corporation, 2001); program(s) used to solve structure: TEXSAN; program(s) used to refine structure: TEXSAN; SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: TEXSAN; PLATON (Spek, 2003).

Figures top

Fig. 1. View of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level. Primed atoms were generated by symmetry (-x, -y, 1 - z).

1,4-Bis(piperidin-1-ylcarbonyl)benzene top

Crystal data top

C₁₈H₂₀N₂O₂	F(000) = 316
M_r = 296.36	D_x = 1.289 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 9.1255 (19) Å	θ = 12.6–16.9°
b = 10.060 (3) Å	µ = 0.09 mm⁻¹
c = 8.6941 (16) Å	T = 295 K
β = 106.991 (14)°	Plate, colourless
V = 763.3 (3) Å³	0.35 × 0.30 × 0.15 mm
Z = 2

Data collection top

Rigaku AFC7R diffractometer	R_int = 0.022
Radiation source: Rigaku rotating anode	θ_max = 27.5°, θ_min = 2.9°
Graphite monochromator	h = −5→11
ω–2θ scans	k = 0→13
1985 measured reflections	l = −11→10
1753 independent reflections	3 standard reflections every 150 reflections
1122 reflections with I > 2σ(I)	intensity decay: 0.9%

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0519P)² + 0.1363P] where P = (F_o² + 2F_c²)/3
1753 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₈H₂₀N₂O₂	V = 763.3 (3) Å³
M_r = 296.36	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.1255 (19) Å	µ = 0.09 mm⁻¹
b = 10.060 (3) Å	T = 295 K
c = 8.6941 (16) Å	0.35 × 0.30 × 0.15 mm
β = 106.991 (14)°

Data collection top

Rigaku AFC7R diffractometer	R_int = 0.022
1985 measured reflections	3 standard reflections every 150 reflections
1753 independent reflections	intensity decay: 0.9%
1122 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.124	H-atom parameters constrained
S = 1.01	Δρ_max = 0.16 e Å⁻³
1753 reflections	Δρ_min = −0.22 e Å⁻³
100 parameters

Special details top

Experimental. The scan width was (1.63 + 0.30tanθ)° with an ω scan speed of 16° per minute (up to 4 scans to achieve I/σ(I) > 10). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1.

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 > 2σ(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	0.34253 (15)	0.20263 (14)	0.59031 (15)	0.0576 (5)
N1	0.33853 (15)	0.09638 (14)	0.36082 (16)	0.0378 (4)
C1	0.28168 (18)	0.12259 (16)	0.48421 (18)	0.0360 (5)
C3	0.2956 (2)	−0.01623 (17)	0.2505 (2)	0.0417 (5)
C4	0.2517 (3)	0.0308 (2)	0.0776 (2)	0.0584 (7)
C5	0.3692 (3)	0.1256 (2)	0.0550 (2)	0.0660 (8)
C6	0.4691 (3)	0.1846 (2)	0.1752 (3)	0.0575 (7)
C7	0.4706 (2)	0.17209 (18)	0.3463 (2)	0.0448 (6)
C8	0.13664 (17)	0.05471 (15)	0.48833 (17)	0.0327 (4)
C9	0.00064 (18)	0.07421 (17)	0.36538 (17)	0.0369 (5)
C10	−0.13454 (17)	0.01931 (17)	0.37753 (17)	0.0364 (4)
H3A	0.38000	−0.07560	0.26880	0.0500*
H3B	0.21100	−0.06100	0.26960	0.0500*
H4A	0.24540	−0.04340	0.00850	0.0700*
H4B	0.15500	0.07400	0.05230	0.0700*
H5	0.37180	0.14410	−0.05130	0.0790*
H6	0.54520	0.23860	0.15170	0.0690*
H7A	0.46810	0.25840	0.38980	0.0540*
H7B	0.56190	0.12800	0.40490	0.0540*
H9	0.00080	0.12510	0.27340	0.0440*
H10	−0.22810	0.03330	0.29200	0.0420*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0557 (8)	0.0690 (9)	0.0491 (7)	−0.0176 (7)	0.0168 (6)	−0.0240 (7)
N1	0.0370 (7)	0.0413 (8)	0.0384 (7)	−0.0063 (6)	0.0161 (6)	−0.0035 (6)
C1	0.0360 (8)	0.0389 (9)	0.0324 (8)	0.0014 (7)	0.0089 (6)	−0.0019 (7)
C3	0.0473 (10)	0.0410 (9)	0.0425 (9)	−0.0050 (8)	0.0219 (8)	−0.0055 (8)
C4	0.0721 (14)	0.0630 (13)	0.0404 (10)	−0.0048 (11)	0.0168 (9)	−0.0049 (9)
C5	0.0999 (18)	0.0626 (13)	0.0434 (11)	−0.0070 (13)	0.0331 (11)	0.0084 (10)
C6	0.0686 (14)	0.0517 (11)	0.0640 (12)	−0.0070 (10)	0.0378 (11)	0.0114 (10)
C7	0.0379 (9)	0.0466 (10)	0.0517 (10)	−0.0053 (7)	0.0159 (8)	0.0057 (8)
C8	0.0322 (8)	0.0387 (8)	0.0284 (7)	0.0041 (6)	0.0109 (6)	−0.0027 (6)
C9	0.0394 (9)	0.0463 (9)	0.0258 (7)	0.0052 (7)	0.0109 (6)	0.0039 (7)
C10	0.0314 (7)	0.0481 (9)	0.0288 (7)	0.0059 (7)	0.0072 (6)	0.0007 (7)

Geometric parameters (Å, º) top

O1—C1	1.228 (2)	C9—C10	1.384 (2)
N1—C1	1.347 (2)	C3—H3A	0.9500
N1—C3	1.462 (2)	C3—H3B	0.9500
N1—C7	1.462 (2)	C4—H4A	0.9500
C1—C8	1.499 (2)	C4—H4B	0.9500
C3—C4	1.514 (2)	C5—H5	0.9500
C4—C5	1.490 (4)	C6—H6	0.9500
C5—C6	1.311 (3)	C7—H7A	0.9500
C6—C7	1.489 (3)	C7—H7B	0.9500
C8—C9	1.395 (2)	C9—H9	0.9500
C8—C10ⁱ	1.389 (2)	C10—H10	0.9600

O1···C9ⁱⁱ	3.290 (2)	H3B···C8	2.4900
O1···H7A	2.4200	H3B···C9	2.6800
O1···H3Aⁱⁱⁱ	2.7800	H3B···H7A^ix	2.5600
O1···H10ⁱ	2.9000	H4A···O1^ix	2.7400
O1···H4A^iv	2.7400	H4A···H10^x	2.5700
O1···H9ⁱⁱ	2.5100	H4B···H7A^v	2.5200
C3···C9	3.262 (3)	H6···C10^iv	2.9700
C9···C3	3.262 (3)	H6···C8^xi	2.7800
C9···O1^v	3.290 (2)	H6···C9^xi	3.0500
C1···H7Bⁱⁱⁱ	2.9200	H7A···O1	2.4200
C6···H3A	2.9300	H7A···H3B^iv	2.5600
C6···H10^vi	3.0600	H7A···H4Bⁱⁱ	2.5200
C8···H3B	2.4900	H7B···C10^vi	3.0500
C8···H6^vii	2.7800	H7B···H10^vi	2.5800
C9···H3B	2.6800	H7B···C1ⁱⁱⁱ	2.9200
C9···H6^vii	3.0500	H9···O1^v	2.5100
C10···H7B^viii	3.0500	H10···C6^viii	3.0600
C10···H6^ix	2.9700	H10···H7B^viii	2.5800
H3A···C6	2.9300	H10···O1ⁱ	2.9000
H3A···O1ⁱⁱⁱ	2.7800	H10···H4A^x	2.5700

C1—N1—C3	125.62 (14)	H3A—C3—H3B	109.00
C1—N1—C7	119.07 (14)	C3—C4—H4A	109.00
C3—N1—C7	114.63 (14)	C3—C4—H4B	109.00
O1—C1—N1	122.12 (16)	C5—C4—H4A	109.00
O1—C1—C8	119.30 (15)	C5—C4—H4B	109.00
N1—C1—C8	118.56 (14)	H4A—C4—H4B	109.00
N1—C3—C4	110.59 (14)	C4—C5—H5	119.00
C3—C4—C5	109.82 (17)	C6—C5—H5	119.00
C4—C5—C6	122.97 (19)	C5—C6—H6	118.00
C5—C6—C7	124.0 (2)	C7—C6—H6	118.00
N1—C7—C6	111.29 (16)	N1—C7—H7A	109.00
C1—C8—C9	120.77 (14)	N1—C7—H7B	109.00
C1—C8—C10ⁱ	119.56 (14)	C6—C7—H7A	109.00
C9—C8—C10ⁱ	119.44 (15)	C6—C7—H7B	109.00
C8—C9—C10	119.92 (14)	H7A—C7—H7B	109.00
C8ⁱ—C10—C9	120.64 (14)	C8—C9—H9	120.00
N1—C3—H3A	109.00	C10—C9—H9	120.00
N1—C3—H3B	109.00	C9—C10—H10	119.00
C4—C3—H3A	109.00	C8ⁱ—C10—H10	120.00
C4—C3—H3B	109.00

C3—N1—C1—O1	165.61 (16)	N1—C1—C8—C10ⁱ	124.35 (17)
C3—N1—C1—C8	−16.4 (2)	N1—C3—C4—C5	47.6 (2)
C7—N1—C1—O1	−4.3 (2)	C3—C4—C5—C6	−16.9 (3)
C7—N1—C1—C8	173.66 (14)	C4—C5—C6—C7	−4.6 (4)
C1—N1—C3—C4	128.43 (19)	C5—C6—C7—N1	−5.4 (3)
C7—N1—C3—C4	−61.2 (2)	C1—C8—C9—C10	−174.84 (15)
C1—N1—C7—C6	−150.58 (16)	C10ⁱ—C8—C9—C10	−0.4 (2)
C3—N1—C7—C6	38.4 (2)	C1—C8—C10ⁱ—C9ⁱ	174.91 (15)
O1—C1—C8—C9	116.88 (18)	C9—C8—C10ⁱ—C9ⁱ	0.4 (2)
O1—C1—C8—C10ⁱ	−57.6 (2)	C8—C9—C10—C8ⁱ	0.4 (2)
N1—C1—C8—C9	−61.2 (2)

Symmetry codes: (i) −x, −y, −z+1; (ii) x+1/2, −y+1/2, z+1/2; (iii) −x+1, −y, −z+1; (iv) −x+1/2, y+1/2, −z+1/2; (v) x−1/2, −y+1/2, z−1/2; (vi) x+1, y, z; (vii) x−1/2, −y+1/2, z+1/2; (viii) x−1, y, z; (ix) −x+1/2, y−1/2, −z+1/2; (x) −x, −y, −z; (xi) x+1/2, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1^v	0.9500	2.5100	3.290 (2)	140.00

Symmetry code: (v) x−1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₈H₂₀N₂O₂
M_r	296.36
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	9.1255 (19), 10.060 (3), 8.6941 (16)
β (°)	106.991 (14)
V (Å³)	763.3 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.35 × 0.30 × 0.15

Data collection
Diffractometer	Rigaku AFC7R
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	1985, 1753, 1122
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.124, 1.01
No. of reflections	1753
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.22

Computer programs: MSC/AFC7 Diffractometer Control (Molecular Structure Corporation, 1999), MSC/AFC7 Diffractometer Control, TEXSAN (Molecular Structure Corporation, 2001), TEXSAN; SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), TEXSAN; PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1ⁱ	0.9500	2.5100	3.290 (2)	140.00

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.

Acknowledgements

The authors acknowledge financial support of this work by the Nanoscale Science and Technology Centre, CSIRO Materials Science and Engineering Division, and Griffith University. The award of a PhD scholarship (to LA) from the CRC for Wood Innovation is gratefully acknowledged.

References

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