(S)-Perillaldehyde azine

Han, L.-L.; Shi, J.-H.; Yan, D.-P.; Ng, S.W.

doi:10.1107/S1600536810004071

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o561

doi:10.1107/S1600536810004071

Open

access

(S)-Perillaldehyde azine

Li-Lu Han,^a Jiang-Hua Shi,^b De-Peng Yan ^b and Seik Weng Ng ^c ^*

^aHunan Yongzhou Vocational College, Yongzhou, Hunan 425100, People's Republic of China, ^bDepartment of Biology and Chemistry, Hunan University of Science and Engineering, Yongzhou, Hunan 425100, People's Republic of China, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 26 January 2010; accepted 2 February 2010; online 6 February 2010)

The C=N–N=C linkage [torsion angle −172.5 (2)°] in the title azine, C₂₀H₂₈N₂, adopts a trans conformation. The six-membered rings adopt sofa conformations.

Related literature

A previous study reported the oxime derivative of S-perillaldehyde; see Yuan et al. (2009 ). Only few crystal structures of azines have been reported, see: Berthou et al. (1970 ); Kim & Lee (2008 ); Marek et al. (1997 ); Rizal et al. (2008 ); Sanz et al. (1999 ).

Experimental

Crystal data

C₂₀H₂₈N₂
M_r = 296.44
Monoclinic, P 2₁
a = 8.8200 (5) Å
b = 9.7603 (6) Å
c = 10.1710 (6) Å
β = 94.970 (1)°
V = 872.29 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 173 K
0.48 × 0.46 × 0.21 mm

Data collection

Bruker SMART APEX diffractometer
7179 measured reflections
2013 independent reflections
1802 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.141
S = 1.12
2013 reflections
201 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: SMART (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810004071/bt5184sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810004071/bt5184Isup2.hkl

checkCIF report

Related literature top

A previous study reported the oxime derivative of S-perillaldehyde; see Yuan et al. (2009). Only few crystal structures of azines have been reported, see: Berthou et al. (1970); Kim & Lee (2008); Marek et al. (1997); Rizal et al. (2008); Sanz et al. (1999).

Experimental top

An ethanol solution (10 ml) of hydrazinium hydroxide (0.5 g, 0.01 mol) was added to a 50% ethanol solution (50 ml) of perillaldehyde (3 g, 0.02 mol); acetic acid (2 ml) was then added. The mixture was heated for two hours. The product was recrystallized from ethyl acetate to afford light-yellow crystals (yield 70%).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C₂₀H₂₈N₂ at the 70% probability level; hydrogen atoms are shown as spheres of arbitrary radius.

(S)-Perillaldehyde azine top

Crystal data top

C₂₀H₂₈N₂	F(000) = 324
M_r = 296.44	D_x = 1.129 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 4048 reflections
a = 8.8200 (5) Å	θ = 2.3–27.2°
b = 9.7603 (6) Å	µ = 0.07 mm⁻¹
c = 10.1710 (6) Å	T = 173 K
β = 94.970 (1)°	Block, yellow
V = 872.29 (9) Å³	0.48 × 0.46 × 0.21 mm
Z = 2

Data collection top

Bruker SMART APEX diffractometer	1802 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.035
Graphite monochromator	θ_max = 27.2°, θ_min = 2.0°
ω scans	h = −11→11
7179 measured reflections	k = −12→12
2013 independent reflections	l = −12→12

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.074P)² + 0.242P] where P = (F_o² + 2F_c²)/3
2013 reflections	(Δ/σ)_max = 0.001
201 parameters	Δρ_max = 0.22 e Å⁻³
1 restraint	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₂₀H₂₈N₂	V = 872.29 (9) Å³
M_r = 296.44	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 8.8200 (5) Å	µ = 0.07 mm⁻¹
b = 9.7603 (6) Å	T = 173 K
c = 10.1710 (6) Å	0.48 × 0.46 × 0.21 mm
β = 94.970 (1)°

Data collection top

Bruker SMART APEX diffractometer	1802 reflections with I > 2σ(I)
7179 measured reflections	R_int = 0.035
2013 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	1 restraint
wR(F²) = 0.141	H-atom parameters constrained
S = 1.12	Δρ_max = 0.22 e Å⁻³
2013 reflections	Δρ_min = −0.23 e Å⁻³
201 parameters

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

	x	y	z	U_iso*/U_eq
N1	1.1573 (3)	0.4999 (3)	0.9681 (2)	0.0344 (5)
N2	1.2864 (3)	0.5570 (3)	1.0416 (2)	0.0340 (5)
C1	0.3418 (3)	0.5570 (4)	0.6676 (3)	0.0432 (7)
H1A	0.2556	0.5311	0.6053	0.065*
H1B	0.3581	0.6561	0.6631	0.065*
H1C	0.3200	0.5317	0.7573	0.065*
C2	0.4821 (3)	0.4836 (3)	0.6326 (3)	0.0335 (6)
C3	0.4827 (4)	0.4131 (4)	0.5213 (3)	0.0451 (8)
H3A	0.3933	0.4085	0.4623	0.054*
H3B	0.5725	0.3672	0.5006	0.054*
C4	0.6201 (3)	0.4954 (3)	0.7323 (3)	0.0303 (6)
H4	0.5881	0.4606	0.8182	0.036*
C5	0.6657 (4)	0.6461 (3)	0.7542 (3)	0.0403 (7)
H5A	0.6717	0.6907	0.6674	0.048*
H5B	0.5856	0.6933	0.7995	0.048*
C6	0.8147 (3)	0.6631 (3)	0.8341 (3)	0.0369 (6)
H6	0.8407	0.7518	0.8673	0.044*
C7	0.9134 (3)	0.5613 (3)	0.8618 (3)	0.0302 (6)
C8	0.8822 (3)	0.4179 (3)	0.8139 (3)	0.0373 (7)
H8A	0.8524	0.3612	0.8882	0.045*
H8B	0.9767	0.3785	0.7837	0.045*
C9	0.7568 (3)	0.4114 (3)	0.7014 (3)	0.0356 (6)
H9A	0.7962	0.4465	0.6196	0.043*
H9B	0.7255	0.3149	0.6860	0.043*
C10	1.0558 (3)	0.5917 (3)	0.9402 (3)	0.0325 (6)
H10	1.0739	0.6824	0.9716	0.039*
C11	1.3954 (3)	0.4699 (3)	1.0567 (3)	0.0321 (6)
H11	1.3816	0.3810	1.0195	0.038*
C12	1.5398 (3)	0.5041 (3)	1.1296 (3)	0.0302 (6)
C13	1.6523 (3)	0.4117 (3)	1.1373 (3)	0.0340 (6)
H13	1.6335	0.3259	1.0948	0.041*
C14	1.8062 (3)	0.4349 (3)	1.2089 (3)	0.0349 (6)
H14A	1.8814	0.4500	1.1436	0.042*
H14B	1.8370	0.3517	1.2603	0.042*
C15	1.8082 (3)	0.5578 (3)	1.3023 (3)	0.0318 (6)
H15	1.7472	0.5319	1.3769	0.038*
C16	1.7255 (3)	0.6772 (3)	1.2292 (3)	0.0370 (7)
H16A	1.7332	0.7600	1.2855	0.044*
H16B	1.7748	0.6974	1.1475	0.044*
C17	1.5580 (3)	0.6425 (3)	1.1939 (3)	0.0384 (7)
H17A	1.5035	0.6437	1.2750	0.046*
H17B	1.5116	0.7131	1.1331	0.046*
C18	1.9656 (3)	0.5985 (3)	1.3620 (3)	0.0342 (6)
C19	1.9691 (4)	0.7035 (4)	1.4708 (3)	0.0460 (8)
H19A	2.0750	0.7240	1.5018	0.069*
H19B	1.9160	0.6674	1.5442	0.069*
H19C	1.9186	0.7875	1.4373	0.069*
C20	2.0927 (3)	0.5473 (4)	1.3233 (3)	0.0407 (7)
H20A	2.1881	0.5766	1.3641	0.049*
H20B	2.0888	0.4812	1.2546	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0284 (11)	0.0386 (13)	0.0355 (12)	−0.0022 (11)	−0.0012 (9)	−0.0030 (11)
N2	0.0286 (12)	0.0386 (13)	0.0342 (11)	−0.0017 (11)	−0.0011 (9)	−0.0028 (11)
C1	0.0339 (15)	0.0515 (18)	0.0434 (15)	0.0057 (15)	−0.0007 (12)	−0.0029 (15)
C2	0.0291 (13)	0.0356 (15)	0.0352 (13)	−0.0007 (13)	−0.0007 (11)	0.0034 (12)
C3	0.0401 (16)	0.052 (2)	0.0420 (17)	0.0017 (16)	−0.0050 (13)	−0.0098 (16)
C4	0.0303 (13)	0.0304 (13)	0.0297 (12)	0.0008 (12)	−0.0003 (10)	−0.0007 (11)
C5	0.0366 (16)	0.0284 (14)	0.0547 (17)	0.0077 (13)	−0.0036 (13)	−0.0055 (14)
C6	0.0350 (15)	0.0281 (14)	0.0466 (15)	−0.0013 (12)	−0.0019 (12)	−0.0054 (13)
C7	0.0287 (13)	0.0328 (14)	0.0289 (12)	−0.0008 (12)	0.0010 (10)	−0.0031 (11)
C8	0.0349 (15)	0.0314 (15)	0.0438 (15)	0.0055 (13)	−0.0064 (12)	−0.0025 (14)
C9	0.0356 (14)	0.0275 (14)	0.0426 (15)	0.0031 (12)	−0.0031 (12)	−0.0060 (13)
C10	0.0316 (14)	0.0328 (15)	0.0334 (13)	−0.0029 (12)	0.0038 (11)	−0.0045 (11)
C11	0.0336 (14)	0.0330 (16)	0.0296 (13)	−0.0038 (12)	0.0029 (10)	0.0011 (11)
C12	0.0299 (13)	0.0320 (14)	0.0288 (12)	−0.0032 (12)	0.0037 (10)	0.0027 (11)
C13	0.0343 (14)	0.0320 (14)	0.0349 (13)	−0.0020 (13)	−0.0015 (11)	0.0011 (12)
C14	0.0309 (14)	0.0318 (15)	0.0411 (15)	0.0020 (12)	−0.0027 (11)	0.0006 (12)
C15	0.0290 (13)	0.0362 (15)	0.0302 (12)	−0.0040 (12)	0.0027 (10)	0.0031 (12)
C16	0.0342 (15)	0.0318 (15)	0.0434 (15)	−0.0035 (12)	−0.0054 (12)	−0.0012 (12)
C17	0.0335 (15)	0.0349 (16)	0.0451 (16)	0.0027 (13)	−0.0061 (12)	−0.0021 (14)
C18	0.0351 (15)	0.0372 (16)	0.0296 (13)	−0.0048 (12)	−0.0011 (11)	0.0054 (11)
C19	0.0404 (17)	0.059 (2)	0.0382 (16)	−0.0084 (16)	0.0010 (12)	−0.0103 (15)
C20	0.0319 (15)	0.0471 (18)	0.0416 (15)	−0.0016 (14)	−0.0048 (12)	0.0004 (15)

Geometric parameters (Å, º) top

N1—C10	1.280 (4)	C10—H10	0.9500
N1—N2	1.421 (3)	C11—C12	1.456 (4)
N2—C11	1.282 (4)	C11—H11	0.9500
C1—C2	1.499 (4)	C12—C13	1.338 (4)
C1—H1A	0.9800	C12—C17	1.503 (4)
C1—H1B	0.9800	C13—C14	1.501 (4)
C1—H1C	0.9800	C13—H13	0.9500
C2—C3	1.325 (4)	C14—C15	1.529 (4)
C2—C4	1.519 (4)	C14—H14A	0.9900
C3—H3A	0.9500	C14—H14B	0.9900
C3—H3B	0.9500	C15—C18	1.519 (4)
C4—C9	1.513 (4)	C15—C16	1.533 (4)
C4—C5	1.537 (4)	C15—H15	1.0000
C4—H4	1.0000	C16—C17	1.528 (4)
C5—C6	1.493 (4)	C16—H16A	0.9900
C5—H5A	0.9900	C16—H16B	0.9900
C5—H5B	0.9900	C17—H17A	0.9900
C6—C7	1.335 (4)	C17—H17B	0.9900
C6—H6	0.9500	C18—C20	1.318 (4)
C7—C10	1.459 (4)	C18—C19	1.507 (4)
C7—C8	1.500 (4)	C19—H19A	0.9800
C8—C9	1.523 (4)	C19—H19B	0.9800
C8—H8A	0.9900	C19—H19C	0.9800
C8—H8B	0.9900	C20—H20A	0.9500
C9—H9A	0.9900	C20—H20B	0.9500
C9—H9B	0.9900

C10—N1—N2	110.8 (3)	C7—C10—H10	119.0
C11—N2—N1	111.2 (2)	N2—C11—C12	121.5 (3)
C2—C1—H1A	109.5	N2—C11—H11	119.3
C2—C1—H1B	109.5	C12—C11—H11	119.3
H1A—C1—H1B	109.5	C13—C12—C11	119.1 (3)
C2—C1—H1C	109.5	C13—C12—C17	122.0 (3)
H1A—C1—H1C	109.5	C11—C12—C17	118.9 (3)
H1B—C1—H1C	109.5	C12—C13—C14	124.2 (3)
C3—C2—C1	121.0 (3)	C12—C13—H13	117.9
C3—C2—C4	123.2 (3)	C14—C13—H13	117.9
C1—C2—C4	115.8 (3)	C13—C14—C15	112.4 (2)
C2—C3—H3A	120.0	C13—C14—H14A	109.1
C2—C3—H3B	120.0	C15—C14—H14A	109.1
H3A—C3—H3B	120.0	C13—C14—H14B	109.1
C9—C4—C2	115.3 (2)	C15—C14—H14B	109.1
C9—C4—C5	110.2 (2)	H14A—C14—H14B	107.9
C2—C4—C5	110.7 (2)	C18—C15—C14	114.5 (2)
C9—C4—H4	106.7	C18—C15—C16	112.0 (2)
C2—C4—H4	106.7	C14—C15—C16	108.4 (2)
C5—C4—H4	106.7	C18—C15—H15	107.2
C6—C5—C4	113.1 (2)	C14—C15—H15	107.2
C6—C5—H5A	108.9	C16—C15—H15	107.2
C4—C5—H5A	108.9	C17—C16—C15	110.8 (2)
C6—C5—H5B	108.9	C17—C16—H16A	109.5
C4—C5—H5B	108.9	C15—C16—H16A	109.5
H5A—C5—H5B	107.8	C17—C16—H16B	109.5
C7—C6—C5	124.0 (3)	C15—C16—H16B	109.5
C7—C6—H6	118.0	H16A—C16—H16B	108.1
C5—C6—H6	118.0	C12—C17—C16	111.4 (3)
C6—C7—C10	118.6 (3)	C12—C17—H17A	109.3
C6—C7—C8	121.9 (2)	C16—C17—H17A	109.3
C10—C7—C8	119.5 (3)	C12—C17—H17B	109.3
C7—C8—C9	112.5 (2)	C16—C17—H17B	109.3
C7—C8—H8A	109.1	H17A—C17—H17B	108.0
C9—C8—H8A	109.1	C20—C18—C19	120.9 (3)
C7—C8—H8B	109.1	C20—C18—C15	123.6 (3)
C9—C8—H8B	109.1	C19—C18—C15	115.6 (3)
H8A—C8—H8B	107.8	C18—C19—H19A	109.5
C4—C9—C8	111.2 (2)	C18—C19—H19B	109.5
C4—C9—H9A	109.4	H19A—C19—H19B	109.5
C8—C9—H9A	109.4	C18—C19—H19C	109.5
C4—C9—H9B	109.4	H19A—C19—H19C	109.5
C8—C9—H9B	109.4	H19B—C19—H19C	109.5
H9A—C9—H9B	108.0	C18—C20—H20A	120.0
N1—C10—C7	122.1 (3)	C18—C20—H20B	120.0
N1—C10—H10	119.0	H20A—C20—H20B	120.0

C10—N1—N2—C11	−172.5 (2)	N1—N2—C11—C12	−179.6 (2)
C3—C2—C4—C9	−4.6 (4)	N2—C11—C12—C13	−176.9 (3)
C1—C2—C4—C9	175.2 (3)	N2—C11—C12—C17	3.0 (4)
C3—C2—C4—C5	121.3 (4)	C11—C12—C13—C14	179.7 (2)
C1—C2—C4—C5	−58.9 (4)	C17—C12—C13—C14	−0.2 (4)
C9—C4—C5—C6	−42.0 (3)	C12—C13—C14—C15	15.4 (4)
C2—C4—C5—C6	−170.7 (2)	C13—C14—C15—C18	−171.5 (2)
C4—C5—C6—C7	12.8 (4)	C13—C14—C15—C16	−45.7 (3)
C5—C6—C7—C10	179.6 (3)	C18—C15—C16—C17	−168.8 (2)
C5—C6—C7—C8	−0.1 (5)	C14—C15—C16—C17	63.9 (3)
C6—C7—C8—C9	17.4 (4)	C13—C12—C17—C16	16.9 (4)
C10—C7—C8—C9	−162.3 (2)	C11—C12—C17—C16	−163.0 (2)
C2—C4—C9—C8	−173.8 (3)	C15—C16—C17—C12	−48.7 (3)
C5—C4—C9—C8	60.0 (3)	C14—C15—C18—C20	9.7 (4)
C7—C8—C9—C4	−47.3 (4)	C16—C15—C18—C20	−114.2 (3)
N2—N1—C10—C7	178.1 (2)	C14—C15—C18—C19	−170.4 (3)
C6—C7—C10—N1	−178.4 (3)	C16—C15—C18—C19	65.7 (3)
C8—C7—C10—N1	1.2 (4)

Experimental details

Crystal data
Chemical formula	C₂₀H₂₈N₂
M_r	296.44
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	173
a, b, c (Å)	8.8200 (5), 9.7603 (6), 10.1710 (6)
β (°)	94.970 (1)
V (Å³)	872.29 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.48 × 0.46 × 0.21

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7179, 2013, 1802
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.642

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.141, 1.12
No. of reflections	2013
No. of parameters	201
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.23

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

We thank the Key Subject Construction Project of Hunan Province (No. 2006–180), the Key Scientific Research Project of Hunan Provincial Education Department (No. 08 A023, 05 C736), the NSF of Hunan Province (09 J J3028) and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Berthou, J., Marzin, C., Rérat, B., Rérat, C. & Uesu, Y. (1970). C. R. Acad. Sci. Ser. C, pp. 918–921. Google Scholar
Bruker (2003). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kim, S. H. & Lee, S. W. (2008). Inorg. Chim. Acta, 361, 137–144. Web of Science CSD CrossRef CAS Google Scholar
Marek, R., St'astná-Sedláčková, I., Toušek, J., Marek, J. & Potacek, M. (1997). Bull. Soc. Chim. Belg. 106, 645–649. CAS Google Scholar
Rizal, M. R., Ali, H. M. & Ng, S. W. (2008). Acta Cryst. E64, o555. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sanz, D., Ponce, M. J., Claramunt, R. M., Fernández-Castaño, C., Foces-Foces, C. & Elguero, J. (1999). J. Phys. Org. Chem. 12, 455–469. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). publCIF. In preparation. Google Scholar
Yuan, X.-Y., Zhang, M. & Ng, S. W. (2009). Acta Cryst. E65, o2149. Web of Science CSD CrossRef IUCr Journals Google Scholar