Perillartine.

THE CHIRAL TITLE COMPOUND [SYSTEMATIC NAME: 4-(1-methyl-vinyl)cyclo-hexene-1-carbaldehyde oxime], C(10)H(15)NO, crystallizes with two mol-ecules in the asymmetric unit, one of which shows disorder of its propenyl substituent over two sets of sites in a 50:50 ratio. In both mol-ecules, the six-membered carbaldehyde oxime ring adopts an approximate envelope conformation in which the C atom bearing the propenyl substituent represents the flap position. In both mol-ecules, the plane passing through the propenyl substituent is nearly perpendicular to the mean plane of the six-membered ring [dihedral angles = 84.6 (6) and 87.4 (3)°]. In the crystal, the two independent mol-ecules are linked by a pair O-H⋯N hydrogen bonds across a pseudo-inversion centre, generating a dimer. The unit cell of the known racemate of the title compound is similar to the cell found here, but with space group P.

Related literature

Perillartine or perillartin [(S)-4-(prop-1-en-2-yl)cyclo­hex-1-ene carbaldehyde oxime], the oxime of perillaldehyde, is 2000 times sweeter than sucrose; see the handbook of artificial sweeteners by O’Brien Nabors & Gelardi (2001 ▶). For the crystal structure of the racemic compound, see: Hooft et al. (1990 ▶).

Experimental

Crystal data

C10H15NO

M = 165.23

Triclinic,

a = 7.2679 (6) Å

b = 8.1702 (7) Å

c = 8.9426 (8) Å

α = 105.150 (1)°

β = 95.658 (1)°

γ = 104.602 (1)°

V = 488.25 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.07 mm−1

T = 293 K

0.48 × 0.42 × 0.22 mm

Data collection

Bruker SMART diffractometer

Absorption correction: none

4074 measured reflections

2078 independent reflections

1457 reflections with I > 2σ(I)

R int = 0.010

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.139

S = 1.07

2078 reflections

234 parameters

21 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.15 e Å−3

Δρmin = −0.12 e Å−3

Data collection: SMART (Bruker, 1997 ▶); 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, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809031225/hb5034sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809031225/hb5034Isup2.hkl

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

C10H15NO	Z = 2
Mr = 165.23	F(000) = 180
Triclinic, P1	Dx = 1.124 Mg m−3
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2679 (6) Å	Cell parameters from 1889 reflections
b = 8.1702 (7) Å	θ = 2.4–26.9°
c = 8.9426 (8) Å	µ = 0.07 mm−1
α = 105.150 (1)°	T = 293 K
β = 95.658 (1)°	Block, colorless
γ = 104.602 (1)°	0.48 × 0.42 × 0.22 mm
V = 488.25 (7) Å3

Bruker SMART diffractometer	1457 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.014
graphite	θmax = 27.1°, θmin = 2.4°
φ and ω scans	h = −9→9
4074 measured reflections	k = −10→10
2078 independent reflections	l = −11→11

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0793P)2 + 0.0172P] where P = (Fo2 + 2Fc2)/3
2078 reflections	(Δ/σ)max < 0.001
234 parameters	Δρmax = 0.15 e Å−3
21 restraints	Δρmin = −0.12 e Å−3

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.5000 (4)	0.5002 (4)	0.5001 (3)	0.0885 (8)
O2	0.7482 (4)	0.9157 (4)	0.6717 (4)	0.0922 (8)
N1	0.4289 (4)	0.6405 (4)	0.4831 (3)	0.0724 (8)
N2	0.8170 (4)	0.7770 (4)	0.6971 (3)	0.0727 (7)
C1	0.2564 (5)	0.5857 (4)	0.4097 (4)	0.0699 (8)
H1A	0.1932	0.4649	0.3775	0.084*
C2	0.1551 (5)	0.7069 (4)	0.3745 (4)	0.0657 (8)
C3	−0.0246 (5)	0.6464 (4)	0.2976 (4)	0.0758 (9)
H3	−0.0836	0.5251	0.2706	0.091*
C4	−0.1401 (5)	0.7574 (4)	0.2510 (4)	0.0776 (9)
H4A	−0.2386	0.7643	0.3161	0.093*
H4B	−0.2048	0.7010	0.1425	0.093*
C5	−0.0167 (5)	0.9448 (4)	0.2672 (4)	0.0760 (9)
H5	0.0572	0.9363	0.1809	0.091*
C6	0.1263 (6)	1.0142 (4)	0.4182 (6)	0.0973 (13)
H6A	0.0572	1.0176	0.5058	0.117*
H6B	0.2013	1.1345	0.4291	0.117*
C7	0.2618 (6)	0.9016 (5)	0.4248 (5)	0.0905 (12)
H7A	0.3552	0.9237	0.3567	0.109*
H7B	0.3320	0.9354	0.5314	0.109*
C8	−0.1413 (5)	1.0638 (4)	0.2484 (4)	0.0784 (10)	0.50
C9	−0.2394 (18)	1.127 (2)	0.3557 (11)	0.088 (3)	0.50
H9A	−0.3134	1.1999	0.3366	0.105*	0.50
H9B	−0.2342	1.0994	0.4501	0.105*	0.50
C10	−0.1478 (19)	1.1072 (18)	0.0954 (12)	0.093 (3)	0.50
H10A	−0.2124	1.0017	0.0107	0.139*	0.50
H10B	−0.0186	1.1541	0.0797	0.139*	0.50
H10C	−0.2167	1.1936	0.0979	0.139*	0.50
C8'	−0.1413 (5)	1.0638 (4)	0.2484 (4)	0.0784 (10)	0.50
C9'	−0.1960 (17)	1.0794 (19)	0.1074 (12)	0.088 (3)	0.50
H9'A	−0.2772	1.1487	0.0964	0.105*	0.50
H9'B	−0.1529	1.0210	0.0200	0.105*	0.50
C10'	−0.208 (2)	1.157 (2)	0.3937 (11)	0.093 (3)	0.50
H10D	−0.2765	1.2350	0.3683	0.139*	0.50
H10E	−0.0981	1.2236	0.4747	0.139*	0.50
H10F	−0.2922	1.0702	0.4303	0.139*	0.50
C11	0.9893 (5)	0.8319 (4)	0.7688 (4)	0.0733 (9)
H11	1.0553	0.9518	0.7953	0.088*
C12	1.0866 (5)	0.7107 (4)	0.8108 (4)	0.0644 (8)
C13	1.2696 (5)	0.7692 (4)	0.8782 (5)	0.0781 (10)
H13	1.3307	0.8898	0.9017	0.094*
C14	1.3864 (5)	0.6556 (4)	0.9198 (5)	0.0798 (10)
H14A	1.4061	0.6763	1.0328	0.096*
H14B	1.5121	0.6889	0.8899	0.096*
C15	1.2887 (4)	0.4597 (4)	0.8383 (4)	0.0632 (7)
H15	1.2949	0.4391	0.7262	0.076*
C16	1.0754 (4)	0.4179 (4)	0.8527 (5)	0.0746 (9)
H16A	1.0134	0.2921	0.8053	0.090*
H16B	1.0640	0.4475	0.9631	0.090*
C17	0.9742 (5)	0.5210 (4)	0.7724 (5)	0.0763 (10)
H17A	0.9523	0.4671	0.6594	0.092*
H17B	0.8492	0.5137	0.8041	0.092*
C18	1.3935 (4)	0.3442 (4)	0.8964 (4)	0.0666 (8)
C19	1.4889 (6)	0.2566 (5)	0.8038 (5)	0.0813 (9)
H19A	1.5548	0.1866	0.8401	0.098*
H19B	1.4904	0.2646	0.7021	0.098*
C20	1.3869 (7)	0.3355 (6)	1.0597 (5)	0.0934 (11)
H20A	1.4500	0.2509	1.0786	0.140*
H20B	1.2548	0.2998	1.0733	0.140*
H20C	1.4516	0.4500	1.1328	0.140*
H1	0.599 (5)	0.568 (5)	0.568 (5)	0.115 (18)*
H2	0.641 (4)	0.866 (5)	0.609 (5)	0.110 (17)*

	U11	U22	U33	U12	U13	U23
O1	0.096 (2)	0.0817 (17)	0.1005 (18)	0.0444 (17)	0.0085 (16)	0.0344 (14)
O2	0.095 (2)	0.0784 (16)	0.114 (2)	0.0444 (16)	0.0000 (17)	0.0349 (15)
N1	0.079 (2)	0.0743 (18)	0.0748 (16)	0.0356 (16)	0.0104 (15)	0.0285 (14)
N2	0.0716 (19)	0.0704 (17)	0.0855 (18)	0.0333 (15)	0.0092 (15)	0.0282 (14)
C1	0.078 (2)	0.0649 (19)	0.0689 (19)	0.0273 (18)	0.0089 (17)	0.0181 (15)
C2	0.068 (2)	0.0613 (18)	0.0666 (18)	0.0211 (15)	0.0059 (15)	0.0160 (14)
C3	0.071 (2)	0.0540 (18)	0.090 (2)	0.0132 (17)	−0.0072 (18)	0.0111 (16)
C4	0.065 (2)	0.0647 (19)	0.090 (2)	0.0149 (16)	−0.0079 (17)	0.0122 (17)
C5	0.0624 (19)	0.072 (2)	0.091 (2)	0.0177 (15)	0.0000 (16)	0.0272 (17)
C6	0.082 (2)	0.0569 (17)	0.134 (3)	0.0146 (16)	−0.035 (2)	0.0212 (19)
C7	0.071 (2)	0.068 (2)	0.119 (3)	0.0139 (18)	−0.021 (2)	0.024 (2)
C8	0.064 (2)	0.067 (2)	0.100 (3)	0.0135 (16)	−0.0078 (17)	0.0302 (18)
C9	0.097 (5)	0.108 (6)	0.076 (3)	0.048 (4)	0.020 (3)	0.040 (3)
C10	0.103 (5)	0.083 (4)	0.093 (4)	0.033 (4)	0.002 (3)	0.027 (3)
C8'	0.064 (2)	0.067 (2)	0.100 (3)	0.0135 (16)	−0.0078 (17)	0.0302 (18)
C9'	0.097 (5)	0.108 (6)	0.076 (3)	0.048 (4)	0.020 (3)	0.040 (3)
C10'	0.103 (5)	0.083 (4)	0.093 (4)	0.033 (4)	0.002 (3)	0.027 (3)
C11	0.075 (2)	0.0609 (19)	0.086 (2)	0.0230 (18)	0.0118 (18)	0.0229 (16)
C12	0.063 (2)	0.0578 (17)	0.0732 (18)	0.0205 (15)	0.0092 (15)	0.0195 (14)
C13	0.064 (2)	0.0537 (18)	0.107 (3)	0.0101 (16)	−0.0006 (18)	0.0200 (17)
C14	0.057 (2)	0.0608 (19)	0.112 (3)	0.0107 (16)	−0.0085 (18)	0.0231 (18)
C15	0.0576 (16)	0.0601 (16)	0.0705 (17)	0.0166 (13)	0.0037 (13)	0.0203 (13)
C16	0.0581 (18)	0.0659 (18)	0.100 (2)	0.0123 (15)	0.0015 (16)	0.0355 (18)
C17	0.056 (2)	0.066 (2)	0.105 (3)	0.0164 (16)	−0.0043 (17)	0.0292 (18)
C18	0.0528 (17)	0.0590 (18)	0.082 (2)	0.0124 (15)	−0.0022 (14)	0.0187 (15)
C19	0.080 (2)	0.0733 (19)	0.092 (2)	0.0299 (18)	0.0063 (18)	0.0227 (17)
C20	0.094 (3)	0.107 (3)	0.095 (2)	0.041 (2)	0.010 (2)	0.047 (2)

O1—N1	1.407 (3)	C9'—H9'A	0.9300
O1—H1	0.85 (4)	C9'—H9'B	0.9300
O2—N2	1.408 (3)	C10'—H10D	0.9600
O2—H2	0.85 (4)	C10'—H10E	0.9600
N1—C1	1.266 (4)	C10'—H10F	0.9600
N2—C11	1.261 (5)	C11—C12	1.455 (4)
C1—C2	1.451 (4)	C11—H11	0.9300
C1—H1A	0.9300	C12—C13	1.316 (5)
C2—C3	1.320 (5)	C12—C17	1.489 (5)
C2—C7	1.506 (5)	C13—C14	1.495 (4)
C3—C4	1.487 (4)	C13—H13	0.9300
C3—H3	0.9300	C14—C15	1.520 (4)
C4—C5	1.529 (5)	C14—H14A	0.9700
C4—H4A	0.9700	C14—H14B	0.9700
C4—H4B	0.9700	C15—C18	1.511 (4)
C5—C6	1.500 (5)	C15—C16	1.527 (4)
C5—C8	1.514 (4)	C15—H15	0.9800
C5—H5	0.9800	C16—C17	1.514 (4)
C6—C7	1.515 (5)	C16—H16A	0.9700
C6—H6A	0.9700	C16—H16B	0.9700
C6—H6B	0.9700	C17—H17A	0.9700
C7—H7A	0.9700	C17—H17B	0.9700
C7—H7B	0.9700	C18—C19	1.316 (5)
C8—C9	1.327 (8)	C18—C20	1.485 (5)
C8—C10	1.500 (8)	C19—H19A	0.9300
C9—H9A	0.9300	C19—H19B	0.9300
C9—H9B	0.9300	C20—H20A	0.9600
C10—H10A	0.9600	C20—H20B	0.9600
C10—H10B	0.9600	C20—H20C	0.9600
C10—H10C	0.9600
N1—O1—H1	94 (3)	H10E—C10'—H10F	109.5
N2—O2—H2	106 (3)	N2—C11—C12	121.0 (3)
C1—N1—O1	111.9 (3)	N2—C11—H11	119.5
C11—N2—O2	112.1 (3)	C12—C11—H11	119.5
N1—C1—C2	121.6 (3)	C13—C12—C11	120.0 (3)
N1—C1—H1A	119.2	C13—C12—C17	121.9 (3)
C2—C1—H1A	119.2	C11—C12—C17	118.0 (3)
C3—C2—C1	120.4 (3)	C12—C13—C14	124.6 (3)
C3—C2—C7	121.3 (3)	C12—C13—H13	117.7
C1—C2—C7	118.3 (3)	C14—C13—H13	117.7
C2—C3—C4	125.1 (3)	C13—C14—C15	112.1 (3)
C2—C3—H3	117.5	C13—C14—H14A	109.2
C4—C3—H3	117.5	C15—C14—H14A	109.2
C3—C4—C5	112.7 (3)	C13—C14—H14B	109.2
C3—C4—H4A	109.1	C15—C14—H14B	109.2
C5—C4—H4A	109.1	H14A—C14—H14B	107.9
C3—C4—H4B	109.1	C18—C15—C14	112.0 (2)
C5—C4—H4B	109.1	C18—C15—C16	114.2 (2)
H4A—C4—H4B	107.8	C14—C15—C16	108.9 (3)
C6—C5—C8	114.0 (3)	C18—C15—H15	107.1
C6—C5—C4	109.6 (3)	C14—C15—H15	107.1
C8—C5—C4	111.3 (3)	C16—C15—H15	107.1
C6—C5—H5	107.2	C17—C16—C15	111.1 (2)
C8—C5—H5	107.2	C17—C16—H16A	109.4
C4—C5—H5	107.2	C15—C16—H16A	109.4
C5—C6—C7	112.3 (3)	C17—C16—H16B	109.4
C5—C6—H6A	109.2	C15—C16—H16B	109.4
C7—C6—H6A	109.2	H16A—C16—H16B	108.0
C5—C6—H6B	109.2	C12—C17—C16	112.7 (3)
C7—C6—H6B	109.2	C12—C17—H17A	109.0
H6A—C6—H6B	107.9	C16—C17—H17A	109.0
C2—C7—C6	111.9 (3)	C12—C17—H17B	109.0
C2—C7—H7A	109.2	C16—C17—H17B	109.0
C6—C7—H7A	109.2	H17A—C17—H17B	107.8
C2—C7—H7B	109.2	C19—C18—C20	122.0 (3)
C6—C7—H7B	109.2	C19—C18—C15	120.0 (3)
H7A—C7—H7B	107.9	C20—C18—C15	118.0 (3)
C9—C8—C10	120.8 (8)	C18—C19—H19A	120.0
C9—C8—C5	124.4 (6)	C18—C19—H19B	120.0
C10—C8—C5	114.7 (6)	H19A—C19—H19B	120.0
C8—C9—H9A	120.0	C18—C20—H20A	109.5
C8—C9—H9B	120.0	C18—C20—H20B	109.5
H9A—C9—H9B	120.0	H20A—C20—H20B	109.5
H9'A—C9'—H9'B	120.0	C18—C20—H20C	109.5
H10D—C10'—H10E	109.5	H20A—C20—H20C	109.5
H10D—C10'—H10F	109.5	H20B—C20—H20C	109.5
O1—N1—C1—C2	−178.2 (3)	O2—N2—C11—C12	178.3 (3)
N1—C1—C2—C3	179.9 (3)	N2—C11—C12—C13	176.4 (3)
N1—C1—C2—C7	1.2 (5)	N2—C11—C12—C17	−2.5 (5)
C1—C2—C3—C4	−178.0 (3)	C11—C12—C13—C14	−177.1 (3)
C7—C2—C3—C4	0.7 (6)	C17—C12—C13—C14	1.7 (6)
C2—C3—C4—C5	13.1 (5)	C12—C13—C14—C15	15.1 (6)
C3—C4—C5—C6	−42.4 (4)	C13—C14—C15—C18	−172.6 (3)
C3—C4—C5—C8	−169.4 (3)	C13—C14—C15—C16	−45.3 (4)
C8—C5—C6—C7	−174.0 (4)	C18—C15—C16—C17	−172.3 (3)
C4—C5—C6—C7	60.5 (5)	C14—C15—C16—C17	61.8 (4)
C3—C2—C7—C6	15.8 (5)	C13—C12—C17—C16	13.8 (5)
C1—C2—C7—C6	−165.5 (3)	C11—C12—C17—C16	−167.3 (3)
C5—C6—C7—C2	−46.7 (5)	C15—C16—C17—C12	−45.5 (4)
C6—C5—C8—C9	−51.0 (9)	C14—C15—C18—C19	−109.8 (4)
C4—C5—C8—C9	73.5 (8)	C16—C15—C18—C19	125.9 (3)
C6—C5—C8—C10	129.0 (7)	C14—C15—C18—C20	69.4 (4)
C4—C5—C8—C10	−106.4 (7)	C16—C15—C18—C20	−54.9 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.85 (4)	2.00 (2)	2.831 (4)	164 (5)
O2—H2···N1	0.85 (4)	2.04 (2)	2.811 (4)	150 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2	0.85 (4)	2.00 (2)	2.831 (4)	164 (5)
O2—H2⋯N1	0.85 (4)	2.04 (2)	2.811 (4)	150 (4)