2-(2-Methyl-6-phenyl-1-propyl-1,4-dihydro­pyridin-4-yl­idene)propane­dinitrile

Kim, Y.H.; Kim, H.J.; Otgonbaatar, E.; Kwak, C.-H.

doi:10.1107/S1600536811005587

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o670

doi:10.1107/S1600536811005587

Open

access

2-(2-Methyl-6-phenyl-1-propyl-1,4-dihydropyridin-4-ylidene)propanedinitrile

Young Hyun Kim,^a Hyung Jin Kim,^a ^* Enkhzul Otgonbaatar ^b and Chee-Hun Kwak ^b ^*

^aSchool of Applied Chemical Engineering, Chonnam National University, Gwangju 500-757, Republic of Korea, and ^bDepartment of Chemistry, Sunchon National University, 315 Maegok Dong, Sunchon, Jeonnam 540-742, Republic of Korea
^*Correspondence e-mail: hyungkim@chonnam.ac.kr, chkwak@sunchon.ac.kr

(Received 1 February 2011; accepted 15 February 2011; online 19 February 2011)

In the title compound, C₁₈H₁₇N₃, the dihedral angle between the dihydropyridine and phenyl rings is 72.57 (5)° and that between the dihydropyridine ring and malononitrile plane is 5.19 (20)°. The C—C bond lengths in the pyridine ring are considerably shorter than those of normal single bonds, indicating that electrons on the dihydropyridine ring, including the non-bonding electrons of the N atom, are delocalized on the ring.

Related literature

For the synthesis of the starting material, see: Tolmachev et al. (2006 ). For a related structure, see: Ha et al. (2009 ).

Experimental

Crystal data

C₁₈H₁₇N₃
M_r = 275.35
Monoclinic, P 2₁ /c
a = 11.5580 (7) Å
b = 9.9179 (6) Å
c = 13.9268 (7) Å
β = 105.707 (2)°
V = 1536.83 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 100 K
0.5 × 0.4 × 0.2 mm

Data collection

Rigaku R-AXIS RAPID II-S diffractometer
Absorption correction: multi-scan (RAPID-AUTO; Rigaku, 2008 ) T_min = 0.966, T_max = 0.986
13505 measured reflections
3185 independent reflections
2321 reflections with I > 2σ(I)
R_int = 0.077

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.134
S = 1.07
3185 reflections
193 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 2008); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005587/bq2278sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811005587/bq2278Isup2.hkl

checkCIF report

Comment top

Recently we have reported the structure of 2-(1-propyl-2,6-distyryl-1,4-pyridin-4-ylidene)malononitrile as a fluorescent dye (Ha et al., 2009). Continuing our study on the (1,4-pyridin-4-ylidene)malononitrile derivatives, the title compound was synthesized and its structure was confirmed by ¹H NMR and X-ray crystal analysis.

In the title compound, C₁₈H₁₇N₃, the dihedral angles between the central pyridine and phenyl ring is 72.57 (5)° and that between the pyridine ring and malonitrile plane (N2 C13 C12 C14 N3 plane) is 5.19 (20)°. The bond distances of C—C bonds in the pyridine ring are considerably shorter than those of normal single bonds (D(C1—C2) = D(C1—C5) = 1.413 (3) Å). These results suggest that the electrons on the pyridine ring including non-bonding electrons of N1 are delocalized on the ring (Fig. 1).

Related literature top

For the synthesis of the starting material, see: Tolmachev et al. (2006). For a related structure, see: Ha et al. (2009).

Experimental top

A mixture of 2-(2-methyl-6-phenyl-4H-pyran-4-ylidene)malononitrile (1.5 g, 6.4 mmol) and n-propylamine (20 ml) was heated at 150 °C for 3 h. The mixture was cooled and concentrated under vacuum. Crude product was recrystallized from MeOH to give crystals suitable for X-ray analysis (1.20 g, 68%). Mp 166–167 °C. ¹H NMR (300 MHz, CDCl₃) δ 7.52–7.26 (m, 5H, Ph), 6.79 (d, 1H, J = 2.5 Hz, C—CH=C—N), 6.70 (d, 1H, J = 2.5 Hz), 3.75 (t, 2H, J = 8.1 Hz, NCH₂CH₂CH₃), 2.50 (s, 3H, CH₃), 1.52 (m, 2H, NCH₂CH₂CH₃), 0.70 (t, 3H, J = 7.4 Hz, NCH₂CH₂CH₃)

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2008); cell refinement: RAPID-AUTO (Rigaku, 2008); data reduction: RAPID-AUTO (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The structure of the title compound with displacement ellipsoids drawn at the 50% probability level for non-H atoms.

2-(2-Methyl-6-phenyl-1-propyl-1,4-dihydropyridin-4-ylidene)propanedinitrile top

Crystal data top

C₁₈H₁₇N₃	F(000) = 584
M_r = 275.35	Z = 4
Monoclinic, P2₁/c	D_x = 1.190 Mg m⁻³
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.5580 (7) Å	Cell parameters from 15051 reflections
b = 9.9179 (6) Å	θ = 27.5–3.0°
c = 13.9268 (7) Å	µ = 0.07 mm⁻¹
β = 105.707 (2)°	T = 100 K
V = 1536.83 (15) Å³	Block, yellow
Z = 4	0.5 × 0.4 × 0.2 mm

Data collection top

Rigaku R-AXIS RAPID II-S diffractometer	3185 independent reflections
Radiation source: fine-focus sealed tube	2321 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.077
ω scans	θ_max = 26.5°, θ_min = 3.0°
Absorption correction: multi-scan (RAPID-AUTO; Rigaku, 2008)	h = −14→14
T_min = 0.966, T_max = 0.986	k = −12→12
13505 measured reflections	l = −16→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.134	w = 1/[σ²(F_o²) + (0.0522P)² + 0.3213P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
3185 reflections	Δρ_max = 0.22 e Å⁻³
193 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.013 (3)

Crystal data top

C₁₈H₁₇N₃	V = 1536.83 (15) Å³
M_r = 275.35	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.5580 (7) Å	µ = 0.07 mm⁻¹
b = 9.9179 (6) Å	T = 100 K
c = 13.9268 (7) Å	0.5 × 0.4 × 0.2 mm
β = 105.707 (2)°

Data collection top

Rigaku R-AXIS RAPID II-S diffractometer	3185 independent reflections
Absorption correction: multi-scan (RAPID-AUTO; Rigaku, 2008)	2321 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.986	R_int = 0.077
13505 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 1.07	Δρ_max = 0.22 e Å⁻³
3185 reflections	Δρ_min = −0.20 e Å⁻³
193 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
C1	0.86513 (14)	0.37654 (15)	0.41005 (10)	0.0322 (4)
C2	0.94627 (14)	0.43142 (16)	0.36078 (11)	0.0350 (4)
H2	1.0277	0.4120	0.3851	0.042*
C3	0.90918 (14)	0.51234 (16)	0.27834 (11)	0.0345 (4)
C4	0.70719 (14)	0.49082 (15)	0.28609 (10)	0.0311 (4)
C5	0.74344 (14)	0.41302 (16)	0.36931 (11)	0.0332 (4)
H5	0.6864	0.3829	0.4004	0.040*
C6	0.57636 (14)	0.51915 (15)	0.24329 (11)	0.0325 (4)
C7	0.51068 (15)	0.45459 (18)	0.15657 (12)	0.0402 (4)
H7	0.5498	0.3993	0.1214	0.048*
C8	0.38795 (16)	0.4724 (2)	0.12290 (13)	0.0466 (4)
H8	0.3443	0.4281	0.0657	0.056*
C9	0.32989 (16)	0.55609 (19)	0.17404 (13)	0.0467 (5)
H9	0.2473	0.5686	0.1506	0.056*
C10	0.39303 (17)	0.62090 (19)	0.25902 (14)	0.0478 (5)
H10	0.3534	0.6773	0.2931	0.057*
C11	0.51660 (15)	0.60193 (18)	0.29407 (12)	0.0409 (4)
H11	0.5594	0.6452	0.3521	0.049*
C12	0.90262 (14)	0.28936 (16)	0.49335 (11)	0.0357 (4)
C13	0.82087 (16)	0.24072 (17)	0.54461 (12)	0.0399 (4)
C14	1.02361 (17)	0.24658 (18)	0.52802 (12)	0.0436 (4)
C15	0.74831 (15)	0.63071 (16)	0.15180 (11)	0.0366 (4)
H15A	0.6704	0.5997	0.1122	0.044*
H15B	0.8041	0.6235	0.1110	0.044*
C16	0.73834 (19)	0.77697 (18)	0.17897 (12)	0.0481 (5)
H16A	0.8174	0.8115	0.2129	0.058*
H16B	0.6877	0.7844	0.2241	0.058*
C17	0.6847 (2)	0.8605 (2)	0.08532 (15)	0.0669 (6)
H17A	0.6826	0.9537	0.1032	0.100*
H17B	0.6045	0.8298	0.0542	0.100*
H17C	0.7333	0.8503	0.0397	0.100*
C18	0.99893 (17)	0.5697 (2)	0.22903 (14)	0.0500 (5)
H18A	0.9884	0.6655	0.2224	0.075*
H18B	0.9869	0.5300	0.1642	0.075*
H18C	1.0788	0.5500	0.2690	0.075*
N1	0.78979 (11)	0.54168 (13)	0.24021 (9)	0.0320 (3)
N2	0.75433 (16)	0.20179 (18)	0.58685 (12)	0.0569 (5)
N3	1.12223 (16)	0.2122 (2)	0.55469 (12)	0.0672 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0369 (9)	0.0294 (8)	0.0286 (7)	−0.0009 (7)	0.0057 (6)	−0.0046 (6)
C2	0.0321 (8)	0.0349 (9)	0.0361 (8)	0.0006 (7)	0.0058 (6)	−0.0010 (6)
C3	0.0334 (9)	0.0337 (9)	0.0367 (8)	−0.0020 (7)	0.0100 (6)	−0.0031 (6)
C4	0.0342 (9)	0.0282 (8)	0.0299 (7)	−0.0015 (6)	0.0069 (6)	−0.0038 (6)
C5	0.0332 (8)	0.0354 (8)	0.0303 (8)	−0.0013 (7)	0.0073 (6)	−0.0003 (6)
C6	0.0333 (8)	0.0324 (8)	0.0306 (7)	0.0024 (7)	0.0068 (6)	0.0039 (6)
C7	0.0382 (9)	0.0434 (10)	0.0372 (8)	0.0010 (7)	0.0070 (7)	−0.0041 (7)
C8	0.0399 (10)	0.0557 (11)	0.0386 (9)	−0.0008 (8)	0.0012 (7)	0.0013 (8)
C9	0.0350 (10)	0.0525 (11)	0.0496 (10)	0.0065 (8)	0.0063 (8)	0.0144 (8)
C10	0.0476 (11)	0.0480 (11)	0.0518 (10)	0.0119 (9)	0.0204 (8)	0.0050 (8)
C11	0.0431 (10)	0.0425 (10)	0.0364 (8)	0.0032 (8)	0.0097 (7)	−0.0027 (7)
C12	0.0371 (9)	0.0361 (9)	0.0320 (8)	0.0022 (7)	0.0062 (6)	0.0017 (6)
C13	0.0469 (10)	0.0386 (9)	0.0326 (8)	0.0038 (8)	0.0081 (7)	0.0025 (7)
C14	0.0484 (11)	0.0502 (11)	0.0321 (8)	0.0099 (9)	0.0105 (7)	0.0071 (7)
C15	0.0431 (9)	0.0387 (9)	0.0276 (7)	0.0021 (7)	0.0091 (7)	0.0022 (6)
C16	0.0662 (13)	0.0414 (10)	0.0380 (9)	0.0068 (9)	0.0163 (8)	0.0044 (7)
C17	0.0989 (18)	0.0518 (12)	0.0534 (11)	0.0250 (12)	0.0265 (11)	0.0160 (9)
C18	0.0451 (11)	0.0524 (11)	0.0554 (11)	−0.0005 (8)	0.0185 (8)	0.0122 (9)
N1	0.0356 (7)	0.0310 (7)	0.0287 (6)	0.0000 (5)	0.0075 (5)	0.0001 (5)
N2	0.0670 (11)	0.0572 (11)	0.0521 (9)	0.0020 (9)	0.0258 (9)	0.0113 (8)
N3	0.0545 (11)	0.0899 (14)	0.0562 (10)	0.0296 (10)	0.0130 (8)	0.0229 (9)

Geometric parameters (Å, º) top

C1—C2	1.412 (2)	C10—H10	0.9300
C1—C5	1.414 (2)	C11—H11	0.9300
C1—C12	1.417 (2)	C12—C13	1.414 (2)
C2—C3	1.371 (2)	C12—C14	1.415 (2)
C2—H2	0.9300	C13—N2	1.154 (2)
C3—N1	1.369 (2)	C14—N3	1.151 (2)
C3—C18	1.502 (2)	C15—N1	1.4852 (18)
C4—C5	1.361 (2)	C15—C16	1.511 (2)
C4—N1	1.3801 (19)	C15—H15A	0.9700
C4—C6	1.494 (2)	C15—H15B	0.9700
C5—H5	0.9300	C16—C17	1.527 (2)
C6—C11	1.384 (2)	C16—H16A	0.9700
C6—C7	1.396 (2)	C16—H16B	0.9700
C7—C8	1.380 (2)	C17—H17A	0.9600
C7—H7	0.9300	C17—H17B	0.9600
C8—C9	1.380 (3)	C17—H17C	0.9600
C8—H8	0.9300	C18—H18A	0.9600
C9—C10	1.371 (3)	C18—H18B	0.9600
C9—H9	0.9300	C18—H18C	0.9600
C10—C11	1.391 (2)

C2—C1—C5	115.20 (13)	C13—C12—C14	117.32 (14)
C2—C1—C12	122.45 (14)	C13—C12—C1	121.55 (14)
C5—C1—C12	122.34 (14)	C14—C12—C1	121.13 (15)
C3—C2—C1	122.29 (15)	N2—C13—C12	179.5 (2)
C3—C2—H2	118.9	N3—C14—C12	178.88 (18)
C1—C2—H2	118.9	N1—C15—C16	113.11 (12)
N1—C3—C2	120.21 (14)	N1—C15—H15A	109.0
N1—C3—C18	119.37 (14)	C16—C15—H15A	109.0
C2—C3—C18	120.42 (15)	N1—C15—H15B	109.0
C5—C4—N1	120.64 (14)	C16—C15—H15B	109.0
C5—C4—C6	119.44 (13)	H15A—C15—H15B	107.8
N1—C4—C6	119.92 (12)	C15—C16—C17	110.33 (14)
C4—C5—C1	122.03 (14)	C15—C16—H16A	109.6
C4—C5—H5	119.0	C17—C16—H16A	109.6
C1—C5—H5	119.0	C15—C16—H16B	109.6
C11—C6—C7	118.97 (15)	C17—C16—H16B	109.6
C11—C6—C4	119.92 (14)	H16A—C16—H16B	108.1
C7—C6—C4	120.90 (14)	C16—C17—H17A	109.5
C8—C7—C6	120.24 (16)	C16—C17—H17B	109.5
C8—C7—H7	119.9	H17A—C17—H17B	109.5
C6—C7—H7	119.9	C16—C17—H17C	109.5
C7—C8—C9	120.04 (16)	H17A—C17—H17C	109.5
C7—C8—H8	120.0	H17B—C17—H17C	109.5
C9—C8—H8	120.0	C3—C18—H18A	109.5
C10—C9—C8	120.53 (17)	C3—C18—H18B	109.5
C10—C9—H9	119.7	H18A—C18—H18B	109.5
C8—C9—H9	119.7	C3—C18—H18C	109.5
C9—C10—C11	119.70 (16)	H18A—C18—H18C	109.5
C9—C10—H10	120.1	H18B—C18—H18C	109.5
C11—C10—H10	120.1	C3—N1—C4	119.59 (12)
C6—C11—C10	120.52 (15)	C3—N1—C15	120.88 (13)
C6—C11—H11	119.7	C4—N1—C15	119.51 (13)
C10—C11—H11	119.7

C5—C1—C2—C3	−1.1 (2)	C4—C6—C11—C10	−175.04 (15)
C12—C1—C2—C3	177.93 (14)	C9—C10—C11—C6	0.6 (3)
C1—C2—C3—N1	−0.6 (2)	C2—C1—C12—C13	176.88 (15)
C1—C2—C3—C18	179.35 (15)	C5—C1—C12—C13	−4.2 (2)
N1—C4—C5—C1	−2.5 (2)	C2—C1—C12—C14	−3.7 (2)
C6—C4—C5—C1	176.43 (14)	C5—C1—C12—C14	175.28 (15)
C2—C1—C5—C4	2.6 (2)	N1—C15—C16—C17	−174.92 (16)
C12—C1—C5—C4	−176.36 (14)	C2—C3—N1—C4	0.9 (2)
C5—C4—C6—C11	69.6 (2)	C18—C3—N1—C4	−179.09 (15)
N1—C4—C6—C11	−111.43 (17)	C2—C3—N1—C15	179.15 (14)
C5—C4—C6—C7	−105.08 (17)	C18—C3—N1—C15	−0.8 (2)
N1—C4—C6—C7	73.9 (2)	C5—C4—N1—C3	0.7 (2)
C11—C6—C7—C8	−0.6 (2)	C6—C4—N1—C3	−178.28 (13)
C4—C6—C7—C8	174.15 (15)	C5—C4—N1—C15	−177.62 (13)
C6—C7—C8—C9	1.1 (3)	C6—C4—N1—C15	3.4 (2)
C7—C8—C9—C10	−0.7 (3)	C16—C15—N1—C3	−93.10 (18)
C8—C9—C10—C11	−0.1 (3)	C16—C15—N1—C4	85.16 (18)
C7—C6—C11—C10	−0.2 (2)

Experimental details

Crystal data
Chemical formula	C₁₈H₁₇N₃
M_r	275.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	11.5580 (7), 9.9179 (6), 13.9268 (7)
β (°)	105.707 (2)
V (Å³)	1536.83 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.5 × 0.4 × 0.2

Data collection
Diffractometer	Rigaku R-AXIS RAPID II-S diffractometer
Absorption correction	Multi-scan (RAPID-AUTO; Rigaku, 2008)
T_min, T_max	0.966, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	13505, 3185, 2321
R_int	0.077
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.134, 1.07
No. of reflections	3185
No. of parameters	193
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.20

Computer programs: RAPID-AUTO (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Acknowledgements

This study was supported financially by Chonnam National University. CHK thanks the RIC, Sunchon National University, for financial support.

References

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Ha, K., Heo, J. & Kim, H. J. (2009). Acta Cryst. E65, o3131. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2008). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tolmachev, A. I., Kachkovskii, A. D., Kudinova, M. A., Kurdiukov, V. V., Ksenzov, S. & Schrader, S. (2006). Dyes Pigm. 74, 348–356. Web of Science CrossRef 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.