2-[(2,3,6,7-Tetra-hydro-1H,5H-benzo[ij]quinolizin-9-yl)methyl-ene]propane-dinitrile.

The π system of the title compound, known as julolidinemalononitrile, C(16)H(15)N(3), is nearly planar, with a 3.5 (1)° twist between the aromatic and dicyano-vinyl groups. The bond lengths indicate significant zwitterionic character in the ground state.

Related literature

For background to julolidinemalononitrile, see: Haidekker & Theodorakis (2007 ▶); Hooker & Torkelson (1995 ▶); Loutfy & Arnold (1982 ▶); Marder et al. (1993 ▶); Mennucci et al. (2009 ▶); Paul & Samanta (2008 ▶); Swalina & Maroncelli (2009 ▶). For related benzyl­idene malononitrile structure data see Wang et al. (2001 ▶); Anti­pin et al. (2003 ▶); van Bolhuis & Kiers (1978 ▶).

Experimental

Crystal data

C16H15N3

M = 249.31

Monoclinic,

a = 4.9587 (9) Å

b = 15.614 (3) Å

c = 16.699 (3) Å

β = 91.609 (3)°

V = 1292.4 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 110 K

0.28 × 0.15 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T min = 0.979, T max = 0.989

7359 measured reflections

3158 independent reflections

2323 reflections with I > 2σ(I)

R int = 0.045

Refinement

R[F 2 > 2σ(F 2)] = 0.070

wR(F 2) = 0.169

S = 1.06

3158 reflections

172 parameters

H-atom parameters not refined

Δρmax = 0.47 e Å−3

Δρmin = −0.28 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809023678/bt2965sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809023678/bt2965Isup2.hkl

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

C16H15N3	F(000) = 528
Mr = 249.31	Dx = 1.281 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 4.9587 (9) Å	Cell parameters from 1409 reflections
b = 15.614 (3) Å	θ = 2.8–26.9°
c = 16.699 (3) Å	µ = 0.08 mm−1
β = 91.609 (3)°	T = 110 K
V = 1292.4 (4) Å3	Block, orange
Z = 4	0.28 × 0.15 × 0.14 mm

Bruker SMAT CCD area-detector diffractometer	3158 independent reflections
Radiation source: fine-focus sealed tube	2323 reflections with I > 2σ(I)
graphite	Rint = 0.045
φ and ω scans	θmax = 28.3°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −6→6
Tmin = 0.979, Tmax = 0.989	k = −17→20
7359 measured reflections	l = −13→22

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)] = 0.070	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.169	H-atom parameters not refined
S = 1.06	w = 1/[σ2(Fo2) + (0.0705P)2 + 0.5857P] where P = (Fo2 + 2Fc2)/3
3158 reflections	(Δ/σ)max < 0.001
172 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
C1	0.2573 (4)	0.10806 (16)	0.50258 (14)	0.0280 (5)
H1A	0.0851	0.1375	0.4999	0.034*
H1B	0.2221	0.0469	0.5024	0.034*
C2	0.4171 (5)	0.13118 (15)	0.43008 (14)	0.0283 (5)
H2A	0.3123	0.1182	0.3817	0.034*
H2B	0.5817	0.0977	0.4297	0.034*
C3	0.4856 (4)	0.22589 (15)	0.43229 (13)	0.0254 (5)
H3A	0.6008	0.2398	0.3881	0.030*
H3B	0.3215	0.2594	0.4264	0.030*
C4	0.6279 (4)	0.24797 (14)	0.51057 (12)	0.0193 (5)
C5	0.5717 (4)	0.20016 (13)	0.58073 (13)	0.0188 (4)
C6	0.6987 (4)	0.22407 (14)	0.65502 (12)	0.0197 (5)
C7	0.6322 (5)	0.17692 (15)	0.73081 (14)	0.0278 (5)
H7A	0.4936	0.2080	0.7586	0.033*
H7B	0.7916	0.1744	0.7658	0.033*
C8	0.5344 (5)	0.08689 (16)	0.71287 (15)	0.0318 (6)
H8A	0.6833	0.0523	0.6947	0.038*
H8B	0.4673	0.0611	0.7612	0.038*
C9	0.3142 (4)	0.08886 (15)	0.64948 (14)	0.0266 (5)
H9A	0.2593	0.0307	0.6367	0.032*
H9B	0.1592	0.1188	0.6699	0.032*
C10	0.8160 (4)	0.31257 (14)	0.51565 (12)	0.0191 (4)
H10	0.8534	0.3430	0.4694	0.023*
C11	0.9550 (4)	0.33494 (14)	0.58745 (12)	0.0186 (4)
C12	0.8864 (4)	0.28912 (14)	0.65663 (12)	0.0200 (5)
H12	0.9710	0.3033	0.7052	0.024*
C13	1.1540 (4)	0.40053 (14)	0.58368 (12)	0.0204 (5)
H13	1.1667	0.4259	0.5335	0.024*
C14	1.3297 (4)	0.43292 (14)	0.64049 (12)	0.0194 (4)
C15	1.5117 (4)	0.50020 (14)	0.62010 (13)	0.0221 (5)
C16	1.3544 (4)	0.40483 (14)	0.72205 (13)	0.0198 (4)
N1	0.4020 (3)	0.13133 (12)	0.57683 (11)	0.0233 (4)
N2	1.6579 (4)	0.55454 (13)	0.60473 (11)	0.0301 (5)
N3	1.3789 (4)	0.38375 (13)	0.78791 (12)	0.0290 (5)

	U11	U22	U33	U12	U13	U23
C1	0.0236 (11)	0.0236 (13)	0.0364 (13)	−0.0022 (9)	−0.0050 (9)	−0.0035 (10)
C2	0.0272 (11)	0.0275 (13)	0.0299 (12)	0.0010 (10)	−0.0054 (9)	−0.0076 (10)
C3	0.0272 (11)	0.0261 (13)	0.0226 (11)	0.0027 (9)	−0.0032 (9)	−0.0011 (9)
C4	0.0194 (10)	0.0182 (11)	0.0204 (10)	0.0055 (8)	0.0009 (8)	−0.0025 (8)
C5	0.0158 (9)	0.0156 (11)	0.0252 (11)	0.0029 (8)	0.0047 (8)	−0.0021 (8)
C6	0.0209 (10)	0.0160 (11)	0.0225 (11)	0.0036 (8)	0.0047 (8)	0.0005 (8)
C7	0.0338 (12)	0.0249 (13)	0.0251 (12)	−0.0042 (10)	0.0063 (9)	0.0022 (10)
C8	0.0331 (13)	0.0279 (14)	0.0347 (13)	−0.0044 (10)	0.0043 (10)	0.0080 (11)
C9	0.0240 (11)	0.0187 (12)	0.0375 (13)	−0.0016 (9)	0.0061 (9)	0.0017 (10)
C10	0.0209 (10)	0.0188 (11)	0.0177 (10)	0.0026 (8)	0.0025 (8)	0.0019 (8)
C11	0.0191 (10)	0.0160 (11)	0.0209 (10)	0.0029 (8)	0.0039 (8)	0.0001 (8)
C12	0.0229 (10)	0.0199 (12)	0.0174 (10)	0.0026 (8)	0.0014 (8)	−0.0007 (8)
C13	0.0228 (10)	0.0197 (12)	0.0189 (10)	0.0020 (8)	0.0043 (8)	0.0027 (9)
C14	0.0203 (10)	0.0161 (11)	0.0220 (10)	0.0009 (8)	0.0059 (8)	−0.0008 (9)
C15	0.0266 (11)	0.0212 (12)	0.0183 (10)	0.0009 (9)	0.0003 (8)	−0.0002 (9)
C16	0.0189 (10)	0.0184 (11)	0.0221 (11)	0.0001 (8)	0.0025 (8)	−0.0023 (9)
N1	0.0210 (9)	0.0204 (10)	0.0284 (10)	−0.0037 (7)	0.0001 (7)	0.0008 (8)
N2	0.0379 (11)	0.0271 (12)	0.0252 (10)	−0.0081 (9)	0.0004 (8)	0.0005 (9)
N3	0.0302 (10)	0.0312 (12)	0.0257 (11)	−0.0018 (8)	0.0009 (8)	−0.0005 (9)

C1—N1	1.461 (3)	C7—H7B	0.9700
C1—C2	1.509 (3)	C8—C9	1.500 (3)
C1—H1A	0.9700	C8—H8A	0.9700
C1—H1B	0.9700	C8—H8B	0.9700
C2—C3	1.518 (3)	C9—N1	1.460 (3)
C2—H2A	0.9700	C9—H9A	0.9700
C2—H2B	0.9700	C9—H9B	0.9700
C3—C4	1.508 (3)	C10—C11	1.410 (3)
C3—H3A	0.9700	C10—H10	0.9300
C3—H3B	0.9700	C11—C12	1.409 (3)
C4—C10	1.375 (3)	C11—C13	1.425 (3)
C4—C5	1.423 (3)	C12—H12	0.9300
C5—N1	1.365 (3)	C13—C14	1.367 (3)
C5—C6	1.425 (3)	C13—H13	0.9300
C6—C12	1.377 (3)	C14—C15	1.432 (3)
C6—C7	1.509 (3)	C14—C16	1.433 (3)
C7—C8	1.514 (3)	C15—N2	1.150 (3)
C7—H7A	0.9700	C16—N3	1.151 (3)
N1—C1—C2	111.41 (18)	C9—C8—C7	110.1 (2)
N1—C1—H1A	109.3	C9—C8—H8A	109.6
C2—C1—H1A	109.3	C7—C8—H8A	109.6
N1—C1—H1B	109.3	C9—C8—H8B	109.6
C2—C1—H1B	109.3	C7—C8—H8B	109.6
H1A—C1—H1B	108.0	H8A—C8—H8B	108.2
C1—C2—C3	109.62 (19)	N1—C9—C8	111.58 (18)
C1—C2—H2A	109.7	N1—C9—H9A	109.3
C3—C2—H2A	109.7	C8—C9—H9A	109.3
C1—C2—H2B	109.7	N1—C9—H9B	109.3
C3—C2—H2B	109.7	C8—C9—H9B	109.3
H2A—C2—H2B	108.2	H9A—C9—H9B	108.0
C4—C3—C2	110.05 (18)	C4—C10—C11	123.28 (19)
C4—C3—H3A	109.7	C4—C10—H10	118.4
C2—C3—H3A	109.7	C11—C10—H10	118.4
C4—C3—H3B	109.7	C12—C11—C10	116.62 (19)
C2—C3—H3B	109.7	C12—C11—C13	125.78 (19)
H3A—C3—H3B	108.2	C10—C11—C13	117.59 (19)
C10—C4—C5	118.83 (19)	C6—C12—C11	122.5 (2)
C10—C4—C3	121.43 (19)	C6—C12—H12	118.8
C5—C4—C3	119.73 (19)	C11—C12—H12	118.8
N1—C5—C4	120.55 (19)	C14—C13—C11	131.6 (2)
N1—C5—C6	120.29 (19)	C14—C13—H13	114.2
C4—C5—C6	119.15 (19)	C11—C13—H13	114.2
C12—C6—C5	119.47 (19)	C13—C14—C15	120.00 (19)
C12—C6—C7	120.5 (2)	C13—C14—C16	125.6 (2)
C5—C6—C7	120.06 (19)	C15—C14—C16	114.40 (18)
C6—C7—C8	111.31 (19)	N2—C15—C14	179.1 (2)
C6—C7—H7A	109.4	N3—C16—C14	178.3 (2)
C8—C7—H7A	109.4	C5—N1—C9	121.04 (19)
C6—C7—H7B	109.4	C5—N1—C1	121.57 (19)
C8—C7—H7B	109.4	C9—N1—C1	116.21 (18)
H7A—C7—H7B	108.0
N1—C1—C2—C3	−56.0 (2)	C5—C6—C12—C11	1.4 (3)
C1—C2—C3—C4	54.6 (2)	C7—C6—C12—C11	180.00 (19)
C2—C3—C4—C10	149.2 (2)	C10—C11—C12—C6	1.6 (3)
C2—C3—C4—C5	−29.5 (3)	C13—C11—C12—C6	−177.4 (2)
C10—C4—C5—N1	−174.91 (18)	C12—C11—C13—C14	3.0 (4)
C3—C4—C5—N1	3.9 (3)	C10—C11—C13—C14	−176.0 (2)
C10—C4—C5—C6	4.0 (3)	C11—C13—C14—C15	−179.9 (2)
C3—C4—C5—C6	−177.27 (18)	C11—C13—C14—C16	0.7 (4)
N1—C5—C6—C12	174.60 (18)	C13—C14—C15—N2	154 (17)
C4—C5—C6—C12	−4.3 (3)	C16—C14—C15—N2	−26 (17)
N1—C5—C6—C7	−4.0 (3)	C13—C14—C16—N3	−179 (100)
C4—C5—C6—C7	177.16 (18)	C15—C14—C16—N3	2(9)
C12—C6—C7—C8	−153.2 (2)	C4—C5—N1—C9	−171.71 (18)
C5—C6—C7—C8	25.4 (3)	C6—C5—N1—C9	9.4 (3)
C6—C7—C8—C9	−50.6 (3)	C4—C5—N1—C1	−4.6 (3)
C7—C8—C9—N1	56.3 (3)	C6—C5—N1—C1	176.57 (19)
C5—C4—C10—C11	−0.8 (3)	C8—C9—N1—C5	−36.2 (3)
C3—C4—C10—C11	−179.57 (19)	C8—C9—N1—C1	156.0 (2)
C4—C10—C11—C12	−2.0 (3)	C2—C1—N1—C5	31.3 (3)
C4—C10—C11—C13	177.13 (19)	C2—C1—N1—C9	−160.98 (19)

Molecule	R—C5	Ar1	Ar2	ΔAr	C11—C13	C13—C14	C—CN	Δpm	C≡N	θ	τ
JDMNa	1.365	1.417	1.376	0.04	1.425	1.367	1.433	0.06	1.151	132	3
N(CH3)2b	1.359	1.410	1.366	0.04	1.423	1.367	1.431	0.06	1.142	132	7
Hc		1.387	1.379	0.01	1.450	1.350	1.440	0.09	1.145	131	10
Fc	1.356	1.377	1.380	0.00	1.454	1.341	1.437	0.10	1.133	132	5