Interaction between a di­methyl­amino group and an electron-deficient alkene in ethyl (E)-2-cyano-3-(8-di­methyl­amino­-1-naphthyl)­propenoate

The interaction between the peri substituents in the title compound, C₁₈H₁₈N₂O₂, measured at 150 K, represents an early stage in the addition reaction of an amino group to an electron-deficient alkene, and has an N...Csp² separation of 2.531 (2) Å; comparison with related structures indicates that the nitrile group activates an alkene to nucleophilic attack more than a coplanar carboxyl­ic ester group.

Computing details

Data collection: DENZO (Otinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: ORTEPIII (Johnson & Burnett, 1996); software used to prepare material for publication: SHELXL93.

Ethyl E-2-Cyano-3-(8-dimethylaminonaphth-1-yl)propenoate

Crystal data

C18H18N2O2	F(000) = 312
Mr = 294.34	Dx = 1.267 Mg m^−3
Triclinic, P1	Melting point = 335–337 K
a = 8.3856 (4) Å	Mo Kα radiation, λ = 0.71069 Å
b = 9.7270 (4) Å	Cell parameters from 11581 reflections
c = 11.1860 (5) Å	θ = 2.6–23.7°
α = 69.274 (3)°	µ = 0.08 mm^−1
β = 68.037 (3)°	T = 150 K
γ = 70.933 (3)°	Plate, yellow
V = 771.31 (6) Å^3	0.3 × 0.3 × 0.1 mm
Z = 2

Data collection

Enraf Nonius KappaCCD area detector diffractometer	3134 independent reflections
Radiation source: Enraf-Nonius FR591 rotating anode	2461 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
Detector resolution: 9.091 pixels mm^-1	θmax = 26.4°, θmin = 2.6°
φ and ω scans to fill Ewald sphere	h = −10→10
Absorption correction: multi-scan using multiple and symmetry-related data measurements via the program SORTAV (Blessing, 1995).	k = −12→12
Tmin = 0.912, Tmax = 0.992	l = −13→13
11581 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.053	All H-atom parameters refined
wR(F^2) = 0.158	Calculated w = 1/[s^2(Fo^2) + ( 0.0865P)^2 + 0.209P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = −0.027
2939 reflections	Δρmax = 0.56 e Å^−3
272 parameters	Δρmin = −0.38 e Å^−3
0 restraints	Extinction correction: SHELXL93 (Sheldrick, 1993), Fc^*=kFc[1+0.001xFc^2l^3/sin(2q)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.053 (10)

Special details

Experimental. ¹H NMR (CDCl₃): 9.21 (1H, s, C=CH), 7.89 (1H, dd, J 7.3, 2.0), 7.66 (1H, dd, J 8.2, 0.9), 7.49 (3H, m), 7.35 (1H, dd, J 7.4, 1.0), 4.40 (2H, q, OCH₂), 2.65 [6H, s, N(CH₃)₂], 1.41 (3H, t, CH₃); ¹³C NMR (CDCl₃): 163.5 (C=O), 161.2 (=CH), 150.1, 135.1, 130.8, 130.7, 129.8, 127.1, 126.7, 125.9, 125.3, 119.5, 115.7 (CN), 96.8 (=C(CN), 62.0 (OCH₂), 45.3 [N(CH₃)₂], 14.3 (ester CH₃); ν(cm^-1): 2224, 1704, 1572, 1258, 1244, 1082, 834, 781, 766, 740, 619; HRMS: 294.1366, C₁₈H₁₈N₂O₂ requires 294.1368.

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 on F² for ALL reflections except for 195 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors

wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating _R_factor_obs 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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.8648 (2)	0.11607 (14)	0.29739 (12)	0.0436 (4)
O2	0.7128 (2)	0.34797 (14)	0.31416 (12)	0.0459 (4)
N1	0.7205 (2)	0.3321 (2)	0.67642 (14)	0.0317 (4)
N2	0.7127 (3)	−0.1417 (2)	0.5963 (2)	0.0480 (5)
C1	0.6035 (2)	0.2969 (2)	0.8090 (2)	0.0294 (4)
C2	0.6154 (3)	0.3296 (2)	0.9149 (2)	0.0406 (5)
C3	0.4988 (3)	0.2899 (2)	1.0433 (2)	0.0448 (5)
C4	0.3734 (3)	0.2158 (2)	1.0662 (2)	0.0369 (4)
C5	0.2278 (2)	0.1022 (2)	0.9817 (2)	0.0349 (4)
C6	0.2133 (2)	0.0677 (2)	0.8789 (2)	0.0376 (4)
C7	0.3242 (2)	0.1122 (2)	0.7482 (2)	0.0337 (4)
C8	0.4493 (2)	0.1900 (2)	0.7218 (2)	0.0260 (4)
C9	0.3563 (2)	0.1802 (2)	0.9600 (2)	0.0298 (4)
C10	0.4710 (2)	0.2233 (2)	0.82888 (15)	0.0255 (4)
C11	0.5545 (2)	0.2415 (2)	0.5816 (2)	0.0284 (4)
C12	0.6576 (2)	0.1481 (2)	0.5038 (2)	0.0308 (4)
C13	0.6885 (2)	−0.0134 (2)	0.5567 (2)	0.0343 (4)
C14	0.7572 (2)	0.1993 (2)	0.3615 (2)	0.0316 (4)
C15	0.8184 (3)	0.4128 (2)	0.1805 (2)	0.0418 (5)
C16	0.9449 (3)	0.4774 (3)	0.1932 (2)	0.0541 (6)
C18	0.8861 (3)	0.2192 (3)	0.6571 (2)	0.0498 (5)
C19	0.7474 (3)	0.4856 (2)	0.6269 (2)	0.0464 (5)
H2	0.711 (3)	0.377 (3)	0.900 (2)	0.051 (6)*
H3	0.509 (3)	0.310 (3)	1.114 (3)	0.057 (7)*
H4	0.299 (3)	0.180 (2)	1.153 (2)	0.042 (5)*
H5	0.152 (3)	0.073 (2)	1.073 (2)	0.049 (6)*
H6	0.124 (3)	0.017 (3)	0.890 (2)	0.052 (6)*
H7	0.310 (3)	0.090 (2)	0.672 (2)	0.042 (5)*
H11	0.539 (2)	0.348 (2)	0.541 (2)	0.023 (4)*
H15A	0.880 (3)	0.328 (2)	0.132 (2)	0.049 (6)*
H15B	0.735 (3)	0.490 (2)	0.133 (2)	0.042 (5)*
H16A	1.030 (4)	0.389 (3)	0.246 (3)	0.067 (7)*
H16B	0.880 (3)	0.562 (3)	0.248 (3)	0.066 (7)*
H16C	1.029 (4)	0.528 (3)	0.092 (3)	0.086 (8)*
H18A	0.953 (3)	0.223 (2)	0.709 (2)	0.052 (6)*
H18B	0.951 (3)	0.248 (3)	0.556 (3)	0.063 (7)*
H18C	0.860 (3)	0.114 (3)	0.688 (2)	0.050 (6)*
H19A	0.807 (3)	0.502 (3)	0.530 (3)	0.059 (7)*
H19B	0.824 (4)	0.499 (3)	0.667 (3)	0.069 (8)*
H19C	0.632 (4)	0.558 (3)	0.643 (2)	0.058 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0498 (8)	0.0374 (7)	0.0308 (7)	−0.0050 (6)	0.0024 (6)	−0.0137 (6)
O2	0.0474 (8)	0.0319 (7)	0.0300 (7)	−0.0001 (6)	0.0069 (6)	−0.0029 (5)
N1	0.0247 (7)	0.0321 (8)	0.0348 (8)	−0.0059 (6)	−0.0059 (6)	−0.0083 (6)
N2	0.0693 (12)	0.0335 (9)	0.0318 (8)	−0.0105 (8)	−0.0035 (8)	−0.0105 (7)
C1	0.0285 (8)	0.0255 (8)	0.0319 (8)	−0.0016 (6)	−0.0086 (7)	−0.0094 (7)
C2	0.0419 (11)	0.0421 (10)	0.0449 (11)	−0.0080 (8)	−0.0161 (9)	−0.0174 (9)
C3	0.0550 (12)	0.0484 (11)	0.0363 (10)	−0.0026 (9)	−0.0179 (9)	−0.0207 (9)
C4	0.0430 (11)	0.0354 (9)	0.0237 (8)	0.0009 (8)	−0.0073 (8)	−0.0092 (7)
C5	0.0309 (9)	0.0338 (9)	0.0272 (8)	−0.0057 (7)	0.0009 (7)	−0.0049 (7)
C6	0.0304 (9)	0.0407 (10)	0.0388 (10)	−0.0147 (8)	−0.0008 (8)	−0.0110 (8)
C7	0.0311 (9)	0.0390 (10)	0.0313 (9)	−0.0095 (7)	−0.0046 (7)	−0.0129 (8)
C8	0.0242 (8)	0.0253 (8)	0.0242 (8)	−0.0014 (6)	−0.0042 (6)	−0.0085 (6)
C9	0.0299 (8)	0.0257 (8)	0.0257 (8)	0.0017 (6)	−0.0063 (7)	−0.0067 (7)
C10	0.0246 (8)	0.0219 (8)	0.0249 (8)	0.0009 (6)	−0.0058 (6)	−0.0073 (6)
C11	0.0267 (8)	0.0294 (9)	0.0260 (8)	−0.0050 (6)	−0.0058 (7)	−0.0070 (7)
C12	0.0319 (9)	0.0294 (8)	0.0258 (8)	−0.0057 (7)	−0.0043 (7)	−0.0068 (7)
C13	0.0417 (10)	0.0329 (10)	0.0226 (8)	−0.0075 (7)	−0.0013 (7)	−0.0101 (7)
C14	0.0318 (9)	0.0299 (9)	0.0272 (8)	−0.0034 (7)	−0.0049 (7)	−0.0079 (7)
C15	0.0438 (11)	0.0332 (9)	0.0282 (9)	−0.0045 (8)	0.0017 (8)	−0.0018 (8)
C16	0.0516 (13)	0.0590 (14)	0.0446 (12)	−0.0128 (11)	−0.0065 (10)	−0.0131 (11)
C18	0.0323 (10)	0.0551 (13)	0.0499 (13)	0.0015 (9)	−0.0090 (9)	−0.0137 (11)
C19	0.0481 (12)	0.0423 (11)	0.0484 (12)	−0.0202 (10)	−0.0120 (10)	−0.0045 (9)

Geometric parameters (Å, º)

O1—C14	1.198 (2)	C7—C8	1.374 (2)
O2—C14	1.328 (2)	C8—C10	1.432 (2)
O2—C15	1.457 (2)	C8—C11	1.478 (2)
N1—C1	1.432 (2)	C9—C10	1.423 (2)
N1—C18	1.459 (2)	C11—H11	0.96 (2)
N1—C19	1.459 (2)	C11—C12	1.346 (2)
N2—C13	1.143 (2)	C12—C13	1.441 (2)
C1—C2	1.376 (3)	C12—C14	1.482 (2)
C1—C10	1.420 (2)	C15—H15B	1.00 (2)
C2—H2	0.98 (2)	C15—H15A	1.04 (2)
C2—C3	1.404 (3)	C15—C16	1.467 (3)
C3—H3	0.92 (2)	C16—H16A	1.08 (3)
C3—C4	1.361 (3)	C16—H16B	1.08 (3)
C4—H4	0.95 (2)	C16—H16C	1.12 (3)
C4—C9	1.416 (2)	C18—H18A	0.96 (2)
C5—H5	0.98 (2)	C18—H18C	1.02 (2)
C5—C6	1.362 (3)	C18—H18B	1.03 (3)
C5—C9	1.415 (3)	C19—H19B	0.97 (3)
C6—H6	0.98 (2)	C19—H19A	0.98 (3)
C6—C7	1.410 (2)	C19—H19C	0.99 (3)
C7—H7	1.00 (2)
C14—O2—C15	116.55 (14)	H11—C11—C12	117.9 (10)
C1—N1—C18	112.84 (14)	H11—C11—C8	117.9 (10)
C1—N1—C19	114.89 (15)	C12—C11—C8	123.80 (15)
C18—N1—C19	112.5 (2)	C11—C12—C13	121.59 (15)
C2—C1—C10	119.9 (2)	C11—C12—C14	124.16 (15)
C2—C1—N1	123.3 (2)	C13—C12—C14	114.14 (14)
C10—C1—N1	116.84 (14)	N2—C13—C12	178.6 (2)
H2—C2—C1	118.6 (13)	O1—C14—O2	124.3 (2)
H2—C2—C3	120.6 (13)	O1—C14—C12	123.8 (2)
C1—C2—C3	120.7 (2)	O2—C14—C12	111.91 (14)
H3—C3—C4	118.9 (15)	H15B—C15—H15A	108.0 (17)
H3—C3—C2	120.2 (15)	H15B—C15—O2	106.9 (12)
C4—C3—C2	120.8 (2)	H15A—C15—O2	107.8 (12)
H4—C4—C3	122.7 (12)	H15B—C15—C16	112.8 (12)
H4—C4—C9	116.9 (12)	H15A—C15—C16	112.6 (12)
C3—C4—C9	120.3 (2)	O2—C15—C16	108.4 (2)
H5—C5—C6	121.5 (13)	H16A—C16—H16B	108.0 (19)
H5—C5—C9	117.8 (13)	H16A—C16—H16C	108 (2)
C6—C5—C9	120.8 (2)	H16B—C16—H16C	109 (2)
H6—C6—C5	123.0 (13)	H16A—C16—C15	109.0 (14)
H6—C6—C7	116.7 (13)	H16B—C16—C15	112.1 (14)
C5—C6—C7	120.3 (2)	H16C—C16—C15	110.6 (15)
H7—C7—C8	119.0 (12)	H18A—C18—H18C	109.5 (18)
H7—C7—C6	119.9 (12)	H18A—C18—H18B	111.4 (19)
C8—C7—C6	121.1 (2)	H18C—C18—H18B	111.7 (19)
C7—C8—C10	119.75 (15)	H18A—C18—N1	108.9 (13)
C7—C8—C11	118.56 (15)	H18C—C18—N1	109.6 (13)
C10—C8—C11	121.65 (14)	H18B—C18—N1	105.7 (14)
C5—C9—C4	121.3 (2)	H19B—C19—H19A	108 (2)
C5—C9—C10	119.5 (2)	H19B—C19—H19C	111 (2)
C4—C9—C10	119.3 (2)	H19A—C19—H19C	110 (2)
C1—C10—C9	118.99 (15)	H19B—C19—N1	111.9 (15)
C1—C10—C8	122.37 (14)	H19A—C19—N1	106.2 (14)
C9—C10—C8	118.64 (14)	H19C—C19—N1	109.4 (14)