Ethyl 5-cyano-8-nitro-2,3,4,4a,5,6-hexahydro-1H-pyrido[1,2-a]quinoline-5-carboxylate.

In the title compound, C(17)H(19)N(3)O(4), the piperidine ring adopts a chair conformation. The crystal structure features inversion dimers linked by pairs of weak C-H⋯N hydrogen bonds.

Related literature

For the therapeutic properties of quinoline derivatives, see: Dalla Via et al. (2008 ▶); Gasparotto et al. (2006 ▶); Ferlin et al. (2000 ▶). A similar heterocyclic structure, Mitomycin C, is used in cancer therapy, see: Crooke & Bradner (1976 ▶); Danishefsky & Ciufolini (1984 ▶); Remers (1980 ▶). For related structures, see: Zhuravleva et al. (2009 ▶); Oliveira et al. (2006 ▶). For ring conformation analysis, see: Cremer & Pople (1975 ▶). For reference bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C17H19N3O4

M = 329.36

Triclinic,

a = 8.8257 (4) Å

b = 9.2256 (5) Å

c = 10.5011 (6) Å

α = 88.246 (4)°

β = 75.089 (2)°

γ = 83.289 (3)°

V = 820.57 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 223 K

0.20 × 0.20 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer

10064 measured reflections

4189 independent reflections

2794 reflections with I > 2σ(I)

R int = 0.04

Refinement

R[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.096

S = 1.04

2503 reflections

217 parameters

H-atom parameters constrained

Δρmax = 0.21 e Å−3

Δρmin = −0.26 e Å−3

Data collection: COLLECT (Nonius, 2001 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: CRYSTALS.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681002283X/bq2218sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681002283X/bq2218Isup2.hkl

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

C17H19N3O4	Z = 2
Mr = 329.36	F(000) = 348
Triclinic, P1	Dx = 1.333 Mg m−3
Hall symbol: -P 1	Melting point: 424 K
a = 8.8257 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.2256 (5) Å	Cell parameters from 10064 reflections
c = 10.5011 (6) Å	θ = 2–29°
α = 88.246 (4)°	µ = 0.10 mm−1
β = 75.089 (2)°	T = 223 K
γ = 83.289 (3)°	Prism, yellow
V = 820.57 (8) Å3	0.20 × 0.20 × 0.20 mm

Nonius KappaCCD diffractometer	Rint = 0.04
graphite	θmax = 29.1°, θmin = 2.0°
φ and ω scans	h = 0→12
10064 measured reflections	k = −11→12
4189 independent reflections	l = −13→14
2794 reflections with I > 2σ(I)

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055	H-atom parameters constrained
wR(F2) = 0.096	w = 1/[σ2(F2) + (0.02P)2 + 0.5P], where P = (max(Fo2,0) + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.0002
2503 reflections	Δρmax = 0.21 e Å−3
217 parameters	Δρmin = −0.26 e Å−3
0 restraints

	x	y	z	Uiso*/Ueq
C1	0.70920 (19)	0.86006 (18)	0.50748 (17)	0.0241
N1	0.70324 (17)	0.85963 (14)	0.63954 (14)	0.0268
O3	0.66155 (17)	0.46173 (14)	0.84947 (13)	0.0393
C9	0.7451 (2)	0.72488 (18)	0.70764 (17)	0.0256
C2	0.6873 (2)	0.99129 (19)	0.43830 (18)	0.0287
C6	0.7271 (2)	0.72669 (18)	0.43802 (17)	0.0269
C5	0.7160 (2)	0.72795 (19)	0.30929 (18)	0.0308
C4	0.6920 (2)	0.8595 (2)	0.24574 (17)	0.0311
O4	0.8187 (2)	0.35165 (15)	0.66714 (15)	0.0548
O2	0.6821 (2)	0.74186 (19)	0.05771 (16)	0.0639
C3	0.6790 (2)	0.99068 (19)	0.30939 (18)	0.0308
C7	0.7604 (2)	0.58338 (19)	0.50323 (18)	0.0325
C8	0.6879 (2)	0.59435 (18)	0.65159 (17)	0.0278
C10	0.9210 (2)	0.7072 (2)	0.70064 (19)	0.0327
N3	0.3802 (2)	0.63652 (18)	0.69548 (19)	0.0450
N2	0.6797 (2)	0.8591 (2)	0.11110 (17)	0.0436
O1	0.6673 (2)	0.97711 (19)	0.05381 (15)	0.0652
C13	0.7303 (2)	0.98771 (19)	0.70769 (18)	0.0310
C17	0.5143 (2)	0.61781 (18)	0.67811 (19)	0.0322
C12	0.9039 (2)	0.9820 (2)	0.70523 (19)	0.0346
C14	0.7321 (2)	0.45278 (19)	0.72194 (19)	0.0328
C11	0.9606 (2)	0.8393 (2)	0.7643 (2)	0.0358
C15	0.6946 (3)	0.3372 (2)	0.9327 (2)	0.0461
C16	0.8465 (4)	0.3441 (3)	0.9667 (3)	0.0711
H91	0.6874	0.7364	0.8009	0.0307*
H51	0.7270	0.6393	0.2640	0.0374*
H31	0.6639	1.0787	0.2640	0.0358*
H71	0.8751	0.5568	0.4875	0.0395*
H72	0.7193	0.5065	0.4655	0.0388*
H101	0.9454	0.6173	0.7460	0.0386*
H102	0.9806	0.7000	0.6083	0.0399*
H122	0.9191	1.0653	0.7543	0.0424*
H121	0.9656	0.9890	0.6138	0.0425*
H112	1.0737	0.8312	0.7531	0.0436*
H111	0.9082	0.8405	0.8586	0.0444*
H152	0.6075	0.3476	1.0124	0.0547*
H151	0.6960	0.2467	0.8845	0.0545*
H162	0.8619	0.2658	1.0269	0.0858*
H161	0.8453	0.4366	1.0086	0.0858*
H163	0.9346	0.3328	0.8875	0.0858*
H21	0.6783	1.0810	0.4814	0.0340*
H131	0.6679	0.9883	0.7985	0.0380*
H132	0.6990	1.0760	0.6639	0.0380*

	U11	U22	U33	U12	U13	U23
C1	0.0202 (8)	0.0264 (9)	0.0259 (9)	−0.0011 (6)	−0.0068 (7)	−0.0010 (7)
N1	0.0338 (9)	0.0213 (7)	0.0269 (8)	0.0003 (6)	−0.0122 (7)	−0.0028 (6)
O3	0.0480 (9)	0.0337 (7)	0.0313 (8)	0.0038 (6)	−0.0057 (6)	0.0066 (6)
C9	0.0293 (9)	0.0242 (8)	0.0237 (9)	−0.0009 (7)	−0.0087 (7)	0.0007 (7)
C2	0.0264 (9)	0.0269 (9)	0.0316 (10)	−0.0020 (7)	−0.0061 (8)	0.0012 (7)
C6	0.0268 (9)	0.0274 (9)	0.0258 (9)	−0.0008 (7)	−0.0066 (7)	0.0000 (7)
C5	0.0332 (10)	0.0331 (10)	0.0262 (9)	−0.0035 (8)	−0.0076 (8)	−0.0024 (7)
C4	0.0301 (10)	0.0422 (11)	0.0206 (9)	−0.0055 (8)	−0.0058 (7)	0.0036 (7)
O4	0.0801 (12)	0.0323 (8)	0.0403 (9)	0.0185 (8)	−0.0056 (8)	0.0011 (6)
O2	0.0985 (15)	0.0666 (11)	0.0350 (9)	−0.0240 (10)	−0.0255 (9)	−0.0007 (8)
C3	0.0245 (9)	0.0345 (10)	0.0313 (10)	−0.0025 (7)	−0.0048 (8)	0.0086 (8)
C7	0.0452 (11)	0.0265 (9)	0.0259 (10)	0.0021 (8)	−0.0115 (9)	−0.0037 (7)
C8	0.0326 (10)	0.0233 (9)	0.0276 (10)	0.0006 (7)	−0.0097 (8)	0.0001 (7)
C10	0.0302 (10)	0.0314 (10)	0.0361 (11)	0.0007 (8)	−0.0101 (8)	0.0039 (8)
N3	0.0402 (11)	0.0384 (10)	0.0596 (12)	−0.0061 (8)	−0.0174 (9)	−0.0034 (8)
N2	0.0455 (11)	0.0574 (12)	0.0267 (9)	−0.0062 (9)	−0.0076 (8)	0.0059 (8)
O1	0.0931 (14)	0.0654 (11)	0.0342 (9)	0.0056 (10)	−0.0195 (9)	0.0154 (8)
C13	0.0372 (11)	0.0257 (9)	0.0320 (10)	−0.0002 (8)	−0.0132 (8)	−0.0046 (7)
C17	0.0422 (12)	0.0223 (9)	0.0349 (10)	−0.0051 (8)	−0.0141 (9)	−0.0009 (7)
C12	0.0362 (11)	0.0338 (10)	0.0358 (11)	−0.0078 (8)	−0.0110 (9)	−0.0017 (8)
C14	0.0400 (11)	0.0265 (9)	0.0321 (10)	−0.0015 (8)	−0.0105 (9)	0.0009 (8)
C11	0.0282 (10)	0.0431 (11)	0.0378 (11)	−0.0062 (8)	−0.0108 (8)	0.0019 (9)
C15	0.0573 (14)	0.0401 (12)	0.0364 (12)	0.0018 (10)	−0.0088 (10)	0.0141 (9)
C16	0.0735 (19)	0.086 (2)	0.0595 (17)	−0.0018 (15)	−0.0330 (15)	0.0224 (14)

C1—N1	1.374 (2)	C7—H72	0.971
C1—C2	1.412 (2)	C8—C17	1.476 (3)
C1—C6	1.422 (2)	C8—C14	1.541 (2)
N1—C9	1.472 (2)	C10—C11	1.525 (3)
N1—C13	1.474 (2)	C10—H101	0.973
O3—C14	1.324 (2)	C10—H102	0.977
O3—C15	1.469 (2)	N3—C17	1.143 (2)
C9—C8	1.546 (2)	N2—O1	1.235 (2)
C9—C10	1.524 (3)	C13—C12	1.520 (3)
C9—H91	0.983	C13—H131	0.970
C2—C3	1.375 (3)	C13—H132	0.970
C2—H21	0.941	C12—C11	1.524 (3)
C6—C5	1.380 (2)	C12—H122	0.979
C6—C7	1.504 (2)	C12—H121	0.979
C5—C4	1.388 (3)	C11—H112	0.969
C5—H51	0.941	C11—H111	0.979
C4—C3	1.379 (3)	C15—C16	1.482 (4)
C4—N2	1.446 (2)	C15—H152	0.979
O4—C14	1.194 (2)	C15—H151	0.987
O2—N2	1.229 (2)	C16—H162	0.966
C3—H31	0.942	C16—H161	0.969
C7—C8	1.526 (2)	C16—H163	0.980
C7—H71	0.985
N1—C1—C2	121.61 (15)	C11—C10—H101	111.3
N1—C1—C6	120.57 (15)	C9—C10—H102	109.0
C2—C1—C6	117.69 (16)	C11—C10—H102	109.9
C1—N1—C9	121.40 (13)	H101—C10—H102	109.1
C1—N1—C13	122.69 (14)	C4—N2—O2	119.05 (17)
C9—N1—C13	109.99 (13)	C4—N2—O1	118.60 (18)
C14—O3—C15	117.40 (15)	O2—N2—O1	122.36 (18)
N1—C9—C8	109.45 (14)	N1—C13—C12	110.21 (14)
N1—C9—C10	110.06 (14)	N1—C13—H131	109.3
C8—C9—C10	114.36 (14)	C12—C13—H131	109.3
N1—C9—H91	107.0	N1—C13—H132	109.3
C8—C9—H91	108.0	C12—C13—H132	109.3
C10—C9—H91	107.7	H131—C13—H132	109.4
C1—C2—C3	121.40 (16)	C8—C17—N3	178.4 (2)
C1—C2—H21	119.3	C13—C12—C11	110.80 (15)
C3—C2—H21	119.3	C13—C12—H122	109.2
C1—C6—C5	120.13 (16)	C11—C12—H122	110.4
C1—C6—C7	120.45 (15)	C13—C12—H121	109.0
C5—C6—C7	119.41 (15)	C11—C12—H121	109.0
C6—C5—C4	120.19 (16)	H122—C12—H121	108.5
C6—C5—H51	119.8	C8—C14—O3	110.12 (15)
C4—C5—H51	120.0	C8—C14—O4	123.73 (18)
C5—C4—C3	120.93 (17)	O3—C14—O4	126.15 (17)
C5—C4—N2	119.57 (17)	C10—C11—C12	111.70 (16)
C3—C4—N2	119.49 (17)	C10—C11—H112	108.7
C4—C3—C2	119.60 (16)	C12—C11—H112	110.4
C4—C3—H31	119.5	C10—C11—H111	109.4
C2—C3—H31	120.9	C12—C11—H111	107.7
C6—C7—C8	110.18 (14)	H112—C11—H111	108.9
C6—C7—H71	110.2	O3—C15—C16	110.69 (19)
C8—C7—H71	108.6	O3—C15—H152	104.8
C6—C7—H72	110.0	C16—C15—H152	110.0
C8—C7—H72	110.7	O3—C15—H151	108.1
H71—C7—H72	107.2	C16—C15—H151	111.3
C9—C8—C7	109.74 (14)	H152—C15—H151	111.7
C9—C8—C17	108.75 (14)	C15—C16—H162	109.3
C7—C8—C17	109.52 (15)	C15—C16—H161	110.0
C9—C8—C14	109.75 (14)	H162—C16—H161	109.0
C7—C8—C14	111.10 (14)	C15—C16—H163	110.6
C17—C8—C14	107.93 (15)	H162—C16—H163	108.3
C9—C10—C11	109.16 (14)	H161—C16—H163	109.6
C9—C10—H101	108.3

D—H···A	D—H	H···A	D···A	D—H···A
C7—H72···N3i	0.97	2.56	3.492 (3)	161

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H72⋯N3i	0.97	2.56	3.492 (3)	161

Symmetry code: (i) .