Dimethyl 8-acetyl-2-methyl-1,2-dihydro-quinoline-2,4-dicarboxyl-ate.

In the title compound, C(16)H(17)NO(5), the six-membered N-containing ring has a half-boat form; the spiro C atom deviates by 0.34 (2) Å from the plane (r.m.s. deviation = 0.051 Å) defined by the N and four aromatic C atoms. Intra-molecular N-H⋯O hydrogen bonding generates an S(6) ring motif and the dihedral angle between the mean plane though the S(6) ring and that through the five-atom half-boat plane is 3.39 (2)°. In the crystal, weak inter-molecular C-H⋯O hydrogen bonds link mol-ecules into zigzag chains along [001] due to c-glide symmetry, and C-H⋯π inter-actions extend along [010].

Related literature

For the preparation of 1,2-dihydro­quinoline, see: Dauphinee & Forrest (1978 ▶); Katritzky et al. (1996 ▶); Elmore et al. (2001 ▶); Lu & Malinakova (2004 ▶); Wang et al. (2009 ▶); Rezgui et al. (1999 ▶). For related structures, see: Yadav et al. (2007 ▶); Kamakshi & Reddy (2007 ▶); Kim et al. (2001 ▶); Sundèn et al. (2007 ▶); Waldmann et al. (2008 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶). For graph-set theory, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C16H17NO5

M = 303.31

Monoclinic,

a = 8.0222 (3) Å

b = 18.2466 (9) Å

c = 10.3478 (4) Å

β = 101.042 (3)°

V = 1486.65 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 296 K

0.74 × 0.43 × 0.23 mm

Data collection

Stoe IPDS 2 diffractometer

Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T min = 0.823, T max = 0.968

14613 measured reflections

3068 independent reflections

2221 reflections with I > 2σ(I)

R int = 0.055

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.169

S = 1.07

14613 reflections

205 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.36 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811003564/si2329sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811003564/si2329Isup2.hkl

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

C16H17NO5	F(000) = 640
Mr = 303.31	Dx = 1.355 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 14613 reflections
a = 8.0222 (3) Å	θ = 2.0–28.0°
b = 18.2466 (9) Å	µ = 0.10 mm−1
c = 10.3478 (4) Å	T = 296 K
β = 101.042 (3)°	Prism, brown
V = 1486.65 (11) Å3	0.74 × 0.43 × 0.23 mm
Z = 4

Stoe IPDS 2 diffractometer	3068 independent reflections
Radiation source: fine-focus sealed tube	2221 reflections with I > 2σ(I)
graphite	Rint = 0.055
rotation method scans	θmax = 26.5°, θmin = 2.2°
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	h = −10→10
Tmin = 0.823, Tmax = 0.968	k = −22→22
14613 measured reflections	l = −12→12

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0846P)2 + 0.2827P] where P = (Fo2 + 2Fc2)/3
14613 reflections	(Δ/σ)max < 0.001
205 parameters	Δρmax = 0.43 e Å−3
1 restraint	Δρmin = −0.36 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 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.

	x	y	z	Uiso*/Ueq
C1	0.4104 (2)	0.37012 (12)	0.3615 (2)	0.0427 (5)
C2	0.5203 (3)	0.39441 (12)	0.4782 (2)	0.0458 (5)
C3	0.4559 (3)	0.39964 (14)	0.5939 (2)	0.0537 (6)
H3	0.5267	0.4161	0.6702	0.064*
C4	0.2911 (3)	0.38117 (16)	0.5987 (2)	0.0582 (6)
H4	0.2512	0.3853	0.6771	0.070*
C5	0.1846 (3)	0.35628 (15)	0.4853 (2)	0.0529 (6)
H5	0.0732	0.3436	0.4887	0.064*
C6	0.2403 (2)	0.34998 (13)	0.3675 (2)	0.0436 (5)
C7	0.6980 (3)	0.41517 (14)	0.4779 (2)	0.0507 (6)
C8	0.8065 (3)	0.44802 (16)	0.5984 (3)	0.0618 (7)
H8A	0.8402	0.4104	0.6630	0.074*
H8B	0.7431	0.4850	0.6341	0.074*
H8C	0.9058	0.4697	0.5751	0.074*
C9	0.1341 (2)	0.32351 (13)	0.2442 (2)	0.0454 (5)
C10	0.1863 (3)	0.32944 (14)	0.1302 (2)	0.0491 (5)
H10	0.1169	0.3113	0.0547	0.059*
C11	0.3514 (3)	0.36395 (13)	0.1178 (2)	0.0462 (5)
C12	−0.0356 (3)	0.28883 (15)	0.2385 (2)	0.0521 (6)
C13	−0.2120 (3)	0.21400 (18)	0.3394 (3)	0.0732 (8)
H13A	−0.2844	0.2489	0.3708	0.088*
H13B	−0.1979	0.1719	0.3960	0.088*
H13C	−0.2625	0.1993	0.2515	0.088*
C14	0.4362 (3)	0.32316 (16)	0.0183 (2)	0.0572 (6)
H14A	0.5410	0.3470	0.0119	0.069*
H14B	0.3620	0.3234	−0.0663	0.069*
H14C	0.4588	0.2735	0.0469	0.069*
C15	0.3165 (3)	0.44329 (14)	0.0688 (2)	0.0496 (6)
C16	0.1661 (4)	0.51590 (18)	−0.1039 (3)	0.0788 (9)
H16A	0.1176	0.5463	−0.0450	0.095*
H16B	0.0861	0.5102	−0.1851	0.095*
H16C	0.2678	0.5384	−0.1211	0.095*
N1	0.4639 (2)	0.36371 (12)	0.24524 (18)	0.0508 (5)
O1	0.7624 (2)	0.40668 (13)	0.38037 (19)	0.0708 (6)
O2	−0.1528 (2)	0.29932 (15)	0.1485 (2)	0.0906 (8)
O3	−0.0469 (2)	0.24724 (11)	0.33918 (18)	0.0657 (5)
O4	0.3796 (3)	0.49676 (12)	0.1243 (2)	0.0794 (6)
O5	0.2062 (2)	0.44499 (10)	−0.04465 (18)	0.0641 (5)
H1	0.566 (2)	0.3785 (15)	0.248 (3)	0.065 (8)*

	U11	U22	U33	U12	U13	U23
C1	0.0390 (10)	0.0448 (12)	0.0419 (11)	0.0046 (9)	0.0017 (8)	0.0007 (9)
C2	0.0438 (11)	0.0449 (12)	0.0450 (12)	0.0039 (9)	−0.0014 (9)	0.0003 (10)
C3	0.0524 (12)	0.0619 (16)	0.0425 (12)	−0.0001 (11)	−0.0015 (10)	−0.0073 (11)
C4	0.0540 (13)	0.0755 (18)	0.0454 (13)	0.0000 (12)	0.0099 (10)	−0.0068 (12)
C5	0.0463 (11)	0.0635 (15)	0.0486 (13)	0.0016 (10)	0.0081 (10)	−0.0037 (11)
C6	0.0397 (10)	0.0455 (12)	0.0431 (12)	0.0025 (8)	0.0018 (8)	−0.0009 (9)
C7	0.0441 (11)	0.0536 (14)	0.0507 (14)	0.0021 (10)	−0.0005 (10)	−0.0018 (11)
C8	0.0503 (12)	0.0684 (17)	0.0611 (16)	−0.0086 (11)	−0.0031 (11)	−0.0069 (13)
C9	0.0392 (10)	0.0497 (13)	0.0446 (12)	0.0008 (9)	0.0013 (9)	0.0021 (10)
C10	0.0422 (10)	0.0575 (14)	0.0440 (12)	−0.0040 (10)	−0.0007 (9)	−0.0034 (10)
C11	0.0407 (10)	0.0574 (14)	0.0391 (11)	−0.0018 (9)	0.0041 (8)	−0.0030 (10)
C12	0.0461 (12)	0.0657 (16)	0.0424 (12)	−0.0063 (10)	0.0027 (10)	−0.0011 (11)
C13	0.0639 (15)	0.086 (2)	0.0689 (18)	−0.0292 (15)	0.0113 (13)	0.0083 (16)
C14	0.0509 (12)	0.0676 (17)	0.0534 (15)	0.0019 (11)	0.0108 (10)	−0.0106 (12)
C15	0.0463 (11)	0.0599 (15)	0.0428 (12)	−0.0056 (10)	0.0095 (9)	−0.0046 (11)
C16	0.0801 (19)	0.077 (2)	0.074 (2)	0.0029 (16)	0.0012 (15)	0.0221 (17)
N1	0.0375 (9)	0.0726 (14)	0.0405 (10)	−0.0042 (9)	0.0032 (8)	−0.0029 (9)
O1	0.0446 (9)	0.1052 (16)	0.0605 (11)	−0.0100 (9)	0.0051 (8)	−0.0129 (11)
O2	0.0528 (10)	0.149 (2)	0.0624 (12)	−0.0263 (11)	−0.0078 (9)	0.0270 (13)
O3	0.0573 (9)	0.0731 (13)	0.0615 (11)	−0.0174 (8)	−0.0020 (8)	0.0178 (10)
O4	0.1003 (15)	0.0624 (12)	0.0673 (13)	−0.0137 (11)	−0.0043 (11)	−0.0087 (10)
O5	0.0648 (10)	0.0631 (12)	0.0566 (11)	−0.0039 (8)	−0.0079 (8)	0.0080 (9)

C1—N1	1.358 (3)	C10—H10	0.9300
C1—C2	1.423 (3)	C11—N1	1.448 (3)
C1—C6	1.426 (3)	C11—C14	1.531 (3)
C2—C3	1.395 (3)	C11—C15	1.542 (3)
C2—C7	1.475 (3)	C12—O2	1.205 (3)
C3—C4	1.374 (3)	C12—O3	1.306 (3)
C3—H3	0.9300	C13—O3	1.457 (3)
C4—C5	1.389 (3)	C13—H13A	0.9600
C4—H4	0.9300	C13—H13B	0.9600
C5—C6	1.381 (3)	C13—H13C	0.9600
C5—H5	0.9300	C14—H14A	0.9600
C6—C9	1.474 (3)	C14—H14B	0.9600
C7—O1	1.229 (3)	C14—H14C	0.9600
C7—C8	1.502 (3)	C15—O4	1.195 (3)
C8—H8A	0.9600	C15—O5	1.328 (3)
C8—H8B	0.9600	C16—O5	1.442 (3)
C8—H8C	0.9600	C16—H16A	0.9600
C9—C10	1.330 (3)	C16—H16B	0.9600
C9—C12	1.492 (3)	C16—H16C	0.9600
C10—C11	1.494 (3)	N1—H1	0.858 (17)
N1—C1—C2	121.97 (18)	N1—C11—C14	109.33 (18)
N1—C1—C6	118.91 (19)	C10—C11—C14	111.6 (2)
C2—C1—C6	119.11 (19)	N1—C11—C15	110.15 (19)
C3—C2—C1	118.56 (19)	C10—C11—C15	108.43 (18)
C3—C2—C7	120.1 (2)	C14—C11—C15	108.15 (19)
C1—C2—C7	121.3 (2)	O2—C12—O3	123.1 (2)
C4—C3—C2	122.1 (2)	O2—C12—C9	122.3 (2)
C4—C3—H3	118.9	O3—C12—C9	114.68 (19)
C2—C3—H3	118.9	O3—C13—H13A	109.5
C3—C4—C5	119.3 (2)	O3—C13—H13B	109.5
C3—C4—H4	120.3	H13A—C13—H13B	109.5
C5—C4—H4	120.3	O3—C13—H13C	109.5
C6—C5—C4	121.5 (2)	H13A—C13—H13C	109.5
C6—C5—H5	119.3	H13B—C13—H13C	109.5
C4—C5—H5	119.3	C11—C14—H14A	109.5
C5—C6—C1	119.4 (2)	C11—C14—H14B	109.5
C5—C6—C9	124.05 (19)	H14A—C14—H14B	109.5
C1—C6—C9	116.55 (19)	C11—C14—H14C	109.5
O1—C7—C2	121.9 (2)	H14A—C14—H14C	109.5
O1—C7—C8	117.6 (2)	H14B—C14—H14C	109.5
C2—C7—C8	120.5 (2)	O4—C15—O5	123.7 (2)
C7—C8—H8A	109.5	O4—C15—C11	125.1 (2)
C7—C8—H8B	109.5	O5—C15—C11	111.1 (2)
H8A—C8—H8B	109.5	O5—C16—H16A	109.5
C7—C8—H8C	109.5	O5—C16—H16B	109.5
H8A—C8—H8C	109.5	H16A—C16—H16B	109.5
H8B—C8—H8C	109.5	O5—C16—H16C	109.5
C10—C9—C6	120.85 (19)	H16A—C16—H16C	109.5
C10—C9—C12	116.1 (2)	H16B—C16—H16C	109.5
C6—C9—C12	123.04 (19)	C1—N1—C11	124.00 (17)
C9—C10—C11	123.1 (2)	C1—N1—H1	114.2 (19)
C9—C10—H10	118.5	C11—N1—H1	116.7 (19)
C11—C10—H10	118.5	C12—O3—C13	116.44 (19)
N1—C11—C10	109.17 (18)	C15—O5—C16	117.0 (2)
N1—C1—C2—C3	179.9 (2)	C12—C9—C10—C11	178.9 (2)
C6—C1—C2—C3	−1.8 (3)	C9—C10—C11—N1	20.8 (3)
N1—C1—C2—C7	1.1 (3)	C9—C10—C11—C14	141.8 (2)
C6—C1—C2—C7	179.3 (2)	C9—C10—C11—C15	−99.2 (3)
C1—C2—C3—C4	0.9 (4)	C10—C9—C12—O2	−37.6 (4)
C7—C2—C3—C4	179.8 (2)	C6—C9—C12—O2	142.5 (3)
C2—C3—C4—C5	0.2 (4)	C10—C9—C12—O3	143.2 (2)
C3—C4—C5—C6	−0.3 (4)	C6—C9—C12—O3	−36.7 (3)
C4—C5—C6—C1	−0.6 (4)	N1—C11—C15—O4	3.5 (3)
C4—C5—C6—C9	179.6 (2)	C10—C11—C15—O4	122.9 (3)
N1—C1—C6—C5	180.0 (2)	C14—C11—C15—O4	−115.9 (3)
C2—C1—C6—C5	1.7 (3)	N1—C11—C15—O5	−176.59 (17)
N1—C1—C6—C9	−0.2 (3)	C10—C11—C15—O5	−57.2 (2)
C2—C1—C6—C9	−178.5 (2)	C14—C11—C15—O5	64.0 (2)
C3—C2—C7—O1	175.0 (3)	C2—C1—N1—C11	−158.1 (2)
C1—C2—C7—O1	−6.1 (4)	C6—C1—N1—C11	23.6 (3)
C3—C2—C7—C8	−5.2 (4)	C10—C11—N1—C1	−32.7 (3)
C1—C2—C7—C8	173.6 (2)	C14—C11—N1—C1	−155.0 (2)
C5—C6—C9—C10	169.4 (2)	C15—C11—N1—C1	86.3 (3)
C1—C6—C9—C10	−10.4 (3)	O2—C12—O3—C13	−0.9 (4)
C5—C6—C9—C12	−10.7 (4)	C9—C12—O3—C13	178.3 (2)
C1—C6—C9—C12	169.5 (2)	O4—C15—O5—C16	1.8 (4)
C6—C9—C10—C11	−1.3 (4)	C11—C15—O5—C16	−178.1 (2)

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86 (2)	1.95 (2)	2.650 (2)	138 (2)
C10—H10···O3i	0.93	2.59	3.517 (3)	174
C14—H14C···Cg1i	0.96	2.89	3.692 (3)	142
C8—H8B···Cg1ii	0.96	2.85	3.501 (3)	126

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.86 (2)	1.95 (2)	2.650 (2)	138 (2)
C10—H10⋯O3i	0.93	2.59	3.517 (3)	174
C14—H14C⋯Cg1i	0.96	2.89	3.692 (3)	142
C8—H8B⋯Cg1ii	0.96	2.85	3.501 (3)	126

Symmetry codes: (i) ; (ii) .