Dimethyl 6-acetyl-2-methyl-1,2-dihydroquinoline-2,4-dicarboxyl-ate.

In the title compound, C(16)H(17)NO(5), the dihydro-pyridine ring adopts a sofa conformation. In the crystal, inter-molecular N-H⋯O hydrogen bonds link the mol-ecules into chains running along the b axis.

Related literature

For the methods reported in the literature for the preparation of 1,2-dihydro­quinolines, see: Hu et al. (2011 ▶); Yadav et al. (2007 ▶, 2008 ▶); Waldmann et al. (2008 ▶). For the biological activity of dihydro­quinolines, see: Craig & Pearson (1971 ▶); Muren & Weissman (1971 ▶); Hamann et al. (1998 ▶); He et al. (2003 ▶); LaMontagne et al. (1989 ▶). For related structures, see: Gültekin et al. (2010 ▶); Gültekin et al. (2011a ▶,b ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C16H17NO5

M = 303.31

Triclinic,

a = 7.9853 (7) Å

b = 8.3950 (7) Å

c = 12.4416 (11) Å

α = 89.308 (7)°

β = 74.436 (7)°

γ = 71.568 (7)°

V = 759.82 (12) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 173 K

0.36 × 0.34 × 0.31 mm

Data collection

Stoe IPDS II two-circle diffractometer

12439 measured reflections

2833 independent reflections

2507 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.121

S = 1.05

2833 reflections

207 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.26 e Å−3

Δρmin = −0.22 e Å−3

Data collection: X-AREA (Stoe & Cie, 2001 ▶); cell refinement: X-AREA; data reduction: X-AREA; 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 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812003650/xu5460sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812003650/xu5460Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812003650/xu5460Isup3.cml

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

C16H17NO5	Z = 2
Mr = 303.31	F(000) = 320
Triclinic, P1	Dx = 1.326 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9853 (7) Å	Cell parameters from 11792 reflections
b = 8.3950 (7) Å	θ = 3.5–25.9°
c = 12.4416 (11) Å	µ = 0.10 mm−1
α = 89.308 (7)°	T = 173 K
β = 74.436 (7)°	Block, light brown
γ = 71.568 (7)°	0.36 × 0.34 × 0.31 mm
V = 759.82 (12) Å3

Stoe IPDS II two-circle diffractometer	2507 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.044
Graphite monochromator	θmax = 25.6°, θmin = 3.4°
ω scans	h = −9→9
12439 measured reflections	k = −10→10
2833 independent reflections	l = −15→15

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0649P)2 + 0.2357P] where P = (Fo2 + 2Fc2)/3
2833 reflections	(Δ/σ)max < 0.001
207 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
O1	0.6972 (2)	−0.1203 (2)	0.18082 (12)	0.0633 (4)
O2	0.69874 (15)	−0.00298 (16)	0.34026 (9)	0.0414 (3)
O3	0.12719 (16)	0.61353 (14)	0.44347 (9)	0.0371 (3)
O4	0.29430 (17)	0.43432 (16)	0.53946 (10)	0.0443 (3)
O5	0.26090 (17)	0.80610 (14)	0.09807 (10)	0.0407 (3)
N1	0.31769 (19)	0.06145 (17)	0.22877 (11)	0.0332 (3)
H1	0.322 (3)	−0.019 (3)	0.1868 (16)	0.037 (5)*
C2	0.4058 (2)	0.01893 (18)	0.31827 (12)	0.0297 (3)
C3	0.34378 (19)	0.17245 (19)	0.39857 (12)	0.0286 (3)
H3	0.3402	0.1582	0.4733	0.034*
C4	0.29367 (18)	0.32849 (18)	0.36578 (12)	0.0271 (3)
C5	0.27307 (19)	0.50723 (18)	0.20096 (12)	0.0278 (3)
H5	0.2688	0.5999	0.2431	0.033*
C6	0.26233 (19)	0.52543 (19)	0.09059 (12)	0.0285 (3)
C7	0.2661 (2)	0.38508 (19)	0.02853 (12)	0.0312 (3)
H7	0.2549	0.3960	−0.0439	0.037*
C8	0.2861 (2)	0.23170 (19)	0.07329 (13)	0.0317 (3)
H8	0.2896	0.1398	0.0307	0.038*
C9	0.30114 (19)	0.21314 (18)	0.18284 (12)	0.0278 (3)
C10	0.28990 (18)	0.35501 (18)	0.24904 (12)	0.0266 (3)
C11	0.3554 (3)	−0.1283 (2)	0.37615 (15)	0.0416 (4)
H11A	0.3912	−0.2219	0.3219	0.062*
H11B	0.2252	−0.0943	0.4101	0.062*
H11C	0.4185	−0.1609	0.4327	0.062*
C12	0.6168 (2)	−0.04291 (18)	0.26972 (12)	0.0317 (3)
C13	0.8977 (2)	−0.0641 (3)	0.30643 (17)	0.0581 (6)
H13A	0.9424	−0.0192	0.3594	0.087*
H13B	0.9422	−0.0287	0.2337	0.087*
H13C	0.9403	−0.1849	0.3038	0.087*
C14	0.2280 (2)	0.47500 (19)	0.45107 (12)	0.0291 (3)
C15	0.2295 (3)	0.5639 (3)	0.63061 (15)	0.0539 (5)
H15A	0.2683	0.5165	0.6940	0.081*
H15B	0.0977	0.6081	0.6507	0.081*
H15C	0.2795	0.6528	0.6075	0.081*
C16	0.2474 (2)	0.69166 (19)	0.04489 (12)	0.0307 (3)
C17	0.2142 (3)	0.7197 (2)	−0.06869 (14)	0.0419 (4)
H17A	0.1961	0.8356	−0.0833	0.063*
H17B	0.1068	0.6923	−0.0700	0.063*
H17C	0.3186	0.6491	−0.1250	0.063*

	U11	U22	U33	U12	U13	U23
O1	0.0535 (8)	0.0781 (10)	0.0459 (8)	−0.0062 (7)	−0.0104 (6)	−0.0292 (7)
O2	0.0269 (6)	0.0580 (8)	0.0346 (6)	−0.0048 (5)	−0.0112 (5)	−0.0073 (5)
O3	0.0436 (6)	0.0307 (6)	0.0299 (6)	−0.0083 (5)	−0.0031 (5)	−0.0014 (4)
O4	0.0470 (7)	0.0484 (7)	0.0329 (6)	−0.0027 (5)	−0.0181 (5)	−0.0132 (5)
O5	0.0535 (7)	0.0332 (6)	0.0390 (6)	−0.0195 (5)	−0.0118 (5)	−0.0013 (5)
N1	0.0456 (8)	0.0279 (7)	0.0355 (7)	−0.0150 (6)	−0.0226 (6)	0.0018 (5)
C2	0.0348 (8)	0.0299 (7)	0.0302 (7)	−0.0130 (6)	−0.0154 (6)	0.0031 (6)
C3	0.0261 (7)	0.0362 (8)	0.0252 (7)	−0.0107 (6)	−0.0089 (5)	−0.0007 (6)
C4	0.0228 (7)	0.0319 (7)	0.0263 (7)	−0.0088 (6)	−0.0063 (5)	−0.0031 (6)
C5	0.0260 (7)	0.0290 (7)	0.0279 (7)	−0.0095 (6)	−0.0056 (6)	−0.0046 (6)
C6	0.0266 (7)	0.0313 (8)	0.0275 (7)	−0.0100 (6)	−0.0064 (6)	−0.0009 (6)
C7	0.0340 (8)	0.0353 (8)	0.0262 (7)	−0.0114 (6)	−0.0110 (6)	−0.0006 (6)
C8	0.0362 (8)	0.0306 (8)	0.0311 (8)	−0.0107 (6)	−0.0139 (6)	−0.0037 (6)
C9	0.0255 (7)	0.0296 (7)	0.0307 (7)	−0.0099 (6)	−0.0106 (6)	−0.0008 (6)
C10	0.0230 (7)	0.0307 (7)	0.0262 (7)	−0.0084 (6)	−0.0072 (5)	−0.0027 (6)
C11	0.0557 (11)	0.0401 (9)	0.0442 (9)	−0.0261 (8)	−0.0266 (8)	0.0126 (7)
C12	0.0389 (8)	0.0268 (7)	0.0292 (7)	−0.0073 (6)	−0.0129 (6)	0.0000 (6)
C13	0.0283 (9)	0.0824 (15)	0.0514 (11)	−0.0004 (9)	−0.0117 (8)	−0.0047 (10)
C14	0.0267 (7)	0.0353 (8)	0.0251 (7)	−0.0123 (6)	−0.0041 (5)	−0.0018 (6)
C15	0.0625 (12)	0.0587 (12)	0.0347 (9)	−0.0097 (10)	−0.0152 (8)	−0.0184 (8)
C16	0.0276 (7)	0.0323 (8)	0.0305 (8)	−0.0106 (6)	−0.0041 (6)	−0.0011 (6)
C17	0.0533 (10)	0.0393 (9)	0.0383 (9)	−0.0188 (8)	−0.0171 (8)	0.0095 (7)

O1—C12	1.196 (2)	C7—H7	0.9300
O2—C12	1.3287 (19)	C8—C7	1.376 (2)
O2—C13	1.447 (2)	C8—H8	0.9300
O3—C14	1.2063 (19)	C9—C8	1.403 (2)
O4—C14	1.3401 (19)	C10—C4	1.474 (2)
O4—C15	1.4476 (19)	C10—C5	1.387 (2)
O5—C16	1.2211 (19)	C10—C9	1.422 (2)
N1—C2	1.4540 (19)	C11—H11A	0.9600
N1—C9	1.372 (2)	C11—H11B	0.9600
N1—H1	0.85 (2)	C11—H11C	0.9600
C2—C11	1.531 (2)	C13—H13A	0.9600
C2—C12	1.543 (2)	C13—H13B	0.9600
C3—C2	1.505 (2)	C13—H13C	0.9600
C3—C4	1.336 (2)	C15—H15A	0.9600
C3—H3	0.9300	C15—H15B	0.9600
C4—C14	1.496 (2)	C15—H15C	0.9600
C5—C6	1.402 (2)	C16—C17	1.509 (2)
C5—H5	0.9300	C17—H17A	0.9600
C6—C7	1.404 (2)	C17—H17B	0.9600
C6—C16	1.482 (2)	C17—H17C	0.9600
C12—O2—C13	116.35 (13)	C9—C10—C4	116.55 (13)
C14—O4—C15	116.25 (14)	C2—C11—H11A	109.5
C2—N1—H1	117.4 (13)	C2—C11—H11B	109.5
C9—N1—C2	120.53 (12)	C2—C11—H11C	109.5
C9—N1—H1	116.4 (13)	H11A—C11—H11B	109.5
N1—C2—C3	108.66 (12)	H11A—C11—H11C	109.5
N1—C2—C11	109.05 (12)	H11B—C11—H11C	109.5
N1—C2—C12	110.27 (12)	O1—C12—O2	124.00 (15)
C3—C2—C11	111.68 (13)	O1—C12—C2	124.45 (14)
C3—C2—C12	110.74 (11)	O2—C12—C2	111.53 (12)
C11—C2—C12	106.42 (13)	O2—C13—H13A	109.5
C2—C3—H3	119.0	O2—C13—H13B	109.5
C4—C3—C2	122.03 (13)	O2—C13—H13C	109.5
C4—C3—H3	119.0	H13A—C13—H13B	109.5
C3—C4—C10	120.21 (13)	H13A—C13—H13C	109.5
C3—C4—C14	119.01 (13)	H13B—C13—H13C	109.5
C10—C4—C14	120.62 (13)	O3—C14—O4	123.01 (14)
C6—C5—H5	119.0	O3—C14—C4	125.35 (14)
C10—C5—C6	121.90 (13)	O4—C14—C4	111.64 (13)
C10—C5—H5	119.0	O4—C15—H15A	109.5
C5—C6—C7	118.37 (13)	O4—C15—H15B	109.5
C5—C6—C16	118.55 (13)	O4—C15—H15C	109.5
C7—C6—C16	123.08 (13)	H15A—C15—H15B	109.5
C6—C7—H7	119.5	H15A—C15—H15C	109.5
C8—C7—C6	121.02 (13)	H15B—C15—H15C	109.5
C8—C7—H7	119.5	O5—C16—C6	120.92 (14)
C7—C8—C9	120.37 (13)	O5—C16—C17	119.68 (14)
C7—C8—H8	119.8	C6—C16—C17	119.41 (13)
C9—C8—H8	119.8	C16—C17—H17A	109.5
N1—C9—C8	120.72 (13)	C16—C17—H17B	109.5
N1—C9—C10	119.52 (13)	H17A—C17—H17B	109.5
C8—C9—C10	119.69 (13)	C16—C17—H17C	109.5
C5—C10—C4	124.87 (13)	H17A—C17—H17C	109.5
C5—C10—C9	118.57 (13)	H17B—C17—H17C	109.5
C13—O2—C12—O1	−2.3 (3)	C10—C4—C14—O4	−159.98 (12)
C13—O2—C12—C2	176.23 (15)	C10—C5—C6—C7	1.0 (2)
C15—O4—C14—O3	3.7 (2)	C10—C5—C6—C16	−179.06 (13)
C15—O4—C14—C4	−176.03 (14)	C5—C6—C7—C8	−2.2 (2)
C9—N1—C2—C3	41.36 (19)	C16—C6—C7—C8	177.88 (14)
C9—N1—C2—C11	163.31 (14)	C5—C6—C16—O5	6.5 (2)
C9—N1—C2—C12	−80.19 (17)	C5—C6—C16—C17	−173.14 (13)
C2—N1—C9—C8	154.73 (14)	C7—C6—C16—O5	−173.48 (14)
C2—N1—C9—C10	−28.4 (2)	C7—C6—C16—C17	6.8 (2)
N1—C2—C12—O1	−33.1 (2)	C9—C8—C7—C6	0.7 (2)
N1—C2—C12—O2	148.35 (13)	N1—C9—C8—C7	178.80 (14)
C3—C2—C12—O1	−153.45 (17)	C10—C9—C8—C7	2.0 (2)
C3—C2—C12—O2	28.05 (17)	C5—C10—C4—C3	−167.68 (14)
C11—C2—C12—O1	85.0 (2)	C5—C10—C4—C14	17.1 (2)
C11—C2—C12—O2	−93.51 (15)	C9—C10—C4—C3	13.5 (2)
C4—C3—C2—N1	−28.33 (19)	C9—C10—C4—C14	−161.74 (13)
C4—C3—C2—C11	−148.66 (14)	C4—C10—C5—C6	−177.15 (13)
C4—C3—C2—C12	92.93 (16)	C9—C10—C5—C6	1.6 (2)
C2—C3—C4—C10	2.8 (2)	C4—C10—C9—N1	−1.1 (2)
C2—C3—C4—C14	178.09 (12)	C4—C10—C9—C8	175.78 (12)
C3—C4—C14—O3	−155.01 (15)	C5—C10—C9—N1	−179.95 (13)
C3—C4—C14—O4	24.69 (19)	C5—C10—C9—C8	−3.1 (2)
C10—C4—C14—O3	20.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5i	0.85 (2)	2.10 (2)	2.9223 (19)	166 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O5i	0.85 (2)	2.10 (2)	2.9223 (19)	166 (2)

Symmetry code: (i) .