Dimethyl 6-bromo-2-methyl-1,2-di-hydro-quinoline-2,4-dicarboxyl-ate.

In the title compound, C(14)H(14)BrNO(4), the dihydro-pyridine ring adopts a screw-boat conformation. In the crystal, pairs of N-H⋯O hydrogen bonds link the mol-ecules into inversion R(2) (2)(10) dimers.

Related literature

For the synthesis of 1,2-dihydro­quinolines, see: Hu et al. (2011 ▶); Yadav et al. (2007 ▶, 2008 ▶); Waldmann et al. (2008 ▶); Zhang & Ji (2011 ▶). 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 ▶, 2011 ▶, 2012 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C14H14BrNO4

M = 340.16

Triclinic,

a = 7.8273 (9) Å

b = 10.4827 (11) Å

c = 10.5029 (12) Å

α = 115.837 (9)°

β = 105.655 (9)°

γ = 96.889 (8)°

V = 718.25 (17) Å3

Z = 2

Mo Kα radiation

μ = 2.87 mm−1

T = 173 K

0.33 × 0.32 × 0.22 mm

Data collection

Stoe IPDS II two-circle diffractometer

Absorption correction: multi-scan (MULABS; Spek, 2009 ▶; Blessing, 1995 ▶) T min = 0.451, T max = 0.571

7423 measured reflections

2692 independent reflections

2267 reflections with I > 2σ(I)

R int = 0.045

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.153

S = 1.21

2692 reflections

189 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.96 e Å−3

Δρmin = −0.46 e Å−3

Data collection: X-AREA (Stoe & Cie, 2001 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2001 ▶); 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/S1600536812005600/xu5465sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812005600/xu5465Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812005600/xu5465Isup3.cml

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

C14H14BrNO4	Z = 2
Mr = 340.16	F(000) = 344
Triclinic, P1	Dx = 1.573 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8273 (9) Å	Cell parameters from 6851 reflections
b = 10.4827 (11) Å	θ = 3.5–25.9°
c = 10.5029 (12) Å	µ = 2.87 mm−1
α = 115.837 (9)°	T = 173 K
β = 105.655 (9)°	Block, yellow
γ = 96.889 (8)°	0.33 × 0.32 × 0.22 mm
V = 718.25 (17) Å3

Stoe IPDS II two-circle diffractometer	2692 independent reflections
Radiation source: fine-focus sealed tube	2267 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
ω scans	θmax = 25.6°, θmin = 3.5°
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)	h = −9→9
Tmin = 0.451, Tmax = 0.571	k = −12→12
7423 measured reflections	l = −12→12

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.153	w = 1/[σ2(Fo2) + (0.0648P)2 + 1.4243P] where P = (Fo2 + 2Fc2)/3
S = 1.21	(Δ/σ)max < 0.001
2692 reflections	Δρmax = 0.96 e Å−3
189 parameters	Δρmin = −0.46 e Å−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.038 (5)

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
Br1	0.98733 (9)	0.36331 (7)	0.80285 (6)	0.0521 (3)
O1	0.3080 (4)	0.0758 (4)	0.0556 (4)	0.0340 (8)
O2	0.2146 (4)	0.2722 (4)	0.0660 (4)	0.0309 (7)
O3	0.7138 (6)	0.6908 (4)	0.6183 (4)	0.0453 (9)
O4	0.6368 (5)	0.7295 (4)	0.4208 (4)	0.0400 (8)
N1	0.6748 (5)	0.2278 (4)	0.1501 (4)	0.0280 (8)
H1	0.678 (13)	0.138 (5)	0.085 (9)	0.11 (3)*
C2	0.5298 (6)	0.2890 (5)	0.1017 (5)	0.0262 (9)
C3	0.5671 (6)	0.4450 (5)	0.2227 (5)	0.0256 (9)
H3	0.5245	0.5116	0.1950	0.031*
C4	0.6599 (6)	0.4919 (5)	0.3699 (5)	0.0249 (9)
C5	0.8118 (6)	0.4208 (5)	0.5664 (5)	0.0308 (10)
H5	0.8093	0.5073	0.6451	0.037*
C6	0.8886 (6)	0.3213 (6)	0.5976 (5)	0.0326 (10)
C7	0.8965 (7)	0.1930 (6)	0.4853 (6)	0.0368 (11)
H7	0.9516	0.1288	0.5096	0.044*
C8	0.8212 (6)	0.1596 (5)	0.3345 (5)	0.0305 (10)
H8	0.8243	0.0720	0.2577	0.037*
C9	0.7412 (5)	0.2573 (5)	0.2986 (5)	0.0239 (9)
C10	0.7378 (6)	0.3919 (5)	0.4170 (5)	0.0237 (9)
C11	0.5237 (7)	0.2779 (6)	−0.0504 (5)	0.0374 (11)
H11A	0.5022	0.1767	−0.1236	0.056*
H11B	0.6393	0.3348	−0.0369	0.056*
H11C	0.4260	0.3153	−0.0856	0.056*
C12	0.3391 (6)	0.1982 (5)	0.0735 (5)	0.0250 (9)
C13	0.0293 (6)	0.1986 (6)	0.0410 (6)	0.0375 (11)
H13A	−0.0441	0.2672	0.0560	0.056*
H13B	0.0354	0.1623	0.1113	0.056*
H13C	−0.0256	0.1177	−0.0608	0.056*
C14	0.6766 (6)	0.6451 (5)	0.4849 (5)	0.0296 (10)
C15	0.6353 (10)	0.8756 (7)	0.5235 (8)	0.0572 (16)
H15A	0.6072	0.9287	0.4692	0.086*
H15B	0.7543	0.9266	0.6029	0.086*
H15C	0.5434	0.8686	0.5668	0.086*

	U11	U22	U33	U12	U13	U23
Br1	0.0640 (4)	0.0637 (5)	0.0362 (3)	0.0183 (3)	0.0110 (3)	0.0345 (3)
O1	0.0334 (17)	0.0248 (17)	0.0434 (19)	0.0079 (14)	0.0182 (14)	0.0139 (15)
O2	0.0225 (15)	0.0373 (18)	0.0417 (18)	0.0120 (13)	0.0114 (13)	0.0257 (15)
O3	0.060 (2)	0.035 (2)	0.0338 (19)	0.0175 (18)	0.0171 (17)	0.0102 (16)
O4	0.054 (2)	0.0290 (18)	0.050 (2)	0.0216 (16)	0.0250 (18)	0.0240 (16)
N1	0.0270 (19)	0.032 (2)	0.0267 (18)	0.0135 (16)	0.0107 (15)	0.0142 (17)
C2	0.024 (2)	0.033 (2)	0.026 (2)	0.0108 (18)	0.0100 (17)	0.0169 (19)
C3	0.022 (2)	0.029 (2)	0.033 (2)	0.0087 (17)	0.0116 (17)	0.0196 (19)
C4	0.024 (2)	0.027 (2)	0.031 (2)	0.0083 (17)	0.0130 (17)	0.0186 (19)
C5	0.033 (2)	0.034 (3)	0.029 (2)	0.010 (2)	0.0124 (18)	0.018 (2)
C6	0.033 (2)	0.041 (3)	0.031 (2)	0.009 (2)	0.0105 (19)	0.025 (2)
C7	0.032 (2)	0.046 (3)	0.048 (3)	0.016 (2)	0.015 (2)	0.035 (3)
C8	0.029 (2)	0.030 (2)	0.036 (2)	0.0144 (19)	0.0129 (19)	0.016 (2)
C9	0.0187 (19)	0.030 (2)	0.029 (2)	0.0077 (17)	0.0115 (16)	0.0171 (18)
C10	0.023 (2)	0.025 (2)	0.028 (2)	0.0072 (17)	0.0108 (16)	0.0157 (18)
C11	0.037 (3)	0.050 (3)	0.032 (2)	0.014 (2)	0.015 (2)	0.024 (2)
C12	0.025 (2)	0.030 (2)	0.0205 (19)	0.0074 (18)	0.0099 (16)	0.0120 (17)
C13	0.022 (2)	0.047 (3)	0.050 (3)	0.007 (2)	0.011 (2)	0.030 (3)
C14	0.026 (2)	0.030 (2)	0.038 (3)	0.0093 (18)	0.0155 (19)	0.019 (2)
C15	0.073 (4)	0.034 (3)	0.079 (4)	0.031 (3)	0.040 (4)	0.029 (3)

Br1—C6	1.905 (5)	C8—H8	0.9300
O2—C13	1.455 (5)	C9—C8	1.395 (6)
O4—C15	1.442 (7)	C10—C5	1.393 (6)
N1—C2	1.452 (6)	C10—C9	1.427 (6)
N1—C9	1.380 (6)	C11—H11A	0.9600
N1—H1	0.899 (10)	C11—H11B	0.9600
C2—C3	1.499 (6)	C11—H11C	0.9600
C2—C11	1.537 (6)	C12—O1	1.197 (6)
C2—C12	1.548 (6)	C12—O2	1.322 (5)
C3—C4	1.344 (6)	C13—H13A	0.9600
C3—H3	0.9300	C13—H13B	0.9600
C4—C10	1.469 (6)	C13—H13C	0.9600
C4—C14	1.493 (6)	C14—O3	1.200 (6)
C5—H5	0.9300	C14—O4	1.344 (6)
C6—C5	1.378 (7)	C15—H15A	0.9600
C7—C6	1.371 (8)	C15—H15B	0.9600
C7—H7	0.9300	C15—H15C	0.9600
C8—C7	1.393 (7)
C12—O2—C13	116.0 (4)	N1—C9—C10	120.0 (4)
C14—O4—C15	114.8 (4)	C8—C9—C10	119.7 (4)
C2—N1—H1	119 (6)	C5—C10—C4	125.1 (4)
C9—N1—C2	120.0 (4)	C5—C10—C9	118.7 (4)
C9—N1—H1	112 (6)	C9—C10—C4	116.2 (4)
N1—C2—C3	109.0 (3)	C2—C11—H11A	109.5
N1—C2—C11	108.4 (4)	C2—C11—H11B	109.5
N1—C2—C12	110.7 (4)	C2—C11—H11C	109.5
C3—C2—C11	112.4 (4)	H11A—C11—H11B	109.5
C3—C2—C12	109.3 (4)	H11A—C11—H11C	109.5
C11—C2—C12	107.0 (3)	H11B—C11—H11C	109.5
C2—C3—H3	118.8	O1—C12—O2	124.9 (4)
C4—C3—C2	122.3 (4)	O1—C12—C2	124.3 (4)
C4—C3—H3	118.8	O2—C12—C2	110.7 (4)
C3—C4—C10	120.3 (4)	O2—C13—H13A	109.5
C3—C4—C14	119.0 (4)	O2—C13—H13B	109.5
C10—C4—C14	120.7 (4)	O2—C13—H13C	109.5
C6—C5—C10	120.0 (4)	H13A—C13—H13B	109.5
C6—C5—H5	120.0	H13A—C13—H13C	109.5
C10—C5—H5	120.0	H13B—C13—H13C	109.5
C5—C6—Br1	119.1 (4)	O3—C14—O4	121.9 (5)
C7—C6—Br1	119.0 (4)	O3—C14—C4	126.2 (4)
C7—C6—C5	122.0 (4)	O4—C14—C4	111.8 (4)
C6—C7—C8	119.5 (4)	O4—C15—H15A	109.5
C6—C7—H7	120.2	O4—C15—H15B	109.5
C8—C7—H7	120.2	O4—C15—H15C	109.5
C7—C8—C9	120.1 (4)	H15A—C15—H15B	109.5
C7—C8—H8	120.0	H15A—C15—H15C	109.5
C9—C8—H8	120.0	H15B—C15—H15C	109.5
N1—C9—C8	120.1 (4)
C9—N1—C2—C3	40.9 (5)	C3—C4—C14—O4	−16.6 (6)
C9—N1—C2—C11	163.5 (4)	C10—C4—C14—O3	−17.1 (7)
C9—N1—C2—C12	−79.4 (5)	C10—C4—C14—O4	165.6 (4)
C2—N1—C9—C8	154.6 (4)	Br1—C6—C5—C10	−179.6 (3)
C2—N1—C9—C10	−29.0 (6)	C7—C6—C5—C10	0.5 (7)
N1—C2—C3—C4	−28.2 (6)	C8—C7—C6—Br1	178.6 (4)
C11—C2—C3—C4	−148.4 (4)	C8—C7—C6—C5	−1.5 (7)
C12—C2—C3—C4	92.9 (5)	C9—C8—C7—C6	1.0 (7)
N1—C2—C12—O1	−17.8 (6)	N1—C9—C8—C7	176.8 (4)
N1—C2—C12—O2	164.7 (3)	C10—C9—C8—C7	0.4 (7)
C3—C2—C12—O1	−137.9 (4)	C4—C10—C5—C6	−177.1 (4)
C3—C2—C12—O2	44.6 (4)	C9—C10—C5—C6	0.9 (6)
C11—C2—C12—O1	100.1 (5)	C4—C10—C9—N1	0.4 (6)
C11—C2—C12—O2	−77.4 (4)	C4—C10—C9—C8	176.9 (4)
C2—C3—C4—C10	3.3 (6)	C5—C10—C9—N1	−177.8 (4)
C2—C3—C4—C14	−174.5 (4)	C5—C10—C9—C8	−1.3 (6)
C3—C4—C10—C5	−169.9 (4)	O1—C12—O2—C13	3.0 (6)
C3—C4—C10—C9	12.0 (6)	C2—C12—O2—C13	−179.5 (4)
C14—C4—C10—C5	7.9 (7)	O3—C14—O4—C15	−2.4 (7)
C14—C4—C10—C9	−170.2 (4)	C4—C14—O4—C15	175.1 (4)
C3—C4—C14—O3	160.7 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.90 (8)	2.12 (8)	3.013 (6)	176 (7)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.90 (8)	2.12 (8)	3.013 (6)	176 (7)

Symmetry code: (i) .