Dimethyl 6-iodo-2-methyl-1,2-di-hydro-quinoline-2,4-di-carboxyl-ate.

In the title compound, C14H14INO4, the di-hydro-pyridine ring adopts a twist conformation. In the crystal, pairs of N-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules into inversion R 2 (2)(10) and R 2 (2)(18) dimers, forming infinite double chains running along the c axis.

Related literature

For the conversion of 1,2-di­hydro­quinoline derivatives to the syntheses of quinolines, see: Dauphinee & Forrest (1978 ▶). For the conversion of 1,2-di­hydro­quinoline derivatives to the syntheses of 1,2,3,4-tetra­hydro­quinolines, see: Katritzky et al. (1996 ▶). For literature methods for the preparation of 1,2-di­hydro­quinolines, see: Dauphinee & Forrest (1978 ▶); Durgadas et al. (2010 ▶); Gültekin & Frey (2012 ▶); Makino et al. (2003 ▶); Yadav et al. (2007 ▶); Waldmann et al. (2008 ▶). For related structures, see: Gültekin et al. (2010 ▶, 2011a ▶,b ▶, 2012a ▶,b ▶). For ring puckering parameters, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C14H14INO4

M = 387.16

Triclinic,

a = 7.7994 (14) Å

b = 10.2797 (8) Å

c = 10.8056 (8) Å

α = 116.862 (3)°

β = 103.956 (4)°

γ = 96.780 (4)°

V = 723.80 (16) Å3

Z = 2

Mo Kα radiation

μ = 2.22 mm−1

T = 100 K

0.76 × 0.65 × 0.48 mm

Data collection

Bruker Kappa APEXII DUO diffractometer

Absorption correction: numerical (Blessing, 1995 ▶) T min = 0.283, T max = 0.415

43287 measured reflections

7044 independent reflections

6902 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.073

S = 1.24

7044 reflections

190 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.88 e Å−3

Δρmin = −1.54 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; 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, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813023544/gw2137sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813023544/gw2137Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813023544/gw2137Isup3.cml

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

C14H14INO4	Z = 2
Mr = 387.16	F(000) = 380
Triclinic, P1	Dx = 1.776 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7994 (14) Å	Cell parameters from 6892 reflections
b = 10.2797 (8) Å	θ = 2.3–36.5°
c = 10.8056 (8) Å	µ = 2.22 mm−1
α = 116.862 (3)°	T = 100 K
β = 103.956 (4)°	Block, yellow
γ = 96.780 (4)°	0.76 × 0.65 × 0.48 mm
V = 723.80 (16) Å3

Bruker Kappa APEXII DUO diffractometer	7044 independent reflections
Radiation source: fine-focus sealed tube	6902 reflections with I > 2σ(I)
Triumph monochromator	Rint = 0.032
φ and ω scans	θmax = 36.5°, θmin = 2.3°
Absorption correction: numerical (Blessing, 1995)	h = −13→13
Tmin = 0.283, Tmax = 0.415	k = −17→17
43287 measured reflections	l = −18→18

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)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.073	w = 1/[σ2(Fo2) + (0.0263P)2 + 0.7072P] where P = (Fo2 + 2Fc2)/3
S = 1.24	(Δ/σ)max < 0.001
7044 reflections	Δρmax = 1.88 e Å−3
190 parameters	Δρmin = −1.54 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: 0.0715 (18)

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
I1	0.017285 (15)	0.670510 (12)	0.215800 (11)	0.02370 (4)
O1	0.28824 (19)	0.31504 (13)	0.37768 (13)	0.0217 (2)
O2	0.34912 (17)	0.25624 (12)	0.55598 (13)	0.01879 (18)
O3	0.69165 (15)	0.92071 (11)	0.93569 (13)	0.01678 (17)
O4	0.78140 (13)	0.71616 (12)	0.92154 (12)	0.01509 (16)
N1	0.32777 (15)	0.77436 (13)	0.85280 (12)	0.01270 (17)
H1	0.335 (4)	0.858 (2)	0.920 (2)	0.020 (6)*
C1	0.46679 (16)	0.70426 (14)	0.88944 (13)	0.01127 (17)
C2	0.42693 (16)	0.54604 (14)	0.76450 (14)	0.01201 (18)
H2	0.472 (3)	0.475 (3)	0.787 (3)	0.013 (5)*
C3	0.33684 (16)	0.50661 (14)	0.62481 (14)	0.01130 (17)
C4	0.26466 (16)	0.61703 (14)	0.59074 (14)	0.01143 (17)
C5	0.19306 (18)	0.59520 (15)	0.44880 (15)	0.01460 (19)
H5	0.1942	0.5060	0.3664	0.018*
C6	0.12035 (19)	0.70379 (16)	0.42832 (15)	0.0157 (2)
C7	0.11561 (19)	0.83472 (16)	0.54662 (16)	0.0165 (2)
H7	0.0636	0.9073	0.5310	0.020*
C8	0.18759 (18)	0.85846 (15)	0.68790 (15)	0.0149 (2)
H8	0.1851	0.9481	0.7693	0.018*
C9	0.26382 (16)	0.75191 (14)	0.71195 (14)	0.01145 (17)
C10	0.47035 (19)	0.70673 (18)	1.03339 (15)	0.0169 (2)
H10A	0.4966	0.8115	1.1121	0.025*
H10B	0.5656	0.6607	1.0599	0.025*
H10C	0.3511	0.6496	1.0199	0.025*
C11	0.65818 (16)	0.79393 (14)	0.91643 (13)	0.01153 (17)
C12	0.96471 (18)	0.78904 (19)	0.94143 (18)	0.0191 (2)
H12A	1.0454	0.7234	0.9438	0.029*
H12B	1.0110	0.8854	1.0343	0.029*
H12C	0.9615	0.8076	0.8597	0.029*
C13	0.31983 (17)	0.35216 (14)	0.50561 (15)	0.01327 (19)
C14	0.3488 (3)	0.10914 (18)	0.4461 (2)	0.0252 (3)
H14A	0.3710	0.0458	0.4910	0.038*
H14B	0.4454	0.1193	0.4050	0.038*
H14C	0.2297	0.0621	0.3674	0.038*

	U11	U22	U33	U12	U13	U23
I1	0.02815 (6)	0.02630 (6)	0.01695 (5)	0.00288 (4)	0.00133 (4)	0.01504 (4)
O1	0.0310 (6)	0.0176 (4)	0.0144 (4)	0.0086 (4)	0.0071 (4)	0.0059 (4)
O2	0.0239 (5)	0.0128 (4)	0.0208 (5)	0.0062 (3)	0.0069 (4)	0.0093 (4)
O3	0.0174 (4)	0.0108 (4)	0.0201 (4)	0.0024 (3)	0.0085 (3)	0.0053 (3)
O4	0.0096 (3)	0.0185 (4)	0.0204 (4)	0.0040 (3)	0.0045 (3)	0.0124 (4)
N1	0.0118 (4)	0.0151 (4)	0.0112 (4)	0.0057 (3)	0.0040 (3)	0.0060 (3)
C1	0.0095 (4)	0.0137 (4)	0.0106 (4)	0.0023 (3)	0.0028 (3)	0.0065 (4)
C2	0.0111 (4)	0.0128 (4)	0.0128 (4)	0.0024 (3)	0.0030 (3)	0.0076 (4)
C3	0.0104 (4)	0.0116 (4)	0.0119 (4)	0.0021 (3)	0.0031 (3)	0.0063 (4)
C4	0.0106 (4)	0.0121 (4)	0.0117 (4)	0.0024 (3)	0.0028 (3)	0.0066 (4)
C5	0.0158 (5)	0.0150 (5)	0.0125 (5)	0.0025 (4)	0.0028 (4)	0.0078 (4)
C6	0.0162 (5)	0.0177 (5)	0.0149 (5)	0.0033 (4)	0.0025 (4)	0.0109 (4)
C7	0.0163 (5)	0.0184 (5)	0.0186 (5)	0.0068 (4)	0.0048 (4)	0.0123 (5)
C8	0.0149 (5)	0.0159 (5)	0.0163 (5)	0.0071 (4)	0.0056 (4)	0.0090 (4)
C9	0.0097 (4)	0.0134 (4)	0.0119 (4)	0.0033 (3)	0.0036 (3)	0.0068 (4)
C10	0.0163 (5)	0.0237 (6)	0.0134 (5)	0.0042 (4)	0.0055 (4)	0.0114 (5)
C11	0.0108 (4)	0.0129 (4)	0.0098 (4)	0.0025 (3)	0.0035 (3)	0.0049 (4)
C12	0.0099 (4)	0.0269 (6)	0.0230 (6)	0.0032 (4)	0.0048 (4)	0.0149 (5)
C13	0.0123 (4)	0.0122 (4)	0.0143 (5)	0.0025 (3)	0.0039 (4)	0.0062 (4)
C14	0.0297 (7)	0.0140 (5)	0.0318 (8)	0.0092 (5)	0.0120 (6)	0.0095 (5)

I1—C6	2.0908 (14)	C4—C9	1.4154 (17)
N1—C1	1.4447 (17)	C5—C6	1.3888 (19)
N1—C9	1.3812 (17)	C5—H5	0.9500
N1—H1	0.821 (17)	C6—C7	1.388 (2)
O1—C13	1.2059 (17)	C7—C8	1.387 (2)
O2—C13	1.3412 (17)	C7—H7	0.9500
O2—C14	1.439 (2)	C8—C9	1.3989 (18)
O3—C11	1.2075 (16)	C8—H8	0.9500
O4—C11	1.3273 (16)	C10—H10A	0.9800
O4—C12	1.4508 (17)	C10—H10B	0.9800
C1—C2	1.5028 (18)	C10—H10C	0.9800
C1—C10	1.5376 (18)	C12—H12A	0.9800
C1—C11	1.5444 (17)	C12—H12B	0.9800
C2—C3	1.3435 (18)	C12—H12C	0.9800
C2—H2	0.94 (2)	C14—H14A	0.9800
C3—C4	1.4728 (17)	C14—H14B	0.9800
C3—C13	1.4890 (18)	C14—H14C	0.9800
C4—C5	1.4002 (18)
C13—O2—C14	114.26 (13)	C7—C8—H8	119.6
C11—O4—C12	115.43 (11)	C9—C8—H8	119.6
C1—N1—H1	115 (2)	N1—C9—C4	120.20 (11)
C9—N1—C1	120.03 (10)	N1—C9—C8	119.93 (11)
C9—N1—H1	116 (2)	C8—C9—C4	119.75 (11)
N1—C1—C2	109.26 (10)	C1—C10—H10A	109.5
N1—C1—C10	108.89 (10)	C1—C10—H10B	109.5
N1—C1—C11	110.73 (10)	C1—C10—H10C	109.5
C2—C1—C10	111.83 (11)	H10A—C10—H10B	109.5
C2—C1—C11	108.91 (10)	H10A—C10—H10C	109.5
C10—C1—C11	107.20 (10)	H10B—C10—H10C	109.5
C1—C2—H2	117.7 (15)	O3—C11—O4	124.68 (12)
C3—C2—C1	121.91 (11)	O3—C11—C1	123.96 (11)
C3—C2—H2	120.4 (15)	O4—C11—C1	111.31 (11)
C2—C3—C4	120.28 (11)	O4—C12—H12A	109.5
C2—C3—C13	118.60 (11)	O4—C12—H12B	109.5
C4—C3—C13	121.05 (11)	O4—C12—H12C	109.5
C5—C4—C3	124.75 (11)	H12A—C12—H12B	109.5
C5—C4—C9	118.89 (11)	H12A—C12—H12C	109.5
C9—C4—C3	116.33 (11)	H12B—C12—H12C	109.5
C4—C5—H5	119.9	O1—C13—O2	122.31 (13)
C6—C5—C4	120.11 (12)	O1—C13—C3	125.09 (12)
C6—C5—H5	119.9	O2—C13—C3	112.57 (11)
C5—C6—I1	119.55 (10)	O2—C14—H14A	109.5
C7—C6—I1	119.26 (10)	O2—C14—H14B	109.5
C7—C6—C5	121.19 (12)	O2—C14—H14C	109.5
C6—C7—H7	120.3	H14A—C14—H14B	109.5
C8—C7—C6	119.31 (12)	H14A—C14—H14C	109.5
C8—C7—H7	120.3	H14B—C14—H14C	109.5
C7—C8—C9	120.73 (12)
C14—O2—C13—O1	3.0 (2)	C2—C3—C4—C9	−11.93 (17)
C14—O2—C13—C3	−175.15 (12)	C13—C3—C4—C5	−6.82 (18)
C12—O4—C11—O3	−4.60 (19)	C13—C3—C4—C9	171.05 (11)
C12—O4—C11—C1	177.95 (11)	C2—C3—C13—O1	−159.19 (14)
C9—N1—C1—C2	−40.61 (15)	C2—C3—C13—O2	18.92 (16)
C9—N1—C1—C10	−163.02 (11)	C4—C3—C13—O1	17.9 (2)
C9—N1—C1—C11	79.35 (14)	C4—C3—C13—O2	−164.00 (11)
C1—N1—C9—C4	28.53 (17)	C3—C4—C5—C6	176.90 (12)
C1—N1—C9—C8	−155.41 (12)	C9—C4—C5—C6	−0.92 (19)
N1—C1—C2—C3	28.17 (16)	C3—C4—C9—N1	−0.21 (17)
C10—C1—C2—C3	148.81 (12)	C3—C4—C9—C8	−176.28 (11)
C11—C1—C2—C3	−92.90 (14)	C5—C4—C9—N1	177.79 (11)
N1—C1—C11—O3	14.82 (17)	C5—C4—C9—C8	1.72 (18)
N1—C1—C11—O4	−167.70 (10)	C4—C5—C6—I1	179.18 (9)
C2—C1—C11—O3	134.99 (13)	C4—C5—C6—C7	−0.5 (2)
C2—C1—C11—O4	−47.53 (14)	I1—C6—C7—C8	−178.59 (10)
C10—C1—C11—O3	−103.84 (15)	C5—C6—C7—C8	1.1 (2)
C10—C1—C11—O4	73.64 (13)	C6—C7—C8—C9	−0.2 (2)
C1—C2—C3—C4	−3.42 (18)	C7—C8—C9—N1	−177.23 (12)
C1—C2—C3—C13	173.68 (11)	C7—C8—C9—C4	−1.15 (19)
C2—C3—C4—C5	170.20 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3i	0.82 (2)	2.17 (2)	2.9795 (19)	169 (2)
C5—H5···O1	0.95	2.22	2.866 (2)	125
C12—H12C···O1ii	0.98	2.46	3.132 (2)	126

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3i	0.82 (2)	2.17 (2)	2.9795 (19)	169 (2)
C5—H5⋯O1	0.95	2.22	2.866 (2)	125
C12—H12C⋯O1ii	0.98	2.46	3.132 (2)	126

Symmetry codes: (i) ; (ii) .