Dimethyl 2-(3-chloro-phen-yl)-6-hy-droxy-6-methyl-4-(methyl-amino)-cyclo-hex-3-ene-1,3-dicarboxyl-ate.

In the title compound, C(18)H(22)ClNO(5), the cyclo-hexene ring adopts a distorted half-chair conformation. The mol-ecular structure is stabilized by pairs of intra-molecular N-H⋯O and O-H⋯O inter-actions, generating S(6) motifs. In the crystal, the mol-ecules are linked by inter-molecular C-H⋯O inter-actions, forming centrosymmetric dimers.

Related literature

For the synthesis see: Pandiarajan et al. (2005 ▶). For related structures, see: Amézquita-Valencia et al. (2009, ▶ 2010) ▶; Venter et al. (2010 ▶). For ring conformational analysis, see: Cremer & Pople (1975 ▶); Nardelli (1983 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C18H22ClNO5

M = 367.82

Monoclinic,

a = 11.962 (3) Å

b = 9.118 (4) Å

c = 17.704 (5) Å

β = 104.890 (3)°

V = 1866.1 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.23 mm−1

T = 293 K

0.25 × 0.22 × 0.2 mm

Data collection

Bruker SMART APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.944, T max = 0.955

17431 measured reflections

4638 independent reflections

3337 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.138

S = 1.04

4638 reflections

231 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.46 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 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811017089/bt5540sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017089/bt5540Isup2.hkl

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

C18H22ClNO5	F(000) = 776
Mr = 367.82	Dx = 1.309 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1222 reflections
a = 11.962 (3) Å	θ = 1.8–28.3°
b = 9.118 (4) Å	µ = 0.23 mm−1
c = 17.704 (5) Å	T = 293 K
β = 104.890 (3)°	Block, colourless
V = 1866.1 (11) Å3	0.25 × 0.22 × 0.2 mm
Z = 4

Bruker SMART APEXII area-detector diffractometer	4638 independent reflections
Radiation source: fine-focus sealed tube	3337 reflections with I > 2σ(I)
graphite	Rint = 0.024
ω and φ scans	θmax = 28.3°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −15→15
Tmin = 0.944, Tmax = 0.955	k = −7→12
17431 measured reflections	l = −23→23

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0627P)2 + 0.4709P] where P = (Fo2 + 2Fc2)/3
4638 reflections	(Δ/σ)max = 0.009
231 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.46 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	0.20024 (13)	0.2336 (2)	0.66810 (9)	0.0491 (4)
H1	0.2693	0.1975	0.6606	0.059*
C2	0.10067 (15)	0.1499 (2)	0.64705 (10)	0.0606 (5)
C3	−0.00304 (16)	0.2004 (3)	0.65606 (12)	0.0762 (7)
H3	−0.0696	0.1434	0.6412	0.091*
C4	−0.00607 (16)	0.3366 (4)	0.68751 (14)	0.0845 (8)
H4	−0.0757	0.3722	0.6944	0.101*
C5	0.09225 (15)	0.4229 (3)	0.70946 (12)	0.0671 (5)
H5	0.0881	0.5157	0.7303	0.081*
C6	0.19700 (12)	0.37074 (19)	0.70030 (9)	0.0454 (4)
C7	0.30800 (12)	0.45902 (17)	0.72953 (8)	0.0404 (3)
H7	0.2868	0.5589	0.7408	0.048*
C8	0.37441 (12)	0.38775 (16)	0.80710 (8)	0.0405 (3)
H8	0.3766	0.2816	0.7989	0.049*
C9	0.49940 (13)	0.44328 (17)	0.83388 (9)	0.0421 (3)
C10	0.56091 (13)	0.39960 (18)	0.77252 (9)	0.0450 (3)
H10A	0.6358	0.4475	0.7843	0.054*
H10B	0.5743	0.2946	0.7758	0.054*
C11	0.49636 (13)	0.43744 (17)	0.68999 (9)	0.0410 (3)
C12	0.38012 (13)	0.46821 (16)	0.67106 (8)	0.0404 (3)
C13	0.32399 (14)	0.51982 (17)	0.59341 (9)	0.0444 (3)
C14	0.15531 (18)	0.6312 (3)	0.51469 (11)	0.0699 (5)
H14A	0.1977	0.7082	0.4976	0.105*
H14B	0.0818	0.6681	0.5184	0.105*
H14C	0.1435	0.5519	0.4778	0.105*
C15	0.68410 (14)	0.4189 (2)	0.65474 (11)	0.0597 (5)
H15A	0.7225	0.4980	0.6869	0.090*
H15B	0.7075	0.4172	0.6068	0.090*
H15C	0.7045	0.3276	0.6818	0.090*
C16	0.56123 (15)	0.3786 (2)	0.91304 (9)	0.0558 (4)
H16A	0.6418	0.4041	0.9251	0.084*
H16B	0.5533	0.2738	0.9112	0.084*
H16C	0.5276	0.4172	0.9526	0.084*
C17	0.31063 (14)	0.41559 (19)	0.86895 (9)	0.0469 (4)
C18	0.2187 (3)	0.3077 (3)	0.95785 (16)	0.0975 (9)
H18A	0.2735	0.3321	1.0061	0.146*
H18B	0.1814	0.2168	0.9638	0.146*
H18C	0.1618	0.3840	0.9442	0.146*
N1	0.56045 (12)	0.43967 (18)	0.63774 (8)	0.0528 (4)
H1A	0.5244	0.4549	0.5897	0.063*
O1	0.36279 (10)	0.51675 (14)	0.53585 (7)	0.0560 (3)
O2	0.21941 (10)	0.57946 (15)	0.58975 (7)	0.0584 (3)
O3	0.50425 (11)	0.59997 (12)	0.83719 (7)	0.0542 (3)
H4A	0.4653	0.6298	0.8660	0.081*
O4	0.29242 (13)	0.53525 (15)	0.89139 (8)	0.0645 (4)
O5	0.27827 (13)	0.29272 (15)	0.89645 (8)	0.0682 (4)
Cl1	0.10795 (6)	−0.02490 (8)	0.60884 (5)	0.1010 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0376 (8)	0.0622 (10)	0.0469 (8)	−0.0061 (7)	0.0098 (6)	0.0010 (8)
C2	0.0497 (9)	0.0767 (13)	0.0517 (10)	−0.0198 (9)	0.0062 (8)	0.0058 (9)
C3	0.0414 (10)	0.119 (2)	0.0647 (12)	−0.0225 (11)	0.0068 (8)	0.0159 (13)
C4	0.0342 (9)	0.140 (2)	0.0821 (15)	0.0098 (12)	0.0193 (9)	0.0128 (16)
C5	0.0430 (9)	0.0944 (15)	0.0655 (11)	0.0141 (10)	0.0169 (8)	−0.0020 (11)
C6	0.0350 (7)	0.0616 (10)	0.0400 (7)	0.0044 (7)	0.0102 (6)	0.0052 (7)
C7	0.0387 (7)	0.0420 (8)	0.0394 (7)	0.0054 (6)	0.0081 (6)	−0.0008 (6)
C8	0.0421 (7)	0.0376 (7)	0.0403 (7)	0.0038 (6)	0.0079 (6)	−0.0009 (6)
C9	0.0426 (8)	0.0385 (8)	0.0417 (7)	0.0042 (6)	0.0044 (6)	−0.0030 (6)
C10	0.0374 (7)	0.0481 (8)	0.0466 (8)	0.0037 (6)	0.0055 (6)	−0.0020 (7)
C11	0.0403 (7)	0.0386 (7)	0.0437 (8)	−0.0035 (6)	0.0102 (6)	−0.0024 (6)
C12	0.0397 (7)	0.0400 (7)	0.0403 (7)	−0.0017 (6)	0.0082 (6)	−0.0007 (6)
C13	0.0426 (8)	0.0434 (8)	0.0448 (8)	−0.0040 (6)	0.0067 (6)	−0.0010 (6)
C14	0.0613 (11)	0.0841 (14)	0.0560 (10)	0.0188 (10)	−0.0002 (9)	0.0116 (10)
C15	0.0439 (9)	0.0733 (12)	0.0662 (11)	0.0014 (8)	0.0220 (8)	0.0039 (9)
C16	0.0540 (9)	0.0634 (11)	0.0444 (8)	0.0121 (8)	0.0024 (7)	0.0013 (8)
C17	0.0467 (8)	0.0512 (9)	0.0415 (8)	0.0065 (7)	0.0089 (6)	0.0045 (7)
C18	0.119 (2)	0.0965 (19)	0.1025 (18)	0.0165 (16)	0.0740 (17)	0.0306 (15)
N1	0.0410 (7)	0.0695 (9)	0.0493 (8)	−0.0001 (6)	0.0142 (6)	0.0047 (7)
O1	0.0550 (7)	0.0707 (8)	0.0418 (6)	−0.0006 (6)	0.0115 (5)	0.0031 (6)
O2	0.0510 (7)	0.0724 (8)	0.0494 (6)	0.0148 (6)	0.0085 (5)	0.0126 (6)
O3	0.0582 (7)	0.0396 (6)	0.0613 (7)	0.0005 (5)	0.0093 (6)	−0.0078 (5)
O4	0.0821 (9)	0.0578 (8)	0.0607 (8)	0.0108 (7)	0.0313 (7)	−0.0045 (6)
O5	0.0826 (9)	0.0585 (8)	0.0754 (9)	0.0083 (7)	0.0420 (7)	0.0149 (7)
Cl1	0.0875 (4)	0.0874 (5)	0.1206 (5)	−0.0422 (3)	0.0133 (4)	−0.0251 (4)

C1—C6	1.379 (2)	C11—N1	1.345 (2)
C1—C2	1.383 (2)	C11—C12	1.373 (2)
C1—H1	0.9300	C12—C13	1.445 (2)
C2—C3	1.370 (3)	C13—O1	1.2237 (19)
C2—Cl1	1.743 (2)	C13—O2	1.350 (2)
C3—C4	1.365 (4)	C14—O2	1.433 (2)
C3—H3	0.9300	C14—H14A	0.9600
C4—C5	1.385 (3)	C14—H14B	0.9600
C4—H4	0.9300	C14—H14C	0.9600
C5—C6	1.388 (2)	C15—N1	1.444 (2)
C5—H5	0.9300	C15—H15A	0.9600
C6—C7	1.525 (2)	C15—H15B	0.9600
C7—C12	1.511 (2)	C15—H15C	0.9600
C7—C8	1.542 (2)	C16—H16A	0.9600
C7—H7	0.9800	C16—H16B	0.9600
C8—C17	1.508 (2)	C16—H16C	0.9600
C8—C9	1.534 (2)	C17—O4	1.200 (2)
C8—H8	0.9800	C17—O5	1.319 (2)
C9—O3	1.430 (2)	C18—O5	1.451 (2)
C9—C10	1.514 (2)	C18—H18A	0.9600
C9—C16	1.525 (2)	C18—H18B	0.9600
C10—C11	1.507 (2)	C18—H18C	0.9600
C10—H10A	0.9700	N1—H1A	0.8600
C10—H10B	0.9700	O3—H4A	0.8200
C6—C1—C2	119.88 (16)	N1—C11—C12	123.34 (14)
C6—C1—H1	120.1	N1—C11—C10	115.45 (13)
C2—C1—H1	120.1	C12—C11—C10	121.20 (13)
C3—C2—C1	121.8 (2)	C11—C12—C13	119.52 (14)
C3—C2—Cl1	119.31 (16)	C11—C12—C7	122.84 (13)
C1—C2—Cl1	118.94 (16)	C13—C12—C7	117.55 (13)
C4—C3—C2	118.21 (19)	O1—C13—O2	120.94 (14)
C4—C3—H3	120.9	O1—C13—C12	127.01 (15)
C2—C3—H3	120.9	O2—C13—C12	112.03 (13)
C3—C4—C5	121.43 (19)	O2—C14—H14A	109.5
C3—C4—H4	119.3	O2—C14—H14B	109.5
C5—C4—H4	119.3	H14A—C14—H14B	109.5
C4—C5—C6	120.0 (2)	O2—C14—H14C	109.5
C4—C5—H5	120.0	H14A—C14—H14C	109.5
C6—C5—H5	120.0	H14B—C14—H14C	109.5
C1—C6—C5	118.74 (17)	N1—C15—H15A	109.5
C1—C6—C7	120.30 (13)	N1—C15—H15B	109.5
C5—C6—C7	120.86 (17)	H15A—C15—H15B	109.5
C12—C7—C6	113.42 (12)	N1—C15—H15C	109.5
C12—C7—C8	112.29 (12)	H15A—C15—H15C	109.5
C6—C7—C8	106.51 (12)	H15B—C15—H15C	109.5
C12—C7—H7	108.1	C9—C16—H16A	109.5
C6—C7—H7	108.1	C9—C16—H16B	109.5
C8—C7—H7	108.1	H16A—C16—H16B	109.5
C17—C8—C9	110.78 (12)	C9—C16—H16C	109.5
C17—C8—C7	109.55 (12)	H16A—C16—H16C	109.5
C9—C8—C7	111.98 (12)	H16B—C16—H16C	109.5
C17—C8—H8	108.1	O4—C17—O5	123.70 (16)
C9—C8—H8	108.1	O4—C17—C8	124.20 (15)
C7—C8—H8	108.1	O5—C17—C8	112.10 (14)
O3—C9—C10	105.67 (13)	O5—C18—H18A	109.5
O3—C9—C16	110.09 (13)	O5—C18—H18B	109.5
C10—C9—C16	110.33 (13)	H18A—C18—H18B	109.5
O3—C9—C8	111.62 (12)	O5—C18—H18C	109.5
C10—C9—C8	107.83 (12)	H18A—C18—H18C	109.5
C16—C9—C8	111.13 (14)	H18B—C18—H18C	109.5
C11—C10—C9	114.41 (13)	C11—N1—C15	126.10 (14)
C11—C10—H10A	108.7	C11—N1—H1A	117.0
C9—C10—H10A	108.7	C15—N1—H1A	117.0
C11—C10—H10B	108.7	C13—O2—C14	116.46 (14)
C9—C10—H10B	108.7	C9—O3—H4A	109.5
H10A—C10—H10B	107.6	C17—O5—C18	116.35 (16)
C6—C1—C2—C3	1.1 (3)	C8—C9—C10—C11	49.17 (18)
C6—C1—C2—Cl1	−178.36 (12)	C9—C10—C11—N1	161.63 (14)
C1—C2—C3—C4	−0.7 (3)	C9—C10—C11—C12	−17.9 (2)
Cl1—C2—C3—C4	178.76 (17)	N1—C11—C12—C13	−6.3 (2)
C2—C3—C4—C5	0.4 (3)	C10—C11—C12—C13	173.14 (14)
C3—C4—C5—C6	−0.6 (3)	N1—C11—C12—C7	177.30 (14)
C2—C1—C6—C5	−1.2 (2)	C10—C11—C12—C7	−3.2 (2)
C2—C1—C6—C7	175.25 (15)	C6—C7—C12—C11	−130.26 (16)
C4—C5—C6—C1	1.0 (3)	C8—C7—C12—C11	−9.5 (2)
C4—C5—C6—C7	−175.46 (17)	C6—C7—C12—C13	53.32 (18)
C1—C6—C7—C12	49.45 (19)	C8—C7—C12—C13	174.13 (13)
C5—C6—C7—C12	−134.17 (16)	C11—C12—C13—O1	13.8 (3)
C1—C6—C7—C8	−74.57 (17)	C7—C12—C13—O1	−169.67 (15)
C5—C6—C7—C8	101.81 (17)	C11—C12—C13—O2	−164.39 (14)
C12—C7—C8—C17	165.93 (13)	C7—C12—C13—O2	12.1 (2)
C6—C7—C8—C17	−69.36 (16)	C9—C8—C17—O4	62.5 (2)
C12—C7—C8—C9	42.61 (17)	C7—C8—C17—O4	−61.5 (2)
C6—C7—C8—C9	167.32 (12)	C9—C8—C17—O5	−116.62 (15)
C17—C8—C9—O3	−69.40 (16)	C7—C8—C17—O5	119.35 (15)
C7—C8—C9—O3	53.22 (16)	C12—C11—N1—C15	175.24 (17)
C17—C8—C9—C10	174.96 (12)	C10—C11—N1—C15	−4.3 (2)
C7—C8—C9—C10	−62.42 (16)	O1—C13—O2—C14	3.0 (2)
C17—C8—C9—C16	53.92 (17)	C12—C13—O2—C14	−178.66 (16)
C7—C8—C9—C16	176.54 (13)	O4—C17—O5—C18	−0.7 (3)
O3—C9—C10—C11	−70.31 (16)	C8—C17—O5—C18	178.47 (18)
C16—C9—C10—C11	170.72 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.86	2.0	2.673 (2)	134
O3—H4A···O4	0.82	2.39	2.990 (2)	131
C15—H15B···O1i	0.96	2.52	3.327 (3)	142

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.86	2.0	2.673 (2)	134
O3—H4A⋯O4	0.82	2.39	2.990 (2)	131
C15—H15B⋯O1i	0.96	2.52	3.327 (3)	142

Symmetry code: (i) .