Crystal structure of ethyl (4R)-2-amino-7-hy-droxy-4-phenyl-4H-chromene-3-carboxyl-ate.

In the title compound, C18H17NO4, the dihedral angle between the phenyl ring and the fused six-membered ring is 77.65 (4)°. The conformation of the mol-ecule is determined in part by an intra-molecular N-H⋯O hydrogen bond between the amino H atom and the carbonyl O atom, forming an S(6) motif. In the crystal, mol-ecules are linked into N-H⋯O hydrogen-bonded inversion dimers which are then connected into chains along [001], forming a two-dimensional network parallel to (100) via O-H⋯O hydrogen bonds. C-H⋯O interactions further contribute to the crystal stability. The ethyl group is disordered over two sets of sites in a 0.801 (5):0.199 (5) ratio.

Related literature

For background to the synthesis and biological activity of mol­ecules having a 4H-chromene or 4H-benzochromene residue, see: Kiyani & Ghorbani (2014 ▸); Kale et al. (2013 ▸); Sabry et al. (2011 ▸); Kidwai et al. (2010 ▸); Mungra et al. (2011 ▸); Cingolani et al. (1969 ▸); Wu et al. (2003 ▸); Perrella et al. (1994 ▸); Patil et al. (1993 ▸); Emmadi et al. (2012 ▸); Wang et al. (2003 ▸); Armesto et al. (1989 ▸).

Experimental

Crystal data

C18H17NO4

M = 311.32

Monoclinic,

a = 31.5071 (7) Å

b = 5.8582 (1) Å

c = 21.2249 (5) Å

β = 130.180 (1)°

V = 2993.11 (11) Å3

Z = 8

Cu Kα radiation

μ = 0.81 mm−1

T = 150 K

0.22 × 0.18 × 0.02 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2014 ▸) T min = 0.91, T max = 0.98

11241 measured reflections

2891 independent reflections

2348 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.101

S = 1.05

2891 reflections

227 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.27 e Å−3

Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2014 ▸); cell refinement: SAINT (Bruker, 2014 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b ▸); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ▸); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015012013/qm2111sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015012013/qm2111Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015012013/qm2111Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015012013/qm2111fig1.tif

The title mol­ecule with labeling scheme and 50% probability ellipsoids. Only one orientation of the disordered ethyl group is shown.

Click here for additional data file.

b . DOI: 10.1107/S2056989015012013/qm2111fig2.tif

Packing viewed down the b axis. N—H⋯O and O—H⋯O hydrogen bonds are shown, respectively as blue and red dotted lines.

CCDC reference: 1408238

Additional supporting information: crystallographic information; 3D view; checkCIF report

C18H17NO4	F(000) = 1312
Mr = 311.32	Dx = 1.382 Mg m−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
a = 31.5071 (7) Å	Cell parameters from 6704 reflections
b = 5.8582 (1) Å	θ = 3.7–72.2°
c = 21.2249 (5) Å	µ = 0.81 mm−1
β = 130.180 (1)°	T = 150 K
V = 2993.11 (11) Å3	Plate, colourless
Z = 8	0.22 × 0.18 × 0.02 mm

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	2891 independent reflections
Radiation source: INCOATEC IµS micro–focus source	2348 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.033
ω scans	θmax = 72.2°, θmin = 3.7°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −38→36
Tmin = 0.91, Tmax = 0.98	k = −6→7
11241 measured reflections	l = −24→26

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)] = 0.038	Hydrogen site location: mixed
wR(F2) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.049P)2 + 1.7699P] where P = (Fo2 + 2Fc2)/3
2891 reflections	(Δ/σ)max < 0.001
227 parameters	Δρmax = 0.27 e Å−3
2 restraints	Δρmin = −0.25 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. H-atoms were placed in calculated positions (C—H = 0.95 - 0.98 Å) and included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached carbon atoms. The ethyl group (C11,C12) is disordered over two sites. The components of the disorder were refined subject to restraints that their geometries be approximately the same.

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.45362 (4)	0.22755 (17)	0.51953 (6)	0.0270 (2)
O2	0.46127 (4)	0.21959 (19)	0.30568 (6)	0.0302 (3)
H2A	0.4494 (9)	0.294 (4)	0.2598 (14)	0.056 (6)*
O3	0.42602 (4)	0.5543 (2)	0.66661 (6)	0.0340 (3)
O4	0.37668 (5)	0.82032 (19)	0.56697 (6)	0.0338 (3)
N1	0.46907 (5)	0.2182 (3)	0.63712 (8)	0.0305 (3)
H1A	0.4890 (8)	0.084 (4)	0.6479 (12)	0.049 (5)*
H1B	0.4647 (8)	0.277 (3)	0.6709 (12)	0.039 (5)*
C1	0.38998 (6)	0.6527 (2)	0.46364 (8)	0.0242 (3)
H1	0.4037	0.8139	0.4768	0.029*
C2	0.40953 (5)	0.5419 (2)	0.42173 (8)	0.0228 (3)
C3	0.39849 (6)	0.6388 (3)	0.35231 (8)	0.0256 (3)
H3	0.3789	0.7795	0.3318	0.031*
C4	0.41512 (6)	0.5365 (3)	0.31246 (8)	0.0260 (3)
H4	0.4070	0.6063	0.2654	0.031*
C5	0.44383 (6)	0.3298 (2)	0.34225 (8)	0.0241 (3)
C6	0.45583 (6)	0.2297 (2)	0.41125 (8)	0.0243 (3)
H6	0.4754	0.0892	0.4320	0.029*
C7	0.43866 (5)	0.3386 (2)	0.44957 (8)	0.0227 (3)
C8	0.44500 (6)	0.3350 (3)	0.56735 (8)	0.0244 (3)
C9	0.41527 (5)	0.5333 (3)	0.54438 (8)	0.0248 (3)
C10	0.40769 (6)	0.6307 (3)	0.59859 (9)	0.0274 (3)
C11	0.35861 (16)	0.9101 (9)	0.60985 (17)	0.0450 (8)	0.801 (5)
H11A	0.3904	0.9738	0.6641	0.054*	0.801 (5)
H11B	0.3409	0.7892	0.6185	0.054*	0.801 (5)
C12	0.31703 (14)	1.0965 (6)	0.55374 (19)	0.0619 (10)	0.801 (5)
H12A	0.3029	1.1656	0.5791	0.093*	0.801 (5)
H12B	0.3353	1.2137	0.5456	0.093*	0.801 (5)
H12C	0.2861	1.0303	0.5003	0.093*	0.801 (5)
C11A	0.3518 (6)	0.940 (5)	0.5958 (8)	0.0450 (8)	0.199 (5)
H11C	0.3677	1.0951	0.6149	0.054*	0.199 (5)
H11D	0.3586	0.8561	0.6421	0.054*	0.199 (5)
C12A	0.2899 (5)	0.953 (3)	0.5230 (7)	0.0619 (10)	0.199 (5)
H12D	0.2712	1.0330	0.5397	0.093*	0.199 (5)
H12E	0.2838	1.0361	0.4777	0.093*	0.199 (5)
H12F	0.2748	0.7983	0.5047	0.093*	0.199 (5)
C13	0.32653 (6)	0.6603 (2)	0.40441 (8)	0.0248 (3)
C14	0.29555 (6)	0.4724 (3)	0.39345 (9)	0.0289 (3)
H14	0.3139	0.3368	0.4240	0.035*
C15	0.23796 (6)	0.4812 (3)	0.33820 (10)	0.0369 (4)
H15	0.2171	0.3520	0.3314	0.044*
C16	0.21071 (7)	0.6774 (3)	0.29294 (10)	0.0415 (4)
H16	0.1713	0.6836	0.2555	0.050*
C17	0.24104 (7)	0.8635 (3)	0.30240 (10)	0.0399 (4)
H17	0.2225	0.9975	0.2707	0.048*
C18	0.29867 (7)	0.8557 (3)	0.35817 (9)	0.0328 (3)
H18	0.3193	0.9854	0.3648	0.039*

	U11	U22	U33	U12	U13	U23
O1	0.0334 (5)	0.0318 (5)	0.0209 (5)	0.0037 (4)	0.0198 (4)	0.0024 (4)
O2	0.0346 (6)	0.0392 (6)	0.0237 (5)	0.0060 (5)	0.0220 (5)	0.0032 (5)
O3	0.0372 (6)	0.0470 (7)	0.0225 (5)	0.0043 (5)	0.0214 (5)	0.0005 (5)
O4	0.0401 (6)	0.0395 (6)	0.0287 (5)	0.0059 (5)	0.0254 (5)	−0.0007 (5)
N1	0.0331 (7)	0.0414 (8)	0.0214 (6)	0.0060 (6)	0.0196 (6)	0.0041 (6)
C1	0.0266 (7)	0.0270 (7)	0.0210 (7)	−0.0031 (6)	0.0163 (6)	−0.0034 (6)
C2	0.0209 (6)	0.0280 (7)	0.0191 (6)	−0.0036 (6)	0.0127 (5)	−0.0033 (6)
C3	0.0240 (7)	0.0293 (7)	0.0235 (7)	−0.0011 (6)	0.0153 (6)	0.0008 (6)
C4	0.0264 (7)	0.0328 (8)	0.0208 (7)	−0.0026 (6)	0.0161 (6)	0.0015 (6)
C5	0.0216 (6)	0.0334 (8)	0.0192 (6)	−0.0036 (6)	0.0140 (5)	−0.0044 (6)
C6	0.0227 (7)	0.0287 (7)	0.0202 (7)	0.0003 (6)	0.0134 (6)	0.0001 (6)
C7	0.0221 (6)	0.0297 (7)	0.0156 (6)	−0.0045 (5)	0.0118 (5)	−0.0011 (5)
C8	0.0221 (7)	0.0349 (8)	0.0174 (6)	−0.0044 (6)	0.0132 (6)	−0.0036 (6)
C9	0.0220 (7)	0.0334 (8)	0.0182 (6)	−0.0026 (6)	0.0127 (6)	−0.0031 (6)
C10	0.0241 (7)	0.0358 (8)	0.0225 (7)	−0.0031 (6)	0.0151 (6)	−0.0042 (6)
C11	0.0614 (14)	0.050 (2)	0.0456 (14)	0.0246 (12)	0.0448 (12)	0.0156 (16)
C12	0.079 (2)	0.074 (2)	0.0624 (18)	0.0394 (17)	0.0588 (18)	0.0292 (16)
C11A	0.0614 (14)	0.050 (2)	0.0456 (14)	0.0246 (12)	0.0448 (12)	0.0156 (16)
C12A	0.079 (2)	0.074 (2)	0.0624 (18)	0.0394 (17)	0.0588 (18)	0.0292 (16)
C13	0.0276 (7)	0.0305 (7)	0.0194 (6)	0.0023 (6)	0.0166 (6)	−0.0012 (6)
C14	0.0298 (7)	0.0344 (8)	0.0252 (7)	0.0014 (6)	0.0190 (6)	−0.0008 (6)
C15	0.0302 (8)	0.0528 (10)	0.0314 (8)	−0.0043 (7)	0.0216 (7)	−0.0079 (8)
C16	0.0257 (8)	0.0665 (12)	0.0272 (8)	0.0113 (8)	0.0148 (7)	−0.0040 (8)
C17	0.0418 (9)	0.0470 (10)	0.0285 (8)	0.0186 (8)	0.0216 (7)	0.0054 (7)
C18	0.0407 (9)	0.0333 (8)	0.0283 (8)	0.0068 (7)	0.0241 (7)	0.0021 (7)

O1—C8	1.3622 (16)	C9—C10	1.4358 (19)
O1—C7	1.3954 (16)	C11—C12	1.521 (4)
O2—C5	1.3679 (17)	C11—H11A	0.9900
O2—H2A	0.90 (2)	C11—H11B	0.9900
O3—C10	1.2419 (18)	C12—H12A	0.9800
O4—C10	1.3387 (18)	C12—H12B	0.9800
O4—C11	1.448 (2)	C12—H12C	0.9800
O4—C11A	1.448 (4)	C11A—C12A	1.519 (6)
N1—C8	1.3366 (19)	C11A—H11C	0.9900
N1—H1A	0.93 (2)	C11A—H11D	0.9900
N1—H1B	0.88 (2)	C12A—H12D	0.9800
C1—C2	1.5164 (18)	C12A—H12E	0.9800
C1—C9	1.5165 (19)	C12A—H12F	0.9800
C1—C13	1.5284 (19)	C13—C14	1.388 (2)
C1—H1	1.0000	C13—C18	1.390 (2)
C2—C7	1.382 (2)	C14—C15	1.387 (2)
C2—C3	1.3976 (19)	C14—H14	0.9500
C3—C4	1.386 (2)	C15—C16	1.384 (2)
C3—H3	0.9500	C15—H15	0.9500
C4—C5	1.395 (2)	C16—C17	1.376 (3)
C4—H4	0.9500	C16—H16	0.9500
C5—C6	1.3846 (19)	C17—C18	1.388 (2)
C6—C7	1.3886 (19)	C17—H17	0.9500
C6—H6	0.9500	C18—H18	0.9500
C8—C9	1.369 (2)
C8—O1—C7	118.99 (11)	O4—C11—H11A	110.8
C5—O2—H2A	110.5 (14)	C12—C11—H11A	110.8
C10—O4—C11	116.23 (19)	O4—C11—H11B	110.8
C10—O4—C11A	127.5 (10)	C12—C11—H11B	110.8
C8—N1—H1A	120.8 (12)	H11A—C11—H11B	108.8
C8—N1—H1B	115.2 (12)	C11—C12—H12A	109.5
H1A—N1—H1B	124.0 (17)	C11—C12—H12B	109.5
C2—C1—C9	110.43 (12)	H12A—C12—H12B	109.5
C2—C1—C13	109.92 (11)	C11—C12—H12C	109.5
C9—C1—C13	113.43 (11)	H12A—C12—H12C	109.5
C2—C1—H1	107.6	H12B—C12—H12C	109.5
C9—C1—H1	107.6	O4—C11A—C12A	106.5 (7)
C13—C1—H1	107.6	O4—C11A—H11C	110.4
C7—C2—C3	116.48 (12)	C12A—C11A—H11C	110.4
C7—C2—C1	121.82 (12)	O4—C11A—H11D	110.4
C3—C2—C1	121.69 (13)	C12A—C11A—H11D	110.4
C4—C3—C2	122.18 (14)	H11C—C11A—H11D	108.6
C4—C3—H3	118.9	C11A—C12A—H12D	109.5
C2—C3—H3	118.9	C11A—C12A—H12E	109.5
C3—C4—C5	119.26 (13)	H12D—C12A—H12E	109.5
C3—C4—H4	120.4	C11A—C12A—H12F	109.5
C5—C4—H4	120.4	H12D—C12A—H12F	109.5
O2—C5—C6	117.71 (13)	H12E—C12A—H12F	109.5
O2—C5—C4	122.20 (12)	C14—C13—C18	118.64 (14)
C6—C5—C4	120.09 (13)	C14—C13—C1	121.35 (13)
C5—C6—C7	118.79 (13)	C18—C13—C1	119.98 (14)
C5—C6—H6	120.6	C15—C14—C13	120.48 (15)
C7—C6—H6	120.6	C15—C14—H14	119.8
C2—C7—C6	123.19 (12)	C13—C14—H14	119.8
C2—C7—O1	122.14 (12)	C16—C15—C14	120.31 (16)
C6—C7—O1	114.67 (12)	C16—C15—H15	119.8
N1—C8—O1	110.23 (13)	C14—C15—H15	119.8
N1—C8—C9	126.67 (13)	C17—C16—C15	119.66 (15)
O1—C8—C9	123.09 (12)	C17—C16—H16	120.2
C8—C9—C10	118.78 (13)	C15—C16—H16	120.2
C8—C9—C1	122.26 (12)	C16—C17—C18	120.10 (16)
C10—C9—C1	118.96 (13)	C16—C17—H17	119.9
O3—C10—O4	121.56 (13)	C18—C17—H17	119.9
O3—C10—C9	126.52 (14)	C17—C18—C13	120.79 (16)
O4—C10—C9	111.92 (12)	C17—C18—H18	119.6
O4—C11—C12	105.0 (2)	C13—C18—H18	119.6
C9—C1—C2—C7	9.72 (18)	C13—C1—C9—C8	115.70 (15)
C13—C1—C2—C7	−116.18 (14)	C2—C1—C9—C10	171.99 (12)
C9—C1—C2—C3	−170.99 (12)	C13—C1—C9—C10	−64.11 (17)
C13—C1—C2—C3	63.11 (17)	C11—O4—C10—O3	−9.3 (3)
C7—C2—C3—C4	0.7 (2)	C11A—O4—C10—O3	−11.6 (12)
C1—C2—C3—C4	−178.58 (13)	C11—O4—C10—C9	169.8 (3)
C2—C3—C4—C5	0.0 (2)	C11A—O4—C10—C9	167.5 (12)
C3—C4—C5—O2	179.81 (13)	C8—C9—C10—O3	0.7 (2)
C3—C4—C5—C6	−0.5 (2)	C1—C9—C10—O3	−179.51 (14)
O2—C5—C6—C7	179.87 (12)	C8—C9—C10—O4	−178.39 (12)
C4—C5—C6—C7	0.1 (2)	C1—C9—C10—O4	1.43 (18)
C3—C2—C7—C6	−1.1 (2)	C10—O4—C11—C12	−170.7 (3)
C1—C2—C7—C6	178.23 (13)	C10—O4—C11A—C12A	−123.6 (13)
C3—C2—C7—O1	178.25 (12)	C2—C1—C13—C14	82.33 (16)
C1—C2—C7—O1	−2.4 (2)	C9—C1—C13—C14	−41.85 (18)
C5—C6—C7—C2	0.7 (2)	C2—C1—C13—C18	−95.55 (15)
C5—C6—C7—O1	−178.71 (12)	C9—C1—C13—C18	140.28 (13)
C8—O1—C7—C2	−7.73 (19)	C18—C13—C14—C15	−0.8 (2)
C8—O1—C7—C6	171.67 (11)	C1—C13—C14—C15	−178.73 (13)
C7—O1—C8—N1	−170.97 (11)	C13—C14—C15—C16	0.4 (2)
C7—O1—C8—C9	9.47 (19)	C14—C15—C16—C17	0.6 (2)
N1—C8—C9—C10	−0.6 (2)	C15—C16—C17—C18	−1.2 (2)
O1—C8—C9—C10	178.86 (12)	C16—C17—C18—C13	0.7 (2)
N1—C8—C9—C1	179.56 (13)	C14—C13—C18—C17	0.3 (2)
O1—C8—C9—C1	−1.0 (2)	C1—C13—C18—C17	178.21 (13)
C2—C1—C9—C8	−8.20 (18)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O2i	0.99	2.58	3.312 (3)	131
C6—H6···O1ii	0.95	2.56	3.4736 (17)	163
N1—H1B···O3	0.88 (2)	1.998 (19)	2.6840 (18)	133.7 (16)
N1—H1A···O2ii	0.93 (2)	2.15 (2)	3.0710 (18)	169.6 (17)
O2—H2A···O3iii	0.90 (2)	1.83 (2)	2.7331 (15)	179 (2)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C11H11AO2i	0.99	2.58	3.312(3)	131
C6H6O1ii	0.95	2.56	3.4736(17)	163
N1H1BO3	0.88(2)	1.998(19)	2.6840(18)	133.7(16)
N1H1AO2ii	0.93(2)	2.15(2)	3.0710(18)	169.6(17)
O2H2AO3iii	0.90(2)	1.83(2)	2.7331(15)	179(2)

Symmetry codes: (i) ; (ii) ; (iii) .