5-Chloro-6-hy-droxy-7,8-dimethyl-chroman-2-one.

In the title mol-ecule, C(11)H(11)ClO(3), the fused pyran ring adopts a half-chair conformation. In the crystal, inter-molecular O-H⋯O hydrogen bonds link mol-ecules into chains along [100]. These chains are inter-connected by weak inter-molecular C-H⋯O contacts which generate R(2) (2)(8) ring motifs, forming sheets parallel to (001). Tetra-gonal symmetry generates an equivalent motif along b. Furthermore, the sheets are linked along the c axis by offset π-π stacking inter-actions involving the benzene rings of adjacent mol-ecules [with centroid-centroid distances of 3.839 (2) Å], together with an additional weak C-H⋯O hydrogen bond, resulting in an overall three-dimensional network.

Related literature

For the synthesis of the starting materials, see: Fieser & Ardao (1956 ▶); Bishop et al. (1963 ▶). For related structures, see: Budzianowski & Katrusiak (2002 ▶); Goswami et al. (2011 ▶). For standard bond lengths, see Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C11H11ClO3

M = 226.65

Tetragonal,

a = 16.1375 (6) Å

c = 7.5887 (6) Å

V = 1976.24 (19) Å3

Z = 8

Mo Kα radiation

μ = 0.37 mm−1

T = 89 K

0.40 × 0.07 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker 2009 ▶) T min = 0.792, T max = 1.00

22360 measured reflections

2030 independent reflections

1618 reflections with I > 2σ(I)

R int = 0.095

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.143

S = 1.07

2030 reflections

141 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.39 e Å−3

Absolute structure: Flack (1983 ▶), 859 Friedel pairs

Flack parameter: −0.04 (12)

Data collection: APEX2 (Bruker 2009 ▶); cell refinement: SAINT (Bruker 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and TITAN2000 (Hunter & Simpson, 1999 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ▶), PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811029345/lh5289sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811029345/lh5289Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811029345/lh5289Isup3.cml

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

C11H11ClO3	Dx = 1.524 Mg m−3
Mr = 226.65	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P421c	Cell parameters from 1966 reflections
Hall symbol: P -4 2n	θ = 2.5–20.6°
a = 16.1375 (6) Å	µ = 0.37 mm−1
c = 7.5887 (6) Å	T = 89 K
V = 1976.24 (19) Å3	Needle, colourless
Z = 8	0.40 × 0.07 × 0.05 mm
F(000) = 944

Bruker APEXII CCD area-detector diffractometer	2030 independent reflections
Radiation source: fine-focus sealed tube	1618 reflections with I > 2σ(I)
graphite	Rint = 0.095
ω scans	θmax = 26.4°, θmin = 3.9°
Absorption correction: multi-scan (SADABS; Bruker 2009)	h = −20→20
Tmin = 0.792, Tmax = 1.00	k = −20→19
22360 measured reflections	l = −9→8

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)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.143	w = 1/[σ2(Fo2) + (0.0781P)2 + 0.6384P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
2030 reflections	Δρmax = 0.33 e Å−3
141 parameters	Δρmin = −0.39 e Å−3
0 restraints	Absolute structure: Flack (1983), 859 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.04 (12)

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
O1	0.29181 (15)	0.46995 (15)	0.9081 (4)	0.0286 (6)
C1	0.2457 (2)	0.3970 (2)	0.8839 (5)	0.0246 (8)
C2	0.1624 (2)	0.4026 (2)	0.9338 (5)	0.0246 (8)
C21	0.1277 (2)	0.4829 (2)	1.0015 (6)	0.0295 (9)
H2A	0.1709	0.5132	1.0655	0.044*
H2B	0.0812	0.4715	1.0810	0.044*
H2C	0.1083	0.5165	0.9021	0.044*
C3	0.1126 (2)	0.3318 (2)	0.9168 (5)	0.0243 (8)
C31	0.02056 (19)	0.3310 (2)	0.9744 (4)	0.0166 (7)
H3A	−0.0132	0.3587	0.8847	0.025*
H3B	0.0148	0.3602	1.0870	0.025*
H3C	0.0019	0.2736	0.9879	0.025*
C4	0.1472 (2)	0.2595 (2)	0.8461 (5)	0.0239 (8)
O4	0.09528 (17)	0.19372 (16)	0.8261 (4)	0.0308 (7)
H4O	0.121 (3)	0.162 (3)	0.769 (6)	0.037*
C5	0.2308 (2)	0.2574 (2)	0.8003 (5)	0.0256 (8)
Cl5	0.27140 (6)	0.16405 (6)	0.72670 (15)	0.0370 (3)
C6	0.2815 (2)	0.3256 (2)	0.8168 (5)	0.0253 (8)
C7	0.3714 (2)	0.3268 (2)	0.7691 (6)	0.0294 (9)
H7A	0.3812	0.2882	0.6699	0.035*
H7B	0.4045	0.3074	0.8709	0.035*
C8	0.3994 (2)	0.4131 (3)	0.7170 (6)	0.0347 (9)
H8A	0.4607	0.4149	0.7194	0.042*
H8B	0.3815	0.4239	0.5943	0.042*
C9	0.3668 (2)	0.4805 (2)	0.8318 (6)	0.0279 (9)
O9	0.40023 (17)	0.54650 (16)	0.8556 (4)	0.0348 (7)

	U11	U22	U33	U12	U13	U23
O1	0.0223 (13)	0.0216 (13)	0.0419 (16)	0.0005 (11)	0.0013 (11)	−0.0028 (11)
C1	0.0241 (19)	0.0182 (17)	0.032 (2)	−0.0010 (15)	−0.0035 (15)	0.0018 (16)
C2	0.0260 (19)	0.0201 (18)	0.0278 (19)	0.0045 (16)	−0.0020 (16)	0.0018 (15)
C21	0.027 (2)	0.0183 (19)	0.043 (2)	−0.0007 (16)	−0.0001 (18)	−0.0065 (17)
C3	0.0210 (19)	0.0255 (18)	0.0263 (18)	0.0006 (15)	−0.0035 (15)	0.0032 (16)
C31	0.0134 (16)	0.0129 (16)	0.0235 (18)	−0.0005 (13)	−0.0005 (13)	0.0001 (14)
C4	0.0262 (19)	0.0184 (17)	0.0270 (18)	−0.0008 (14)	−0.0024 (15)	0.0024 (15)
O4	0.0281 (15)	0.0227 (14)	0.0418 (17)	−0.0042 (12)	−0.0004 (13)	−0.0031 (12)
C5	0.0287 (19)	0.0177 (17)	0.031 (2)	0.0034 (15)	−0.0003 (17)	0.0001 (15)
Cl5	0.0364 (6)	0.0255 (5)	0.0492 (6)	0.0042 (4)	−0.0028 (5)	−0.0048 (5)
C6	0.0259 (19)	0.0222 (19)	0.0279 (19)	0.0049 (15)	−0.0044 (15)	0.0016 (15)
C7	0.0213 (17)	0.0247 (18)	0.042 (2)	0.0044 (14)	−0.0024 (17)	−0.0012 (18)
C8	0.0212 (19)	0.042 (2)	0.041 (2)	−0.0005 (16)	−0.0001 (17)	−0.002 (2)
C9	0.0193 (18)	0.025 (2)	0.039 (2)	0.0000 (15)	−0.0036 (16)	0.0061 (17)
O9	0.0273 (14)	0.0227 (14)	0.0543 (19)	−0.0014 (12)	−0.0046 (14)	0.0067 (13)

O1—C9	1.353 (4)	C4—O4	1.361 (4)
O1—C1	1.404 (4)	C4—C5	1.394 (5)
C1—C6	1.386 (5)	O4—H4O	0.78 (4)
C1—C2	1.399 (5)	C5—C6	1.377 (5)
C2—C3	1.402 (5)	C5—Cl5	1.735 (3)
C2—C21	1.503 (5)	C6—C7	1.495 (5)
C21—H2A	0.9800	C7—C8	1.517 (5)
C21—H2B	0.9800	C7—H7A	0.9900
C21—H2C	0.9800	C7—H7B	0.9900
C3—C4	1.401 (5)	C8—C9	1.489 (6)
C3—C31	1.549 (5)	C8—H8A	0.9900
C31—H3A	0.9800	C8—H8B	0.9900
C31—H3B	0.9800	C9—O9	1.207 (4)
C31—H3C	0.9800
C9—O1—C1	121.6 (3)	C5—C4—C3	120.1 (3)
C6—C1—C2	123.6 (3)	C4—O4—H4O	104 (3)
C6—C1—O1	121.6 (3)	C6—C5—C4	122.2 (3)
C2—C1—O1	114.8 (3)	C6—C5—Cl5	120.0 (3)
C1—C2—C3	118.2 (3)	C4—C5—Cl5	117.8 (3)
C1—C2—C21	120.4 (3)	C5—C6—C1	116.8 (3)
C3—C2—C21	121.3 (3)	C5—C6—C7	124.3 (3)
C2—C21—H2A	109.5	C1—C6—C7	118.9 (3)
C2—C21—H2B	109.5	C6—C7—C8	111.3 (3)
H2A—C21—H2B	109.5	C6—C7—H7A	109.4
C2—C21—H2C	109.5	C8—C7—H7A	109.4
H2A—C21—H2C	109.5	C6—C7—H7B	109.4
H2B—C21—H2C	109.5	C8—C7—H7B	109.4
C4—C3—C2	119.1 (3)	H7A—C7—H7B	108.0
C4—C3—C31	118.9 (3)	C9—C8—C7	114.4 (3)
C2—C3—C31	122.1 (3)	C9—C8—H8A	108.7
C3—C31—H3A	109.5	C7—C8—H8A	108.7
C3—C31—H3B	109.5	C9—C8—H8B	108.7
H3A—C31—H3B	109.5	C7—C8—H8B	108.7
C3—C31—H3C	109.5	H8A—C8—H8B	107.6
H3A—C31—H3C	109.5	O9—C9—O1	116.5 (4)
H3B—C31—H3C	109.5	O9—C9—C8	125.1 (4)
O4—C4—C5	123.3 (3)	O1—C9—C8	118.3 (3)
O4—C4—C3	116.6 (3)
C9—O1—C1—C6	15.2 (5)	C3—C4—C5—Cl5	176.0 (3)
C9—O1—C1—C2	−165.2 (3)	C4—C5—C6—C1	0.8 (6)
C6—C1—C2—C3	0.7 (6)	Cl5—C5—C6—C1	−177.1 (3)
O1—C1—C2—C3	−178.9 (3)	C4—C5—C6—C7	−179.8 (4)
C6—C1—C2—C21	−178.5 (4)	Cl5—C5—C6—C7	2.2 (5)
O1—C1—C2—C21	1.9 (5)	C2—C1—C6—C5	−0.2 (6)
C1—C2—C3—C4	−1.8 (5)	O1—C1—C6—C5	179.3 (3)
C21—C2—C3—C4	177.4 (3)	C2—C1—C6—C7	−179.6 (4)
C1—C2—C3—C31	177.9 (3)	O1—C1—C6—C7	0.0 (6)
C21—C2—C3—C31	−2.9 (6)	C5—C6—C7—C8	152.5 (4)
C2—C3—C4—O4	−177.5 (3)	C1—C6—C7—C8	−28.2 (5)
C31—C3—C4—O4	2.8 (5)	C6—C7—C8—C9	42.6 (5)
C2—C3—C4—C5	2.5 (6)	C1—O1—C9—O9	177.5 (4)
C31—C3—C4—C5	−177.2 (3)	C1—O1—C9—C8	1.3 (5)
O4—C4—C5—C6	177.9 (4)	C7—C8—C9—O9	153.5 (4)
C3—C4—C5—C6	−2.0 (6)	C7—C8—C9—O1	−30.7 (5)
O4—C4—C5—Cl5	−4.0 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O9i	0.99	2.55	3.463 (5)	154.
C7—H7B···O1ii	0.99	2.64	3.588 (5)	160.
C7—H7B···O9ii	0.99	2.68	3.357 (5)	126.
O4—H4O···O9iii	0.78 (4)	2.12 (5)	2.748 (4)	137 (4)
C8—H8B···O4iv	0.99	2.39	3.328 (5)	158.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O9i	0.99	2.55	3.463 (5)	154
C7—H7B⋯O1ii	0.99	2.64	3.588 (5)	160
C7—H7B⋯O9ii	0.99	2.68	3.357 (5)	126
O4—H4O⋯O9iii	0.78 (4)	2.12 (5)	2.748 (4)	137 (4)
C8—H8B⋯O4iv	0.99	2.39	3.328 (5)	158

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