(3-Chloro-phen-yl){2-eth-oxy-5-[(Z)-hydroxy(phen-yl)methyl-idene]cyclo-penta-1,3-dien-1-yl}methanone.

The title compound, C(21)H(17)ClO(3), which crystallizes as one of two possible oxo/hy-droxy-fulvene prototropic tautomers, possesses a strong intra-molecular O-H⋯O hydrogen bond that closes a seven-membered ring. The dihedral angles between the central five-membered ring and two pendant rings are 55.05 (9) and 44.51 (10)°. The crystal packing is characterized by weak inter-molecular C-H⋯O inter-actions between an H atom of the oxymethyl-ene unit and the carbonyl group of an adjacent mol-ecule, resulting in formation of chains of mol-ecules along the a axis.

Related literature

For the structures of related 2-acyl-6-hydoxyfulvene derivatives, see: Ferguson et al. (1975 ▶); Dong et al. (2004 ▶, 2006 ▶). For more information on the synthesis of 2-acyl-6-hydoxyfulvene derivatives, see: Dong et al. (2004 ▶, 2006 ▶). For preparation details, see: Christl et al. (1998 ▶). For compounds obtained from 2-acyl-6-hydoxyfulvenes, see: Dong et al. (2004 ▶); Li et al. (2008 ▶); Snyder et al. (2005 ▶). For complexes based on 2-acyl-6-hydoxyfulvenes, see: Dong et al. (2004 ▶, 2006 ▶); Wang et al. (2005 ▶). For their various applications, see: Hong et al. (2005 ▶); Kondo et al. (1992 ▶); Vicente et al. (1995 ▶).

Experimental

Crystal data

C21H17ClO3

M = 352.80

Monoclinic,

a = 8.1369 (16) Å

b = 27.737 (6) Å

c = 7.6709 (15) Å

β = 98.51 (3)°

V = 1712.2 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.24 mm−1

T = 297 K

0.30 × 0.29 × 0.26 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.932, T max = 0.940

15678 measured reflections

3002 independent reflections

2683 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.061

wR(F 2) = 0.125

S = 1.17

3002 reflections

231 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.29 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT-Plus (Bruker, 2000 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811055279/ld2041sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811055279/ld2041Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811055279/ld2041Isup3.cml

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

C21H17ClO3	F(000) = 736
Mr = 352.80	Dx = 1.369 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3314 reflections
a = 8.1369 (16) Å	θ = 2.5–23.2°
b = 27.737 (6) Å	µ = 0.24 mm−1
c = 7.6709 (15) Å	T = 297 K
β = 98.51 (3)°	Block, yellow
V = 1712.2 (6) Å3	0.30 × 0.29 × 0.26 mm
Z = 4

Bruker SMART APEX CCD area-detector diffractometer	3002 independent reflections
Radiation source: fine-focus sealed tube	2683 reflections with I > 2σ(I)
graphite	Rint = 0.040
phi and ω scans	θmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→9
Tmin = 0.932, Tmax = 0.940	k = −32→32
15678 measured reflections	l = −9→9

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ2(Fo2) + (0.0346P)2 + 1.0364P] where P = (Fo2 + 2Fc2)/3
3002 reflections	(Δ/σ)max < 0.001
231 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.29 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 > 2σ(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
Cl1	0.18516 (11)	0.68353 (3)	0.59613 (12)	0.0710 (3)
O1	0.4203 (2)	0.43102 (8)	0.1762 (3)	0.0672 (6)
O2	0.4234 (2)	0.51880 (8)	0.1798 (4)	0.0765 (7)
C15	0.1504 (3)	0.50390 (9)	0.2264 (3)	0.0368 (6)
C19	0.2853 (3)	0.53450 (10)	0.2149 (4)	0.0466 (7)
C14	0.1450 (3)	0.45072 (9)	0.2082 (3)	0.0374 (6)
C16	−0.0122 (3)	0.51749 (9)	0.2502 (3)	0.0352 (5)
C17	−0.1124 (3)	0.47648 (9)	0.2510 (3)	0.0424 (6)
H17	−0.2239	0.4761	0.2651	0.051*
C1	0.2831 (3)	0.58783 (9)	0.2398 (4)	0.0428 (6)
C2	0.2385 (3)	0.60855 (9)	0.3890 (4)	0.0452 (6)
H2	0.2033	0.5894	0.4757	0.054*
C18	−0.0174 (3)	0.43706 (9)	0.2275 (3)	0.0417 (6)
H18	−0.0553	0.4054	0.2246	0.050*
C3	0.2463 (3)	0.65780 (10)	0.4090 (4)	0.0486 (7)
C13	0.2684 (3)	0.41810 (10)	0.1820 (3)	0.0442 (6)
C7	0.2423 (3)	0.36553 (9)	0.1635 (3)	0.0435 (6)
C6	0.3382 (3)	0.61725 (11)	0.1155 (4)	0.0534 (7)
H6	0.3711	0.6037	0.0153	0.064*
C4	0.2980 (4)	0.68732 (11)	0.2852 (5)	0.0608 (8)
H4	0.3012	0.7206	0.3003	0.073*
C8	0.1071 (4)	0.34512 (10)	0.0608 (4)	0.0539 (7)
H8	0.0261	0.3649	−0.0002	0.065*
C5	0.3449 (4)	0.66657 (11)	0.1384 (5)	0.0634 (9)
H5	0.3818	0.6859	0.0531	0.076*
C12	0.3628 (4)	0.33490 (11)	0.2487 (4)	0.0604 (8)
H12	0.4573	0.3477	0.3157	0.073*
C10	0.2075 (5)	0.26619 (12)	0.1346 (5)	0.0813 (11)
H10	0.1952	0.2329	0.1260	0.098*
C9	0.0901 (5)	0.29571 (11)	0.0471 (5)	0.0705 (9)
H9	−0.0024	0.2826	−0.0225	0.085*
C11	0.3434 (5)	0.28564 (13)	0.2348 (5)	0.0786 (11)
H11	0.4240	0.2655	0.2946	0.094*
O3	−0.0580 (2)	0.56340 (6)	0.2675 (2)	0.0435 (4)
C20	−0.2232 (3)	0.57156 (10)	0.3075 (4)	0.0461 (7)
H20A	−0.2425	0.5518	0.4070	0.055*
H20B	−0.3049	0.5631	0.2070	0.055*
C21	−0.2378 (4)	0.62365 (11)	0.3506 (4)	0.0577 (8)
H21A	−0.1538	0.6320	0.4475	0.087*
H21B	−0.3456	0.6298	0.3825	0.087*
H21C	−0.2234	0.6428	0.2497	0.087*
H1	0.436 (5)	0.4691 (17)	0.188 (6)	0.127 (16)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0812 (6)	0.0519 (5)	0.0806 (6)	0.0001 (4)	0.0148 (4)	−0.0210 (4)
O1	0.0454 (12)	0.0493 (13)	0.1120 (19)	0.0028 (10)	0.0289 (12)	−0.0124 (12)
O2	0.0396 (11)	0.0527 (13)	0.145 (2)	−0.0082 (10)	0.0392 (13)	−0.0193 (14)
C15	0.0341 (13)	0.0366 (14)	0.0405 (14)	−0.0013 (10)	0.0079 (11)	−0.0027 (11)
C19	0.0372 (15)	0.0462 (16)	0.0584 (17)	−0.0032 (12)	0.0133 (13)	−0.0069 (13)
C14	0.0377 (14)	0.0361 (14)	0.0391 (14)	−0.0024 (11)	0.0080 (11)	0.0017 (11)
C16	0.0337 (12)	0.0357 (14)	0.0363 (13)	−0.0013 (11)	0.0054 (10)	0.0005 (11)
C17	0.0321 (13)	0.0446 (15)	0.0516 (16)	−0.0043 (11)	0.0100 (11)	0.0035 (12)
C1	0.0298 (13)	0.0419 (15)	0.0571 (17)	−0.0047 (11)	0.0079 (12)	−0.0031 (13)
C2	0.0381 (14)	0.0407 (15)	0.0570 (17)	−0.0072 (12)	0.0082 (12)	0.0003 (13)
C18	0.0439 (15)	0.0341 (14)	0.0479 (15)	−0.0064 (11)	0.0093 (12)	0.0007 (11)
C3	0.0394 (15)	0.0409 (16)	0.0636 (18)	−0.0024 (12)	0.0011 (13)	−0.0041 (14)
C13	0.0442 (15)	0.0457 (16)	0.0442 (15)	0.0018 (12)	0.0116 (12)	−0.0026 (12)
C7	0.0525 (16)	0.0415 (15)	0.0398 (15)	0.0057 (13)	0.0180 (12)	−0.0011 (12)
C6	0.0431 (15)	0.0594 (19)	0.0591 (18)	−0.0100 (14)	0.0121 (13)	−0.0015 (14)
C4	0.0570 (18)	0.0378 (16)	0.085 (2)	−0.0051 (14)	0.0036 (17)	0.0043 (16)
C8	0.0642 (19)	0.0423 (16)	0.0556 (18)	0.0028 (14)	0.0106 (15)	−0.0011 (13)
C5	0.067 (2)	0.0508 (19)	0.074 (2)	−0.0106 (16)	0.0143 (17)	0.0181 (16)
C12	0.0607 (19)	0.0574 (19)	0.064 (2)	0.0195 (15)	0.0121 (15)	0.0002 (15)
C10	0.115 (3)	0.0354 (18)	0.100 (3)	0.008 (2)	0.038 (3)	0.0013 (18)
C9	0.087 (2)	0.0418 (18)	0.083 (2)	−0.0044 (17)	0.0135 (19)	−0.0096 (17)
C11	0.096 (3)	0.056 (2)	0.088 (3)	0.035 (2)	0.026 (2)	0.0172 (19)
O3	0.0324 (9)	0.0378 (10)	0.0620 (12)	−0.0001 (8)	0.0133 (8)	−0.0033 (8)
C20	0.0316 (13)	0.0542 (17)	0.0541 (16)	0.0054 (12)	0.0111 (12)	−0.0029 (13)
C21	0.0549 (18)	0.0573 (19)	0.0633 (19)	0.0160 (14)	0.0166 (15)	−0.0047 (15)

Cl1—C3	1.740 (3)	C7—C12	1.385 (4)
O1—C13	1.294 (3)	C6—C5	1.379 (4)
O1—H1	1.07 (5)	C6—H6	0.9300
O2—C19	1.271 (3)	C4—C5	1.369 (5)
O2—H1	1.38 (5)	C4—H4	0.9300
C15—C19	1.400 (3)	C8—C9	1.380 (4)
C15—C16	1.414 (3)	C8—H8	0.9300
C15—C14	1.482 (3)	C5—H5	0.9300
C19—C1	1.492 (4)	C12—C11	1.378 (5)
C14—C13	1.388 (3)	C12—H12	0.9300
C14—C18	1.404 (3)	C10—C9	1.358 (5)
C16—O3	1.339 (3)	C10—C11	1.361 (5)
C16—C17	1.400 (3)	C10—H10	0.9300
C17—C18	1.366 (4)	C9—H9	0.9300
C17—H17	0.9300	C11—H11	0.9300
C1—C2	1.376 (4)	O3—C20	1.440 (3)
C1—C6	1.379 (4)	C20—C21	1.491 (4)
C2—C3	1.375 (4)	C20—H20A	0.9700
C2—H2	0.9300	C20—H20B	0.9700
C18—H18	0.9300	C21—H21A	0.9600
C3—C4	1.366 (4)	C21—H21B	0.9600
C13—C7	1.477 (4)	C21—H21C	0.9600
C7—C8	1.377 (4)
C13—O1—H1	112 (2)	C5—C6—H6	119.7
C19—O2—H1	113.3 (18)	C1—C6—H6	119.7
C19—C15—C16	127.1 (2)	C3—C4—C5	118.2 (3)
C19—C15—C14	127.6 (2)	C3—C4—H4	120.9
C16—C15—C14	105.2 (2)	C5—C4—H4	120.9
O2—C19—C15	122.1 (2)	C7—C8—C9	121.0 (3)
O2—C19—C1	113.2 (2)	C7—C8—H8	119.5
C15—C19—C1	124.7 (2)	C9—C8—H8	119.5
C13—C14—C18	123.5 (2)	C4—C5—C6	120.7 (3)
C13—C14—C15	130.6 (2)	C4—C5—H5	119.6
C18—C14—C15	105.9 (2)	C6—C5—H5	119.6
O3—C16—C17	127.0 (2)	C11—C12—C7	120.5 (3)
O3—C16—C15	123.1 (2)	C11—C12—H12	119.8
C17—C16—C15	109.9 (2)	C7—C12—H12	119.8
C18—C17—C16	108.0 (2)	C9—C10—C11	119.6 (3)
C18—C17—H17	126.0	C9—C10—H10	120.2
C16—C17—H17	126.0	C11—C10—H10	120.2
C2—C1—C6	118.7 (3)	C10—C9—C8	120.4 (3)
C2—C1—C19	122.0 (2)	C10—C9—H9	119.8
C6—C1—C19	119.1 (2)	C8—C9—H9	119.8
C3—C2—C1	119.6 (3)	C10—C11—C12	120.7 (3)
C3—C2—H2	120.2	C10—C11—H11	119.6
C1—C2—H2	120.2	C12—C11—H11	119.6
C17—C18—C14	111.0 (2)	C16—O3—C20	116.93 (19)
C17—C18—H18	124.5	O3—C20—C21	107.9 (2)
C14—C18—H18	124.5	O3—C20—H20A	110.1
C4—C3—C2	122.1 (3)	C21—C20—H20A	110.1
C4—C3—Cl1	118.9 (2)	O3—C20—H20B	110.1
C2—C3—Cl1	119.0 (2)	C21—C20—H20B	110.1
O1—C13—C14	122.6 (2)	H20A—C20—H20B	108.4
O1—C13—C7	113.2 (2)	C20—C21—H21A	109.5
C14—C13—C7	124.1 (2)	C20—C21—H21B	109.5
C8—C7—C12	117.8 (3)	H21A—C21—H21B	109.5
C8—C7—C13	123.5 (2)	C20—C21—H21C	109.5
C12—C7—C13	118.6 (3)	H21A—C21—H21C	109.5
C5—C6—C1	120.7 (3)	H21B—C21—H21C	109.5
C16—C15—C19—O2	−174.5 (3)	C18—C14—C13—O1	−175.3 (3)
C14—C15—C19—O2	2.5 (5)	C15—C14—C13—O1	2.9 (4)
C16—C15—C19—C1	4.9 (4)	C18—C14—C13—C7	2.8 (4)
C14—C15—C19—C1	−178.2 (3)	C15—C14—C13—C7	−179.0 (3)
C19—C15—C14—C13	2.5 (5)	O1—C13—C7—C8	−137.3 (3)
C16—C15—C14—C13	179.9 (3)	C14—C13—C7—C8	44.5 (4)
C19—C15—C14—C18	−179.1 (3)	O1—C13—C7—C12	40.3 (4)
C16—C15—C14—C18	−1.6 (3)	C14—C13—C7—C12	−137.9 (3)
C19—C15—C16—O3	−0.9 (4)	C2—C1—C6—C5	−1.4 (4)
C14—C15—C16—O3	−178.4 (2)	C19—C1—C6—C5	−177.1 (3)
C19—C15—C16—C17	178.7 (3)	C2—C3—C4—C5	−0.8 (4)
C14—C15—C16—C17	1.2 (3)	Cl1—C3—C4—C5	−179.7 (2)
O3—C16—C17—C18	179.3 (2)	C12—C7—C8—C9	1.7 (4)
C15—C16—C17—C18	−0.3 (3)	C13—C7—C8—C9	179.3 (3)
O2—C19—C1—C2	−126.2 (3)	C3—C4—C5—C6	0.8 (5)
C15—C19—C1—C2	54.4 (4)	C1—C6—C5—C4	0.3 (5)
O2—C19—C1—C6	49.3 (4)	C8—C7—C12—C11	−2.2 (4)
C15—C19—C1—C6	−130.1 (3)	C13—C7—C12—C11	−180.0 (3)
C6—C1—C2—C3	1.4 (4)	C11—C10—C9—C8	−0.6 (5)
C19—C1—C2—C3	176.9 (2)	C7—C8—C9—C10	−0.3 (5)
C16—C17—C18—C14	−0.8 (3)	C9—C10—C11—C12	0.1 (6)
C13—C14—C18—C17	−179.9 (2)	C7—C12—C11—C10	1.3 (5)
C15—C14—C18—C17	1.5 (3)	C17—C16—O3—C20	6.2 (4)
C1—C2—C3—C4	−0.3 (4)	C15—C16—O3—C20	−174.3 (2)
C1—C2—C3—Cl1	178.6 (2)	C16—O3—C20—C21	170.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	1.07 (5)	1.38 (5)	2.435 (3)	168 (5)
C20—H20B···O2i	0.97	2.51	3.246 (3)	133

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	1.07 (5)	1.38 (5)	2.435 (3)	168 (5)
C20—H20B⋯O2i	0.97	2.51	3.246 (3)	133

Symmetry code: (i) .