π-Bond cooperativity and anticooperativity effects in resonance-assisted hydrogen bonds (RAHBs)

Bond cooperativity effects, which are typical of `resonant' chains or rings of π-conjugated hydrocarbons, can also occur in hydrogen-bonded systems in the form of σ-bond and π-bond cooperativity or anticooperativity. σ-Bond cooperativity is associated with the long chains of O—H...O bonds in water and alcohols while σ-bond anticooperativity occurs when the cooperative chain is interrupted by a local defect reversing the bond polarity. π-Bond cooperativity is the driving force controlling resonance-assisted hydrogen bonds (RAHBs), while π-bond anticooperativity has never been considered so far and is investigated here by studying couples of hydrogen-bonded β-enolone and/or β-enaminone six-membered rings fused through a common C=O or C—C bond. The effect is studied by X-ray crystal structure determination of five compounds [(2Z)-1-(2-hydroxyphenyl)-3-phenyl-1,3-propanedione enol (1), (2Z)-1-(2-hydroxy-5-chlorophenyl)-3-phenyl-1,3-propanedione enol (2), (2Z)-1-(2-hydroxy-5-methylphenyl)-3-phenyl-1,3-propanedione enol (3), (2Z)-1-(2-hydroxy-4-methyl-5-chlorophenyl)-3-phenyl-1,3-propanedione enol (4) and dimethyl(2E)-3-hydroxy-2-{[(4-chlorophenyl)amino]carbonyl}pent-2-enedioate (5)] and by extensive analysis of related fragments found in the CSD (Cambridge Structural Database). It is shown that fusion through the C=O bond is always anticooperative and such to weaken the symmetric O—H...O...H—O and N—H...O...H—N bonds formed, but not the asymmetric O—H...O...H—N bond. Fusion through the C—C bond may produce either cooperative or anticooperative hydrogen bonds, the former being more stable than the latter and giving rise to a unique resonance-assisted ten-membered ring running all around the two fused six-membered rings, which can be considered a type of tautomerism never described before.

Computing details

Data collection: Kappa-CCD server software (Nonius, 1997) for (1); Kappa CCD server software (Nonius, 1997) for (2), (3); Kappa CCD server software (1997) for (4); Kappa CCd server software (Nonius, 1997) for (5). Cell refinement: DENZO-SMN (Otwinowski & Minor, 1997) for (1), (3); DENZO SMN (Otwinowski & Minor, 1997) for (2), (5); DENZO-SMN (Otwinowski & Minor (1997) for (4). Data reduction: DENZO-SMN (Otwinowski & Minor, 1997) for (1), (3); DENZO SMN (Otwinowski & Minor, 1997) for (2), (5); DENZO-SMN (Otwinowski & Minor (1997) for (4). For all compounds, program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP III (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997), PARST (Nardelli, 1995).

Figures

(1) (2Z)-1-(2-hydroxyphenyl)-3-phenyl-1,3-propanedione enol

Crystal data

C15H12O3	F(000) = 1008
Mr = 240.25	Dx = 1.364 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71070 Å
a = 27.299 (2) Å	Cell parameters from 4754 reflections
b = 5.4343 (2) Å	θ = 2.4–27.5°
c = 17.576 (1) Å	µ = 0.10 mm^−1
β = 116.215 (2)°	T = 295 K
V = 2339.2 (3) Å^3	Prism, yellow
Z = 8	0.26 × 0.12 × 0.10 mm

Data collection

Nonius Kappa CCD diffractometer	1862 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
Graphite monochromator	θmax = 27.5°, θmin = 2.4°
ϕ scans and ω scans	h = −35→35
4754 measured reflections	k = −7→7
2663 independent reflections	l = −22→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: difference Fourier map
wR(F^2) = 0.147	All H-atom parameters refined
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0596P)^2 + 0.7909P] where P = (Fo^2 + 2Fc^2)/3
2663 reflections	(Δ/σ)max = 0.001
211 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.98128 (5)	−0.2576 (2)	0.03225 (7)	0.0532 (3)
O2	1.07578 (6)	−0.4365 (2)	0.11500 (9)	0.0622 (4)
O3	0.88164 (5)	−0.1103 (3)	−0.04633 (8)	0.0647 (4)
C1	0.99219 (6)	−0.0936 (3)	0.08871 (10)	0.0439 (4)
C2	1.04514 (7)	−0.0866 (3)	0.15945 (11)	0.0487 (4)
C3	1.08464 (7)	−0.2538 (3)	0.16912 (10)	0.0438 (4)
C4	1.14060 (6)	−0.2499 (3)	0.23925 (10)	0.0442 (4)
C5	1.17842 (8)	−0.4248 (4)	0.24168 (13)	0.0576 (5)
C6	1.23117 (8)	−0.4202 (4)	0.30647 (14)	0.0666 (6)
C7	1.24668 (8)	−0.2460 (4)	0.36888 (14)	0.0628 (5)
C8	1.20940 (8)	−0.0731 (4)	0.36719 (14)	0.0652 (6)
C9	1.15676 (7)	−0.0745 (4)	0.30298 (13)	0.0582 (5)
C10	0.94946 (6)	0.0848 (3)	0.08046 (10)	0.0437 (4)
C11	0.89621 (7)	0.0643 (3)	0.01419 (11)	0.0486 (4)
C12	0.85615 (8)	0.2313 (4)	0.00927 (13)	0.0595 (5)
C13	0.86761 (8)	0.4148 (4)	0.06780 (13)	0.0606 (5)
C14	0.91996 (8)	0.4417 (4)	0.13249 (13)	0.0588 (5)
C15	0.95990 (8)	0.2792 (3)	0.13770 (12)	0.0513 (4)
H20	1.0398 (11)	−0.413 (4)	0.0730 (16)	0.084 (7)*
H30	0.9161 (14)	−0.228 (6)	−0.0306 (19)	0.133 (11)*
H15	0.9967 (8)	0.300 (3)	0.1824 (13)	0.058 (5)*
H2	1.0525 (8)	0.038 (4)	0.1994 (13)	0.063 (6)*
H5	1.1667 (7)	−0.563 (3)	0.1952 (12)	0.056 (5)*
H6	1.2561 (11)	−0.545 (4)	0.3060 (15)	0.087 (7)*
H7	1.2857 (10)	−0.248 (4)	0.4135 (14)	0.082 (7)*
H8	1.2193 (10)	0.050 (5)	0.4106 (16)	0.090 (8)*
H9	1.1315 (9)	0.047 (4)	0.3039 (13)	0.070 (6)*
H12	0.8201 (10)	0.206 (4)	−0.0375 (14)	0.080 (7)*
H13	0.8391 (9)	0.522 (4)	0.0631 (13)	0.074 (6)*
H14	0.9286 (9)	0.575 (4)	0.1734 (14)	0.073 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0454 (7)	0.0580 (7)	0.0494 (7)	0.0002 (5)	0.0146 (6)	−0.0087 (6)
O2	0.0482 (8)	0.0622 (8)	0.0619 (9)	0.0067 (6)	0.0113 (7)	−0.0181 (6)
O3	0.0442 (7)	0.0735 (9)	0.0613 (8)	0.0023 (6)	0.0094 (6)	−0.0081 (7)
C1	0.0413 (9)	0.0466 (8)	0.0448 (9)	−0.0029 (7)	0.0199 (7)	0.0016 (7)
C2	0.0413 (9)	0.0504 (9)	0.0475 (10)	0.0019 (7)	0.0133 (8)	−0.0053 (8)
C3	0.0423 (9)	0.0436 (8)	0.0458 (9)	−0.0023 (6)	0.0198 (7)	−0.0013 (7)
C4	0.0381 (9)	0.0442 (8)	0.0488 (9)	−0.0003 (6)	0.0180 (8)	0.0031 (7)
C5	0.0494 (10)	0.0571 (11)	0.0587 (12)	0.0090 (8)	0.0170 (9)	−0.0041 (9)
C6	0.0480 (11)	0.0715 (13)	0.0706 (13)	0.0168 (10)	0.0173 (10)	0.0000 (11)
C7	0.0403 (10)	0.0715 (13)	0.0651 (12)	0.0029 (9)	0.0129 (9)	0.0034 (10)
C8	0.0458 (10)	0.0666 (12)	0.0694 (13)	−0.0035 (9)	0.0130 (10)	−0.0146 (10)
C9	0.0416 (10)	0.0566 (11)	0.0672 (12)	0.0031 (8)	0.0157 (9)	−0.0106 (9)
C10	0.0397 (9)	0.0490 (9)	0.0425 (9)	0.0002 (7)	0.0181 (7)	0.0059 (7)
C11	0.0416 (9)	0.0539 (10)	0.0473 (10)	−0.0002 (7)	0.0168 (8)	0.0055 (8)
C12	0.0428 (10)	0.0691 (12)	0.0596 (12)	0.0083 (9)	0.0164 (9)	0.0102 (10)
C13	0.0542 (11)	0.0623 (11)	0.0695 (13)	0.0169 (9)	0.0311 (10)	0.0139 (10)
C14	0.0629 (12)	0.0569 (11)	0.0607 (12)	0.0073 (9)	0.0310 (10)	0.0014 (9)
C15	0.0453 (10)	0.0574 (10)	0.0492 (10)	0.0047 (8)	0.0192 (8)	0.0017 (8)

Geometric parameters (Å, º)

O1—C1	1.2675 (19)	C7—C8	1.376 (3)
O2—C3	1.3214 (19)	C7—H7	1.01 (2)
O2—H20	0.94 (3)	C8—C9	1.381 (3)
O3—C11	1.348 (2)	C8—H8	0.96 (3)
O3—H30	1.07 (3)	C9—H9	0.96 (2)
C1—C2	1.431 (2)	C10—C15	1.399 (2)
C1—C10	1.474 (2)	C10—C11	1.409 (2)
C2—C3	1.362 (2)	C11—C12	1.394 (3)
C2—H2	0.93 (2)	C12—C13	1.366 (3)
C3—C4	1.480 (2)	C12—H12	0.97 (2)
C4—C9	1.386 (2)	C13—C14	1.386 (3)
C4—C5	1.390 (2)	C13—H13	0.95 (2)
C5—C6	1.386 (3)	C14—C15	1.374 (3)
C5—H5	1.049 (19)	C14—H14	0.98 (2)
C6—C7	1.367 (3)	C15—H15	0.97 (2)
C6—H6	0.96 (3)
C3—O2—H20	105.0 (14)	C7—C8—H8	120.9 (14)
C11—O3—H30	107.4 (16)	C9—C8—H8	118.7 (14)
O1—C1—C2	119.78 (14)	C8—C9—C4	120.63 (17)
O1—C1—C10	118.90 (14)	C8—C9—H9	118.6 (13)
C2—C1—C10	121.32 (15)	C4—C9—H9	120.8 (13)
C3—C2—C1	122.05 (16)	C15—C10—C11	117.52 (15)
C3—C2—H2	119.7 (12)	C15—C10—C1	121.67 (15)
C1—C2—H2	118.3 (12)	C11—C10—C1	120.81 (15)
O2—C3—C2	121.90 (15)	O3—C11—C12	117.35 (16)
O2—C3—C4	113.80 (14)	O3—C11—C10	123.02 (15)
C2—C3—C4	124.30 (15)	C12—C11—C10	119.64 (17)
C9—C4—C5	118.58 (16)	C13—C12—C11	121.06 (18)
C9—C4—C3	121.73 (15)	C13—C12—H12	123.2 (13)
C5—C4—C3	119.69 (15)	C11—C12—H12	115.7 (13)
C6—C5—C4	120.06 (18)	C12—C13—C14	120.32 (18)
C6—C5—H5	120.1 (10)	C12—C13—H13	118.5 (13)
C4—C5—H5	119.8 (10)	C14—C13—H13	121.2 (13)
C7—C6—C5	120.84 (19)	C15—C14—C13	119.15 (19)
C7—C6—H6	121.6 (15)	C15—C14—H14	120.2 (13)
C5—C6—H6	117.5 (15)	C13—C14—H14	120.7 (13)
C6—C7—C8	119.46 (19)	C14—C15—C10	122.27 (18)
C6—C7—H7	117.7 (12)	C14—C15—H15	119.0 (11)
C8—C7—H7	122.8 (12)	C10—C15—H15	118.8 (11)
C7—C8—C9	120.4 (2)

(2) (2Z)-1-(2-hydroxy-5-chlorophenyl)-3-phenyl-1,3-propanedione enol

Crystal data

C15H11ClO3	F(000) = 568
Mr = 274.69	Dx = 1.429 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71070 Å
a = 13.932 (1) Å	Cell parameters from 5187 reflections
b = 5.3108 (2) Å	θ = 1.7–27.5°
c = 17.878 (1) Å	µ = 0.30 mm^−1
β = 105.137 (3)°	T = 295 K
V = 1276.9 (1) Å^3	Prism, yellow
Z = 4	0.33 × 0.12 × 0.09 mm

Data collection

Nonius Kappa CCD diffractometer	2098 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.036
Graphite monochromator	θmax = 27.5°, θmin = 1.7°
ϕ scans and ω scans	h = −18→18
5187 measured reflections	k = −6→6
2903 independent reflections	l = −23→22

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: difference Fourier map
wR(F^2) = 0.155	All H-atom parameters refined
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0628P)^2 + 0.4171P] where P = (Fo^2 + 2Fc^2)/3
2903 reflections	(Δ/σ)max < 0.001
216 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.37899 (5)	0.61864 (13)	0.02895 (4)	0.0720 (3)
O1	0.06832 (13)	−0.2578 (3)	0.01348 (9)	0.0598 (4)
O2	0.02363 (16)	−0.4856 (4)	−0.11610 (12)	0.0709 (5)
O3	0.12351 (15)	−0.0571 (4)	0.14978 (10)	0.0671 (5)
C1	0.12399 (16)	−0.1127 (4)	−0.01217 (13)	0.0476 (5)
C2	0.13109 (17)	−0.1391 (4)	−0.09002 (13)	0.0512 (5)
C3	0.08171 (16)	−0.3212 (4)	−0.13836 (13)	0.0488 (5)
C4	0.08757 (16)	−0.3556 (4)	−0.21924 (13)	0.0496 (5)
C5	0.1425 (2)	−0.1946 (5)	−0.25276 (15)	0.0641 (7)
C6	0.1468 (2)	−0.2289 (6)	−0.32860 (16)	0.0695 (7)
C7	0.0974 (2)	−0.4252 (5)	−0.37128 (16)	0.0662 (7)
C8	0.0437 (3)	−0.5874 (6)	−0.33911 (18)	0.0797 (9)
C9	0.0378 (2)	−0.5544 (6)	−0.26320 (16)	0.0690 (7)
C10	0.18195 (15)	0.0806 (4)	0.04010 (12)	0.0452 (5)
C11	0.17968 (17)	0.0945 (4)	0.11808 (13)	0.0519 (5)
C12	0.2389 (2)	0.2712 (5)	0.16682 (15)	0.0652 (7)
C13	0.2990 (2)	0.4322 (5)	0.13993 (15)	0.0624 (6)
C14	0.30071 (16)	0.4201 (4)	0.06310 (14)	0.0514 (5)
C15	0.24350 (16)	0.2493 (4)	0.01391 (13)	0.0489 (5)
H20	0.023 (2)	−0.438 (6)	−0.070 (2)	0.083 (10)*
H30	0.093 (3)	−0.165 (7)	0.114 (2)	0.108 (13)*
H2	0.170 (2)	−0.033 (5)	−0.1089 (16)	0.073 (8)*
H5	0.172 (3)	−0.043 (6)	−0.228 (2)	0.097 (10)*
H6	0.184 (2)	−0.118 (5)	−0.3494 (17)	0.069 (8)*
H7	0.1011 (19)	−0.446 (5)	−0.4242 (16)	0.065 (7)*
H8	0.016 (3)	−0.731 (6)	−0.364 (2)	0.097 (10)*
H9	0.008 (2)	−0.673 (6)	−0.2394 (19)	0.090 (10)*
H12	0.237 (2)	0.280 (5)	0.2202 (18)	0.075 (8)*
H13	0.338 (2)	0.551 (6)	0.1725 (19)	0.087 (9)*
H15	0.2466 (18)	0.242 (5)	−0.0399 (15)	0.059 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0664 (4)	0.0716 (4)	0.0802 (5)	−0.0208 (3)	0.0228 (3)	−0.0032 (3)
O1	0.0695 (11)	0.0627 (10)	0.0519 (10)	−0.0158 (8)	0.0246 (8)	−0.0009 (8)
O2	0.0904 (14)	0.0693 (11)	0.0583 (11)	−0.0323 (10)	0.0290 (10)	−0.0100 (9)
O3	0.0806 (13)	0.0803 (12)	0.0465 (10)	−0.0164 (10)	0.0276 (9)	−0.0014 (9)
C1	0.0466 (11)	0.0506 (11)	0.0461 (12)	−0.0009 (9)	0.0131 (9)	0.0016 (9)
C2	0.0543 (13)	0.0588 (13)	0.0428 (12)	−0.0108 (10)	0.0165 (10)	−0.0021 (10)
C3	0.0480 (11)	0.0498 (11)	0.0486 (12)	−0.0024 (9)	0.0128 (10)	0.0008 (9)
C4	0.0499 (12)	0.0499 (12)	0.0485 (12)	0.0005 (9)	0.0117 (10)	−0.0046 (9)
C5	0.0814 (18)	0.0620 (15)	0.0533 (14)	−0.0145 (13)	0.0252 (13)	−0.0120 (11)
C6	0.0805 (18)	0.0778 (18)	0.0563 (15)	−0.0097 (15)	0.0289 (14)	−0.0083 (13)
C7	0.0710 (17)	0.0800 (18)	0.0481 (14)	0.0055 (14)	0.0163 (12)	−0.0100 (13)
C8	0.089 (2)	0.084 (2)	0.0630 (18)	−0.0194 (17)	0.0146 (15)	−0.0266 (15)
C9	0.0784 (18)	0.0707 (17)	0.0578 (16)	−0.0201 (14)	0.0178 (13)	−0.0125 (13)
C10	0.0458 (11)	0.0509 (11)	0.0399 (11)	0.0039 (9)	0.0131 (9)	−0.0001 (9)
C11	0.0546 (13)	0.0600 (13)	0.0426 (12)	0.0005 (10)	0.0154 (10)	0.0011 (10)
C12	0.0779 (18)	0.0752 (17)	0.0442 (14)	−0.0064 (13)	0.0190 (12)	−0.0080 (12)
C13	0.0628 (15)	0.0674 (15)	0.0549 (15)	−0.0064 (12)	0.0120 (12)	−0.0137 (12)
C14	0.0460 (12)	0.0534 (12)	0.0549 (13)	0.0003 (9)	0.0134 (10)	−0.0020 (10)
C15	0.0500 (12)	0.0545 (12)	0.0440 (12)	0.0001 (10)	0.0154 (10)	−0.0007 (10)

Geometric parameters (Å, º)

Cl1—C14	1.738 (2)	C6—H6	0.92 (3)
O1—C1	1.261 (3)	C7—C8	1.362 (4)
O2—C3	1.320 (3)	C7—H7	0.97 (3)
O2—H20	0.86 (3)	C8—C9	1.392 (4)
O3—C11	1.346 (3)	C8—H8	0.91 (3)
O3—H30	0.88 (4)	C9—H9	0.91 (3)
C1—C2	1.428 (3)	C10—C15	1.402 (3)
C1—C10	1.478 (3)	C10—C11	1.405 (3)
C2—C3	1.359 (3)	C11—C12	1.395 (3)
C2—H2	0.91 (3)	C12—C13	1.369 (4)
C3—C4	1.481 (3)	C12—H12	0.96 (3)
C4—C5	1.384 (3)	C13—C14	1.381 (4)
C4—C9	1.389 (3)	C13—H13	0.93 (3)
C5—C6	1.385 (4)	C14—C15	1.366 (3)
C5—H5	0.96 (3)	C15—H15	0.98 (3)
C6—C7	1.367 (4)
C3—O2—H20	104 (2)	C7—C8—H8	122 (2)
C11—O3—H30	108 (2)	C9—C8—H8	117 (2)
O1—C1—C2	120.0 (2)	C4—C9—C8	120.0 (3)
O1—C1—C10	118.74 (19)	C4—C9—H9	119 (2)
C2—C1—C10	121.24 (19)	C8—C9—H9	121 (2)
C3—C2—C1	122.5 (2)	C15—C10—C11	118.2 (2)
C3—C2—H2	117.4 (18)	C15—C10—C1	120.89 (19)
C1—C2—H2	120.1 (18)	C11—C10—C1	120.89 (19)
O2—C3—C2	121.8 (2)	O3—C11—C12	116.9 (2)
O2—C3—C4	114.0 (2)	O3—C11—C10	123.6 (2)
C2—C3—C4	124.1 (2)	C12—C11—C10	119.5 (2)
C5—C4—C9	118.4 (2)	C13—C12—C11	121.1 (2)
C5—C4—C3	121.6 (2)	C13—C12—H12	119.8 (17)
C9—C4—C3	120.0 (2)	C11—C12—H12	119.0 (17)
C4—C5—C6	120.9 (2)	C12—C13—C14	119.4 (2)
C4—C5—H5	123 (2)	C12—C13—H13	121.1 (19)
C6—C5—H5	116 (2)	C14—C13—H13	119.5 (19)
C7—C6—C5	120.1 (3)	C15—C14—C13	120.8 (2)
C7—C6—H6	121.0 (18)	C15—C14—Cl1	119.40 (18)
C5—C6—H6	118.9 (18)	C13—C14—Cl1	119.77 (18)
C8—C7—C6	119.9 (3)	C14—C15—C10	121.0 (2)
C8—C7—H7	121.0 (16)	C14—C15—H15	119.6 (15)
C6—C7—H7	119.0 (16)	C10—C15—H15	119.5 (15)
C7—C8—C9	120.7 (3)

(3) (2Z)-1-(2-hydroxy-5-methylphenyl)-3-phenyl-1,3-propanedione enol

Crystal data

C16H14O3	Dx = 1.295 Mg m^−3
Mr = 254.27	Mo Kα radiation, λ = 0.71070 Å
Orthorhombic, Pca21	Cell parameters from 16585 reflections
a = 17.602 (1) Å	θ = 2.5–28°
b = 6.8423 (2) Å	µ = 0.09 mm^−1
c = 21.662 (1) Å	T = 295 K
V = 2609.0 (2) Å^3	Prism, yellow
Z = 8	0.26 × 0.21 × 0.14 mm
F(000) = 1072

Data collection

Nonius Kappa CCD diffractometer	3242 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.066
Graphite monochromator	θmax = 28.0°, θmin = 2.5°
ϕ scans and ω scans	h = −23→23
16585 measured reflections	k = −9→9
5825 independent reflections	l = −28→28

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.052	w = 1/[σ^2(Fo^2) + (0.0564P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.128	(Δ/σ)max = 0.002
S = 1.00	Δρmax = 0.16 e Å^−3
5825 reflections	Δρmin = −0.15 e Å^−3
455 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0147 (14)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.7 (11)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1A	0.08091 (13)	−0.0892 (2)	0.1380	0.0559 (6)
O2A	0.11158 (14)	−0.3610 (3)	0.06435 (13)	0.0601 (6)
O3A	0.06488 (12)	0.2003 (3)	0.21239 (13)	0.0549 (6)
C1A	0.03865 (17)	−0.0098 (4)	0.09731 (18)	0.0433 (8)
C2A	0.02821 (19)	−0.1049 (4)	0.03915 (17)	0.0503 (8)
C3A	0.06312 (18)	−0.2761 (4)	0.02524 (15)	0.0466 (7)
C4A	0.0521 (2)	−0.3885 (4)	−0.03246 (17)	0.0492 (8)
C5A	0.0092 (2)	−0.3169 (5)	−0.08065 (19)	0.0623 (9)
C6A	−0.0034 (3)	−0.4288 (5)	−0.1326 (2)	0.0739 (11)
C7A	0.0251 (3)	−0.6139 (5)	−0.1365 (2)	0.0840 (14)
C8A	0.0701 (3)	−0.6858 (5)	−0.0893 (2)	0.0874 (14)
C9A	0.0833 (3)	−0.5740 (5)	−0.0374 (2)	0.0682 (11)
C10A	0.00279 (16)	0.1781 (3)	0.11223 (16)	0.0416 (6)
C11A	0.01821 (17)	0.2745 (4)	0.16804 (15)	0.0456 (7)
C12A	−0.0155 (2)	0.4548 (4)	0.1806 (2)	0.0517 (8)
C13A	−0.06399 (19)	0.5382 (4)	0.13817 (19)	0.0527 (8)
C14A	−0.08265 (18)	0.4450 (4)	0.08352 (17)	0.0502 (8)
C15A	−0.04858 (18)	0.2681 (4)	0.07094 (17)	0.0484 (7)
C16A	−0.1374 (3)	0.5350 (7)	0.0391 (2)	0.0723 (11)
O1B	0.17626 (13)	−0.4486 (3)	0.18156 (11)	0.0549 (5)
O2B	0.14282 (14)	−0.1826 (3)	0.25675 (14)	0.0655 (6)
O3B	0.19601 (13)	−0.7342 (3)	0.10606 (13)	0.0550 (5)
C1B	0.21741 (19)	−0.5294 (4)	0.22173 (18)	0.0460 (8)
C2B	0.2265 (2)	−0.4363 (4)	0.28053 (17)	0.0505 (8)
C3B	0.19044 (17)	−0.2674 (4)	0.29563 (16)	0.0474 (7)
C4B	0.20214 (18)	−0.1577 (4)	0.35321 (16)	0.0498 (8)
C5B	0.2426 (2)	−0.2347 (5)	0.40239 (18)	0.0665 (10)
C6B	0.2573 (3)	−0.1235 (6)	0.4542 (2)	0.0773 (12)
C7B	0.2322 (3)	0.0662 (6)	0.4570 (2)	0.0725 (12)
C8B	0.1914 (2)	0.1454 (5)	0.4096 (2)	0.0715 (11)
C9B	0.1754 (2)	0.0326 (4)	0.35750 (19)	0.0589 (10)
C10B	0.25549 (16)	−0.7153 (3)	0.20711 (15)	0.0416 (6)
C11B	0.24125 (17)	−0.8100 (4)	0.15025 (16)	0.0453 (7)
C12B	0.2746 (2)	−0.9889 (4)	0.13923 (19)	0.0530 (9)
C13B	0.32167 (19)	−1.0746 (4)	0.18086 (18)	0.0528 (8)
C14B	0.33809 (19)	−0.9849 (4)	0.23765 (17)	0.0479 (8)
C15B	0.30402 (18)	−0.8066 (4)	0.24870 (16)	0.0470 (7)
C16B	0.3905 (3)	−1.0796 (5)	0.2838 (2)	0.0639 (10)
H20A	0.111 (2)	−0.286 (5)	0.104 (2)	0.098 (12)*
H30A	0.078 (2)	0.062 (6)	0.193 (2)	0.104 (13)*
H2A	−0.0104 (19)	−0.042 (4)	0.0093 (15)	0.044 (8)*
H5A	−0.012 (2)	−0.184 (5)	−0.0758 (16)	0.069 (9)*
H6A	−0.035 (2)	−0.373 (5)	−0.1629 (19)	0.073 (10)*
H7A	0.015 (2)	−0.704 (5)	−0.174 (2)	0.091 (11)*
H8A	0.099 (2)	−0.822 (5)	−0.0969 (16)	0.089 (11)*
H9A	0.116 (2)	−0.631 (5)	−0.0044 (16)	0.063 (9)*
H12A	−0.0041 (19)	0.526 (4)	0.2193 (18)	0.059 (9)*
H13A	−0.0820 (19)	0.666 (4)	0.1425 (15)	0.065 (9)*
H15A	−0.0600 (17)	0.207 (4)	0.0300 (14)	0.046 (7)*
H161	−0.132 (4)	0.473 (7)	−0.002 (3)	0.13 (2)*
H162	−0.128 (3)	0.664 (7)	0.028 (2)	0.109 (15)*
H163	−0.190 (3)	0.514 (6)	0.052 (3)	0.117 (18)*
H20B	0.148 (3)	−0.258 (5)	0.218 (2)	0.090 (11)*
H30B	0.175 (3)	−0.617 (6)	0.122 (2)	0.098 (13)*
H2B	0.2521 (19)	−0.487 (3)	0.3070 (16)	0.040 (8)*
H5B	0.261 (2)	−0.365 (5)	0.4002 (16)	0.074 (10)*
H6B	0.285 (2)	−0.187 (5)	0.490 (2)	0.085 (11)*
H7B	0.244 (2)	0.142 (5)	0.4967 (18)	0.072 (10)*
H8B	0.176 (2)	0.294 (5)	0.4072 (16)	0.080 (10)*
H9B	0.1453 (19)	0.082 (4)	0.3228 (16)	0.061 (9)*
H12B	0.2629 (18)	−1.053 (4)	0.0984 (18)	0.060 (9)*
H13B	0.3442 (17)	−1.197 (4)	0.1726 (13)	0.052 (8)*
H15B	0.3193 (19)	−0.733 (4)	0.2887 (16)	0.063 (9)*
H164	0.398 (3)	−1.219 (6)	0.2786 (19)	0.105 (13)*
H165	0.384 (3)	−1.027 (6)	0.326 (2)	0.110 (16)*
H166	0.446 (3)	−1.037 (5)	0.281 (2)	0.097 (15)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.0676 (16)	0.0465 (10)	0.0537 (12)	0.0114 (9)	−0.0136 (12)	−0.0006 (9)
O2A	0.0720 (16)	0.0566 (11)	0.0515 (13)	0.0201 (10)	−0.0126 (12)	−0.0041 (10)
O3A	0.0586 (16)	0.0558 (12)	0.0501 (13)	0.0061 (9)	−0.0077 (11)	−0.0020 (9)
C1A	0.0448 (18)	0.0414 (13)	0.044 (2)	−0.0002 (11)	−0.0028 (15)	0.0060 (11)
C2A	0.059 (2)	0.0440 (15)	0.0477 (18)	0.0061 (12)	−0.0068 (15)	0.0042 (12)
C3A	0.0519 (19)	0.0455 (15)	0.0424 (16)	0.0006 (12)	0.0026 (13)	0.0073 (11)
C4A	0.056 (2)	0.0478 (15)	0.0438 (18)	0.0006 (13)	0.0083 (15)	0.0005 (12)
C5A	0.076 (3)	0.0622 (19)	0.049 (2)	0.0108 (17)	0.0004 (18)	−0.0035 (15)
C6A	0.084 (3)	0.088 (2)	0.050 (3)	0.013 (2)	−0.012 (2)	−0.0059 (18)
C7A	0.124 (4)	0.077 (2)	0.051 (2)	0.010 (2)	0.000 (2)	−0.0191 (19)
C8A	0.140 (4)	0.068 (2)	0.054 (2)	0.024 (2)	0.002 (2)	−0.0129 (17)
C9A	0.089 (3)	0.0610 (19)	0.055 (2)	0.0161 (18)	0.000 (2)	−0.0044 (16)
C10A	0.0427 (18)	0.0393 (13)	0.0429 (15)	−0.0003 (10)	0.0046 (13)	0.0045 (11)
C11A	0.0456 (18)	0.0470 (14)	0.0443 (17)	0.0005 (12)	0.0005 (14)	0.0048 (11)
C12A	0.057 (2)	0.0459 (15)	0.052 (2)	0.0002 (13)	0.0039 (17)	−0.0059 (13)
C13A	0.055 (2)	0.0428 (16)	0.061 (2)	0.0068 (12)	0.0125 (17)	0.0026 (14)
C14A	0.049 (2)	0.0463 (14)	0.055 (2)	0.0071 (12)	0.0062 (16)	0.0139 (12)
C15A	0.0506 (19)	0.0496 (14)	0.0450 (17)	0.0030 (12)	0.0014 (14)	0.0084 (13)
C16A	0.072 (3)	0.070 (2)	0.076 (3)	0.0230 (19)	−0.007 (2)	0.014 (2)
O1B	0.0684 (16)	0.0479 (10)	0.0483 (12)	0.0115 (9)	−0.0131 (11)	−0.0044 (9)
O2B	0.0842 (18)	0.0596 (12)	0.0527 (14)	0.0302 (11)	−0.0183 (13)	−0.0111 (10)
O3B	0.0665 (15)	0.0588 (13)	0.0398 (12)	0.0082 (10)	−0.0065 (11)	−0.0063 (9)
C1B	0.055 (2)	0.0393 (14)	0.043 (2)	0.0015 (12)	−0.0008 (16)	−0.0007 (11)
C2B	0.062 (2)	0.0466 (15)	0.0432 (18)	0.0147 (13)	−0.0126 (15)	−0.0026 (12)
C3B	0.054 (2)	0.0452 (14)	0.0433 (16)	0.0085 (12)	−0.0027 (14)	−0.0031 (11)
C4B	0.056 (2)	0.0496 (16)	0.0436 (17)	0.0086 (13)	−0.0009 (14)	−0.0059 (12)
C5B	0.082 (3)	0.065 (2)	0.0523 (19)	0.0291 (18)	−0.0103 (18)	−0.0091 (16)
C6B	0.090 (3)	0.093 (3)	0.049 (2)	0.030 (2)	−0.011 (2)	−0.0131 (19)
C7B	0.087 (3)	0.078 (2)	0.053 (3)	0.0094 (19)	0.005 (2)	−0.0261 (18)
C8B	0.094 (3)	0.062 (2)	0.058 (2)	0.0182 (18)	0.003 (2)	−0.0159 (17)
C9B	0.074 (3)	0.0569 (19)	0.046 (2)	0.0161 (15)	−0.0012 (19)	−0.0079 (14)
C10B	0.0436 (18)	0.0402 (13)	0.0409 (15)	0.0006 (10)	0.0051 (13)	−0.0017 (11)
C11B	0.0452 (18)	0.0489 (14)	0.0419 (16)	−0.0016 (12)	0.0032 (14)	−0.0025 (11)
C12B	0.061 (2)	0.0530 (16)	0.045 (2)	0.0019 (13)	0.0036 (18)	−0.0125 (13)
C13B	0.056 (2)	0.0476 (15)	0.055 (2)	0.0089 (14)	0.0075 (17)	−0.0084 (14)
C14B	0.0432 (19)	0.0504 (15)	0.050 (2)	0.0068 (12)	0.0041 (15)	−0.0040 (12)
C15B	0.050 (2)	0.0464 (15)	0.0450 (17)	0.0042 (12)	0.0016 (15)	−0.0078 (12)
C16B	0.062 (3)	0.064 (2)	0.066 (2)	0.0190 (17)	−0.010 (2)	−0.0114 (17)

Geometric parameters (Å, º)

O1A—C1A	1.275 (3)	O1B—C1B	1.260 (4)
O2A—C3A	1.335 (3)	O2B—C3B	1.322 (3)
O2A—H20A	1.00 (4)	O2B—H20B	0.98 (4)
O3A—C11A	1.362 (3)	O3B—C11B	1.349 (3)
O3A—H30A	1.06 (5)	O3B—H30B	0.95 (4)
C1A—C2A	1.430 (4)	C1B—C2B	1.433 (4)
C1A—C10A	1.469 (4)	C1B—C10B	1.472 (4)
C2A—C3A	1.357 (4)	C2B—C3B	1.358 (4)
C2A—H2A	1.03 (3)	C2B—H2B	0.81 (3)
C3A—C4A	1.480 (4)	C3B—C4B	1.470 (4)
C4A—C5A	1.378 (5)	C4B—C5B	1.386 (4)
C4A—C9A	1.387 (5)	C4B—C9B	1.388 (4)
C5A—C6A	1.379 (5)	C5B—C6B	1.381 (5)
C5A—H5A	0.98 (3)	C5B—H5B	0.95 (3)
C6A—C7A	1.365 (5)	C6B—C7B	1.372 (5)
C6A—H6A	0.94 (4)	C6B—H6B	1.01 (4)
C7A—C8A	1.383 (6)	C7B—C8B	1.366 (6)
C7A—H7A	1.03 (4)	C7B—H7B	1.03 (4)
C8A—C9A	1.379 (5)	C8B—C9B	1.395 (5)
C8A—H8A	1.08 (3)	C8B—H8B	1.05 (3)
C9A—H9A	0.99 (4)	C9B—H9B	0.98 (4)
C10A—C11A	1.404 (4)	C10B—C15B	1.390 (4)
C10A—C15A	1.413 (4)	C10B—C11B	1.414 (4)
C11A—C12A	1.396 (4)	C11B—C12B	1.379 (4)
C12A—C13A	1.378 (5)	C12B—C13B	1.357 (5)
C12A—H12A	0.99 (4)	C12B—H12B	1.01 (4)
C13A—C14A	1.384 (5)	C13B—C14B	1.405 (4)
C13A—H13A	0.94 (3)	C13B—H13B	0.94 (3)
C14A—C15A	1.378 (4)	C14B—C15B	1.381 (4)
C14A—C16A	1.495 (5)	C14B—C16B	1.507 (5)
C15A—H15A	1.00 (3)	C15B—H15B	1.04 (3)
C16A—H161	0.99 (6)	C16B—H164	0.97 (4)
C16A—H162	0.93 (5)	C16B—H165	0.99 (5)
C16A—H163	0.98 (6)	C16B—H166	1.02 (5)
C3A—O2A—H20A	108 (2)	C3B—O2B—H20B	105 (2)
C11A—O3A—H30A	100 (2)	C11B—O3B—H30B	108 (3)
O1A—C1A—C2A	119.4 (2)	O1B—C1B—C2B	118.9 (2)
O1A—C1A—C10A	118.2 (3)	O1B—C1B—C10B	119.5 (3)
C2A—C1A—C10A	122.5 (3)	C2B—C1B—C10B	121.6 (3)
C3A—C2A—C1A	122.0 (3)	C3B—C2B—C1B	122.7 (3)
C3A—C2A—H2A	121.3 (16)	C3B—C2B—H2B	117 (2)
C1A—C2A—H2A	116.6 (16)	C1B—C2B—H2B	120 (2)
O2A—C3A—C2A	121.6 (3)	O2B—C3B—C2B	121.1 (3)
O2A—C3A—C4A	113.2 (2)	O2B—C3B—C4B	113.9 (2)
C2A—C3A—C4A	125.2 (3)	C2B—C3B—C4B	125.0 (3)
C5A—C4A—C9A	118.9 (3)	C5B—C4B—C9B	118.7 (3)
C5A—C4A—C3A	121.8 (3)	C5B—C4B—C3B	122.0 (2)
C9A—C4A—C3A	119.3 (3)	C9B—C4B—C3B	119.3 (3)
C4A—C5A—C6A	120.6 (3)	C6B—C5B—C4B	120.8 (3)
C4A—C5A—H5A	117 (2)	C6B—C5B—H5B	120 (2)
C6A—C5A—H5A	123 (2)	C4B—C5B—H5B	120 (2)
C7A—C6A—C5A	120.4 (4)	C7B—C6B—C5B	119.8 (3)
C7A—C6A—H6A	123 (2)	C7B—C6B—H6B	122 (2)
C5A—C6A—H6A	116 (2)	C5B—C6B—H6B	118 (2)
C6A—C7A—C8A	119.7 (4)	C8B—C7B—C6B	120.7 (3)
C6A—C7A—H7A	123 (2)	C8B—C7B—H7B	122.6 (19)
C8A—C7A—H7A	118 (2)	C6B—C7B—H7B	116.6 (19)
C9A—C8A—C7A	120.1 (3)	C7B—C8B—C9B	119.7 (3)
C9A—C8A—H8A	122 (2)	C7B—C8B—H8B	124 (2)
C7A—C8A—H8A	118.0 (19)	C9B—C8B—H8B	116 (2)
C8A—C9A—C4A	120.3 (4)	C4B—C9B—C8B	120.3 (3)
C8A—C9A—H9A	117.7 (19)	C4B—C9B—H9B	117.1 (19)
C4A—C9A—H9A	122.1 (19)	C8B—C9B—H9B	122.6 (18)
C11A—C10A—C15A	117.7 (2)	C15B—C10B—C11B	117.9 (2)
C11A—C10A—C1A	121.2 (2)	C15B—C10B—C1B	121.9 (2)
C15A—C10A—C1A	121.2 (3)	C11B—C10B—C1B	120.2 (2)
O3A—C11A—C12A	116.6 (3)	O3B—C11B—C12B	118.0 (3)
O3A—C11A—C10A	123.3 (2)	O3B—C11B—C10B	123.1 (2)
C12A—C11A—C10A	120.1 (3)	C12B—C11B—C10B	118.8 (3)
C13A—C12A—C11A	120.0 (3)	C13B—C12B—C11B	121.9 (3)
C13A—C12A—H12A	119.1 (19)	C13B—C12B—H12B	121.4 (17)
C11A—C12A—H12A	120.9 (19)	C11B—C12B—H12B	116.7 (17)
C12A—C13A—C14A	121.8 (3)	C12B—C13B—C14B	121.2 (3)
C12A—C13A—H13A	122 (2)	C12B—C13B—H13B	120.9 (17)
C14A—C13A—H13A	116 (2)	C14B—C13B—H13B	117.9 (17)
C15A—C14A—C13A	118.1 (3)	C15B—C14B—C13B	116.6 (3)
C15A—C14A—C16A	121.0 (3)	C15B—C14B—C16B	122.0 (3)
C13A—C14A—C16A	120.9 (3)	C13B—C14B—C16B	121.3 (3)
C14A—C15A—C10A	122.4 (3)	C14B—C15B—C10B	123.5 (3)
C14A—C15A—H15A	117.0 (16)	C14B—C15B—H15B	117.5 (17)
C10A—C15A—H15A	120.5 (16)	C10B—C15B—H15B	118.9 (16)
C14A—C16A—H161	110 (3)	C14B—C16B—H164	116 (3)
C14A—C16A—H162	116 (3)	C14B—C16B—H165	113 (3)
H161—C16A—H162	99 (4)	H164—C16B—H165	119 (3)
C14A—C16A—H163	111 (3)	C14B—C16B—H166	115 (2)
H161—C16A—H163	107 (5)	H164—C16B—H166	98 (3)
H162—C16A—H163	113 (4)	H165—C16B—H166	94 (4)

(4) (2Z)-1-(2-hydroxy-4-methyl-5-chlorophenyl)-3-phenyl-1,3-propanedione enol

Crystal data

C16H13ClO3	F(000) = 600
Mr = 288.71	Dx = 1.413 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71070 Å
a = 14.147 (1) Å	Cell parameters from 5414 reflections
b = 5.3300 (3) Å	θ = 3.0–27.5°
c = 18.618 (2) Å	µ = 0.29 mm^−1
β = 104.777 (4)°	T = 295 K
V = 1357.4 (2) Å^3	Prism, yellow
Z = 4	0.48 × 0.11 × 0.07 mm

Data collection

Nonius Kappa CCD diffractometer	2210 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.049
Graphite monochromator	θmax = 27.5°, θmin = 3.0°
ϕ scans and ω scans	h = −18→18
5414 measured reflections	k = −6→6
3078 independent reflections	l = −24→23

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: difference Fourier map
wR(F^2) = 0.160	All H-atom parameters refined
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0652P)^2 + 0.3211P] where P = (Fo^2 + 2Fc^2)/3
3078 reflections	(Δ/σ)max < 0.001
233 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.42 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.61718 (5)	1.08215 (13)	−0.01326 (4)	0.0684 (3)
O1	0.93055 (14)	0.2348 (3)	−0.00791 (10)	0.0619 (5)
O2	0.97198 (16)	−0.0121 (4)	0.11356 (12)	0.0701 (6)
O3	0.88526 (17)	0.4733 (4)	−0.13311 (11)	0.0742 (6)
C1	0.87488 (17)	0.3740 (4)	0.01827 (13)	0.0496 (5)
C2	0.86620 (18)	0.3339 (5)	0.09237 (13)	0.0525 (6)
C3	0.91447 (17)	0.1488 (4)	0.13671 (13)	0.0478 (5)
C4	0.90833 (17)	0.1060 (4)	0.21409 (13)	0.0477 (5)
C5	0.8559 (2)	0.2670 (5)	0.24816 (14)	0.0583 (6)
C6	0.8546 (2)	0.2320 (6)	0.32156 (15)	0.0651 (7)
C7	0.9040 (2)	0.0365 (5)	0.36132 (16)	0.0657 (7)
C8	0.9540 (3)	−0.1277 (6)	0.32795 (17)	0.0714 (8)
C9	0.9570 (2)	−0.0946 (5)	0.25450 (16)	0.0630 (7)
C10	0.81909 (17)	0.5727 (4)	−0.02872 (12)	0.0469 (5)
C11	0.82638 (19)	0.6124 (4)	−0.10230 (13)	0.0533 (6)
C12	0.7710 (2)	0.7987 (5)	−0.14550 (14)	0.0601 (7)
C13	0.70543 (18)	0.9469 (4)	−0.12148 (13)	0.0511 (5)
C14	0.69912 (17)	0.9060 (4)	−0.04817 (12)	0.0470 (5)
C15	0.75375 (17)	0.7275 (4)	−0.00388 (13)	0.0490 (5)
C16	0.6451 (3)	1.1397 (6)	−0.17072 (18)	0.0655 (7)
H20	0.970 (3)	0.029 (8)	0.066 (3)	0.116 (14)*
H30	0.918 (3)	0.348 (7)	−0.097 (2)	0.106 (12)*
H2	0.824 (2)	0.447 (5)	0.1082 (17)	0.071 (8)*
H5	0.822 (2)	0.412 (5)	0.2217 (16)	0.061 (7)*
H6	0.823 (2)	0.355 (5)	0.3434 (16)	0.063 (7)*
H7	0.902 (2)	0.006 (6)	0.412 (2)	0.087 (9)*
H8	0.989 (3)	−0.258 (7)	0.353 (2)	0.096 (11)*
H9	0.992 (3)	−0.193 (7)	0.232 (2)	0.096 (11)*
H12	0.775 (2)	0.821 (6)	−0.1995 (19)	0.083 (9)*
H15	0.7471 (19)	0.709 (5)	0.0439 (15)	0.057 (7)*
H16A	0.662 (3)	1.298 (8)	−0.159 (2)	0.107 (13)*
H16B	0.639 (3)	1.101 (7)	−0.224 (2)	0.101 (12)*
H16C	0.580 (4)	1.131 (8)	−0.174 (3)	0.129 (16)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0731 (5)	0.0813 (5)	0.0611 (4)	0.0264 (3)	0.0361 (3)	0.0065 (3)
O1	0.0718 (11)	0.0657 (10)	0.0576 (10)	0.0195 (8)	0.0338 (9)	0.0007 (8)
O2	0.0905 (14)	0.0646 (11)	0.0653 (12)	0.0278 (10)	0.0386 (11)	0.0069 (9)
O3	0.0953 (15)	0.0863 (13)	0.0574 (11)	0.0309 (11)	0.0496 (11)	0.0083 (10)
C1	0.0497 (13)	0.0547 (13)	0.0498 (13)	0.0020 (10)	0.0227 (10)	−0.0021 (10)
C2	0.0570 (14)	0.0581 (13)	0.0481 (13)	0.0102 (11)	0.0240 (11)	0.0011 (10)
C3	0.0502 (13)	0.0470 (11)	0.0504 (12)	0.0011 (9)	0.0205 (10)	−0.0033 (9)
C4	0.0504 (13)	0.0441 (11)	0.0504 (12)	−0.0019 (9)	0.0162 (10)	0.0015 (9)
C5	0.0689 (16)	0.0581 (14)	0.0537 (14)	0.0094 (12)	0.0261 (12)	0.0094 (11)
C6	0.0801 (18)	0.0679 (16)	0.0570 (15)	0.0047 (14)	0.0351 (14)	0.0067 (12)
C7	0.0805 (19)	0.0699 (16)	0.0517 (15)	−0.0064 (14)	0.0263 (14)	0.0115 (12)
C8	0.085 (2)	0.0637 (17)	0.0657 (17)	0.0110 (14)	0.0203 (15)	0.0198 (14)
C9	0.0760 (18)	0.0542 (14)	0.0621 (16)	0.0096 (12)	0.0236 (14)	0.0061 (12)
C10	0.0511 (13)	0.0543 (12)	0.0414 (11)	0.0022 (9)	0.0226 (10)	−0.0003 (9)
C11	0.0606 (14)	0.0607 (14)	0.0480 (13)	0.0060 (11)	0.0310 (11)	0.0006 (10)
C12	0.0741 (17)	0.0687 (15)	0.0484 (14)	0.0072 (13)	0.0360 (13)	0.0069 (11)
C13	0.0561 (14)	0.0549 (13)	0.0472 (12)	−0.0010 (10)	0.0220 (11)	0.0055 (10)
C14	0.0484 (12)	0.0545 (12)	0.0441 (12)	0.0015 (9)	0.0229 (10)	−0.0004 (9)
C15	0.0530 (13)	0.0590 (13)	0.0419 (12)	0.0023 (10)	0.0247 (10)	0.0012 (10)
C16	0.076 (2)	0.0671 (18)	0.0581 (17)	0.0100 (14)	0.0259 (15)	0.0143 (13)

Geometric parameters (Å, º)

Cl1—C14	1.741 (2)	C7—C8	1.370 (4)
O1—C1	1.267 (3)	C7—H7	0.97 (4)
O2—C3	1.327 (3)	C8—C9	1.390 (4)
O2—H20	0.91 (4)	C8—H8	0.90 (4)
O3—C11	1.348 (3)	C9—H9	0.90 (4)
O3—H30	0.98 (4)	C10—C15	1.402 (3)
C1—C2	1.432 (3)	C10—C11	1.416 (3)
C1—C10	1.469 (3)	C11—C12	1.387 (4)
C2—C3	1.354 (3)	C12—C13	1.377 (3)
C2—H2	0.95 (3)	C12—H12	1.03 (3)
C3—C4	1.483 (3)	C13—C14	1.407 (3)
C4—C9	1.385 (3)	C13—C16	1.492 (4)
C4—C5	1.389 (3)	C14—C15	1.363 (3)
C5—C6	1.384 (4)	C15—H15	0.92 (3)
C5—H5	0.97 (3)	C16—H16A	0.89 (4)
C6—C7	1.363 (4)	C16—H16B	0.99 (4)
C6—H6	0.94 (3)	C16—H16C	0.91 (5)
C3—O2—H20	107 (3)	C4—C9—H9	117 (2)
C11—O3—H30	109 (2)	C8—C9—H9	123 (2)
O1—C1—C2	119.8 (2)	C15—C10—C11	116.6 (2)
O1—C1—C10	119.1 (2)	C15—C10—C1	121.79 (19)
C2—C1—C10	121.1 (2)	C11—C10—C1	121.6 (2)
C3—C2—C1	122.8 (2)	O3—C11—C12	117.8 (2)
C3—C2—H2	122.4 (18)	O3—C11—C10	122.3 (2)
C1—C2—H2	114.8 (18)	C12—C11—C10	119.9 (2)
O2—C3—C2	121.9 (2)	C13—C12—C11	123.3 (2)
O2—C3—C4	114.1 (2)	C13—C12—H12	117.6 (18)
C2—C3—C4	124.0 (2)	C11—C12—H12	118.9 (18)
C9—C4—C5	118.6 (2)	C12—C13—C14	116.2 (2)
C9—C4—C3	120.2 (2)	C12—C13—C16	121.5 (2)
C5—C4—C3	121.3 (2)	C14—C13—C16	122.3 (2)
C6—C5—C4	120.7 (2)	C15—C14—C13	121.9 (2)
C6—C5—H5	118.8 (17)	C15—C14—Cl1	118.64 (16)
C4—C5—H5	120.5 (17)	C13—C14—Cl1	119.44 (18)
C7—C6—C5	120.4 (3)	C14—C15—C10	122.1 (2)
C7—C6—H6	122.1 (17)	C14—C15—H15	118.5 (16)
C5—C6—H6	117.4 (17)	C10—C15—H15	119.4 (16)
C6—C7—C8	119.6 (3)	C13—C16—H16A	115 (3)
C6—C7—H7	122 (2)	C13—C16—H16B	111 (2)
C8—C7—H7	119 (2)	H16A—C16—H16B	114 (3)
C7—C8—C9	120.9 (3)	C13—C16—H16C	115 (3)
C7—C8—H8	122 (2)	H16A—C16—H16C	106 (4)
C9—C8—H8	117 (2)	H16B—C16—H16C	95 (3)
C4—C9—C8	119.8 (3)

(5)

Crystal data

C14H13HClNO6	Z = 2
Mr = 327.71	F(000) = 340
Triclinic, P1	Dx = 1.555 Mg m^−3
a = 5.6849 (1) Å	Mo Kα radiation, λ = 0.71070 Å
b = 9.0280 (2) Å	Cell parameters from 6530 reflections
c = 14.8742 (4) Å	θ = 1.4–30.5°
α = 74.923 (1)°	µ = 0.30 mm^−1
β = 83.543 (2)°	T = 100 K
γ = 71.815 (2)°	Prismatic, colourless
V = 699.89 (3) Å^3	0.52 × 0.35 × 0.16 mm

Data collection

Nonius Kappa CCD diffractometer	3680 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
Graphite monochromator	θmax = 30.5°, θmin = 1.4°
ϕ scans and ω scans	h = −8→8
14589 measured reflections	k = −11→12
4119 independent reflections	l = −20→21

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: difference Fourier map
wR(F^2) = 0.084	All H-atom parameters refined
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0241P)^2 + 0.393P] where P = (Fo^2 + 2Fc^2)/3
4119 reflections	(Δ/σ)max = 0.001
260 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.72278 (6)	0.67396 (4)	0.80134 (2)	0.02131 (8)
N1	1.15346 (18)	0.77222 (12)	1.11743 (7)	0.01496 (19)
O1	0.85429 (15)	0.97255 (10)	1.16568 (6)	0.01689 (17)
O2	0.90903 (17)	1.06695 (11)	1.29759 (6)	0.01891 (18)
O3	1.54817 (17)	0.63363 (11)	1.21802 (7)	0.0231 (2)
O4	1.18313 (17)	0.73549 (11)	1.48518 (6)	0.02133 (19)
O5	1.50717 (16)	0.80777 (10)	1.51302 (6)	0.01822 (18)
O6	1.60177 (15)	0.74474 (10)	1.32843 (6)	0.01704 (17)
C1	1.0671 (2)	0.87171 (13)	1.17487 (8)	0.0131 (2)
C2	1.2274 (2)	0.86095 (13)	1.24929 (7)	0.0132 (2)
C3	1.1306 (2)	0.96485 (13)	1.30840 (8)	0.0143 (2)
C4	1.4694 (2)	0.73721 (13)	1.26210 (8)	0.0140 (2)
C5	1.2601 (2)	0.97650 (14)	1.38834 (8)	0.0158 (2)
C6	1.3095 (2)	0.82574 (14)	1.46621 (8)	0.0151 (2)
C7	1.5708 (3)	0.66553 (15)	1.58847 (9)	0.0220 (2)
C8	1.8356 (2)	0.61951 (15)	1.34838 (9)	0.0175 (2)
C9	1.0384 (2)	0.75887 (13)	1.04176 (7)	0.0133 (2)
C10	0.7884 (2)	0.83052 (14)	1.02230 (8)	0.0161 (2)
C11	0.6947 (2)	0.80583 (14)	0.94680 (8)	0.0167 (2)
C12	0.8493 (2)	0.70884 (13)	0.89244 (8)	0.0152 (2)
C13	1.0982 (2)	0.63688 (14)	0.91028 (8)	0.0164 (2)
C14	1.1910 (2)	0.66299 (14)	0.98517 (8)	0.0156 (2)
H1	1.303 (3)	0.703 (2)	1.1317 (12)	0.033 (5)*
H2	0.848 (4)	1.048 (3)	1.242 (2)	0.072 (8)
H51	1.415 (3)	1.001 (2)	1.3676 (12)	0.026 (4)*
H52	1.147 (3)	1.064 (2)	1.4122 (11)	0.025 (4)*
H71	1.725 (3)	0.6654 (19)	1.6114 (11)	0.022 (4)*
H72	1.441 (3)	0.672 (2)	1.6384 (12)	0.025 (4)*
H73	1.596 (3)	0.569 (2)	1.5644 (12)	0.028 (4)*
H81	1.918 (3)	0.6563 (19)	1.3875 (11)	0.023 (4)*
H82	1.936 (3)	0.607 (2)	1.2914 (12)	0.027 (4)*
H83	1.805 (3)	0.519 (2)	1.3801 (12)	0.030 (4)*
H11	0.520 (3)	0.8551 (19)	0.9320 (11)	0.022 (4)*
H10	0.679 (3)	0.8954 (19)	1.0607 (11)	0.020 (4)*
H13	1.206 (3)	0.568 (2)	0.8718 (12)	0.027 (4)*
H14	1.364 (3)	0.6164 (18)	1.0003 (11)	0.020 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.02636 (16)	0.02430 (15)	0.01704 (14)	−0.00828 (12)	−0.00690 (11)	−0.00780 (11)
N1	0.0139 (4)	0.0158 (4)	0.0145 (4)	−0.0007 (4)	−0.0049 (3)	−0.0052 (3)
O1	0.0156 (4)	0.0174 (4)	0.0169 (4)	−0.0010 (3)	−0.0042 (3)	−0.0061 (3)
O2	0.0179 (4)	0.0197 (4)	0.0185 (4)	0.0000 (3)	−0.0049 (3)	−0.0085 (3)
O3	0.0218 (4)	0.0225 (4)	0.0244 (5)	0.0034 (3)	−0.0100 (4)	−0.0127 (4)
O4	0.0239 (4)	0.0241 (4)	0.0177 (4)	−0.0119 (4)	−0.0050 (3)	−0.0002 (3)
O5	0.0225 (4)	0.0180 (4)	0.0158 (4)	−0.0071 (3)	−0.0080 (3)	−0.0023 (3)
O6	0.0145 (4)	0.0199 (4)	0.0168 (4)	−0.0025 (3)	−0.0055 (3)	−0.0054 (3)
C1	0.0152 (5)	0.0129 (5)	0.0114 (5)	−0.0051 (4)	−0.0017 (4)	−0.0014 (4)
C2	0.0152 (5)	0.0132 (5)	0.0113 (5)	−0.0045 (4)	−0.0027 (4)	−0.0018 (4)
C3	0.0175 (5)	0.0124 (5)	0.0129 (5)	−0.0051 (4)	−0.0023 (4)	−0.0016 (4)
C4	0.0152 (5)	0.0150 (5)	0.0117 (5)	−0.0052 (4)	−0.0025 (4)	−0.0014 (4)
C5	0.0206 (6)	0.0134 (5)	0.0148 (5)	−0.0047 (4)	−0.0047 (4)	−0.0044 (4)
C6	0.0173 (5)	0.0167 (5)	0.0123 (5)	−0.0039 (4)	−0.0023 (4)	−0.0059 (4)
C7	0.0283 (7)	0.0197 (6)	0.0172 (6)	−0.0055 (5)	−0.0105 (5)	−0.0012 (4)
C8	0.0125 (5)	0.0202 (5)	0.0187 (5)	−0.0040 (4)	−0.0050 (4)	−0.0021 (4)
C9	0.0155 (5)	0.0131 (5)	0.0116 (5)	−0.0039 (4)	−0.0034 (4)	−0.0025 (4)
C10	0.0148 (5)	0.0166 (5)	0.0172 (5)	−0.0022 (4)	−0.0026 (4)	−0.0067 (4)
C11	0.0158 (5)	0.0156 (5)	0.0187 (5)	−0.0028 (4)	−0.0055 (4)	−0.0042 (4)
C12	0.0202 (5)	0.0151 (5)	0.0120 (5)	−0.0070 (4)	−0.0042 (4)	−0.0028 (4)
C13	0.0185 (5)	0.0164 (5)	0.0150 (5)	−0.0044 (4)	−0.0003 (4)	−0.0057 (4)
C14	0.0146 (5)	0.0156 (5)	0.0164 (5)	−0.0031 (4)	−0.0023 (4)	−0.0044 (4)
H2	0.017 (12)	0.037 (14)	0.13 (2)	0.016 (10)	−0.002 (14)	0.012 (16)

Geometric parameters (Å, º)

Cl1—C12	1.7422 (11)	C5—H51	0.972 (17)
N1—H1	0.893 (19)	C5—C6	1.5124 (16)
N1—C1	1.3443 (14)	C7—H71	0.976 (16)
N1—C9	1.4124 (14)	C7—H72	0.984 (17)
O1—C1	1.2633 (14)	C7—H73	0.994 (17)
O1—H2	1.46 (3)	C8—H81	0.965 (17)
O2—C3	1.3063 (15)	C8—H83	0.971 (18)
O2—H2	1.01 (3)	C8—H82	0.979 (17)
O3—C4	1.2233 (14)	C9—C10	1.3940 (15)
O4—C6	1.2080 (14)	C9—C14	1.3989 (15)
O5—C6	1.3334 (14)	C10—H10	0.961 (16)
O5—C7	1.4461 (15)	C10—C11	1.3905 (16)
O6—C4	1.3334 (13)	C11—H11	0.978 (16)
O6—C8	1.4524 (14)	C11—C12	1.3860 (16)
C1—C2	1.4769 (15)	C12—C13	1.3838 (16)
C2—C3	1.3977 (15)	C13—H13	0.980 (17)
C2—C4	1.4717 (15)	C13—C14	1.3861 (16)
C3—C5	1.5089 (15)	C14—H14	0.968 (16)
C5—H52	0.971 (17)
H1—N1—C1	113.6 (12)	H71—C7—H73	110.8 (14)
H1—N1—C9	117.0 (12)	H72—C7—H73	111.0 (14)
C1—N1—C9	129.35 (10)	H71—C7—O5	104.8 (9)
C1—O1—H2	100.4 (8)	H72—C7—O5	110.5 (10)
C3—O2—H2	103.7 (11)	H73—C7—O5	109.7 (10)
C6—O5—C7	115.10 (9)	H81—C8—H83	111.7 (14)
C4—O6—C8	116.59 (9)	H81—C8—H82	109.7 (14)
O1—C1—N1	121.13 (10)	H83—C8—H82	109.6 (14)
O1—C1—C2	120.45 (10)	H81—C8—O6	104.5 (10)
N1—C1—C2	118.42 (10)	H83—C8—O6	109.8 (10)
C3—C2—C4	123.24 (10)	H82—C8—O6	111.5 (10)
C3—C2—C1	116.89 (10)	C10—C9—C14	119.50 (10)
C4—C2—C1	119.74 (9)	C10—C9—N1	124.67 (10)
O2—C3—C2	121.21 (10)	C14—C9—N1	115.82 (10)
O2—C3—C5	112.44 (10)	H10—C10—C11	119.2 (9)
C2—C3—C5	126.34 (10)	H10—C10—C9	121.3 (9)
O3—C4—O6	121.03 (10)	C11—C10—C9	119.48 (11)
O3—C4—C2	124.92 (10)	H11—C11—C12	119.4 (9)
O6—C4—C2	114.04 (10)	H11—C11—C10	120.7 (9)
H52—C5—H51	109.0 (14)	C12—C11—C10	119.86 (11)
H52—C5—C3	105.5 (10)	C13—C12—C11	121.66 (10)
H51—C5—C3	111.5 (10)	C13—C12—Cl1	119.73 (9)
H52—C5—C6	108.5 (10)	C11—C12—Cl1	118.59 (9)
H51—C5—C6	109.4 (10)	H13—C13—C12	121.1 (10)
C3—C5—C6	112.72 (9)	H13—C13—C14	120.7 (10)
O4—C6—O5	124.32 (11)	C12—C13—C14	118.22 (11)
O4—C6—C5	124.62 (10)	H14—C14—C13	121.6 (9)
O5—C6—C5	111.04 (10)	H14—C14—C9	117.2 (9)
H71—C7—H72	109.8 (13)	C13—C14—C9	121.27 (11)