3,4-Dihy­droxy-1,6-bis­(4-meth­oxy­phen­yl)hexa-2,4-diene-1,6-dione, its 4-methyl­phenyl analogue, and a potassium salt of 2-hy­droxy-4-(4-meth­oxy­phen­yl)-4-oxobut-2-enoic acid

Reaction of 4-meth­oxy­aceto­phenone with diethyl oxalate under basic conditions produced 3,4-dihy­droxy-1,6-bis­(4-meth­oxy­phenyl)hexa-2,4-diene-1,6-dione, C₂₀H₁₈O₆, (1). The mol­ecules lie across a crystallographic inversion centre and intra­molecular hydrogen bonding, similar to acetyl­acetone, is observed, confirming that the mol­ecule is in the di-enol-dione tautomeric form. Additional O—H...O hydrogen bonds link the mol­ecules into chains parallel to the b axis. The structure is compared with that of redetermined 4-methyl­phenyl com­pound 3,4-dihy­droxy-1,6-bis­(4-methyl­phenyl)hexa-2,4-diene-1,6-dione, C₂₀H₁₈O₄, (2), which crystallizes in a similar fashion. The salt, catena-poly[[μ₂-2-hy­droxy-4-(4-meth­oxy­phenyl)-4-oxo­but-2-enoato-κ³O¹,O²:O⁴][μ₂-2-hy­droxy-4-(4-meth­oxy­phenyl)-4-oxobut-2-enoic acid-κ²O¹:O⁴]potassium], [K(C₁₁H₉O₅)(C₁₁H₁₀O₅)]_n, (3), was isolated as a by-product of the synthesis of (1). The two organic species are linked by a strong hydrogen bond between the carb­oxy­lic acid and carboxyl­ate groups. They are further stabilized and linked into a double-chain structure via the seven-coordinate potassium ion.

Computing details

For all compounds, data collection: SHELXTL (Sheldrick, 2008); cell refinement: SHELXTL (Sheldrick, 2008); data reduction: SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008). Software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004) and publCIF (Westrip 2010) for compound1, compound3; SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004) and publCIF (Westrip, 2010) for compound2.

(compound1) 3,4-Dihydroxy-1,6-bis(4-methoxyphenyl)hexa-2,4-diene-1,6-dione

Crystal data

C20H18O6	F(000) = 372
Mr = 354.34	Dx = 1.471 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6419 reflections
a = 15.4385 (6) Å	θ = 2.7–30.4°
b = 6.1475 (2) Å	µ = 0.11 mm^−1
c = 8.7281 (3) Å	T = 116 K
β = 105.029 (2)°	Plate, yellow
V = 800.03 (5) Å^3	0.55 × 0.33 × 0.12 mm
Z = 2

Data collection

Bruker APEXII CCD area-detector diffractometer	2313 independent reflections
Radiation source: fine-focus sealed tube	2155 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ and ω scans	θmax = 30.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −20→21
Tmin = 0.943, Tmax = 0.987	k = −8→8
16170 measured reflections	l = −12→12

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)] = 0.043	Hydrogen site location: difference Fourier map
wR(F^2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0523P)^2 + 0.2726P] where P = (Fo^2 + 2Fc^2)/3
2313 reflections	(Δ/σ)max < 0.001
122 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.32 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	−0.00663 (6)	0.71487 (12)	0.97532 (10)	0.02027 (19)
H1	−0.0476 (10)	0.642 (2)	0.8907 (18)	0.024*
O2	−0.12517 (5)	0.63048 (12)	0.72353 (9)	0.01960 (18)
O3	−0.41635 (6)	1.05028 (14)	0.16040 (10)	0.0264 (2)
C1	−0.02613 (7)	0.92265 (16)	0.94117 (12)	0.0153 (2)
C2	−0.08909 (7)	0.98991 (17)	0.80906 (12)	0.0168 (2)
H2	−0.1000	1.1407	0.7894	0.020*
C3	−0.13895 (7)	0.83071 (17)	0.69928 (12)	0.0162 (2)
C4	−0.20934 (7)	0.90088 (17)	0.55747 (12)	0.0166 (2)
C5	−0.27195 (8)	0.74536 (17)	0.48004 (13)	0.0195 (2)
H5	−0.2677	0.6003	0.5188	0.023*
C6	−0.33969 (8)	0.80018 (18)	0.34814 (13)	0.0221 (2)
H6	−0.3820	0.6936	0.2974	0.026*
C7	−0.34583 (8)	1.01304 (18)	0.28942 (13)	0.0196 (2)
C8	−0.28320 (7)	1.16862 (17)	0.36206 (12)	0.0192 (2)
H8	−0.2863	1.3120	0.3205	0.023*
C9	−0.21571 (7)	1.11223 (17)	0.49676 (12)	0.0182 (2)
H9	−0.1736	1.2191	0.5478	0.022*
C10	−0.43629 (8)	1.27080 (19)	0.11246 (15)	0.0256 (3)
H10A	−0.4505	1.3524	0.1993	0.031*
H10B	−0.4879	1.2747	0.0192	0.031*
H10C	−0.3842	1.3366	0.0859	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0253 (4)	0.0111 (3)	0.0207 (4)	0.0012 (3)	−0.0008 (3)	−0.0001 (3)
O2	0.0235 (4)	0.0139 (3)	0.0202 (4)	0.0000 (3)	0.0037 (3)	0.0001 (3)
O3	0.0272 (5)	0.0211 (4)	0.0235 (4)	0.0017 (3)	−0.0069 (3)	−0.0026 (3)
C1	0.0176 (5)	0.0125 (4)	0.0156 (4)	0.0001 (3)	0.0038 (4)	0.0000 (4)
C2	0.0197 (5)	0.0137 (4)	0.0158 (4)	0.0002 (3)	0.0022 (4)	0.0003 (4)
C3	0.0175 (5)	0.0160 (4)	0.0155 (4)	0.0001 (3)	0.0047 (3)	0.0004 (4)
C4	0.0174 (5)	0.0168 (4)	0.0149 (4)	−0.0005 (4)	0.0029 (4)	−0.0016 (4)
C5	0.0223 (5)	0.0149 (4)	0.0198 (5)	−0.0011 (4)	0.0026 (4)	−0.0011 (4)
C6	0.0231 (6)	0.0178 (5)	0.0218 (5)	−0.0025 (4)	−0.0003 (4)	−0.0048 (4)
C7	0.0200 (5)	0.0202 (5)	0.0165 (5)	0.0013 (4)	0.0011 (4)	−0.0030 (4)
C8	0.0211 (5)	0.0171 (5)	0.0181 (5)	−0.0008 (4)	0.0025 (4)	0.0004 (4)
C9	0.0186 (5)	0.0172 (5)	0.0177 (5)	−0.0024 (4)	0.0024 (4)	−0.0007 (4)
C10	0.0250 (6)	0.0243 (5)	0.0240 (5)	0.0025 (4)	0.0002 (4)	0.0032 (4)

Geometric parameters (Å, º)

O1—C1	1.3284 (12)	C5—C6	1.3813 (15)
O1—H1	0.951 (15)	C5—H5	0.9500
O2—C3	1.2577 (12)	C6—C7	1.3996 (15)
O3—C7	1.3675 (13)	C6—H6	0.9500
O3—C10	1.4285 (14)	C7—C8	1.3906 (15)
C1—C2	1.3653 (14)	C8—C9	1.3974 (14)
C1—C1^i	1.476 (2)	C8—H8	0.9500
C2—C3	1.4443 (14)	C9—H9	0.9500
C2—H2	0.9500	C10—H10A	0.9800
C3—C4	1.4837 (14)	C10—H10B	0.9800
C4—C9	1.3970 (15)	C10—H10C	0.9800
C4—C5	1.4023 (14)
C1—O1—H1	102.2 (9)	C5—C6—H6	120.1
C7—O3—C10	117.72 (9)	C7—C6—H6	120.1
O1—C1—C2	123.44 (9)	O3—C7—C8	124.84 (10)
O1—C1—C1^i	114.34 (11)	O3—C7—C6	114.96 (10)
C2—C1—C1^i	122.23 (11)	C8—C7—C6	120.20 (10)
C1—C2—C3	119.69 (9)	C7—C8—C9	119.44 (10)
C1—C2—H2	120.2	C7—C8—H8	120.3
C3—C2—H2	120.2	C9—C8—H8	120.3
O2—C3—C2	120.91 (9)	C4—C9—C8	120.91 (10)
O2—C3—C4	118.70 (9)	C4—C9—H9	119.5
C2—C3—C4	120.37 (9)	C8—C9—H9	119.5
C9—C4—C5	118.65 (10)	O3—C10—H10A	109.5
C9—C4—C3	123.44 (9)	O3—C10—H10B	109.5
C5—C4—C3	117.91 (9)	H10A—C10—H10B	109.5
C6—C5—C4	120.90 (10)	O3—C10—H10C	109.5
C6—C5—H5	119.5	H10A—C10—H10C	109.5
C4—C5—H5	119.5	H10B—C10—H10C	109.5
C5—C6—C7	119.87 (10)
O1—C1—C2—C3	0.73 (16)	C4—C5—C6—C7	0.61 (18)
C1^i—C1—C2—C3	−179.17 (12)	C10—O3—C7—C8	−10.96 (17)
C1—C2—C3—O2	−0.05 (16)	C10—O3—C7—C6	168.78 (10)
C1—C2—C3—C4	178.32 (10)	C5—C6—C7—O3	−178.81 (10)
O2—C3—C4—C9	−163.46 (10)	C5—C6—C7—C8	0.94 (18)
C2—C3—C4—C9	18.13 (16)	O3—C7—C8—C9	177.88 (10)
O2—C3—C4—C5	15.87 (15)	C6—C7—C8—C9	−1.84 (17)
C2—C3—C4—C5	−162.54 (10)	C5—C4—C9—C8	0.27 (16)
C9—C4—C5—C6	−1.20 (17)	C3—C4—C9—C8	179.59 (10)
C3—C4—C5—C6	179.44 (10)	C7—C8—C9—C4	1.24 (16)

Symmetry code: (i) −x, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.951 (15)	1.631 (15)	2.5224 (11)	154.4 (14)
O1—H1···O1^ii	0.951 (15)	2.526 (15)	2.6760 (15)	88.5 (9)

Symmetry code: (ii) −x, −y+1, −z+2.

(compound2) 3,4-Dihydroxy-1,6-bis(4-methylphenyl)hexa-2,4-diene-1,6-dione

Crystal data

C20H18O4	F(000) = 340
Mr = 322.34	Dx = 1.365 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5544 reflections
a = 14.7710 (6) Å	θ = 2.8–30.7°
b = 6.1622 (2) Å	µ = 0.10 mm^−1
c = 8.6184 (3) Å	T = 116 K
β = 91.896 (2)°	Plate, yellow
V = 784.03 (5) Å^3	0.62 × 0.46 × 0.06 mm
Z = 2

Data collection

Bruker APEXII CCD area-detector diffractometer	2288 independent reflections
Radiation source: fine-focus sealed tube	2150 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
φ and ω scans	θmax = 30.0°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −20→20
Tmin = 0.944, Tmax = 0.994	k = −8→8
19282 measured reflections	l = −12→12

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)] = 0.067	Hydrogen site location: difference Fourier map
wR(F^2) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 1.25	w = 1/[σ^2(Fo^2) + (0.0474P)^2 + 0.5796P] where P = (Fo^2 + 2Fc^2)/3
2288 reflections	(Δ/σ)max < 0.001
116 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.32 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	0.00746 (9)	0.28418 (18)	0.52331 (14)	0.0208 (3)
H1	0.0479 (15)	0.356 (4)	0.589 (3)	0.025*
O2	0.12923 (8)	0.36429 (19)	0.72956 (13)	0.0203 (3)
C1	0.02699 (11)	0.0771 (2)	0.54860 (17)	0.0159 (3)
C2	0.09117 (11)	0.0077 (2)	0.65506 (18)	0.0175 (3)
H2	0.0990 (14)	−0.144 (3)	0.670 (2)	0.021*
C3	0.14247 (11)	0.1644 (3)	0.74647 (17)	0.0169 (3)
C4	0.21345 (11)	0.0898 (3)	0.86024 (17)	0.0174 (3)
C5	0.27745 (12)	0.2403 (3)	0.91639 (19)	0.0213 (3)
H5	0.2746	0.3861	0.8807	0.026*
C6	0.34485 (12)	0.1800 (3)	1.0230 (2)	0.0240 (4)
H6	0.3880	0.2843	1.0589	0.029*
C7	0.34998 (11)	−0.0329 (3)	1.07841 (19)	0.0217 (3)
C8	0.28543 (12)	−0.1814 (3)	1.02491 (19)	0.0216 (3)
H8	0.2871	−0.3257	1.0638	0.026*
C9	0.21839 (12)	−0.1234 (3)	0.91558 (19)	0.0199 (3)
H9	0.1759	−0.2286	0.8785	0.024*
C10	0.42402 (13)	−0.1005 (3)	1.1934 (2)	0.0306 (4)
H10A	0.4808	−0.1191	1.1394	0.037*
H10B	0.4074	−0.2379	1.2422	0.037*
H10C	0.4319	0.0117	1.2734	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0289 (6)	0.0104 (5)	0.0227 (6)	0.0004 (4)	−0.0055 (5)	−0.0011 (4)
O2	0.0276 (6)	0.0138 (5)	0.0196 (5)	−0.0009 (4)	−0.0003 (5)	−0.0004 (4)
C1	0.0207 (7)	0.0126 (6)	0.0146 (6)	0.0004 (5)	0.0020 (5)	−0.0007 (5)
C2	0.0235 (8)	0.0138 (7)	0.0152 (7)	−0.0006 (6)	−0.0007 (6)	−0.0001 (5)
C3	0.0204 (7)	0.0168 (7)	0.0137 (6)	−0.0005 (6)	0.0028 (5)	0.0003 (5)
C4	0.0212 (7)	0.0177 (7)	0.0133 (6)	−0.0005 (6)	0.0019 (5)	−0.0016 (5)
C5	0.0263 (8)	0.0172 (7)	0.0204 (7)	−0.0032 (6)	0.0002 (6)	−0.0008 (6)
C6	0.0239 (8)	0.0245 (8)	0.0235 (8)	−0.0051 (6)	−0.0022 (6)	−0.0029 (6)
C7	0.0207 (8)	0.0258 (8)	0.0186 (7)	0.0012 (6)	−0.0001 (6)	−0.0024 (6)
C8	0.0261 (8)	0.0178 (7)	0.0206 (7)	0.0008 (6)	−0.0012 (6)	−0.0001 (6)
C9	0.0246 (8)	0.0171 (7)	0.0180 (7)	−0.0023 (6)	−0.0010 (6)	−0.0003 (6)
C10	0.0250 (9)	0.0353 (10)	0.0310 (9)	0.0028 (7)	−0.0057 (7)	−0.0024 (8)

Geometric parameters (Å, º)

O1—C1	1.3248 (18)	C5—H5	0.9500
O1—H1	0.92 (2)	C6—C7	1.397 (2)
O2—C3	1.2552 (19)	C6—H6	0.9500
C1—C2	1.366 (2)	C7—C8	1.390 (2)
C1—C1^i	1.482 (3)	C7—C10	1.510 (2)
C2—C3	1.445 (2)	C8—C9	1.391 (2)
C2—H2	0.95 (2)	C8—H8	0.9500
C3—C4	1.485 (2)	C9—H9	0.9500
C4—C9	1.399 (2)	C10—H10A	0.9800
C4—C5	1.399 (2)	C10—H10B	0.9800
C5—C6	1.383 (2)	C10—H10C	0.9800
C1—O1—H1	103.3 (14)	C5—C6—H6	119.7
O1—C1—C2	123.67 (14)	C7—C6—H6	119.7
O1—C1—C1^i	114.48 (17)	C8—C7—C6	118.44 (16)
C2—C1—C1^i	121.85 (17)	C8—C7—C10	120.67 (16)
C1—C2—C3	119.81 (14)	C6—C7—C10	120.88 (16)
C1—C2—H2	118.6 (13)	C7—C8—C9	121.39 (16)
C3—C2—H2	121.5 (13)	C7—C8—H8	119.3
O2—C3—C2	121.04 (15)	C9—C8—H8	119.3
O2—C3—C4	118.97 (14)	C8—C9—C4	120.02 (15)
C2—C3—C4	119.98 (14)	C8—C9—H9	120.0
C9—C4—C5	118.53 (15)	C4—C9—H9	120.0
C9—C4—C3	122.93 (14)	C7—C10—H10A	109.5
C5—C4—C3	118.53 (14)	C7—C10—H10B	109.5
C6—C5—C4	121.01 (16)	H10A—C10—H10B	109.5
C6—C5—H5	119.5	C7—C10—H10C	109.5
C4—C5—H5	119.5	H10A—C10—H10C	109.5
C5—C6—C7	120.59 (16)	H10B—C10—H10C	109.5
O1—C1—C2—C3	−0.5 (2)	C3—C4—C5—C6	179.73 (15)
C1^i—C1—C2—C3	179.62 (17)	C4—C5—C6—C7	−0.7 (3)
C1—C2—C3—O2	−0.2 (2)	C5—C6—C7—C8	−0.5 (3)
C1—C2—C3—C4	−178.88 (14)	C5—C6—C7—C10	179.30 (17)
O2—C3—C4—C9	163.58 (15)	C6—C7—C8—C9	1.7 (3)
C2—C3—C4—C9	−17.7 (2)	C10—C7—C8—C9	−178.10 (16)
O2—C3—C4—C5	−15.4 (2)	C7—C8—C9—C4	−1.7 (3)
C2—C3—C4—C5	163.33 (15)	C5—C4—C9—C8	0.5 (2)
C9—C4—C5—C6	0.7 (2)	C3—C4—C9—C8	−178.51 (15)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.92 (2)	1.68 (2)	2.5351 (17)	153 (2)
O1—H1···O1^ii	0.92 (2)	2.54 (2)	2.698 (2)	89.7 (14)

Symmetry code: (ii) −x, −y+1, −z+1.

(compound3) catena-poly[[µ₂-2-hydroxy-4-(4-methoxyphenyl)-4-oxobut-2-enoato-κ²O¹,O²][µ₂-2-hydroxy-4-(4-methoxyphenyl)-4-oxobut-2-enoic acid-κO¹]potassium]

Crystal data

[K(C11H9O5)(C11H10O5)]	F(000) = 1000
Mr = 482.47	Dx = 1.551 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9844 reflections
a = 15.3832 (4) Å	θ = 2.7–33.6°
b = 6.3481 (1) Å	µ = 0.32 mm^−1
c = 21.1606 (5) Å	T = 116 K
β = 90.582 (1)°	Block, orange
V = 2066.31 (8) Å^3	0.57 × 0.55 × 0.39 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	6026 independent reflections
Radiation source: fine-focus sealed tube	5402 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
φ and ω scans	θmax = 30.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −21→21
Tmin = 0.840, Tmax = 0.886	k = −8→8
52473 measured reflections	l = −29→29

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.090	w = 1/[σ^2(Fo^2) + (0.0465P)^2 + 0.7703P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
6026 reflections	Δρmax = 0.47 e Å^−3
316 parameters	Δρmin = −0.42 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0018 (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
K1	0.094861 (16)	0.35025 (4)	0.081718 (11)	0.02174 (7)
O1	0.10832 (5)	−0.25622 (12)	0.12862 (4)	0.02025 (16)
H1	0.0616 (10)	−0.146 (2)	0.1106 (7)	0.024*
O2	0.19157 (5)	0.02958 (12)	0.14601 (4)	0.01979 (16)
O3	0.23039 (5)	−0.51295 (12)	0.16089 (4)	0.02209 (17)
H2	0.2761 (10)	−0.580 (3)	0.1754 (7)	0.027*
O4	0.37824 (5)	−0.58187 (12)	0.21043 (4)	0.02280 (17)
O8	0.71085 (5)	−0.13407 (13)	0.32273 (5)	0.02622 (18)
C1	0.17878 (7)	−0.15990 (15)	0.14749 (5)	0.01563 (18)
C2	0.24789 (7)	−0.31033 (16)	0.17157 (5)	0.01602 (18)
C3	0.32152 (7)	−0.23950 (16)	0.20031 (5)	0.01704 (19)
H3	0.3295 (9)	−0.094 (2)	0.2060 (7)	0.020*
C4	0.38838 (7)	−0.38792 (16)	0.21960 (5)	0.01727 (19)
C5	0.47061 (7)	−0.31106 (16)	0.24838 (5)	0.01718 (19)
C6	0.54056 (7)	−0.45201 (17)	0.25357 (6)	0.0221 (2)
H6	0.5335	−0.5935	0.2399	0.027*
C7	0.61938 (7)	−0.38761 (18)	0.27830 (6)	0.0244 (2)
H7	0.6666	−0.4839	0.2806	0.029*
C8	0.63018 (7)	−0.18150 (17)	0.29998 (5)	0.0195 (2)
C9	0.56060 (7)	−0.04037 (17)	0.29702 (5)	0.0196 (2)
H9	0.5669	0.0987	0.3130	0.024*
C10	0.48194 (7)	−0.10559 (17)	0.27046 (5)	0.0186 (2)
H10	0.4351	−0.0085	0.2673	0.022*
C11	0.72737 (8)	0.07866 (19)	0.34241 (6)	0.0270 (2)
H11A	0.7198	0.1736	0.3063	0.032*
H11B	0.7870	0.0899	0.3587	0.032*
H11C	0.6865	0.1177	0.3757	0.032*
O21	0.00426 (5)	−0.00255 (12)	0.08664 (4)	0.02243 (17)
O22	−0.08478 (5)	−0.24898 (12)	0.04660 (4)	0.02125 (16)
O23	−0.09110 (5)	0.30340 (12)	0.04625 (4)	0.01976 (16)
H22	−0.1306 (10)	0.386 (2)	0.0348 (7)	0.024*
O24	−0.23541 (5)	0.43226 (12)	−0.00102 (4)	0.02236 (17)
O28	−0.59212 (5)	0.11734 (14)	−0.11483 (5)	0.02695 (19)
C21	−0.06453 (6)	−0.06570 (15)	0.05847 (5)	0.01456 (18)
C22	−0.12488 (7)	0.11186 (15)	0.03830 (5)	0.01493 (18)
C23	−0.20529 (7)	0.07281 (16)	0.01429 (5)	0.01698 (19)
H23	−0.2255 (9)	−0.066 (2)	0.0116 (7)	0.020*
C24	−0.26057 (7)	0.24507 (16)	−0.00662 (5)	0.01689 (19)
C25	−0.34704 (6)	0.20051 (16)	−0.03497 (5)	0.01650 (19)
C26	−0.40475 (7)	0.36872 (16)	−0.04486 (5)	0.0202 (2)
H26	−0.3879	0.5072	−0.0330	0.024*
C27	−0.48552 (7)	0.33529 (18)	−0.07160 (6)	0.0228 (2)
H27	−0.5242	0.4503	−0.0776	0.027*
C28	−0.51075 (7)	0.13258 (17)	−0.09002 (5)	0.0196 (2)
C29	−0.45353 (7)	−0.03595 (17)	−0.08203 (6)	0.0212 (2)
H29	−0.4697	−0.1734	−0.0954	0.025*
C30	−0.37267 (7)	−0.00053 (17)	−0.05422 (5)	0.0201 (2)
H30	−0.3340	−0.1156	−0.0482	0.024*
C31	−0.62155 (8)	−0.0852 (2)	−0.13503 (6)	0.0278 (2)
H31A	−0.5838	−0.1373	−0.1686	0.033*
H31B	−0.6813	−0.0741	−0.1511	0.033*
H31C	−0.6197	−0.1831	−0.0992	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.02692 (13)	0.01534 (11)	0.02285 (12)	−0.00585 (8)	−0.00509 (9)	−0.00186 (8)
O1	0.0181 (4)	0.0139 (3)	0.0286 (4)	−0.0009 (3)	−0.0086 (3)	0.0010 (3)
O2	0.0204 (4)	0.0137 (3)	0.0252 (4)	−0.0008 (3)	−0.0055 (3)	0.0001 (3)
O3	0.0232 (4)	0.0131 (3)	0.0298 (4)	0.0011 (3)	−0.0099 (3)	0.0011 (3)
O4	0.0246 (4)	0.0166 (3)	0.0271 (4)	0.0022 (3)	−0.0061 (3)	−0.0004 (3)
O8	0.0151 (4)	0.0239 (4)	0.0396 (5)	0.0013 (3)	−0.0071 (3)	0.0008 (3)
C1	0.0165 (4)	0.0151 (4)	0.0153 (4)	0.0005 (3)	−0.0020 (3)	−0.0002 (3)
C2	0.0185 (5)	0.0139 (4)	0.0157 (4)	0.0004 (3)	−0.0020 (4)	0.0010 (3)
C3	0.0180 (5)	0.0155 (4)	0.0175 (5)	0.0013 (3)	−0.0029 (4)	−0.0002 (3)
C4	0.0182 (5)	0.0186 (4)	0.0150 (4)	0.0012 (4)	−0.0014 (4)	0.0002 (3)
C5	0.0163 (4)	0.0184 (4)	0.0169 (5)	0.0026 (4)	−0.0015 (4)	0.0008 (3)
C6	0.0208 (5)	0.0172 (5)	0.0284 (6)	0.0042 (4)	−0.0036 (4)	0.0002 (4)
C7	0.0183 (5)	0.0208 (5)	0.0339 (6)	0.0063 (4)	−0.0035 (4)	0.0017 (4)
C8	0.0144 (4)	0.0220 (5)	0.0220 (5)	0.0020 (4)	−0.0019 (4)	0.0037 (4)
C9	0.0172 (5)	0.0187 (5)	0.0229 (5)	0.0025 (4)	−0.0031 (4)	−0.0012 (4)
C10	0.0164 (5)	0.0193 (5)	0.0202 (5)	0.0048 (4)	−0.0022 (4)	−0.0012 (4)
C11	0.0197 (5)	0.0265 (6)	0.0348 (6)	−0.0025 (4)	−0.0026 (5)	−0.0007 (5)
O21	0.0185 (4)	0.0140 (3)	0.0346 (4)	−0.0009 (3)	−0.0112 (3)	0.0001 (3)
O22	0.0229 (4)	0.0131 (3)	0.0277 (4)	−0.0023 (3)	−0.0056 (3)	−0.0009 (3)
O23	0.0196 (4)	0.0115 (3)	0.0280 (4)	−0.0002 (3)	−0.0056 (3)	−0.0003 (3)
O24	0.0213 (4)	0.0159 (3)	0.0297 (4)	−0.0002 (3)	−0.0068 (3)	−0.0005 (3)
O28	0.0174 (4)	0.0265 (4)	0.0368 (5)	−0.0006 (3)	−0.0097 (3)	−0.0003 (3)
C21	0.0144 (4)	0.0134 (4)	0.0159 (4)	−0.0001 (3)	−0.0008 (3)	0.0008 (3)
C22	0.0163 (4)	0.0131 (4)	0.0153 (4)	0.0000 (3)	−0.0002 (3)	0.0000 (3)
C23	0.0160 (4)	0.0144 (4)	0.0204 (5)	−0.0003 (3)	−0.0024 (4)	0.0012 (3)
C24	0.0162 (4)	0.0176 (4)	0.0168 (4)	0.0006 (3)	−0.0015 (3)	0.0004 (3)
C25	0.0149 (4)	0.0177 (4)	0.0169 (5)	0.0008 (3)	−0.0016 (3)	0.0007 (3)
C26	0.0194 (5)	0.0162 (4)	0.0249 (5)	0.0017 (4)	−0.0033 (4)	−0.0016 (4)
C27	0.0185 (5)	0.0197 (5)	0.0300 (6)	0.0043 (4)	−0.0051 (4)	−0.0008 (4)
C28	0.0156 (5)	0.0227 (5)	0.0206 (5)	−0.0005 (4)	−0.0023 (4)	0.0014 (4)
C29	0.0189 (5)	0.0178 (5)	0.0268 (5)	−0.0014 (4)	−0.0037 (4)	−0.0001 (4)
C30	0.0173 (5)	0.0173 (5)	0.0256 (5)	0.0011 (4)	−0.0032 (4)	0.0012 (4)
C31	0.0230 (5)	0.0320 (6)	0.0284 (6)	−0.0072 (5)	−0.0056 (4)	−0.0017 (5)

Geometric parameters (Å, º)

K1—O21	2.6404 (8)	C10—K1^vi	3.3665 (11)
K1—O1^i	2.6953 (8)	C10—H10	0.9500
K1—O22^ii	2.7931 (9)	C11—H11A	0.9800
K1—O3^i	2.7994 (8)	C11—H11B	0.9800
K1—O2	2.8578 (8)	C11—H11C	0.9800
K1—O23	2.9651 (8)	O21—C21	1.2740 (12)
K1—O24^iii	3.0939 (9)	O21—H1	1.361 (15)
K1—C10^iv	3.3665 (11)	O22—C21	1.2297 (12)
K1—C21^ii	3.5003 (10)	O22—K1^ii	2.7931 (9)
K1—K1^iii	4.8876 (5)	O23—C22	1.3323 (12)
O1—C1	1.3037 (12)	O23—H22	0.836 (16)
O1—K1^v	2.6953 (8)	O24—C24	1.2549 (13)
O1—H1	1.071 (15)	O24—K1^iii	3.0939 (9)
O2—C1	1.2193 (12)	O28—C28	1.3559 (13)
O3—C2	1.3329 (12)	O28—C31	1.4270 (15)
O3—K1^v	2.7994 (8)	C21—C22	1.5188 (14)
O3—H2	0.875 (16)	C21—K1^ii	3.5003 (10)
O4—C4	1.2559 (13)	C22—C23	1.3554 (14)
O8—C8	1.3603 (13)	C23—C24	1.4516 (14)
O8—C11	1.4351 (15)	C23—H23	0.938 (15)
C1—C2	1.5135 (14)	C24—C25	1.4810 (14)
C2—C3	1.3569 (14)	C25—C30	1.3952 (14)
C3—C4	1.4503 (14)	C25—C26	1.4029 (14)
C3—H3	0.939 (15)	C26—C27	1.3765 (15)
C4—C5	1.4810 (14)	C26—H26	0.9500
C5—C10	1.3959 (14)	C27—C28	1.3984 (15)
C5—C6	1.4030 (14)	C27—H27	0.9500
C6—C7	1.3778 (16)	C28—C29	1.3946 (15)
C6—H6	0.9500	C29—C30	1.3890 (14)
C7—C8	1.3959 (16)	C29—H29	0.9500
C7—H7	0.9500	C30—H30	0.9500
C8—C9	1.3967 (14)	C31—H31A	0.9800
C9—C10	1.3919 (14)	C31—H31B	0.9800
C9—H9	0.9500	C31—H31C	0.9800
O21—K1—O1^i	144.12 (3)	C5—C6—H6	119.6
O21—K1—O22^ii	79.57 (3)	C6—C7—C8	120.28 (10)
O1^i—K1—O22^ii	125.07 (2)	C6—C7—H7	119.9
O21—K1—O3^i	129.03 (3)	C8—C7—H7	119.9
O1^i—K1—O3^i	55.82 (2)	O8—C8—C7	115.39 (9)
O22^ii—K1—O3^i	133.38 (3)	O8—C8—C9	124.74 (10)
O21—K1—O2	69.48 (2)	C7—C8—C9	119.86 (10)
O1^i—K1—O2	116.57 (2)	C10—C9—C8	119.34 (10)
O22^ii—K1—O2	108.81 (2)	C10—C9—H9	120.3
O3^i—K1—O2	63.58 (2)	C8—C9—H9	120.3
O21—K1—O23	54.31 (2)	C9—C10—C5	121.21 (9)
O1^i—K1—O23	104.86 (2)	C9—C10—K1^vi	87.79 (7)
O22^ii—K1—O23	71.76 (2)	C5—C10—K1^vi	100.92 (7)
O3^i—K1—O23	153.30 (3)	C9—C10—H10	119.4
O2—K1—O23	123.05 (2)	C5—C10—H10	119.4
O21—K1—O24^iii	140.57 (3)	K1^vi—C10—H10	81.2
O1^i—K1—O24^iii	74.82 (2)	O8—C11—H11A	109.5
O22^ii—K1—O24^iii	66.32 (2)	O8—C11—H11B	109.5
O3^i—K1—O24^iii	70.82 (2)	H11A—C11—H11B	109.5
O2—K1—O24^iii	102.55 (2)	O8—C11—H11C	109.5
O23—K1—O24^iii	125.66 (2)	H11A—C11—H11C	109.5
O21—K1—C10^iv	81.00 (3)	H11B—C11—H11C	109.5
O1^i—K1—C10^iv	66.86 (3)	C21—O21—K1	133.21 (7)
O22^ii—K1—C10^iv	154.94 (3)	C21—O21—H1	119.7 (6)
O3^i—K1—C10^iv	71.60 (3)	K1—O21—H1	104.0 (6)
O2—K1—C10^iv	78.63 (3)	C21—O22—K1^ii	115.33 (7)
O23—K1—C10^iv	84.07 (2)	C22—O23—K1	119.84 (6)
O24^iii—K1—C10^iv	136.84 (2)	C22—O23—H22	104.7 (10)
O21—K1—C21^ii	61.96 (3)	K1—O23—H22	135.0 (10)
O1^i—K1—C21^ii	143.08 (2)	C24—O24—K1^iii	125.95 (7)
O22^ii—K1—C21^ii	18.52 (2)	C28—O28—C31	117.98 (9)
O3^i—K1—C21^ii	139.40 (3)	O22—C21—O21	126.93 (9)
O2—K1—C21^ii	95.75 (2)	O22—C21—C22	119.46 (9)
O23—K1—C21^ii	67.28 (2)	O21—C21—C22	113.60 (8)
O24^iii—K1—C21^ii	81.40 (2)	O22—C21—K1^ii	46.16 (5)
C10^iv—K1—C21^ii	141.75 (2)	O21—C21—K1^ii	131.45 (7)
O21—K1—K1^iii	92.650 (18)	C22—C21—K1^ii	93.95 (6)
O1^i—K1—K1^iii	86.737 (17)	O23—C22—C23	124.58 (9)
O22^ii—K1—K1^iii	51.303 (17)	O23—C22—C21	113.91 (9)
O3^i—K1—K1^iii	137.606 (18)	C23—C22—C21	121.50 (9)
O2—K1—K1^iii	156.663 (18)	C22—C23—C24	120.40 (9)
O23—K1—K1^iii	44.949 (16)	C22—C23—H23	119.7 (9)
O24^iii—K1—K1^iii	81.459 (16)	C24—C23—H23	119.9 (9)
C10^iv—K1—K1^iii	114.35 (2)	O24—C24—C23	120.36 (9)
C21^ii—K1—K1^iii	61.807 (17)	O24—C24—C25	119.60 (9)
C1—O1—K1^v	127.44 (6)	C23—C24—C25	120.04 (9)
C1—O1—H1	110.8 (8)	C30—C25—C26	118.44 (9)
K1^v—O1—H1	115.2 (8)	C30—C25—C24	122.89 (9)
C1—O2—K1	129.17 (7)	C26—C25—C24	118.64 (9)
C2—O3—K1^v	123.28 (6)	C27—C26—C25	120.74 (10)
C2—O3—H2	104.5 (10)	C27—C26—H26	119.6
K1^v—O3—H2	130.5 (10)	C25—C26—H26	119.6
C8—O8—C11	117.98 (9)	C26—C27—C28	120.22 (10)
O2—C1—O1	126.06 (10)	C26—C27—H27	119.9
O2—C1—C2	121.21 (9)	C28—C27—H27	119.9
O1—C1—C2	112.72 (8)	O28—C28—C29	124.84 (10)
O3—C2—C3	124.19 (9)	O28—C28—C27	115.22 (10)
O3—C2—C1	114.32 (9)	C29—C28—C27	119.94 (10)
C3—C2—C1	121.47 (9)	C30—C29—C28	119.25 (10)
C2—C3—C4	119.81 (9)	C30—C29—H29	120.4
C2—C3—H3	119.4 (9)	C28—C29—H29	120.4
C4—C3—H3	120.7 (9)	C29—C30—C25	121.39 (10)
O4—C4—C3	120.45 (10)	C29—C30—H30	119.3
O4—C4—C5	119.39 (9)	C25—C30—H30	119.3
C3—C4—C5	120.13 (9)	O28—C31—H31A	109.5
C10—C5—C6	118.46 (10)	O28—C31—H31B	109.5
C10—C5—C4	123.28 (9)	H31A—C31—H31B	109.5
C6—C5—C4	118.25 (10)	O28—C31—H31C	109.5
C7—C6—C5	120.79 (10)	H31A—C31—H31C	109.5
C7—C6—H6	119.6	H31B—C31—H31C	109.5
O21—K1—O2—C1	14.89 (9)	C10^iv—K1—O21—C21	112.06 (10)
O1^i—K1—O2—C1	156.16 (9)	C21^ii—K1—O21—C21	−58.09 (10)
O22^ii—K1—O2—C1	−55.74 (10)	K1^iii—K1—O21—C21	−2.18 (10)
O3^i—K1—O2—C1	174.39 (10)	O21—K1—O23—C22	−13.80 (7)
O23—K1—O2—C1	24.30 (10)	O1^i—K1—O23—C22	−161.10 (7)
O24^iii—K1—O2—C1	−124.71 (9)	O22^ii—K1—O23—C22	76.32 (7)
C10^iv—K1—O2—C1	99.44 (9)	O3^i—K1—O23—C22	−121.11 (8)
C21^ii—K1—O2—C1	−42.27 (9)	O2—K1—O23—C22	−24.66 (8)
K1^iii—K1—O2—C1	−27.13 (12)	O24^iii—K1—O23—C22	117.13 (7)
K1—O2—C1—O1	−12.97 (16)	C10^iv—K1—O23—C22	−96.97 (7)
K1—O2—C1—C2	165.83 (7)	C21^ii—K1—O23—C22	57.12 (7)
K1^v—O1—C1—O2	150.54 (9)	K1^iii—K1—O23—C22	129.34 (8)
K1^v—O1—C1—C2	−28.34 (12)	K1^ii—O22—C21—O21	−115.23 (10)
K1^v—O3—C2—C3	−167.82 (8)	K1^ii—O22—C21—C22	64.36 (11)
K1^v—O3—C2—C1	10.92 (12)	K1—O21—C21—O22	152.29 (8)
O2—C1—C2—O3	−169.60 (10)	K1—O21—C21—C22	−27.32 (14)
O1—C1—C2—O3	9.35 (13)	K1—O21—C21—K1^ii	91.77 (10)
O2—C1—C2—C3	9.18 (16)	K1—O23—C22—C23	−170.99 (8)
O1—C1—C2—C3	−171.88 (10)	K1—O23—C22—C21	8.72 (11)
O3—C2—C3—C4	2.06 (16)	O22—C21—C22—O23	−171.70 (9)
C1—C2—C3—C4	−176.58 (9)	O21—C21—C22—O23	7.94 (13)
C2—C3—C4—O4	−0.69 (16)	K1^ii—C21—C22—O23	−131.02 (8)
C2—C3—C4—C5	177.25 (10)	O22—C21—C22—C23	8.02 (15)
O4—C4—C5—C10	−168.35 (10)	O21—C21—C22—C23	−172.34 (10)
C3—C4—C5—C10	13.69 (16)	K1^ii—C21—C22—C23	48.70 (10)
O4—C4—C5—C6	11.75 (15)	O23—C22—C23—C24	1.78 (16)
C3—C4—C5—C6	−166.21 (10)	C21—C22—C23—C24	−177.91 (9)
C10—C5—C6—C7	−1.75 (17)	K1^iii—O24—C24—C23	73.12 (12)
C4—C5—C6—C7	178.16 (11)	K1^iii—O24—C24—C25	−106.63 (10)
C5—C6—C7—C8	1.48 (19)	C22—C23—C24—O24	−2.02 (16)
C11—O8—C8—C7	176.55 (11)	C22—C23—C24—C25	177.73 (10)
C11—O8—C8—C9	−3.15 (17)	O24—C24—C25—C30	166.98 (10)
C6—C7—C8—O8	−179.24 (11)	C23—C24—C25—C30	−12.77 (16)
C6—C7—C8—C9	0.48 (18)	O24—C24—C25—C26	−10.87 (15)
O8—C8—C9—C10	177.59 (10)	C23—C24—C25—C26	169.37 (10)
C7—C8—C9—C10	−2.10 (17)	C30—C25—C26—C27	1.46 (17)
C8—C9—C10—C5	1.82 (17)	C24—C25—C26—C27	179.41 (10)
C8—C9—C10—K1^vi	103.26 (10)	C25—C26—C27—C28	−0.77 (18)
C6—C5—C10—C9	0.09 (16)	C31—O28—C28—C29	−0.75 (17)
C4—C5—C10—C9	−179.81 (10)	C31—O28—C28—C27	179.51 (10)
C6—C5—C10—K1^vi	−93.99 (10)	C26—C27—C28—O28	178.95 (11)
C4—C5—C10—K1^vi	86.11 (10)	C26—C27—C28—C29	−0.81 (18)
O1^i—K1—O21—C21	85.91 (11)	O28—C28—C29—C30	−178.08 (11)
O22^ii—K1—O21—C21	−52.02 (10)	C27—C28—C29—C30	1.65 (17)
O3^i—K1—O21—C21	169.40 (9)	C28—C29—C30—C25	−0.94 (17)
O2—K1—O21—C21	−166.79 (10)	C26—C25—C30—C29	−0.60 (17)
O23—K1—O21—C21	22.92 (9)	C24—C25—C30—C29	−178.45 (10)
O24^iii—K1—O21—C21	−81.94 (10)

Symmetry codes: (i) x, y+1, z; (ii) −x, −y, −z; (iii) −x, −y+1, −z; (iv) −x+1/2, y+1/2, −z+1/2; (v) x, y−1, z; (vi) −x+1/2, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O21	1.071 (15)	1.361 (15)	2.4322 (10)	178.2 (15)
O3—H2···O4	0.875 (16)	1.731 (16)	2.5326 (11)	151.1 (15)
O23—H22···O24	0.836 (16)	1.800 (16)	2.5599 (11)	150.4 (15)