2-Hydroxyisophthalic acid: hydrogen-bonding patterns in the monohydrate and the tetraphenylphosphonium salt. An instance of dramatic acidity enhancement by symmetric, internally hydrogen-bonded anion stabilization

The monohydrate of the title phenolic diacid (C₈H₆O₅·H₂O, 2-hydroxybenzene-1,3-dioic acid or 3-carboxysalicylic acid) adopts a planar conformation, with the phenol hydrogen internally hydrogen-bonded to the carbonyl of one highly ordered carboxyl, which, in turn, donates a hydrogen bond to the oxygen of water. The second carboxyl is disordered and hydrogen-bonded both to water and to the disordered carboxyl of a centrosymmetrically related neighbor in a static disorder arrangement extending over two full asymmetric units. The water accepts either one or two hydrogen bonds and donates a long bifurcated hydrogen bond shared equally by O atoms of the phenol and the disordered carboxyl. The hydrogen bonding includes no standard carboxyl pairing and is entirely two-dimensional. The resulting planar ribbons stack translationally at a distance of 3.413 (8) Å, in an offset arrangement having non-translational interplanar distances of 0.821 (5) and 2.592 (6) Å. This structure is compared with two previously reported for this compound. The title compound forms a monoanion, whose tetraphenylphosphonium salt is described (C₃₂H₂₅O₅P, tetraphenylphosphonium 2,6-dicarboxy­phenolate, tetraphenylphosphonium 2-oxidoiso­phthalic acid or tetraphenylphosphonium 3-carboxysalicylate). The phenol oxygen is the site of formal negative charge on the anion, which is stabilized in a planar arrangement by symmetrical hydrogen bonds from both ortho-carboxyl groups. The energetics of this arrangement, the phenol and carboxyl acidities, and factors affecting those acidities and providing anion stabilization are discussed.

S1. Refinement

All H atoms for (1) were found in electron-density difference maps. The C-bound Hs were allowed to refine. The phenolic H and the ordered carboxyl H (on O2) were allowed to vary positionally and their displacement parameters were fixed at 0.080 Ų. The disordered carboxyl Hs were set at 50% occupancy (after allowing this occupancy to vary and finding 50%) and were placed at 0.82 Šfrom O4 and O5 and allowed to refine as riding atoms with displacement parameters fixed at 0.080 Ų. Water Hs calculated using the program HYDROGEN (Nardelli, 1999) were allowed to ride on the water O and their displacement parameters were fixed at 0.080 Ų. The observed disorder of the C8 carboxyl is reflected by the high values of the U_equiv parameters and the R_max/R_min ratios for atoms O4 & O5. The high U_equiv and R_max/R_min ratios for atom O6 may be attributable to the electron density of the inadequately modeled H atoms.

Computing details

For both compounds, data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXP-97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

(1) '2-hydroxybenzene-1,2-dioic acid'

Crystal data

C8H6O5·H2O	Z = 2
Mr = 200.14	F(000) = 208
Triclinic, P1	Dx = 1.610 Mg m^−3 Dm = 1.60 Mg m^−3 Dm measured by flotation in BrCCl3/cyclohexane
Hall symbol: -P 1	Melting point: 373 K
a = 3.6673 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7608 (19) Å	Cell parameters from 24 reflections
c = 11.8421 (15) Å	θ = 8.7–19.7°
α = 97.647 (13)°	µ = 0.14 mm^−1
β = 90.219 (13)°	T = 296 K
γ = 100.537 (16)°	Square prism, pale yellow
V = 412.87 (15) Å^3	0.40 × 0.30 × 0.20 mm

Data collection

Siemens P4 diffractometer	1574 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.059
Graphite monochromator	θmax = 30.0°, θmin = 1.7°
2θ/θ scans	h = −1→5
Absorption correction: numerical Sheldrick (1997)	k = −13→13
Tmin = 0.95, Tmax = 0.98	l = −16→16
3409 measured reflections	3 standard reflections every 97 reflections
2400 independent reflections	intensity decay: variation <2.0%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.059	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.186	w = 1/[σ^2(Fo^2) + (0.1001P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.46
2400 reflections	Δρmax = 0.39 e Å^−3
148 parameters	Δρmin = −0.42 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00 (3)

Special details

Experimental. 'crystal mounted on glass fiber using epoxy resin'

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 statisticallyabout 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	Occ. (<1)
O1	0.3605 (5)	0.11802 (13)	0.48484 (10)	0.0500 (4)
O2	0.2067 (4)	0.31251 (14)	0.43745 (11)	0.0487 (4)
H2	0.220 (8)	0.259 (3)	0.365 (3)	0.080*
O3	0.3721 (4)	0.07821 (11)	0.69435 (9)	0.0390 (4)
H3	0.410 (8)	0.073 (3)	0.617 (3)	0.080*
O4	0.2829 (6)	0.25056 (17)	1.03056 (11)	0.0667 (6)
H4	0.2884	0.1960	1.0773	0.080*	0.50
O5	0.4104 (5)	0.06883 (14)	0.91522 (10)	0.0549 (5)
H5	0.4471	0.0428	0.9766	0.080*	0.50
O6	0.2622 (8)	0.1569 (2)	0.23472 (14)	0.0933 (8)
H106	0.3356	0.0770	0.2206	0.080*
H206	0.0751	0.1497	0.1878	0.080*
C1	0.2465 (4)	0.29125 (16)	0.63348 (12)	0.0288 (3)
C2	0.3000 (5)	0.20891 (15)	0.72026 (12)	0.0279 (4)
C3	0.2761 (5)	0.26611 (16)	0.83498 (12)	0.0306 (4)
C4	0.2062 (5)	0.40280 (18)	0.85941 (14)	0.0362 (4)
H4A	0.191 (7)	0.445 (3)	0.940 (2)	0.056 (6)*
C5	0.1559 (6)	0.48321 (18)	0.77515 (15)	0.0391 (4)
H5A	0.095 (6)	0.572 (3)	0.7961 (19)	0.050 (6)*
C6	0.1750 (5)	0.42655 (17)	0.66251 (14)	0.0347 (4)
H6	0.136 (7)	0.477 (2)	0.6001 (19)	0.050 (6)*
C7	0.2765 (5)	0.23265 (16)	0.51308 (13)	0.0324 (4)
C8	0.3257 (5)	0.18936 (18)	0.93217 (13)	0.0363 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0899 (12)	0.0398 (7)	0.0278 (6)	0.0307 (7)	0.0055 (6)	0.0052 (5)
O2	0.0799 (11)	0.0426 (7)	0.0309 (6)	0.0239 (7)	0.0025 (6)	0.0143 (5)
O3	0.0697 (9)	0.0271 (6)	0.0251 (5)	0.0211 (6)	0.0028 (5)	0.0040 (4)
O4	0.1230 (16)	0.0604 (9)	0.0241 (6)	0.0384 (10)	0.0058 (7)	0.0027 (6)
O5	0.0967 (13)	0.0471 (8)	0.0299 (6)	0.0341 (8)	0.0008 (7)	0.0087 (5)
O6	0.173 (2)	0.0796 (13)	0.0370 (8)	0.0383 (14)	0.0075 (10)	0.0219 (7)
C1	0.0323 (8)	0.0284 (7)	0.0278 (7)	0.0093 (6)	0.0023 (6)	0.0059 (5)
C2	0.0342 (8)	0.0244 (6)	0.0263 (6)	0.0089 (6)	0.0019 (6)	0.0028 (5)
C3	0.0354 (9)	0.0320 (7)	0.0249 (7)	0.0088 (7)	0.0010 (6)	0.0018 (5)
C4	0.0393 (10)	0.0361 (8)	0.0329 (8)	0.0117 (7)	0.0030 (7)	−0.0035 (6)
C5	0.0451 (10)	0.0281 (7)	0.0456 (9)	0.0145 (7)	0.0021 (8)	0.0001 (6)
C6	0.0385 (10)	0.0298 (7)	0.0389 (8)	0.0119 (7)	0.0024 (7)	0.0078 (6)
C7	0.0420 (9)	0.0312 (7)	0.0266 (7)	0.0104 (7)	0.0021 (6)	0.0082 (5)
C8	0.0455 (10)	0.0391 (8)	0.0245 (7)	0.0095 (7)	0.0010 (6)	0.0028 (6)

Geometric parameters (Å, º)

O1—C7	1.219 (2)	C1—C6	1.392 (2)
O2—C7	1.3163 (18)	C1—C2	1.420 (2)
O2—H2	0.95 (3)	C1—C7	1.476 (2)
O3—C2	1.3459 (17)	C2—C3	1.408 (2)
O3—H3	0.92 (3)	C3—C4	1.397 (2)
O4—C8	1.261 (2)	C3—C8	1.482 (2)
O4—H4	0.8200	C4—C5	1.380 (2)
O5—C8	1.262 (2)	C4—H4A	0.99 (2)
O5—H5	0.8200	C5—C6	1.382 (2)
O6—H106	0.8668	C5—H5A	0.93 (2)
O6—H206	0.8677	C6—H6	0.97 (2)
C7—O2—H2	106.2 (19)	C5—C4—H4A	117.6 (15)
C2—O3—H3	102.1 (18)	C3—C4—H4A	120.0 (15)
C8—O4—H4	109.5	C4—C5—C6	118.86 (14)
C8—O5—H5	109.5	C4—C5—H5A	118.8 (14)
H106—O6—H206	104.6	C6—C5—H5A	122.2 (14)
C6—C1—C2	120.01 (14)	C5—C6—C1	121.07 (15)
C6—C1—C7	120.84 (13)	C5—C6—H6	122.3 (14)
C2—C1—C7	119.13 (13)	C1—C6—H6	116.7 (14)
O3—C2—C3	120.02 (13)	O1—C7—O2	121.81 (14)
O3—C2—C1	121.11 (13)	O1—C7—C1	122.61 (13)
C3—C2—C1	118.87 (13)	O2—C7—C1	115.58 (14)
C4—C3—C2	118.77 (14)	O4—C8—O5	122.56 (16)
C4—C3—C8	117.85 (13)	O4—C8—C3	116.99 (15)
C2—C3—C8	123.38 (14)	O5—C8—C3	120.45 (13)
C5—C4—C3	122.41 (14)
C6—C1—C2—O3	−179.51 (16)	C4—C5—C6—C1	−0.5 (3)
C7—C1—C2—O3	−0.9 (2)	C2—C1—C6—C5	0.2 (3)
C6—C1—C2—C3	0.6 (2)	C7—C1—C6—C5	−178.34 (16)
C7—C1—C2—C3	179.14 (15)	C6—C1—C7—O1	175.52 (18)
O3—C2—C3—C4	179.09 (15)	C2—C1—C7—O1	−3.0 (3)
C1—C2—C3—C4	−1.0 (2)	C6—C1—C7—O2	−4.4 (3)
O3—C2—C3—C8	−0.1 (3)	C2—C1—C7—O2	177.02 (15)
C1—C2—C3—C8	179.77 (15)	C4—C3—C8—O4	3.4 (3)
C2—C3—C4—C5	0.7 (3)	C2—C3—C8—O4	−177.32 (19)
C8—C3—C4—C5	179.98 (17)	C4—C3—C8—O5	−175.92 (18)
C3—C4—C5—C6	0.1 (3)	C2—C3—C8—O5	3.3 (3)

(2) 'tetraphenylphosphonium 2-hydroxybenzene-1,3-dioate'

Crystal data

C24H20P·C8H5O5	F(000) = 1088
Mr = 520.49	Dx = 1.297 Mg m^−3
Monoclinic, P21/c	Melting point: 446 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 15.287 (5) Å	Cell parameters from 22 reflections
b = 8.027 (3) Å	θ = 4.1–10.5°
c = 22.144 (7) Å	µ = 0.14 mm^−1
β = 101.15 (2)°	T = 296 K
V = 2665.7 (15) Å^3	Prism, colourless
Z = 4	0.50 × 0.44 × 0.26 mm

Data collection

Siemens P4 diffractometer	2544 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
Graphite monochromator	θmax = 25.0°, θmin = 2.1°
2θ/θ scans	h = −18→1
Absorption correction: numerical Sheldrick (1997)	k = −9→1
Tmin = 0.94, Tmax = 0.97	l = −26→26
6087 measured reflections	3 standard reflections every 97 reflections
4707 independent reflections	intensity decay: variation <1.3%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.063	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.137	w = 1/[σ^2(Fo^2) + (0.0417P)^2 + 0.5629P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
4707 reflections	Δρmax = 0.17 e Å^−3
350 parameters	Δρmin = −0.24 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0030 (5)

Special details

Experimental. 'crystal mounted on glass fiber using cyanoacrylate cement'

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
P1	0.27966 (6)	0.37526 (11)	0.83276 (4)	0.0446 (3)
O1	0.0967 (3)	0.0399 (4)	0.66868 (17)	0.0991 (11)
H1A	0.161 (3)	0.045 (5)	0.6667 (17)	0.080*
O2	−0.0272 (2)	0.1402 (4)	0.61367 (18)	0.1194 (13)
O3	0.24116 (17)	0.0958 (3)	0.63760 (12)	0.0666 (7)
O4	0.3879 (2)	0.3074 (4)	0.52447 (14)	0.0986 (11)
O5	0.38415 (19)	0.1569 (4)	0.60659 (16)	0.0882 (10)
H5A	0.341 (3)	0.125 (5)	0.6295 (17)	0.080*
C1	0.1064 (3)	0.1942 (5)	0.57844 (19)	0.0620 (10)
C2	0.1990 (2)	0.1788 (4)	0.58979 (17)	0.0517 (9)
C3	0.2475 (3)	0.2559 (4)	0.54914 (17)	0.0544 (9)
C4	0.2016 (3)	0.3465 (5)	0.50000 (18)	0.0780 (13)
H4	0.2334	0.3992	0.4736	0.094*
C5	0.1106 (4)	0.3608 (7)	0.4891 (2)	0.1013 (16)
H5	0.0809	0.4216	0.4556	0.122*
C6	0.0641 (3)	0.2841 (6)	0.5284 (2)	0.0898 (14)
H6	0.0023	0.2932	0.5210	0.108*
C7	0.0525 (3)	0.1218 (6)	0.6208 (3)	0.0800 (13)
C8	0.3446 (3)	0.2421 (6)	0.5582 (2)	0.0694 (12)
C9	0.1854 (2)	0.2413 (4)	0.82796 (14)	0.0450 (9)
C10	0.1966 (2)	0.0710 (4)	0.83535 (16)	0.0537 (9)
H10A	0.2537	0.0261	0.8434	0.064*
C11	0.1242 (3)	−0.0319 (5)	0.83094 (17)	0.0680 (11)
H11A	0.1323	−0.1463	0.8357	0.082*
C12	0.0402 (3)	0.0330 (5)	0.81962 (17)	0.0672 (11)
H12A	−0.0087	−0.0372	0.8170	0.081*
C13	0.0277 (2)	0.2005 (6)	0.81215 (18)	0.0662 (11)
H13A	−0.0299	0.2437	0.8042	0.079*
C14	0.0992 (2)	0.3055 (5)	0.81623 (15)	0.0548 (10)
H14A	0.0901	0.4196	0.8112	0.066*
C15	0.2614 (2)	0.5114 (4)	0.76774 (15)	0.0435 (8)
C16	0.2138 (2)	0.4571 (4)	0.71155 (16)	0.0560 (10)
H16A	0.1873	0.3523	0.7083	0.067*
C17	0.2056 (3)	0.5579 (5)	0.66057 (17)	0.0634 (11)
H17A	0.1742	0.5206	0.6228	0.076*
C18	0.2433 (3)	0.7121 (5)	0.66521 (19)	0.0677 (12)
H18A	0.2375	0.7800	0.6306	0.081*
C19	0.2901 (3)	0.7676 (5)	0.72092 (19)	0.0757 (12)
H19A	0.3155	0.8732	0.7240	0.091*
C20	0.2992 (2)	0.6675 (5)	0.77176 (17)	0.0634 (11)
H20A	0.3313	0.7052	0.8093	0.076*
C21	0.2995 (2)	0.4990 (4)	0.90088 (14)	0.0459 (9)
C22	0.3843 (2)	0.5639 (5)	0.92279 (16)	0.0618 (10)
H22A	0.4318	0.5338	0.9045	0.074*
C23	0.3971 (3)	0.6721 (5)	0.97144 (19)	0.0751 (12)
H23A	0.4536	0.7156	0.9862	0.090*
C24	0.3273 (3)	0.7167 (5)	0.99850 (19)	0.0780 (13)
H24A	0.3365	0.7902	1.0316	0.094*
C25	0.2446 (3)	0.6542 (5)	0.97720 (18)	0.0738 (12)
H25A	0.1974	0.6856	0.9956	0.089*
C26	0.2301 (2)	0.5444 (5)	0.92848 (16)	0.0568 (10)
H26A	0.1734	0.5012	0.9143	0.068*
C27	0.3749 (2)	0.2488 (4)	0.83079 (15)	0.0458 (9)
C28	0.4169 (2)	0.1701 (5)	0.88372 (16)	0.0594 (10)
H28A	0.3984	0.1902	0.9207	0.071*
C29	0.4862 (3)	0.0619 (5)	0.8822 (2)	0.0731 (12)
H29A	0.5141	0.0074	0.9178	0.088*
C30	0.5133 (3)	0.0354 (5)	0.8277 (2)	0.0805 (13)
H30A	0.5609	−0.0361	0.8268	0.097*
C31	0.4723 (3)	0.1111 (6)	0.77465 (19)	0.0764 (12)
H31A	0.4914	0.0909	0.7379	0.092*
C32	0.4024 (2)	0.2178 (4)	0.77606 (17)	0.0572 (10)
H32A	0.3735	0.2692	0.7400	0.069*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0440 (5)	0.0427 (5)	0.0463 (5)	0.0021 (5)	0.0073 (4)	0.0012 (5)
O1	0.095 (2)	0.094 (3)	0.119 (3)	−0.016 (2)	0.048 (2)	0.015 (2)
O2	0.064 (2)	0.106 (3)	0.197 (4)	−0.015 (2)	0.049 (2)	−0.018 (3)
O3	0.0685 (17)	0.0592 (17)	0.0729 (17)	0.0042 (14)	0.0150 (15)	0.0173 (15)
O4	0.096 (2)	0.126 (3)	0.085 (2)	−0.046 (2)	0.0452 (19)	−0.023 (2)
O5	0.0615 (18)	0.114 (3)	0.088 (2)	−0.0055 (19)	0.0113 (16)	−0.003 (2)
C1	0.057 (2)	0.055 (2)	0.075 (3)	−0.002 (2)	0.012 (2)	−0.005 (2)
C2	0.059 (2)	0.040 (2)	0.055 (2)	−0.0043 (18)	0.0089 (19)	−0.0057 (19)
C3	0.065 (2)	0.049 (2)	0.052 (2)	−0.008 (2)	0.018 (2)	−0.009 (2)
C4	0.111 (4)	0.073 (3)	0.052 (3)	−0.003 (3)	0.020 (3)	0.003 (2)
C5	0.108 (4)	0.115 (4)	0.070 (3)	0.024 (4)	−0.010 (3)	0.011 (3)
C6	0.068 (3)	0.098 (4)	0.096 (4)	0.011 (3)	−0.002 (3)	−0.004 (3)
C7	0.063 (3)	0.065 (3)	0.117 (4)	−0.010 (3)	0.031 (3)	−0.013 (3)
C8	0.076 (3)	0.071 (3)	0.065 (3)	−0.027 (3)	0.024 (3)	−0.032 (3)
C9	0.047 (2)	0.043 (2)	0.044 (2)	−0.0011 (17)	0.0075 (16)	0.0013 (17)
C10	0.054 (2)	0.047 (2)	0.061 (2)	0.0003 (18)	0.0110 (19)	0.0024 (19)
C11	0.073 (3)	0.050 (2)	0.081 (3)	−0.009 (2)	0.014 (2)	−0.003 (2)
C12	0.064 (3)	0.066 (3)	0.070 (3)	−0.020 (2)	0.009 (2)	−0.005 (2)
C13	0.044 (2)	0.076 (3)	0.078 (3)	−0.006 (2)	0.011 (2)	−0.007 (2)
C14	0.052 (2)	0.049 (2)	0.061 (2)	0.0015 (19)	0.0046 (18)	0.0032 (19)
C15	0.046 (2)	0.036 (2)	0.046 (2)	0.0014 (16)	0.0057 (16)	0.0047 (17)
C16	0.068 (2)	0.040 (2)	0.057 (2)	0.001 (2)	0.004 (2)	0.004 (2)
C17	0.084 (3)	0.050 (2)	0.053 (2)	0.010 (2)	0.006 (2)	0.000 (2)
C18	0.099 (3)	0.048 (2)	0.060 (3)	0.007 (2)	0.025 (2)	0.012 (2)
C19	0.100 (3)	0.048 (3)	0.075 (3)	−0.013 (2)	0.009 (3)	0.007 (2)
C20	0.070 (3)	0.054 (3)	0.060 (2)	−0.007 (2)	−0.002 (2)	0.006 (2)
C21	0.0427 (19)	0.048 (2)	0.045 (2)	0.0021 (17)	0.0044 (16)	0.0031 (17)
C22	0.052 (2)	0.071 (3)	0.060 (2)	−0.002 (2)	0.0046 (19)	−0.009 (2)
C23	0.063 (3)	0.085 (3)	0.072 (3)	−0.017 (2)	−0.001 (2)	−0.018 (3)
C24	0.084 (3)	0.081 (3)	0.064 (3)	−0.002 (3)	0.003 (3)	−0.026 (2)
C25	0.071 (3)	0.084 (3)	0.067 (3)	0.005 (3)	0.015 (2)	−0.021 (3)
C26	0.050 (2)	0.060 (2)	0.058 (2)	0.0020 (19)	0.0057 (18)	−0.004 (2)
C27	0.0435 (19)	0.045 (2)	0.048 (2)	0.0048 (17)	0.0069 (17)	0.0022 (18)
C28	0.058 (2)	0.068 (3)	0.053 (2)	0.015 (2)	0.0127 (19)	0.002 (2)
C29	0.065 (3)	0.075 (3)	0.074 (3)	0.023 (2)	0.001 (2)	0.007 (2)
C30	0.067 (3)	0.076 (3)	0.097 (4)	0.027 (2)	0.013 (3)	−0.005 (3)
C31	0.071 (3)	0.092 (3)	0.070 (3)	0.023 (3)	0.024 (2)	−0.005 (3)
C32	0.057 (2)	0.058 (2)	0.058 (2)	0.006 (2)	0.0160 (19)	0.011 (2)

Geometric parameters (Å, º)

P1—C27	1.783 (3)	C15—C20	1.376 (4)
P1—C21	1.783 (3)	C15—C16	1.385 (4)
P1—C9	1.785 (3)	C16—C17	1.375 (4)
P1—C15	1.786 (3)	C16—H16A	0.9300
O1—C7	1.318 (5)	C17—C18	1.361 (5)
O1—H1A	1.00 (4)	C17—H17A	0.9300
O2—C7	1.206 (5)	C18—C19	1.375 (5)
O3—C2	1.310 (4)	C18—H18A	0.9300
O4—C8	1.209 (4)	C19—C20	1.368 (5)
O5—C8	1.315 (5)	C19—H19A	0.9300
O5—H5A	0.94 (4)	C20—H20A	0.9300
C1—C6	1.375 (5)	C21—C26	1.372 (4)
C1—C2	1.395 (5)	C21—C22	1.395 (4)
C1—C7	1.482 (6)	C22—C23	1.368 (5)
C2—C3	1.414 (5)	C22—H22A	0.9300
C3—C4	1.382 (5)	C23—C24	1.370 (5)
C3—C8	1.463 (5)	C23—H23A	0.9300
C4—C5	1.369 (6)	C24—C25	1.357 (5)
C4—H4	0.9300	C24—H24A	0.9300
C5—C6	1.371 (6)	C25—C26	1.377 (5)
C5—H5	0.9300	C25—H25A	0.9300
C6—H6	0.9300	C26—H26A	0.9300
C9—C10	1.383 (5)	C27—C28	1.376 (4)
C9—C14	1.392 (4)	C27—C32	1.379 (4)
C10—C11	1.369 (5)	C28—C29	1.374 (5)
C10—H10A	0.9300	C28—H28A	0.9300
C11—C12	1.363 (5)	C29—C30	1.367 (5)
C11—H11A	0.9300	C29—H29A	0.9300
C12—C13	1.363 (5)	C30—C31	1.363 (5)
C12—H12A	0.9300	C30—H30A	0.9300
C13—C14	1.369 (5)	C31—C32	1.374 (5)
C13—H13A	0.9300	C31—H31A	0.9300
C14—H14A	0.9300	C32—H32A	0.9300
C27—P1—C21	109.41 (16)	C16—C15—P1	120.3 (3)
C27—P1—C9	108.05 (16)	C17—C16—C15	120.1 (3)
C21—P1—C9	112.90 (16)	C17—C16—H16A	120.0
C27—P1—C15	109.27 (16)	C15—C16—H16A	120.0
C21—P1—C15	108.40 (15)	C18—C17—C16	120.2 (4)
C9—P1—C15	108.77 (16)	C18—C17—H17A	119.9
C7—O1—H1A	108 (2)	C16—C17—H17A	119.9
C8—O5—H5A	109 (2)	C17—C18—C19	120.1 (4)
C6—C1—C2	119.6 (4)	C17—C18—H18A	120.0
C6—C1—C7	118.9 (4)	C19—C18—H18A	120.0
C2—C1—C7	121.4 (4)	C20—C19—C18	120.1 (4)
O3—C2—C1	120.9 (3)	C20—C19—H19A	120.0
O3—C2—C3	120.1 (3)	C18—C19—H19A	120.0
C1—C2—C3	119.0 (4)	C19—C20—C15	120.4 (4)
C4—C3—C2	118.9 (4)	C19—C20—H20A	119.8
C4—C3—C8	119.7 (4)	C15—C20—H20A	119.8
C2—C3—C8	121.5 (4)	C26—C21—C22	119.5 (3)
C5—C4—C3	121.8 (4)	C26—C21—P1	120.4 (3)
C5—C4—H4	119.1	C22—C21—P1	119.8 (3)
C3—C4—H4	119.1	C23—C22—C21	119.5 (4)
C4—C5—C6	118.9 (5)	C23—C22—H22A	120.2
C4—C5—H5	120.5	C21—C22—H22A	120.2
C6—C5—H5	120.5	C22—C23—C24	120.4 (4)
C5—C6—C1	121.8 (4)	C22—C23—H23A	119.8
C5—C6—H6	119.1	C24—C23—H23A	119.8
C1—C6—H6	119.1	C25—C24—C23	120.3 (4)
O2—C7—O1	121.0 (5)	C25—C24—H24A	119.9
O2—C7—C1	122.7 (5)	C23—C24—H24A	119.9
O1—C7—C1	116.3 (4)	C24—C25—C26	120.5 (4)
O4—C8—O5	120.5 (4)	C24—C25—H25A	119.8
O4—C8—C3	123.0 (5)	C26—C25—H25A	119.8
O5—C8—C3	116.5 (4)	C21—C26—C25	119.8 (4)
C10—C9—C14	118.6 (3)	C21—C26—H26A	120.1
C10—C9—P1	120.6 (3)	C25—C26—H26A	120.1
C14—C9—P1	120.8 (3)	C28—C27—C32	119.6 (3)
C11—C10—C9	120.6 (4)	C28—C27—P1	119.3 (3)
C11—C10—H10A	119.7	C32—C27—P1	120.9 (3)
C9—C10—H10A	119.7	C29—C28—C27	120.3 (3)
C12—C11—C10	120.1 (4)	C29—C28—H28A	119.9
C12—C11—H11A	119.9	C27—C28—H28A	119.9
C10—C11—H11A	120.0	C30—C29—C28	119.1 (4)
C11—C12—C13	120.3 (4)	C30—C29—H29A	120.4
C11—C12—H12A	119.8	C28—C29—H29A	120.4
C13—C12—H12A	119.8	C31—C30—C29	121.6 (4)
C12—C13—C14	120.5 (4)	C31—C30—H30A	119.2
C12—C13—H13A	119.8	C29—C30—H30A	119.2
C14—C13—H13A	119.8	C30—C31—C32	119.2 (4)
C13—C14—C9	120.0 (3)	C30—C31—H31A	120.4
C13—C14—H14A	120.0	C32—C31—H31A	120.4
C9—C14—H14A	120.0	C31—C32—C27	120.1 (3)
C20—C15—C16	119.1 (3)	C31—C32—H32A	119.9
C20—C15—P1	120.4 (3)	C27—C32—H32A	119.9
C6—C1—C2—O3	179.0 (4)	C27—P1—C15—C16	84.5 (3)
C7—C1—C2—O3	1.8 (6)	C21—P1—C15—C16	−156.3 (3)
C6—C1—C2—C3	−0.3 (6)	C9—P1—C15—C16	−33.2 (3)
C7—C1—C2—C3	−177.5 (3)	C20—C15—C16—C17	0.7 (5)
O3—C2—C3—C4	−178.3 (3)	P1—C15—C16—C17	−175.1 (3)
C1—C2—C3—C4	1.1 (5)	C15—C16—C17—C18	−0.7 (6)
O3—C2—C3—C8	1.5 (5)	C16—C17—C18—C19	0.2 (6)
C1—C2—C3—C8	−179.2 (3)	C17—C18—C19—C20	0.4 (6)
C2—C3—C4—C5	−1.2 (6)	C18—C19—C20—C15	−0.5 (6)
C8—C3—C4—C5	179.0 (4)	C16—C15—C20—C19	−0.1 (6)
C3—C4—C5—C6	0.6 (8)	P1—C15—C20—C19	175.7 (3)
C4—C5—C6—C1	0.3 (8)	C27—P1—C21—C26	−149.3 (3)
C2—C1—C6—C5	−0.4 (7)	C9—P1—C21—C26	−29.0 (3)
C7—C1—C6—C5	176.9 (5)	C15—P1—C21—C26	91.6 (3)
C6—C1—C7—O2	−1.0 (7)	C27—P1—C21—C22	37.1 (3)
C2—C1—C7—O2	176.3 (4)	C9—P1—C21—C22	157.4 (3)
C6—C1—C7—O1	−178.6 (4)	C15—P1—C21—C22	−82.0 (3)
C2—C1—C7—O1	−1.3 (6)	C26—C21—C22—C23	−0.1 (5)
C4—C3—C8—O4	0.2 (6)	P1—C21—C22—C23	173.6 (3)
C2—C3—C8—O4	−179.6 (4)	C21—C22—C23—C24	−0.1 (6)
C4—C3—C8—O5	178.7 (4)	C22—C23—C24—C25	−0.1 (7)
C2—C3—C8—O5	−1.1 (5)	C23—C24—C25—C26	0.4 (7)
C27—P1—C9—C10	12.3 (3)	C22—C21—C26—C25	0.4 (5)
C21—P1—C9—C10	−108.8 (3)	P1—C21—C26—C25	−173.2 (3)
C15—P1—C9—C10	130.8 (3)	C24—C25—C26—C21	−0.6 (6)
C27—P1—C9—C14	−167.2 (3)	C21—P1—C27—C28	42.9 (3)
C21—P1—C9—C14	71.7 (3)	C9—P1—C27—C28	−80.3 (3)
C15—P1—C9—C14	−48.7 (3)	C15—P1—C27—C28	161.5 (3)
C14—C9—C10—C11	0.3 (5)	C21—P1—C27—C32	−142.6 (3)
P1—C9—C10—C11	−179.2 (3)	C9—P1—C27—C32	94.2 (3)
C9—C10—C11—C12	−0.5 (6)	C15—P1—C27—C32	−24.0 (3)
C10—C11—C12—C13	0.5 (6)	C32—C27—C28—C29	0.4 (6)
C11—C12—C13—C14	−0.3 (6)	P1—C27—C28—C29	174.9 (3)
C12—C13—C14—C9	0.1 (6)	C27—C28—C29—C30	0.8 (6)
C10—C9—C14—C13	−0.1 (5)	C28—C29—C30—C31	−1.3 (7)
P1—C9—C14—C13	179.4 (3)	C29—C30—C31—C32	0.5 (7)
C27—P1—C15—C20	−91.2 (3)	C30—C31—C32—C27	0.7 (6)
C21—P1—C15—C20	28.0 (3)	C28—C27—C32—C31	−1.2 (5)
C9—P1—C15—C20	151.1 (3)	P1—C27—C32—C31	−175.6 (3)