Methyl 2,3-dideoxy-2-S-methylmercurio-2-thio-[beta]-D-manno-oct-2-ulo­pyranosonate-(2,6)

The hexo­pyran­osyl ring of the title compound, [Hg(CH₃)(C₉H₁₅O₇S)], adopts the ⁴C₁ chair conformation, and the anomeric configuration of the thio­methyl­mercury linkage is [beta]. The compound exists as two symmetry-independent conformers, A and B, within the unit cell, and each shows an almost linear S-Hg-C arrangement. Most of the bond distances and angles in A and B are similar, although a marked difference exists in the side-chain conformation. Weak secondary intramolecular (between Hg and ring O) and intermolecular (between A and B conformers) interactions are documented.

S1. Comment

For structure-function studies of glycosidases, we have recently reported on the synthesis of a series of mono- and disaccharides, in which methylmercury or phenylmercury is covalently attached to anomeric thioglycosides (Belakhov et al., 2000). It was predicted that the examination of these compounds, in the form of stable binary complexes with appropriate enzymes, should provide both the specific binding and the heavy-atom derivative for complete X-ray analysis. Indeed, the similar thiomercuric analogues of sialic acid were used to determine the crystallographic phases for pertussis toxin (Shigeta et al., 1994), and 9-O-acetylsialic acid esterase (Fitz et al., 1996) from influenza C virus. The title thiomercuric derivative, (I), was designed as a model compound for a structure-function study of enzymes involved in the biosynthetic formation and utilization of 3-deoxy-D-manno-2-octulosonic acid (Kdo). This unique eight-carbon sugar is a specific constituent of the lipopolysaccharides of most Gram-negative bacteria, and is required by them for growth and virulence (Unger, 1981; Unger & Anderson, 1983). Several groups have therefore pursued inhibition of Kdo metabolism as a strategy for the development of novel antibacterial drugs (Hammond et al., 1987; Goldman et al., 1987; Baasov & Kohen, 1995; Liang et al., 1998; Du et al., 1999). As part of this program, the crystal structure of the title compound, (I), has been determined. \sch

Interestingly, an analysis of the crystallographic data reveals that (I) exists as two symmetry-independent molecules, A and B, within the unit cell. A view of conformer A of the molecule of (I) together with the atomic numbering scheme is shown in Fig. 1. The geometry observed for the pyranose ring is a ⁴C₁ chair, while the thiomercuryl moiety is oriented cis to the hydroxyl groups at positions C4 and C5, indicating the β-anomeric configuration. The Hg atom has an almost linear stereochemistry, with normal Hg—S and Hg—C distances and S—Hg—C angles of 175.7 (15) and 176.7 (10)° for the two conformers OK? (Table 1). These values are in agreement with those found for CH₃—Hg—S moieties in the Cambridge Structural Database (CSD, April 2001 release; Allen & Kennard, 1993).

As illustrated in Fig. 2, while most of the bond distances and angles in conformers A and B are very similar, marked differences exist at the thiomethylmercury side-chain conformation. This is clearly seen by comparing three torsion angles, C1—C2—S—Hg, C3—C2—S—Hg and O1—C2—S—Hg, showing differences of 15.7 (11), 18.1 (10) and 16.1 (10)°, respectively (Table 1).

The presence of two similar independent structures, A and B, has also been reported for other thiomercury derivatives (Kuz'mina & Struchkov, 1984; Tasende et al., 1990; Zukerman-Schpector et al., 1991; Varela et al., 1993; Bravo et al., 1985; Castano et al., 1991; Hutton et al., 1980). This phenomenon was attributed to a low residual Lewis acidity of Hg in these complexes, leading to the formation of `secondary bonds' that are intermediate in strength between covalent and van der Waals bonds (Kuz'mina & Struchkov, 1984). Indeed, the intramolecular Hg···O1 distances in molecules A and B of (I) were found to be 2.955 (11) and 3.155 (11) Å, respectively. These distances are smaller than the sum of the van der Waals radii for the atoms concerned, confirming the presence of a secondary interaction in this part of the molecule, similar to that observed in (2-mercaptobenzothiazolato)methylmercury(II) (Bravo et al., 1985) and in (2-mercaptobenzooxazolato)methylmercury(II) (Castano et al., 1991).

It is of note that, in the latter compound, in addition to an intramolecular Hg···N interaction, an additional intermolecular Hg···O interaction was also observed. In compound (I), however, if we take the values of 3.35 and 3.10 Å for Hg···S and Hg···O, as the sums of the van der Waals radii of Hg and S and Hg and O, respectively (Kuz'mina & Struchkov, 1984), no additional secondary interactions through the Hg atom are observed. This may be due to the presence of an intermolecular hydrogen-bonding network (Table 2). There are rather strong hydrogen bonds both between the molecules of each conformer [O2A—H···O7A and O2B—H···O7B], and between the two different conformers [O6A—H···O3B and O6B—H···O3A]. Because of the presence of these hydrogen bonds, the crystal can be regarded as made up ofa three-dimensional network.

S2. Experimental

Compound (I) was synthesized according to the reported procedure of Belakhov et al. (2000), and its purity was established by a combination of ¹H NMR, ¹³C NMR, two-dimensional-COSY Please expand, and mass spectroscopic analyses. X-ray quality crystals of (I) were obtained by recrystallization from a methanol solution.

S3. Refinement

Because the crystal was a very small colourless plate, it was impossible to obtain an accurate measurement of the crystal faces. A little splitting was also found in some of the reflections and TWIN options (SHELXL97; Sheldrick, 1997) were used in the final refinement. Initially, the positions of the H atoms of the donor atoms were generated as idealized OH groups. During the refinement, the coordinates of atoms H2OA and H2OB were treated as riding on their parent atoms (O2A and O2B, respectively). Attempts to find the H atoms on atoms O3 and O7, using NFIX 81 or NFIX 147 options (SHELXL97), failed because, even in idealized positions, short contacts between donor and acceptor H atoms were found (H7A···H2OA 1.81 Å and H3B···H6OA 1.51 Å). The choice between which atoms were donors and which acceptors was based on measurement of the O—H···O angles. Short O···O distances involving atoms O3 or O7, except for those listed in Table 2, were 2.74 (2)–2.76 (2) Å for O3A···O2B(2 - x, y + 1/2, 2 - z) and O7B···O7A(2 - x, y + 1/2, 2 - z).

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN (Molecular Structure Corporation, 1999).

Figures

	Fig. 1. A view of molecule A of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Views of the chair conformations of (a) molecule A and (b) molecule B.

Methyl 3-deoxy-2-S-methylmercurio-2-thio-β-D-manno-2-octulosonate-(2,6)

Crystal data

[Hg(CH3)(C9H15O7S)]	F(000) = 920
Mr = 482.89	Dx = 2.213 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71070 Å
a = 7.306 (1) Å	Cell parameters from 19347 reflections
b = 15.247 (3) Å	θ = 1.2–25.4°
c = 13.014 (2) Å	µ = 10.79 mm^−1
β = 91.10 (3)°	T = 293 K
V = 1449.4 (4) Å^3	Plate, colourless
Z = 4	0.10 × 0.10 × 0.02 mm

Data collection

Nonius KappaCCD area-detector diffractometer	5084 independent reflections
Radiation source: fine-focus sealed tube	4777 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
ϕ and ω scans	θmax = 25.1°, θmin = 2.7°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −8→8
Tmin = 0.388, Tmax = 0.806	k = −18→18
11530 measured reflections	l = −15→15

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.064	w = 1/[σ^2(Fo^2) + (0.0956P)^2 + 11.7784P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.172	(Δ/σ)max = 0.009
S = 1.06	Δρmax = 4.38 e Å^−3
5084 reflections	Δρmin = −1.78 e Å^−3
349 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
3 restraints	Extinction coefficient: 0.0040 (7)
Primary atom site location: structure-invariant direct methods	Absolute structure: (Flack, 1983), 2408 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.010 (19)

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
Hg1A	0.56409 (14)	0.77997 (6)	0.93025 (7)	0.0592 (3)
S1A	0.5106 (10)	0.9311 (4)	0.9450 (4)	0.0553 (13)
O1A	0.5247 (15)	0.8934 (8)	0.7470 (8)	0.032 (2)
O2A	0.5173 (19)	1.1506 (8)	0.6462 (10)	0.047 (3)
H2OA	0.5207	1.1739	0.5892	0.071*
O3A	0.7418 (16)	1.0038 (9)	0.6214 (10)	0.046 (3)
O4A	0.1798 (19)	0.8585 (10)	0.7881 (13)	0.054 (3)
O5A	0.122 (3)	0.9951 (16)	0.8357 (15)	0.085 (5)
O6A	0.5667 (18)	0.8438 (9)	0.4772 (9)	0.046 (3)
H6OA	0.4635	0.8322	0.4695	0.069*
O7A	0.582 (3)	0.6715 (9)	0.5669 (12)	0.065 (4)
C1A	0.226 (3)	0.9403 (12)	0.8101 (14)	0.045 (4)
C2A	0.432 (3)	0.9536 (10)	0.8159 (13)	0.039 (4)
C3A	0.484 (3)	1.0467 (12)	0.7901 (13)	0.038 (4)
H3A2	0.6122	1.0561	0.8084	0.046*
H3A3	0.4116	1.0871	0.8299	0.046*
C4A	0.454 (2)	1.0656 (10)	0.6735 (14)	0.036 (4)
H4A	0.3220	1.0627	0.6581	0.043*
C5A	0.548 (2)	0.9991 (12)	0.6080 (11)	0.034 (3)
H5A	0.5156	1.0096	0.5356	0.041*
C6A	0.483 (2)	0.9069 (11)	0.6391 (12)	0.031 (3)
H6A	0.3503	0.9019	0.6267	0.037*
C7A	0.581 (3)	0.8325 (11)	0.5844 (12)	0.038 (4)
H7A	0.7107	0.8328	0.6053	0.046*
C8A	0.496 (3)	0.7460 (11)	0.6148 (16)	0.051 (5)
H8A1	0.5059	0.7396	0.6888	0.061*
H8A2	0.3672	0.7467	0.5959	0.061*
C9A	0.613 (7)	0.650 (2)	0.906 (4)	0.119 (15)
H91A	0.5345	0.6293	0.8511	0.178*
H92A	0.5881	0.6178	0.9675	0.178*
H93A	0.7383	0.6420	0.8879	0.178*
C10A	−0.011 (3)	0.8422 (19)	0.7757 (16)	0.062 (6)
H10A	−0.0313	0.8034	0.7185	0.092*
H10B	−0.0737	0.8965	0.7633	0.092*
H10C	−0.0562	0.8155	0.8370	0.092*
Hg1B	0.91891 (12)	0.9919	1.04501 (6)	0.0542 (3)
S1B	0.9713 (8)	0.8398 (3)	1.0635 (4)	0.0467 (11)
O1B	0.9999 (16)	0.8953 (7)	1.2555 (9)	0.033 (2)
O2B	1.0271 (18)	0.6442 (8)	1.3804 (9)	0.046 (3)
H2OB	1.0495	0.6540	1.4417	0.070*
O3B	1.2330 (16)	0.7930 (9)	1.3956 (10)	0.044 (3)
O4B	0.643 (2)	0.9158 (9)	1.2082 (11)	0.048 (3)
O5B	0.5970 (17)	0.7741 (7)	1.1971 (13)	0.057 (4)
O6B	1.069 (2)	0.9635 (9)	1.5213 (10)	0.049 (3)
H6OB	0.9523	0.9700	1.5502	0.073*
O7B	1.053 (2)	1.1305 (9)	1.4146 (12)	0.061 (4)
C1B	0.702 (2)	0.8351 (9)	1.2046 (13)	0.039 (4)
C2B	0.908 (2)	0.8275 (11)	1.1997 (13)	0.037 (4)
C3B	0.973 (2)	0.7356 (11)	1.2356 (13)	0.036 (4)
H31B	0.9007	0.6907	1.2010	0.043*
H32B	1.1002	0.7271	1.2185	0.043*
C4B	0.950 (2)	0.7282 (10)	1.3515 (14)	0.036 (4)
H4B	0.8194	0.7284	1.3668	0.044*
C5B	1.040 (2)	0.8033 (11)	1.4063 (12)	0.035 (3)
H5B	1.0106	0.8008	1.4794	0.042*
C6B	0.978 (2)	0.8880 (12)	1.3632 (13)	0.036 (4)
H6B	0.8466	0.8928	1.3762	0.043*
C7B	1.070 (2)	0.9690 (11)	1.4105 (13)	0.039 (4)
H7B	1.1981	0.9684	1.3898	0.046*
C8B	0.986 (3)	1.0525 (12)	1.3708 (15)	0.049 (5)
H81	1.0044	1.0551	1.2972	0.058*
H82	0.8551	1.0498	1.3814	0.058*
C9B	0.889 (5)	1.125 (2)	1.032 (3)	0.086 (9)
H91B	0.7801	1.1378	0.9921	0.129*
H92B	0.9933	1.1491	0.9982	0.129*
H93B	0.8793	1.1504	1.0990	0.129*
C10B	0.454 (3)	0.928 (2)	1.2173 (18)	0.071 (7)
H101	0.4136	0.9729	1.1703	0.106*
H102	0.4274	0.9455	1.2863	0.106*
H103	0.3917	0.8742	1.2015	0.106*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Hg1A	0.0847 (6)	0.0389 (4)	0.0537 (4)	−0.0061 (4)	−0.0062 (4)	0.0069 (4)
S1A	0.093 (4)	0.041 (3)	0.032 (2)	−0.002 (3)	−0.006 (2)	0.0000 (19)
O1A	0.041 (6)	0.030 (6)	0.027 (5)	−0.002 (5)	0.003 (4)	−0.002 (4)
O2A	0.056 (8)	0.031 (6)	0.055 (8)	−0.001 (6)	0.010 (6)	0.008 (6)
O3A	0.043 (6)	0.039 (7)	0.056 (7)	−0.006 (5)	0.011 (5)	−0.012 (6)
O4A	0.043 (7)	0.054 (8)	0.064 (9)	−0.007 (6)	0.003 (6)	−0.004 (7)
O5A	0.079 (10)	0.092 (14)	0.084 (12)	0.021 (11)	0.036 (9)	0.024 (12)
O6A	0.059 (7)	0.049 (7)	0.029 (6)	−0.014 (6)	−0.001 (5)	−0.004 (5)
O7A	0.104 (12)	0.030 (7)	0.060 (9)	0.017 (7)	−0.007 (9)	−0.014 (6)
C1A	0.073 (12)	0.030 (8)	0.034 (8)	0.010 (9)	0.011 (8)	−0.001 (7)
C2A	0.054 (10)	0.026 (7)	0.036 (8)	0.010 (7)	−0.008 (8)	−0.004 (6)
C3A	0.051 (10)	0.039 (9)	0.025 (7)	0.000 (7)	0.006 (6)	0.004 (7)
C4A	0.042 (9)	0.017 (7)	0.048 (10)	−0.001 (6)	0.001 (7)	0.003 (7)
C5A	0.047 (8)	0.031 (8)	0.024 (6)	−0.001 (8)	0.003 (6)	−0.001 (6)
C6A	0.037 (8)	0.032 (8)	0.024 (7)	0.005 (6)	−0.003 (6)	−0.010 (6)
C7A	0.054 (10)	0.036 (9)	0.024 (7)	0.004 (7)	−0.007 (7)	−0.008 (6)
C8A	0.086 (14)	0.015 (7)	0.050 (11)	−0.009 (8)	−0.007 (10)	−0.002 (7)
C9A	0.18 (4)	0.046 (17)	0.13 (3)	0.01 (2)	−0.04 (3)	−0.006 (19)
C10A	0.067 (13)	0.085 (17)	0.033 (10)	−0.020 (12)	−0.002 (9)	−0.008 (10)
Hg1B	0.0732 (5)	0.0374 (4)	0.0521 (4)	−0.0051 (4)	0.0059 (3)	0.0066 (3)
S1B	0.069 (3)	0.039 (3)	0.032 (2)	0.006 (2)	0.001 (2)	−0.0010 (18)
O1B	0.045 (6)	0.022 (5)	0.034 (6)	−0.001 (4)	0.005 (5)	−0.005 (4)
O2B	0.053 (7)	0.032 (7)	0.054 (8)	0.015 (6)	0.008 (6)	0.012 (6)
O3B	0.037 (6)	0.048 (7)	0.047 (6)	−0.003 (5)	−0.003 (5)	−0.003 (6)
O4B	0.061 (8)	0.033 (7)	0.050 (8)	−0.001 (6)	0.001 (6)	0.007 (6)
O5B	0.057 (7)	0.016 (5)	0.098 (11)	−0.009 (6)	−0.011 (7)	0.006 (7)
O6B	0.061 (8)	0.051 (8)	0.035 (6)	0.008 (6)	−0.007 (6)	−0.011 (5)
O7B	0.091 (10)	0.031 (7)	0.059 (9)	−0.012 (7)	0.004 (8)	−0.012 (6)
C1B	0.052 (9)	0.032 (9)	0.033 (8)	0.001 (7)	0.001 (7)	0.003 (7)
C2B	0.047 (9)	0.031 (8)	0.034 (8)	−0.002 (7)	−0.003 (7)	−0.001 (6)
C3B	0.045 (9)	0.029 (8)	0.034 (8)	−0.006 (7)	0.002 (7)	0.001 (6)
C4B	0.039 (8)	0.022 (8)	0.048 (9)	0.002 (6)	−0.002 (7)	0.013 (7)
C5B	0.041 (8)	0.036 (9)	0.030 (7)	0.005 (7)	0.009 (6)	−0.003 (6)
C6B	0.044 (9)	0.037 (10)	0.026 (8)	−0.003 (7)	0.009 (6)	−0.003 (7)
C7B	0.048 (9)	0.038 (9)	0.030 (7)	0.002 (7)	0.001 (7)	−0.010 (6)
C8B	0.086 (14)	0.023 (8)	0.037 (9)	−0.002 (8)	−0.006 (9)	0.004 (7)
C9B	0.10 (2)	0.061 (18)	0.10 (2)	0.000 (15)	0.016 (18)	−0.011 (16)
C10B	0.044 (11)	0.12 (2)	0.048 (12)	0.016 (12)	0.004 (9)	0.019 (13)

Geometric parameters (Å, º)

Hg1A—C9A	2.04 (3)	Hg1B—C9B	2.05 (4)
Hg1A—S1A	2.346 (6)	Hg1B—S1B	2.362 (5)
S1A—C2A	1.798 (17)	S1B—C2B	1.850 (18)
O1A—C6A	1.446 (18)	O1B—C6B	1.42 (2)
O1A—C2A	1.46 (2)	O1B—C2B	1.42 (2)
O2A—C4A	1.42 (2)	O2B—C4B	1.446 (18)
O2A—H2OA	0.82	O2B—H2OB	0.83
O3A—C5A	1.43 (2)	O3B—C5B	1.43 (2)
O4A—C1A	1.32 (2)	O4B—C1B	1.30 (2)
O4A—C10A	1.42 (3)	O4B—C10B	1.40 (3)
O5A—C1A	1.19 (3)	O5B—C1B	1.207 (9)
O6A—C7A	1.41 (2)	O6B—C7B	1.44 (2)
O6A—H6OA	0.78	O6B—H6OB	0.94
O7A—C8A	1.44 (3)	O7B—C8B	1.40 (2)
C1A—C2A	1.51 (3)	C1B—C2B	1.52 (2)
C2A—C3A	1.51 (2)	C2B—C3B	1.55 (2)
C3A—C4A	1.56 (2)	C3B—C4B	1.52 (3)
C3A—H3A2	0.9700	C3B—H31B	0.9700
C3A—H3A3	0.9700	C3B—H32B	0.9700
C4A—C5A	1.50 (2)	C4B—C5B	1.49 (2)
C4A—H4A	0.9800	C4B—H4B	0.9800
C5A—C6A	1.54 (2)	C5B—C6B	1.48 (2)
C5A—H5A	0.9800	C5B—H5B	0.9800
C6A—C7A	1.53 (2)	C6B—C7B	1.53 (2)
C6A—H6A	0.9800	C6B—H6B	0.9800
C7A—C8A	1.51 (2)	C7B—C8B	1.50 (2)
C7A—H7A	0.9800	C7B—H7B	0.9800
C8A—H8A1	0.9700	C8B—H81	0.9700
C8A—H8A2	0.9700	C8B—H82	0.9700
C9A—H91A	0.9600	C9B—H91B	0.9600
C9A—H92A	0.9600	C9B—H92B	0.9600
C9A—H93A	0.9600	C9B—H93B	0.9600
C10A—H10A	0.9600	C10B—H101	0.9600
C10A—H10B	0.9600	C10B—H102	0.9600
C10A—H10C	0.9600	C10B—H103	0.9600
C9A—Hg1A—S1A	175.7 (15)	H10B—C10A—H10C	109.5
C2A—S1A—Hg1A	99.3 (6)	C9B—Hg1B—S1B	176.7 (10)
C6A—O1A—C2A	114.5 (12)	C2B—S1B—Hg1B	98.8 (6)
C4A—O2A—H2OA	129	C6B—O1B—C2B	112.7 (13)
C1A—O4A—C10A	115.9 (19)	C4B—O2B—H2OB	99
C7A—O6A—H6OA	99	C1B—O4B—C10B	116.8 (19)
O5A—C1A—O4A	124 (2)	C7B—O6B—H6OB	115
O5A—C1A—C2A	122 (2)	O5B—C1B—O4B	121.6 (16)
O4A—C1A—C2A	112.9 (15)	O5B—C1B—C2B	124.6 (16)
O1A—C2A—C1A	110.9 (13)	O4B—C1B—C2B	113.6 (12)
O1A—C2A—C3A	109.2 (15)	O1B—C2B—C1B	112.4 (14)
C1A—C2A—C3A	111.8 (14)	O1B—C2B—C3B	111.5 (12)
O1A—C2A—S1A	108.0 (10)	C1B—C2B—C3B	110.7 (14)
C1A—C2A—S1A	108.8 (14)	O1B—C2B—S1B	107.0 (11)
C3A—C2A—S1A	108.0 (12)	C1B—C2B—S1B	107.4 (12)
C2A—C3A—C4A	111.0 (14)	C3B—C2B—S1B	107.5 (12)
C2A—C3A—H3A2	109.4	C4B—C3B—C2B	109.1 (14)
C4A—C3A—H3A2	109.4	C4B—C3B—H31B	109.9
C2A—C3A—H3A3	109.4	C2B—C3B—H31B	109.9
C4A—C3A—H3A3	109.4	C4B—C3B—H32B	109.9
H3A2—C3A—H3A3	108.0	C2B—C3B—H32B	109.9
O2A—C4A—C5A	108.5 (15)	H31B—C3B—H32B	108.3
O2A—C4A—C3A	111.6 (14)	O2B—C4B—C5B	112.9 (13)
C5A—C4A—C3A	111.7 (13)	O2B—C4B—C3B	105.9 (15)
O2A—C4A—H4A	108.3	C5B—C4B—C3B	111.1 (14)
C5A—C4A—H4A	108.3	O2B—C4B—H4B	108.9
C3A—C4A—H4A	108.3	C5B—C4B—H4B	108.9
O3A—C5A—C4A	111.3 (13)	C3B—C4B—H4B	108.9
O3A—C5A—C6A	109.0 (13)	O3B—C5B—C6B	110.9 (14)
C4A—C5A—C6A	108.6 (13)	O3B—C5B—C4B	107.2 (13)
O3A—C5A—H5A	109.3	C6B—C5B—C4B	111.0 (14)
C4A—C5A—H5A	109.3	O3B—C5B—H5B	109.2
C6A—C5A—H5A	109.3	C6B—C5B—H5B	109.2
O1A—C6A—C7A	104.7 (12)	C4B—C5B—H5B	109.2
O1A—C6A—C5A	108.9 (12)	O1B—C6B—C5B	113.8 (14)
C7A—C6A—C5A	113.8 (14)	O1B—C6B—C7B	106.1 (13)
O1A—C6A—H6A	109.8	C5B—C6B—C7B	115.0 (14)
C7A—C6A—H6A	109.8	O1B—C6B—H6B	107.2
C5A—C6A—H6A	109.8	C5B—C6B—H6B	107.2
O6A—C7A—C8A	110.0 (14)	C7B—C6B—H6B	107.2
O6A—C7A—C6A	110.1 (14)	O6B—C7B—C8B	112.5 (15)
C8A—C7A—C6A	109.0 (16)	O6B—C7B—C6B	110.2 (14)
O6A—C7A—H7A	109.2	C8B—C7B—C6B	111.9 (14)
C8A—C7A—H7A	109.2	O6B—C7B—H7B	107.3
C6A—C7A—H7A	109.2	C8B—C7B—H7B	107.3
O7A—C8A—C7A	113.0 (19)	C6B—C7B—H7B	107.3
O7A—C8A—H8A1	109.0	O7B—C8B—C7B	116.3 (16)
C7A—C8A—H8A1	109.0	O7B—C8B—H81	108.2
O7A—C8A—H8A2	109.0	C7B—C8B—H81	108.2
C7A—C8A—H8A2	109.0	O7B—C8B—H82	108.2
H8A1—C8A—H8A2	107.8	C7B—C8B—H82	108.2
Hg1A—C9A—H91A	109.5	H81—C8B—H82	107.4
Hg1A—C9A—H92A	109.5	Hg1B—C9B—H91B	109.5
H91A—C9A—H92A	109.5	Hg1B—C9B—H92B	109.5
Hg1A—C9A—H93A	109.5	H91B—C9B—H92B	109.5
H91A—C9A—H93A	109.5	Hg1B—C9B—H93B	109.5
H92A—C9A—H93A	109.5	H91B—C9B—H93B	109.5
O4A—C10A—H10A	109.5	H92B—C9B—H93B	109.5
O4A—C10A—H10B	109.5	O4B—C10B—H101	109.5
H10A—C10A—H10B	109.5	O4B—C10B—H102	109.5
O4A—C10A—H10C	109.5	O4B—C10B—H103	109.5
H10A—C10A—H10C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2A—H2OA···O7A^i	0.82	2.15	2.87 (2)	146
O6A—H6OA···O3B^ii	0.78	2.01	2.75 (2)	158
O2B—H2OB···O7B^iii	0.83	2.06	2.75 (2)	141
O6B—H6OB···O3A^iv	0.94	1.88	2.81 (2)	168

Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) x−1, y, z−1; (iii) −x+2, y−1/2, −z+3; (iv) x, y, z+1.