Two salts of di-p-toluoyltartaric acid with aromatic amines

The structures of bis­[(R)-(+)-1-phenyl­ethyl­ammonium] (2R,3R)-(−)-2,3-di-p-toluoyloxybutane­dioate methanol disolvate monohydrate, 2C₈H₁₂N⁺·C₂₀H₁₆O₈²⁻·2CH₄O·H₂O, (I), and bis­(benzyl­ammonium) (2R,3R)-(−)-2,3-di-p-toluoyl­oxy­butane­­dioate dihydrate, 2C₇H₁₀N⁺·C₂₀H₁₆O₈²⁻·2H₂O, (II), exhibit extensive hydrogen bonding, with (N—)H...O and (O—)H...O distances in the ranges 2.716 (2)–2.929 (3) and 2.687 (2)–2.767 (2) Å, respectively, in (I), and 2.673 (2)–2.888 (2) and 2.785 (2)–2.931 (2) Å, respectively, in (II). The amine groups are protonated and the carboxyl­ate groups of the tartrate anions are fully deprotonated. The conformation of the toluoyltartrate anion and its mol­ecular parameters are similar in both structures.

S1. Comment

This work arose from a systematic study of chiral host acids with amine guests. Previous examples of the structures derived from the host (2R,3R)-(-)-di-O-p-toluoyltartaric acid or its enantiomer with amines showed that the acid is mono-deprotonated (Liao et al. 2003; Hansen et al. 1998). Liao et al. (2003) have characterized the structure of (R)-α-{[(1,1-dimethylethyl)ammonio]methyl}-(3,5-dihydroxyphenyl)methanol (2S,3S)-di-O-toluoyltartrate monohydrate, in which the N atom on the base is protonated and one of the carboxylic acid moieties is deprotonated. The anhydrous salt of the same compound has similar features [Cambridge Structural Database (CSD; Allen, 2002), reference codes GACXUE and GACYEP01, respectively]. Hansen et al. (1998) have described the structure of (+)-(R)-3-(N,N-dimethylammonio)-1,1-diphenyl-1-butanol (-)-(2R,3R)-O,O'-di-p-toloyltartrate, in which the base is again protonated on the N atom and one carboxylic acid moiety is anionic (CSD reference code GORCAR). In contrast, the structure of (2S,5S)-1,6-diammonio-2,5-dimethyl-3,4-dithiahexane (2S,3S)-di-O-(4-toluoyl)tartrate ethanol solvate sesquihydrate (Elz et al., 1987) shows the thiahexane to be bis-protonated and the tartrate to have lost two H atoms (CSD reference code FEWLEY). We noted these features by observing the C—O bond lengths of the carboxylic acid moieties in which there was no ambiguity as to whether the carboxylic acid moiety was deprotonated or not. In addition, the corresponding amines displayed an extra H atom at N, the geometry of which was tetrahedral. We have also analysed differences in the conformations of the tartrate anions and have noted that the absolute value of the torsion angle about the central C—C bond is approximately 76° in the completely deprotonated anion, but is reduced to 61–70° in the monoprotonated species. There were no discernible patterns in the other four torsion angles in the adjacent C—O and O—C bonds of the tartrates, which are described later.

We have characterized the structures of (2R,3R)-toluoyltartaric acid, L, with (R)-(+)-1-phenylethylamine (A) and benzylamine (B) (see scheme), and present the results here. The former forms a compound with the stoichiometry L.2A·2MeOH·H₂O [compound (I); Fig. 1] and the latter a compound with the stoichiometry L.2B·2H₂O [compound (II); Fig. 2].

Compound (I) crystallizes in the space group P2₁ with Z = 2. The refinement showed that the N atoms of the amines are protonated and the carboxyl moieties of the acid exhibit similar C—O bond lengths, ranging from 1.240 (3) to 1.257 (3) Å, so they may be represented as (CO₂)⁻ moieties.

The structure is extensively hydrogen-bonded, as shown in Fig. 3. There are double ribbons of the toluoyltartrate anions running in the [010] direction, which are bridged by 1-phenylethylammonium cations and water molecules, while the methanol molecules are hydrogen bonded to the amine and the acid ions. Details of the hydrogen bonding are given in Table 2.

The conformation of the toluoyltartrate anion is governed by the torsion angles about the central C—C bond and the adjacent C—O and O—C bonds. These are reported in Table 1, together with salient bond lengths. The conformation is such that the aromatic toluoyl moieties lie approximately perpendicular to each other.

Compound (II) crystallizes in the space group P2₁2₁2₁ with Z = 4. The toluoyltartaric acid again forms anions, with both its carboxyl moieties deprotonated, and the amines display protonated N atoms. The packing is such that the structure forms infinite sheets perpendicular to [001] and is held together by hydrogen bonds, in which the water molecules and amine cations bridge the acid anions. This is shown in Fig. 4. Details of the hydrogen bonding are given in Table 4. The conformation of the toluoyltartrate in this structure is similar to that of (I), as are the C—O bond lengths of the anionic carboxyl moiety (Table 3).

We note that the absolute values of the torsion angles about the central C—C bond of the anions in these compounds are close to that found in the dithiahexane compound elucidated by Elz et al. (1987).

S2. Experimental

Tartaric acid and the appropriate amine guest, in a mole ratio of 1:2, were dissolved in warm wet methanol solvent (Temperature? Ratio of alcohol and water?). The resultant solutions were allowed to stand at room temperature. Colourless crystals of (I) and (II) appeared after a few days from their respective mother liquor.

S3. Refinement

Both structure solutions and refinements proceeded routinely. Friedel equivalents were merged in the final refinement cycles. All non-H atoms were refined anisotropically. The functional H atoms of the methanol hydroxyl group, the water hydroxyl group and the amine cation NH₃⁺ were located in a difference electron-density map and refined independently with simple bond-length constraints (Restraints?). [Please give details of restraints used and ranges of refined distances.] The remaining H atoms were placed in idealized positions in a riding model, with C—H = 0.95–1.00 Å, and refined with U_iso(H) = 1.2–1.5U_eq(C).

Computing details

For both compounds, 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: ORTEP-3 (Farrugia, 1997), X-SEED (Barbour, 2001) and POVRAY (Cason, Year?); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the asymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. All H atoms have been omitted for clarity.
	Fig. 2. A view of the asymmetric unit of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. All H atoms have been omitted for clarity.
	Fig. 3. A projection of the structure of (I), viewed along [100], showing the network of hydrogen bonding. Various shading is used for different molecules and bonds, and hydrogen bonds are shown as dotted lines. All H atoms have been omitted for clarity.
	Fig. 4. A perspective view of (II), along [100], showing the infinite sheets of the hydrogen-bonding network running perpendicular to [001]. Hydrogen bonds are shown as dotted lines. All H atoms have been omitted for clarity.

(I) bis[(R)-(+)-1-phenylethylammonium] (2R,3R)-(-)-2,3-di-p-toluoyloxybutanedioate methanol disolvate monohydrate

Crystal data

2C8H12N^+·C20H16O8^2^−·2CH4O·H2O	F(000) = 760
Mr = 710.80	Dx = 1.242 Mg m^−3
Monoclinic, P21	Melting point: not measured K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 10.9366 (1) Å	Cell parameters from 43385 reflections
b = 8.0785 (1) Å	θ = 3.8–26.4°
c = 22.0995 (2) Å	µ = 0.09 mm^−1
β = 103.324 (1)°	T = 113 K
V = 1899.96 (3) Å^3	Prism, colourless
Z = 2	0.40 × 0.40 × 0.35 mm

Data collection

Nonius Kappa CCD area-detector diffractometer	3969 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.009
Graphite monochromator	θmax = 26.4°, θmin = 4.2°
1.2° ϕ scans and ω scans	h = −13→13
7708 measured reflections	k = −10→10
7708 independent reflections	l = −27→27

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)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0488P)^2 + 0.6269P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max = 0.001
7708 reflections	Δρmax = 0.38 e Å^−3
502 parameters	Δρmin = −0.26 e Å^−3
11 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.035 (3)

Special details

Experimental. Half sphere of data collected using COLLECT strategy (Nonius, 2000). Crystal to detector distance = 35 mm; combination of ϕ and ω scans of 1.2°, 40 s per °, 2 iterations.

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	0.43263 (16)	0.6310 (2)	0.33632 (8)	0.0251 (4)
O2	0.49430 (15)	0.7944 (2)	0.41991 (7)	0.0232 (3)
O3	0.57209 (15)	1.2349 (2)	0.28196 (7)	0.0231 (3)
O4	0.64452 (14)	1.0498 (2)	0.22387 (7)	0.0222 (3)
O5	0.40860 (13)	0.8900 (2)	0.25667 (6)	0.0188 (3)
O6	0.22347 (14)	0.9170 (2)	0.28353 (7)	0.0258 (4)
O7	0.67107 (13)	0.81505 (19)	0.31307 (7)	0.0182 (3)
O8	0.84887 (14)	0.9665 (2)	0.33804 (8)	0.0239 (4)
O41	0.8126 (2)	1.0909 (3)	0.14869 (12)	0.0573 (7)
O51	0.62194 (16)	0.7457 (2)	0.16569 (8)	0.0304 (4)*
O61	0.44125 (19)	0.3114 (2)	0.37065 (9)	0.0322 (4)
N21	0.42734 (19)	0.1116 (3)	0.46770 (9)	0.0235 (4)
N31	0.48447 (18)	0.5304 (3)	0.22150 (9)	0.0226 (4)
C1	0.4638 (2)	0.7666 (3)	0.36273 (10)	0.0187 (4)
C2	0.47025 (19)	0.9173 (3)	0.32111 (9)	0.0177 (4)
H2	0.4291	1.0134	0.3370	0.021*
C3	0.60531 (19)	0.9638 (3)	0.32204 (10)	0.0175 (4)
H3	0.6452	1.0122	0.3635	0.021*
C4	0.60896 (18)	1.0931 (3)	0.27086 (10)	0.0180 (4)
C5	0.28199 (19)	0.9076 (3)	0.24356 (10)	0.0200 (4)
C6	0.2279 (2)	0.9206 (3)	0.17572 (10)	0.0226 (5)
C7	0.3012 (2)	0.9489 (3)	0.13326 (11)	0.0267 (5)
H7	0.3902	0.9517	0.1469	0.032*
C8	0.2453 (2)	0.9732 (4)	0.07107 (12)	0.0338 (6)
H8	0.2963	0.9927	0.0423	0.041*
C9	0.1150 (3)	0.9694 (4)	0.05017 (12)	0.0382 (6)
C10	0.0428 (2)	0.9387 (4)	0.09291 (13)	0.0405 (7)
H10	−0.0461	0.9337	0.0791	0.049*
C11	0.0971 (2)	0.9153 (4)	0.15494 (12)	0.0325 (6)
H11	0.0459	0.8957	0.1836	0.039*
C12	0.0539 (3)	1.0028 (6)	−0.01719 (14)	0.0586 (10)
H12C	−0.0030	0.9115	−0.0338	0.088*
H12B	0.1189	1.0122	−0.0410	0.088*
H12A	0.0062	1.1064	−0.0205	0.088*
C13	0.79791 (19)	0.8364 (3)	0.32204 (10)	0.0183 (4)
C14	0.8628 (2)	0.6832 (3)	0.31045 (10)	0.0183 (4)
C15	0.9850 (2)	0.6969 (3)	0.30298 (11)	0.0231 (5)
H15	1.0220	0.8031	0.3023	0.028*
C16	1.0530 (2)	0.5564 (3)	0.29654 (12)	0.0267 (5)
H16	1.1371	0.5672	0.2922	0.032*
C17	1.0006 (2)	0.3997 (3)	0.29625 (11)	0.0256 (5)
C18	0.8757 (2)	0.3874 (3)	0.30105 (12)	0.0271 (5)
H18	0.8370	0.2816	0.2990	0.033*
C19	0.8078 (2)	0.5269 (3)	0.30871 (11)	0.0225 (5)
H19	0.7236	0.5164	0.3128	0.027*
C20	1.0744 (3)	0.2453 (4)	0.29061 (14)	0.0344 (6)
H20C	1.0660	0.2189	0.2466	0.052*
H20A	1.0420	0.1531	0.3111	0.052*
H20B	1.1631	0.2635	0.3105	0.052*
C21	0.2857 (2)	0.1047 (3)	0.44991 (11)	0.0267 (5)
H21	0.2597	0.0928	0.4037	0.032*
C22	0.2375 (2)	−0.0442 (3)	0.47825 (11)	0.0272 (5)
C23	0.1547 (4)	−0.1501 (6)	0.44080 (15)	0.0765 (15)
H23	0.1307	−0.1297	0.3973	0.092*
C24	0.1055 (4)	−0.2862 (6)	0.46522 (18)	0.0852 (17)
H24	0.0483	−0.3576	0.4385	0.102*
C25	0.1391 (3)	−0.3182 (4)	0.52799 (13)	0.0415 (7)
H25	0.1044	−0.4098	0.5452	0.050*
C26	0.2244 (3)	−0.2145 (4)	0.56548 (12)	0.0371 (6)
H26	0.2509	−0.2374	0.6087	0.045*
C27	0.2720 (3)	−0.0779 (4)	0.54123 (11)	0.0343 (6)
H27	0.3289	−0.0064	0.5680	0.041*
C28	0.2339 (3)	0.2681 (4)	0.46704 (14)	0.0374 (6)
H28A	0.1422	0.2686	0.4523	0.056*
H28C	0.2697	0.3593	0.4475	0.056*
H28B	0.2562	0.2818	0.5123	0.056*
C31	0.3672 (2)	0.5026 (3)	0.17225 (11)	0.0265 (5)
H31	0.3231	0.6112	0.1627	0.032*
C32	0.3971 (2)	0.4375 (3)	0.11329 (10)	0.0239 (5)
C33	0.3242 (3)	0.4885 (4)	0.05607 (12)	0.0346 (6)
H33	0.2596	0.5681	0.0546	0.042*
C34	0.3454 (3)	0.4238 (4)	0.00136 (12)	0.0425 (7)
H34	0.2940	0.4573	−0.0375	0.051*
C35	0.4403 (3)	0.3116 (5)	0.00291 (12)	0.0444 (8)
H35	0.4563	0.2699	−0.0347	0.053*
C36	0.5126 (3)	0.2595 (5)	0.05951 (13)	0.0439 (7)
H36	0.5778	0.1811	0.0607	0.053*
C37	0.4904 (2)	0.3210 (4)	0.11455 (11)	0.0325 (6)
H37	0.5394	0.2830	0.1533	0.039*
C38	0.2818 (3)	0.3860 (4)	0.19759 (14)	0.0409 (7)
H38A	0.2021	0.3730	0.1668	0.061*
H38C	0.2655	0.4320	0.2360	0.061*
H38B	0.3227	0.2778	0.2063	0.061*
C41	0.8471 (3)	1.2483 (5)	0.13378 (18)	0.0555 (9)
H41C	0.8456	1.3240	0.1682	0.083*
H41A	0.7880	1.2872	0.0962	0.083*
H41B	0.9320	1.2449	0.1264	0.083*
C51	0.7326 (3)	0.6892 (4)	0.14846 (12)	0.0356 (6)
H51C	0.7800	0.7845	0.1386	0.053*
H51A	0.7091	0.6174	0.1119	0.053*
H51B	0.7847	0.6269	0.1830	0.053*
H21B	0.461 (3)	0.009 (2)	0.4576 (14)	0.036 (8)*
H61B	0.434 (4)	0.4279 (14)	0.3695 (19)	0.067 (12)*
H31B	0.541 (2)	0.601 (3)	0.2058 (13)	0.039 (8)*
H21A	0.454 (3)	0.179 (4)	0.4372 (13)	0.051 (10)*
H41	0.756 (3)	1.107 (7)	0.1776 (16)	0.085 (15)*
H21C	0.454 (2)	0.141 (4)	0.5107 (6)	0.029 (7)*
H31A	0.524 (3)	0.427 (2)	0.2353 (14)	0.041 (8)*
H51	0.650 (3)	0.843 (3)	0.1925 (15)	0.063 (11)*
H31C	0.464 (3)	0.582 (4)	0.2564 (10)	0.037 (8)*
H61A	0.489 (3)	0.277 (6)	0.3425 (15)	0.072 (13)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0381 (9)	0.0137 (8)	0.0272 (8)	0.0002 (7)	0.0150 (7)	0.0000 (6)
O2	0.0302 (8)	0.0195 (8)	0.0219 (7)	0.0014 (7)	0.0100 (6)	0.0027 (7)
O3	0.0298 (8)	0.0141 (8)	0.0274 (8)	0.0030 (7)	0.0105 (6)	0.0026 (6)
O4	0.0258 (7)	0.0197 (8)	0.0236 (7)	0.0015 (7)	0.0111 (6)	0.0019 (7)
O5	0.0185 (7)	0.0174 (8)	0.0215 (7)	0.0028 (6)	0.0064 (6)	0.0018 (6)
O6	0.0214 (7)	0.0265 (9)	0.0319 (8)	−0.0005 (7)	0.0109 (6)	−0.0011 (7)
O7	0.0179 (7)	0.0139 (7)	0.0236 (7)	0.0030 (6)	0.0063 (6)	0.0011 (6)
O8	0.0212 (7)	0.0183 (8)	0.0317 (8)	−0.0004 (6)	0.0052 (6)	−0.0029 (7)
O41	0.0675 (15)	0.0475 (14)	0.0702 (16)	−0.0074 (12)	0.0432 (13)	−0.0048 (12)
O61	0.0466 (10)	0.0172 (9)	0.0405 (10)	0.0039 (8)	0.0262 (8)	0.0051 (8)
N21	0.0318 (10)	0.0188 (9)	0.0214 (9)	0.0010 (9)	0.0088 (8)	−0.0004 (8)
N31	0.0310 (10)	0.0155 (9)	0.0228 (9)	0.0020 (8)	0.0095 (7)	−0.0001 (8)
C1	0.0206 (10)	0.0131 (10)	0.0260 (11)	0.0035 (8)	0.0125 (8)	0.0024 (8)
C2	0.0200 (10)	0.0146 (10)	0.0196 (9)	0.0019 (8)	0.0068 (8)	0.0001 (8)
C3	0.0198 (9)	0.0121 (10)	0.0215 (10)	0.0022 (8)	0.0068 (8)	0.0003 (8)
C4	0.0154 (9)	0.0164 (10)	0.0222 (10)	−0.0006 (8)	0.0040 (8)	0.0017 (8)
C5	0.0192 (9)	0.0116 (10)	0.0303 (11)	−0.0006 (8)	0.0083 (8)	−0.0004 (9)
C6	0.0223 (10)	0.0158 (11)	0.0289 (11)	0.0020 (9)	0.0040 (8)	−0.0004 (9)
C7	0.0245 (10)	0.0242 (12)	0.0309 (11)	0.0004 (10)	0.0053 (9)	0.0012 (10)
C8	0.0326 (12)	0.0379 (15)	0.0308 (12)	0.0009 (11)	0.0069 (10)	0.0058 (11)
C9	0.0372 (13)	0.0422 (16)	0.0313 (13)	0.0065 (12)	−0.0001 (11)	0.0010 (12)
C10	0.0238 (11)	0.0530 (19)	0.0410 (14)	0.0045 (13)	−0.0002 (10)	−0.0049 (14)
C11	0.0228 (11)	0.0379 (15)	0.0362 (13)	0.0011 (11)	0.0055 (9)	−0.0025 (12)
C12	0.0496 (17)	0.085 (3)	0.0347 (15)	0.0104 (19)	−0.0046 (13)	0.0061 (18)
C13	0.0185 (9)	0.0180 (11)	0.0185 (9)	0.0019 (9)	0.0044 (8)	0.0021 (8)
C14	0.0192 (10)	0.0179 (11)	0.0178 (9)	0.0027 (9)	0.0041 (8)	0.0011 (8)
C15	0.0222 (10)	0.0204 (11)	0.0273 (11)	−0.0019 (9)	0.0072 (9)	−0.0019 (9)
C16	0.0192 (10)	0.0269 (13)	0.0371 (12)	0.0003 (10)	0.0126 (9)	−0.0031 (10)
C17	0.0259 (11)	0.0218 (12)	0.0313 (12)	0.0041 (10)	0.0112 (9)	0.0015 (10)
C18	0.0288 (12)	0.0152 (11)	0.0402 (13)	0.0007 (9)	0.0138 (10)	0.0027 (10)
C19	0.0186 (10)	0.0198 (11)	0.0303 (11)	0.0000 (9)	0.0084 (8)	0.0023 (10)
C20	0.0319 (13)	0.0253 (13)	0.0494 (16)	0.0066 (11)	0.0162 (11)	0.0008 (12)
C21	0.0281 (11)	0.0268 (12)	0.0243 (11)	−0.0001 (10)	0.0042 (9)	0.0036 (10)
C22	0.0297 (11)	0.0272 (13)	0.0245 (11)	0.0014 (10)	0.0060 (9)	0.0044 (10)
C23	0.104 (3)	0.079 (3)	0.0295 (15)	−0.058 (3)	−0.0200 (17)	0.0237 (17)
C24	0.098 (3)	0.087 (3)	0.050 (2)	−0.065 (3)	−0.027 (2)	0.030 (2)
C25	0.0457 (15)	0.0374 (16)	0.0430 (15)	−0.0041 (13)	0.0133 (12)	0.0163 (13)
C26	0.0597 (17)	0.0288 (14)	0.0255 (12)	0.0056 (13)	0.0153 (11)	0.0050 (11)
C27	0.0525 (15)	0.0274 (13)	0.0217 (11)	−0.0005 (12)	0.0060 (10)	−0.0007 (10)
C28	0.0367 (14)	0.0302 (15)	0.0467 (15)	0.0085 (12)	0.0122 (12)	0.0071 (12)
C31	0.0277 (11)	0.0192 (12)	0.0322 (12)	0.0047 (10)	0.0061 (9)	−0.0010 (10)
C32	0.0259 (11)	0.0204 (12)	0.0253 (10)	−0.0034 (9)	0.0054 (8)	0.0011 (9)
C33	0.0342 (12)	0.0300 (14)	0.0344 (13)	−0.0034 (11)	−0.0029 (10)	0.0058 (11)
C34	0.0489 (16)	0.0490 (18)	0.0238 (12)	−0.0172 (15)	−0.0038 (11)	0.0078 (13)
C35	0.0481 (16)	0.063 (2)	0.0244 (12)	−0.0205 (16)	0.0121 (11)	−0.0118 (14)
C36	0.0384 (14)	0.057 (2)	0.0367 (14)	0.0056 (14)	0.0096 (11)	−0.0159 (14)
C37	0.0356 (12)	0.0362 (15)	0.0236 (11)	0.0081 (12)	0.0027 (9)	−0.0032 (11)
C38	0.0367 (14)	0.0472 (17)	0.0448 (15)	−0.0086 (13)	0.0218 (12)	−0.0116 (14)
C41	0.0544 (19)	0.049 (2)	0.066 (2)	−0.0035 (17)	0.0207 (16)	0.0036 (18)
C51	0.0417 (14)	0.0385 (15)	0.0286 (12)	0.0071 (13)	0.0121 (11)	0.0028 (12)

Geometric parameters (Å, º)

O1—C1	1.251 (3)	C16—H16	0.9500
O2—C1	1.251 (3)	C17—C18	1.398 (3)
O3—C4	1.257 (3)	C17—C20	1.506 (3)
O4—C4	1.240 (3)	C18—C19	1.381 (3)
O5—C2	1.445 (2)	C18—H18	0.9500
O7—C3	1.437 (2)	C19—H19	0.9500
C1—C2	1.537 (3)	C20—H20C	0.9800
C2—C3	1.520 (3)	C20—H20A	0.9800
C3—C4	1.547 (3)	C20—H20B	0.9800
O7—C13	1.366 (2)	C21—C22	1.507 (4)
O6—C5	1.207 (3)	C21—C28	1.519 (4)
O5—C5	1.355 (2)	C21—H21	1.0000
O8—C13	1.204 (3)	C22—C23	1.375 (4)
O41—C41	1.387 (5)	C22—C27	1.383 (3)
O41—H41	1.00 (4)	C23—C24	1.387 (5)
O51—C51	1.425 (3)	C23—H23	0.9500
O51—H51	0.99 (3)	C24—C25	1.375 (5)
O61—H61B	0.944 (12)	C24—H24	0.9500
O61—H61A	0.94 (3)	C25—C26	1.379 (4)
N21—C21	1.509 (3)	C25—H25	0.9500
N21—H21B	0.95 (3)	C26—C27	1.379 (4)
N21—H21A	0.96 (3)	C26—H26	0.9500
N21—H21C	0.959 (10)	C27—H27	0.9500
N31—C31	1.495 (3)	C28—H28A	0.9800
N31—H31B	0.958 (10)	C28—H28C	0.9800
N31—H31A	0.953 (10)	C28—H28B	0.9800
N31—H31C	0.95 (3)	C31—C32	1.509 (3)
C2—H2	1.0000	C31—C38	1.522 (4)
C3—H3	1.0000	C31—H31	1.0000
C5—C6	1.483 (3)	C32—C37	1.383 (3)
C6—C7	1.386 (3)	C32—C33	1.393 (3)
C6—C11	1.399 (3)	C33—C34	1.385 (4)
C7—C8	1.384 (3)	C33—H33	0.9500
C7—H7	0.9500	C34—C35	1.372 (5)
C8—C9	1.393 (4)	C34—H34	0.9500
C8—H8	0.9500	C35—C36	1.382 (4)
C9—C10	1.387 (4)	C35—H35	0.9500
C9—C12	1.509 (4)	C36—C37	1.386 (4)
C10—C11	1.376 (4)	C36—H36	0.9500
C10—H10	0.9500	C37—H37	0.9500
C11—H11	0.9500	C38—H38A	0.9800
C12—H12C	0.9800	C38—H38C	0.9800
C12—H12B	0.9800	C38—H38B	0.9800
C12—H12A	0.9800	C41—H41C	0.9800
C13—C14	1.478 (3)	C41—H41A	0.9800
C14—C15	1.388 (3)	C41—H41B	0.9800
C14—C19	1.395 (3)	C51—H51C	0.9800
C15—C16	1.383 (3)	C51—H51A	0.9800
C15—H15	0.9500	C51—H51B	0.9800
C16—C17	1.389 (4)
C5—O5—C2	114.60 (15)	C18—C19—H19	120.0
C13—O7—C3	113.48 (16)	C14—C19—H19	120.0
C41—O41—H41	106 (3)	C17—C20—H20C	109.5
C51—O51—H51	105 (2)	C17—C20—H20A	109.5
H61B—O61—H61A	109 (4)	H20C—C20—H20A	109.5
C21—N21—H21B	109.9 (19)	C17—C20—H20B	109.5
C21—N21—H21A	107 (2)	H20C—C20—H20B	109.5
H21B—N21—H21A	97 (3)	H20A—C20—H20B	109.5
C21—N21—H21C	108.9 (16)	C22—C21—N21	111.0 (2)
H21B—N21—H21C	114 (3)	C22—C21—C28	113.8 (2)
H21A—N21—H21C	119 (3)	N21—C21—C28	108.8 (2)
C31—N31—H31B	109.9 (18)	C22—C21—H21	107.7
C31—N31—H31A	110 (2)	N21—C21—H21	107.7
H31B—N31—H31A	111 (3)	C28—C21—H21	107.7
C31—N31—H31C	109.7 (18)	C23—C22—C27	118.2 (3)
H31B—N31—H31C	109 (3)	C23—C22—C21	119.5 (2)
H31A—N31—H31C	107 (3)	C27—C22—C21	122.4 (2)
O2—C1—O1	127.5 (2)	C22—C23—C24	121.3 (3)
O2—C1—C2	115.11 (19)	C22—C23—H23	119.3
O1—C1—C2	117.36 (18)	C24—C23—H23	119.3
O5—C2—C3	106.40 (16)	C25—C24—C23	120.2 (3)
O5—C2—C1	113.17 (18)	C25—C24—H24	119.9
C3—C2—C1	111.48 (17)	C23—C24—H24	119.9
O5—C2—H2	108.6	C24—C25—C26	118.6 (3)
C3—C2—H2	108.6	C24—C25—H25	120.7
C1—C2—H2	108.6	C26—C25—H25	120.7
O7—C3—C2	107.91 (17)	C27—C26—C25	121.0 (2)
O7—C3—C4	111.45 (16)	C27—C26—H26	119.5
C2—C3—C4	110.22 (16)	C25—C26—H26	119.5
O7—C3—H3	109.1	C26—C27—C22	120.6 (3)
C2—C3—H3	109.1	C26—C27—H27	119.7
C4—C3—H3	109.1	C22—C27—H27	119.7
O4—C4—O3	126.6 (2)	C21—C28—H28A	109.5
O4—C4—C3	119.19 (19)	C21—C28—H28C	109.5
O3—C4—C3	114.16 (18)	H28A—C28—H28C	109.5
O6—C5—O5	122.56 (19)	C21—C28—H28B	109.5
O6—C5—C6	125.49 (19)	H28A—C28—H28B	109.5
O5—C5—C6	111.91 (17)	H28C—C28—H28B	109.5
C7—C6—C11	119.3 (2)	N31—C31—C32	111.13 (18)
C7—C6—C5	122.5 (2)	N31—C31—C38	108.8 (2)
C11—C6—C5	118.0 (2)	C32—C31—C38	112.1 (2)
C8—C7—C6	120.2 (2)	N31—C31—H31	108.3
C8—C7—H7	119.9	C32—C31—H31	108.3
C6—C7—H7	119.9	C38—C31—H31	108.3
C7—C8—C9	120.7 (2)	C37—C32—C33	119.0 (2)
C7—C8—H8	119.7	C37—C32—C31	121.7 (2)
C9—C8—H8	119.7	C33—C32—C31	119.2 (2)
C10—C9—C8	118.6 (2)	C34—C33—C32	120.3 (3)
C10—C9—C12	120.8 (3)	C34—C33—H33	119.8
C8—C9—C12	120.6 (3)	C32—C33—H33	119.8
C11—C10—C9	121.3 (2)	C35—C34—C33	120.4 (2)
C11—C10—H10	119.3	C35—C34—H34	119.8
C9—C10—H10	119.3	C33—C34—H34	119.8
C10—C11—C6	119.8 (2)	C34—C35—C36	119.7 (3)
C10—C11—H11	120.1	C34—C35—H35	120.2
C6—C11—H11	120.1	C36—C35—H35	120.2
C9—C12—H12C	109.5	C35—C36—C37	120.4 (3)
C9—C12—H12B	109.5	C35—C36—H36	119.8
H12C—C12—H12B	109.5	C37—C36—H36	119.8
C9—C12—H12A	109.5	C32—C37—C36	120.2 (2)
H12C—C12—H12A	109.5	C32—C37—H37	119.9
H12B—C12—H12A	109.5	C36—C37—H37	119.9
O8—C13—O7	122.57 (19)	C31—C38—H38A	109.5
O8—C13—C14	124.99 (19)	C31—C38—H38C	109.5
O7—C13—C14	112.43 (18)	H38A—C38—H38C	109.5
C15—C14—C19	119.3 (2)	C31—C38—H38B	109.5
C15—C14—C13	117.9 (2)	H38A—C38—H38B	109.5
C19—C14—C13	122.76 (18)	H38C—C38—H38B	109.5
C16—C15—C14	120.1 (2)	O41—C41—H41C	109.5
C16—C15—H15	119.9	O41—C41—H41A	109.5
C14—C15—H15	119.9	H41C—C41—H41A	109.5
C15—C16—C17	121.16 (19)	O41—C41—H41B	109.5
C15—C16—H16	119.4	H41C—C41—H41B	109.5
C17—C16—H16	119.4	H41A—C41—H41B	109.5
C16—C17—C18	118.3 (2)	O51—C51—H51C	109.5
C16—C17—C20	121.8 (2)	O51—C51—H51A	109.5
C18—C17—C20	119.9 (2)	H51C—C51—H51A	109.5
C19—C18—C17	120.9 (2)	O51—C51—H51B	109.5
C19—C18—H18	119.6	H51C—C51—H51B	109.5
C17—C18—H18	119.6	H51A—C51—H51B	109.5
C18—C19—C14	120.10 (19)
C5—O5—C2—C3	−156.8 (2)	O8—C13—C14—C19	162.0 (2)
C5—O5—C2—C1	80.5 (2)	O7—C13—C14—C19	−17.5 (3)
O2—C1—C2—O5	−167.05 (17)	C19—C14—C15—C16	−2.7 (3)
O1—C1—C2—O5	14.9 (3)	C13—C14—C15—C16	175.3 (2)
O2—C1—C2—C3	73.1 (2)	C14—C15—C16—C17	1.2 (4)
O1—C1—C2—C3	−105.0 (2)	C15—C16—C17—C18	1.6 (4)
C13—O7—C3—C2	−171.0 (2)	C15—C16—C17—C20	−178.7 (3)
C13—O7—C3—C4	67.9 (2)	C16—C17—C18—C19	−2.9 (4)
O5—C2—C3—O7	−76.3 (2)	C20—C17—C18—C19	177.4 (2)
C1—C2—C3—O7	47.5 (2)	C17—C18—C19—C14	1.4 (4)
O5—C2—C3—C4	45.6 (2)	C15—C14—C19—C18	1.5 (3)
C1—C2—C3—C4	169.39 (17)	C13—C14—C19—C18	−176.5 (2)
O7—C3—C4—O4	12.6 (3)	N21—C21—C22—C23	−127.8 (3)
C2—C3—C4—O4	−107.2 (2)	C28—C21—C22—C23	109.1 (4)
O7—C3—C4—O3	−168.47 (17)	N21—C21—C22—C27	53.2 (3)
C2—C3—C4—O3	71.7 (2)	C28—C21—C22—C27	−69.9 (3)
C2—O5—C5—O6	−12.1 (3)	C27—C22—C23—C24	0.7 (7)
C2—O5—C5—C6	165.5 (2)	C21—C22—C23—C24	−178.3 (4)
O6—C5—C6—C7	164.0 (2)	C22—C23—C24—C25	−0.1 (8)
O5—C5—C6—C7	−13.6 (3)	C23—C24—C25—C26	−1.4 (7)
O6—C5—C6—C11	−11.4 (4)	C24—C25—C26—C27	2.3 (5)
O5—C5—C6—C11	171.0 (2)	C25—C26—C27—C22	−1.7 (4)
C11—C6—C7—C8	0.6 (4)	C23—C22—C27—C26	0.2 (5)
C5—C6—C7—C8	−174.8 (2)	C21—C22—C27—C26	179.2 (2)
C6—C7—C8—C9	−0.1 (4)	N31—C31—C32—C37	40.2 (3)
C7—C8—C9—C10	−0.8 (5)	C38—C31—C32—C37	−81.7 (3)
C7—C8—C9—C12	177.5 (3)	N31—C31—C32—C33	−143.7 (2)
C8—C9—C10—C11	1.2 (5)	C38—C31—C32—C33	94.4 (3)
C12—C9—C10—C11	−177.1 (3)	C37—C32—C33—C34	−0.3 (4)
C9—C10—C11—C6	−0.7 (5)	C31—C32—C33—C34	−176.5 (2)
C7—C6—C11—C10	−0.2 (4)	C32—C33—C34—C35	−1.5 (4)
C5—C6—C11—C10	175.4 (3)	C33—C34—C35—C36	1.9 (5)
C3—O7—C13—O8	2.5 (3)	C34—C35—C36—C37	−0.5 (5)
C3—O7—C13—C14	−178.0 (2)	C33—C32—C37—C36	1.6 (4)
O8—C13—C14—C15	−16.0 (3)	C31—C32—C37—C36	177.8 (3)
O7—C13—C14—C15	164.54 (19)	C35—C36—C37—C32	−1.2 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21A···O61	0.95 (3)	1.80 (2)	2.716 (3)	158 (3)
N21—H21B···O2^i	0.96 (1)	1.99 (1)	2.929 (3)	166 (3)
N21—H21C···O2^ii	0.95 (1)	1.95 (2)	2.846 (3)	155 (3)
N31—H31A···O3^i	0.95 (3)	1.87 (1)	2.795 (3)	162 (3)
N31—H31B···O51	0.96 (1)	1.82 (1)	2.768 (3)	170 (3)
N31—H31C···O1	0.95 (3)	1.92 (1)	2.843 (2)	165 (3)
O41—H41···O4	1.00 (4)	1.82 (2)	2.767 (3)	158 (5)
O51—H51···O4	0.99 (3)	1.82 (2)	2.757 (3)	158 (3)
O61—H61A···O3^i	0.94 (3)	1.81 (3)	2.750 (2)	172 (4)
O61—H61B···O1	0.94 (1)	1.80 (2)	2.687 (2)	156 (4)

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

(II) Bis(benylammonium) (2R,3R)-(-)-2,3-di-p-toluoyloxybutanedioate dihydrate

Crystal data

2C7H10N^+·C20H16O8^2^−·2H2O	Dx = 1.249 Mg m^−3
Mr = 636.68	Melting point: not measured K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 28526 reflections
a = 6.8805 (1) Å	θ = 4.3–27.2°
b = 19.2606 (1) Å	µ = 0.09 mm^−1
c = 25.5545 (2) Å	T = 113 K
V = 3386.55 (6) Å^3	Prism, colourless
Z = 4	0.35 × 0.25 × 0.25 mm
F(000) = 1352

Data collection

Nonius Kappa CCD area-detector diffractometer	3955 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 27.2°, θmin = 4.3°
1.2° ϕ scans and ω scans	h = −8→8
28533 measured reflections	k = −24→24
4225 independent reflections	l = −32→32

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)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.084	w = 1/[σ^2(Fo^2) + (0.048P)^2 + 0.6428P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
4225 reflections	Δρmax = 0.28 e Å^−3
458 parameters	Δρmin = −0.26 e Å^−3
10 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.017 (2)

Special details

Experimental. Half sphere of data collected using COLLECT strategy (Nonius, 2000). Crystal to detector distance = 36 mm; combination of ϕ and ω scans of 1.2°, 60 s per °, 2 iterations.

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	0.33566 (17)	0.03978 (6)	0.28175 (5)	0.0244 (3)
O2	0.64601 (18)	0.03542 (6)	0.25560 (5)	0.0253 (3)
O3	0.26410 (17)	0.28670 (6)	0.24921 (5)	0.0230 (3)
O4	0.57696 (18)	0.29712 (6)	0.27143 (5)	0.0251 (3)
O5	0.62623 (17)	0.16345 (5)	0.21189 (4)	0.0205 (2)
O6	0.51992 (19)	0.10642 (6)	0.14061 (5)	0.0295 (3)
O7	0.55520 (16)	0.17262 (5)	0.32548 (4)	0.0195 (2)
O8	0.3413 (2)	0.21682 (10)	0.38221 (6)	0.0542 (5)
O41	0.1472 (2)	0.41262 (6)	0.20589 (6)	0.0307 (3)
O51	0.98173 (18)	0.10972 (6)	0.28272 (5)	0.0290 (3)
N21	0.7301 (2)	0.40433 (7)	0.20404 (6)	0.0266 (3)
N31	0.9297 (2)	0.25097 (7)	0.30575 (6)	0.0247 (3)
C1	0.4861 (2)	0.06404 (8)	0.26049 (6)	0.0196 (3)
C2	0.4579 (2)	0.13857 (7)	0.23949 (6)	0.0187 (3)
H2	0.3443	0.1389	0.2151	0.022*
C3	0.4158 (2)	0.18741 (7)	0.28461 (6)	0.0181 (3)
H3	0.2828	0.1769	0.2983	0.022*
C4	0.4212 (2)	0.26425 (8)	0.26732 (6)	0.0185 (3)
C5	0.6402 (3)	0.14244 (8)	0.16165 (6)	0.0215 (3)
C6	0.8176 (3)	0.16925 (8)	0.13568 (6)	0.0221 (3)
C7	0.9560 (3)	0.20864 (8)	0.16180 (7)	0.0256 (3)
H7	0.9379	0.2199	0.1977	0.031*
C8	1.1202 (3)	0.23148 (10)	0.13565 (7)	0.0298 (4)
H8	1.2137	0.2587	0.1538	0.036*
C9	1.1503 (3)	0.21518 (9)	0.08327 (7)	0.0294 (4)
C10	1.0125 (3)	0.17495 (10)	0.05773 (7)	0.0301 (4)
H10	1.0321	0.1629	0.0221	0.036*
C11	0.8476 (3)	0.15219 (9)	0.08319 (7)	0.0274 (4)
H11	0.7545	0.1249	0.0650	0.033*
C12	1.3301 (3)	0.24014 (13)	0.05544 (8)	0.0447 (5)
H12A	1.3175	0.2311	0.0179	0.067*
H12C	1.4439	0.2155	0.0691	0.067*
H12B	1.3459	0.2901	0.0613	0.067*
C13	0.4907 (3)	0.18590 (9)	0.37432 (7)	0.0269 (4)
C14	0.6260 (3)	0.16301 (9)	0.41548 (7)	0.0257 (4)
C15	0.7930 (3)	0.12479 (9)	0.40495 (7)	0.0290 (4)
H15	0.8176	0.1086	0.3705	0.035*
C16	0.9229 (3)	0.11047 (10)	0.44471 (8)	0.0388 (5)
H16	1.0377	0.0849	0.4372	0.047*
C17	0.8877 (4)	0.13302 (11)	0.49569 (8)	0.0430 (5)
C18	0.7170 (4)	0.16865 (12)	0.50588 (8)	0.0443 (5)
H18	0.6886	0.1826	0.5407	0.053*
C19	0.5884 (3)	0.18407 (11)	0.46668 (7)	0.0363 (4)
H19	0.4732	0.2092	0.4744	0.044*
C20	1.0316 (5)	0.11925 (15)	0.53895 (10)	0.0644 (8)
H20C	1.0048	0.0738	0.5546	0.097*
H20B	1.0199	0.1554	0.5657	0.097*
H20A	1.1637	0.1196	0.5246	0.097*
C21	0.6365 (3)	0.36911 (9)	0.15866 (8)	0.0343 (4)
H21D	0.4957	0.3644	0.1658	0.041*
H21E	0.6913	0.3218	0.1553	0.041*
C22	0.6627 (4)	0.40659 (9)	0.10768 (8)	0.0358 (5)
C23	0.5155 (5)	0.44949 (11)	0.08932 (10)	0.0578 (7)
H23	0.4028	0.4565	0.1101	0.069*
C24	0.5300 (8)	0.48183 (14)	0.04171 (12)	0.0810 (12)
H24	0.4287	0.5114	0.0299	0.097*
C25	0.6880 (8)	0.47153 (16)	0.01180 (12)	0.0855 (13)
H25	0.6954	0.4929	−0.0216	0.103*
C26	0.8398 (6)	0.4304 (2)	0.02885 (12)	0.0846 (12)
H26	0.9522	0.4246	0.0077	0.102*
C27	0.8269 (5)	0.39682 (15)	0.07807 (10)	0.0578 (7)
H27	0.9296	0.3682	0.0903	0.069*
C31	0.9356 (3)	0.28543 (8)	0.35819 (7)	0.0275 (4)
H31E	1.0503	0.2687	0.3779	0.033*
H31D	0.8177	0.2728	0.3783	0.033*
C32	0.9460 (3)	0.36328 (8)	0.35255 (6)	0.0244 (3)
C33	1.1244 (3)	0.39668 (11)	0.35171 (9)	0.0385 (5)
H33	1.2412	0.3707	0.3546	0.046*
C34	1.1310 (4)	0.46842 (13)	0.34660 (10)	0.0531 (7)
H34	1.2529	0.4916	0.3462	0.064*
C35	0.9626 (5)	0.50598 (10)	0.34212 (9)	0.0534 (7)
H35	0.9687	0.5550	0.3384	0.064*
C36	0.7850 (4)	0.47338 (10)	0.34293 (8)	0.0408 (5)
H36	0.6687	0.4997	0.3401	0.049*
C37	0.7766 (3)	0.40159 (9)	0.34785 (7)	0.0278 (4)
H37	0.6542	0.3787	0.3480	0.033*
H21A	0.8687 (15)	0.4048 (13)	0.2000 (9)	0.041 (6)*
H31A	1.031 (3)	0.2643 (12)	0.2826 (7)	0.039 (6)*
H41A	0.201 (4)	0.3767 (10)	0.2261 (9)	0.054 (7)*
H21B	0.691 (3)	0.3812 (10)	0.2352 (6)	0.030 (5)*
H31B	0.942 (4)	0.2020 (5)	0.3098 (9)	0.043 (6)*
H41B	0.211 (5)	0.4508 (12)	0.2210 (12)	0.079 (10)*
H51B	0.877 (3)	0.0874 (12)	0.2666 (9)	0.049 (7)*
H21C	0.695 (4)	0.4519 (6)	0.2091 (9)	0.043 (6)*
H31C	0.809 (2)	0.2630 (11)	0.2897 (8)	0.030 (5)*
H51A	1.091 (3)	0.0805 (11)	0.2825 (10)	0.052 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0205 (6)	0.0160 (5)	0.0368 (6)	−0.0019 (5)	0.0028 (5)	0.0024 (5)
O2	0.0200 (6)	0.0175 (5)	0.0384 (7)	0.0032 (5)	0.0007 (5)	−0.0010 (5)
O3	0.0188 (6)	0.0181 (5)	0.0320 (6)	0.0009 (5)	−0.0034 (5)	0.0019 (5)
O4	0.0206 (6)	0.0163 (5)	0.0385 (6)	−0.0018 (5)	−0.0011 (5)	0.0020 (5)
O5	0.0190 (6)	0.0191 (5)	0.0234 (5)	−0.0023 (4)	0.0028 (5)	−0.0013 (4)
O6	0.0287 (7)	0.0297 (6)	0.0300 (6)	−0.0062 (6)	0.0001 (5)	−0.0045 (5)
O7	0.0172 (5)	0.0189 (5)	0.0223 (5)	0.0007 (5)	−0.0002 (5)	0.0004 (4)
O8	0.0374 (9)	0.0924 (13)	0.0326 (7)	0.0332 (10)	−0.0003 (7)	−0.0118 (8)
O41	0.0301 (7)	0.0214 (6)	0.0406 (7)	0.0019 (5)	−0.0048 (6)	0.0022 (5)
O51	0.0186 (6)	0.0218 (6)	0.0465 (7)	0.0011 (5)	−0.0016 (6)	−0.0076 (5)
N21	0.0298 (8)	0.0163 (6)	0.0338 (8)	0.0031 (6)	0.0044 (7)	0.0007 (6)
N31	0.0167 (6)	0.0184 (6)	0.0388 (8)	0.0001 (6)	0.0006 (6)	−0.0014 (6)
C1	0.0201 (8)	0.0151 (6)	0.0237 (7)	−0.0007 (6)	−0.0024 (6)	−0.0025 (6)
C2	0.0158 (7)	0.0164 (6)	0.0240 (7)	−0.0011 (6)	−0.0001 (6)	−0.0004 (6)
C3	0.0148 (7)	0.0163 (7)	0.0233 (7)	0.0001 (6)	−0.0013 (6)	0.0006 (6)
C4	0.0175 (7)	0.0155 (7)	0.0224 (7)	0.0007 (6)	0.0018 (6)	−0.0020 (6)
C5	0.0237 (8)	0.0159 (6)	0.0248 (7)	0.0024 (7)	0.0000 (7)	−0.0005 (6)
C6	0.0233 (8)	0.0182 (7)	0.0247 (8)	0.0042 (7)	0.0023 (7)	0.0011 (6)
C7	0.0277 (9)	0.0247 (8)	0.0245 (8)	−0.0011 (7)	0.0032 (7)	0.0005 (6)
C8	0.0278 (9)	0.0306 (8)	0.0311 (9)	−0.0050 (8)	0.0020 (7)	0.0009 (7)
C9	0.0267 (9)	0.0316 (9)	0.0300 (9)	0.0038 (8)	0.0050 (8)	0.0096 (7)
C10	0.0324 (10)	0.0363 (9)	0.0216 (8)	0.0074 (8)	0.0031 (7)	0.0037 (7)
C11	0.0281 (9)	0.0301 (8)	0.0241 (8)	0.0019 (8)	−0.0009 (7)	−0.0014 (7)
C12	0.0374 (11)	0.0604 (13)	0.0362 (10)	−0.0079 (11)	0.0107 (10)	0.0103 (10)
C13	0.0263 (9)	0.0292 (8)	0.0253 (8)	0.0026 (7)	0.0025 (7)	−0.0019 (7)
C14	0.0272 (9)	0.0249 (8)	0.0250 (8)	−0.0006 (7)	0.0000 (7)	0.0027 (6)
C15	0.0347 (10)	0.0267 (8)	0.0256 (8)	0.0047 (8)	−0.0014 (8)	0.0021 (7)
C16	0.0429 (11)	0.0368 (10)	0.0366 (10)	0.0117 (10)	−0.0065 (10)	0.0013 (8)
C17	0.0553 (14)	0.0408 (10)	0.0329 (10)	0.0075 (11)	−0.0150 (10)	−0.0003 (8)
C18	0.0579 (14)	0.0494 (12)	0.0256 (9)	0.0107 (12)	−0.0035 (10)	−0.0036 (9)
C19	0.0400 (11)	0.0410 (10)	0.0278 (9)	0.0056 (9)	0.0022 (8)	−0.0006 (8)
C20	0.078 (2)	0.0713 (17)	0.0435 (12)	0.0238 (17)	−0.0290 (14)	−0.0080 (12)
C21	0.0395 (11)	0.0227 (8)	0.0408 (10)	−0.0046 (8)	0.0030 (9)	−0.0025 (7)
C22	0.0484 (12)	0.0221 (8)	0.0367 (10)	−0.0063 (9)	0.0015 (9)	−0.0061 (7)
C23	0.086 (2)	0.0360 (11)	0.0519 (13)	0.0122 (13)	−0.0125 (14)	−0.0040 (10)
C24	0.147 (4)	0.0446 (13)	0.0520 (15)	0.005 (2)	−0.024 (2)	0.0001 (12)
C25	0.162 (4)	0.0501 (15)	0.0443 (15)	−0.038 (2)	−0.018 (2)	0.0026 (12)
C26	0.104 (3)	0.094 (2)	0.0558 (16)	−0.048 (2)	0.0332 (19)	−0.0228 (17)
C27	0.0596 (16)	0.0585 (14)	0.0551 (14)	−0.0141 (14)	0.0160 (13)	−0.0103 (12)
C31	0.0266 (8)	0.0223 (7)	0.0336 (9)	0.0012 (7)	0.0004 (8)	0.0015 (7)
C32	0.0258 (9)	0.0212 (7)	0.0262 (8)	−0.0020 (7)	0.0029 (7)	−0.0014 (6)
C33	0.0331 (10)	0.0378 (10)	0.0444 (11)	−0.0105 (9)	0.0048 (9)	−0.0035 (9)
C34	0.0651 (17)	0.0436 (12)	0.0506 (13)	−0.0343 (13)	0.0000 (12)	0.0039 (11)
C35	0.094 (2)	0.0211 (9)	0.0453 (11)	−0.0136 (12)	−0.0155 (14)	0.0052 (8)
C36	0.0649 (15)	0.0232 (9)	0.0344 (10)	0.0109 (10)	−0.0106 (10)	−0.0038 (8)
C37	0.0311 (9)	0.0240 (8)	0.0283 (9)	0.0022 (7)	0.0020 (8)	−0.0030 (7)

Geometric parameters (Å, º)

O1—C1	1.259 (2)	C14—C15	1.391 (3)
O2—C1	1.237 (2)	C14—C19	1.394 (2)
O3—C4	1.253 (2)	C15—C16	1.381 (3)
O4—C4	1.249 (2)	C15—H15	0.9500
O5—C2	1.438 (2)	C16—C17	1.394 (3)
O7—C3	1.446 (2)	C16—H16	0.9500
C1—C2	1.545 (2)	C17—C18	1.385 (3)
C2—C3	1.516 (2)	C17—C20	1.508 (3)
C3—C4	1.545 (2)	C18—C19	1.369 (3)
O5—C5	1.350 (2)	C18—H18	0.9500
O6—C5	1.206 (2)	C19—H19	0.9500
O7—C13	1.349 (2)	C20—H20C	0.9800
O8—C13	1.205 (2)	C20—H20B	0.9800
O41—H41A	0.939 (10)	C20—H20A	0.9800
O41—H41B	0.94 (3)	C21—C22	1.500 (3)
O51—H51B	0.937 (10)	C21—H21D	0.9900
O51—H51A	0.937 (10)	C21—H21E	0.9900
N21—C21	1.490 (2)	C22—C27	1.373 (4)
N21—H21A	0.959 (10)	C22—C23	1.389 (4)
N21—H21B	0.951 (10)	C23—C24	1.371 (4)
N21—H21C	0.956 (10)	C23—H23	0.9500
N31—C31	1.496 (2)	C24—C25	1.343 (6)
N31—H31A	0.949 (10)	C24—H24	0.9500
N31—H31B	0.952 (10)	C25—C26	1.382 (6)
N31—H31C	0.955 (10)	C25—H25	0.9500
C2—H2	1.0000	C26—C27	1.417 (4)
C3—H3	1.0000	C26—H26	0.9500
C5—C6	1.482 (2)	C27—H27	0.9500
C6—C7	1.388 (2)	C31—C32	1.508 (2)
C6—C11	1.397 (2)	C31—H31E	0.9900
C7—C8	1.385 (3)	C31—H31D	0.9900
C7—H7	0.9500	C32—C37	1.385 (3)
C8—C9	1.391 (3)	C32—C33	1.385 (3)
C8—H8	0.9500	C33—C34	1.389 (3)
C9—C10	1.388 (3)	C33—H33	0.9500
C9—C12	1.505 (3)	C34—C35	1.371 (4)
C10—C11	1.379 (3)	C34—H34	0.9500
C10—H10	0.9500	C35—C36	1.374 (4)
C11—H11	0.9500	C35—H35	0.9500
C12—H12A	0.9800	C36—C37	1.390 (3)
C12—H12C	0.9800	C36—H36	0.9500
C12—H12B	0.9800	C37—H37	0.9500
C13—C14	1.472 (3)
C5—O5—C2	115.08 (12)	C16—C15—H15	120.1
C13—O7—C3	114.37 (13)	C14—C15—H15	120.1
H41A—O41—H41B	100 (2)	C15—C16—C17	120.8 (2)
H51B—O51—H51A	110 (2)	C15—C16—H16	119.6
C21—N21—H21A	110.4 (15)	C17—C16—H16	119.6
C21—N21—H21B	108.4 (13)	C18—C17—C16	118.51 (19)
H21A—N21—H21B	112 (2)	C18—C17—C20	120.4 (2)
C21—N21—H21C	115.6 (15)	C16—C17—C20	121.1 (2)
H21A—N21—H21C	105 (2)	C19—C18—C17	121.18 (19)
H21B—N21—H21C	105 (2)	C19—C18—H18	119.4
C31—N31—H31A	114.7 (14)	C17—C18—H18	119.4
C31—N31—H31B	109.9 (14)	C18—C19—C14	120.2 (2)
H31A—N31—H31B	106 (2)	C18—C19—H19	119.9
C31—N31—H31C	107.5 (13)	C14—C19—H19	119.9
H31A—N31—H31C	107.7 (17)	C17—C20—H20C	109.5
H31B—N31—H31C	111 (2)	C17—C20—H20B	109.5
O2—C1—O1	127.56 (14)	H20C—C20—H20B	109.5
O2—C1—C2	119.40 (14)	C17—C20—H20A	109.5
O1—C1—C2	113.04 (14)	H20C—C20—H20A	109.5
O5—C2—C3	108.66 (12)	H20B—C20—H20A	109.5
O5—C2—C1	112.25 (13)	N21—C21—C22	113.89 (15)
C3—C2—C1	109.66 (12)	N21—C21—H21D	108.8
O5—C2—H2	108.7	C22—C21—H21D	108.8
C3—C2—H2	108.7	N21—C21—H21E	108.8
C1—C2—H2	108.7	C22—C21—H21E	108.8
O7—C3—C2	107.49 (12)	H21D—C21—H21E	107.7
O7—C3—C4	112.29 (12)	C27—C22—C23	119.7 (2)
C2—C3—C4	111.86 (12)	C27—C22—C21	120.8 (2)
O7—C3—H3	108.4	C23—C22—C21	119.5 (2)
C2—C3—H3	108.4	C24—C23—C22	121.1 (3)
C4—C3—H3	108.4	C24—C23—H23	119.4
O4—C4—O3	126.61 (13)	C22—C23—H23	119.4
O4—C4—C3	118.82 (14)	C25—C24—C23	119.8 (4)
O3—C4—C3	114.56 (13)	C25—C24—H24	120.1
O6—C5—O5	123.22 (16)	C23—C24—H24	120.1
O6—C5—C6	124.45 (15)	C24—C25—C26	121.1 (3)
O5—C5—C6	112.33 (14)	C24—C25—H25	119.4
C7—C6—C11	119.25 (16)	C26—C25—H25	119.4
C7—C6—C5	122.69 (15)	C25—C26—C27	119.6 (3)
C11—C6—C5	118.04 (16)	C25—C26—H26	120.2
C8—C7—C6	120.10 (16)	C27—C26—H26	120.2
C8—C7—H7	119.9	C22—C27—C26	118.6 (3)
C6—C7—H7	119.9	C22—C27—H27	120.7
C7—C8—C9	120.96 (18)	C26—C27—H27	120.7
C7—C8—H8	119.5	N31—C31—C32	110.89 (14)
C9—C8—H8	119.5	N31—C31—H31E	109.5
C10—C9—C8	118.49 (17)	C32—C31—H31E	109.5
C10—C9—C12	121.16 (17)	N31—C31—H31D	109.5
C8—C9—C12	120.34 (18)	C32—C31—H31D	109.5
C11—C10—C9	121.18 (16)	H31E—C31—H31D	108.0
C11—C10—H10	119.4	C37—C32—C33	119.79 (15)
C9—C10—H10	119.4	C37—C32—C31	119.85 (17)
C10—C11—C6	120.01 (17)	C33—C32—C31	120.36 (18)
C10—C11—H11	120.0	C32—C33—C34	119.5 (2)
C6—C11—H11	120.0	C32—C33—H33	120.2
C9—C12—H12A	109.5	C34—C33—H33	120.2
C9—C12—H12C	109.5	C35—C34—C33	120.3 (2)
H12A—C12—H12C	109.5	C35—C34—H34	119.8
C9—C12—H12B	109.5	C33—C34—H34	119.8
H12A—C12—H12B	109.5	C34—C35—C36	120.61 (17)
H12C—C12—H12B	109.5	C34—C35—H35	119.7
O8—C13—O7	121.95 (17)	C36—C35—H35	119.7
O8—C13—C14	124.61 (17)	C35—C36—C37	119.6 (2)
O7—C13—C14	113.33 (15)	C35—C36—H36	120.2
C15—C14—C19	119.28 (17)	C37—C36—H36	120.2
C15—C14—C13	122.87 (16)	C32—C37—C36	120.2 (2)
C19—C14—C13	117.77 (17)	C32—C37—H37	119.9
C16—C15—C14	119.86 (17)	C36—C37—H37	119.9
C5—O5—C2—C3	−156.6 (1)	O8—C13—C14—C15	177.1 (2)
C5—O5—C2—C1	81.94 (15)	O7—C13—C14—C15	−6.6 (2)
O2—C1—C2—O5	5.00 (19)	O8—C13—C14—C19	−6.3 (3)
O1—C1—C2—O5	−175.61 (13)	O7—C13—C14—C19	169.93 (16)
O2—C1—C2—C3	−115.88 (16)	C19—C14—C15—C16	−2.5 (3)
O1—C1—C2—C3	63.51 (17)	C13—C14—C15—C16	174.04 (19)
C13—O7—C3—C2	−151.0 (1)	C14—C15—C16—C17	0.9 (3)
C13—O7—C3—C4	85.53 (16)	C15—C16—C17—C18	1.6 (3)
O5—C2—C3—O7	−76.5 (1)	C15—C16—C17—C20	−178.3 (2)
C1—C2—C3—O7	46.49 (16)	C16—C17—C18—C19	−2.6 (3)
O5—C2—C3—C4	47.17 (17)	C20—C17—C18—C19	177.3 (2)
C1—C2—C3—C4	170.19 (13)	C17—C18—C19—C14	1.0 (3)
O7—C3—C4—O4	28.5 (2)	C15—C14—C19—C18	1.5 (3)
C2—C3—C4—O4	−92.48 (17)	C13—C14—C19—C18	−175.2 (2)
O7—C3—C4—O3	−152.91 (13)	N21—C21—C22—C27	84.8 (2)
C2—C3—C4—O3	86.13 (17)	N21—C21—C22—C23	−97.8 (2)
C2—O5—C5—O6	1.2 (2)	C27—C22—C23—C24	0.7 (4)
C2—O5—C5—C6	−179.4 (1)	C21—C22—C23—C24	−176.7 (2)
O6—C5—C6—C7	−177.72 (16)	C22—C23—C24—C25	0.7 (4)
O5—C5—C6—C7	2.9 (2)	C23—C24—C25—C26	−2.0 (5)
O6—C5—C6—C11	0.4 (2)	C24—C25—C26—C27	1.8 (5)
O5—C5—C6—C11	−178.94 (14)	C23—C22—C27—C26	−0.9 (3)
C11—C6—C7—C8	1.0 (2)	C21—C22—C27—C26	176.5 (2)
C5—C6—C7—C8	179.11 (16)	C25—C26—C27—C22	−0.3 (4)
C6—C7—C8—C9	−0.4 (3)	N31—C31—C32—C37	87.1 (2)
C7—C8—C9—C10	−0.5 (3)	N31—C31—C32—C33	−92.5 (2)
C7—C8—C9—C12	−179.74 (18)	C37—C32—C33—C34	0.5 (3)
C8—C9—C10—C11	0.9 (3)	C31—C32—C33—C34	−179.86 (19)
C12—C9—C10—C11	−179.87 (18)	C32—C33—C34—C35	−0.3 (4)
C9—C10—C11—C6	−0.4 (3)	C33—C34—C35—C36	0.4 (4)
C7—C6—C11—C10	−0.6 (3)	C34—C35—C36—C37	−0.6 (3)
C5—C6—C11—C10	−178.81 (15)	C33—C32—C37—C36	−0.8 (3)
C3—O7—C13—O8	−10.3 (2)	C31—C32—C37—C36	179.64 (17)
C3—O7—C13—C14	173.4 (1)	C35—C36—C37—C32	0.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21A···O41^i	0.96 (1)	1.93 (1)	2.875 (2)	169 (2)
N21—H21B···O4	0.95 (1)	2.02 (1)	2.888 (2)	150 (2)
N21—H21C···O1^ii	0.96 (1)	1.72 (1)	2.673 (2)	172 (2)
N31—H31A···O3^i	0.95 (1)	1.87 (1)	2.803 (2)	168 (2)
N31—H31B···O51	0.95 (1)	1.93 (1)	2.807 (2)	153 (2)
N31—H31C···O4	0.96 (1)	1.79 (1)	2.729 (2)	168 (2)
O41—H41A···O3	0.94 (1)	1.88 (1)	2.785 (2)	160 (2)
O41—H41B···O2^ii	0.94 (3)	2.00 (3)	2.931 (2)	173 (3)
O51—H51A···O1^i	0.94 (1)	1.86 (1)	2.783 (2)	168 (2)
O51—H51B···O2	0.94 (1)	1.90 (1)	2.804 (2)	162 (2)

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