Bis(L-glutamic acid) sulfate hemihydrate

The unit cell of the crystal structure of the title compound, 2C₅H₁₀NO₄·SO₄·0.5H₂O, contains eight crystallographically independent glutamic acid residues protonated at the N atom, four sulfate anions and two water mol­ecules. The glutamic acid residues are in different conformations. Both the α- and γ-carboxyl groups are involved in strong O—H...O hydrogen bonding; at the same time each residue shows a different hydrogen-bonding scheme. Owing to the differences in con­formational features and hydrogen-bonding patterns of each residue, there is no pseudosymmetry or higher symmetry in the structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.033
• wR factor = 0.087
• Data-to-parameter ratio = 6.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_213  Alert C Atom C214    has ADP max/min Ratio ...........       3.20 prolate

PLAT_213  Alert C Atom O81C    has ADP max/min Ratio ...........       3.70 prolate

General Notes



ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      1.132
          Tmax scaled      0.878 Tmin scaled      0.826

REFLT_03
         From the CIF: _diffrn_reflns_theta_max           25.00
         From the CIF: _reflns_number_total               6238
         Count of symmetry unique reflns         5961
         Completeness (_total/calc)            104.65%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured       277
         Fraction of Friedel pairs measured     0.046
         Are heavy atom types Z>Si present          yes
          WARNING: Large fraction of Friedel related reflns may
                   be needed to determine absolute structure


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

---

S1. Comment

Glutamic acid is a dicarboxylic amino acid which is a significant constituent in protein. It also plays an important role in metabolism process of sugar and fats. The crystal structures of L-glutamic acid (Hirokawa, 1955), L-glutamic acid hydrochloride (Sequeira et al., 1972), DL-glutamic acid monohydrate (Ciunik & Glowiak, 1983) and anhydrous DL-glutamic acid (Dunitz & Schweizer, 1995) have been reported. In order to determine the hydrogen-bonding pattern and conformation of protonated glutamic acid cation in the crystal of its sulfate, the X-ray diffraction study of the title compound, (I), was undertaken.

The unit cell contains eight crystallographically independent protonated glutamic acid residues, four independent sulfate anions and two water molecules (Fig. 1). An attempt to look for higher symmetry using the LEPAGE program (Spek, 1999) resulted in a C-centred monoclinic cell with a transformation (100/102/010). However, the intensity data did not conform to a monoclinic system (R_int = 0.58).

The average bond lengths and angles of sulfate anions confirm its nearly ideal tetrahedral symmetry. The geometries of the glutamic acid residues agree well with L-glutamic acid hydrochloride (Sequeira et al., 1972). In the present study, the doubly bonded O atoms of α- and γ-carboxyl groups are labelled as A and C and the single bonded O atoms are labelled as B and D, respectively.

The backbone conformation angle ψ¹ indicates the cis form for all eight residues. The branched side-chain conformation angle χ¹ is in the sterically least-favoured closed gauche I conformation and χ² is in the trans form for all the residues as found in DL-glutamic acid hydrochloride (Sequeria et al., 1972) except for residues II and III. In the case of residues II and III, the conformation angle χ¹ is in trans form for the former [-172.2 (6)°] and sterically most favoured open gauche II conformation for the latter [-64.6 (4)°].

The conformation angles χ³¹ and χ³² indicate the cis and trans form for all residues except for residue II where the conformation is in trans and cis form [-179.0 (7) and -2(1)°].

All the O atoms of sulfate anions are involved in hydrogen bonding with amino and γ-carboxyl group or water molecules. It plays a vital role in stabilizing the structure (Fig. 2).

All the α-carboxyl O atoms (B) form strong O—H···O hydrogen bonds with γ-carboxyl O atoms (C) with the exception of residues II and V, which form a strong O—H···O hydrogen bond with water molecules. These amino acids are interconnected by the hydrogen bonding as corrugated sheets as found in DL-lysine complexes (Saraswathi et al., 2001).

The γ-carboxyl O atoms (D) form strong O—H···O hydrogen bonds with sulfate anions in a three-dimensional hydrogen-bonding network. Interestingly, in the case of residue VIII, it forms a chelated O—H···O hydrogen bond with the sulfate anion.

There are three types of N—H···O hydrogen bonding in the crystal of the title compoud, viz. two-centered, three-centered and chelated three-centered hydrogen bonding. Two-centered N–H···O hydrogen bonding is observed in the case of amino N atom with (i) the α- and γ-carboxyl O atom (A and C), (ii) the sulfate anions in all residues except residue III It is very interesting to note that among these, residue I and IV are involved only in two-centered N—H···O hydrogen bonds. Three-centered hydrogen bonds are observed in residues II, III, V and VIII involving the amino N and the carboxyl O atoms (A and C). Chelated three-centered hydrogen bondings are engaged in residues III, V, VI and VII involving the amino N atom of the glutamic acid residue and the O atoms of the sulfate anion (Jeffrey & Saenger, 1991). Interestingly, in the case of residue III, only the three-centered and chelated type of hydrogen bonding are observed, while in the case of residue VII, two such chelated three-centered hydrogen bonds are engaged.

In the amino group of residues I and IV, a class-I hydrogen-bonding pattern, involving three two-centred hydrogen bonding (Jeffrey & Saenger, 1991), is present. In the case of residues II, VI and VIII, a class-II hydrogen-bonding pattern, with one three-centred hydrogen bonding and two two-centred hydrogen bonding, is observed, while in the case of residues V and VII, a class-III hydrogen-bonding structure, with two three-centred hydrogen bonding and one two-centred hydrogen bonding, is observed. Interestingly, in the case of residue III, the sterically least favourable class-IV hydrogen-bonding pattern, with only three-centred hydrogen bonding, is observed. In general, the class-II hydrogen-bonding pattern is the most favoured configuration and occurrence of class-IV is rare.

Both water molecules form a O—H···O hydrogen bonding with the sulfate anions and the γ-carboxyl group (C) of the glutamic acid residues.

In the present study, the residues are aggregated as characteristic layers along the diagonal plane. The glutamic acid residues II, IV, VI and VIII, sulfate anions 2 and 3, and the OW1 water molecule are interconnected by hydrogen-bonded ribbons as a linear chain along the diagonal (011) plane (Fig. 3). Similarly, the residues I, III, V and VII, sulfate anions 1 and 4, and the OW2 water molecule are interconnected by hydrogen-bonded (Fig. 4) ribbons running as an infinite chain parallel to the same diagonal plane and lying in between two adjacent ribbons of the first type.

S2. Experimental

The title compound was crystallized by slow evaporation from an aqueous solution of L-glutamic acid and sulfuric acid in a 2:1 stoichiometric ratio.

S3. Refinement

The H atoms attached to water molecules were located and refined in the isotropic approximation (O—H = 0.79–0.94 Å). All other H atoms were placed in geometrically calculated positions and included in the refinement in a riding-model approximation with U_iso equal to 1.2U_eq of the carrier atom.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1999); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The asymmetric unit of the title compound with the atom-numbering scheme and 50% probability displacement ellipsoids (Johnson, 1976).
	Fig. 2. Packing diagram of the crystal viewed down the a axis.
	Fig. 3. Packing diagram of the crystal viewed down the b axis (for the sake of clarity only glutamic acid residues II, IV, VI and VIII, sulfate anions 2 and 3, and the first water molecule are shown).
	Fig. 4. Packing diagram of the crystal viewed down the c axis (for the sake of clarity only glutamic acid residues I, III, V and VII, sulfate anions 1 and 4, and the second water molecule are shown).

Bis(L-glutamic acid) sulfate hemihydrate

Crystal data

2C5H10NO4^+·SO4^2^−·0.5H2O	Z = 4
Mr = 401.35	F(000) = 844
Triclinic, P1	Dx = 1.574 Mg m^−3 Dm = 1.568 Mg m^−3 Dm measured by flotation in carbon tetrachloride and xylene
a = 12.536 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.596 (2) Å	Cell parameters from 25 reflections
c = 13.306 (2) Å	θ = 11.3–13.6°
α = 79.09 (1)°	µ = 0.26 mm^−1
β = 62.05 (1)°	T = 293 K
γ = 65.88 (1)°	Needle, colorless
V = 1693.9 (5) Å^3	0.6 × 0.6 × 0.5 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	5814 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 25.0°, θmin = 1.7°
ω–2θ scans	h = 0→14
Absorption correction: ψ scan (North et al., 1968)	k = −13→14
Tmin = 0.730, Tmax = 0.776	l = −13→15
6238 measured reflections	3 standard reflections every 60 min
6238 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.033	w = 1/[σ^2(Fo^2) + (0.055P)^2 + 0.7347P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.087	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.42 e Å^−3
6238 reflections	Δρmin = −0.32 e Å^−3
936 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
3 restraints	Extinction coefficient: 0.0219 (11)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack, (1983); 298 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.06 (6)

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
S1	0.89414 (8)	0.83198 (7)	0.55962 (7)	0.0280 (2)
O11	0.9579 (3)	0.8278 (5)	0.6275 (3)	0.0851 (15)
O12	0.9784 (3)	0.8449 (3)	0.4415 (2)	0.0557 (8)
O13	0.8625 (4)	0.7303 (3)	0.5734 (4)	0.0833 (14)
O14	0.7679 (3)	0.9309 (3)	0.6012 (2)	0.0473 (7)
S2	0.39345 (9)	0.07025 (7)	0.82172 (8)	0.0292 (2)
O21	0.4676 (3)	0.0820 (3)	0.7006 (2)	0.0468 (7)
O22	0.4032 (4)	−0.0497 (3)	0.8480 (4)	0.0870 (16)
O23	0.4436 (3)	0.1050 (4)	0.8846 (3)	0.0763 (13)
O24	0.2566 (3)	0.1465 (2)	0.8577 (2)	0.0384 (6)
S3	0.35802 (8)	0.55049 (7)	0.35519 (7)	0.02470 (19)
O31	0.4005 (3)	0.6452 (3)	0.3437 (3)	0.0454 (7)
O32	0.4490 (3)	0.4403 (2)	0.3754 (2)	0.0395 (6)
O33	0.3487 (3)	0.5374 (2)	0.2528 (2)	0.0406 (7)
O34	0.2267 (3)	0.5790 (3)	0.4510 (2)	0.0427 (7)
S4	0.86182 (8)	0.30737 (8)	0.07589 (7)	0.0279 (2)
O41	0.9563 (3)	0.2206 (3)	0.1131 (3)	0.0555 (8)
O42	0.9182 (3)	0.3919 (3)	0.0036 (3)	0.0478 (7)
O43	0.7382 (3)	0.3642 (3)	0.1714 (3)	0.0497 (8)
O44	0.8350 (3)	0.2476 (3)	0.0105 (3)	0.0529 (8)
O11A	0.0725 (3)	0.4852 (3)	0.1525 (3)	0.0494 (7)
O11B	0.2397 (3)	0.5417 (3)	0.0450 (3)	0.0558 (9)
H1B	0.2002	0.5925	0.0937	0.084*
C111	0.1746 (4)	0.4748 (3)	0.0693 (3)	0.0345 (8)
C112	0.2422 (4)	0.3794 (3)	−0.0173 (3)	0.0316 (8)
H112	0.3250	0.3317	−0.0143	0.038*
N111	0.1664 (3)	0.3038 (3)	0.0194 (3)	0.0327 (7)
H11A	0.1938	0.2584	−0.0383	0.049*
H11B	0.0826	0.3476	0.0414	0.049*
H11C	0.1771	0.2598	0.0772	0.049*
C113	0.2755 (4)	0.4177 (4)	−0.1405 (3)	0.0381 (9)
H11D	0.3288	0.4638	−0.1616	0.046*
H11E	0.3267	0.3492	−0.1888	0.046*
C114	0.1597 (5)	0.4871 (5)	−0.1625 (4)	0.0590 (13)
H11F	0.1044	0.5526	−0.1103	0.071*
H11G	0.1102	0.4391	−0.1487	0.071*
C115	0.1988 (4)	0.5317 (4)	−0.2841 (4)	0.0398 (9)
O11C	0.2575 (3)	0.5963 (3)	−0.3217 (3)	0.0448 (7)
O11D	0.1605 (3)	0.4979 (3)	−0.3441 (3)	0.0544 (8)
H1H	0.1854	0.5251	−0.4084	0.082*
O21A	−0.1021 (3)	−0.0092 (3)	0.8785 (3)	0.0467 (7)
O21B	0.0550 (4)	−0.1851 (3)	0.8477 (3)	0.0607 (9)
H2B	0.0047	−0.2041	0.8388	0.091*
C211	0.0047 (4)	−0.0744 (3)	0.8680 (3)	0.0325 (8)
C212	0.0941 (4)	−0.0340 (3)	0.8853 (3)	0.0302 (8)
H21A	0.1850	−0.0800	0.8372	0.036*
N222	0.0663 (3)	0.0902 (3)	0.8553 (3)	0.0301 (7)
H22A	0.1185	0.1141	0.8653	0.045*
H22B	−0.0160	0.1317	0.8997	0.045*
H22C	0.0799	0.0999	0.7829	0.045*
C213	0.0695 (5)	−0.0457 (4)	1.0112 (3)	0.0453 (10)
H21B	0.1163	−0.0076	1.0227	0.054*
H21C	−0.0224	−0.0071	1.0590	0.054*
C214	0.1115 (10)	−0.1680 (5)	1.0450 (5)	0.118 (4)
H21D	0.2057	−0.2008	1.0072	0.142*
H21E	0.0806	−0.2086	1.0158	0.142*
C215	0.0692 (6)	−0.1950 (4)	1.1706 (4)	0.0544 (13)
O21C	0.1025 (4)	−0.2908 (3)	1.1994 (3)	0.0542 (8)
O21D	−0.0002 (5)	−0.1038 (3)	1.2394 (3)	0.0836 (15)
H2F	−0.0188	−0.1259	1.3055	0.125*
O31A	0.3345 (3)	0.2939 (3)	0.1785 (3)	0.0475 (7)
O31B	0.4258 (3)	0.1011 (3)	0.1653 (3)	0.0548 (9)
H3B	0.3589	0.1073	0.1637	0.082*
C311	0.4226 (4)	0.2048 (3)	0.1729 (3)	0.0315 (8)
C312	0.5440 (3)	0.1986 (3)	0.1766 (3)	0.0259 (7)
H31A	0.6203	0.1458	0.1166	0.031*
N333	0.5484 (3)	0.3168 (3)	0.1538 (3)	0.0285 (6)
H33A	0.6131	0.3177	0.1644	0.043*
H33B	0.4735	0.3674	0.2011	0.043*
H33C	0.5612	0.3365	0.0824	0.043*
C313	0.5421 (4)	0.1518 (4)	0.2918 (3)	0.0340 (8)
H31B	0.4682	0.2058	0.3507	0.041*
H31C	0.5296	0.0783	0.3056	0.041*
C314	0.6635 (5)	0.1333 (4)	0.3017 (4)	0.0431 (10)
H31D	0.7388	0.1006	0.2311	0.052*
H31E	0.6617	0.2077	0.3138	0.052*
C315	0.6756 (4)	0.0529 (3)	0.3985 (3)	0.0355 (9)
O31C	0.6642 (4)	−0.0410 (3)	0.4133 (3)	0.0578 (9)
O31D	0.6979 (3)	0.0923 (2)	0.4660 (2)	0.0477 (8)
H3F	0.7032	0.0449	0.5166	0.072*
O41A	0.6074 (3)	0.2339 (3)	0.9270 (2)	0.0437 (7)
O41B	0.7360 (4)	0.3273 (3)	0.8054 (2)	0.0531 (8)
H4B	0.6961	0.3743	0.8577	0.080*
C411	0.6931 (4)	0.2412 (3)	0.8368 (3)	0.0318 (8)
C412	0.7642 (3)	0.1516 (3)	0.7427 (3)	0.0282 (8)
H41A	0.8559	0.1175	0.7278	0.034*
N444	0.7108 (3)	0.0570 (3)	0.7842 (3)	0.0306 (7)
H44A	0.7364	0.0137	0.7255	0.046*
H44B	0.6244	0.0882	0.8183	0.046*
H44C	0.7398	0.0126	0.8334	0.046*
C413	0.7568 (3)	0.2072 (3)	0.6321 (3)	0.0285 (7)
H41B	0.8042	0.2593	0.6035	0.034*
H41C	0.7987	0.1467	0.5757	0.034*
C414	0.6186 (4)	0.2747 (3)	0.6473 (3)	0.0309 (8)
H41D	0.5728	0.2214	0.6732	0.037*
H41E	0.5760	0.3323	0.7066	0.037*
C415	0.6060 (4)	0.3351 (3)	0.5430 (3)	0.0282 (7)
O41C	0.6914 (3)	0.3585 (2)	0.4601 (2)	0.0370 (6)
O41D	0.4898 (3)	0.3614 (2)	0.5526 (2)	0.0404 (7)
H4F	0.4850	0.3944	0.4947	0.061*
O51A	0.1523 (3)	0.0100 (2)	0.6287 (2)	0.0385 (6)
O51B	0.3267 (3)	0.0384 (3)	0.4872 (3)	0.0544 (9)
H5B	0.3082	0.0900	0.5286	0.082*
C511	0.2441 (4)	−0.0133 (3)	0.5373 (3)	0.0298 (8)
C512	0.2775 (3)	−0.1087 (3)	0.4615 (3)	0.0263 (7)
H51A	0.3713	−0.1530	0.4316	0.032*
N555	0.2099 (3)	−0.1885 (3)	0.5303 (3)	0.0312 (7)
H55A	0.2441	−0.2535	0.4911	0.047*
H55B	0.1259	−0.1544	0.5467	0.047*
H55C	0.2191	−0.2057	0.5945	0.047*
C513	0.2459 (4)	−0.0574 (3)	0.3598 (3)	0.0300 (8)
H51B	0.3133	−0.0296	0.3045	0.036*
H51C	0.2484	−0.1193	0.3240	0.036*
C514	0.1159 (4)	0.0410 (3)	0.3886 (3)	0.0332 (8)
H51D	0.0476	0.0103	0.4330	0.040*
H51E	0.1069	0.0972	0.4356	0.040*
C515	0.0975 (4)	0.1022 (3)	0.2860 (3)	0.0306 (8)
O51C	0.1830 (3)	0.1266 (3)	0.2023 (2)	0.0425 (7)
O51D	−0.0180 (3)	0.1290 (3)	0.2961 (2)	0.0403 (7)
H5F	−0.0229	0.1620	0.2382	0.060*
O61A	0.8369 (3)	0.5348 (2)	0.4112 (2)	0.0395 (6)
O61B	0.9292 (3)	0.3415 (2)	0.4107 (3)	0.0435 (7)
H6B	0.8617	0.3449	0.4124	0.065*
C611	0.9269 (4)	0.4469 (3)	0.4078 (3)	0.0285 (8)
C612	1.0502 (3)	0.4451 (3)	0.4043 (3)	0.0285 (7)
H61A	1.1244	0.4009	0.3371	0.034*
N666	1.0443 (3)	0.5678 (3)	0.3925 (3)	0.0365 (8)
H66A	1.1110	0.5694	0.3992	0.055*
H66B	0.9702	0.6117	0.4467	0.055*
H66C	1.0482	0.5952	0.3246	0.055*
C613	1.0684 (3)	0.3875 (3)	0.5101 (3)	0.0271 (7)
H61B	1.0783	0.3067	0.5122	0.032*
H61C	1.1477	0.3889	0.5047	0.032*
C614	0.9554 (4)	0.4468 (3)	0.6203 (3)	0.0308 (8)
H61D	0.9453	0.5277	0.6175	0.037*
H61E	0.8764	0.4450	0.6253	0.037*
C615	0.9708 (4)	0.3927 (3)	0.7254 (3)	0.0302 (8)
O61C	1.0507 (3)	0.2991 (2)	0.7278 (3)	0.0468 (8)
O61D	0.8856 (3)	0.4590 (2)	0.8149 (2)	0.0387 (6)
H6F	0.8967	0.4272	0.8708	0.058*
O71A	0.3825 (3)	0.7818 (2)	0.6482 (2)	0.0401 (6)
O71B	0.4783 (3)	0.5892 (3)	0.6526 (3)	0.0572 (9)
H7B	0.4131	0.5898	0.6518	0.086*
C711	0.4713 (4)	0.6965 (3)	0.6501 (3)	0.0312 (8)
C712	0.5906 (3)	0.6984 (3)	0.6516 (3)	0.0270 (7)
H71A	0.6666	0.6576	0.5834	0.032*
N777	0.5790 (3)	0.8212 (3)	0.6438 (3)	0.0376 (8)
H77A	0.6510	0.8240	0.6392	0.056*
H77B	0.5111	0.8598	0.7055	0.056*
H77C	0.5680	0.8536	0.5822	0.056*
C713	0.6097 (4)	0.6352 (3)	0.7557 (3)	0.0324 (8)
H71B	0.6373	0.5523	0.7462	0.039*
H71C	0.6787	0.6486	0.7593	0.039*
C714	0.4890 (4)	0.6733 (3)	0.8671 (3)	0.0429 (10)
H71D	0.4715	0.7523	0.8833	0.051*
H71E	0.4162	0.6748	0.8578	0.051*
C715	0.4956 (4)	0.5986 (3)	0.9683 (3)	0.0329 (8)
O71C	0.5668 (3)	0.4991 (2)	0.9635 (2)	0.0443 (7)
O71D	0.4088 (3)	0.6557 (2)	1.0626 (2)	0.0459 (7)
H7F	0.4135	0.6140	1.1170	0.069*
O81A	0.6027 (3)	0.7434 (2)	0.3993 (2)	0.0404 (6)
O81B	0.7564 (4)	0.8013 (3)	0.2601 (3)	0.0618 (10)
H8B	0.7294	0.8519	0.3060	0.093*
C811	0.6904 (4)	0.7324 (3)	0.3057 (3)	0.0333 (8)
C812	0.7377 (4)	0.6371 (3)	0.2228 (3)	0.0292 (7)
H812	0.8308	0.5942	0.2002	0.035*
N888	0.6689 (3)	0.5565 (3)	0.2860 (3)	0.0304 (7)
H88A	0.7017	0.4946	0.2430	0.046*
H88B	0.5847	0.5926	0.3035	0.046*
H88C	0.6789	0.5339	0.3496	0.046*
C813	0.7192 (4)	0.6863 (3)	0.1156 (3)	0.0333 (8)
H81A	0.7374	0.6224	0.0719	0.040*
H81B	0.7823	0.7223	0.0695	0.040*
C814	0.5837 (4)	0.7757 (3)	0.1374 (3)	0.0370 (9)
H81C	0.5218	0.7371	0.1753	0.044*
H81D	0.5612	0.8346	0.1889	0.044*
C815	0.5697 (5)	0.8343 (5)	0.0336 (4)	0.0550 (13)
O81C	0.6571 (4)	0.8227 (7)	−0.0583 (4)	0.163 (4)
O81D	0.4519 (3)	0.8995 (3)	0.0523 (3)	0.0501 (8)
H8E	0.4502	0.9294	−0.0076	0.075*
OW1	0.3168 (4)	0.1925 (3)	0.5882 (3)	0.0419 (7)
H1WA	0.360 (5)	0.158 (4)	0.627 (4)	0.053 (15)*
H1WB	0.250 (6)	0.237 (5)	0.630 (4)	0.049 (16)*
OW2	0.9207 (4)	0.7206 (3)	0.8310 (3)	0.0481 (8)
H2WA	0.923 (6)	0.736 (6)	0.768 (6)	0.08 (2)*
H2WB	0.830 (8)	0.761 (6)	0.868 (6)	0.09 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0270 (5)	0.0313 (5)	0.0249 (4)	−0.0124 (4)	−0.0109 (4)	0.0043 (3)
O11	0.0422 (19)	0.179 (5)	0.0380 (18)	−0.041 (2)	−0.0208 (16)	0.001 (2)
O12	0.059 (2)	0.072 (2)	0.0251 (14)	−0.0240 (18)	−0.0102 (14)	0.0018 (14)
O13	0.059 (2)	0.0401 (19)	0.112 (3)	−0.0244 (18)	−0.001 (2)	−0.002 (2)
O14	0.0498 (18)	0.0435 (16)	0.0388 (16)	0.0011 (14)	−0.0241 (14)	−0.0082 (12)
S2	0.0283 (5)	0.0254 (4)	0.0307 (5)	−0.0069 (4)	−0.0140 (4)	0.0029 (3)
O21	0.0381 (16)	0.0532 (18)	0.0358 (15)	−0.0128 (14)	−0.0115 (13)	0.0058 (13)
O22	0.082 (3)	0.0257 (16)	0.084 (3)	−0.0119 (18)	0.006 (2)	0.0108 (16)
O23	0.0404 (19)	0.123 (3)	0.064 (2)	−0.003 (2)	−0.0311 (18)	−0.038 (2)
O24	0.0289 (14)	0.0405 (15)	0.0461 (16)	−0.0089 (12)	−0.0173 (12)	−0.0071 (12)
S3	0.0245 (4)	0.0271 (4)	0.0226 (4)	−0.0096 (3)	−0.0108 (3)	0.0018 (3)
O31	0.0393 (16)	0.0369 (15)	0.0616 (19)	−0.0185 (13)	−0.0174 (15)	−0.0058 (13)
O32	0.0451 (16)	0.0292 (13)	0.0422 (15)	−0.0039 (12)	−0.0268 (14)	0.0033 (11)
O33	0.0536 (18)	0.0429 (15)	0.0289 (14)	−0.0151 (14)	−0.0246 (13)	0.0046 (11)
O34	0.0305 (14)	0.0636 (19)	0.0287 (14)	−0.0178 (14)	−0.0090 (12)	0.0020 (13)
S4	0.0236 (4)	0.0341 (5)	0.0228 (4)	−0.0099 (4)	−0.0086 (4)	0.0011 (3)
O41	0.054 (2)	0.061 (2)	0.059 (2)	−0.0228 (17)	−0.0369 (17)	0.0208 (16)
O42	0.0436 (17)	0.0622 (19)	0.0422 (16)	−0.0312 (15)	−0.0191 (14)	0.0183 (14)
O43	0.0361 (16)	0.0592 (19)	0.0431 (17)	−0.0219 (14)	0.0027 (13)	−0.0224 (14)
O44	0.0369 (16)	0.065 (2)	0.0551 (19)	−0.0127 (15)	−0.0137 (14)	−0.0281 (16)
O11A	0.0399 (17)	0.0531 (17)	0.0392 (16)	−0.0149 (14)	−0.0037 (14)	−0.0084 (13)
O11B	0.061 (2)	0.0537 (19)	0.0466 (17)	−0.0331 (17)	−0.0036 (16)	−0.0151 (15)
C111	0.034 (2)	0.038 (2)	0.0285 (19)	−0.0107 (17)	−0.0138 (17)	0.0021 (15)
C112	0.0304 (19)	0.045 (2)	0.0225 (17)	−0.0180 (17)	−0.0112 (15)	0.0018 (15)
N111	0.0335 (16)	0.0327 (16)	0.0250 (15)	−0.0114 (13)	−0.0091 (13)	0.0033 (12)
C113	0.042 (2)	0.042 (2)	0.031 (2)	−0.0190 (18)	−0.0136 (18)	0.0001 (16)
C114	0.051 (3)	0.086 (4)	0.046 (3)	−0.037 (3)	−0.026 (2)	0.029 (3)
C115	0.042 (2)	0.053 (2)	0.040 (2)	−0.032 (2)	−0.0243 (19)	0.0186 (19)
O11D	0.070 (2)	0.078 (2)	0.0426 (17)	−0.0568 (19)	−0.0292 (16)	0.0224 (15)
O11C	0.0518 (18)	0.0529 (18)	0.0469 (17)	−0.0335 (15)	−0.0295 (15)	0.0184 (14)
O21A	0.0470 (18)	0.0455 (16)	0.0598 (19)	−0.0174 (14)	−0.0356 (15)	0.0092 (14)
O21B	0.062 (2)	0.0388 (17)	0.100 (3)	−0.0188 (16)	−0.048 (2)	−0.0034 (17)
C211	0.037 (2)	0.0332 (19)	0.0289 (19)	−0.0134 (17)	−0.0178 (17)	0.0076 (15)
C212	0.0315 (19)	0.0305 (18)	0.0289 (18)	−0.0135 (16)	−0.0150 (16)	0.0090 (14)
N222	0.0316 (16)	0.0326 (16)	0.0265 (15)	−0.0134 (13)	−0.0121 (13)	0.0010 (12)
C213	0.055 (3)	0.053 (3)	0.034 (2)	−0.025 (2)	−0.024 (2)	0.0109 (18)
C214	0.196 (9)	0.052 (3)	0.039 (3)	0.011 (4)	−0.049 (4)	0.004 (2)
C215	0.087 (4)	0.057 (3)	0.027 (2)	−0.028 (3)	−0.029 (2)	0.000 (2)
O21C	0.079 (2)	0.0387 (17)	0.0361 (16)	−0.0241 (16)	−0.0167 (16)	0.0016 (13)
O21D	0.164 (5)	0.0371 (18)	0.0453 (19)	−0.027 (2)	−0.056 (3)	0.0137 (15)
O31A	0.0347 (16)	0.0433 (16)	0.064 (2)	−0.0095 (13)	−0.0273 (15)	0.0055 (14)
O31B	0.063 (2)	0.0405 (17)	0.093 (3)	−0.0283 (15)	−0.057 (2)	0.0166 (16)
C311	0.033 (2)	0.0311 (19)	0.0315 (19)	−0.0108 (17)	−0.0188 (16)	0.0095 (15)
C312	0.0284 (18)	0.0257 (17)	0.0245 (17)	−0.0103 (15)	−0.0129 (14)	0.0026 (13)
N333	0.0301 (16)	0.0280 (15)	0.0264 (15)	−0.0134 (13)	−0.0113 (13)	0.0054 (12)
C313	0.040 (2)	0.042 (2)	0.0260 (18)	−0.0232 (18)	−0.0162 (17)	0.0124 (15)
C314	0.058 (3)	0.056 (3)	0.039 (2)	−0.037 (2)	−0.033 (2)	0.0214 (19)
C315	0.049 (2)	0.031 (2)	0.038 (2)	−0.0184 (18)	−0.0276 (19)	0.0074 (16)
O31C	0.108 (3)	0.0401 (17)	0.061 (2)	−0.0380 (19)	−0.061 (2)	0.0140 (15)
O31D	0.082 (2)	0.0365 (15)	0.0491 (17)	−0.0299 (15)	−0.0453 (17)	0.0113 (13)
O41A	0.0578 (18)	0.0497 (16)	0.0244 (13)	−0.0305 (15)	−0.0087 (13)	−0.0022 (11)
O41B	0.075 (2)	0.0622 (19)	0.0323 (15)	−0.0480 (18)	−0.0099 (14)	−0.0054 (13)
C411	0.036 (2)	0.041 (2)	0.0241 (18)	−0.0192 (17)	−0.0141 (17)	0.0020 (15)
C412	0.0257 (18)	0.038 (2)	0.0242 (17)	−0.0127 (16)	−0.0133 (15)	0.0025 (14)
N444	0.0345 (17)	0.0288 (15)	0.0263 (15)	−0.0071 (13)	−0.0157 (13)	0.0007 (12)
C413	0.0299 (19)	0.0326 (18)	0.0230 (17)	−0.0106 (15)	−0.0126 (15)	0.0006 (14)
C414	0.0289 (19)	0.0383 (19)	0.0252 (18)	−0.0134 (16)	−0.0126 (15)	0.0049 (15)
C415	0.0301 (18)	0.0256 (17)	0.0327 (19)	−0.0104 (14)	−0.0176 (16)	0.0029 (14)
O41C	0.0363 (15)	0.0456 (15)	0.0356 (15)	−0.0213 (13)	−0.0201 (13)	0.0131 (12)
O41D	0.0334 (15)	0.0524 (17)	0.0384 (15)	−0.0159 (13)	−0.0232 (13)	0.0148 (12)
O51A	0.0432 (16)	0.0427 (15)	0.0257 (14)	−0.0182 (13)	−0.0085 (13)	−0.0037 (11)
O51B	0.062 (2)	0.068 (2)	0.0406 (17)	−0.0471 (18)	−0.0078 (15)	−0.0036 (15)
C511	0.035 (2)	0.0334 (19)	0.0254 (18)	−0.0141 (16)	−0.0163 (17)	0.0038 (14)
C512	0.0214 (16)	0.0280 (17)	0.0250 (17)	−0.0076 (14)	−0.0079 (14)	−0.0001 (13)
N555	0.0363 (17)	0.0231 (15)	0.0297 (16)	−0.0089 (13)	−0.0139 (14)	0.0031 (12)
C513	0.035 (2)	0.0279 (17)	0.0228 (17)	−0.0077 (15)	−0.0114 (15)	−0.0020 (13)
C514	0.0310 (19)	0.0350 (19)	0.0278 (18)	−0.0118 (16)	−0.0105 (16)	0.0052 (15)
C515	0.034 (2)	0.0284 (18)	0.036 (2)	−0.0153 (15)	−0.0187 (17)	0.0046 (15)
O51C	0.0392 (16)	0.0562 (18)	0.0399 (16)	−0.0278 (14)	−0.0227 (14)	0.0225 (13)
O51D	0.0359 (15)	0.0493 (17)	0.0443 (16)	−0.0212 (13)	−0.0236 (13)	0.0109 (13)
O61A	0.0320 (14)	0.0397 (15)	0.0474 (16)	−0.0090 (13)	−0.0222 (13)	0.0025 (12)
O61B	0.0413 (17)	0.0384 (16)	0.0598 (19)	−0.0158 (13)	−0.0276 (15)	−0.0015 (13)
C611	0.0307 (19)	0.0356 (19)	0.0177 (15)	−0.0112 (17)	−0.0107 (14)	0.0011 (13)
C612	0.0241 (18)	0.0311 (18)	0.0261 (17)	−0.0080 (15)	−0.0104 (15)	0.0025 (14)
N666	0.0296 (17)	0.0415 (19)	0.0396 (18)	−0.0201 (15)	−0.0165 (15)	0.0175 (15)
C613	0.0252 (17)	0.0253 (17)	0.0270 (17)	−0.0038 (14)	−0.0140 (15)	0.0023 (13)
C614	0.0294 (19)	0.0298 (17)	0.0298 (18)	−0.0081 (15)	−0.0136 (16)	0.0021 (14)
C615	0.0303 (19)	0.0290 (18)	0.0315 (18)	−0.0150 (16)	−0.0128 (16)	0.0070 (14)
O61C	0.0449 (17)	0.0364 (16)	0.0388 (16)	−0.0050 (14)	−0.0164 (14)	0.0147 (12)
O61D	0.0437 (16)	0.0430 (15)	0.0268 (13)	−0.0129 (13)	−0.0180 (12)	0.0057 (11)
O71A	0.0324 (14)	0.0413 (15)	0.0475 (16)	−0.0118 (13)	−0.0223 (13)	0.0071 (12)
O71B	0.059 (2)	0.0361 (16)	0.102 (3)	−0.0207 (15)	−0.054 (2)	0.0036 (17)
C711	0.033 (2)	0.034 (2)	0.0304 (19)	−0.0128 (17)	−0.0173 (16)	0.0024 (15)
C712	0.0232 (17)	0.0284 (18)	0.0264 (17)	−0.0088 (14)	−0.0100 (14)	0.0024 (14)
N777	0.0368 (18)	0.0367 (18)	0.045 (2)	−0.0216 (15)	−0.0191 (16)	0.0092 (14)
C713	0.0268 (19)	0.036 (2)	0.0290 (19)	−0.0112 (16)	−0.0110 (16)	0.0061 (15)
C714	0.047 (2)	0.037 (2)	0.029 (2)	−0.0063 (18)	−0.0131 (18)	0.0038 (16)
C715	0.043 (2)	0.030 (2)	0.0287 (19)	−0.0155 (17)	−0.0174 (17)	0.0034 (15)
O71C	0.0547 (18)	0.0313 (15)	0.0336 (15)	−0.0073 (14)	−0.0169 (14)	0.0018 (11)
O71D	0.064 (2)	0.0346 (14)	0.0272 (14)	−0.0131 (14)	−0.0155 (14)	0.0023 (11)
O81A	0.0417 (16)	0.0386 (14)	0.0350 (15)	−0.0119 (13)	−0.0125 (14)	−0.0055 (11)
O81B	0.087 (3)	0.066 (2)	0.0490 (19)	−0.056 (2)	−0.0179 (18)	−0.0039 (16)
C811	0.038 (2)	0.0345 (19)	0.036 (2)	−0.0157 (17)	−0.0231 (18)	0.0053 (15)
C812	0.0293 (19)	0.0290 (18)	0.0292 (18)	−0.0100 (15)	−0.0142 (15)	0.0027 (14)
N888	0.0336 (17)	0.0269 (15)	0.0292 (15)	−0.0095 (13)	−0.0138 (14)	−0.0004 (12)
C813	0.033 (2)	0.0348 (19)	0.0262 (18)	−0.0077 (16)	−0.0116 (16)	−0.0021 (14)
C814	0.036 (2)	0.039 (2)	0.033 (2)	−0.0116 (17)	−0.0173 (18)	0.0063 (16)
C815	0.041 (3)	0.071 (3)	0.031 (2)	−0.006 (2)	−0.013 (2)	0.008 (2)
O81C	0.049 (3)	0.262 (8)	0.042 (2)	0.029 (4)	−0.006 (2)	0.050 (3)
O81D	0.0449 (18)	0.0574 (19)	0.0390 (16)	−0.0075 (15)	−0.0243 (14)	0.0092 (14)
OW1	0.0484 (19)	0.0441 (17)	0.0383 (16)	−0.0157 (15)	−0.0234 (16)	−0.0020 (14)
OW2	0.053 (2)	0.0576 (19)	0.0414 (18)	−0.0277 (17)	−0.0232 (16)	0.0089 (15)

Geometric parameters (Å, º)

S1—O11	1.443 (4)	C414—C415	1.496 (5)
S1—O13	1.445 (4)	C414—H41D	0.9700
S1—O12	1.449 (3)	C414—H41E	0.9700
S1—O14	1.480 (3)	C415—O41C	1.216 (5)
S2—O21	1.449 (3)	C415—O41D	1.301 (5)
S2—O22	1.453 (3)	O41D—H4F	0.8200
S2—O23	1.464 (4)	O51A—C511	1.198 (4)
S2—O24	1.468 (3)	O51B—C511	1.297 (5)
S3—O31	1.451 (3)	O51B—H5B	0.8200
S3—O33	1.466 (3)	C511—C512	1.512 (5)
S3—O32	1.467 (3)	C512—N555	1.480 (5)
S3—O34	1.479 (3)	C512—C513	1.539 (5)
S4—O43	1.456 (3)	C512—H51A	0.9800
S4—O41	1.459 (3)	N555—H55A	0.8900
S4—O42	1.465 (3)	N555—H55B	0.8900
S4—O44	1.472 (3)	N555—H55C	0.8900
O11A—C111	1.213 (5)	C513—C514	1.511 (5)
O11B—C111	1.301 (5)	C513—H51B	0.9700
O11B—H1B	0.8200	C513—H51C	0.9700
C111—C112	1.505 (5)	C514—C515	1.504 (5)
C112—N111	1.476 (5)	C514—H51D	0.9700
C112—C113	1.522 (5)	C514—H51E	0.9700
C112—H112	0.9800	C515—O51C	1.227 (5)
N111—H11A	0.8900	C515—O51D	1.290 (5)
N111—H11B	0.8900	O51D—H5F	0.8200
N111—H11C	0.8900	O61A—C611	1.204 (4)
C113—C114	1.491 (6)	O61B—C611	1.310 (5)
C113—H11D	0.9700	O61B—H6B	0.8200
C113—H11E	0.9700	C611—C612	1.515 (5)
C114—C115	1.520 (6)	C612—N666	1.498 (5)
C114—H11F	0.9700	C612—C613	1.530 (5)
C114—H11G	0.9700	C612—H61A	0.9800
C115—O11C	1.202 (5)	N666—H66A	0.8900
C115—O11D	1.306 (5)	N666—H66B	0.8900
O11D—H1H	0.8200	N666—H66C	0.8900
O21A—C211	1.207 (5)	C613—C614	1.522 (5)
O21B—C211	1.296 (5)	C613—H61B	0.9700
O21B—H2B	0.8200	C613—H61C	0.9700
C211—C212	1.522 (5)	C614—C615	1.498 (5)
C212—N222	1.476 (5)	C614—H61D	0.9700
C212—C213	1.544 (5)	C614—H61E	0.9700
C212—H21A	0.9800	C615—O61C	1.202 (5)
N222—H22A	0.8900	C615—O61D	1.307 (5)
N222—H22B	0.8900	O61D—H6F	0.8200
N222—H22C	0.8900	O71A—C711	1.197 (5)
C213—C214	1.466 (7)	O71B—C711	1.313 (5)
C213—H21B	0.9700	O71B—H7B	0.8200
C213—H21C	0.9700	C711—C712	1.515 (5)
C214—C215	1.513 (7)	C712—N777	1.482 (5)
C214—H21D	0.9700	C712—C713	1.533 (5)
C214—H21E	0.9700	C712—H71A	0.9800
C215—O21C	1.158 (6)	N777—H77A	0.8900
C215—O21D	1.323 (6)	N777—H77B	0.8900
O21D—H2F	0.8200	N777—H77C	0.8900
O31A—C311	1.195 (5)	C713—C714	1.513 (5)
O31B—C311	1.311 (5)	C713—H71B	0.9700
O31B—H3B	0.8200	C713—H71C	0.9700
C311—C312	1.514 (5)	C714—C715	1.506 (5)
C312—N333	1.481 (4)	C714—H71D	0.9700
C312—C313	1.528 (5)	C714—H71E	0.9700
C312—H31A	0.9800	C715—O71C	1.197 (5)
N333—H33A	0.8900	C715—O71D	1.304 (5)
N333—H33B	0.8900	O71D—H7F	0.8200
N333—H33C	0.8900	O81A—C811	1.199 (5)
C313—C314	1.508 (6)	O81B—C811	1.313 (5)
C313—H31B	0.9700	O81B—H8B	0.8200
C313—H31C	0.9700	C811—C812	1.521 (5)
C314—C315	1.507 (5)	C812—N888	1.482 (5)
C314—H31D	0.9700	C812—C813	1.527 (5)
C314—H31E	0.9700	C812—H812	0.9800
C315—O31C	1.216 (5)	N888—H88A	0.8900
C315—O31D	1.284 (5)	N888—H88B	0.8900
O31D—H3F	0.8200	N888—H88C	0.8900
O41A—C411	1.197 (5)	C813—C814	1.528 (5)
O41B—C411	1.317 (5)	C813—H81A	0.9700
O41B—H4B	0.8200	C813—H81B	0.9700
C411—C412	1.518 (5)	C814—C815	1.489 (5)
C412—N444	1.493 (5)	C814—H81C	0.9700
C412—C413	1.533 (5)	C814—H81D	0.9700
C412—H41A	0.9800	C815—O81C	1.183 (6)
N444—H44A	0.8900	C815—O81D	1.288 (6)
N444—H44B	0.8900	O81D—H8E	0.8200
N444—H44C	0.8900	OW1—H1WA	0.85 (6)
C413—C414	1.515 (5)	OW1—H1WB	0.79 (6)
C413—H41B	0.9700	OW2—H2WA	0.81 (7)
C413—H41C	0.9700	OW2—H2WB	0.94 (8)
O11—S1—O13	113.0 (3)	H41B—C413—H41C	107.8
O11—S1—O12	108.1 (2)	C415—C414—C413	115.2 (3)
O13—S1—O12	110.2 (2)	C415—C414—H41D	108.5
O11—S1—O14	107.6 (2)	C413—C414—H41D	108.5
O13—S1—O14	105.4 (2)	C415—C414—H41E	108.5
O12—S1—O14	112.48 (19)	C413—C414—H41E	108.5
O21—S2—O22	109.7 (2)	H41D—C414—H41E	107.5
O21—S2—O23	109.7 (2)	O41C—C415—O41D	123.7 (3)
O22—S2—O23	109.7 (3)	O41C—C415—C414	125.2 (3)
O21—S2—O24	110.34 (17)	O41D—C415—C414	111.1 (3)
O22—S2—O24	109.5 (2)	C415—O41D—H4F	109.5
O23—S2—O24	107.82 (18)	C511—O51B—H5B	109.5
O31—S3—O33	111.49 (18)	O51A—C511—O51B	126.8 (4)
O31—S3—O32	110.60 (18)	O51A—C511—C512	123.3 (3)
O33—S3—O32	108.29 (16)	O51B—C511—C512	109.8 (3)
O31—S3—O34	107.75 (18)	N555—C512—C511	109.3 (3)
O33—S3—O34	107.75 (17)	N555—C512—C513	112.6 (3)
O32—S3—O34	110.94 (17)	C511—C512—C513	111.0 (3)
O43—S4—O41	112.1 (2)	N555—C512—H51A	107.9
O43—S4—O42	111.36 (19)	C511—C512—H51A	107.9
O41—S4—O42	108.39 (19)	C513—C512—H51A	107.9
O43—S4—O44	106.62 (18)	C512—N555—H55A	109.5
O41—S4—O44	108.2 (2)	C512—N555—H55B	109.5
O42—S4—O44	110.1 (2)	H55A—N555—H55B	109.5
C111—O11B—H1B	109.5	C512—N555—H55C	109.5
O11A—C111—O11B	124.9 (4)	H55A—N555—H55C	109.5
O11A—C111—C112	123.0 (4)	H55B—N555—H55C	109.5
O11B—C111—C112	112.0 (3)	C514—C513—C512	115.2 (3)
N111—C112—C111	108.8 (3)	C514—C513—H51B	108.5
N111—C112—C113	112.0 (3)	C512—C513—H51B	108.5
C111—C112—C113	116.3 (3)	C514—C513—H51C	108.5
N111—C112—H112	106.4	C512—C513—H51C	108.5
C111—C112—H112	106.4	H51B—C513—H51C	107.5
C113—C112—H112	106.4	C515—C514—C513	113.8 (3)
C112—N111—H11A	109.5	C515—C514—H51D	108.8
C112—N111—H11B	109.5	C513—C514—H51D	108.8
H11A—N111—H11B	109.5	C515—C514—H51E	108.8
C112—N111—H11C	109.5	C513—C514—H51E	108.8
H11A—N111—H11C	109.5	H51D—C514—H51E	107.7
H11B—N111—H11C	109.5	O51C—C515—O51D	123.4 (3)
C114—C113—C112	113.9 (3)	O51C—C515—C514	123.3 (3)
C114—C113—H11D	108.8	O51D—C515—C514	113.3 (3)
C112—C113—H11D	108.8	C515—O51D—H5F	109.5
C114—C113—H11E	108.8	C611—O61B—H6B	109.5
C112—C113—H11E	108.8	O61A—C611—O61B	124.7 (4)
H11D—C113—H11E	107.7	O61A—C611—C612	123.8 (3)
C113—C114—C115	111.5 (4)	O61B—C611—C612	111.5 (3)
C113—C114—H11F	109.3	N666—C612—C611	108.2 (3)
C115—C114—H11F	109.3	N666—C612—C613	111.1 (3)
C113—C114—H11G	109.3	C611—C612—C613	111.7 (3)
C115—C114—H11G	109.3	N666—C612—H61A	108.6
H11F—C114—H11G	108.0	C611—C612—H61A	108.6
O11C—C115—O11D	122.1 (4)	C613—C612—H61A	108.6
O11C—C115—C114	122.6 (4)	C612—N666—H66A	109.5
O11D—C115—C114	115.3 (4)	C612—N666—H66B	109.5
C115—O11D—H1H	109.5	H66A—N666—H66B	109.5
C211—O21B—H2B	109.5	C612—N666—H66C	109.5
O21A—C211—O21B	126.0 (4)	H66A—N666—H66C	109.5
O21A—C211—C212	122.1 (3)	H66B—N666—H66C	109.5
O21B—C211—C212	111.8 (3)	C614—C613—C612	113.0 (3)
N222—C212—C211	109.2 (3)	C614—C613—H61B	109.0
N222—C212—C213	107.3 (3)	C612—C613—H61B	109.0
C211—C212—C213	110.8 (3)	C614—C613—H61C	109.0
N222—C212—H21A	109.8	C612—C613—H61C	109.0
C211—C212—H21A	109.8	H61B—C613—H61C	107.8
C213—C212—H21A	109.8	C615—C614—C613	114.2 (3)
C212—N222—H22A	109.5	C615—C614—H61D	108.7
C212—N222—H22B	109.5	C613—C614—H61D	108.7
H22A—N222—H22B	109.5	C615—C614—H61E	108.7
C212—N222—H22C	109.5	C613—C614—H61E	108.7
H22A—N222—H22C	109.5	H61D—C614—H61E	107.6
H22B—N222—H22C	109.5	O61C—C615—O61D	124.0 (3)
C214—C213—C212	111.5 (4)	O61C—C615—C614	124.2 (3)
C214—C213—H21B	109.3	O61D—C615—C614	111.9 (3)
C212—C213—H21B	109.3	C615—O61D—H6F	109.5
C214—C213—H21C	109.3	C711—O71B—H7B	109.5
C212—C213—H21C	109.3	O71A—C711—O71B	125.1 (4)
H21B—C213—H21C	108.0	O71A—C711—C712	124.1 (3)
C213—C214—C215	118.0 (5)	O71B—C711—C712	110.8 (3)
C213—C214—H21D	107.8	N777—C712—C711	108.0 (3)
C215—C214—H21D	107.8	N777—C712—C713	113.2 (3)
C213—C214—H21E	107.8	C711—C712—C713	111.7 (3)
C215—C214—H21E	107.8	N777—C712—H71A	107.9
H21D—C214—H21E	107.1	C711—C712—H71A	107.9
O21C—C215—O21D	124.9 (4)	C713—C712—H71A	107.9
O21C—C215—C214	119.3 (4)	C712—N777—H77A	109.5
O21D—C215—C214	115.7 (4)	C712—N777—H77B	109.5
C215—O21D—H2F	109.5	H77A—N777—H77B	109.5
C311—O31B—H3B	109.5	C712—N777—H77C	109.5
O31A—C311—O31B	124.8 (4)	H77A—N777—H77C	109.5
O31A—C311—C312	123.4 (3)	H77B—N777—H77C	109.5
O31B—C311—C312	111.8 (3)	C714—C713—C712	113.8 (3)
N333—C312—C311	107.7 (3)	C714—C713—H71B	108.8
N333—C312—C313	112.4 (3)	C712—C713—H71B	108.8
C311—C312—C313	109.8 (3)	C714—C713—H71C	108.8
N333—C312—H31A	109.0	C712—C713—H71C	108.8
C311—C312—H31A	109.0	H71B—C713—H71C	107.7
C313—C312—H31A	109.0	C715—C714—C713	115.4 (3)
C312—N333—H33A	109.5	C715—C714—H71D	108.4
C312—N333—H33B	109.5	C713—C714—H71D	108.4
H33A—N333—H33B	109.5	C715—C714—H71E	108.4
C312—N333—H33C	109.5	C713—C714—H71E	108.4
H33A—N333—H33C	109.5	H71D—C714—H71E	107.5
H33B—N333—H33C	109.5	O71C—C715—O71D	124.4 (3)
C314—C313—C312	114.3 (3)	O71C—C715—C714	125.0 (3)
C314—C313—H31B	108.7	O71D—C715—C714	110.5 (3)
C312—C313—H31B	108.7	C715—O71D—H7F	109.5
C314—C313—H31C	108.7	C811—O81B—H8B	109.5
C312—C313—H31C	108.7	O81A—C811—O81B	125.0 (4)
H31B—C313—H31C	107.6	O81A—C811—C812	123.9 (3)
C315—C314—C313	111.6 (3)	O81B—C811—C812	111.0 (3)
C315—C314—H31D	109.3	N888—C812—C811	106.9 (3)
C313—C314—H31D	109.3	N888—C812—C813	113.2 (3)
C315—C314—H31E	109.3	C811—C812—C813	112.1 (3)
C313—C314—H31E	109.3	N888—C812—H812	108.1
H31D—C314—H31E	108.0	C811—C812—H812	108.1
O31C—C315—O31D	122.1 (3)	C813—C812—H812	108.1
O31C—C315—C314	123.7 (4)	C812—N888—H88A	109.5
O31D—C315—C314	114.2 (3)	C812—N888—H88B	109.5
C315—O31D—H3F	109.5	H88A—N888—H88B	109.5
C411—O41B—H4B	109.5	C812—N888—H88C	109.5
O41A—C411—O41B	125.2 (4)	H88A—N888—H88C	109.5
O41A—C411—C412	123.3 (3)	H88B—N888—H88C	109.5
O41B—C411—C412	111.5 (3)	C812—C813—C814	114.7 (3)
N444—C412—C411	108.5 (3)	C812—C813—H81A	108.6
N444—C412—C413	112.9 (3)	C814—C813—H81A	108.6
C411—C412—C413	111.5 (3)	C812—C813—H81B	108.6
N444—C412—H41A	107.9	C814—C813—H81B	108.6
C411—C412—H41A	107.9	H81A—C813—H81B	107.6
C413—C412—H41A	107.9	C815—C814—C813	114.9 (3)
C412—N444—H44A	109.5	C815—C814—H81C	108.6
C412—N444—H44B	109.5	C813—C814—H81C	108.6
H44A—N444—H44B	109.5	C815—C814—H81D	108.6
C412—N444—H44C	109.5	C813—C814—H81D	108.6
H44A—N444—H44C	109.5	H81C—C814—H81D	107.5
H44B—N444—H44C	109.5	O81C—C815—O81D	122.0 (4)
C414—C413—C412	113.0 (3)	O81C—C815—C814	124.2 (4)
C414—C413—H41B	109.0	O81D—C815—C814	113.8 (4)
C412—C413—H41B	109.0	C815—O81D—H8E	109.5
C414—C413—H41C	109.0	H1WA—OW1—H1WB	106 (5)
C412—C413—H41C	109.0	H2WA—OW2—H2WB	93 (6)
O11A—C111—C112—N111	−1.9 (5)	O51A—C511—C512—N555	−18.2 (5)
O11B—C111—C112—N111	176.9 (3)	O51B—C511—C512—N555	163.2 (3)
O11A—C111—C112—C113	125.7 (4)	O51A—C511—C512—C513	106.6 (4)
O11B—C111—C112—C113	−55.6 (5)	O51B—C511—C512—C513	−72.0 (4)
N111—C112—C113—C114	61.3 (5)	N555—C512—C513—C514	78.2 (4)
C111—C112—C113—C114	−64.6 (5)	C511—C512—C513—C514	−44.6 (4)
C112—C113—C114—C115	175.1 (4)	C512—C513—C514—C515	170.2 (3)
C113—C114—C115—O11C	−61.4 (7)	C513—C514—C515—O51C	−41.7 (5)
C113—C114—C115—O11D	120.7 (5)	C513—C514—C515—O51D	139.9 (3)
O21A—C211—C212—N222	−29.5 (5)	O61A—C611—C612—N666	−6.3 (5)
O21B—C211—C212—N222	154.0 (3)	O61B—C611—C612—N666	175.9 (3)
O21A—C211—C212—C213	88.5 (4)	O61A—C611—C612—C613	116.3 (4)
O21B—C211—C212—C213	−88.0 (4)	O61B—C611—C612—C613	−61.4 (4)
N222—C212—C213—C214	−172.2 (6)	N666—C612—C613—C614	62.9 (4)
C211—C212—C213—C214	68.6 (6)	C611—C612—C613—C614	−58.1 (4)
C212—C213—C214—C215	−167.5 (7)	C612—C613—C614—C615	−179.7 (3)
C213—C214—C215—O21C	−179.0 (7)	C613—C614—C615—O61C	−13.5 (5)
C213—C214—C215—O21D	−1.8 (11)	C613—C614—C615—O61D	167.4 (3)
O31A—C311—C312—N333	−16.3 (5)	O71A—C711—C712—N777	−3.1 (5)
O31B—C311—C312—N333	165.0 (3)	O71B—C711—C712—N777	177.7 (3)
O31A—C311—C312—C313	106.4 (4)	O71A—C711—C712—C713	122.0 (4)
O31B—C311—C312—C313	−72.4 (4)	O71B—C711—C712—C713	−57.2 (4)
N333—C312—C313—C314	−64.6 (4)	N777—C712—C713—C714	72.2 (4)
C311—C312—C313—C314	175.6 (3)	C711—C712—C713—C714	−50.0 (4)
C312—C313—C314—C315	−161.4 (3)	C712—C713—C714—C715	168.9 (3)
C313—C314—C315—O31C	49.6 (6)	C713—C714—C715—O71C	−22.9 (6)
C313—C314—C315—O31D	−129.7 (4)	C713—C714—C715—O71D	159.9 (4)
O41A—C411—C412—N444	−1.3 (5)	O81A—C811—C812—N888	−7.9 (5)
O41B—C411—C412—N444	179.9 (3)	O81B—C811—C812—N888	173.5 (3)
O41A—C411—C412—C413	123.7 (4)	O81A—C811—C812—C813	116.8 (4)
O41B—C411—C412—C413	−55.1 (4)	O81B—C811—C812—C813	−61.9 (4)
N444—C412—C413—C414	67.1 (4)	N888—C812—C813—C814	72.0 (4)
C411—C412—C413—C414	−55.3 (4)	C811—C812—C813—C814	−49.1 (5)
C412—C413—C414—C415	177.5 (3)	C812—C813—C814—C815	173.0 (4)
C413—C414—C415—O41C	−19.5 (5)	C813—C814—C815—O81C	−6.8 (9)
C413—C414—C415—O41D	161.5 (3)	C813—C814—C815—O81D	172.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11B—H1B···O21C^i	0.82	1.83	2.644 (4)	176
O21B—H2B···OW2^ii	0.82	1.72	2.525 (5)	165
O31B—H3B···O51C	0.82	1.93	2.733 (4)	165
O41B—H4B···O71C	0.82	1.92	2.720 (4)	164
O51B—H5B···OW1	0.82	1.70	2.495 (4)	163
O61B—H6B···O41C	0.82	1.86	2.657 (4)	164
O71B—H7B···O11C^iii	0.82	1.78	2.591 (4)	169
O81B—H8B···O31C^iv	0.82	1.81	2.625 (5)	177
O11D—H1H···O34^v	0.82	1.77	2.585 (4)	173
O21D—H2F···O12^vi	0.82	1.76	2.555 (4)	161
O31D—H3F···O14^vii	0.82	1.81	2.604 (4)	162
O41D—H4F···O32	0.82	1.78	2.577 (4)	164
O51D—H5F···O41^viii	0.82	1.78	2.595 (4)	172
O61D—H6F···O42^iii	0.82	1.86	2.659 (4)	166
O71D—H7F···O33^iii	0.82	1.86	2.625 (4)	155
O81D—H8E···O22^i	0.82	2.20	2.958 (6)	153
O81D—H8E···O23^i	0.82	2.39	3.081 (6)	142
N111—H11A···O24^v	0.89	1.82	2.708 (4)	171
N111—H11B···O42^viii	0.89	2.18	2.943 (5)	144
N111—H11C···O51C	0.89	2.13	2.998 (4)	164
N222—H22A···O24	0.89	1.89	2.767 (4)	168
N222—H22B···O44^ix	0.89	1.95	2.801 (4)	160
N222—H22C···O51A	0.89	2.15	2.913 (4)	144
N222—H22C···O61C^viii	0.89	2.40	2.835 (4)	110
N333—H33A···O43	0.89	1.93	2.795 (4)	164
N333—H33A···O44	0.89	2.46	2.992 (4)	119
N333—H33B···O33	0.89	2.08	2.886 (4)	151
N333—H33B···O32	0.89	2.49	3.061 (4)	122
N333—H33C···O71C^v	0.89	2.34	3.070 (4)	139
N333—H33C···O41A^v	0.89	2.36	3.036 (4)	133
N444—H44A···O14^vii	0.89	1.92	2.804 (4)	172
N444—H44B···O23	0.89	1.94	2.797 (5)	161
N444—H44C···O21A^x	0.89	2.23	2.922 (4)	134
N555—H55A···O31^vii	0.89	2.15	2.928 (4)	146
N555—H55A···O34^vii	0.89	2.39	3.193 (4)	151
N555—H55B···O11^ii	0.89	1.95	2.727 (5)	145
N555—H55C···O71A^vii	0.89	2.41	3.095 (4)	134
N555—H55C···O11C^xi	0.89	2.48	3.056 (4)	123
N666—H66A···O34^x	0.89	1.92	2.798 (4)	166
N666—H66A···O33^x	0.89	2.59	3.254 (4)	132
N666—H66B···O13	0.89	2.02	2.844 (5)	154
N666—H66C···O21C^xii	0.89	2.03	2.807 (4)	145
N777—H77A···O13	0.89	2.20	2.962 (5)	143
N777—H77A···O14	0.89	2.21	2.992 (5)	147
N777—H77B···O22^iv	0.89	1.97	2.830 (5)	162
N777—H77B···O21^iv	0.89	2.62	3.084 (5)	114
N777—H77C···O31C^iv	0.89	2.43	3.160 (5)	140
N888—H88A···O43	0.89	1.84	2.717 (4)	169
N888—H88B···O31	0.89	1.95	2.827 (4)	170
N888—H88C···O41C	0.89	2.40	3.084 (4)	134
N888—H88C···O61A	0.89	2.48	3.151 (4)	133
OW1—H1WA···O21	0.85 (6)	1.88 (6)	2.732 (4)	175 (5)
OW1—H1WB···O61C^viii	0.79 (6)	2.07 (6)	2.803 (5)	155 (5)
OW2—H2WA···O11	0.81 (7)	1.96 (7)	2.706 (5)	151 (6)
OW2—H2WB···O81C^iii	0.94 (8)	1.78 (8)	2.725 (6)	174 (6)

Symmetry codes: (i) x, y+1, z−1; (ii) x−1, y−1, z; (iii) x, y, z+1; (iv) x, y+1, z; (v) x, y, z−1; (vi) x−1, y−1, z+1; (vii) x, y−1, z; (viii) x−1, y, z; (ix) x−1, y, z+1; (x) x+1, y, z; (xi) x, y−1, z+1; (xii) x+1, y+1, z−1.