Download citation
Download citation
link to html
The crystal structure of L-methionyl-L-alanine, C8H16N2O3S, is very similar to that of L-valyl-L-alanine [Görbitz & Gundersen (1996). Acta Cryst. C52, 1764-1767] and other related dipeptides in space group P61, but there are seven mol­ecules in the asymmetric unit. The Z value of 42 is the highest ever observed for a chiral mol­ecule.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103019280/fg1702sup1.cif
Contains datablocks MA, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103019280/fg1702MAsup2.hkl
Contains datablock MA

CCDC reference: 224669

Comment top

The crystal structure of L-Val-L-Ala (VA; Görbitz & Gundersen, 1996) comprised the first example of nanotube formation by such a small molecule. Subsequently, the retroanalogue L-Ala-L-Val (Görbitz, 2002a), as well as a series of other dipeptides with L-Ala, L-Val and L-Ile residues (Görbitz, 2003), have been found to form structures very similar to VA, differing only in the way the side chains partly fill the channels along the hexagonal axes, which translates directly to pore size.

To investigate whether crystallization in the VA class is compatible with dipeptides incorporating unbranched side chains (apart from the methyl group of L-Ala), crystallization and structure determination have been carried out for the title compound, L-Met-L-Ala, hereinafter MA. \sch

Compound MA was crystallized for the first time in our laboratory in 1996 using 2-propanol as the precipitating agent. High initial solute concentrations led to the formation of ultrathin plates that were, after several attempts, found to be the 1:2 2-propanol solvate (Görbitz, 2000), while bundles of very thin needles appeared when low concentrations were used (0.16–0.32 mg of peptide in 30 µl of water). At the time, we had a traditional diffractometer with a scintillation counter that was able to detect only a few hundred reflections for one of these crystals. It was not possible to solve the structure from this experimental material, but the apparent cell dimensions [P61, a = 14.261 (7) and c = 9.715 (5) Å] indicated that the MA structure was very similar to that of VA [a = 14.424 (4) and c = 9.996 (6) Å; Görbitz & Gundersen, 1996]. Later, it was found that larger needles could be grown with acetonitrile rather than 2-propanol as the precipitating agent, and when data were collected using a CCD detector it immediately became evident that the MA unit cell was in fact much larger, with Z' = 7, and that the first data collection had provided a sub-cell of the true crystal lattice.

Structures with Z'= 7 are extremely uncommon; the C-terminal dipeptide fragment (Boc-L-Phe-L-Leu-OBzl) of enkephalin, in space group P21 (Antolić et al., 1999), is the only example in the Cambridge Structural Database [CSD, Version 5.24; Allen, 2002]. There is also just a single observation of Z = 42 (acoradiene in space group R3, Z' = 2.33; Chen & Lin, 1993), while about 25 organic molecules, all achiral, have Z > 42 (Z' 0.5–16). Statistical data for Z' values have been provided by Kumar et al. (2000).

The seven independent peptide molecules in the crystal structure of MA are shown in Fig. 1. Bond lengths and angles are normal. Torsion angles are listed in Table 1. The peptide main chain is observed in three different conformations: extended (molecules A, B and D), semi-extended (molecules C and E) and S-shaped (molecules F and G). Structures in the VA class all have extended conformations, with ψ1 in the range 151–171° and ϕ2 in the range −129 – −154° (Görbitz, 2003).

An understanding of the side-chain conformations in MA can be gained by considering the crystal-packing arrangement shown in Fig. 2. Compared with the VA class, the lengths of the a and b axes are more than doubled [from approximately 14.2 to 37.6488 (15) Å], which makes room for the increase from Z' = 1 to Z' = 7. In the process, two different types of hydrophobic columns are created.

Column 1 and its surroundings on the hexagonal axis closely mimic the structures of the VA class. The side chains in these structures are unable to fill the central cavity, leaving a conspicuous empty (or solvent-filled) channel or nanotube of varying diameter (Görbitz & Gundersen, 1996; Görbitz, 2002a, 2003). The long L-Met side chains of molecule A, however, can fill these channels more or less completely, but not in a very straightforward manner, since selection of any one L-Met conformation leads to serious intermolecular steric conflict between adjacent molecules related by the 61 screw axis. Accordingly, the side chain is heavily disordered. The refinement of the structure applied six different orientations, A1—A6 (Table 1), which can conveniently be divided into two groups, namely A1 and A2 with χ11 = gauche+, and A3—A6 with χ11 = gauche-.

The rare gauche+/trans/trans A1 conformation, observed only once before in peptides (for D,L-Ala-L,D-Met; Guillot et al., 2001), is exceptional, in that it does not create side-chain-side-chain conflict when introduced in adjacent molecule-A positions. Instead, atom C41A comes close to the C7B methyl group of one (but not both) of the two neighbouring B molecules. This forces a disorder for molecule B, with two alternative L-Ala methyl positions (Fig. 1). Each molecule A in conformation A1 must be flanked by one B molecule in the major orientation and one in the minor orientation. It follows that adjacent A1 conformations are prohibited.

Conformation A2 is essentially the same as A1, but the torsion angles are shifted to more awkward values (Table 1), which serves to eliminate the conflict with atom C7B, at the expense of reintroducing side-chain conflict with neighbouring molecules in conformations A1 and A2. The result of this analysis is that two neighbouring A molecules must always have side-chain orientations from different groups [(A1, A2) or (A3—A6)] in order to avoid steric conflict. The sum of the occupancies for A1 and A2 should thus ideally be 1/2, the same as for A3—A6. This is in close agreement with the refinement results (Table 1; sum of all occupancies constrained to 1.00).

Column 2 has no crystallographic symmetry, but the peptide backbones are related by pseudo-sixfold screw symmetry. The column is generated from an intricate close-packing of L-Met side chains from molecules B, C, D, E, F and G, together with minor contributions from the L-Ala side chains of molecules A, C, D, E, F and G (the L-Ala side chain of molecule B is part of column 1).

It is noteworthy that, in three previous structures of peptides with N-terminal L-Met residues [L-Met-L-Met (Stenkamp & Jensen, 1975), L-Met-L-Glu-L-His-L-Phe hydrate (Admiraal & Vos, 1983) and L-Met-L-Ala 2-propanol solvate (Z' = 2; Görbitz, 2000)], both χ11 and χ12 torsion angles were trans. The MA conformations represent a clear departure from this pattern. Overall, molecules C and E are very similar, while the other molecules differ in either their side-chain or their main-chain conformations.

The hydrogen-bond geometry for MA is listed in Table 2. The hydrogen bonding in the MA crystal structure closely follows the pattern of the VA class, including the left-handed dipeptide double helix described previously (Görbitz & Gundersen, 1996; Görbitz, 2002b, 2003). In the VA class, this motif involves molecules related by threefold screw symmetry, as seen for G molecules in the MA structure (G, G* and G# in Fig. 2). Pseudo-threefold screw symmetry, which is very accurate if the side chains are disregarded, relates molecules A + B + C and D + E + F in exactly the same manner.

Experimental top

The title compound was obtained from Bachem and used as received. Crystals of MA were grown by slow diffusion of acteonitrile into an aqueous solution of the peptide.

Refinement top

Due to the low parameter-to-reflection ratio, only fully ordered S and O atoms, and the terminal C atoms of the L-Met side chains, were refined anisotropically. A full anisotropic refinement (908 parameters) was found to give only a very moderate decrease in the R value (to 0.0556) and a small increase in the s.u.s of the geometric parameters. Refinement of the complex disorder for the L-Met side chain of peptide molecule A was handled by mild SHELXTL SAME 0.02 0.03 constraints (Sheldrick, 1997) for six different orientations. H atoms were placed geometrically and refined with constraints. Free rotation of amino and methyl groups (without disorder) was permitted. Uiso(H) values were 1.2Ueq of the carrier atom, or 1.5Ueq for methyl and amino groups. Friedel pairs were merged in the final refinements.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The seven molecules in the asymmetric unit of MA, with the atomic numbering scheme. Displacement ellipsoids and spheres are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. For molecule A, six alternative side-chain orientations are shown; a thick black line (to atom C41A) is used for the most populated one (A1; see Table 1). For molecule B, there is disorder at C6B—C7B. The major component [occupancy 0.609 (18)] is shown with open bonds, the minor component as a stick drawing.
[Figure 2] Fig. 2. The crystal packing of MA viewed along the c axis. Side chains are shown in light grey. The letters A—G identify the seven independent peptide molecules in the asymmetric unit, which are shown in more detail in the inset, along with two additional G molecules, G* [at symmetry position (1 − x, 1 + x-y, z − 2/3)] and G# [at symmetry position (y-x, 1 − x, z − 1/3)]. Two unit cells are shown; the larger is the true unit cell, while the smaller is the subcell found in the earlier investigation of an MA crystal. The latter also corresponds to the true unit cell in the VA class. Note that the illustration does not tell the full story about Column 1, since the extended A3 conformation (see Table 1) for L-Met is shown for all A molecules. This side chain is in fact disordered over six positions.
L-Methionyl-L-alanine top
Crystal data top
C8H16N2O3SDx = 1.295 Mg m3
Mr = 220.29Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P61Cell parameters from 14292 reflections
a = 37.6488 (15) Åθ = 1.1–25.1°
c = 9.6613 (8) ŵ = 0.27 mm1
V = 11859.6 (12) Å3T = 105 K
Z = 42Needle, colourless
F(000) = 49560.80 × 0.18 × 0.15 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer
7460 independent reflections
Radiation source: fine-focus sealed tube4308 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.195
Detector resolution: 8.3 pixels mm-1θmax = 25.1°, θmin = 1.1°
Sets of exposures each taken over 0.3° ω rotation scansh = 4444
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
k = 4044
Tmin = 0.789, Tmax = 0.960l = 118
79465 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.145H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0446P)2 + 18.1456P]
where P = (Fo2 + 2Fc2)/3
7460 reflections(Δ/σ)max = 0.001
633 parametersΔρmax = 0.48 e Å3
93 restraintsΔρmin = 0.35 e Å3
Crystal data top
C8H16N2O3SZ = 42
Mr = 220.29Mo Kα radiation
Hexagonal, P61µ = 0.27 mm1
a = 37.6488 (15) ÅT = 105 K
c = 9.6613 (8) Å0.80 × 0.18 × 0.15 mm
V = 11859.6 (12) Å3
Data collection top
Siemens SMART CCD area-detector
diffractometer
7460 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
4308 reflections with I > 2σ(I)
Tmin = 0.789, Tmax = 0.960Rint = 0.195
79465 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05893 restraints
wR(F2) = 0.145H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0446P)2 + 18.1456P]
where P = (Fo2 + 2Fc2)/3
7460 reflectionsΔρmax = 0.48 e Å3
633 parametersΔρmin = 0.35 e Å3
Special details top

Geometry. All H atoms are in theoretical positions, X—H bonds and X—Y—H bond angles have only been listed for molecule C (first molecule without any kind of disorder)

Refinement. Data were collected by measuring three sets of exposures with the detector set at 2θ = 26°, crystal-to-detector distance 4.98 cm. Refinement of F2 against ALL reflections.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O1A0.18323 (15)0.22244 (17)0.7450 (6)0.0369 (15)
O2A0.06150 (16)0.2261 (2)0.8514 (6)0.0516 (19)
O3A0.10056 (14)0.26074 (15)1.0316 (6)0.0271 (13)
N1A0.17569 (17)0.18119 (18)0.5228 (7)0.0267 (16)*
H1A0.16980.16210.45560.040*
H2A0.18850.17650.59440.040*
H3A0.19240.20670.48760.040*
N2A0.12328 (14)0.22243 (13)0.7239 (5)0.0261 (15)*
H4A0.10000.21350.67890.031*
C11A0.13697 (14)0.17837 (13)0.5730 (5)0.025 (2)*0.285 (9)
H11A0.12380.18530.49590.030*0.285 (9)
C21A0.10979 (14)0.13439 (13)0.6146 (5)0.052 (4)*0.285 (9)
H2110.10670.11650.53520.062*0.285 (9)
H2120.08220.12990.63800.062*0.285 (9)
C31A0.1268 (7)0.1221 (5)0.740 (3)0.056 (9)*0.285 (9)
H3110.12800.13900.82000.068*0.285 (9)
H3120.15530.12910.71820.068*0.285 (9)
S11A0.0983 (4)0.0686 (3)0.7905 (12)0.066 (3)*0.285 (9)
C41A0.1398 (8)0.0654 (9)0.872 (4)0.077 (11)*0.285 (9)
H4110.12980.03730.90380.116*0.285 (9)
H4120.15010.08430.95040.116*0.285 (9)
H4130.16190.07300.80440.116*0.285 (9)
C12A0.13697 (14)0.17837 (13)0.5730 (5)0.025 (2)*0.190 (8)
H12A0.12610.18780.49530.030*0.190 (8)
C22A0.1024 (6)0.1373 (10)0.619 (6)0.052 (4)*0.190 (8)
H2210.08570.12210.53760.062*0.190 (8)
H2220.08450.14150.68390.062*0.190 (8)
C32A0.1189 (10)0.1118 (9)0.691 (5)0.056 (9)*0.190 (8)
H3210.14230.13020.75030.068*0.190 (8)
H3220.12950.10080.61860.068*0.190 (8)
S12A0.0819 (6)0.0696 (4)0.7947 (17)0.066 (3)*0.190 (8)
C42A0.0836 (16)0.0282 (9)0.708 (5)0.077 (11)*0.190 (8)
H4210.11090.03830.66800.116*0.190 (8)
H4220.06300.01750.63410.116*0.190 (8)
H4230.07780.00630.77450.116*0.190 (8)
C13A0.13697 (14)0.17837 (13)0.5730 (5)0.025 (2)*0.229 (7)
H13A0.12520.18690.49540.030*0.229 (7)
C23A0.1060 (12)0.1339 (7)0.609 (4)0.052 (4)*0.229 (7)
H2310.08580.13310.67660.062*0.229 (7)
H2320.12040.12070.65270.062*0.229 (7)
C33A0.0834 (7)0.1099 (7)0.476 (3)0.032 (8)*0.229 (7)
H3310.09930.09790.43540.038*0.229 (7)
H3320.08410.12990.40760.038*0.229 (7)
S13A0.0317 (3)0.0700 (4)0.4937 (13)0.054 (3)*0.229 (7)
C43A0.0234 (13)0.0414 (12)0.338 (4)0.087 (16)*0.229 (7)
H4310.00560.02010.33210.130*0.229 (7)
H4320.04040.02850.33920.130*0.229 (7)
H4330.03070.05980.25860.130*0.229 (7)
C14A0.13697 (14)0.17837 (13)0.5730 (5)0.025 (2)*0.142 (6)
H14A0.12080.18200.49770.030*0.142 (6)
C24A0.1124 (18)0.1377 (8)0.652 (3)0.052 (4)*0.142 (6)
H2410.09250.13990.71320.062*0.142 (6)
H2420.13160.13400.71260.062*0.142 (6)
C34A0.0888 (13)0.0989 (7)0.561 (5)0.032 (8)*0.142 (6)
H3410.07170.07570.62380.038*0.142 (6)
H3420.10930.09310.51890.038*0.142 (6)
S14A0.0563 (7)0.0988 (6)0.425 (2)0.054 (3)*0.142 (6)
C44A0.048 (3)0.0548 (19)0.328 (7)0.087 (16)*0.142 (6)
H4410.02670.04890.25660.130*0.142 (6)
H4420.03790.03110.38940.130*0.142 (6)
H4430.07320.06020.28300.130*0.142 (6)
C15A0.13697 (14)0.17837 (13)0.5730 (5)0.025 (2)*0.101 (5)
H15A0.12280.18430.49640.030*0.101 (5)
C25A0.109 (3)0.1356 (7)0.634 (4)0.052 (4)*0.101 (5)
H2510.08180.13280.65270.062*0.101 (5)
H2520.12060.13370.72360.062*0.101 (5)
C35A0.103 (2)0.0992 (9)0.543 (5)0.032 (8)*0.101 (5)
H3510.08540.07370.59560.038*0.101 (5)
H3520.12970.10140.53010.038*0.101 (5)
S15A0.0800 (8)0.0926 (8)0.375 (3)0.054 (3)*0.101 (5)
C45A0.081 (6)0.049 (4)0.310 (10)0.087 (16)*0.101 (5)
H4510.06790.04130.21900.130*0.101 (5)
H4520.06600.02560.37420.130*0.101 (5)
H4530.10950.05480.30260.130*0.101 (5)
C16A0.13697 (14)0.17837 (13)0.5730 (5)0.025 (2)*0.051 (5)
H16A0.12200.18340.49680.030*0.051 (5)
C26A0.109 (5)0.1387 (17)0.652 (7)0.052 (4)*0.051 (5)
H2610.08220.13750.66920.062*0.051 (5)
H2620.12130.13980.74320.062*0.051 (5)
C36A0.100 (2)0.0990 (8)0.58 (2)0.032 (8)*0.051 (5)
H3610.11780.08940.62100.038*0.051 (5)
H3620.10990.10640.48040.038*0.051 (5)
S16A0.0490 (15)0.0564 (14)0.572 (6)0.054 (3)*0.051 (5)
C5A0.1498 (2)0.2104 (2)0.6874 (9)0.0259 (19)*
C6A0.1336 (2)0.2509 (2)0.8409 (8)0.0259 (19)*
H61A0.14960.24470.90940.031*
C7A0.1607 (2)0.2958 (2)0.7940 (9)0.034 (2)*
H71A0.18510.29880.74660.051*
H72A0.16920.31390.87510.051*
H73A0.14520.30320.73060.051*
C8A0.0947 (2)0.2451 (2)0.9135 (9)0.0265 (19)*
O1B0.20914 (19)0.2428 (2)1.0720 (7)0.0514 (18)
O2B0.2107 (2)0.11874 (19)1.1726 (7)0.062 (2)
O3B0.18084 (17)0.12809 (16)1.3539 (6)0.0349 (14)
N1B0.25303 (18)0.28194 (18)0.8571 (7)0.0280 (16)*
H1B0.27300.29730.79470.042*
H2B0.25390.29820.92830.042*
H3B0.22810.27060.81520.042*
C1B0.25972 (18)0.2490 (2)0.9113 (8)0.0221 (18)*
H11B0.25810.23060.83400.027*
C2B0.3007 (2)0.2661 (2)0.9851 (8)0.035 (2)*
H21B0.30520.24311.00970.042*
H22B0.29950.27931.07230.042*
C3B0.3373 (2)0.2975 (2)0.8990 (9)0.043 (2)*
H31B0.36260.30560.95240.051*
H32B0.33470.32230.88820.051*
S1B0.34361 (7)0.28148 (8)0.7287 (3)0.0584 (8)
C4B0.3612 (3)0.2467 (3)0.7781 (14)0.087 (4)
H41B0.36570.23460.69490.130*
H42B0.34050.22490.83660.130*
H43B0.38700.26170.82960.130*
C5B0.2256 (2)0.2252 (2)1.0137 (9)0.032 (2)*0.609 (18)
N2B0.21559 (18)0.18678 (18)1.0442 (7)0.0292 (16)*0.609 (18)
H4B0.22500.17320.99700.035*0.609 (18)
C6B0.1871 (4)0.1685 (4)1.1650 (14)0.025 (4)*0.609 (18)
H61B0.19210.19001.23510.030*0.609 (18)
C7B0.1423 (4)0.1484 (4)1.1077 (16)0.046 (5)*0.609 (18)
H71B0.13760.16961.06790.069*0.609 (18)
H72B0.12280.13451.18330.069*0.609 (18)
H73B0.13840.12831.03610.069*0.609 (18)
C8B0.1928 (2)0.1343 (2)1.2299 (9)0.031 (2)*0.609 (18)
C52B0.2256 (2)0.2252 (2)1.0137 (9)0.032 (2)*0.391 (18)
N22B0.21559 (18)0.18678 (18)1.0442 (7)0.0292 (16)*0.391 (18)
H44B0.23300.17921.01550.035*0.391 (18)
C62B0.1795 (4)0.1553 (5)1.119 (2)0.039 (7)*0.391 (18)
H62B0.16400.16751.16280.047*0.391 (18)
C72B0.1513 (7)0.1200 (6)1.016 (2)0.093 (13)*0.391 (18)
H74B0.14190.13120.94210.139*0.391 (18)
H75B0.12750.09871.06600.139*0.391 (18)
H76B0.16690.10810.97530.139*0.391 (18)
C82B0.1928 (2)0.1343 (2)1.2299 (9)0.031 (2)*0.391 (18)
S1C0.11237 (7)0.33742 (7)0.4718 (3)0.0447 (7)
O1C0.20555 (16)0.25792 (15)0.4151 (6)0.0371 (15)
O2C0.31654 (18)0.39087 (16)0.5201 (6)0.0431 (16)
O3C0.30297 (16)0.34630 (15)0.6904 (6)0.0318 (14)
N1C0.15996 (17)0.26467 (17)0.2057 (6)0.0232 (15)*
H1C0.14530.27150.14730.035*
H2C0.14260.24510.26600.035*
H3C0.17370.25480.15580.035*
N2C0.25790 (17)0.32187 (18)0.3684 (7)0.0245 (16)*
H4C0.26550.34390.31760.029*
C1C0.1901 (2)0.3019 (2)0.2845 (8)0.0264 (19)*
H11C0.20570.32540.21980.032*
C2C0.1681 (2)0.3134 (2)0.3947 (9)0.031 (2)*
H21C0.15300.28980.45770.037*
H22C0.18900.33650.45040.037*
C3C0.1382 (2)0.3256 (3)0.3373 (9)0.037 (2)*
H31C0.11750.30300.27980.044*
H32C0.15330.34990.27690.044*
C4C0.0750 (3)0.2869 (3)0.5347 (10)0.048 (3)
H41C0.05910.28960.61000.072*
H42C0.08920.27280.56890.072*
H43C0.05650.27090.45900.072*
C5C0.2192 (2)0.2916 (2)0.3601 (8)0.0236 (19)*
C6C0.2888 (2)0.3204 (2)0.4581 (8)0.0240 (18)*
H61C0.27590.29340.50710.029*
C7C0.3241 (2)0.3246 (2)0.3712 (9)0.036 (2)*
H71C0.31390.30200.30460.053*
H72C0.34460.32380.43140.053*
H73C0.33660.35070.32130.053*
C8C0.3032 (2)0.3548 (2)0.5656 (10)0.0273 (19)*
S1D0.55988 (7)0.65229 (7)0.0389 (3)0.0414 (6)
O1D0.39930 (14)0.51352 (14)0.2271 (5)0.0233 (12)
O2D0.51081 (15)0.49066 (16)0.3427 (6)0.0301 (14)
O3D0.47308 (14)0.47098 (15)0.5357 (5)0.0251 (13)
N1D0.41305 (16)0.55734 (17)0.0054 (6)0.0194 (14)*
H1D0.42110.57520.06690.029*
H2D0.40610.56790.07840.029*
H3D0.39100.53300.02020.029*
N2D0.45478 (17)0.50522 (16)0.2125 (6)0.0198 (14)*
H4D0.47760.51130.16820.024*
C1D0.4474 (2)0.5506 (2)0.0464 (8)0.0173 (17)*
H11D0.45200.53590.03130.021*
C2D0.4879 (2)0.5908 (2)0.0717 (8)0.0244 (19)*
H21D0.48250.60980.12620.029*
H22D0.50670.58490.12600.029*
C3D0.5085 (2)0.6112 (2)0.0659 (8)0.0265 (19)*
H31D0.49230.62200.11170.032*
H32D0.50900.59050.12780.032*
C4D0.5736 (3)0.6661 (3)0.2178 (10)0.046 (3)
H41D0.60190.68900.22330.069*
H42D0.55500.67420.25910.069*
H43D0.57140.64240.26820.069*
C5D0.4322 (2)0.5217 (2)0.1710 (8)0.0164 (17)*
C6D0.4420 (2)0.4773 (2)0.3301 (8)0.0212 (18)*
H61D0.42630.48510.39490.025*
C7D0.4138 (2)0.4328 (2)0.2851 (9)0.029 (2)*
H71D0.39020.43070.23460.043*
H72D0.40410.41510.36700.043*
H73D0.42890.42410.22480.043*
C8D0.4791 (2)0.4807 (2)0.4093 (9)0.0239 (19)*
S1E0.44667 (7)0.37542 (7)0.0899 (3)0.0418 (6)
O1E0.37015 (15)0.47775 (15)0.0811 (6)0.0305 (14)
O2E0.25479 (19)0.34443 (16)0.0128 (6)0.0489 (17)
O3E0.27593 (15)0.38887 (15)0.1882 (6)0.0285 (13)
N1E0.41613 (17)0.47283 (17)0.2927 (7)0.0233 (15)*
H1E0.43010.46680.35650.035*
H2E0.43380.48940.22640.035*
H3E0.40420.48590.33490.035*
N2E0.31676 (17)0.41394 (17)0.1332 (7)0.0215 (15)*
H4E0.30880.39210.18560.026*
C1E0.3838 (2)0.4342 (2)0.2276 (8)0.0228 (18)*
H11E0.36740.41380.30090.027*
C2E0.4024 (2)0.4161 (2)0.1295 (8)0.0275 (19)*
H21E0.42030.43740.06210.033*
H22E0.38000.39340.07700.033*
C3E0.4274 (2)0.4001 (2)0.2015 (9)0.031 (2)*
H31E0.45090.42340.24850.037*
H32E0.41010.38040.27380.037*
C4E0.4879 (2)0.4189 (2)0.0025 (11)0.045 (3)
H41E0.50100.40930.06360.068*
H42E0.47690.43400.04710.068*
H43E0.50820.43700.07070.068*
C5E0.3560 (2)0.4443 (2)0.1410 (8)0.0215 (18)*
C6E0.2870 (2)0.4155 (2)0.0431 (8)0.0232 (18)*
H61E0.30050.44200.00880.028*
C7E0.2512 (2)0.4126 (2)0.1276 (9)0.037 (2)*
H71E0.26150.43590.19150.056*
H72E0.23110.41320.06490.056*
H73E0.23820.38700.18030.056*
C8E0.2716 (2)0.3797 (2)0.0612 (9)0.0259 (19)*
S1F0.22974 (6)0.44203 (7)0.2393 (3)0.0391 (6)
O1F0.36847 (15)0.49991 (15)0.5758 (6)0.0285 (13)
O2F0.36876 (15)0.59318 (15)0.6888 (5)0.0263 (13)
O3F0.42758 (15)0.60012 (15)0.7674 (5)0.0296 (14)
N1F0.32798 (17)0.45291 (17)0.3430 (6)0.0214 (15)*
H1F0.30850.43740.27930.032*
H2F0.32660.43690.41560.032*
H3F0.35330.46420.30340.032*
N2F0.37579 (16)0.55468 (16)0.4544 (6)0.0181 (14)*
H4F0.36590.56390.39010.022*
C1F0.3206 (2)0.4865 (2)0.3935 (8)0.0185 (17)*
H11F0.31880.50200.31240.022*
C2F0.2815 (2)0.4692 (2)0.4766 (8)0.028 (2)*
H21F0.27550.49160.49390.034*
H22F0.28650.46030.56760.034*
C3F0.2435 (2)0.4331 (2)0.4124 (9)0.029 (2)*
H31F0.21990.42560.47480.034*
H32F0.24790.40930.40780.034*
C4F0.2128 (3)0.4784 (3)0.2804 (12)0.056 (3)
H41F0.20460.48650.19520.084*
H42F0.23530.50270.32460.084*
H43F0.18930.46550.34370.084*
C5F0.3575 (2)0.5149 (2)0.4810 (8)0.0238 (19)*
C6F0.4126 (2)0.5834 (2)0.5327 (8)0.0233 (18)*
H61F0.43020.57070.54550.028*
C7F0.4369 (2)0.6232 (2)0.4517 (9)0.034 (2)*
H71F0.44440.61730.36100.051*
H72F0.46180.64190.50300.051*
H73F0.42000.63610.43900.051*
C8F0.4016 (2)0.5927 (2)0.6747 (8)0.0215 (18)*
S1G0.48922 (7)0.69230 (6)1.1627 (3)0.0366 (6)
O1G0.34698 (14)0.65748 (15)1.0745 (6)0.0250 (12)
O2G0.36663 (15)0.58233 (15)1.1957 (5)0.0272 (13)
O3G0.30482 (16)0.56694 (15)1.2755 (5)0.0303 (14)
N1G0.38671 (17)0.70903 (17)0.8385 (7)0.0225 (15)*
H1G0.40420.72310.76800.034*
H2G0.38990.72670.90780.034*
H3G0.36040.69660.80700.034*
N2G0.34686 (16)0.60675 (16)0.9478 (6)0.0172 (14)*
H4G0.35730.60060.87630.021*
C1G0.3961 (2)0.6773 (2)0.8922 (8)0.0190 (17)*
H11G0.40120.66340.81310.023*
C2G0.4341 (2)0.6986 (2)0.9830 (8)0.0258 (19)*
H21G0.42840.71201.06140.031*
H22G0.45680.72040.92830.031*
C3G0.4478 (2)0.6695 (2)1.0402 (9)0.032 (2)*
H31G0.45640.65860.96180.038*
H32G0.42400.64611.08520.038*
C4G0.5302 (3)0.7288 (3)1.0552 (13)0.059 (3)
H41G0.55520.74371.11070.089*
H42G0.52270.74831.01680.089*
H43G0.53500.71440.97950.089*
C5G0.3600 (2)0.6458 (2)0.9777 (8)0.0194 (17)*
C6G0.3152 (2)0.5736 (2)1.0320 (7)0.0185 (17)*
H61G0.29020.57641.03410.022*
C7G0.3041 (2)0.5319 (2)0.9698 (8)0.0269 (19)*
H71G0.29450.53030.87460.040*
H72G0.28240.51001.02520.040*
H73G0.32840.52870.96990.040*
C8G0.3302 (2)0.5750 (2)1.1805 (8)0.0208 (18)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.030 (3)0.053 (4)0.036 (4)0.027 (3)0.013 (3)0.018 (3)
O2A0.020 (3)0.091 (5)0.039 (4)0.024 (3)0.010 (3)0.027 (4)
O3A0.024 (3)0.037 (3)0.025 (3)0.019 (3)0.003 (3)0.007 (3)
O1B0.071 (5)0.081 (5)0.037 (4)0.063 (4)0.008 (4)0.008 (4)
O2B0.081 (5)0.050 (4)0.072 (5)0.044 (4)0.043 (4)0.016 (4)
O3B0.054 (4)0.033 (3)0.025 (3)0.028 (3)0.006 (3)0.005 (3)
S1B0.0396 (14)0.0586 (17)0.070 (2)0.0191 (13)0.0136 (15)0.0148 (16)
C4B0.066 (8)0.078 (8)0.125 (12)0.042 (7)0.026 (8)0.006 (9)
S1C0.0449 (14)0.0439 (14)0.0554 (17)0.0298 (12)0.0001 (13)0.0101 (13)
O1C0.029 (3)0.028 (3)0.046 (4)0.008 (3)0.010 (3)0.006 (3)
O2C0.064 (4)0.029 (3)0.031 (4)0.019 (3)0.023 (3)0.009 (3)
O3C0.045 (3)0.026 (3)0.023 (3)0.016 (3)0.002 (3)0.002 (3)
C4C0.034 (5)0.068 (7)0.044 (6)0.027 (5)0.004 (5)0.004 (6)
S1D0.0281 (12)0.0357 (13)0.0466 (15)0.0057 (11)0.0023 (12)0.0006 (12)
O1D0.019 (3)0.028 (3)0.024 (3)0.013 (2)0.007 (3)0.003 (3)
O2D0.022 (3)0.049 (4)0.028 (3)0.024 (3)0.006 (3)0.014 (3)
O3D0.025 (3)0.033 (3)0.022 (3)0.018 (3)0.000 (3)0.005 (3)
C4D0.036 (5)0.040 (5)0.056 (7)0.014 (4)0.013 (5)0.013 (5)
S1E0.0378 (13)0.0390 (13)0.0541 (16)0.0233 (11)0.0053 (13)0.0156 (13)
O1E0.028 (3)0.028 (3)0.033 (3)0.012 (3)0.005 (3)0.009 (3)
O2E0.073 (4)0.022 (3)0.037 (4)0.013 (3)0.012 (4)0.003 (3)
O3E0.033 (3)0.022 (3)0.026 (3)0.010 (3)0.005 (3)0.003 (3)
C4E0.029 (5)0.042 (5)0.064 (7)0.017 (4)0.013 (5)0.024 (5)
S1F0.0295 (12)0.0375 (13)0.0462 (16)0.0138 (10)0.0087 (12)0.0020 (12)
O1F0.032 (3)0.029 (3)0.026 (3)0.016 (3)0.009 (3)0.002 (3)
O2F0.029 (3)0.039 (3)0.020 (3)0.023 (3)0.000 (3)0.002 (3)
O3F0.031 (3)0.029 (3)0.021 (3)0.009 (3)0.012 (3)0.002 (3)
C4F0.038 (5)0.054 (6)0.081 (9)0.027 (5)0.009 (6)0.000 (6)
S1G0.0356 (13)0.0321 (12)0.0436 (15)0.0181 (11)0.0097 (12)0.0013 (11)
O1G0.025 (3)0.031 (3)0.022 (3)0.016 (2)0.002 (3)0.008 (3)
O2G0.029 (3)0.028 (3)0.028 (3)0.016 (3)0.005 (3)0.000 (3)
O3G0.033 (3)0.032 (3)0.022 (3)0.014 (3)0.004 (3)0.003 (3)
C4G0.033 (5)0.035 (5)0.099 (9)0.008 (4)0.002 (6)0.022 (6)
Geometric parameters (Å, º) top
O1A—C5A1.237 (9)C4C—H41C0.9800
O2A—C8A1.242 (9)C4C—H42C0.9800
O3A—C8A1.252 (9)C4C—H43C0.9800
N1A—C11A1.489 (7)C6C—C7C1.511 (10)
N2A—C5A1.333 (8)C6C—C8C1.531 (11)
N2A—C6A1.471 (9)C6C—H61C1.0000
C11A—C21A1.5019C7C—H71C0.9800
C11A—C5A1.525 (9)C7C—H72C0.9800
C21A—C31A1.544 (13)C7C—H73C0.9800
C31A—S11A1.815 (12)S1D—C3D1.790 (7)
S11A—C41A1.803 (13)S1D—C4D1.804 (10)
C22A—C32A1.547 (14)O1D—C5D1.240 (8)
C32A—S12A1.806 (12)O2D—C8D1.239 (8)
S12A—C42A1.796 (14)O3D—C8D1.262 (9)
C23A—C33A1.56 (2)N1D—C1D1.488 (8)
C33A—S13A1.777 (18)N2D—C5D1.342 (9)
S13A—C43A1.78 (2)N2D—C6D1.455 (9)
C24A—C34A1.55 (2)C1D—C5D1.529 (10)
C34A—S14A1.796 (19)C1D—C2D1.539 (9)
S14A—C44A1.79 (2)C2D—C3D1.537 (11)
C25A—C35A1.54 (2)C6D—C7D1.533 (10)
C35A—S15A1.79 (2)C6D—C8D1.540 (10)
S15A—C45A1.78 (2)S1E—C3E1.798 (8)
C26A—C36A1.54 (2)S1E—C4E1.806 (9)
C36A—S16A1.79 (2)O1E—C5E1.239 (8)
C6A—C8A1.537 (11)O2E—C8E1.243 (9)
C6A—C7A1.541 (10)O3E—C8E1.263 (9)
O1B—C5B1.244 (9)N1E—C1E1.489 (9)
O2B—C8B1.221 (9)N2E—C5E1.344 (9)
O3B—C8B1.261 (10)N2E—C6E1.442 (9)
N1B—C1B1.480 (9)C1E—C2E1.528 (10)
C1B—C5B1.510 (10)C1E—C5E1.529 (10)
C1B—C2B1.519 (7)C2E—C3E1.514 (10)
C2B—C3B1.536 (10)C6E—C7E1.533 (10)
C3B—S1B1.808 (8)C6E—C8E1.543 (10)
S1B—C4B1.803 (10)S1F—C4F1.820 (9)
C5B—N2B1.334 (9)S1F—C3F1.830 (8)
N2B—C6B1.500 (11)O1F—C5F1.249 (9)
C6B—C8B1.542 (12)O2F—C8F1.254 (8)
C6B—C7B1.563 (18)O3F—C8F1.250 (8)
C62B—C72B1.57 (2)N1F—C1F1.505 (8)
S1C—C3C1.807 (9)N2F—C5F1.324 (9)
S1C—C4C1.815 (9)N2F—C6F1.471 (9)
O1C—C5C1.226 (8)C1F—C2F1.508 (10)
O2C—C8C1.269 (9)C1F—C5F1.517 (10)
O3C—C8C1.246 (10)C2F—C3F1.529 (10)
N1C—C1C1.497 (9)C6F—C8F1.523 (11)
N1C—H1C0.9100C6F—C7F1.525 (10)
N1C—H2C0.9100S1G—C3G1.797 (8)
N1C—H3C0.9100S1G—C4G1.797 (10)
N2C—C5C1.330 (9)O1G—C5G1.235 (8)
N2C—C6C1.474 (9)O2G—C8G1.266 (8)
N2C—H4C0.8800O3G—C8G1.248 (9)
C1C—C5C1.519 (10)N1G—C1G1.497 (8)
C1C—C2C1.538 (10)N2G—C5G1.329 (8)
C1C—H11C1.0000N2G—C6G1.467 (9)
C2C—C3C1.517 (10)C1G—C2G1.522 (10)
C2C—H21C0.9900C1G—C5G1.522 (10)
C2C—H22C0.9900C2G—C3G1.529 (10)
C3C—H31C0.9900C6G—C8G1.532 (11)
C3C—H32C0.9900C6G—C7G1.532 (9)
C5A—N2A—C6A118.8 (6)N2C—C6C—C8C108.6 (6)
N1A—C11A—C21A105.6 (3)C7C—C6C—C8C111.6 (6)
N1A—C11A—C5A105.6 (5)N2C—C6C—H61C108.9
C21A—C11A—C5A116.7 (3)C7C—C6C—H61C108.9
C11A—C21A—C31A112.5 (6)C8C—C6C—H61C108.9
C21A—C31A—S11A116.1 (10)C6C—C7C—H71C109.5
C41A—S11A—C31A98.0 (9)C6C—C7C—H72C109.5
C22A—C32A—S12A115.1 (12)H71C—C7C—H72C109.5
C42A—S12A—C32A99.0 (10)C6C—C7C—H73C109.5
C23A—C33A—S13A117.2 (17)H71C—C7C—H73C109.5
C33A—S13A—C43A102.4 (15)H72C—C7C—H73C109.5
C24A—C34A—S14A119 (2)O3C—C8C—O2C123.9 (8)
C44A—S14A—C34A101.4 (17)O3C—C8C—C6C119.1 (7)
C25A—C35A—S15A120 (2)O2C—C8C—C6C116.9 (8)
C45A—S15A—C35A102.5 (18)C3D—S1D—C4D98.0 (4)
C26A—C36A—S16A119 (2)C5D—N2D—C6D120.7 (6)
O1A—C5A—N2A123.6 (7)N1D—C1D—C5D106.4 (5)
O1A—C5A—C11A118.5 (6)N1D—C1D—C2D113.3 (6)
N2A—C5A—C11A117.8 (6)C5D—C1D—C2D114.1 (6)
N2A—C6A—C8A111.2 (6)C3D—C2D—C1D111.0 (6)
N2A—C6A—C7A111.3 (6)C2D—C3D—S1D111.3 (5)
C8A—C6A—C7A110.7 (6)O1D—C5D—N2D122.6 (7)
O2A—C8A—O3A126.9 (8)O1D—C5D—C1D119.5 (6)
O2A—C8A—C6A118.3 (8)N2D—C5D—C1D117.8 (6)
O3A—C8A—C6A114.7 (7)N2D—C6D—C7D111.5 (6)
N1B—C1B—C5B106.1 (6)N2D—C6D—C8D111.7 (6)
N1B—C1B—C2B111.9 (6)C7D—C6D—C8D109.5 (6)
C5B—C1B—C2B109.1 (6)O2D—C8D—O3D126.5 (7)
C1B—C2B—C3B113.7 (6)O2D—C8D—C6D117.6 (7)
C2B—C3B—S1B117.0 (5)O3D—C8D—C6D115.7 (7)
C4B—S1B—C3B99.2 (5)C3E—S1E—C4E101.4 (4)
O1B—C5B—N2B122.1 (8)C5E—N2E—C6E123.0 (6)
O1B—C5B—C1B119.0 (7)N1E—C1E—C2E111.4 (6)
N2B—C5B—C1B118.8 (7)N1E—C1E—C5E108.4 (6)
C5B—N2B—C6B114.8 (7)C2E—C1E—C5E107.2 (6)
N2B—C6B—C8B109.4 (7)C3E—C2E—C1E114.0 (7)
N2B—C6B—C7B107.3 (11)C2E—C3E—S1E114.9 (6)
C8B—C6B—C7B107.9 (10)O1E—C5E—N2E124.7 (7)
O2B—C8B—O3B125.1 (8)O1E—C5E—C1E120.5 (6)
O2B—C8B—C6B123.8 (9)N2E—C5E—C1E114.7 (6)
O3B—C8B—C6B110.7 (8)N2E—C6E—C7E110.4 (6)
C3C—S1C—C4C102.3 (4)N2E—C6E—C8E108.7 (6)
C1C—N1C—H1C109.5C7E—C6E—C8E110.6 (6)
C1C—N1C—H2C109.5O2E—C8E—O3E125.8 (8)
H1C—N1C—H2C109.5O2E—C8E—C6E117.0 (8)
C1C—N1C—H3C109.5O3E—C8E—C6E117.1 (7)
H1C—N1C—H3C109.5C4F—S1F—C3F100.1 (4)
H2C—N1C—H3C109.5C5F—N2F—C6F119.8 (6)
C5C—N2C—C6C123.4 (6)N1F—C1F—C2F111.1 (6)
C5C—N2C—H4C118.3N1F—C1F—C5F106.5 (5)
C6C—N2C—H4C118.3C2F—C1F—C5F111.1 (6)
N1C—C1C—C5C108.1 (6)C1F—C2F—C3F116.5 (7)
N1C—C1C—C2C110.7 (6)C2F—C3F—S1F115.7 (5)
C5C—C1C—C2C107.4 (6)O1F—C5F—N2F123.4 (7)
N1C—C1C—H11C110.2O1F—C5F—C1F118.9 (6)
C5C—C1C—H11C110.2N2F—C5F—C1F117.6 (7)
C2C—C1C—H11C110.2N2F—C6F—C8F111.6 (6)
C3C—C2C—C1C114.7 (7)N2F—C6F—C7F109.9 (6)
C3C—C2C—H21C108.6C8F—C6F—C7F109.5 (6)
C1C—C2C—H21C108.6O3F—C8F—O2F125.9 (7)
C3C—C2C—H22C108.6O3F—C8F—C6F115.2 (6)
C1C—C2C—H22C108.6O2F—C8F—C6F118.9 (7)
H21C—C2C—H22C107.6C3G—S1G—C4G101.1 (5)
C2C—C3C—S1C112.6 (6)C5G—N2G—C6G121.1 (6)
C2C—C3C—H31C109.1N1G—C1G—C2G108.3 (5)
S1C—C3C—H31C109.1N1G—C1G—C5G109.6 (5)
C2C—C3C—H32C109.1C2G—C1G—C5G109.6 (6)
S1C—C3C—H32C109.1C1G—C2G—C3G113.4 (6)
H31C—C3C—H32C107.8C2G—C3G—S1G114.8 (5)
S1C—C4C—H41C109.5O1G—C5G—N2G124.3 (7)
S1C—C4C—H42C109.5O1G—C5G—C1G119.5 (6)
H41C—C4C—H42C109.5N2G—C5G—C1G116.0 (6)
S1C—C4C—H43C109.5N2G—C6G—C8G111.2 (6)
H41C—C4C—H43C109.5N2G—C6G—C7G110.1 (6)
H42C—C4C—H43C109.5C8G—C6G—C7G108.0 (6)
O1C—C5C—N2C124.9 (7)O3G—C8G—O2G125.6 (7)
O1C—C5C—C1C119.4 (7)O3G—C8G—C6G117.2 (6)
N2C—C5C—C1C115.6 (7)O2G—C8G—C6G117.2 (7)
N2C—C6C—C7C109.8 (6)
N1A—C11A—C21A—C31A65.8 (16)N1D—C1D—C5D—O1D9.4 (8)
C5A—C11A—C21A—C31A51.2 (16)C2D—C1D—C5D—O1D116.2 (7)
C11A—C21A—C31A—S11A175.6 (16)N1D—C1D—C5D—N2D168.5 (6)
C21A—C31A—S11A—C41A154 (2)C2D—C1D—C5D—N2D65.8 (8)
C22A—C32A—S12A—C42A121 (5)C5D—N2D—C6D—C7D88.7 (8)
C23A—C33A—S13A—C43A162 (3)C5D—N2D—C6D—C8D148.4 (6)
C24A—C34A—S14A—C44A166 (4)N2D—C6D—C8D—O2D29.5 (9)
C25A—C35A—S15A—C45A178 (8)C7D—C6D—C8D—O2D94.5 (8)
C6A—N2A—C5A—O1A1.3 (10)N2D—C6D—C8D—O3D153.6 (6)
C6A—N2A—C5A—C11A175.5 (5)C7D—C6D—C8D—O3D82.4 (8)
N1A—C11A—C5A—O1A21.3 (8)N1E—C1E—C2E—C3E67.8 (8)
C21A—C11A—C5A—O1A95.6 (7)C5E—C1E—C2E—C3E173.7 (6)
N1A—C11A—C5A—N2A161.7 (5)C1E—C2E—C3E—S1E175.9 (5)
C21A—C11A—C5A—N2A81.3 (7)C4E—S1E—C3E—C2E74.7 (7)
C5A—N2A—C6A—C8A151.7 (6)C6E—N2E—C5E—O1E5.8 (12)
C5A—N2A—C6A—C7A84.4 (8)C6E—N2E—C5E—C1E172.0 (6)
N2A—C6A—C8A—O2A16.8 (10)N1E—C1E—C5E—O1E33.5 (10)
C7A—C6A—C8A—O2A107.4 (8)C2E—C1E—C5E—O1E86.8 (8)
N2A—C6A—C8A—O3A163.6 (6)N1E—C1E—C5E—N2E148.5 (6)
C7A—C6A—C8A—O3A72.2 (9)C2E—C1E—C5E—N2E91.1 (8)
N1B—C1B—C2B—C3B52.0 (9)C5E—N2E—C6E—C7E120.1 (7)
C5B—C1B—C2B—C3B169.0 (6)C5E—N2E—C6E—C8E118.4 (7)
C1B—C2B—C3B—S1B54.3 (9)N2E—C6E—C8E—O2E59.7 (9)
C2B—C3B—S1B—C4B72.8 (7)C7E—C6E—C8E—O2E61.7 (9)
N1B—C1B—C5B—O1B25.6 (9)N2E—C6E—C8E—O3E122.7 (7)
C2B—C1B—C5B—O1B95.1 (9)C7E—C6E—C8E—O3E115.9 (8)
N1B—C1B—C5B—N2B158.0 (7)N1F—C1F—C2F—C3F48.5 (9)
C2B—C1B—C5B—N2B81.4 (9)C5F—C1F—C2F—C3F166.8 (6)
O1B—C5B—N2B—C6B7.1 (13)C1F—C2F—C3F—S1F55.6 (8)
C1B—C5B—N2B—C6B169.2 (8)C4F—S1F—C3F—C2F69.8 (6)
C5B—N2B—C6B—C8B154.9 (9)C6F—N2F—C5F—O1F4.2 (11)
C5B—N2B—C6B—C7B88.2 (11)C6F—N2F—C5F—C1F177.8 (6)
N2B—C6B—C8B—O2B15.3 (16)N1F—C1F—C5F—O1F51.8 (9)
C7B—C6B—C8B—O2B101.3 (11)C2F—C1F—C5F—O1F69.3 (8)
N2B—C6B—C8B—O3B157.5 (9)N1F—C1F—C5F—N2F130.1 (7)
C7B—C6B—C8B—O3B86.0 (12)C2F—C1F—C5F—N2F108.9 (8)
N1C—C1C—C2C—C3C63.5 (9)C5F—N2F—C6F—C8F79.7 (8)
C5C—C1C—C2C—C3C178.7 (6)C5F—N2F—C6F—C7F158.6 (7)
C1C—C2C—C3C—S1C178.4 (5)N2F—C6F—C8F—O3F148.8 (6)
C4C—S1C—C3C—C2C76.0 (7)C7F—C6F—C8F—O3F89.3 (8)
C6C—N2C—C5C—O1C6.9 (12)N2F—C6F—C8F—O2F32.5 (9)
C6C—N2C—C5C—C1C168.5 (6)C7F—C6F—C8F—O2F89.4 (8)
N1C—C1C—C5C—O1C40.6 (10)N1G—C1G—C2G—C3G177.8 (6)
C2C—C1C—C5C—O1C78.9 (9)C5G—C1G—C2G—C3G62.7 (8)
N1C—C1C—C5C—N2C143.7 (7)C1G—C2G—C3G—S1G173.6 (6)
C2C—C1C—C5C—N2C96.8 (8)C4G—S1G—C3G—C2G65.5 (7)
C5C—N2C—C6C—C7C120.5 (8)C6G—N2G—C5G—O1G0.9 (11)
C5C—N2C—C6C—C8C117.2 (8)C6G—N2G—C5G—C1G173.7 (6)
N2C—C6C—C8C—O3C128.9 (7)N1G—C1G—C5G—O1G54.2 (9)
C7C—C6C—C8C—O3C110.0 (8)C2G—C1G—C5G—O1G64.5 (8)
N2C—C6C—C8C—O2C54.5 (9)N1G—C1G—C5G—N2G131.0 (7)
C7C—C6C—C8C—O2C66.7 (9)C2G—C1G—C5G—N2G110.3 (7)
N1D—C1D—C2D—C3D77.0 (8)C5G—N2G—C6G—C8G63.6 (8)
C5D—C1D—C2D—C3D161.1 (6)C5G—N2G—C6G—C7G176.7 (6)
C1D—C2D—C3D—S1D169.0 (5)N2G—C6G—C8G—O3G141.2 (6)
C4D—S1D—C3D—C2D177.5 (6)C7G—C6G—C8G—O3G97.9 (7)
C6D—N2D—C5D—O1D1.9 (10)N2G—C6G—C8G—O2G41.9 (8)
C6D—N2D—C5D—C1D179.8 (6)C7G—C6G—C8G—O2G79.1 (8)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O3Bi0.911.822.661 (8)153
N1A—H2A···O2Aii0.911.902.761 (8)158
N1A—H3A···O1C0.911.872.728 (8)156
N2A—H4A···O3Biii0.882.203.034 (7)159
N1B—H1B···O3C0.911.902.729 (8)150
N1B—H2B···O2Eiv0.911.912.765 (8)156
N1B—H3B···O1A0.911.882.685 (8)146
N2B—H4B···O3Aii0.882.082.932 (8)162
N1C—H1C···O3Ai0.911.892.742 (8)155
N1C—H2C···O2Biii0.911.832.675 (8)153
N1C—H3C···O1Bi0.911.802.702 (8)169
N2C—H4C···O3E0.881.982.853 (8)172
N1D—H1D···O3Fi0.911.812.702 (8)166
N1D—H2D···O2Gi0.912.142.994 (8)155
N1D—H3D···O1E0.911.912.729 (7)148
N2D—H4D···O3Dv0.882.072.943 (8)170
N1E—H1E···O3Di0.911.862.739 (8)161
N1E—H2E···O2Dv0.911.952.718 (8)141
N1E—H3E···O1Fi0.911.882.775 (8)166
N2E—H4E···O3Ci0.882.022.887 (8)168
N1F—H1F···O3E0.911.842.676 (8)152
N1F—H2F···O2C0.911.872.750 (8)161
N1F—H3F···O1D0.911.942.747 (7)146
N2F—H4F···O2Gi0.882.002.794 (8)150
N1G—H1G···O3Gvi0.911.802.693 (8)165
N1G—H2G···O2Fvii0.911.962.846 (8)165
N1G—H3G···O1Gviii0.911.882.741 (7)156
N2G—H4G···O2F0.881.922.761 (8)161
Symmetry codes: (i) x, y, z1; (ii) y, x+y, z1/6; (iii) xy, x, z5/6; (iv) x, y, z+1; (v) x+1, y+1, z1/2; (vi) y+1, xy+1, z2/3; (vii) y+1, xy+1, z+1/3; (viii) x+y, x+1, z1/3.

Experimental details

Crystal data
Chemical formulaC8H16N2O3S
Mr220.29
Crystal system, space groupHexagonal, P61
Temperature (K)105
a, c (Å)37.6488 (15), 9.6613 (8)
V3)11859.6 (12)
Z42
Radiation typeMo Kα
µ (mm1)0.27
Crystal size (mm)0.80 × 0.18 × 0.15
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.789, 0.960
No. of measured, independent and
observed [I > 2σ(I)] reflections
79465, 7460, 4308
Rint0.195
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.145, 1.03
No. of reflections7460
No. of parameters633
No. of restraints93
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0446P)2 + 18.1456P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.48, 0.35

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXTL (Bruker, 2000), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O3Bi0.911.822.661 (8)153
N1A—H2A···O2Aii0.911.902.761 (8)158
N1A—H3A···O1C0.911.872.728 (8)156
N2A—H4A···O3Biii0.882.203.034 (7)159
N1B—H1B···O3C0.911.902.729 (8)150
N1B—H2B···O2Eiv0.911.912.765 (8)156
N1B—H3B···O1A0.911.882.685 (8)146
N2B—H4B···O3Aii0.882.082.932 (8)162
N1C—H1C···O3Ai0.911.892.742 (8)155
N1C—H2C···O2Biii0.911.832.675 (8)153
N1C—H3C···O1Bi0.911.802.702 (8)169
N2C—H4C···O3E0.881.982.853 (8)172
N1D—H1D···O3Fi0.911.812.702 (8)166
N1D—H2D···O2Gi0.912.142.994 (8)155
N1D—H3D···O1E0.911.912.729 (7)148
N2D—H4D···O3Dv0.882.072.943 (8)170
N1E—H1E···O3Di0.911.862.739 (8)161
N1E—H2E···O2Dv0.911.952.718 (8)141
N1E—H3E···O1Fi0.911.882.775 (8)166
N2E—H4E···O3Ci0.882.022.887 (8)168
N1F—H1F···O3E0.911.842.676 (8)152
N1F—H2F···O2C0.911.872.750 (8)161
N1F—H3F···O1D0.911.942.747 (7)146
N2F—H4F···O2Gi0.882.002.794 (8)150
N1G—H1G···O3Gvi0.911.802.693 (8)165
N1G—H2G···O2Fvii0.911.962.846 (8)165
N1G—H3G···O1Gviii0.911.882.741 (7)156
N2G—H4G···O2F0.881.922.761 (8)161
Symmetry codes: (i) x, y, z1; (ii) y, x+y, z1/6; (iii) xy, x, z5/6; (iv) x, y, z+1; (v) x+1, y+1, z1/2; (vi) y+1, xy+1, z2/3; (vii) y+1, xy+1, z+1/3; (viii) x+y, x+1, z1/3.
Torsion angles for molecules A-G of MA top
MoleculeN1-C1-C5-N2C1-C5-N2-C6C5-N2-C6-C8N2-C6-C8-O2N1-C1-C2-C3C1-C2-C3-S1C2-C3-S1-C4Occupancy
(ψ1)(ω1)(ϕ2)(ψT)(a)(χ11)(χ12)(χ13)
A1161.7 (5)175.5 (5)-151.7 (6)-16.8 (10)65.8 (16)-175.6 (16)154 (2)0.285 (9)
A2161.7 (5)175.5 (5)-151.7 (6)-16.8 (10)35 (6)162 (3)121 (5)0.190 (8)
A3161.7 (5)175.5 (5)-151.7 (6)-16.8 (10)-83 (3)-147 (3)-162 (4)0.229 (7)
A4161.7 (5)175.5 (5)-151.7 (6)-16.8 (10)-78 (4)-50 (6)165 (4)0.142 (6)
A5161.7 (5)175.5 (5)-151.7 (6)-16.8 (10)-49 (5)-60 (6)154 (2)0.101 (5)
A6161.7 (5)175.5 (5)-151.7 (6)-16.8 (10)-50 (14)-135 (8)(b)0.051 (5)
B (major)158.0 (7)169.2 (8)-154.9 (9)-15.3 (16)-52.0 (9)-54.3 (9)-72.8 (7)0.609 (18)
B (minor)158.0 (7)-167.8 (11)-133.1 (11)-59.0 (17)-52.0 (9)-54.3 (9)-72.8 (7)0.391 (18)
C143.7 (7)168.5 (6)-117.2 (8)-54.5 (9)-63.5 (9)178.4 (5)-76.0 (7)1.0
D168.5 (6)-179.8 (6)-148.4 (6)-29.5 (9)-77.0 (8)-169.0 (5)177.5 (6)1.0
E148.5 (6)172.0 (6)-118.4 (4)-59.7 (9)-67.8 (8)-175.9 (5)-74.7 (7)1.0
F130.1 (7)-177.8 (6)-79.7 (8)-32.5 (9)-48.5 (9)-55.6 (8)-69.8 (6)1.0
G131.0 (7)173.7 (6)-63.6 (8)-41.9 (8)-177.8 (6)-173.6 (6)-65.5 (7)1.0
(a) Measured to the O atom giving the smallest positive or negative value. (b) C atom not located.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds