L-Me­thionyl-L-alanine-2-propanol (1/2)

The crystal structure of the title compound, C₈H₁₆N₂O₃S·2C₃H₈O, is divided into hydro­phobic and hydro­philic layers. Two peptide mol­ecules in the asymmetric unit are related by pseudo-translational symmetry along the a axis, as are two of the four 2-propanol mol­ecules. The last two 2-propanol mol­ecules in the asymmetric unit have different relative orientations and hydrogen-bond interactions.

S1. Comment

Like several other dipeptides with two hydrophobic residues (Görbitz, 1999a,b, and references therein), the crystal structure of the title compound, (I), is divided into hydrophobic and hydrophilic layers, but the specific molecular arrangement is different from those observed previously. The two dipeptide molecules A and B in the asymmetric unit are stacked in an alternating sequence along the a axis with pseudo-translational symmetry. The geometries of the L-Met residues of A an B are almost identical, and both side chains are in the trans,trans,gauche- conformation for χ¹, χ² and χ³. The general pseudo-translational symmetry along the a axis includes the two 2-propanol solvent molecules C and F, but not D and E which have different orientations.

As expected, two of the three amino H atoms of each peptide molecule are engaged in hydrogen bonding in the hydrophilic layers, while 2-propanol molecules C and F, which are very similarly embedded in the hydrophobic layers, serve the important roles as acceptors for the remaining amino H atoms. The 2-propanol molecules C, D and F are donors in O—H···O—H interactions, but molecule E is unique in donating its hydroxylic H atom to a carboxylate group. The acceptor atom, O2B, is made available through a rotation of the carboxylate group compared with peptide molecule A, with N2—C6—C8—O2 = 11.5 (6)° compared to −13.2 (7)° for A. Unlike O2A, O2B can then no longer accept an amino H atom, which is instead accepted by O3B.

The unit cell for the thin needle-shaped crystals also obtained in the crystallization experiments has a = b = 14.2459 (12) Å, c = 9.7152 (11) Å, α = β = 90° and γ = 120°. An unambiguous determination of the space group was not possible, but we suspect that the structure is closely related to the hexagonal P6₁ structures of L-Val-L-Ala (Görbitz & Gundersen, 1996), L-Val-L-Val and L-Ala-L-Ile (Görbitz, 2000).

S2. Experimental

Crystals of the title compound were prepared by vapour diffusion of 2-propanol into 30 µl of an aqueous solution of the dipeptide. At low initial solute concentration (0.16–0.32 mg in 30 µl of water), bundles of exceedingly thin needles were formed which were too small for collection of X-ray data (<0.01 mm), but permitted determination of the unit cell. A second polymorph in the shape of ultrathin plates appeared (together with the needles) when higher concentrations were used. The plates are soft and easily bent, and can not be cut without inflicting substantial damage. They furthermore decay within a few s when exposed to air. The specimen used for data collection was obtained from a test tube containing 0.64 mg of the peptide, and was transferred to a drop of oil before being attached to the glass rod.

Thin plates were also obtained with 1-propanol as precipitating agent, but no unit cell was found for any of the crystals tested. 2-Butanol, on the other hand, gave very thin needles, while methanol and ethanol failed to give precipitates in the diffusion experiments.

S3. Refinement

The data collection nominally covered over a hemisphere of reciprocal space by a combination of three sets of exposures with the detector set at 2θ = 29° and a 4.95 cm crystal-to-detector distance.

Displacement ellipsoids for the solvent molecule are quite large, and for molecules C, E and F the disorder has been resolved into a major and a minor position, with occupancies 0.68 (2):0.32 (2), 0.896 (13):0.104 (13) and 0.806 (7):0.194 (7), respectively. For C and E, the disorder arises from a rotation around the O1—C2 bond, while for F, O1 and C2 are also shifted to alternative positions.

Heavy atoms were refined anisotropically, except for the O and C atoms of the least populated positions of the disordered 2-propanol molecules C, E and F, which were refined isotropically (C) or assigned U_iso values equivalent to U_eq for the corresponding atom in the most populated position. A mild SHELXTL (Sheldrick, 1997) SAME constraint (s1 = 0.006 and s2 = 0.009) was used for the geometry of the two peptide molecules, and similar commands (s1 = 0.008 and s2 = 0.012) for the geometry of all 2-propanol molecules. H atoms were placed geometrically and refined with a riding model which included free rotation for amino groups and methyl groups with occupancy greater than 0.5. Hydroxylic H atoms were constrained to have tetrahedral geometry and rotated so as to minimize the distance to the closest acceptor, but with deviations from perfect staggered positions not exceeding 30°. U_iso values were constrained to be 1.2U_eq of the carrier atom, or 1.5U_eq for methyl, hydroxyl and amino groups.

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 1997).

L-Methionyl-L-alanine 2-propanol solvate

Crystal data

C8H16N2O3S·2C3H8O	F(000) = 744
Mr = 340.48	Dx = 1.118 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 9.9277 (2) Å	Cell parameters from 4393 reflections
b = 16.4556 (3) Å	θ = 2–25°
c = 12.4895 (2) Å	µ = 0.18 mm^−1
β = 97.594 (1)°	T = 150 K
V = 2022.47 (6) Å^3	Plate, colourless
Z = 4	0.80 × 0.48 × 0.01 mm

Data collection

Siemens SMART CCD diffractometer	6911 independent reflections
Radiation source: fine-focus sealed tube	4437 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.093
Detector resolution: 8.3 pixels mm^-1	θmax = 25.0°, θmin = 2.1°
Sets of exposures each taken over 0.3° ω rotation scans	h = −11→11
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −19→19
Tmin = 0.865, Tmax = 0.998	l = −14→14
14839 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.078	w = 1/[σ^2(Fo^2) + (0.040P)^2 + 1.5P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.202	(Δ/σ)max = 0.014
S = 1.01	Δρmax = 0.53 e Å^−3
6911 reflections	Δρmin = −0.30 e Å^−3
448 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
198 restraints	Extinction coefficient: 0.0070 (16)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 3230 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.01 (16)

Special details

Refinement. Flack parameter calculated from merging of 3230 Friedel pairs

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1A	0.2282 (2)	0.17232 (14)	0.84163 (16)	0.0915 (6)
O1A	−0.0601 (3)	0.1049 (2)	0.4775 (4)	0.0619 (11)
O2A	0.2888 (3)	−0.0977 (2)	0.5129 (4)	0.0611 (11)
O3A	0.1201 (3)	−0.18671 (18)	0.5102 (4)	0.0618 (11)
N1A	0.1041 (4)	0.2411 (2)	0.4313 (3)	0.0439 (10)
H1A	0.1704	0.2791	0.4301	0.066*
H2A	0.0297	0.2645	0.4540	0.066*
H3A	0.0813	0.2204	0.3638	0.066*
N2A	0.1305 (3)	0.02973 (19)	0.4767 (3)	0.0426 (10)
H4A	0.2193	0.0313	0.4783	0.051*
C1A	0.1548 (4)	0.1741 (2)	0.5073 (4)	0.0432 (12)
H11A	0.2500	0.1600	0.4965	0.052*
C2A	0.1533 (5)	0.2042 (3)	0.6219 (4)	0.0480 (12)
H21A	0.0582	0.2105	0.6363	0.058*
H22A	0.1980	0.2580	0.6305	0.058*
C3A	0.2290 (7)	0.1430 (3)	0.7041 (5)	0.0744 (18)
H31A	0.3243	0.1379	0.6897	0.089*
H32A	0.1857	0.0890	0.6927	0.089*
C4A	0.3376 (8)	0.2583 (5)	0.8515 (6)	0.097 (2)
H41A	0.3473	0.2797	0.9253	0.145*
H42A	0.2990	0.3003	0.8010	0.145*
H43A	0.4270	0.2422	0.8335	0.145*
C5A	0.0644 (4)	0.0993 (2)	0.4851 (4)	0.0420 (12)
C6A	0.0628 (4)	−0.0490 (2)	0.4651 (4)	0.0474 (13)
H61A	−0.0095	−0.0504	0.5136	0.057*
C7A	−0.0025 (6)	−0.0630 (3)	0.3503 (5)	0.0719 (18)
H71A	−0.0611	−0.0167	0.3264	0.108*
H72A	−0.0572	−0.1127	0.3469	0.108*
H73A	0.0683	−0.0686	0.3030	0.108*
C8A	0.1668 (4)	−0.1154 (2)	0.5006 (4)	0.0490 (13)
S1B	0.2703 (2)	0.66958 (15)	0.16478 (17)	0.0916 (6)
O1B	0.5559 (3)	0.6103 (2)	0.5374 (3)	0.0586 (11)
O2B	0.2226 (3)	0.4381 (2)	0.4017 (3)	0.0586 (10)
O3B	0.3336 (3)	0.33245 (18)	0.4827 (3)	0.0549 (10)
N1B	0.4242 (4)	0.7599 (2)	0.5637 (3)	0.0458 (11)
H1B	0.3760	0.8066	0.5499	0.069*
H2B	0.5095	0.7667	0.5459	0.069*
H3B	0.4294	0.7476	0.6352	0.069*
N2B	0.3525 (3)	0.54732 (19)	0.5299 (4)	0.0470 (11)
H4B	0.2641	0.5542	0.5260	0.056*
C1B	0.3547 (4)	0.6919 (2)	0.4980 (4)	0.0440 (13)
H11B	0.2590	0.6867	0.5140	0.053*
C2B	0.3545 (5)	0.7129 (3)	0.3797 (4)	0.0520 (13)
H21B	0.4487	0.7114	0.3619	0.062*
H22B	0.3190	0.7687	0.3660	0.062*
C3B	0.2648 (6)	0.6517 (3)	0.3058 (5)	0.0714 (17)
H31B	0.1696	0.6560	0.3207	0.086*
H32B	0.2965	0.5957	0.3239	0.086*
C4B	0.1806 (9)	0.7636 (5)	0.1482 (7)	0.118 (3)
H41B	0.1719	0.7803	0.0722	0.177*
H42B	0.2306	0.8053	0.1932	0.177*
H43B	0.0899	0.7569	0.1699	0.177*
C5B	0.4308 (4)	0.6124 (2)	0.5257 (4)	0.0437 (13)
C6B	0.4068 (4)	0.4650 (2)	0.5406 (4)	0.0481 (14)
H61B	0.4965	0.4652	0.5124	0.058*
C7B	0.4315 (6)	0.4376 (3)	0.6569 (5)	0.0687 (17)
H71B	0.5002	0.4725	0.6973	0.103*
H72B	0.4636	0.3812	0.6601	0.103*
H73B	0.3466	0.4411	0.6887	0.103*
C8B	0.3124 (4)	0.4089 (2)	0.4687 (4)	0.0448 (12)
O1C	0.4489 (5)	0.7337 (3)	0.7847 (4)	0.0997 (17)	0.677 (18)
H1C	0.4850	0.7703	0.8272	0.150*
C1C	0.2379 (11)	0.6617 (11)	0.7601 (11)	0.135 (6)	0.677 (18)
H11C	0.2754	0.6147	0.7259	0.203*	0.677 (18)
H12C	0.2070	0.7023	0.7048	0.203*	0.677 (18)
H13C	0.1610	0.6443	0.7962	0.203*	0.677 (18)
C2C	0.3459 (9)	0.6983 (7)	0.8417 (9)	0.090 (7)	0.677 (18)
H21C	0.3056	0.7407	0.8853	0.108*	0.677 (18)
C3C	0.4142 (15)	0.6342 (8)	0.9137 (11)	0.123 (6)	0.677 (18)
H31C	0.4580	0.5950	0.8704	0.185*	0.677 (18)
H32C	0.3467	0.6063	0.9510	0.185*	0.677 (18)
H33C	0.4830	0.6593	0.9671	0.185*	0.677 (18)
O12C	0.4489 (5)	0.7337 (3)	0.7847 (4)	0.0997 (17)	0.323 (18)
C12C	0.2162 (14)	0.7400 (19)	0.807 (3)	0.156 (16)*	0.323 (18)
H14C	0.2148	0.7991	0.8159	0.234*	0.323 (18)
H15C	0.1451	0.7153	0.8435	0.234*	0.323 (18)
H16C	0.1998	0.7268	0.7295	0.234*	0.323 (18)
C22C	0.3523 (15)	0.7074 (12)	0.8542 (14)	0.108 (19)*	0.323 (18)
H22C	0.3780	0.7290	0.9289	0.130*	0.323 (18)
C32C	0.352 (3)	0.6171 (12)	0.855 (3)	0.131 (13)*	0.323 (18)
H34C	0.4441	0.5971	0.8778	0.196*	0.323 (18)
H35C	0.3191	0.5968	0.7827	0.196*	0.323 (18)
H36C	0.2916	0.5978	0.9060	0.196*	0.323 (18)
O1D	0.5978 (4)	−0.1430 (2)	0.8885 (3)	0.0759 (12)
H1D	0.6699	−0.1342	0.8604	0.114*
C1D	0.4878 (8)	−0.0328 (5)	0.7862 (6)	0.115 (3)
H11D	0.5651	−0.0176	0.7491	0.172*
H12D	0.4297	0.0148	0.7915	0.172*
H13D	0.4353	−0.0757	0.7453	0.172*
C2D	0.5387 (7)	−0.0632 (4)	0.8970 (6)	0.093 (2)
H21D	0.6106	−0.0253	0.9313	0.111*
C3D	0.4306 (8)	−0.0697 (6)	0.9676 (7)	0.123 (3)
H31D	0.4719	−0.0784	1.0424	0.184*
H32D	0.3712	−0.1157	0.9441	0.184*
H33D	0.3771	−0.0195	0.9629	0.184*
O1E	0.1652 (4)	0.3782 (2)	0.2026 (3)	0.0696 (11)	0.896 (13)
H1E	0.1821	0.3987	0.2654	0.104*
C1E	−0.0471 (9)	0.4478 (8)	0.1984 (10)	0.144 (5)	0.896 (13)
H11E	−0.0260	0.4860	0.2584	0.216*	0.896 (13)
H12E	−0.0750	0.3956	0.2263	0.216*	0.896 (13)
H13E	−0.1212	0.4697	0.1468	0.216*	0.896 (13)
C2E	0.0755 (8)	0.4357 (5)	0.1434 (6)	0.098 (3)	0.896 (13)
H21E	0.1239	0.4888	0.1409	0.117*	0.896 (13)
C3E	0.0437 (11)	0.4037 (6)	0.0316 (6)	0.122 (4)	0.896 (13)
H31E	0.1134	0.4219	−0.0118	0.182*	0.896 (13)
H32E	−0.0453	0.4239	−0.0006	0.182*	0.896 (13)
H33E	0.0422	0.3442	0.0336	0.182*	0.896 (13)
O12E	0.1652 (4)	0.3782 (2)	0.2026 (3)	0.0696 (11)	0.104 (13)
C12E	−0.003 (7)	0.482 (4)	0.209 (9)	0.140*	0.104 (13)
H14E	0.0663	0.5228	0.2324	0.210*	0.104 (13)
H15E	−0.0300	0.4543	0.2724	0.210*	0.104 (13)
H16E	−0.0820	0.5077	0.1681	0.210*	0.104 (13)
C22E	0.055 (4)	0.420 (3)	0.139 (4)	0.096*	0.104 (13)
H22E	0.0903	0.4488	0.0774	0.115*	0.104 (13)
C32E	−0.048 (5)	0.359 (5)	0.096 (7)	0.120*	0.104 (13)
H34E	−0.0067	0.3204	0.0501	0.180*	0.104 (13)
H35E	−0.1246	0.3863	0.0533	0.180*	0.104 (13)
H36E	−0.0797	0.3299	0.1562	0.180*	0.104 (13)
O1F	0.1040 (7)	0.2156 (3)	0.2105 (5)	0.090 (2)	0.806 (7)
H1F	0.0939	0.2593	0.1742	0.136*	0.806 (7)
C1F	0.0579 (10)	0.1151 (7)	0.0724 (9)	0.119 (4)	0.806 (7)
H11F	−0.0019	0.1537	0.0294	0.178*	0.806 (7)
H12F	0.0049	0.0833	0.1183	0.178*	0.806 (7)
H13F	0.0992	0.0785	0.0240	0.178*	0.806 (7)
C2F	0.1679 (7)	0.1609 (5)	0.1421 (6)	0.077 (3)	0.806 (7)
H21F	0.2253	0.1919	0.0962	0.116*	0.806 (7)
C3F	0.2533 (13)	0.1028 (7)	0.2137 (10)	0.146 (5)	0.806 (7)
H31F	0.3318	0.1317	0.2518	0.219*	0.806 (7)
H32F	0.2850	0.0592	0.1699	0.219*	0.806 (7)
H33F	0.1992	0.0796	0.2664	0.219*	0.806 (7)
O12F	0.228 (3)	0.1562 (15)	0.2713 (19)	0.092*	0.194 (7)
H2F	0.3021	0.1328	0.2963	0.138*	0.194 (7)
C12F	0.259 (5)	0.055 (2)	0.140 (3)	0.120*	0.194 (7)
H34F	0.3538	0.0481	0.1724	0.180*	0.194 (7)
H35F	0.2513	0.0436	0.0623	0.180*	0.194 (7)
H36F	0.2010	0.0175	0.1739	0.180*	0.194 (7)
C22F	0.215 (3)	0.1408 (16)	0.1567 (19)	0.080*	0.194 (7)
H22F	0.2736	0.1794	0.1217	0.120*	0.194 (7)
C32F	0.070 (5)	0.154 (3)	0.113 (4)	0.150*	0.194 (7)
H37F	0.0445	0.2101	0.1250	0.225*	0.194 (7)
H38F	0.0127	0.1170	0.1489	0.225*	0.194 (7)
H39F	0.0570	0.1424	0.0349	0.225*	0.194 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1A	0.1140 (15)	0.1014 (13)	0.0610 (12)	−0.0102 (11)	0.0188 (11)	0.0088 (10)
O1A	0.0345 (18)	0.0431 (16)	0.109 (4)	−0.0002 (14)	0.011 (2)	−0.002 (2)
O2A	0.0407 (19)	0.0439 (17)	0.099 (3)	−0.0004 (14)	0.011 (2)	0.0034 (19)
O3A	0.047 (2)	0.0397 (17)	0.102 (3)	−0.0004 (14)	0.022 (2)	0.0054 (19)
N1A	0.041 (2)	0.0417 (19)	0.050 (3)	−0.0014 (16)	0.009 (2)	−0.0027 (18)
N2A	0.0286 (18)	0.0379 (19)	0.062 (3)	0.0023 (15)	0.0075 (19)	0.0002 (19)
C1A	0.030 (2)	0.039 (2)	0.061 (4)	0.0011 (18)	0.009 (2)	0.003 (2)
C2A	0.051 (3)	0.046 (2)	0.045 (4)	0.001 (2)	0.003 (3)	0.001 (2)
C3A	0.088 (4)	0.060 (3)	0.077 (5)	−0.004 (3)	0.018 (4)	0.000 (3)
C4A	0.116 (6)	0.108 (5)	0.064 (6)	−0.010 (5)	0.005 (5)	−0.011 (4)
C5A	0.030 (2)	0.040 (2)	0.056 (4)	0.0013 (18)	0.006 (2)	−0.002 (2)
C6A	0.036 (2)	0.038 (2)	0.069 (4)	−0.0021 (18)	0.010 (3)	0.002 (2)
C7A	0.063 (3)	0.056 (3)	0.091 (5)	−0.007 (3)	−0.012 (3)	0.005 (3)
C8A	0.039 (3)	0.043 (2)	0.068 (4)	−0.0029 (19)	0.015 (3)	0.002 (2)
S1B	0.1044 (14)	0.1030 (13)	0.0684 (13)	0.0003 (11)	0.0158 (11)	−0.0068 (11)
O1B	0.0354 (18)	0.0421 (16)	0.098 (3)	0.0005 (14)	0.0091 (19)	0.0030 (19)
O2B	0.050 (2)	0.0557 (19)	0.068 (3)	0.0024 (16)	−0.001 (2)	−0.0111 (18)
O3B	0.0479 (19)	0.0415 (18)	0.077 (3)	−0.0033 (14)	0.0141 (19)	−0.0047 (17)
N1B	0.042 (2)	0.0383 (19)	0.057 (3)	−0.0043 (15)	0.008 (2)	−0.0017 (19)
N2B	0.0316 (19)	0.0384 (19)	0.070 (3)	−0.0002 (15)	0.004 (2)	−0.0010 (19)
C1B	0.029 (2)	0.042 (2)	0.061 (4)	−0.0045 (17)	0.005 (2)	−0.006 (2)
C2B	0.046 (3)	0.050 (3)	0.057 (4)	−0.001 (2)	0.000 (3)	0.001 (3)
C3B	0.081 (4)	0.065 (3)	0.070 (5)	−0.004 (3)	0.019 (4)	−0.006 (3)
C4B	0.143 (7)	0.118 (6)	0.085 (7)	0.021 (6)	−0.017 (6)	0.023 (5)
C5B	0.033 (2)	0.033 (2)	0.065 (4)	0.0003 (18)	0.007 (2)	0.001 (2)
C6B	0.034 (2)	0.035 (2)	0.073 (4)	0.0008 (18)	0.000 (3)	−0.004 (2)
C7B	0.080 (4)	0.058 (3)	0.065 (5)	0.009 (3)	−0.002 (3)	−0.002 (3)
C8B	0.032 (2)	0.049 (2)	0.055 (4)	0.0028 (19)	0.010 (2)	−0.005 (2)
O1C	0.140 (4)	0.104 (4)	0.060 (3)	−0.049 (3)	0.031 (3)	−0.010 (3)
C1C	0.107 (8)	0.175 (11)	0.129 (10)	−0.031 (7)	0.038 (7)	0.003 (8)
C2C	0.117 (11)	0.090 (9)	0.073 (9)	−0.014 (5)	0.049 (7)	−0.021 (6)
C3C	0.148 (9)	0.139 (9)	0.086 (8)	−0.004 (7)	0.026 (7)	0.016 (7)
O12C	0.140 (4)	0.104 (4)	0.060 (3)	−0.049 (3)	0.031 (3)	−0.010 (3)
O1D	0.094 (3)	0.076 (2)	0.057 (3)	0.000 (2)	0.006 (2)	0.003 (2)
C1D	0.116 (7)	0.114 (7)	0.110 (8)	0.033 (5)	−0.004 (6)	0.019 (6)
C2D	0.102 (5)	0.080 (4)	0.092 (6)	0.010 (4)	−0.002 (5)	−0.017 (4)
C3D	0.135 (7)	0.140 (8)	0.101 (8)	0.007 (6)	0.044 (6)	−0.011 (6)
O1E	0.073 (2)	0.065 (2)	0.065 (3)	0.0094 (19)	−0.014 (2)	−0.009 (2)
C1E	0.116 (7)	0.161 (8)	0.151 (8)	0.049 (6)	−0.001 (6)	0.001 (7)
C2E	0.098 (6)	0.096 (6)	0.085 (7)	0.029 (5)	−0.036 (5)	−0.013 (5)
C3E	0.136 (7)	0.125 (7)	0.085 (7)	0.025 (6)	−0.053 (5)	−0.016 (5)
O12E	0.073 (2)	0.065 (2)	0.065 (3)	0.0094 (19)	−0.014 (2)	−0.009 (2)
O1F	0.150 (6)	0.067 (3)	0.061 (4)	−0.012 (3)	0.040 (4)	−0.015 (3)
C1F	0.108 (6)	0.141 (7)	0.106 (7)	−0.016 (6)	0.008 (6)	−0.026 (6)
C2F	0.086 (7)	0.086 (6)	0.064 (6)	−0.007 (5)	0.023 (5)	−0.007 (5)
C3F	0.161 (8)	0.160 (8)	0.119 (8)	0.048 (7)	0.028 (7)	0.010 (7)

Geometric parameters (Å, º)

S1A—C4A	1.778 (7)	C3C—H31C	0.9800
S1A—C3A	1.785 (6)	C3C—H32C	0.9800
O1A—C5A	1.230 (4)	C3C—H33C	0.9800
O2A—C8A	1.236 (4)	C12C—C22C	1.501 (9)
O3A—C8A	1.274 (4)	C12C—H14C	0.9800
N1A—C1A	1.497 (5)	C12C—H15C	0.9800
N1A—H1A	0.9100	C12C—H16C	0.9800
N1A—H2A	0.9100	C22C—C32C	1.487 (9)
N1A—H3A	0.9100	C22C—H22C	1.0000
N2A—C5A	1.331 (4)	C32C—H34C	0.9800
N2A—C6A	1.458 (5)	C32C—H35C	0.9800
N2A—H4A	0.8800	C32C—H36C	0.9800
C1A—C2A	1.516 (6)	O1D—C2D	1.449 (6)
C1A—C5A	1.527 (5)	O1D—H1D	0.8504
C1A—H11A	1.0000	C1D—C2D	1.495 (7)
C2A—C3A	1.559 (6)	C1D—H11D	0.9800
C2A—H21A	0.9900	C1D—H12D	0.9800
C2A—H22A	0.9900	C1D—H13D	0.9800
C3A—H31A	0.9900	C2D—C3D	1.480 (8)
C3A—H32A	0.9900	C2D—H21D	1.0000
C4A—H41A	0.9800	C3D—H31D	0.9800
C4A—H42A	0.9800	C3D—H32D	0.9800
C4A—H43A	0.9800	C3D—H33D	0.9800
C6A—C7A	1.511 (7)	O1E—C2E	1.436 (6)
C6A—C8A	1.527 (5)	O1E—H1E	0.8502
C6A—H61A	1.0000	C1E—C2E	1.488 (8)
C7A—H71A	0.9800	C1E—H11E	0.9800
C7A—H72A	0.9800	C1E—H12E	0.9800
C7A—H73A	0.9800	C1E—H13E	0.9800
S1B—C4B	1.784 (7)	C2E—C3E	1.486 (8)
S1B—C3B	1.794 (6)	C2E—H21E	1.0000
O1B—C5B	1.232 (4)	C3E—H31E	0.9800
O2B—C8B	1.237 (5)	C3E—H32E	0.9800
O3B—C8B	1.284 (4)	C3E—H33E	0.9800
N1B—C1B	1.500 (5)	C12E—C22E	1.498 (9)
N1B—H1B	0.9100	C12E—H14E	0.9800
N1B—H2B	0.9100	C12E—H15E	0.9800
N1B—H3B	0.9100	C12E—H16E	0.9800
N2B—C5B	1.329 (4)	C22E—C32E	1.486 (9)
N2B—C6B	1.457 (4)	C22E—H22E	1.0000
N2B—H4B	0.8800	C32E—H34E	0.9800
C1B—C2B	1.517 (6)	C32E—H35E	0.9800
C1B—C5B	1.527 (5)	C32E—H36E	0.9800
C1B—H11B	1.0000	O1F—C2F	1.445 (6)
C2B—C3B	1.562 (6)	O1F—H1F	0.8491
C2B—H21B	0.9900	C1F—C2F	1.505 (8)
C2B—H22B	0.9900	C1F—H11F	0.9800
C3B—H31B	0.9900	C1F—H12F	0.9800
C3B—H32B	0.9900	C1F—H13F	0.9800
C4B—H41B	0.9800	C2F—C3F	1.493 (8)
C4B—H42B	0.9800	C2F—H21F	1.0000
C4B—H43B	0.9800	C3F—H31F	0.9800
C6B—C7B	1.510 (7)	C3F—H32F	0.9800
C6B—C8B	1.521 (5)	C3F—H33F	0.9800
C6B—H61B	1.0000	C3F—H2F	1.1882
C7B—H71B	0.9800	O12F—C22F	1.442 (8)
C7B—H72B	0.9800	O12F—H2F	0.8497
C7B—H73B	0.9800	C12F—C22F	1.500 (9)
O1C—C2C	1.443 (6)	C12F—H34F	0.9800
O1C—H1C	0.8511	C12F—H35F	0.9800
C1C—C2C	1.504 (9)	C12F—H36F	0.9800
C1C—H11C	0.9800	C22F—C32F	1.487 (9)
C1C—H12C	0.9800	C22F—H22F	1.0000
C1C—H13C	0.9800	C32F—H37F	0.9800
C2C—C3C	1.490 (9)	C32F—H38F	0.9800
C2C—H21C	1.0000	C32F—H39F	0.9800
C4A—S1A—C3A	101.6 (3)	H71B—C7B—H73B	109.5
C1A—N1A—H1A	109.5	H72B—C7B—H73B	109.5
C1A—N1A—H2A	109.5	O2B—C8B—O3B	124.2 (4)
H1A—N1A—H2A	109.5	O2B—C8B—C6B	119.8 (4)
C1A—N1A—H3A	109.5	O3B—C8B—C6B	116.0 (4)
H1A—N1A—H3A	109.5	C2C—O1C—H1C	104.2
H2A—N1A—H3A	109.5	O1C—C2C—C3C	106.7 (7)
C5A—N2A—C6A	123.2 (3)	O1C—C2C—C1C	108.4 (7)
C5A—N2A—H4A	118.4	C3C—C2C—C1C	110.7 (8)
C6A—N2A—H4A	118.4	O1C—C2C—H21C	110.3
N1A—C1A—C2A	108.2 (3)	C3C—C2C—H21C	110.3
N1A—C1A—C5A	109.7 (3)	C1C—C2C—H21C	110.3
C2A—C1A—C5A	110.8 (4)	C22C—C12C—H14C	109.5
N1A—C1A—H11A	109.3	C22C—C12C—H15C	109.5
C2A—C1A—H11A	109.3	H14C—C12C—H15C	109.5
C5A—C1A—H11A	109.3	C22C—C12C—H16C	109.5
C1A—C2A—C3A	110.3 (4)	H14C—C12C—H16C	109.5
C1A—C2A—H21A	109.6	H15C—C12C—H16C	109.5
C3A—C2A—H21A	109.6	C32C—C22C—C12C	110.8 (9)
C1A—C2A—H22A	109.6	C32C—C22C—H22C	110.3
C3A—C2A—H22A	109.6	C12C—C22C—H22C	110.4
H21A—C2A—H22A	108.1	C22C—C32C—H34C	109.5
C2A—C3A—S1A	113.4 (4)	C22C—C32C—H35C	109.5
C2A—C3A—H31A	108.9	H34C—C32C—H35C	109.5
S1A—C3A—H31A	108.9	C22C—C32C—H36C	109.5
C2A—C3A—H32A	108.9	H34C—C32C—H36C	109.5
S1A—C3A—H32A	108.9	H35C—C32C—H36C	109.5
H31A—C3A—H32A	107.7	C2D—O1D—H1D	104.3
S1A—C4A—H41A	109.5	C2D—C1D—H11D	109.5
S1A—C4A—H42A	109.5	C2D—C1D—H12D	109.5
H41A—C4A—H42A	109.5	H11D—C1D—H12D	109.5
S1A—C4A—H43A	109.5	C2D—C1D—H13D	109.5
H41A—C4A—H43A	109.5	H11D—C1D—H13D	109.5
H42A—C4A—H43A	109.5	H12D—C1D—H13D	109.5
O1A—C5A—N2A	124.0 (3)	O1D—C2D—C3D	108.1 (6)
O1A—C5A—C1A	120.9 (3)	O1D—C2D—C1D	109.0 (5)
N2A—C5A—C1A	115.1 (3)	C3D—C2D—C1D	113.1 (6)
N2A—C6A—C7A	111.4 (4)	O1D—C2D—H21D	108.9
N2A—C6A—C8A	108.8 (3)	C3D—C2D—H21D	108.9
C7A—C6A—C8A	110.8 (4)	C1D—C2D—H21D	108.9
N2A—C6A—H61A	108.6	C2D—C3D—H31D	109.5
C7A—C6A—H61A	108.6	C2D—C3D—H32D	109.5
C8A—C6A—H61A	108.6	H31D—C3D—H32D	109.5
C6A—C7A—H71A	109.5	C2D—C3D—H33D	109.5
C6A—C7A—H72A	109.5	H31D—C3D—H33D	109.5
H71A—C7A—H72A	109.5	H32D—C3D—H33D	109.5
C6A—C7A—H73A	109.5	C2E—O1E—H1E	104.3
H71A—C7A—H73A	109.5	O1E—C2E—C3E	106.8 (5)
H72A—C7A—H73A	109.5	O1E—C2E—C1E	109.9 (6)
O2A—C8A—O3A	124.6 (4)	C3E—C2E—C1E	113.3 (7)
O2A—C8A—C6A	118.8 (3)	O1E—C2E—H21E	108.9
O3A—C8A—C6A	116.5 (3)	C3E—C2E—H21E	108.9
C4B—S1B—C3B	100.2 (3)	C1E—C2E—H21E	108.9
C1B—N1B—H1B	109.5	C22E—C12E—H14E	109.5
C1B—N1B—H2B	109.5	C22E—C12E—H15E	109.5
H1B—N1B—H2B	109.5	H14E—C12E—H15E	109.5
C1B—N1B—H3B	109.5	C22E—C12E—H16E	109.5
H1B—N1B—H3B	109.5	H14E—C12E—H16E	109.5
H2B—N1B—H3B	109.5	H15E—C12E—H16E	109.5
C5B—N2B—C6B	122.8 (3)	C32E—C22E—C12E	111.7 (10)
C5B—N2B—H4B	118.6	C32E—C22E—H22E	109.5
C6B—N2B—H4B	118.6	C12E—C22E—H22E	109.5
N1B—C1B—C2B	107.8 (3)	C22E—C32E—H34E	109.5
N1B—C1B—C5B	109.6 (3)	C22E—C32E—H35E	109.5
C2B—C1B—C5B	110.6 (4)	H34E—C32E—H35E	109.5
N1B—C1B—H11B	109.6	C22E—C32E—H36E	109.4
C2B—C1B—H11B	109.6	H34E—C32E—H36E	109.5
C5B—C1B—H11B	109.6	H35E—C32E—H36E	109.5
C1B—C2B—C3B	110.9 (4)	C2F—O1F—H1F	104.1
C1B—C2B—H21B	109.5	O1F—C2F—C3F	107.7 (6)
C3B—C2B—H21B	109.5	O1F—C2F—C1F	108.2 (6)
C1B—C2B—H22B	109.5	C3F—C2F—C1F	109.7 (7)
C3B—C2B—H22B	109.5	O1F—C2F—H21F	110.4
H21B—C2B—H22B	108.1	C3F—C2F—H21F	110.4
C2B—C3B—S1B	112.7 (4)	C1F—C2F—H21F	110.4
C2B—C3B—H31B	109.1	C2F—C3F—H2F	112.9
S1B—C3B—H31B	109.1	H31F—C3F—H2F	33.9
C2B—C3B—H32B	109.1	H32F—C3F—H2F	131.7
S1B—C3B—H32B	109.1	H33F—C3F—H2F	77.0
H31B—C3B—H32B	107.8	C22F—O12F—H2F	104.3
S1B—C4B—H41B	109.5	C22F—C12F—H34F	109.5
S1B—C4B—H42B	109.5	C22F—C12F—H35F	109.5
H41B—C4B—H42B	109.5	H34F—C12F—H35F	109.5
S1B—C4B—H43B	109.5	C22F—C12F—H36F	109.5
H41B—C4B—H43B	109.5	H34F—C12F—H36F	109.5
H42B—C4B—H43B	109.5	H35F—C12F—H36F	109.5
O1B—C5B—N2B	123.9 (3)	O12F—C22F—C32F	107.4 (9)
O1B—C5B—C1B	120.8 (3)	O12F—C22F—C12F	108.3 (9)
N2B—C5B—C1B	115.2 (3)	C32F—C22F—C12F	111.6 (10)
N2B—C6B—C7B	112.2 (4)	O12F—C22F—H22F	109.8
N2B—C6B—C8B	108.6 (3)	C32F—C22F—H22F	109.8
C7B—C6B—C8B	113.3 (4)	C12F—C22F—H22F	109.8
N2B—C6B—H61B	107.5	C22F—C32F—H37F	109.5
C7B—C6B—H61B	107.5	C22F—C32F—H38F	109.5
C8B—C6B—H61B	107.5	H37F—C32F—H38F	109.5
C6B—C7B—H71B	109.5	C22F—C32F—H39F	109.5
C6B—C7B—H72B	109.5	H37F—C32F—H39F	109.5
H71B—C7B—H72B	109.5	H38F—C32F—H39F	109.5
C6B—C7B—H73B	109.5
N1A—C1A—C2A—C3A	−169.9 (4)	N1B—C1B—C2B—C3B	−171.4 (4)
C5A—C1A—C2A—C3A	69.7 (5)	C5B—C1B—C2B—C3B	68.7 (5)
C1A—C2A—C3A—S1A	−178.4 (4)	C1B—C2B—C3B—S1B	−176.0 (4)
C4A—S1A—C3A—C2A	−69.8 (5)	C4B—S1B—C3B—C2B	−69.3 (5)
C6A—N2A—C5A—O1A	−4.5 (8)	C6B—N2B—C5B—O1B	−4.9 (9)
C6A—N2A—C5A—C1A	174.5 (4)	C6B—N2B—C5B—C1B	171.5 (4)
N1A—C1A—C5A—O1A	−49.2 (6)	N1B—C1B—C5B—O1B	−42.1 (6)
C2A—C1A—C5A—O1A	70.3 (6)	C2B—C1B—C5B—O1B	76.6 (6)
N1A—C1A—C5A—N2A	131.8 (4)	N1B—C1B—C5B—N2B	141.3 (4)
C2A—C1A—C5A—N2A	−108.7 (5)	C2B—C1B—C5B—N2B	−99.9 (5)
C5A—N2A—C6A—C7A	79.1 (6)	C5B—N2B—C6B—C7B	93.9 (6)
C5A—N2A—C6A—C8A	−158.5 (5)	C5B—N2B—C6B—C8B	−140.1 (5)
N2A—C6A—C8A—O2A	−13.2 (7)	N2B—C6B—C8B—O2B	11.5 (6)
C7A—C6A—C8A—O2A	109.5 (5)	C7B—C6B—C8B—O2B	136.9 (5)
N2A—C6A—C8A—O3A	170.1 (5)	N2B—C6B—C8B—O3B	−168.7 (4)
C7A—C6A—C8A—O3A	−67.1 (6)	C7B—C6B—C8B—O3B	−43.4 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O3B	0.91	1.88	2.734 (5)	155
N1A—H2A···O3A^i	0.91	1.80	2.706 (5)	176
N1A—H3A···O1F	0.91	1.96	2.790 (7)	151
N2A—H4A···O1B^ii	0.88	2.61	3.410 (5)	151
C1A—H11B···O1B^ii	1.00	2.18	3.176 (5)	171
N1B—H1B···O2A^iii	0.91	1.83	2.735 (5)	175
N1B—H2B···O3B^iv	0.91	1.97	2.813 (5)	153
N1B—H3B···O1C	0.91	1.87	2.772 (6)	174
N2B—H4B···O1A^i	0.88	2.19	3.044 (5)	165
C1B—H11A···O1A^i	1.00	2.40	3.307 (5)	150
O1C—H1C···O1D^iii	0.85	1.91	2.734 (6)	163
O1D—H1D···O1E^ii	0.85	1.92	2.768 (6)	176
O1E—H1E···O2B	0.85	1.82	2.666 (5)	177
O1F—H1F···O1E	0.85	2.09	2.748 (7)	133

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