Supramolecular assembling using synthons with NH-CO(S)-CS-NH and NH-CO-CO-NH functionalities: crystal structures of (S,S)-N,N'-monothiooxalyldileucine methyl ester and its dithio analogue

To compare the structural properties of oxalamide and thiooxalamide groups in the formation of hydrogen bonds suitable for supramolecular assemblies a series of retropeptides was studied. Some of them, having oxalamide bridges, are gelators of organic solvents and water. However, retropeptides with oxygen replaced by the sp² sulfur have not exhibited such properties. The crystal structures of the two title compounds are homostructural, i.e. they have similar packing arrangements. The monothio compound crystallizes in the orthorhombic space group P2₁2₁2₁ with two molecules in the asymmetric unit arranged in a hydrogen-bond network with an approximate 4₁ axis along the crystallographic b axis. However, the dithio and dioxo analogues crystallize in the tetragonal space group P4₁ with similar packing patterns and hydrogen-bonding systems arranged in agreement with a crystallographic 4₁ axis. Thus, these two analogues are isostructural having closely related hydrogen-bonding patterns in spite of the different size and polarity of oxygen and sulfur which serve as the proton acceptors.

Computing details

Data collection: CAD-4 EXPRESS (Enraf Nonius, 1994) for (I); Collect (Nonius BV, 1997-2000) for (II). Cell refinement: CAD-4 EXPRESS (Enraf Nonius, 1994) for (I); HKL SCALEPACK (Otwinowski & Minor 1997) for (II). Data reduction: XCAD4 (Harms & Wocadlo, 1995) for (I); HKL DENZO and SCALEPACK (Otwinowski & Minor 1997) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997). Software used to prepare material for publication: PLATON (Spek, 1990) for (I); WinGX publication routines (Farrugia, 1999) for (II).

Figures

(I) N,N'-monotiooxalyl-bis(L-leucine methyl ester)

Crystal data

C16H28N2O5S	F(000) = 1552
Mr = 360.46	Dx = 1.119 Mg m^−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54128 Å
Hall symbol: P 2ac 2ab	Cell parameters from 20 reflections
a = 12.562 (9) Å	θ = 9–19°
b = 16.156 (5) Å	µ = 1.55 mm^−1
c = 21.086 (8) Å	T = 293 K
V = 4279 (4) Å^3	Prism, yellow
Z = 8	0.4 × 0.2 × 0.15 mm

Data collection

Enraf Nonius CAD4 diffractometer	Rint = 0.035
non–profiled ω/2θ scans	θmax = 76.4°, θmin = 3.5°
Absorption correction: ψ scan North A.C.T., Phillips D.C. & Mathews F.S. (1968) Acta. Cryst. A24, 351 Number of ψ scan sets used was 7 Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied.	h = 0→15
Tmin = 0.752, Tmax = 0.791	k = 0→20
9699 measured reflections	l = −26→26
8972 independent reflections	3 standard reflections every 120 min
4033 reflections with I > 2σ(I)	intensity decay: 5%

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0634P)^2 + 0.8826P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.060	(Δ/σ)max = 0.002
wR(F^2) = 0.174	Δρmax = 0.24 e Å^−3
S = 1.01	Δρmin = −0.16 e Å^−3
8972 reflections	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
433 parameters	Absolute structure parameter: −0.01 (3)
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
S11	0.97619 (12)	0.33587 (8)	0.31144 (6)	0.0933 (4)
O1	0.8294 (3)	0.54782 (19)	0.30879 (13)	0.0828 (9)
O2	0.6739 (3)	0.3967 (3)	0.1880 (2)	0.1227 (14)
O3	0.6221 (3)	0.5235 (3)	0.16328 (18)	0.1195 (13)
O21	0.8128 (4)	0.4070 (3)	0.4880 (2)	0.1411 (16)
O31	0.9370 (4)	0.3190 (3)	0.5193 (2)	0.1386 (16)
N1	0.8671 (3)	0.4609 (2)	0.22801 (16)	0.0703 (10)
H1	0.9031	0.4184	0.2161	0.084*
N11	0.9405 (3)	0.4588 (2)	0.38999 (16)	0.0786 (11)
H11	0.9164	0.508	0.3957	0.094*
C1	0.8703 (3)	0.4839 (3)	0.2881 (2)	0.0602 (10)
C2	0.8042 (4)	0.5057 (3)	0.1815 (2)	0.0741 (12)
H2	0.7985	0.5638	0.1943	0.089*
C3	0.6939 (4)	0.4676 (4)	0.1787 (2)	0.0856 (14)
C4	0.5132 (5)	0.4929 (5)	0.1574 (4)	0.159 (3)
H41	0.467	0.5378	0.1459	0.238*
H42	0.4907	0.47	0.1972	0.238*
H43	0.5105	0.4509	0.1253	0.238*
C5	0.8534 (4)	0.5005 (3)	0.1158 (2)	0.0837 (14)
H51	0.8658	0.4427	0.1058	0.1*
H52	0.8023	0.5216	0.0853	0.1*
C6	0.9563 (5)	0.5469 (4)	0.1076 (3)	0.1129 (19)
H6	1.0055	0.5292	0.141	0.135*
C7	1.0055 (7)	0.5247 (6)	0.0431 (4)	0.189 (4)
H71	1.0713	0.5542	0.0378	0.284*
H72	0.9572	0.5399	0.0098	0.284*
H73	1.0188	0.4663	0.0414	0.284*
C8	0.9416 (6)	0.6393 (4)	0.1128 (4)	0.176 (3)
H81	1.0092	0.6663	0.1077	0.264*
H82	0.9129	0.6525	0.1538	0.264*
H83	0.8936	0.6578	0.0804	0.264*
C11	0.9317 (3)	0.4263 (2)	0.3326 (2)	0.0618 (11)
C21	0.9881 (4)	0.4170 (3)	0.4440 (2)	0.0828 (13)
H21	1.0324	0.3716	0.428	0.099*
C31	0.9021 (6)	0.3804 (4)	0.4848 (3)	0.0954 (16)
C41	0.8611 (7)	0.2828 (5)	0.5639 (4)	0.180 (4)
H411	0.8948	0.2385	0.5867	0.271*
H412	0.8009	0.2617	0.541	0.271*
H413	0.8379	0.3244	0.5933	0.271*
C51	1.0583 (5)	0.4747 (3)	0.4818 (2)	0.1011 (17)
H511	1.0866	0.4444	0.5178	0.121*
H512	1.0143	0.519	0.4985	0.121*
C61	1.1511 (6)	0.5134 (5)	0.4463 (3)	0.131 (2)
H61	1.1218	0.5419	0.4091	0.157*
C71	1.2049 (8)	0.5783 (5)	0.4875 (5)	0.202 (4)
H711	1.1527	0.6169	0.5026	0.303*
H712	1.2575	0.6072	0.4629	0.303*
H713	1.2387	0.5518	0.5229	0.303*
C81	1.2280 (7)	0.4490 (7)	0.4226 (4)	0.187 (4)
H811	1.1903	0.4089	0.3976	0.281*
H812	1.2611	0.422	0.458	0.281*
H813	1.2815	0.4751	0.397	0.281*
S13	0.88969 (11)	0.09017 (8)	0.23114 (8)	0.1045 (5)
O12	0.9117 (2)	0.30274 (19)	0.14608 (15)	0.0815 (9)
O22	1.0976 (4)	0.1287 (2)	0.05469 (16)	0.1258 (15)
O23	0.6028 (5)	0.1787 (5)	0.1320 (3)	0.195 (3)
O32	1.2046 (5)	0.2287 (3)	0.0290 (2)	0.172 (2)
O33	0.5314 (4)	0.0995 (3)	0.2026 (3)	0.180 (2)
N12	1.0372 (3)	0.2054 (2)	0.16303 (16)	0.0692 (10)
H12	1.0516	0.1607	0.1835	0.083*
N13	0.7671 (3)	0.2173 (2)	0.20851 (18)	0.0823 (11)
H13	0.7611	0.2668	0.1939	0.099*
C12	0.9395 (4)	0.2359 (3)	0.16768 (19)	0.0646 (11)
C13	0.8603 (4)	0.1819 (3)	0.20357 (19)	0.0663 (11)
C22	1.1200 (3)	0.2424 (3)	0.1260 (2)	0.0715 (12)
H22	1.0976	0.2983	0.1139	0.086*
C23	0.6733 (4)	0.1806 (3)	0.2364 (3)	0.0937 (15)
H23	0.6951	0.132	0.261	0.112*
C32	1.1375 (5)	0.1926 (3)	0.0667 (2)	0.0937 (16)
C33	0.5988 (6)	0.1522 (5)	0.1837 (5)	0.128 (2)
C42	1.2292 (9)	0.1851 (6)	−0.0306 (4)	0.238 (6)
H421	1.2794	0.217	−0.0547	0.356*
H422	1.1651	0.1781	−0.0547	0.356*
H423	1.2591	0.1319	−0.0211	0.356*
C43	0.4556 (7)	0.0778 (7)	0.1509 (6)	0.267 (7)
H431	0.4045	0.0385	0.1665	0.4*
H432	0.494	0.054	0.116	0.4*
H433	0.4193	0.1268	0.137	0.4*
C52	1.2238 (4)	0.2486 (3)	0.1633 (3)	0.0893 (15)
H521	1.2409	0.1942	0.1797	0.107*
H522	1.28	0.2641	0.1341	0.107*
C53	0.6160 (4)	0.2404 (4)	0.2807 (3)	0.1057 (17)
H531	0.5936	0.2883	0.2564	0.127*
H532	0.5524	0.2136	0.2967	0.127*
C62	1.2244 (5)	0.3078 (5)	0.2167 (3)	0.124 (2)
H62	1.1626	0.2961	0.2436	0.149*
C63	0.6815 (5)	0.2698 (5)	0.3364 (3)	0.129 (2)
H63	0.7482	0.2919	0.3192	0.155*
C72	1.3251 (6)	0.2984 (6)	0.2569 (4)	0.195 (4)
H721	1.3236	0.3378	0.291	0.292*
H722	1.3866	0.3081	0.231	0.292*
H723	1.3281	0.2434	0.2741	0.292*
C73	0.6222 (7)	0.3424 (6)	0.3678 (4)	0.203 (4)
H731	0.6619	0.3614	0.4039	0.304*
H732	0.553	0.3242	0.3813	0.304*
H733	0.6145	0.3867	0.3379	0.304*
C82	1.2170 (7)	0.3956 (4)	0.1945 (4)	0.184 (4)
H821	1.2172	0.4319	0.2306	0.275*
H822	1.1522	0.4031	0.171	0.275*
H823	1.2767	0.4081	0.1678	0.275*
C83	0.7104 (7)	0.2020 (7)	0.3817 (4)	0.188 (4)
H831	0.751	0.2247	0.4162	0.281*
H832	0.752	0.161	0.3601	0.281*
H833	0.6467	0.1771	0.398	0.281*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S11	0.1154 (10)	0.0755 (8)	0.0890 (8)	0.0199 (8)	−0.0116 (8)	−0.0128 (7)
O1	0.112 (2)	0.0697 (18)	0.0671 (17)	0.0213 (18)	−0.0075 (18)	−0.0096 (16)
O2	0.088 (2)	0.102 (3)	0.178 (4)	−0.007 (2)	−0.017 (3)	0.019 (3)
O3	0.100 (3)	0.128 (3)	0.130 (3)	0.023 (3)	−0.020 (2)	0.030 (3)
O21	0.129 (4)	0.163 (4)	0.132 (3)	0.024 (3)	0.017 (3)	0.046 (3)
O31	0.154 (4)	0.119 (3)	0.143 (4)	0.010 (3)	−0.013 (3)	0.055 (3)
N1	0.083 (3)	0.065 (2)	0.063 (2)	0.0101 (19)	−0.004 (2)	−0.0099 (19)
N11	0.107 (3)	0.065 (2)	0.063 (2)	0.018 (2)	−0.011 (2)	−0.0063 (19)
C1	0.058 (3)	0.058 (3)	0.064 (3)	−0.005 (2)	0.002 (2)	0.002 (2)
C2	0.088 (3)	0.067 (3)	0.067 (3)	0.010 (3)	−0.007 (3)	0.002 (2)
C3	0.092 (4)	0.096 (4)	0.069 (3)	0.005 (4)	−0.009 (3)	0.011 (3)
C4	0.084 (4)	0.220 (8)	0.172 (6)	0.015 (5)	−0.041 (4)	0.013 (6)
C5	0.102 (4)	0.077 (3)	0.072 (3)	−0.004 (3)	−0.003 (3)	0.004 (2)
C6	0.092 (4)	0.138 (5)	0.109 (4)	−0.010 (4)	0.015 (3)	0.000 (4)
C7	0.170 (7)	0.238 (9)	0.159 (7)	−0.027 (7)	0.078 (6)	−0.001 (7)
C8	0.173 (7)	0.103 (5)	0.251 (10)	−0.057 (5)	0.017 (7)	0.010 (5)
C11	0.061 (3)	0.057 (2)	0.067 (3)	−0.010 (2)	0.003 (2)	0.002 (2)
C21	0.097 (4)	0.081 (3)	0.070 (3)	0.020 (3)	−0.012 (3)	0.002 (3)
C31	0.108 (5)	0.096 (4)	0.082 (4)	0.011 (4)	0.001 (4)	0.014 (3)
C41	0.182 (8)	0.173 (7)	0.186 (7)	−0.030 (6)	0.001 (6)	0.106 (6)
C51	0.123 (5)	0.096 (4)	0.085 (3)	0.001 (4)	−0.031 (4)	0.007 (3)
C61	0.128 (6)	0.152 (6)	0.112 (5)	−0.018 (5)	−0.035 (5)	0.014 (5)
C71	0.194 (8)	0.174 (7)	0.239 (10)	−0.067 (7)	−0.079 (8)	0.002 (7)
C81	0.127 (6)	0.263 (11)	0.172 (7)	−0.012 (7)	0.006 (6)	−0.030 (8)
S13	0.0988 (10)	0.0828 (9)	0.1318 (11)	0.0093 (8)	0.0268 (9)	0.0293 (8)
O12	0.082 (2)	0.070 (2)	0.093 (2)	0.0120 (17)	0.0012 (17)	0.0160 (17)
O22	0.212 (5)	0.092 (3)	0.073 (2)	−0.039 (3)	0.010 (3)	−0.003 (2)
O23	0.156 (5)	0.268 (7)	0.163 (5)	−0.072 (5)	−0.028 (5)	−0.017 (5)
O32	0.241 (6)	0.128 (3)	0.148 (4)	−0.060 (4)	0.116 (4)	−0.036 (3)
O33	0.123 (4)	0.191 (5)	0.227 (6)	−0.076 (4)	0.020 (4)	−0.046 (5)
N12	0.070 (2)	0.066 (2)	0.072 (2)	0.005 (2)	0.009 (2)	0.0116 (17)
N13	0.069 (3)	0.080 (2)	0.099 (3)	0.001 (2)	0.006 (2)	0.012 (2)
C12	0.071 (3)	0.062 (3)	0.060 (3)	0.003 (2)	−0.002 (2)	−0.004 (2)
C13	0.065 (3)	0.073 (3)	0.061 (3)	0.000 (2)	−0.004 (2)	0.000 (2)
C22	0.071 (3)	0.062 (3)	0.082 (3)	−0.003 (2)	0.009 (3)	0.000 (2)
C23	0.070 (3)	0.098 (4)	0.113 (4)	−0.007 (3)	0.010 (3)	0.009 (3)
C32	0.131 (5)	0.066 (3)	0.084 (4)	−0.012 (3)	0.024 (3)	−0.001 (3)
C33	0.089 (5)	0.135 (6)	0.162 (7)	−0.022 (4)	0.023 (6)	−0.025 (6)
C42	0.381 (15)	0.191 (8)	0.142 (6)	−0.056 (9)	0.165 (8)	−0.057 (6)
C43	0.151 (8)	0.267 (12)	0.383 (16)	−0.033 (8)	−0.023 (10)	−0.175 (13)
C52	0.073 (3)	0.080 (3)	0.114 (4)	0.002 (3)	0.015 (3)	0.004 (3)
C53	0.081 (4)	0.112 (4)	0.124 (4)	−0.008 (3)	0.029 (4)	0.000 (4)
C62	0.091 (4)	0.176 (7)	0.107 (4)	0.001 (4)	0.000 (4)	−0.039 (5)
C63	0.091 (4)	0.166 (6)	0.130 (6)	−0.034 (5)	0.010 (4)	−0.029 (5)
C72	0.148 (6)	0.262 (10)	0.175 (7)	−0.040 (7)	−0.066 (6)	−0.022 (7)
C73	0.187 (8)	0.203 (8)	0.218 (9)	−0.026 (8)	0.043 (7)	−0.104 (7)
C82	0.183 (7)	0.100 (5)	0.268 (10)	0.023 (5)	−0.078 (7)	−0.083 (6)
C83	0.175 (8)	0.253 (11)	0.135 (6)	0.002 (8)	−0.020 (6)	0.025 (7)

Geometric parameters (Å, º)

S11—C11	1.627 (4)	S13—C13	1.634 (4)
O1—C1	1.233 (5)	O12—C12	1.223 (5)
O2—C3	1.189 (6)	O22—C32	1.175 (6)
O3—C3	1.318 (6)	O23—C33	1.174 (8)
O3—C4	1.459 (7)	O32—C32	1.297 (6)
O21—C31	1.203 (6)	O32—C42	1.472 (7)
O31—C31	1.305 (6)	O33—C33	1.264 (8)
O31—C41	1.461 (8)	O33—C43	1.489 (10)
N1—C1	1.322 (5)	N12—C12	1.326 (5)
N1—C2	1.452 (5)	N12—C22	1.431 (5)
N1—H1	0.86	N12—H12	0.86
N11—C11	1.324 (5)	N13—C13	1.307 (5)
N11—C21	1.452 (5)	N13—C23	1.445 (6)
N11—H11	0.86	N13—H13	0.86
C1—C11	1.529 (6)	C12—C13	1.525 (6)
C2—C3	1.517 (7)	C22—C32	1.505 (7)
C2—C5	1.520 (6)	C22—C52	1.525 (6)
C2—H2	0.98	C22—H22	0.98
C4—H41	0.96	C23—C33	1.524 (10)
C4—H42	0.96	C23—C53	1.524 (7)
C4—H43	0.96	C23—H23	0.98
C5—C6	1.505 (7)	C42—H421	0.96
C5—H51	0.97	C42—H422	0.96
C5—H52	0.97	C42—H423	0.96
C6—C8	1.507 (9)	C43—H431	0.96
C6—C7	1.536 (8)	C43—H432	0.96
C6—H6	0.98	C43—H433	0.96
C7—H71	0.96	C52—C62	1.477 (7)
C7—H72	0.96	C52—H521	0.97
C7—H73	0.96	C52—H522	0.97
C8—H81	0.96	C53—C63	1.509 (8)
C8—H82	0.96	C53—H531	0.97
C8—H83	0.96	C53—H532	0.97
C21—C31	1.504 (7)	C62—C82	1.497 (9)
C21—C51	1.512 (7)	C62—C72	1.531 (9)
C21—H21	0.98	C62—H62	0.98
C41—H411	0.96	C63—C83	1.498 (10)
C41—H412	0.96	C63—C73	1.540 (9)
C41—H413	0.96	C63—H63	0.98
C51—C61	1.519 (8)	C72—H721	0.96
C51—H511	0.97	C72—H722	0.96
C51—H512	0.97	C72—H723	0.96
C61—C81	1.505 (9)	C73—H731	0.96
C61—C71	1.520 (9)	C73—H732	0.96
C61—H61	0.98	C73—H733	0.96
C71—H711	0.96	C82—H821	0.96
C71—H712	0.96	C82—H822	0.96
C71—H713	0.96	C82—H823	0.96
C81—H811	0.96	C83—H831	0.96
C81—H812	0.96	C83—H832	0.96
C81—H813	0.96	C83—H833	0.96
C3—O3—C4	115.5 (5)	C32—O32—C42	116.3 (5)
C31—O31—C41	116.3 (5)	C33—O33—C43	110.9 (8)
C1—N1—C2	121.6 (4)	C12—N12—C22	123.9 (4)
C1—N1—H1	119.2	C12—N12—H12	118.1
C2—N1—H1	119.2	C22—N12—H12	118.1
C11—N11—C21	124.6 (4)	C13—N13—C23	125.7 (4)
C11—N11—H11	117.7	C13—N13—H13	117.2
C21—N11—H11	117.7	C23—N13—H13	117.2
O1—C1—N1	124.2 (4)	O12—C12—N12	124.4 (4)
O1—C1—C11	120.2 (4)	O12—C12—C13	120.2 (4)
N1—C1—C11	115.6 (4)	N12—C12—C13	115.3 (4)
N1—C2—C3	108.7 (4)	N13—C13—C12	111.9 (4)
N1—C2—C5	111.5 (4)	N13—C13—S13	124.8 (3)
C3—C2—C5	108.2 (4)	C12—C13—S13	123.2 (3)
N1—C2—H2	109.4	N12—C22—C32	109.6 (4)
C3—C2—H2	109.4	N12—C22—C52	111.6 (4)
C5—C2—H2	109.4	C32—C22—C52	109.8 (4)
O2—C3—O3	123.8 (5)	N12—C22—H22	108.6
O2—C3—C2	125.3 (5)	C32—C22—H22	108.6
O3—C3—C2	110.9 (5)	C52—C22—H22	108.6
O3—C4—H41	109.5	N13—C23—C33	109.1 (5)
O3—C4—H42	109.5	N13—C23—C53	112.0 (4)
H41—C4—H42	109.5	C33—C23—C53	110.4 (5)
O3—C4—H43	109.5	N13—C23—H23	108.4
H41—C4—H43	109.5	C33—C23—H23	108.4
H42—C4—H43	109.5	C53—C23—H23	108.4
C6—C5—C2	115.2 (4)	O22—C32—O32	122.7 (5)
C6—C5—H51	108.5	O22—C32—C22	125.9 (5)
C2—C5—H51	108.5	O32—C32—C22	111.3 (5)
C6—C5—H52	108.5	O23—C33—O33	124.5 (9)
C2—C5—H52	108.5	O23—C33—C23	122.8 (7)
H51—C5—H52	107.5	O33—C33—C23	112.7 (8)
C8—C6—C5	112.3 (5)	O32—C42—H421	109.5
C8—C6—C7	110.2 (6)	O32—C42—H422	109.5
C5—C6—C7	109.3 (5)	H421—C42—H422	109.5
C8—C6—H6	108.3	O32—C42—H423	109.5
C5—C6—H6	108.3	H421—C42—H423	109.5
C7—C6—H6	108.3	H422—C42—H423	109.5
C6—C7—H71	109.5	O33—C43—H431	109.5
C6—C7—H72	109.5	O33—C43—H432	109.5
H71—C7—H72	109.5	H431—C43—H432	109.5
C6—C7—H73	109.5	O33—C43—H433	109.5
H71—C7—H73	109.5	H431—C43—H433	109.5
H72—C7—H73	109.5	H432—C43—H433	109.5
C6—C8—H81	109.5	C62—C52—C22	116.1 (4)
C6—C8—H82	109.5	C62—C52—H521	108.3
H81—C8—H82	109.5	C22—C52—H521	108.3
C6—C8—H83	109.5	C62—C52—H522	108.3
H81—C8—H83	109.5	C22—C52—H522	108.3
H82—C8—H83	109.5	H521—C52—H522	107.4
N11—C11—C1	111.2 (3)	C63—C53—C23	114.7 (5)
N11—C11—S11	125.3 (3)	C63—C53—H531	108.6
C1—C11—S11	123.5 (3)	C23—C53—H531	108.6
N11—C21—C31	109.6 (4)	C63—C53—H532	108.6
N11—C21—C51	111.5 (4)	C23—C53—H532	108.6
C31—C21—C51	111.1 (4)	H531—C53—H532	107.6
N11—C21—H21	108.2	C52—C62—C82	112.0 (6)
C31—C21—H21	108.2	C52—C62—C72	111.3 (6)
C51—C21—H21	108.2	C82—C62—C72	108.5 (7)
O21—C31—O31	123.6 (6)	C52—C62—H62	108.3
O21—C31—C21	124.2 (5)	C82—C62—H62	108.3
O31—C31—C21	112.1 (5)	C72—C62—H62	108.3
O31—C41—H411	109.5	C83—C63—C53	113.5 (6)
O31—C41—H412	109.5	C83—C63—C73	113.5 (7)
H411—C41—H412	109.5	C53—C63—C73	108.1 (7)
O31—C41—H413	109.5	C83—C63—H63	107.1
H411—C41—H413	109.5	C53—C63—H63	107.1
H412—C41—H413	109.5	C73—C63—H63	107.1
C21—C51—C61	116.1 (5)	C62—C72—H721	109.5
C21—C51—H511	108.3	C62—C72—H722	109.5
C61—C51—H511	108.3	H721—C72—H722	109.5
C21—C51—H512	108.3	C62—C72—H723	109.5
C61—C51—H512	108.3	H721—C72—H723	109.5
H511—C51—H512	107.4	H722—C72—H723	109.5
C81—C61—C51	111.9 (6)	C63—C73—H731	109.5
C81—C61—C71	112.4 (7)	C63—C73—H732	109.5
C51—C61—C71	110.1 (7)	H731—C73—H732	109.5
C81—C61—H61	107.4	C63—C73—H733	109.5
C51—C61—H61	107.4	H731—C73—H733	109.5
C71—C61—H61	107.4	H732—C73—H733	109.5
C61—C71—H711	109.5	C62—C82—H821	109.5
C61—C71—H712	109.5	C62—C82—H822	109.5
H711—C71—H712	109.5	H821—C82—H822	109.5
C61—C71—H713	109.5	C62—C82—H823	109.5
H711—C71—H713	109.5	H821—C82—H823	109.5
H712—C71—H713	109.5	H822—C82—H823	109.5
C61—C81—H811	109.5	C63—C83—H831	109.5
C61—C81—H812	109.5	C63—C83—H832	109.5
H811—C81—H812	109.5	H831—C83—H832	109.5
C61—C81—H813	109.5	C63—C83—H833	109.5
H811—C81—H813	109.5	H831—C83—H833	109.5
H812—C81—H813	109.5	H832—C83—H833	109.5
C2—N1—C1—O1	−6.6 (6)	C22—N12—C12—O12	−7.2 (7)
C2—N1—C1—C11	174.7 (3)	C22—N12—C12—C13	173.6 (4)
C1—N1—C2—C3	−90.8 (5)	C23—N13—C13—C12	176.2 (4)
C1—N1—C2—C5	149.9 (4)	C23—N13—C13—S13	−2.9 (7)
C4—O3—C3—O2	−0.6 (8)	O12—C12—C13—N13	−1.9 (6)
C4—O3—C3—C2	178.3 (5)	N12—C12—C13—N13	177.4 (4)
N1—C2—C3—O2	−31.1 (7)	O12—C12—C13—S13	177.2 (3)
C5—C2—C3—O2	90.2 (6)	N12—C12—C13—S13	−3.5 (5)
N1—C2—C3—O3	150.0 (4)	C12—N12—C22—C32	−105.5 (5)
C5—C2—C3—O3	−88.6 (5)	C12—N12—C22—C52	132.6 (4)
N1—C2—C5—C6	−69.2 (5)	C13—N13—C23—C33	−102.7 (6)
C3—C2—C5—C6	171.2 (5)	C13—N13—C23—C53	134.8 (5)
C2—C5—C6—C8	−66.5 (7)	C42—O32—C32—O22	−0.2 (11)
C2—C5—C6—C7	170.8 (5)	C42—O32—C32—C22	179.3 (7)
C21—N11—C11—C1	175.7 (4)	N12—C22—C32—O22	−6.9 (8)
C21—N11—C11—S11	−2.5 (6)	C52—C22—C32—O22	116.1 (7)
O1—C1—C11—N11	−5.6 (5)	N12—C22—C32—O32	173.6 (5)
N1—C1—C11—N11	173.1 (4)	C52—C22—C32—O32	−63.4 (6)
O1—C1—C11—S11	172.5 (3)	C43—O33—C33—O23	−1.9 (12)
N1—C1—C11—S11	−8.7 (5)	C43—O33—C33—C23	176.1 (6)
C11—N11—C21—C31	−98.7 (5)	N13—C23—C33—O23	−21.1 (10)
C11—N11—C21—C51	137.8 (5)	C53—C23—C33—O23	102.4 (9)
C41—O31—C31—O21	−0.4 (9)	N13—C23—C33—O33	161.0 (5)
C41—O31—C31—C21	176.0 (6)	C53—C23—C33—O33	−75.6 (7)
N11—C21—C31—O21	−26.9 (8)	N12—C22—C52—C62	−68.7 (6)
C51—C21—C31—O21	96.8 (7)	C32—C22—C52—C62	169.5 (5)
N11—C21—C31—O31	156.7 (4)	N13—C23—C53—C63	−60.6 (7)
C51—C21—C31—O31	−79.6 (6)	C33—C23—C53—C63	177.6 (6)
N11—C21—C51—C61	−59.5 (6)	C22—C52—C62—C82	−67.7 (7)
C31—C21—C51—C61	177.9 (5)	C22—C52—C62—C72	170.6 (5)
C21—C51—C61—C81	−62.0 (7)	C23—C53—C63—C83	−64.9 (7)
C21—C51—C61—C71	172.3 (5)	C23—C53—C63—C73	168.3 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O12	0.86	2.38	3.135 (5)	146
N1—H1···S11	0.86	2.58	3.009 (4)	112
N11—H11···O22^i	0.86	2.22	3.021 (5)	155
N12—H12···O1^ii	0.86	2.36	3.105 (5)	145
N12—H12···S13	0.86	2.54	2.993 (4)	114
N13—H13···O2	0.86	2.37	3.155 (6)	152
N11—H11···O1	0.86	2.23	2.636 (5)	109
N13—H13···O12	0.86	2.22	2.634 (5)	109

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

(II) N,N'-ditiooxalyl-bis(L-leucine methyl ester)

Crystal data

C16H28N2O4S2	Dx = 1.207 Mg m^−3
Mr = 376.52	Mo Kα radiation, λ = 0.71069 Å
Tetragonal, P41	Cell parameters from 1504 reflections
Hall symbol: P 4w	θ = 2.6–23.0°
a = 11.3877 (4) Å	µ = 0.27 mm^−1
c = 15.9829 (6) Å	T = 293 K
V = 2072.66 (13) Å^3	Prism, yellow
Z = 4	0.5 × 0.2 × 0.2 mm
F(000) = 808

Data collection

KappaCCD diffractometer	Rint = 0
CCD rotation images, thick slices scans	θmax = 25.0°, θmin = 2.6°
2866 measured reflections	h = −12→12
2851 independent reflections	k = −8→8
2608 reflections with I > 2σ(I)	l = −17→17

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0638P)^2 + 0.7469P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.038	(Δ/σ)max < 0.001
wR(F^2) = 0.112	Δρmax = 0.20 e Å^−3
S = 1.10	Δρmin = −0.21 e Å^−3
2851 reflections	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
217 parameters	Absolute structure parameter: 0.33 (2)
1 restraint

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.

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

	x	y	z	Uiso*/Ueq
C81	0.6516 (7)	1.1643 (4)	0.2957 (4)	0.101 (2)
H812	0.6865	1.2369	0.278	0.151*
H818	0.7009	1.1278	0.3369	0.151*
H811	0.5757	1.1796	0.3195	0.151*
S1	0.90612 (9)	0.70581 (9)	0.12699 (6)	0.0519 (3)
S11	0.92925 (8)	0.92406 (9)	0.34729 (5)	0.0492 (3)
O31	0.5774 (2)	0.7926 (2)	0.41050 (16)	0.0508 (7)
N11	0.7645 (3)	0.8427 (3)	0.24545 (17)	0.0379 (7)
H11	0.7478	0.8092	0.1987	0.045*
O3	1.3029 (2)	0.5792 (3)	0.20480 (19)	0.0597 (8)
C31	0.6000 (3)	0.7814 (3)	0.3295 (3)	0.0444 (9)
N1	1.0701 (3)	0.7891 (3)	0.22841 (18)	0.0398 (7)
H1	1.0876	0.8322	0.2708	0.048*
C21	0.6662 (3)	0.8863 (3)	0.2959 (2)	0.0376 (8)
H21	0.6974	0.9316	0.343	0.045*
O2	1.1986 (3)	0.6287 (3)	0.3169 (2)	0.0714 (9)
C2	1.1662 (3)	0.7299 (3)	0.1859 (2)	0.0387 (8)
H2	1.1333	0.686	0.1387	0.046*
C5	1.2551 (3)	0.8192 (3)	0.1511 (2)	0.0440 (9)
H52	1.28	0.8706	0.1961	0.053*
H51	1.3238	0.7772	0.1314	0.053*
C3	1.2223 (3)	0.6426 (3)	0.2454 (2)	0.0464 (10)
C51	0.5843 (3)	0.9654 (3)	0.2445 (2)	0.0427 (9)
H511	0.5621	0.9244	0.1937	0.051*
H512	0.5132	0.9796	0.2765	0.051*
C1	0.9586 (3)	0.7824 (3)	0.2074 (2)	0.0339 (8)
C11	0.8761 (3)	0.8506 (3)	0.2658 (2)	0.0339 (8)
O21	0.5715 (3)	0.6990 (3)	0.2882 (2)	0.0799 (11)
C7	1.2952 (5)	0.9884 (4)	0.0564 (3)	0.0710 (13)
H72	1.2646	1.0343	0.011	0.106*
H71	1.3677	0.9524	0.0396	0.106*
H73	1.309	1.0384	0.1038	0.106*
C6	1.2073 (3)	0.8940 (4)	0.0799 (2)	0.0510 (10)
H6	1.1358	0.933	0.0998	0.061*
C61	0.6383 (3)	1.0830 (3)	0.2209 (3)	0.0496 (10)
H61	0.7173	1.0673	0.1993	0.06*
C8	1.1745 (4)	0.8202 (4)	0.0027 (3)	0.0656 (12)
H82	1.1188	0.7609	0.0185	0.098*
H83	1.2437	0.7835	−0.0194	0.098*
H81	1.1403	0.8701	−0.0391	0.098*
C71	0.5701 (5)	1.1425 (5)	0.1522 (3)	0.0737 (14)
H712	0.6066	1.2162	0.1388	0.111*
H713	0.491	1.1561	0.1706	0.111*
H711	0.5694	1.0933	0.1035	0.111*
C4	1.3661 (4)	0.4929 (4)	0.2544 (4)	0.0759 (14)
H42	1.4217	0.4526	0.2195	0.114*
H43	1.3116	0.4373	0.2773	0.114*
H41	1.4069	0.5318	0.2991	0.114*
C41	0.5110 (4)	0.6977 (4)	0.4482 (3)	0.0691 (13)
H412	0.4989	0.714	0.5065	0.104*
H413	0.5537	0.6255	0.4423	0.104*
H411	0.4363	0.6908	0.4207	0.104*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C81	0.175 (7)	0.049 (3)	0.079 (4)	−0.004 (4)	−0.048 (4)	−0.005 (3)
S1	0.0479 (6)	0.0611 (6)	0.0465 (6)	−0.0025 (5)	0.0047 (4)	−0.0235 (5)
S11	0.0454 (5)	0.0609 (6)	0.0414 (5)	−0.0009 (5)	0.0025 (4)	−0.0188 (5)
O31	0.0564 (16)	0.0573 (17)	0.0388 (15)	−0.0053 (13)	0.0085 (12)	0.0081 (12)
N11	0.0418 (18)	0.0458 (17)	0.0259 (15)	−0.0037 (14)	0.0085 (13)	−0.0086 (13)
O3	0.0465 (15)	0.0667 (18)	0.0659 (19)	0.0113 (14)	0.0121 (14)	0.0133 (16)
C31	0.044 (2)	0.039 (2)	0.051 (3)	0.0018 (17)	0.0173 (17)	−0.0055 (19)
N1	0.0423 (18)	0.0480 (18)	0.0293 (15)	−0.0032 (14)	0.0070 (13)	−0.0062 (13)
C21	0.041 (2)	0.038 (2)	0.034 (2)	−0.0025 (16)	0.0074 (16)	−0.0065 (15)
O2	0.113 (3)	0.0548 (18)	0.0457 (19)	0.0131 (17)	0.0172 (17)	0.0103 (14)
C2	0.0375 (19)	0.050 (2)	0.0283 (19)	0.0012 (16)	0.0075 (15)	−0.0028 (16)
C5	0.041 (2)	0.056 (2)	0.035 (2)	0.0026 (17)	0.0089 (16)	0.0018 (17)
C3	0.053 (2)	0.045 (2)	0.042 (3)	−0.0050 (18)	0.0026 (19)	−0.0045 (18)
C51	0.038 (2)	0.053 (2)	0.036 (2)	−0.0045 (17)	0.0055 (16)	−0.0075 (17)
C1	0.040 (2)	0.0345 (18)	0.0273 (18)	−0.0036 (15)	0.0061 (16)	−0.0008 (14)
C11	0.042 (2)	0.0318 (18)	0.0284 (18)	−0.0062 (15)	0.0080 (15)	0.0016 (14)
O21	0.100 (3)	0.0601 (19)	0.080 (2)	−0.0316 (19)	0.050 (2)	−0.0273 (18)
C7	0.081 (3)	0.071 (3)	0.061 (3)	−0.007 (3)	0.013 (2)	0.015 (2)
C6	0.049 (2)	0.061 (2)	0.042 (2)	0.007 (2)	0.0158 (19)	0.0112 (19)
C61	0.045 (2)	0.052 (2)	0.052 (2)	−0.0018 (18)	−0.0027 (19)	0.0079 (19)
C8	0.073 (3)	0.086 (3)	0.038 (2)	−0.007 (3)	−0.003 (2)	0.020 (2)
C71	0.087 (3)	0.070 (3)	0.065 (3)	−0.001 (3)	−0.014 (3)	0.015 (2)
C4	0.059 (3)	0.059 (3)	0.110 (4)	0.005 (2)	0.001 (3)	0.019 (3)
C41	0.066 (3)	0.072 (3)	0.070 (3)	−0.003 (2)	0.025 (3)	0.027 (3)

Geometric parameters (Å, º)

C81—C61	1.520 (7)	C5—H51	0.97
C81—H812	0.96	C51—C61	1.521 (6)
C81—H818	0.96	C51—H511	0.97
C81—H811	0.96	C51—H512	0.97
S1—C1	1.665 (4)	C1—C11	1.535 (4)
S11—C11	1.662 (4)	C7—C6	1.517 (6)
O31—C31	1.326 (5)	C7—H72	0.96
O31—C41	1.450 (5)	C7—H71	0.96
N11—C11	1.315 (5)	C7—H73	0.96
N11—C21	1.466 (4)	C6—C8	1.538 (6)
N11—H11	0.86	C6—H6	0.98
O3—C3	1.335 (5)	C61—C71	1.506 (6)
O3—C4	1.454 (6)	C61—H61	0.98
C31—O21	1.193 (5)	C8—H82	0.96
C31—C21	1.511 (5)	C8—H83	0.96
N1—C1	1.315 (5)	C8—H81	0.96
N1—C2	1.454 (5)	C71—H712	0.96
N1—H1	0.86	C71—H713	0.96
C21—C51	1.535 (5)	C71—H711	0.96
C21—H21	0.98	C4—H42	0.96
O2—C3	1.185 (5)	C4—H43	0.96
C2—C3	1.517 (6)	C4—H41	0.96
C2—C5	1.540 (5)	C41—H412	0.96
C2—H2	0.98	C41—H413	0.96
C5—C6	1.522 (5)	C41—H411	0.96
C5—H52	0.97
C61—C81—H812	109.5	C11—C1—S1	121.0 (2)
C61—C81—H818	109.5	N11—C11—C1	114.0 (3)
H812—C81—H818	109.5	N11—C11—S11	125.4 (3)
C61—C81—H811	109.5	C1—C11—S11	120.5 (2)
H812—C81—H811	109.5	C6—C7—H72	109.5
H818—C81—H811	109.5	C6—C7—H71	109.5
C31—O31—C41	115.8 (3)	H72—C7—H71	109.5
C11—N11—C21	125.4 (3)	C6—C7—H73	109.5
C11—N11—H11	117.3	H72—C7—H73	109.5
C21—N11—H11	117.3	H71—C7—H73	109.5
C3—O3—C4	116.2 (4)	C7—C6—C5	110.2 (4)
O21—C31—O31	124.3 (4)	C7—C6—C8	110.5 (4)
O21—C31—C21	124.1 (4)	C5—C6—C8	112.4 (3)
O31—C31—C21	111.6 (3)	C7—C6—H6	107.9
C1—N1—C2	125.5 (3)	C5—C6—H6	107.9
C1—N1—H1	117.3	C8—C6—H6	107.9
C2—N1—H1	117.3	C71—C61—C81	110.5 (4)
N11—C21—C31	108.0 (3)	C71—C61—C51	111.6 (3)
N11—C21—C51	111.7 (3)	C81—C61—C51	112.4 (4)
C31—C21—C51	110.6 (3)	C71—C61—H61	107.3
N11—C21—H21	108.9	C81—C61—H61	107.3
C31—C21—H21	108.9	C51—C61—H61	107.3
C51—C21—H21	108.9	C6—C8—H82	109.5
N1—C2—C3	109.2 (3)	C6—C8—H83	109.5
N1—C2—C5	110.9 (3)	H82—C8—H83	109.5
C3—C2—C5	112.5 (3)	C6—C8—H81	109.5
N1—C2—H2	108	H82—C8—H81	109.5
C3—C2—H2	108	H83—C8—H81	109.5
C5—C2—H2	108	C61—C71—H712	109.5
C6—C5—C2	113.8 (3)	C61—C71—H713	109.5
C6—C5—H52	108.8	H712—C71—H713	109.5
C2—C5—H52	108.8	C61—C71—H711	109.5
C6—C5—H51	108.8	H712—C71—H711	109.5
C2—C5—H51	108.8	H713—C71—H711	109.5
H52—C5—H51	107.7	O3—C4—H42	109.5
O2—C3—O3	123.6 (4)	O3—C4—H43	109.5
O2—C3—C2	126.6 (4)	H42—C4—H43	109.5
O3—C3—C2	109.8 (3)	O3—C4—H41	109.5
C61—C51—C21	113.8 (3)	H42—C4—H41	109.5
C61—C51—H511	108.8	H43—C4—H41	109.5
C21—C51—H511	108.8	O31—C41—H412	109.5
C61—C51—H512	108.8	O31—C41—H413	109.5
C21—C51—H512	108.8	H412—C41—H413	109.5
H511—C51—H512	107.7	O31—C41—H411	109.5
N1—C1—C11	114.0 (3)	H412—C41—H411	109.5
N1—C1—S1	125.0 (3)	H413—C41—H411	109.5
C41—O31—C31—O21	−1.5 (6)	N1—C1—C11—N11	−179.2 (3)
C41—O31—C31—C21	178.3 (3)	S1—C1—C11—N11	−0.6 (4)
O21—C31—C21—N11	−47.1 (5)	N1—C1—C11—S11	−0.2 (4)
O21—C31—C21—C51	75.3 (5)	S1—C1—C11—S11	178.5 (2)
O31—C31—C21—C51	−104.5 (4)	C2—C5—C6—C7	173.4 (3)
C1—N1—C2—C5	119.4 (4)	C2—C5—C6—C8	−62.9 (4)
C3—C2—C5—C6	169.6 (3)	C21—C51—C61—C71	164.3 (3)
C4—O3—C3—O2	−2.5 (6)	C21—C51—C61—C81	−70.9 (5)
C4—O3—C3—C2	178.8 (3)	C11—N11—C21—C51	128.0 (4)
N1—C2—C3—O2	−4.8 (5)	C11—C1—N1—C2	177.8 (3)
C5—C2—C3—O2	118.9 (4)	C1—N1—C2—C3	−116.0 (4)
C5—C2—C3—O3	−62.5 (4)	N1—C2—C3—O3	173.8 (3)
C31—C21—C51—C61	170.1 (3)	N1—C2—C5—C6	−67.7 (4)
C2—N1—C1—C11	177.7 (3)	C1—C11—N11—C21	171.9 (3)
C2—N1—C1—S1	−0.9 (5)	C11—N11—C21—C31	−110.3 (4)
C21—N11—C11—C1	171.9 (3)	N11—C21—C31—O31	133.1 (3)
C21—N11—C11—S11	−7.1 (5)	N11—C21—C51—C61	−69.7 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O2^i	0.86	2.51	3.280 (4)	150
N1—H1···S1^ii	0.86	3.02	3.732 (3)	142
N11—H11···S1	0.86	2.44	2.935 (3)	117
N1—H1···S11	0.86	2.42	2.923 (3)	118

Symmetry codes: (i) y, −x+2, z−1/4; (ii) −y+2, x, z+1/4.