Synchrotron powder diffraction in a systematic study of 4′-[2-(tosylamino)benzylideneamino]-2,3-benzo-15-crown-5 complexes

Dorokhov, A.V.; Chernyshov, D.Y.; Burlov, A.S.; Garnovskii, A.D.; Ivanova, I.S.; Pyatova, E.N.; Tsivadze, A.Y.; Aslanov, L.A.; Chernyshev, V.V.

doi:10.1107/S0108768107003898

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Synchrotron powder diffraction in a systematic study of 4'-[2-(tosylamino)benzylideneamino]-2,3-benzo-15-crown-5 complexes

A. V. Dorokhov, D. Y. Chernyshov, A. S. Burlov, A. D. Garnovskii, I. S. Ivanova, E. N. Pyatova, A. Y. Tsivadze, L. A. Aslanov and V. V. Chernyshev

The crystal structures of two compounds, CuL₂ and LiNCS·HL [HL = 4'-[2-(tosylamino)benzylideneamino]-2,3-benzo-15-crown-5], have been determined from synchrotron powder diffraction data. Both compounds crystallize in the monoclinic space group P2₁/c and with one molecule in the asymmetric unit. In CuL₂ the four N atoms of two bidentate L ligands coordinate the Cu^II ion in a distorted tetrahedral geometry with Cu-N distances of 1.98 (5)-2.05 (5) Å, while two O atoms from two sulfoxide groups complete the distorted octahedral Cu coordination [Cu-O 2.64 (4), 2.74 (4) Å]. In LiNCS·HL, lithium is coordinated by all five ether O atoms with Li-O distances of 2.03 (3)-2.50 (3) Å and an N atom from the thiocyanate moiety [Li-N 1.98 (3) Å] in a distorted pentagonal pyramidal geometry. Preliminary potentiometric selectivity measurements for ion-selective electrodes (ISEs) based on CuL₂ and ZnL₂ demonstrated significant differences in their selectivity. In order to find a possible reason for this, theoretical calculations at the DFT (B3LYP) level were performed. These calculations used the crystal structures of CuL₂, LiNCS·HL, ZnL₂ and HL as input geometries for the minimum energy optimization in vacuo. The results indicate that in ML₂ complexes (M = Cu, Zn) the electronic structure of the metal ion determines the spatial orientation of benzo-15-crown-5 macrocycles, and their different orientation in CuL₂ and ZnL₂ results in different potentiometric selectivities of ISEs based on these compounds.

Keywords: crown ether; synchrotron powder diffraction data; structure solution from powder diffraction data; DFT calculations.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768107003898/kd5008sup1.cif Contains datablocks CuL2, LiNCS, global
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768107003898/kd5008LiNCSsup2.rtv Contains datablock LiNCS
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768107003898/kd5008CuL2sup3.rtv Contains datablock CuL2
	Portable Document Format (PDF) file https://doi.org/10.1107/S0108768107003898/kd5008sup4.pdf Supplementary material

CCDC references: 650625; 650626

Computing details top

For both compounds, cell refinement: LSPAID (Visser et al., 1986); data reduction: MRIA (Zlokazov et al., 1992); program(s) used to solve structure: MRIA; program(s) used to refine structure: MRIA; molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: MRIA.

Figures top

(CuL2) top

Crystal data top

C₅₆H₆₂CuN₄O₁₄S₂	F(000) = 2396
M_r = 1142.79	D_x = 1.436 Mg m⁻³
Monoclinic, P2₁/c	Synchrotron radiation, λ = 0.51966(1) Å
a = 19.0356 (6) Å	µ = 0.30 mm⁻¹
b = 17.4332 (6) Å	T = 295 K
c = 17.4180 (6) Å	Particle morphology: no specific habit
β = 113.824 (3)°	black
V = 5287.7 (3) Å³	cylinder, 15 × 0.3 mm
Z = 4	Specimen preparation: Prepared at 295 K and 101.3(2) kPa

Data collection top

ESRF powder diffractometer	Data collection mode: transmission
Radiation source: BM1B bending magnet at ESRF, synchrotron radiation	Scan method: continuous
Si 111 double crystal monochromator	2θ_min = 1.017°, 2θ_max = 22.014°, 2θ_step = 0.003°
Specimen mounting: Specimen was sealed in a 0.3 mm diameter borosilicate glass capillary

Refinement top

Refinement on I_net	277 parameters
Least-squares matrix: full with fixed elements per cycle	233 restraints
R_p = 0.046	72 constraints
R_wp = 0.063	H-atom parameters not refined
R_exp = 0.048	Weighting scheme based on measured s.u.'s
χ² = 1.700	(Δ/σ)_max = 0.027
7000 data points	Background function: Chebyshev polynomial up to the 5th order
Profile function: split-type pseudo-Voigt (Toraya, 1986)	Preferred orientation correction: March-Dollase texture correction (Dollase, 1986). Direction of preferred orientation - 100, texture parameter r = 0.94(2).

Crystal data top

C₅₆H₆₂CuN₄O₁₄S₂	V = 5287.7 (3) Å³
M_r = 1142.79	Z = 4
Monoclinic, P2₁/c	Synchrotron radiation, λ = 0.51966(1) Å
a = 19.0356 (6) Å	µ = 0.30 mm⁻¹
b = 17.4332 (6) Å	T = 295 K
c = 17.4180 (6) Å	cylinder, 15 × 0.3 mm
β = 113.824 (3)°

Data collection top

ESRF powder diffractometer	Scan method: continuous
Specimen mounting: Specimen was sealed in a 0.3 mm diameter borosilicate glass capillary	2θ_min = 1.017°, 2θ_max = 22.014°, 2θ_step = 0.003°
Data collection mode: transmission

Refinement top

R_p = 0.046	7000 data points
R_wp = 0.063	277 parameters
R_exp = 0.048	233 restraints
χ² = 1.700	H-atom parameters not refined

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1A	0.401 (3)	0.094 (3)	0.380 (4)	0.05 (1)*
H1A	0.4242	0.1393	0.3740	0.05*
C2A	0.327 (3)	0.096 (4)	0.378 (3)	0.05 (1) (1)*
C3A	0.293 (3)	0.028 (3)	0.389 (4)	0.05 (1)*
H3A	0.2435	0.0300	0.3881	0.05*
C4A	0.333 (3)	−0.042 (4)	0.402 (3)	0.05 (1)*
H4A	0.3097	−0.0865	0.4094	0.05*
C5A	0.407 (3)	−0.044 (3)	0.403 (3)	0.05 (1)*
C6A	0.441 (3)	0.024 (3)	0.393 (4)	0.05 (1)*
H6A	0.4907	0.0223	0.3947	0.05*
C7A	0.448 (3)	−0.120 (4)	0.417 (4)	0.05 (1)*
H7A1	0.4152	−0.1598	0.4227	0.05*
H7A2	0.4941	−0.1178	0.4675	0.05*
H7A3	0.4606	−0.1314	0.3703	0.05*
S8A	0.2769 (10)	0.1830 (10)	0.3609 (11)	0.034 (18)*
N9A	0.236 (3)	0.182 (3)	0.426 (3)	0.05 (1)*
C10A	0.280 (3)	0.196 (3)	0.512 (4)	0.05 (1)*
C11A	0.362 (3)	0.201 (4)	0.544 (4)	0.05 (1)*
H11A	0.3860	0.1952	0.5075	0.05*
C12A	0.406 (3)	0.215 (4)	0.629 (4)	0.05 (1)*
H12A	0.4589	0.2202	0.6488	0.05*
C13A	0.369 (3)	0.221 (4)	0.685 (4)	0.05 (1)*
H13A	0.3982	0.2277	0.7415	0.05*
C14A	0.290 (3)	0.216 (3)	0.655 (3)	0.05 (1)*
H14A	0.2670	0.2213	0.6924	0.05*
C15A	0.243 (3)	0.202 (3)	0.568 (3)	0.05 (1)*
C16A	0.161 (3)	0.202 (4)	0.546 (4)	0.05 (1)*
H16A	0.1466	0.2105	0.5906	0.05*
N17A	0.105 (3)	0.191 (3)	0.474 (3)	0.05 (1)*
C18A	0.027 (3)	0.166 (4)	0.458 (4)	0.05 (1)*
C19A	−0.036 (3)	0.201 (4)	0.397 (4)	0.05 (1)*
H19A	−0.0276	0.2417	0.3664	0.05*
C20A	−0.112 (3)	0.178 (3)	0.380 (4)	0.05 (1)*
C21A	−0.124 (3)	0.115 (3)	0.425 (3)	0.05 (1)*
C22A	−0.060 (3)	0.080 (4)	0.487 (4)	0.05 (1)*
H22A	−0.0669	0.0383	0.5166	0.05*
C23A	0.015 (3)	0.105 (3)	0.504 (4)	0.05 (1)*
H23A	0.0561	0.0816	0.5470	0.05*
O24A	0.2144 (19)	0.176 (2)	0.279 (2)	0.05 (1)*
O25A	0.327 (2)	0.247 (2)	0.373 (2)	0.05 (1)*
O26A	−0.172 (2)	0.214 (2)	0.321 (3)	0.05 (1)*
O27A	−0.197 (2)	0.093 (2)	0.409 (2)	0.05 (1)*
C28A	−0.223 (3)	0.028 (4)	0.441 (4)	0.05 (1)*
H28A	−0.2059	0.0332	0.5011	0.05*
H28B	−0.2007	−0.0186	0.4295	0.05*
C29A	−0.312 (3)	0.025 (3)	0.398 (4)	0.05 (1)*
H29A	−0.3298	−0.0003	0.3432	0.05*
H29B	−0.3337	−0.0008	0.4324	0.05*
O30A	−0.328 (2)	0.104 (2)	0.390 (2)	0.05 (1)*
C31A	−0.396 (3)	0.147 (3)	0.360 (4)	0.05 (1)*
H31A	−0.4390	0.1162	0.3584	0.05*
H31B	−0.4070	0.1656	0.3038	0.05*
C32A	−0.382 (3)	0.215 (4)	0.422 (4)	0.05 (1)*
H32A	−0.4292	0.2321	0.4256	0.05*
H32B	−0.3441	0.2032	0.4775	0.05*
O33A	−0.3550 (19)	0.269 (2)	0.382 (3)	0.05 (1)*
C34A	−0.323 (3)	0.342 (4)	0.404 (4)	0.05 (1)*
H34A	−0.2951	0.3479	0.4638	0.05*
H34B	−0.3608	0.3824	0.3822	0.05*
C35A	−0.267 (3)	0.341 (3)	0.358 (3)	0.05 (1)*
H35A	−0.2575	0.3926	0.3445	0.05*
H35B	−0.2187	0.3177	0.3939	0.05*
O36A	−0.303 (2)	0.297 (2)	0.282 (2)	0.05 (1)*
C37A	−0.259 (3)	0.310 (4)	0.234 (4)	0.05 (1)*
H37A	−0.2600	0.3644	0.2213	0.05*
H37B	−0.2819	0.2827	0.1810	0.05*
C38A	−0.175 (3)	0.284 (3)	0.280 (4)	0.05 (1)*
H38A	−0.1513	0.2787	0.2408	0.05*
H38B	−0.1466	0.3226	0.3214	0.05*
C1B	−0.014 (3)	−0.048 (4)	0.165 (4)	0.06 (1)*
H1B	−0.0537	−0.0580	0.1811	0.05*
C2B	0.044 (3)	0.004 (4)	0.210 (3)	0.06 (1)*
C3B	0.103 (3)	0.020 (3)	0.185 (4)	0.06 (1)*
H3B	0.1406	0.0554	0.2140	0.05*
C4B	0.106 (3)	−0.018 (4)	0.115 (4)	0.06 (1)*
H4B	0.1460	−0.0087	0.0992	0.05*
C5B	0.048 (3)	−0.070 (4)	0.069 (4)	0.06 (1)*
C6B	−0.012 (3)	−0.085 (4)	0.094 (4)	0.06 (1)*
H6B	−0.0506	−0.1188	0.0632	0.05*
C7B	0.052 (3)	−0.109 (3)	−0.007 (3)	0.06 (1)*
H7B1	0.0084	−0.1432	−0.0312	0.05*
H7B2	0.0983	−0.1384	0.0099	0.05*
H7B3	0.0502	−0.0714	−0.0473	0.05*
S8B	0.0417 (11)	0.0499 (12)	0.2986 (13)	0.054 (19)*
N9B	0.030 (3)	0.142 (3)	0.284 (3)	0.06 (1)*
C10B	−0.036 (3)	0.171 (4)	0.218 (4)	0.06 (1)*
C11B	−0.103 (3)	0.127 (3)	0.176 (4)	0.06 (1)*
H11B	−0.1042	0.0766	0.1940	0.05*
C12B	−0.166 (3)	0.155 (3)	0.109 (3)	0.06 (1)*
H12B	−0.2093	0.1243	0.0833	0.05*
C13B	−0.165 (3)	0.230 (3)	0.079 (4)	0.06 (1)*
H13B	−0.2066	0.2490	0.0334	0.05*
C14B	−0.101 (3)	0.276 (4)	0.120 (4)	0.06 (1)*
H14B	−0.1015	0.3259	0.1014	0.05*
C15B	−0.035 (3)	0.248 (4)	0.189 (4)	0.06 (1)*
C16B	0.028 (3)	0.301 (4)	0.221 (4)	0.06 (1)*
H16B	0.0224	0.3500	0.1978	0.05*
N17B	0.096 (3)	0.283 (3)	0.285 (3)	0.06 (1)*
C18B	0.153 (3)	0.346 (3)	0.320 (4)	0.06 (1)*
C19B	0.188 (3)	0.359 (3)	0.405 (3)	0.06 (1)*
H19B	0.1777	0.3277	0.4424	0.05*
C20B	0.239 (3)	0.422 (4)	0.435 (4)	0.06 (1)*
C21B	0.251 (3)	0.472 (4)	0.377 (4)	0.06 (1)*
C22B	0.216 (3)	0.457 (4)	0.291 (3)	0.06 (1)*
H22B	0.2257	0.4874	0.2532	0.05*
C23B	0.165 (3)	0.395 (3)	0.262 (4)	0.06 (1)*
H23B	0.1399	0.3865	0.2043	0.05*
O24B	0.116 (2)	0.042 (2)	0.367 (2)	0.06 (1)*
O25B	−0.0226 (19)	0.025 (2)	0.317 (3)	0.06 (1)*
O26B	0.2726 (18)	0.445 (2)	0.518 (2)	0.06 (1)*
O27B	0.301 (2)	0.533 (2)	0.407 (2)	0.06 (1)*
C28B	0.315 (3)	0.587 (4)	0.354 (4)	0.06 (1)*
H28C	0.2678	0.6136	0.3203	0.05*
H28D	0.3323	0.5604	0.3157	0.05*
C29B	0.376 (3)	0.647 (4)	0.403 (4)	0.06 (1)*
H29C	0.3839	0.6820	0.3643	0.05*
H29D	0.3579	0.6760	0.4390	0.05*
O30B	0.446 (2)	0.610 (2)	0.453 (3)	0.06 (1)*
C31B	0.507 (4)	0.650 (4)	0.517 (4)	0.06 (1)*
H31C	0.4852	0.6884	0.5414	0.05*
H31D	0.5387	0.6749	0.4937	0.05*
C32B	0.556 (3)	0.594 (4)	0.587 (4)	0.06 (1)*
H32C	0.5608	0.5445	0.5630	0.05*
H32D	0.6068	0.6144	0.6180	0.05*
O33B	0.5148 (19)	0.585 (2)	0.640 (2)	0.06 (1)*
C34B	0.509 (3)	0.508 (4)	0.664 (4)	0.06 (1)*
H34C	0.5599	0.4890	0.6967	0.05*
H34D	0.4872	0.4770	0.6132	0.05*
C35B	0.459 (3)	0.497 (4)	0.714 (3)	0.06 (1)*
H35C	0.4918	0.4843	0.7719	0.05*
H35D	0.4312	0.5432	0.7132	0.05*
O36B	0.408 (2)	0.436 (2)	0.677 (2)	0.06 (1)*
C37B	0.330 (3)	0.441 (4)	0.669 (4)	0.06 (1)*
H37C	0.3160	0.4949	0.6680	0.05*
H37D	0.3256	0.4171	0.7169	0.05*
C38B	0.278 (3)	0.402 (3)	0.588 (4)	0.06 (1)*
H38C	0.2982	0.3510	0.5849	0.05*
H38D	0.2271	0.3950	0.5873	0.05*
Cu	0.1231 (5)	0.1930 (5)	0.3659 (6)	0.015 (4)*

Geometric parameters (Å, º) top

Cu—N9A	1.98 (5)	C20B—C21B	1.42 (9)
Cu—N9B	1.98 (5)	C21A—C22A	1.40 (8)
Cu—N17A	2.05 (5)	C21B—C22B	1.40 (8)
Cu—N17B	2.03 (5)	C22A—C23A	1.41 (9)
Cu—O24A	2.74 (4)	C22B—C23B	1.38 (9)
Cu—O24B	2.64 (4)	C28A—C29A	1.57 (9)
S8A—O24A	1.45 (4)	C28B—C29B	1.54 (9)
S8A—O25A	1.43 (4)	C31A—C32A	1.57 (9)
S8A—N9A	1.61 (5)	C31B—C32B	1.55 (9)
S8A—C2A	1.75 (7)	C34A—C35A	1.55 (9)
S8B—O24B	1.44 (4)	C34B—C35B	1.54 (9)
S8B—O25B	1.45 (4)	C37A—C38A	1.54 (9)
S8B—N9B	1.63 (6)	C37B—C38B	1.53 (9)
S8B—C2B	1.75 (6)	C1A—H1A	0.93
O26A—C20A	1.34 (7)	C1B—H1B	0.93
O26A—C38A	1.40 (6)	C3A—H3A	0.93
O26B—C20B	1.38 (7)	C3B—H3B	0.93
O26B—C38B	1.41 (7)	C4A—H4A	0.93
O27A—C21A	1.35 (7)	C4B—H4B	0.93
O27A—C28A	1.44 (8)	C6A—H6A	0.93
O27B—C21B	1.38 (8)	C6B—H6B	0.93
O27B—C28B	1.42 (8)	C7A—H7A1	0.96
O30A—C29A	1.41 (6)	C7A—H7A2	0.96
O30A—C31A	1.40 (7)	C7A—H7A3	0.96
O30B—C29B	1.42 (7)	C7B—H7B1	0.96
O30B—C31B	1.43 (8)	C7B—H7B2	0.96
O33A—C32A	1.38 (8)	C7B—H7B3	0.96
O33A—C34A	1.42 (8)	C11A—H11A	0.93
O33B—C32B	1.44 (7)	C11B—H11B	0.92
O33B—C34B	1.42 (8)	C12A—H12A	0.93
O36A—C35A	1.42 (6)	C12B—H12B	0.93
O36A—C37A	1.42 (7)	C13A—H13A	0.93
O36B—C35B	1.42 (7)	C13B—H13B	0.93
O36B—C37B	1.44 (8)	C14A—H14A	0.93
N9A—C10A	1.41 (8)	C14B—H14B	0.93
N9B—C10B	1.41 (8)	C16A—H16A	0.93
N17A—C16A	1.29 (8)	C16B—H16B	0.93
N17A—C18A	1.46 (9)	C19A—H19A	0.93
N17B—C16B	1.36 (8)	C19B—H19B	0.93
N17B—C18B	1.49 (8)	C22A—H22A	0.93
C1A—C2A	1.40 (9)	C22B—H22B	0.93
C1A—C6A	1.41 (8)	C23A—H23A	0.93
C1B—C2B	1.39 (9)	C23B—H23B	0.93
C1B—C6B	1.41 (9)	C28A—H28A	0.97
C2A—C3A	1.40 (9)	C28A—H28B	0.97
C2B—C3B	1.40 (9)	C28B—H28C	0.97
C3A—C4A	1.41 (9)	C28B—H28D	0.97
C3B—C4B	1.41 (9)	C29A—H29A	0.97
C4A—C5A	1.40 (9)	C29A—H29B	0.97
C4B—C5B	1.40 (9)	C29B—H29C	0.97
C5A—C6A	1.39 (8)	C29B—H29D	0.97
C5A—C7A	1.51 (9)	C31A—H31A	0.97
C5B—C6B	1.40 (9)	C31A—H31B	0.97
C5B—C7B	1.52 (8)	C31B—H31C	0.97
C10A—C11A	1.43 (9)	C31B—H31D	0.96
C10A—C15A	1.42 (8)	C32A—H32A	0.97
C10B—C11B	1.42 (9)	C32A—H32B	0.97
C10B—C15B	1.44 (10)	C32B—H32C	0.97
C11A—C12A	1.40 (9)	C32B—H32D	0.97
C11B—C12B	1.39 (8)	C34A—H34A	0.97
C12A—C13A	1.40 (9)	C34A—H34B	0.97
C12B—C13B	1.41 (7)	C34B—H34C	0.97
C13A—C14A	1.38 (9)	C34B—H34D	0.97
C13B—C14B	1.39 (9)	C35A—H35A	0.97
C14A—C15A	1.44 (7)	C35A—H35B	0.97
C14B—C15B	1.43 (9)	C35B—H35C	0.97
C15A—C16A	1.45 (9)	C35B—H35D	0.97
C15B—C16B	1.44 (9)	C37A—H37A	0.97
C18A—C19A	1.38 (9)	C37A—H37B	0.97
C18A—C23A	1.40 (9)	C37B—H37C	0.97
C18B—C19B	1.37 (8)	C37B—H37D	0.97
C18B—C23B	1.41 (8)	C38A—H38A	0.97
C19A—C20A	1.41 (9)	C38A—H38B	0.97
C19B—C20B	1.42 (9)	C38B—H38C	0.97
C20A—C21A	1.42 (8)	C38B—H38D	0.97

O24A—Cu—O24B	86.7 (11)	C2A—C3A—H3A	119
O24A—Cu—N9A	59.2 (15)	C4A—C3A—H3A	121
O24A—Cu—N9B	97.8 (18)	C2B—C3B—H3B	121
O24A—Cu—N17A	152.3 (18)	C4B—C3B—H3B	120
O24A—Cu—N17B	75.0 (18)	C3A—C4A—H4A	119
O24B—Cu—N9A	87.0 (18)	C5A—C4A—H4A	121
O24B—Cu—N9B	61.5 (17)	C3B—C4B—H4B	120
O24B—Cu—N17A	87.0 (17)	C5B—C4B—H4B	120
O24B—Cu—N17B	141.0 (16)	C1A—C6A—H6A	120
N9A—Cu—N9B	143 (2)	C5A—C6A—H6A	119
N9A—Cu—N17A	94 (2)	C1B—C6B—H6B	120
N9A—Cu—N17B	111 (2)	C5B—C6B—H6B	120
N9B—Cu—N17A	103 (2)	C5A—C7A—H7A1	109
N9B—Cu—N17B	87 (2)	C5A—C7A—H7A2	109
N17A—Cu—N17B	124 (2)	C5A—C7A—H7A3	109
O24A—S8A—O25A	116 (2)	H7A1—C7A—H7A2	109
O24A—S8A—N9A	105 (3)	H7A1—C7A—H7A3	109
O24A—S8A—C2A	106 (2)	H7A2—C7A—H7A3	109
O25A—S8A—N9A	113 (3)	C5B—C7B—H7B1	109
O25A—S8A—C2A	111 (3)	C5B—C7B—H7B2	109
N9A—S8A—C2A	105 (3)	C5B—C7B—H7B3	109
O24B—S8B—O25B	115 (2)	H7B1—C7B—H7B2	109
O24B—S8B—N9B	104 (3)	H7B1—C7B—H7B3	109
O24B—S8B—C2B	109 (3)	H7B2—C7B—H7B3	110
O25B—S8B—N9B	105 (3)	C10A—C11A—H11A	119
O25B—S8B—C2B	112 (3)	C12A—C11A—H11A	120
N9B—S8B—C2B	111 (3)	C10B—C11B—H11B	119
Cu—O24A—S8A	84.2 (17)	C12B—C11B—H11B	120
Cu—O24B—S8B	86.3 (18)	C11A—C12A—H12A	120
Cu—N17A—C18A	111 (4)	C13A—C12A—H12A	120
C16A—N17A—C18A	127 (6)	C11B—C12B—H12B	120
Cu—N17B—C16B	130 (5)	C13B—C12B—H12B	120
Cu—N17B—C18B	110 (4)	C12A—C13A—H13A	120
C16B—N17B—C18B	117 (5)	C14A—C13A—H13A	119
C2A—C1A—C6A	120 (5)	C12B—C13B—H13B	121
C2B—C1B—C6B	120 (6)	C14B—C13B—H13B	120
S8A—C2A—C1A	120 (5)	C13A—C14A—H14A	119
S8A—C2A—C3A	120 (5)	C15A—C14A—H14A	119
C1A—C2A—C3A	120 (6)	C13B—C14B—H14B	119
S8B—C2B—C1B	121 (5)	C15B—C14B—H14B	120
S8B—C2B—C3B	119 (5)	N17A—C16A—H16A	115
C1B—C2B—C3B	120 (5)	C15A—C16A—H16A	115
C2A—C3A—C4A	120 (6)	N17B—C16B—H16B	118
C2B—C3B—C4B	120 (6)	C15B—C16B—H16B	119
C3A—C4A—C5A	120 (6)	C18A—C19A—H19A	118
C3B—C4B—C5B	120 (6)	C20A—C19A—H19A	119
C4A—C5A—C6A	119 (5)	C18B—C19B—H19B	120
C4A—C5A—C7A	118 (5)	C20B—C19B—H19B	120
C6A—C5A—C7A	122 (6)	C21A—C22A—H22A	120
C4B—C5B—C6B	120 (6)	C23A—C22A—H22A	119
C4B—C5B—C7B	119 (6)	C21B—C22B—H22B	119
C6B—C5B—C7B	121 (6)	C23B—C22B—H22B	120
C1A—C6A—C5A	121 (6)	C18A—C23A—H23A	120
C1B—C6B—C5B	120 (6)	C22A—C23A—H23A	119
N9A—C10A—C11A	121 (5)	C18B—C23B—H23B	121
N9A—C10A—C15A	120 (5)	C22B—C23B—H23B	120
C11A—C10A—C15A	120 (6)	O27A—C28A—H28A	110
C20A—O26A—C38A	130 (5)	O27A—C28A—H28B	110
C20B—O26B—C38B	126 (4)	C29A—C28A—H28A	109
C21A—O27A—C28A	128 (4)	C29A—C28A—H28B	110
C21B—O27B—C28B	123 (4)	H28A—C28A—H28B	109
C29A—O30A—C31A	134 (4)	O27B—C28B—H28C	110
C29B—O30B—C31B	122 (5)	O27B—C28B—H28D	109
C32A—O33A—C34A	130 (4)	C29B—C28B—H28C	109
C32B—O33B—C34B	115 (4)	C29B—C28B—H28D	108
C35A—O36A—C37A	110 (4)	H28C—C28B—H28D	107
C35B—O36B—C37B	119 (4)	O30A—C29A—H29A	111
Cu—N9A—S8A	111 (3)	O30A—C29A—H29B	112
Cu—N9A—C10A	127 (4)	C28A—C29A—H29A	111
S8A—N9A—C10A	120 (4)	C28A—C29A—H29B	112
Cu—N9B—S8B	108 (3)	H29A—C29A—H29B	109
Cu—N9B—C10B	132 (4)	O30B—C29B—H29C	110
S8B—N9B—C10B	120 (5)	O30B—C29B—H29D	109
Cu—N17A—C16A	121 (5)	C28B—C29B—H29C	110
N9B—C10B—C11B	123 (6)	C28B—C29B—H29D	109
N9B—C10B—C15B	119 (6)	H29C—C29B—H29D	109
C11B—C10B—C15B	118 (6)	O30A—C31A—H31A	111
C10A—C11A—C12A	121 (6)	O30A—C31A—H31B	111
C10B—C11B—C12B	121 (5)	C32A—C31A—H31A	111
C11A—C12A—C13A	119 (6)	C32A—C31A—H31B	111
C11B—C12B—C13B	121 (5)	H31A—C31A—H31B	109
C12A—C13A—C14A	121 (6)	O30B—C31B—H31C	109
C12B—C13B—C14B	119 (6)	O30B—C31B—H31D	110
C13A—C14A—C15A	121 (5)	C32B—C31B—H31C	109
C13B—C14B—C15B	122 (6)	C32B—C31B—H31D	110
C10A—C15A—C14A	118 (5)	H31C—C31B—H31D	109
C10A—C15A—C16A	127 (5)	O33A—C32A—H32A	111
C14A—C15A—C16A	115 (5)	O33A—C32A—H32B	111
C10B—C15B—C14B	119 (6)	C31A—C32A—H32A	112
C10B—C15B—C16B	126 (6)	C31A—C32A—H32B	112
C14B—C15B—C16B	115 (6)	H32A—C32A—H32B	109
N17A—C16A—C15A	129 (6)	O33B—C32B—H32C	110
N17B—C16B—C15B	123 (6)	O33B—C32B—H32D	111
N17A—C18A—C19A	121 (6)	C31B—C32B—H32C	110
N17A—C18A—C23A	120 (6)	C31B—C32B—H32D	111
C19A—C18A—C23A	119 (6)	H32C—C32B—H32D	109
N17B—C18B—C19B	121 (5)	O33A—C34A—H34A	112
N17B—C18B—C23B	117 (5)	O33A—C34A—H34B	112
C19B—C18B—C23B	122 (5)	C35A—C34A—H34A	111
C18A—C19A—C20A	122 (6)	C35A—C34A—H34B	110
C18B—C19B—C20B	119 (5)	H34A—C34A—H34B	110
O26A—C20A—C19A	121 (5)	O33B—C34B—H34C	109
O26A—C20A—C21A	120 (5)	O33B—C34B—H34D	108
C19A—C20A—C21A	119 (6)	C35B—C34B—H34C	109
O26B—C20B—C19B	125 (5)	C35B—C34B—H34D	108
O26B—C20B—C21B	115 (6)	H34C—C34B—H34D	108
C19B—C20B—C21B	120 (6)	O36A—C35A—H35A	110
O27A—C21A—C20A	119 (5)	O36A—C35A—H35B	110
O27A—C21A—C22A	123 (5)	C34A—C35A—H35A	110
C20A—C21A—C22A	119 (6)	C34A—C35A—H35B	109
O27B—C21B—C20B	119 (5)	H35A—C35A—H35B	109
O27B—C21B—C22B	122 (6)	O36B—C35B—H35C	109
C20B—C21B—C22B	119 (6)	O36B—C35B—H35D	111
C21A—C22A—C23A	121 (6)	C34B—C35B—H35C	109
C21B—C22B—C23B	121 (6)	C34B—C35B—H35D	110
C18A—C23A—C22A	120 (6)	H35C—C35B—H35D	109
C18B—C23B—C22B	119 (6)	O36A—C37A—H37A	110
O27A—C28A—C29A	108 (5)	O36A—C37A—H37B	109
O27B—C28B—C29B	113 (5)	C38A—C37A—H37A	109
O30A—C29A—C28A	100 (4)	C38A—C37A—H37B	109
O30B—C29B—C28B	110 (5)	H37A—C37A—H37B	108
O30A—C31A—C32A	106 (5)	O36B—C37B—H37C	110
O30B—C31B—C32B	110 (5)	O36B—C37B—H37D	109
O33A—C32A—C31A	99 (5)	C38B—C37B—H37C	110
O33B—C32B—C31B	105 (5)	C38B—C37B—H37D	110
O33A—C34A—C35A	99 (5)	H37C—C37B—H37D	108
O33B—C34B—C35B	115 (5)	O26A—C38A—H38A	110
O36A—C35A—C34A	112 (5)	O26A—C38A—H38B	109
O36B—C35B—C34B	108 (5)	C37A—C38A—H38A	110
O36A—C37A—C38A	112 (5)	C37A—C38A—H38B	109
O36B—C37B—C38B	108 (5)	H38A—C38A—H38B	108
O26A—C38A—C37A	110 (5)	O26B—C38B—H38C	110
O26B—C38B—C37B	110 (5)	O26B—C38B—H38D	109
C2A—C1A—H1A	120	C37B—C38B—H38C	110
C6A—C1A—H1A	120	C37B—C38B—H38D	109
C2B—C1B—H1B	120	H38C—C38B—H38D	109
C6B—C1B—H1B	120

N17B—Cu—N9A—C10A	111 (5)	C31B—O30B—C29B—C28B	−167 (5)
O24A—Cu—N9B—S8B	82 (3)	C29B—O30B—C31B—C32B	152 (5)
O24B—Cu—N9B—S8B	0 (2)	C34A—O33A—C32A—C31A	−172 (5)
N9A—Cu—N9B—S8B	34 (5)	C32A—O33A—C34A—C35A	148 (6)
N17A—Cu—N9B—S8B	−80 (3)	C34B—O33B—C32B—C31B	135 (5)
N17B—Cu—N9B—S8B	156 (3)	C32B—O33B—C34B—C35B	−175 (5)
O24A—Cu—N9B—C10B	−94 (6)	C37A—O36A—C35A—C34A	168 (5)
O24B—Cu—N9B—C10B	−176 (7)	C35A—O36A—C37A—C38A	57 (6)
O24A—Cu—N17B—C18B	−82 (4)	C37B—O36B—C35B—C34B	−140 (5)
O24B—Cu—N17B—C18B	−147 (3)	C35B—O36B—C37B—C38B	145 (4)
N9A—Cu—N17B—C18B	−34 (5)	Cu—N9A—C10A—C15A	15 (7)
N9B—Cu—N17B—C18B	179 (4)	S8A—N9A—C10A—C11A	−8 (7)
N17A—Cu—N17B—C18B	76 (5)	Cu—N9A—C10A—C11A	−167 (5)
N17B—Cu—O24B—S8B	−39 (4)	S8A—N9A—C10A—C15A	174 (4)
S8B—Cu—N9A—S8A	84 (3)	S8B—N9B—C10B—C11B	17 (9)
O24A—Cu—N9A—S8A	7 (2)	S8B—N9B—C10B—C15B	−160 (5)
O24B—Cu—N9A—S8A	95 (3)	Cu—N9B—C10B—C15B	15 (9)
N9B—Cu—N9A—S8A	65 (5)	Cu—N9B—C10B—C11B	−168 (5)
S8B—Cu—O24A—S8A	−124.5 (15)	Cu—N17A—C18A—C23A	127 (5)
O24B—Cu—O24A—S8A	−95.5 (17)	Cu—N17A—C18A—C19A	−53 (7)
N9A—Cu—O24A—S8A	−7 (2)	C18A—N17A—C16A—C15A	158 (6)
N9B—Cu—O24A—S8A	−156 (2)	C16A—N17A—C18A—C19A	136 (7)
N17A—Cu—O24A—S8A	−18 (4)	Cu—N17B—C18B—C23B	152 (4)
N17B—Cu—O24A—S8A	119 (2)	Cu—N17B—C16B—C15B	−13 (9)
O24A—Cu—O24B—S8B	−100.4 (18)	C18B—N17B—C16B—C15B	−172 (6)
N9A—Cu—O24B—S8B	−160 (2)	C16B—N17B—C18B—C19B	130 (6)
N9B—Cu—O24B—S8B	0 (2)	Cu—N17B—C18B—C19B	−33 (7)
N17A—Cu—O24B—S8B	107 (2)	C16B—N17B—C18B—C23B	−45 (8)
O24A—Cu—N17A—C18A	−146 (4)	C6A—C1A—C2A—S8A	−179 (5)
O24B—Cu—N17A—C18A	−69 (4)	C6A—C1A—C2A—C3A	0 (9)
N9A—Cu—N17A—C18A	−156 (4)	C2A—C1A—C6A—C5A	1 (9)
N9B—Cu—N17A—C18A	−9 (5)	C6B—C1B—C2B—S8B	−180 (5)
N17A—Cu—N9A—S8A	−179 (3)	S8A—C2A—C3A—C4A	179 (4)
N17B—Cu—N9A—S8A	−50 (3)	C1A—C2A—C3A—C4A	0 (8)
O24A—Cu—N9A—C10A	167 (5)	C1B—C2B—C3B—C4B	−1 (9)
O24B—Cu—N9A—C10A	−105 (5)	S8B—C2B—C3B—C4B	178 (5)
N9B—Cu—N9A—C10A	−135 (5)	C2A—C3A—C4A—C5A	−1 (8)
N17A—Cu—N9A—C10A	−18 (5)	C2B—C3B—C4B—C5B	2 (9)
N9A—Cu—N17A—C16A	16 (5)	C3A—C4A—C5A—C6A	1 (8)
N9B—Cu—N17A—C16A	163 (5)	C3A—C4A—C5A—C7A	−180 (5)
N17B—Cu—N17A—C16A	−102 (5)	C3B—C4B—C5B—C7B	179 (6)
N17A—Cu—N9B—C10B	105 (6)	C7A—C5A—C6A—C1A	180 (6)
N17B—Cu—N9B—C10B	−20 (6)	C4A—C5A—C6A—C1A	−1 (8)
O24A—Cu—N17A—C16A	26 (7)	C7B—C5B—C6B—C1B	180 (6)
O24B—Cu—N17A—C16A	103 (5)	C11A—C10A—C15A—C14A	2 (8)
N17B—Cu—N17A—C18A	85 (5)	C11A—C10A—C15A—C16A	177 (6)
N9A—Cu—N9B—C10B	−141 (5)	N9A—C10A—C11A—C12A	180 (6)
O24A—Cu—N17B—C16B	117 (6)	N9A—C10A—C15A—C16A	−6 (9)
O24B—Cu—N17B—C16B	53 (7)	C15A—C10A—C11A—C12A	−3 (9)
N9A—Cu—N17B—C16B	165 (5)	N9A—C10A—C15A—C14A	180 (5)
N9B—Cu—N17B—C16B	18 (6)	N9B—C10B—C11B—C12B	−177 (6)
N17A—Cu—N17B—C16B	−85 (6)	N9B—C10B—C15B—C14B	178 (6)
O24A—S8A—N9A—C10A	−173 (4)	C11B—C10B—C15B—C16B	−178 (6)
O25A—S8A—N9A—Cu	116 (3)	C11B—C10B—C15B—C14B	0 (9)
N9A—S8A—O24A—Cu	8 (2)	C15B—C10B—C11B—C12B	0 (9)
C2A—S8A—N9A—Cu	−122 (3)	C10B—C11B—C12B—C13B	1 (9)
C2A—S8A—N9A—C10A	76 (5)	C11B—C12B—C13B—C14B	−3 (9)
O25A—S8A—N9A—C10A	−46 (5)	C12A—C13A—C14A—C15A	2 (9)
O25A—S8A—O24A—Cu	−118 (2)	C12B—C13B—C14B—C15B	3 (9)
C2A—S8A—O24A—Cu	118 (2)	C13A—C14A—C15A—C10A	−2 (8)
O24A—S8A—N9A—Cu	−11 (3)	C13A—C14A—C15A—C16A	−177 (6)
O25A—S8A—C2A—C1A	−16 (5)	C13B—C14B—C15B—C10B	−2 (9)
N9A—S8A—C2A—C1A	−138 (5)	C13B—C14B—C15B—C16B	176 (6)
O24A—S8A—C2A—C1A	112 (5)	C14A—C15A—C16A—N17A	−180 (6)
N9A—S8A—C2A—C3A	42 (5)	C14B—C15B—C16B—N17B	−178 (6)
O25A—S8A—C2A—C3A	165 (4)	N17A—C18A—C23A—C22A	−178 (6)
O24A—S8A—C2A—C3A	−68 (5)	N17A—C18A—C19A—C20A	180 (6)
O25B—S8B—N9B—Cu	122 (3)	C19A—C18A—C23A—C22A	1 (9)
C2B—S8B—O24B—Cu	119 (3)	N17B—C18B—C23B—C22B	178 (6)
Cu—S8B—N9B—C10B	176 (7)	C23B—C18B—C19B—C20B	−2 (9)
O24B—S8B—N9B—C10B	177 (5)	C19B—C18B—C23B—C22B	2 (9)
C2B—S8B—N9B—Cu	−117 (3)	N17B—C18B—C19B—C20B	−177 (5)
C2B—S8B—N9B—C10B	59 (6)	C18A—C19A—C20A—O26A	179 (6)
O25B—S8B—N9B—C10B	−62 (5)	C18A—C19A—C20A—C21A	−2 (9)
Cu—S8B—C2B—C3B	21 (6)	C18B—C19B—C20B—C21B	2 (9)
O24B—S8B—C2B—C3B	−50 (6)	C18B—C19B—C20B—O26B	174 (6)
O25B—S8B—C2B—C3B	−178 (5)	O26A—C20A—C21A—C22A	−179 (5)
O24B—S8B—N9B—Cu	1 (4)	C19A—C20A—C21A—O27A	−180 (5)
O24B—S8B—C2B—C1B	130 (5)	O26A—C20A—C21A—O27A	−1 (8)
O25B—S8B—C2B—C1B	1 (6)	C19A—C20A—C21A—C22A	3 (8)
N9B—S8B—C2B—C1B	−115 (6)	O26B—C20B—C21B—C22B	−176 (5)
O25B—S8B—O24B—Cu	−115 (2)	C19B—C20B—C21B—O27B	−180 (5)
N9B—S8B—O24B—Cu	0 (2)	C19B—C20B—C21B—C22B	−3 (9)
N9B—S8B—C2B—C3B	65 (6)	O26B—C20B—C21B—O27B	7 (9)
Cu—S8B—C2B—C1B	−159 (4)	C20A—C21A—C22A—C23A	−1 (9)
C38A—O26A—C20A—C19A	−14 (9)	O27A—C21A—C22A—C23A	−179 (5)
C20A—O26A—C38A—C37A	−166 (5)	C20B—C21B—C22B—C23B	4 (9)
C38A—O26A—C20A—C21A	168 (5)	O27B—C21B—C22B—C23B	−180 (6)
C38B—O26B—C20B—C21B	−171 (5)	C21A—C22A—C23A—C18A	0 (9)
C20B—O26B—C38B—C37B	171 (5)	C21B—C22B—C23B—C18B	−3 (9)
C38B—O26B—C20B—C19B	17 (9)	O27A—C28A—C29A—O30A	−35 (6)
C28A—O27A—C21A—C20A	175 (5)	O27B—C28B—C29B—O30B	58 (7)
C28A—O27A—C21A—C22A	−7 (8)	O30A—C31A—C32A—O33A	92 (5)
C21A—O27A—C28A—C29A	−177 (5)	O30B—C31B—C32B—O33B	−82 (6)
C28B—O27B—C21B—C22B	5 (9)	O33A—C34A—C35A—O36A	35 (6)
C21B—O27B—C28B—C29B	−177 (5)	O33B—C34B—C35B—O36B	132 (5)
C28B—O27B—C21B—C20B	−178 (6)	O36A—C37A—C38A—O26A	40 (7)
C29A—O30A—C31A—C32A	141 (5)	O36B—C37B—C38B—O26B	−72 (6)
C31A—O30A—C29A—C28A	−177 (5)

(LiNCS) top

Crystal data top

C₂₉H₃₂LiN₃O₇S₂	F(000) = 1272
M_r = 605.66	D_x = 1.295 Mg m⁻³
Monoclinic, P2₁/c	Synchrotron radiation, λ = 0.52000(1) Å
a = 9.2918 (3) Å	µ = 0.12 mm⁻¹
b = 23.0117 (7) Å	T = 295 K
c = 15.2798 (5) Å	Particle morphology: no specific habit
β = 108.063 (2)°	yellow
V = 3106.11 (17) Å³	cylinder, 15 × 0.3 mm
Z = 4	Specimen preparation: Prepared at 295 K and 101.3(2) kPa

Data collection top

ESRF powder diffractometer	Data collection mode: transmission
Radiation source: BM1B bending magnet at ESRF, synchrotron radiation	Scan method: continuous
Si 111 double crystal monochromator	2θ_min = 3.024°, 2θ_max = 23.024°, 2θ_step = 0.004°
Specimen mounting: Specimen was sealed in a 0.3 mm diameter borosilicate glass capillary

Refinement top

Refinement on I_net	213 parameters
Least-squares matrix: full with fixed elements per cycle	124 restraints
R_p = 0.044	39 constraints
R_wp = 0.055	H-atom parameters not refined
R_exp = 0.027	Weighting scheme based on measured s.u.'s
χ² = 3.920	(Δ/σ)_max = 0.035
5001 data points	Background function: Chebyshev polynomial up to the 5th order
Profile function: split-type pseudo-Voigt (Toraya, 1986)	Preferred orientation correction: March-Dollase texture correction (Dollase, 1986). Direction of preferred orientation - 001, texture parameter r = 0.910(9).

Crystal data top

C₂₉H₃₂LiN₃O₇S₂	V = 3106.11 (17) Å³
M_r = 605.66	Z = 4
Monoclinic, P2₁/c	Synchrotron radiation, λ = 0.52000(1) Å
a = 9.2918 (3) Å	µ = 0.12 mm⁻¹
b = 23.0117 (7) Å	T = 295 K
c = 15.2798 (5) Å	cylinder, 15 × 0.3 mm
β = 108.063 (2)°

Data collection top

ESRF powder diffractometer	Scan method: continuous
Specimen mounting: Specimen was sealed in a 0.3 mm diameter borosilicate glass capillary	2θ_min = 3.024°, 2θ_max = 23.024°, 2θ_step = 0.004°
Data collection mode: transmission

Refinement top

R_p = 0.044	5001 data points
R_wp = 0.055	213 parameters
R_exp = 0.027	124 restraints
χ² = 3.920	H-atom parameters not refined

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.7423 (14)	0.2958 (5)	0.0474 (9)	0.034 (5)*
H1	0.6820	0.3119	0.0796	0.050*
C2	0.6752 (17)	0.2707 (6)	−0.0392 (9)	0.034 (5)*
C3	0.7670 (18)	0.2493 (6)	−0.0888 (9)	0.034 (1)*
H3	0.7233	0.2367	−0.1490	0.050*
C4	0.9248 (17)	0.2466 (6)	−0.0486 (9)	0.034 (5)*
H4	0.9839	0.2266	−0.0778	0.050*
C5	0.9926 (18)	0.2743 (6)	0.0363 (10)	0.034 (5)*
C6	0.9004 (18)	0.2965 (5)	0.0855 (8)	0.034 (5)*
H6	0.9444	0.3118	0.1440	0.050*
C7	1.1629 (17)	0.2778 (6)	0.0743 (8)	0.034 (5)*
H7A	1.2069	0.2605	0.0314	0.050*
H7B	1.1968	0.2573	0.1318	0.050*
H7C	1.1932	0.3177	0.0838	0.050*
S8	0.4794 (8)	0.2611 (3)	−0.0808 (4)	0.082 (8)*
N9	0.4078 (16)	0.3236 (6)	−0.1250 (9)	0.034 (5)*
H9B	0.4187	0.3469	−0.0794	0.050*
C10	0.4563 (19)	0.3539 (10)	−0.1906 (13)	0.034 (5)*
C11	0.5057 (17)	0.3253 (6)	−0.2584 (10)	0.034 (5)*
H11	0.5110	0.2849	−0.2578	0.050*
C12	0.5464 (16)	0.3558 (7)	−0.3258 (8)	0.034 (5)*
H12	0.5773	0.3358	−0.3697	0.050*
C13	0.5407 (14)	0.4169 (6)	−0.3274 (8)	0.034 (5)*
H13	0.5729	0.4375	−0.3702	0.050*
C14	0.4865 (17)	0.4461 (6)	−0.2645 (10)	0.034 (5)*
H14	0.4722	0.4861	−0.2698	0.050*
C15	0.4524 (16)	0.4160 (7)	−0.1922 (9)	0.034 (5)*
C16	0.4053 (16)	0.4516 (6)	−0.1269 (9)	0.034 (5)*
H16	0.4069	0.4918	−0.1325	0.050*
N17	0.3599 (12)	0.4289 (4)	−0.0593 (7)	0.034 (5)*
C18	0.2904 (15)	0.4635 (6)	−0.0021 (10)	0.034 (5)*
C19	0.2885 (15)	0.4413 (6)	0.0825 (10)	0.034 (5)*
H19	0.3321	0.4052	0.1019	0.050*
C20	0.221 (2)	0.4727 (9)	0.1389 (12)	0.034 (5)*
C21	0.1504 (19)	0.5264 (8)	0.1077 (12)	0.034 (5)*
C22	0.1619 (14)	0.5501 (5)	0.0252 (8)	0.034 (5)*
H22	0.1302	0.5880	0.0090	0.050*
C23	0.2201 (15)	0.5173 (6)	−0.0324 (7)	0.034 (5)*
H23	0.2126	0.5308	−0.0909	0.050*
O24	0.4429 (12)	0.2225 (4)	−0.1593 (6)	0.034 (5)*
O25	0.4152 (13)	0.2436 (5)	−0.0105 (8)	0.034 (5)*
O26	0.2132 (11)	0.4505 (4)	0.2206 (6)	0.034 (5)*
O27	0.0917 (12)	0.5572 (5)	0.1652 (7)	0.034 (5)*
C28	0.0445 (15)	0.6164 (7)	0.1523 (8)	0.034 (5)*
H28A	−0.0305	0.6213	0.0924	0.050*
H28B	0.1302	0.6412	0.1554	0.050*
C29	−0.0243 (15)	0.6328 (6)	0.2297 (9)	0.034 (5)*
H29A	−0.0408	0.6744	0.2300	0.050*
H29B	−0.1205	0.6132	0.2198	0.050*
O30	0.0807 (11)	0.6149 (4)	0.3146 (6)	0.034 (5)*
C31	0.0385 (15)	0.6308 (6)	0.3933 (9)	0.034 (5)*
H31A	−0.0629	0.6171	0.3870	0.050*
H31B	0.0407	0.6727	0.4004	0.050*
C32	0.1550 (16)	0.6018 (7)	0.4778 (8)	0.034 (5)*
H32A	0.2538	0.6196	0.4896	0.050*
H32B	0.1231	0.6061	0.5322	0.050*
O33	0.1609 (10)	0.5421 (4)	0.4556 (6)	0.034 (5)*
C34	0.2534 (15)	0.5072 (7)	0.5275 (8)	0.034 (5)*
H34A	0.2180	0.5088	0.5808	0.050*
H34B	0.3573	0.5206	0.5453	0.050*
C35	0.2422 (15)	0.4441 (6)	0.4895 (9)	0.034 (5)*
H35A	0.3211	0.4200	0.5294	0.050*
H35B	0.1447	0.4272	0.4857	0.050*
O36	0.2598 (11)	0.4479 (4)	0.3997 (6)	0.034 (5)*
C37	0.2527 (15)	0.3924 (6)	0.3568 (9)	0.034 (5)*
H37A	0.1517	0.3762	0.3432	0.050*
H37B	0.3238	0.3658	0.3973	0.050*
C38	0.2931 (16)	0.4013 (6)	0.2667 (10)	0.034 (5)*
H38A	0.4012	0.4073	0.2807	0.050*
H38B	0.2649	0.3671	0.2278	0.050*
S39	−0.2921 (5)	0.3885 (2)	0.2488 (3)	0.073 (8)*
C40	−0.1545 (16)	0.4374 (6)	0.2745 (9)	0.053 (11)*
N41	−0.0681 (14)	0.4732 (5)	0.2815 (7)	0.053 (11)*
Li42	0.115 (3)	0.5193 (11)	0.2887 (16)	0.053 (11)*

Geometric parameters (Å, º) top

S8—O24	1.442 (11)	C18—C19	1.40 (2)
S8—O25	1.442 (14)	C19—C20	1.41 (2)
S8—N9	1.643 (15)	C20—C21	1.42 (3)
S8—C2	1.742 (18)	C21—C22	1.40 (2)
S39—C40	1.656 (15)	C22—C23	1.395 (18)
O26—C20	1.37 (2)	C28—C29	1.552 (19)
O26—C38	1.417 (17)	C31—C32	1.555 (19)
O26—Li42	2.24 (3)	C34—C35	1.55 (2)
O27—C21	1.36 (2)	C37—C38	1.55 (2)
O27—C28	1.42 (2)	C1—H1	0.93
O27—Li42	2.03 (3)	C3—H3	0.93
O30—C29	1.424 (16)	C4—H4	0.93
O30—C31	1.423 (17)	C6—H6	0.93
O30—Li42	2.27 (3)	C7—H7A	0.96
O33—C32	1.421 (18)	C7—H7B	0.96
O33—C34	1.419 (16)	C7—H7C	0.96
O33—Li42	2.50 (3)	C11—H11	0.93
O36—C35	1.433 (16)	C12—H12	0.93
O36—C37	1.425 (16)	C13—H13	0.93
O36—Li42	2.44 (3)	C14—H14	0.93
N9—C10	1.40 (2)	C16—H16	0.93
N17—C16	1.338 (18)	C19—H19	0.93
N17—C18	1.471 (18)	C22—H22	0.93
N41—C40	1.136 (19)	C23—H23	0.93
N41—Li42	1.98 (3)	C28—H28A	0.97
N9—H9B	0.86	C28—H28B	0.97
C1—C2	1.399 (18)	C29—H29A	0.97
C1—C6	1.41 (2)	C29—H29B	0.97
C2—C3	1.40 (2)	C31—H31A	0.97
C3—C4	1.40 (2)	C31—H31B	0.97
C4—C5	1.40 (2)	C32—H32A	0.97
C5—C6	1.40 (2)	C32—H32B	0.97
C5—C7	1.51 (2)	C34—H34A	0.97
C10—C11	1.42 (2)	C34—H34B	0.97
C10—C15	1.43 (3)	C35—H35A	0.97
C11—C12	1.39 (2)	C35—H35B	0.97
C12—C13	1.41 (2)	C37—H37A	0.97
C13—C14	1.39 (2)	C37—H37B	0.97
C14—C15	1.42 (2)	C38—H38A	0.97
C15—C16	1.46 (2)	C38—H38B	0.97
C18—C23	1.41 (2)

O24—S8—O25	113.5 (8)	H7A—C7—H7B	109
O24—S8—N9	103.7 (7)	C5—C7—H7A	109
O24—S8—C2	109.6 (8)	C5—C7—H7B	109
O25—S8—N9	110.1 (8)	C5—C7—H7C	109
O25—S8—C2	112.8 (8)	H7B—C7—H7C	109
N9—S8—C2	106.5 (8)	C10—C11—H11	119
C20—O26—C38	125.5 (13)	C12—C11—H11	119
C20—O26—Li42	108.2 (12)	C13—C12—H12	120
C38—O26—Li42	123.9 (10)	C11—C12—H12	120
C21—O27—C28	125.2 (12)	O33—C32—H32B	110
C21—O27—Li42	115.1 (13)	H32A—C32—H32B	109
C28—O27—Li42	118.5 (11)	C31—C32—H32B	110
C29—O30—C31	113.8 (11)	C31—C32—H32A	110
C29—O30—Li42	102.5 (9)	C35—C34—H34B	110
C31—O30—Li42	119.1 (10)	C35—C34—H34A	110
C32—O33—C34	115.0 (10)	O33—C34—H34B	110
C35—O36—C37	112.7 (10)	O33—C34—H34A	110
C35—O36—Li42	120.1 (10)	H34A—C34—H34B	109
C37—O36—Li42	110.3 (9)	O36—C35—H35A	110
S8—N9—C10	123.2 (13)	O36—C35—H35B	110
C16—N17—C18	122.9 (11)	C34—C35—H35A	110
C40—N41—Li42	165.3 (14)	C34—C35—H35B	110
C10—N9—H9B	106.45	H35A—C35—H35B	109
S8—N9—H9B	106.60	O36—C37—H37A	110
C2—C1—C6	119.8 (13)	O36—C37—H37B	110
S8—C2—C3	119.9 (11)	C38—C37—H37A	110
S8—C2—C1	120.4 (12)	C12—C13—H13	120
C1—C2—C3	119.4 (14)	C14—C13—H13	120
C18—C23—C22	120.0 (11)	C15—C14—H14	119
O27—C28—C29	108.2 (11)	C13—C14—H14	119
O30—C29—C28	107.1 (11)	N17—C16—H16	119
O30—C31—C32	106.8 (11)	C15—C16—H16	119
O33—C32—C31	106.3 (10)	C18—C19—H19	119
C34—O33—Li42	122.7 (12)	C20—C19—H19	119
C32—O33—Li42	116.2 (11)	C23—C22—H22	120
O33—C34—C35	106.7 (10)	C21—C22—H22	120
O36—C35—C34	107.0 (10)	C18—C23—H23	120
O36—C37—C38	107.4 (11)	C22—C23—H23	120
O26—C38—C37	108.5 (11)	O27—C28—H28A	110
S39—C40—N41	171.5 (13)	O27—C28—H28B	110
C2—C3—C4	120.5 (12)	H28A—C28—H28B	108
C3—C4—C5	119.7 (14)	C29—C28—H28B	110
C6—C5—C7	121.1 (12)	C29—C28—H28A	110
C4—C5—C7	119.7 (14)	O30—C29—H29B	110
C4—C5—C6	119.1 (15)	O30—C29—H29A	110
C1—C6—C5	120.7 (12)	C28—C29—H29B	110
N9—C10—C11	122.5 (18)	H29A—C29—H29B	108
N9—C10—C15	119.5 (16)	C28—C29—H29A	110
C11—C10—C15	118.0 (16)	C32—C31—H31A	110
C10—C11—C12	121.8 (15)	C32—C31—H31B	110
C11—C12—C13	119.9 (13)	O30—C31—H31A	110
C12—C13—C14	119.6 (12)	O30—C31—H31B	110
C13—C14—C15	121.3 (13)	H31A—C31—H31B	109
C10—C15—C14	119.1 (14)	O33—C32—H32A	110
C10—C15—C16	124.4 (14)	C38—C37—H37B	110
C14—C15—C16	116.4 (13)	H37A—C37—H37B	108
N17—C16—C15	122.4 (12)	C37—C38—H38A	110
C19—C18—C23	119.1 (13)	C37—C38—H38B	110
N17—C18—C23	121.6 (12)	O26—C38—H38B	110
N17—C18—C19	119.2 (12)	O26—C38—H38A	110
C18—C19—C20	121.2 (14)	H38A—C38—H38B	108
O26—C20—C21	118.6 (16)	O30—Li42—N41	111.3 (13)
O26—C20—C19	122.0 (16)	O36—Li42—N41	87.7 (10)
C19—C20—C21	119.2 (16)	O27—Li42—O30	76.3 (9)
O27—C21—C22	122.0 (15)	O27—Li42—O36	144.2 (14)
O27—C21—C20	118.4 (15)	O27—Li42—N41	109.5 (13)
C20—C21—C22	119.0 (16)	O30—Li42—O36	127.4 (11)
C21—C22—C23	120.6 (12)	O26—Li42—O27	79.1 (9)
C2—C1—H1	120	O26—Li42—O30	149.5 (13)
C6—C1—H1	120	O26—Li42—O36	68.4 (8)
C2—C3—H3	120	O26—Li42—N41	93.7 (11)
C4—C3—H3	120	N41—Li42—O33	92.7 (10)
C5—C4—H4	120	O27—Li42—O33	142.1 (14)
C3—C4—H4	120	O26—Li42—O33	131.1 (12)
C5—C6—H6	120	O30—Li42—O33	67.0 (9)
C1—C6—H6	120	O36—Li42—O33	63.5 (8)
H7A—C7—H7C	110

O24—S8—N9—C10	−63.0 (16)	Li42—O36—C37—C38	49.8 (14)
O25—S8—N9—C10	175.3 (14)	C35—O36—Li42—O26	−164.2 (10)
C2—S8—N9—C10	52.6 (16)	Li42—O36—C35—C34	−47.8 (15)
O24—S8—C2—C3	8.8 (14)	C35—O36—C37—C38	−173.0 (11)
O25—S8—C2—C3	136.3 (12)	C37—O36—C35—C34	179.6 (11)
N9—S8—C2—C3	−102.8 (12)	C35—O36—Li42—O27	170 (2)
N9—S8—C2—C1	82.2 (12)	C37—O36—Li42—O26	−30.6 (11)
O24—S8—C2—C1	−166.2 (10)	C35—O36—Li42—N41	−69.3 (13)
O25—S8—C2—C1	−38.7 (14)	C37—O36—Li42—N41	64.3 (12)
C20—O26—Li42—N41	115.6 (12)	S8—N9—C10—C11	34 (2)
C20—O26—Li42—O27	6.4 (14)	S8—N9—C10—C15	−148.2 (14)
C20—O26—Li42—O30	−30 (3)	C16—N17—C18—C19	−160.7 (14)
C20—O26—Li42—O36	−158.4 (11)	C18—N17—C16—C15	−170.6 (13)
Li42—O26—C20—C19	175.2 (16)	C16—N17—C18—C23	22 (2)
C38—O26—Li42—O30	133 (2)	C6—C1—C2—S8	171.7 (10)
C38—O26—Li42—O36	4.9 (13)	C6—C1—C2—C3	−3.4 (19)
C38—O26—Li42—N41	−81.1 (14)	C2—C1—C6—C5	2.7 (18)
C38—O26—Li42—O27	169.7 (11)	C1—C2—C3—C4	7 (2)
C38—O26—C20—C19	12 (2)	S8—C2—C3—C4	−167.9 (11)
Li42—O26—C38—C37	19.1 (17)	C2—C3—C4—C5	−10 (2)
Li42—O26—C20—C21	−9 (2)	C3—C4—C5—C6	9 (2)
C20—O26—C38—C37	179.5 (14)	C3—C4—C5—C7	−172.9 (13)
C38—O26—C20—C21	−171.7 (15)	C7—C5—C6—C1	176.6 (12)
C28—O27—C21—C20	167.2 (15)	C4—C5—C6—C1	−5.7 (19)
C28—O27—Li42—O26	−171.7 (11)	N9—C10—C15—C14	−173.4 (15)
C28—O27—Li42—N41	98.1 (15)	N9—C10—C15—C16	2 (3)
C28—O27—C21—C22	−4 (2)	C11—C10—C15—C14	5 (2)
C21—O27—C28—C29	176.4 (14)	C11—C10—C15—C16	−179.7 (15)
Li42—O27—C21—C20	0 (2)	N9—C10—C11—C12	176.6 (15)
C28—O27—Li42—O30	−10.0 (14)	C15—C10—C11—C12	−1 (2)
C21—O27—Li42—N41	−93.4 (16)	C10—C11—C12—C13	1 (2)
C21—O27—Li42—O30	158.5 (12)	C11—C12—C13—C14	−4 (2)
C21—O27—Li42—O26	−3.3 (14)	C12—C13—C14—C15	7 (2)
Li42—O27—C28—C29	−16.4 (17)	C13—C14—C15—C10	−8 (2)
C28—O27—Li42—O36	−147.0 (19)	C13—C14—C15—C16	176.3 (14)
C21—O27—Li42—O36	21 (3)	C10—C15—C16—N17	0 (2)
Li42—O27—C21—C22	−171.3 (15)	C14—C15—C16—N17	175.3 (14)
C31—O30—Li42—N41	56.7 (15)	N17—C18—C23—C22	−177.2 (12)
C29—O30—Li42—O27	36.0 (11)	N17—C18—C19—C20	−178.7 (14)
Li42—O30—C31—C32	52.6 (15)	C23—C18—C19—C20	−2 (2)
C31—O30—Li42—O27	162.6 (10)	C19—C18—C23—C22	6 (2)
C29—O30—Li42—O26	73 (3)	C18—C19—C20—O26	177.8 (15)
C31—O30—Li42—O26	−160 (2)	C18—C19—C20—C21	2 (3)
C29—O30—C31—C32	173.7 (11)	O26—C20—C21—C22	178.0 (15)
C29—O30—Li42—O36	−174.1 (14)	C19—C20—C21—C22	−6 (3)
C31—O30—Li42—O36	−47 (2)	O26—C20—C21—O27	7 (3)
C29—O30—Li42—N41	−69.9 (13)	C19—C20—C21—O27	−177.0 (15)
Li42—O30—C29—C28	−54.3 (13)	O27—C21—C22—C23	−179.0 (14)
C31—O30—C29—C28	175.7 (11)	C20—C21—C22—C23	10 (2)
C32—O33—C34—C35	179.4 (11)	C21—C22—C23—C18	−10 (2)
C34—O33—C32—C31	−175.4 (11)	O27—C28—C29—O30	49.4 (14)
C35—O36—Li42—O30	46 (2)	O30—C31—C32—O33	−51.2 (14)
C37—O36—Li42—O27	−57 (3)	O33—C34—C35—O36	45.8 (14)
C37—O36—Li42—O30	179.6 (14)	O36—C37—C38—O26	−44.9 (14)

Experimental details

	(CuL2)	(LiNCS)
Crystal data
Chemical formula	C₅₆H₆₂CuN₄O₁₄S₂	C₂₉H₃₂LiN₃O₇S₂
M_r	1142.79	605.66
Crystal system, space group	Monoclinic, P2₁/c	Monoclinic, P2₁/c
Temperature (K)	295	295
a, b, c (Å)	19.0356 (6), 17.4332 (6), 17.4180 (6)	9.2918 (3), 23.0117 (7), 15.2798 (5)
β (°)	113.824 (3)	108.063 (2)
V (Å³)	5287.7 (3)	3106.11 (17)
Z	4	4
Radiation type	Synchrotron, λ = 0.51966(1) Å	Synchrotron, λ = 0.52000(1) Å
µ (mm⁻¹)	0.30	0.12
Specimen shape, size (mm)	Cylinder, 15 × 0.3	Cylinder, 15 × 0.3

Data collection
Diffractometer	ESRF powder diffractometer	ESRF powder diffractometer
Specimen mounting	Specimen was sealed in a 0.3 mm diameter borosilicate glass capillary	Specimen was sealed in a 0.3 mm diameter borosilicate glass capillary
Data collection mode	Transmission	Transmission
Scan method	Continuous	Continuous
2θ values (°)	2θ_min = 1.017 2θ_max = 22.014 2θ_step = 0.003	2θ_min = 3.024 2θ_max = 23.024 2θ_step = 0.004

Refinement
R factors and goodness of fit	R_p = 0.046, R_wp = 0.063, R_exp = 0.048, χ² = 1.700	R_p = 0.044, R_wp = 0.055, R_exp = 0.027, χ² = 3.920
No. of data points	7000	5001
No. of parameters	277	213
No. of restraints	233	124
H-atom treatment	H-atom parameters not refined	H-atom parameters not refined

Computer programs: LSPAID (Visser et al., 1986), MRIA (Zlokazov et al., 1992), MRIA, PLATON (Spek, 2003).

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