A bis-copper(II)–[D-βVal^3,7]ascidiacyclamide complex enveloping two square pyramids and sharing an apex atom from a carbonate anion

The four azole rings place structural restrictions on ascidiacyclamide (ASC). As a result, the structure of ASC exists in an equilibrium between two major forms (i.e. folded and square). [D-βVal^3,7]Ascidiacyclamide (βASC) was synthesized by replacing two D-Val-Thz (Val is valine and Thz is thiazole) blocks with D-β-Valine (D-βVal-Thz). This modification expands the peptide ring; the original 24-membered macrocycle of ASC becomes a 26-membered ring. Circular dichroism (CD) spectra showed that, in solution, the structural equilibrium is maintained with βASC, but the folded form is dominant. A copper complex was prepared, namely [[D-βVal^3,7]ascidia­cyclamide­(2−)]aqua-μ-carbonato-dicopper(II) mono­hydrate, [Cu₂(C₃₈H₅₄N₈O₆S₂)(CO₃)(H₂O)]·H₂O, to determine the effect of the change in ring size on the coordinated structure. The obtained bis-Cu^II–βASC complex contains two water mol­ecules and a carbonate anion. Two Cu^II ions are chelated by three N-donor atoms of two Thz–Ile–Oxz (Ile is isoleucine and Oxz is oxazoline) units. An O atom of the carbonate anion bridges two Cu^II ions, forming two square pyramids. These features are similar to the previously reported structure of the Cu^II–ASC complex, but the two pyramids are enveloped inside the peptide and share one apex. In the Cu^II–ASC complex, the apex of each square pyramid is an O atom of a water mol­ecule, and the two pyramids are oriented toward the outside of the peptide. The incorporated β-amino acids of βASC make the space inside the peptide large enough to envelop the two square pyramids. The observed structural changes in the bis-Cu^II–βASC complex arising from ring expansion are particularly inter­esting in the context of the previously reported structure of the Cu^II–ASC complex.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015) and PLATON (Spek, 2009).

[[D-βVal^3,7]Ascidiacyclamide(2-)]aqua-µ-carbonato-dicopper(II) monohydrate

Crystal data

[Cu2(CO3)(C38H54N8O6S2)(H2O)]·H2O	F(000) = 1052
Mr = 1006.13	Dx = 1.393 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 12.6321 (17) Å	Cell parameters from 6711 reflections
b = 13.9512 (19) Å	θ = 2.3–26.6°
c = 14.792 (2) Å	µ = 1.04 mm^−1
β = 113.077 (2)°	T = 240 K
V = 2398.3 (6) Å^3	Needle, blue
Z = 2	0.50 × 0.20 × 0.15 mm

Data collection

Bruker SMART APEX diffractometer	8140 independent reflections
Radiation source: M18XCE rotating anode	5984 reflections with I > 2σ(I)
Detector resolution: 8.366 pixels mm^-1	Rint = 0.075
ω–scan	θmax = 25.7°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
Tmin = 0.625, Tmax = 1.0	k = −16→17
13331 measured reflections	l = −18→17

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.115	w = 1/[σ^2(Fo^2) + (0.1787P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.283	(Δ/σ)max = 0.002
S = 1.04	Δρmax = 2.01 e Å^−3
8140 reflections	Δρmin = −1.98 e Å^−3
560 parameters	Absolute structure: Refined as a 2-component inversion twin.
37 restraints	Absolute structure parameter: 0.15 (4)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a 2-component twin

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

	x	y	z	Uiso*/Ueq
Cu1	0.08972 (13)	0.16232 (10)	0.08884 (10)	0.0330 (4)
Cu2	0.40676 (14)	0.14684 (11)	0.36439 (10)	0.0368 (5)
N1	0.0869 (10)	0.3008 (7)	0.0740 (8)	0.033 (3)
C1	0.1322 (11)	0.3401 (9)	0.0049 (9)	0.030 (3)
H1	0.071655	0.380045	−0.043631	0.036*
C2	0.2392 (12)	0.4037 (9)	0.0570 (9)	0.035 (3)
H2	0.220782	0.444768	0.103475	0.042*
C3	0.2642 (14)	0.4682 (11)	−0.0094 (11)	0.042 (3)
H3A	0.193752	0.502252	−0.050156	0.051*
H3B	0.289883	0.430713	−0.053044	0.051*
C4	0.3394 (13)	0.3392 (12)	0.1198 (11)	0.049 (4)
H4A	0.315134	0.298833	0.161566	0.073*
H4B	0.362852	0.299215	0.077233	0.073*
H4C	0.403713	0.378675	0.160336	0.073*
C5	0.3583 (18)	0.5419 (13)	0.0476 (12)	0.061 (5)
H5A	0.372940	0.583738	0.001367	0.092*
H5B	0.332502	0.579892	0.090028	0.092*
H5C	0.428553	0.508411	0.087143	0.092*
C6	0.1533 (11)	0.2544 (10)	−0.0479 (9)	0.033 (3)
N7	0.1544 (9)	0.1704 (8)	−0.0177 (7)	0.030 (2)
C7	0.1828 (12)	0.1095 (10)	−0.0865 (10)	0.037 (3)
H7	0.120345	0.061811	−0.114591	0.045*
C8	0.1789 (12)	0.1758 (10)	−0.1675 (9)	0.038 (3)
H8	0.251621	0.170251	−0.177708	0.046*
O8	0.1722 (9)	0.2707 (7)	−0.1286 (6)	0.039 (2)
C9	0.0796 (15)	0.1624 (12)	−0.2631 (10)	0.054 (4)
H9A	0.083818	0.099381	−0.289183	0.081*
H9B	0.008291	0.168129	−0.253293	0.081*
H9C	0.081865	0.211033	−0.309216	0.081*
C10	0.2978 (12)	0.0542 (9)	−0.0390 (9)	0.035 (3)
O10	0.3457 (10)	0.0308 (9)	−0.0931 (7)	0.056 (3)
N11	0.3333 (10)	0.0295 (8)	0.0542 (7)	0.035 (2)
H11	0.297838	0.050819	0.090046	0.042*
C11	0.4333 (12)	−0.0342 (11)	0.0971 (10)	0.041 (2)
H11A	0.487165	−0.020453	0.064869	0.050*
C12	0.4033 (14)	−0.1428 (12)	0.0843 (12)	0.049 (2)
H12	0.386213	−0.162874	0.141376	0.059*
C13	0.5119 (15)	−0.1992 (12)	0.0895 (13)	0.059 (4)
H13A	0.576856	−0.181600	0.148979	0.089*
H13B	0.497644	−0.267419	0.090169	0.089*
H13C	0.528836	−0.183561	0.032705	0.089*
C14	0.3006 (18)	−0.1675 (14)	−0.0064 (15)	0.069 (4)
H14A	0.287822	−0.236229	−0.008725	0.103*
H14B	0.233360	−0.134696	−0.005367	0.103*
H14C	0.313881	−0.147768	−0.063931	0.103*
C15	0.4951 (13)	−0.0127 (11)	0.2067 (9)	0.041 (3)
H15A	0.442796	−0.027575	0.239240	0.049*
H15B	0.561589	−0.055508	0.234121	0.049*
C16	0.5358 (12)	0.0882 (10)	0.2310 (9)	0.037 (3)
N17	0.5100 (9)	0.1461 (10)	0.2864 (7)	0.035 (2)
C17	0.5641 (12)	0.2356 (10)	0.2959 (9)	0.035 (3)
C18	0.6303 (13)	0.2449 (12)	0.2451 (10)	0.046 (3)
H18	0.672498	0.299976	0.243800	0.055*
S18	0.6267 (4)	0.1398 (3)	0.1820 (3)	0.0563 (10)
C19	0.5444 (14)	0.3062 (10)	0.3615 (10)	0.040 (3)
O19	0.5943 (9)	0.3850 (7)	0.3784 (7)	0.044 (2)
N21	0.4684 (11)	0.2748 (8)	0.3957 (8)	0.040 (3)
C21	0.4435 (13)	0.3284 (10)	0.4697 (10)	0.040 (3)
H21	0.516896	0.353967	0.518149	0.048*
C22	0.3617 (13)	0.4123 (11)	0.4274 (10)	0.041 (3)
H22	0.393244	0.451795	0.388277	0.049*
C23	0.3523 (15)	0.4753 (13)	0.5069 (12)	0.056 (4)
H23A	0.430084	0.490539	0.554116	0.068*
H23B	0.313730	0.439098	0.541965	0.068*
C24	0.2396 (16)	0.3767 (13)	0.3569 (12)	0.059 (4)
H24A	0.246746	0.336322	0.306197	0.088*
H24B	0.204914	0.340314	0.394040	0.088*
H24C	0.191447	0.431522	0.326644	0.088*
C25	0.286 (2)	0.5702 (16)	0.4696 (17)	0.087 (7)
H25A	0.284080	0.606295	0.524847	0.131*
H25B	0.324820	0.607603	0.436303	0.131*
H25C	0.208268	0.556074	0.424132	0.131*
C26	0.4010 (12)	0.2533 (10)	0.5192 (9)	0.039 (3)
N27	0.3622 (11)	0.1725 (8)	0.4758 (8)	0.039 (3)
C27	0.3144 (17)	0.1153 (10)	0.5387 (11)	0.051 (4)
H27	0.345064	0.049129	0.548121	0.062*
C28	0.3660 (14)	0.1724 (13)	0.6366 (10)	0.054 (4)
H28	0.309711	0.179072	0.667607	0.065*
O28	0.3949 (10)	0.2671 (8)	0.6061 (7)	0.049 (3)
C29	0.4807 (18)	0.1301 (16)	0.7089 (13)	0.076 (6)
H29A	0.466735	0.067816	0.731357	0.115*
H29B	0.533353	0.123079	0.676125	0.115*
H29C	0.514110	0.172623	0.764840	0.115*
C30	0.1888 (15)	0.1142 (10)	0.4939 (10)	0.044 (4)
O30	0.1311 (11)	0.1716 (11)	0.5180 (10)	0.078 (4)
N31	0.1424 (13)	0.0468 (9)	0.4258 (9)	0.048 (3)
H31	0.188330	0.011267	0.408942	0.058*
C31	0.0166 (19)	0.0289 (13)	0.3770 (13)	0.065 (3)
H31A	−0.023164	0.072650	0.406154	0.078*
C32	−0.016 (2)	−0.0747 (15)	0.3904 (14)	0.072 (3)
H32	0.016286	−0.117949	0.354825	0.086*
C33	0.036 (2)	−0.0998 (17)	0.4974 (16)	0.091 (5)
H33A	0.015809	−0.165051	0.506452	0.137*
H33B	0.119235	−0.094131	0.521306	0.137*
H33C	0.007494	−0.056315	0.533786	0.137*
C34	−0.150 (2)	−0.0838 (15)	0.3432 (15)	0.076 (4)
H34A	−0.177558	−0.066502	0.274273	0.114*
H34B	−0.171651	−0.149302	0.349374	0.114*
H34C	−0.183188	−0.041099	0.376663	0.114*
C35	−0.0212 (15)	0.0542 (12)	0.2681 (10)	0.047 (4)
H35A	0.030705	0.022428	0.242793	0.056*
H35B	−0.098598	0.028412	0.232277	0.056*
C36	−0.0227 (11)	0.1593 (13)	0.2469 (9)	0.040 (3)
N37	0.0107 (10)	0.1989 (9)	0.1822 (8)	0.036 (3)
C37	−0.0086 (11)	0.2967 (10)	0.1787 (9)	0.035 (3)
C38	−0.0570 (14)	0.3301 (12)	0.2402 (10)	0.045 (3)
H38	−0.076508	0.394391	0.244998	0.054*
S38	−0.0766 (3)	0.2395 (3)	0.3060 (3)	0.0486 (9)
C39	0.0311 (12)	0.3528 (9)	0.1117 (9)	0.035 (3)
O39	0.0090 (9)	0.4402 (7)	0.1006 (7)	0.044 (2)
C40	0.2614 (13)	0.0290 (9)	0.2524 (10)	0.036 (3)
O41	0.2494 (8)	0.1086 (7)	0.2098 (7)	0.042 (2)
O42	0.3421 (9)	0.0208 (8)	0.3400 (7)	0.046 (2)
O43	0.2008 (12)	−0.0433 (7)	0.2117 (8)	0.059 (3)
O44	0.0360 (10)	0.0283 (7)	0.0679 (7)	0.046 (2)
O45	0.2544 (11)	−0.0391 (11)	−0.2914 (9)	0.068 (3)
H44A	0.019350	0.017270	0.010070	0.082*
H44B	0.098730	−0.002375	0.100750	0.082*
H45A	0.283640	−0.016565	−0.229053	0.082*
H45B	0.296765	−0.067455	−0.317890	0.082*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0348 (9)	0.0274 (8)	0.0452 (8)	−0.0008 (7)	0.0246 (7)	−0.0012 (6)
Cu2	0.0380 (9)	0.0357 (10)	0.0397 (8)	0.0003 (7)	0.0185 (7)	−0.0011 (6)
N1	0.042 (8)	0.018 (5)	0.046 (6)	0.003 (4)	0.024 (6)	0.002 (4)
C1	0.025 (7)	0.026 (6)	0.039 (6)	0.000 (5)	0.013 (6)	0.002 (5)
C2	0.033 (8)	0.034 (7)	0.040 (6)	0.000 (6)	0.016 (6)	−0.008 (5)
C3	0.043 (9)	0.039 (8)	0.053 (8)	−0.005 (7)	0.027 (7)	−0.003 (6)
C4	0.029 (8)	0.049 (9)	0.050 (8)	0.001 (7)	−0.004 (7)	0.004 (6)
C5	0.080 (14)	0.050 (10)	0.068 (10)	−0.027 (9)	0.044 (10)	0.004 (8)
C6	0.023 (7)	0.030 (7)	0.047 (7)	−0.001 (5)	0.015 (6)	0.002 (5)
N7	0.035 (6)	0.031 (6)	0.035 (5)	−0.004 (5)	0.025 (5)	0.000 (4)
C7	0.022 (7)	0.038 (7)	0.051 (7)	−0.002 (6)	0.014 (7)	−0.002 (6)
C8	0.041 (8)	0.043 (8)	0.039 (6)	0.005 (6)	0.024 (6)	0.002 (5)
O8	0.049 (6)	0.032 (5)	0.046 (5)	−0.002 (4)	0.032 (5)	0.001 (4)
C9	0.064 (10)	0.045 (8)	0.046 (7)	−0.001 (9)	0.013 (7)	0.006 (7)
C10	0.028 (7)	0.030 (7)	0.045 (7)	−0.001 (6)	0.012 (6)	−0.008 (5)
O10	0.060 (7)	0.070 (7)	0.047 (5)	0.032 (6)	0.031 (6)	0.000 (5)
N11	0.037 (7)	0.033 (6)	0.041 (5)	0.015 (5)	0.021 (5)	0.001 (4)
C11	0.030 (6)	0.041 (5)	0.059 (5)	0.006 (4)	0.024 (5)	−0.009 (4)
C12	0.036 (5)	0.046 (5)	0.066 (5)	0.007 (4)	0.020 (5)	−0.009 (4)
C13	0.047 (7)	0.046 (7)	0.079 (7)	0.012 (6)	0.020 (6)	−0.012 (6)
C14	0.051 (8)	0.056 (7)	0.080 (8)	0.006 (7)	0.005 (7)	−0.010 (6)
C15	0.035 (8)	0.051 (9)	0.035 (6)	0.011 (6)	0.011 (6)	0.002 (6)
C16	0.021 (7)	0.039 (7)	0.039 (7)	0.004 (6)	−0.002 (6)	−0.005 (5)
N17	0.028 (6)	0.044 (7)	0.036 (5)	0.002 (6)	0.015 (5)	0.001 (5)
C17	0.035 (8)	0.026 (7)	0.045 (7)	−0.001 (6)	0.018 (6)	0.006 (5)
C18	0.034 (8)	0.056 (10)	0.050 (7)	−0.003 (7)	0.021 (7)	−0.002 (7)
S18	0.056 (2)	0.054 (2)	0.079 (2)	−0.0084 (19)	0.048 (2)	−0.017 (2)
C19	0.047 (9)	0.035 (8)	0.042 (7)	0.004 (6)	0.020 (7)	0.007 (5)
O19	0.044 (6)	0.035 (5)	0.063 (6)	−0.013 (5)	0.030 (5)	−0.010 (4)
N21	0.046 (8)	0.036 (6)	0.044 (6)	−0.005 (5)	0.025 (6)	0.001 (5)
C21	0.045 (9)	0.034 (7)	0.050 (7)	0.004 (6)	0.027 (7)	−0.011 (6)
C22	0.036 (8)	0.041 (8)	0.048 (7)	−0.005 (6)	0.019 (7)	−0.010 (6)
C23	0.042 (10)	0.055 (10)	0.068 (9)	0.007 (8)	0.018 (8)	−0.025 (8)
C24	0.044 (11)	0.056 (10)	0.060 (9)	−0.002 (8)	0.002 (8)	−0.009 (7)
C25	0.090 (17)	0.065 (13)	0.106 (15)	0.009 (12)	0.037 (14)	−0.038 (11)
C26	0.041 (8)	0.034 (7)	0.045 (7)	0.001 (6)	0.022 (7)	−0.010 (5)
N27	0.053 (7)	0.032 (6)	0.044 (5)	0.001 (6)	0.032 (6)	−0.008 (5)
C27	0.090 (14)	0.022 (7)	0.057 (8)	0.004 (7)	0.044 (10)	−0.003 (6)
C28	0.054 (10)	0.071 (12)	0.039 (7)	−0.014 (9)	0.020 (7)	−0.003 (7)
O28	0.062 (7)	0.046 (6)	0.047 (5)	−0.007 (5)	0.029 (6)	−0.005 (4)
C29	0.071 (14)	0.077 (14)	0.058 (10)	−0.015 (11)	0.002 (10)	0.007 (9)
C30	0.066 (11)	0.040 (8)	0.038 (7)	−0.003 (7)	0.033 (8)	0.003 (5)
O30	0.058 (8)	0.084 (10)	0.091 (8)	0.000 (7)	0.027 (7)	−0.048 (8)
N31	0.061 (9)	0.035 (7)	0.053 (6)	−0.001 (6)	0.028 (7)	−0.004 (5)
C31	0.090 (9)	0.051 (7)	0.069 (6)	−0.027 (6)	0.046 (7)	0.004 (5)
C32	0.094 (9)	0.056 (6)	0.074 (6)	−0.028 (6)	0.043 (7)	0.005 (5)
C33	0.109 (11)	0.070 (8)	0.086 (8)	−0.029 (8)	0.028 (9)	0.008 (7)
C34	0.094 (10)	0.063 (8)	0.082 (8)	−0.033 (8)	0.046 (8)	0.005 (7)
C35	0.053 (10)	0.048 (9)	0.047 (7)	−0.014 (7)	0.029 (8)	−0.002 (6)
C36	0.026 (7)	0.048 (8)	0.046 (6)	−0.006 (7)	0.012 (6)	0.006 (7)
N37	0.019 (6)	0.055 (7)	0.032 (5)	0.003 (5)	0.006 (5)	−0.009 (4)
C37	0.014 (7)	0.046 (8)	0.035 (6)	0.004 (5)	0.001 (6)	−0.006 (5)
C38	0.039 (9)	0.050 (9)	0.042 (7)	0.011 (7)	0.012 (7)	−0.006 (6)
S38	0.049 (2)	0.057 (2)	0.053 (2)	−0.0045 (19)	0.035 (2)	−0.0059 (17)
C39	0.031 (8)	0.032 (7)	0.039 (6)	0.006 (6)	0.012 (6)	−0.007 (5)
O39	0.051 (7)	0.039 (6)	0.051 (5)	0.012 (5)	0.031 (5)	0.003 (4)
C40	0.045 (9)	0.019 (6)	0.055 (7)	0.000 (5)	0.031 (7)	0.001 (5)
O41	0.035 (6)	0.038 (6)	0.054 (5)	0.000 (4)	0.020 (5)	−0.002 (4)
O42	0.045 (7)	0.046 (6)	0.049 (5)	−0.011 (5)	0.021 (5)	0.005 (4)
O43	0.071 (9)	0.027 (6)	0.072 (7)	−0.005 (5)	0.021 (6)	0.001 (5)
O44	0.044 (7)	0.044 (6)	0.051 (5)	−0.010 (5)	0.019 (5)	−0.009 (4)
O45	0.061 (9)	0.074 (9)	0.073 (7)	0.012 (7)	0.030 (7)	−0.016 (6)

Geometric parameters (Å, º)

Cu1—N1	1.944 (10)	C18—H18	0.9400
Cu1—O44	1.971 (10)	C19—O19	1.243 (18)
Cu1—N7	2.043 (9)	C19—N21	1.323 (19)
Cu1—N37	2.061 (10)	N21—C21	1.458 (17)
Cu1—O41	2.236 (10)	C21—C26	1.49 (2)
Cu2—O42	1.913 (10)	C21—C22	1.52 (2)
Cu2—N21	1.930 (12)	C21—H21	0.9900
Cu2—N27	1.971 (10)	C22—C23	1.509 (19)
Cu2—N17	2.052 (10)	C22—C24	1.57 (2)
Cu2—O41	2.430 (10)	C22—H22	0.9900
Cu2—C40	2.536 (14)	C23—C25	1.55 (3)
N1—C39	1.282 (17)	C23—H23A	0.9800
N1—C1	1.460 (16)	C23—H23B	0.9800
C1—C6	1.508 (18)	C24—H24A	0.9700
C1—C2	1.546 (18)	C24—H24B	0.9700
C1—H1	0.9900	C24—H24C	0.9700
C2—C3	1.455 (19)	C25—H25A	0.9700
C2—C4	1.53 (2)	C25—H25B	0.9700
C2—H2	0.9900	C25—H25C	0.9700
C3—C5	1.55 (2)	C26—N27	1.296 (18)
C3—H3A	0.9800	C26—O28	1.330 (15)
C3—H3B	0.9800	N27—C27	1.519 (19)
C4—H4A	0.9700	C27—C30	1.46 (3)
C4—H4B	0.9700	C27—C28	1.55 (2)
C4—H4C	0.9700	C27—H27	0.9900
C5—H5A	0.9700	C28—O28	1.49 (2)
C5—H5B	0.9700	C28—C29	1.54 (3)
C5—H5C	0.9700	C28—H28	0.9900
C6—N7	1.253 (18)	C29—H29A	0.9700
C6—O8	1.326 (15)	C29—H29B	0.9700
N7—C7	1.473 (17)	C29—H29C	0.9700
C7—C8	1.500 (19)	C30—O30	1.227 (18)
C7—C10	1.549 (19)	C30—N31	1.335 (19)
C7—H7	0.9900	N31—C31	1.49 (3)
C8—O8	1.459 (17)	N31—H31	0.8700
C8—C9	1.49 (2)	C31—C35	1.53 (2)
C8—H8	0.9900	C31—C32	1.54 (2)
C9—H9A	0.9700	C31—H31A	0.9900
C9—H9B	0.9700	C32—C33	1.50 (3)
C9—H9C	0.9700	C32—C34	1.56 (3)
C10—O10	1.222 (16)	C32—H32	0.9900
C10—N11	1.316 (17)	C33—H33A	0.9700
N11—C11	1.470 (18)	C33—H33B	0.9700
N11—H11	0.8700	C33—H33C	0.9700
C11—C15	1.529 (19)	C34—H34A	0.9700
C11—C12	1.56 (2)	C34—H34B	0.9700
C11—H11A	0.9900	C34—H34C	0.9700
C12—C14	1.50 (2)	C35—C36	1.50 (2)
C12—C13	1.56 (2)	C35—H35A	0.9800
C12—H12	0.9900	C35—H35B	0.9800
C13—H13A	0.9700	C36—N37	1.309 (17)
C13—H13B	0.9700	C36—S38	1.716 (16)
C13—H13C	0.9700	N37—C37	1.383 (18)
C14—H14A	0.9700	C37—C38	1.36 (2)
C14—H14B	0.9700	C37—C39	1.49 (2)
C14—H14C	0.9700	C38—S38	1.671 (17)
C15—C16	1.49 (2)	C38—H38	0.9400
C15—H15A	0.9800	C39—O39	1.248 (17)
C15—H15B	0.9800	C40—O41	1.256 (17)
C16—N17	1.281 (17)	C40—O43	1.267 (18)
C16—S18	1.737 (15)	C40—O42	1.302 (17)
N17—C17	1.404 (19)	O44—H44A	0.811 (9)
C17—C18	1.331 (19)	O44—H44B	0.863 (11)
C17—C19	1.470 (19)	O45—H45A	0.905 (12)
C18—S18	1.730 (16)	O45—H45B	0.871 (12)
N1—Cu1—O44	159.2 (5)	S18—C18—H18	125.3
N1—Cu1—N7	81.6 (5)	C18—S18—C16	90.4 (7)
O44—Cu1—N7	98.5 (4)	O19—C19—N21	127.1 (13)
N1—Cu1—N37	80.6 (5)	O19—C19—C17	121.4 (13)
O44—Cu1—N37	96.5 (5)	N21—C19—C17	111.5 (12)
N7—Cu1—N37	161.6 (5)	C19—N21—C21	121.3 (12)
N1—Cu1—O41	113.2 (4)	C19—N21—Cu2	120.0 (10)
O44—Cu1—O41	87.4 (4)	C21—N21—Cu2	117.9 (9)
N7—Cu1—O41	97.3 (4)	N21—C21—C26	103.5 (11)
N37—Cu1—O41	93.9 (4)	N21—C21—C22	113.4 (12)
O42—Cu2—N21	176.4 (4)	C26—C21—C22	115.0 (12)
O42—Cu2—N27	94.8 (5)	N21—C21—H21	108.2
N21—Cu2—N27	81.5 (5)	C26—C21—H21	108.2
O42—Cu2—N17	102.0 (5)	C22—C21—H21	108.2
N21—Cu2—N17	81.6 (5)	C23—C22—C21	112.1 (12)
N27—Cu2—N17	157.4 (5)	C23—C22—C24	110.3 (13)
O42—Cu2—O41	59.3 (4)	C21—C22—C24	111.3 (13)
N21—Cu2—O41	122.2 (4)	C23—C22—H22	107.7
N27—Cu2—O41	115.5 (4)	C21—C22—H22	107.7
N17—Cu2—O41	86.3 (4)	C24—C22—H22	107.7
O42—Cu2—C40	30.1 (4)	C22—C23—C25	114.6 (15)
N21—Cu2—C40	151.3 (5)	C22—C23—H23A	108.6
N27—Cu2—C40	107.0 (5)	C25—C23—H23A	108.6
N17—Cu2—C40	95.0 (4)	C22—C23—H23B	108.6
O41—Cu2—C40	29.2 (4)	C25—C23—H23B	108.6
C39—N1—C1	121.8 (11)	H23A—C23—H23B	107.6
C39—N1—Cu1	120.1 (9)	C22—C24—H24A	109.5
C1—N1—Cu1	117.2 (8)	C22—C24—H24B	109.5
N1—C1—C6	105.2 (10)	H24A—C24—H24B	109.5
N1—C1—C2	111.8 (10)	C22—C24—H24C	109.5
C6—C1—C2	114.6 (11)	H24A—C24—H24C	109.5
N1—C1—H1	108.3	H24B—C24—H24C	109.5
C6—C1—H1	108.3	C23—C25—H25A	109.5
C2—C1—H1	108.3	C23—C25—H25B	109.5
C3—C2—C4	115.2 (13)	H25A—C25—H25B	109.5
C3—C2—C1	113.3 (11)	C23—C25—H25C	109.5
C4—C2—C1	108.6 (11)	H25A—C25—H25C	109.5
C3—C2—H2	106.4	H25B—C25—H25C	109.5
C4—C2—H2	106.4	N27—C26—O28	116.8 (12)
C1—C2—H2	106.4	N27—C26—C21	120.4 (11)
C2—C3—C5	111.5 (12)	O28—C26—C21	122.7 (12)
C2—C3—H3A	109.3	C26—N27—C27	108.5 (10)
C5—C3—H3A	109.3	C26—N27—Cu2	113.3 (9)
C2—C3—H3B	109.3	C27—N27—Cu2	136.8 (9)
C5—C3—H3B	109.3	C30—C27—N27	110.5 (13)
H3A—C3—H3B	108.0	C30—C27—C28	114.3 (13)
C2—C4—H4A	109.5	N27—C27—C28	100.4 (12)
C2—C4—H4B	109.5	C30—C27—H27	110.4
H4A—C4—H4B	109.5	N27—C27—H27	110.4
C2—C4—H4C	109.5	C28—C27—H27	110.4
H4A—C4—H4C	109.5	O28—C28—C29	106.0 (13)
H4B—C4—H4C	109.5	O28—C28—C27	103.6 (10)
C3—C5—H5A	109.5	C29—C28—C27	112.7 (16)
C3—C5—H5B	109.5	O28—C28—H28	111.4
H5A—C5—H5B	109.5	C29—C28—H28	111.4
C3—C5—H5C	109.5	C27—C28—H28	111.4
H5A—C5—H5C	109.5	C26—O28—C28	106.2 (11)
H5B—C5—H5C	109.5	C28—C29—H29A	109.5
N7—C6—O8	120.0 (12)	C28—C29—H29B	109.5
N7—C6—C1	122.5 (11)	H29A—C29—H29B	109.5
O8—C6—C1	117.5 (11)	C28—C29—H29C	109.5
C6—N7—C7	105.4 (10)	H29A—C29—H29C	109.5
C6—N7—Cu1	112.0 (9)	H29B—C29—H29C	109.5
C7—N7—Cu1	141.3 (9)	O30—C30—N31	123.0 (16)
N7—C7—C8	104.8 (11)	O30—C30—C27	121.7 (13)
N7—C7—C10	114.4 (11)	N31—C30—C27	115.3 (14)
C8—C7—C10	113.6 (11)	C30—N31—C31	123.7 (15)
N7—C7—H7	107.9	C30—N31—H31	118.2
C8—C7—H7	107.9	C31—N31—H31	118.2
C10—C7—H7	107.9	N31—C31—C35	107.8 (13)
O8—C8—C9	109.3 (12)	N31—C31—C32	112.7 (18)
O8—C8—C7	103.5 (9)	C35—C31—C32	111.3 (15)
C9—C8—C7	115.6 (13)	N31—C31—H31A	108.3
O8—C8—H8	109.4	C35—C31—H31A	108.3
C9—C8—H8	109.4	C32—C31—H31A	108.3
C7—C8—H8	109.4	C33—C32—C31	109.0 (16)
C6—O8—C8	105.0 (10)	C33—C32—C34	114.0 (18)
C8—C9—H9A	109.5	C31—C32—C34	108.6 (18)
C8—C9—H9B	109.5	C33—C32—H32	108.4
H9A—C9—H9B	109.5	C31—C32—H32	108.4
C8—C9—H9C	109.5	C34—C32—H32	108.4
H9A—C9—H9C	109.5	C32—C33—H33A	109.5
H9B—C9—H9C	109.5	C32—C33—H33B	109.5
O10—C10—N11	124.3 (13)	H33A—C33—H33B	109.5
O10—C10—C7	116.9 (12)	C32—C33—H33C	109.5
N11—C10—C7	118.6 (12)	H33A—C33—H33C	109.5
C10—N11—C11	119.5 (11)	H33B—C33—H33C	109.5
C10—N11—H11	120.3	C32—C34—H34A	109.5
C11—N11—H11	120.3	C32—C34—H34B	109.5
N11—C11—C15	109.5 (11)	H34A—C34—H34B	109.5
N11—C11—C12	114.2 (12)	C32—C34—H34C	109.5
C15—C11—C12	108.6 (13)	H34A—C34—H34C	109.5
N11—C11—H11A	108.1	H34B—C34—H34C	109.5
C15—C11—H11A	108.1	C36—C35—C31	114.8 (13)
C12—C11—H11A	108.1	C36—C35—H35A	108.6
C14—C12—C11	114.7 (14)	C31—C35—H35A	108.6
C14—C12—C13	111.4 (14)	C36—C35—H35B	108.6
C11—C12—C13	108.5 (13)	C31—C35—H35B	108.6
C14—C12—H12	107.3	H35A—C35—H35B	107.5
C11—C12—H12	107.3	N37—C36—C35	125.8 (14)
C13—C12—H12	107.3	N37—C36—S38	113.7 (13)
C12—C13—H13A	109.5	C35—C36—S38	120.4 (10)
C12—C13—H13B	109.5	C36—N37—C37	110.0 (12)
H13A—C13—H13B	109.5	C36—N37—Cu1	139.9 (11)
C12—C13—H13C	109.5	C37—N37—Cu1	110.0 (9)
H13A—C13—H13C	109.5	C38—C37—N37	115.5 (13)
H13B—C13—H13C	109.5	C38—C37—C39	128.2 (13)
C12—C14—H14A	109.5	N37—C37—C39	116.2 (11)
C12—C14—H14B	109.5	C37—C38—S38	109.7 (12)
H14A—C14—H14B	109.5	C37—C38—H38	125.1
C12—C14—H14C	109.5	S38—C38—H38	125.1
H14A—C14—H14C	109.5	C38—S38—C36	91.0 (7)
H14B—C14—H14C	109.5	O39—C39—N1	128.9 (13)
C16—C15—C11	115.1 (12)	O39—C39—C37	118.9 (11)
C16—C15—H15A	108.5	N1—C39—C37	112.2 (11)
C11—C15—H15A	108.5	O41—C40—O43	122.2 (14)
C16—C15—H15B	108.5	O41—C40—O42	118.1 (12)
C11—C15—H15B	108.5	O43—C40—O42	119.6 (12)
H15A—C15—H15B	107.5	O41—C40—Cu2	70.7 (8)
N17—C16—C15	126.8 (13)	O43—C40—Cu2	167.0 (11)
N17—C16—S18	112.4 (11)	O42—C40—Cu2	47.4 (6)
C15—C16—S18	120.8 (10)	C40—O41—Cu1	126.3 (9)
C16—N17—C17	112.9 (11)	C40—O41—Cu2	80.1 (8)
C16—N17—Cu2	137.7 (11)	Cu1—O41—Cu2	145.9 (5)
C17—N17—Cu2	109.3 (8)	C40—O42—Cu2	102.5 (8)
C18—C17—N17	114.8 (13)	Cu1—O44—H44A	106.1 (9)
C18—C17—C19	127.9 (14)	Cu1—O44—H44B	101.5 (8)
N17—C17—C19	117.4 (11)	H44A—O44—H44B	107.6 (12)
C17—C18—S18	109.5 (12)	H45A—O45—H45B	122.6 (15)
C17—C18—H18	125.3
C39—N1—C1—C6	−160.9 (12)	N21—C21—C22—C23	−171.0 (13)
Cu1—N1—C1—C6	8.3 (13)	C26—C21—C22—C23	70.1 (16)
C39—N1—C1—C2	74.2 (16)	N21—C21—C22—C24	65.0 (16)
Cu1—N1—C1—C2	−116.6 (10)	C26—C21—C22—C24	−53.9 (16)
N1—C1—C2—C3	−161.0 (11)	C21—C22—C23—C25	170.7 (16)
C6—C1—C2—C3	79.4 (14)	C24—C22—C23—C25	−65 (2)
N1—C1—C2—C4	69.7 (14)	N21—C21—C26—N27	−20.4 (19)
C6—C1—C2—C4	−49.9 (14)	C22—C21—C26—N27	103.9 (15)
C4—C2—C3—C5	−63.8 (17)	N21—C21—C26—O28	163.3 (13)
C1—C2—C3—C5	170.3 (13)	C22—C21—C26—O28	−72.4 (18)
N1—C1—C6—N7	−14.1 (17)	O28—C26—N27—C27	2.2 (19)
C2—C1—C6—N7	109.1 (14)	C21—C26—N27—C27	−174.4 (13)
N1—C1—C6—O8	166.4 (11)	O28—C26—N27—Cu2	−166.8 (10)
C2—C1—C6—O8	−70.4 (15)	C21—C26—N27—Cu2	16.7 (18)
O8—C6—N7—C7	2.0 (16)	C26—N27—C27—C30	106.7 (14)
C1—C6—N7—C7	−177.5 (11)	Cu2—N27—C27—C30	−88.1 (17)
O8—C6—N7—Cu1	−167.7 (9)	C26—N27—C27—C28	−14.3 (17)
C1—C6—N7—Cu1	12.8 (16)	Cu2—N27—C27—C28	150.8 (13)
C6—N7—C7—C8	−8.4 (14)	C30—C27—C28—O28	−98.3 (14)
Cu1—N7—C7—C8	156.3 (11)	N27—C27—C28—O28	20.0 (16)
C6—N7—C7—C10	116.7 (13)	C30—C27—C28—C29	147.6 (14)
Cu1—N7—C7—C10	−78.6 (16)	N27—C27—C28—C29	−94.2 (15)
N7—C7—C8—O8	11.1 (13)	N27—C26—O28—C28	11.9 (18)
C10—C7—C8—O8	−114.5 (12)	C21—C26—O28—C28	−171.6 (13)
N7—C7—C8—C9	−108.3 (13)	C29—C28—O28—C26	99.0 (14)
C10—C7—C8—C9	126.1 (13)	C27—C28—O28—C26	−19.9 (16)
N7—C6—O8—C8	5.5 (16)	N27—C27—C30—O30	−95.4 (16)
C1—C6—O8—C8	−175.0 (11)	C28—C27—C30—O30	17 (2)
C9—C8—O8—C6	113.7 (12)	N27—C27—C30—N31	84.6 (15)
C7—C8—O8—C6	−10.0 (13)	C28—C27—C30—N31	−163.1 (13)
N7—C7—C10—O10	−155.0 (12)	O30—C30—N31—C31	−5 (2)
C8—C7—C10—O10	−34.8 (18)	C27—C30—N31—C31	175.3 (13)
N7—C7—C10—N11	29.7 (17)	C30—N31—C31—C35	114.3 (16)
C8—C7—C10—N11	150.0 (12)	C30—N31—C31—C32	−122.4 (17)
O10—C10—N11—C11	−3 (2)	N31—C31—C32—C33	51 (2)
C7—C10—N11—C11	171.6 (12)	C35—C31—C32—C33	172.5 (19)
C10—N11—C11—C15	151.0 (13)	N31—C31—C32—C34	176.0 (15)
C10—N11—C11—C12	−87.0 (16)	C35—C31—C32—C34	−63 (2)
N11—C11—C12—C14	30.3 (19)	N31—C31—C35—C36	−72.0 (19)
C15—C11—C12—C14	152.8 (14)	C32—C31—C35—C36	163.9 (17)
N11—C11—C12—C13	155.7 (13)	C31—C35—C36—N37	139.9 (15)
C15—C11—C12—C13	−81.8 (15)	C31—C35—C36—S38	−42.7 (19)
N11—C11—C15—C16	−58.1 (17)	C35—C36—N37—C37	176.8 (13)
C12—C11—C15—C16	176.7 (12)	S38—C36—N37—C37	−0.8 (14)
C11—C15—C16—N17	123.1 (15)	C35—C36—N37—Cu1	−7 (2)
C11—C15—C16—S18	−56.2 (16)	S38—C36—N37—Cu1	175.4 (9)
C15—C16—N17—C17	178.9 (12)	C36—N37—C37—C38	−0.4 (17)
S18—C16—N17—C17	−1.8 (14)	Cu1—N37—C37—C38	−177.8 (10)
C15—C16—N17—Cu2	−3 (2)	C36—N37—C37—C39	176.9 (11)
S18—C16—N17—Cu2	176.3 (8)	Cu1—N37—C37—C39	−0.5 (14)
C16—N17—C17—C18	1.1 (17)	N37—C37—C38—S38	1.4 (16)
Cu2—N17—C17—C18	−177.6 (10)	C39—C37—C38—S38	−175.5 (11)
C16—N17—C17—C19	−177.4 (12)	C37—C38—S38—C36	−1.4 (11)
Cu2—N17—C17—C19	4.0 (14)	N37—C36—S38—C38	1.3 (11)
N17—C17—C18—S18	0.2 (16)	C35—C36—S38—C38	−176.4 (12)
C19—C17—C18—S18	178.4 (12)	C1—N1—C39—O39	−2 (2)
C17—C18—S18—C16	−0.9 (12)	Cu1—N1—C39—O39	−171.1 (12)
N17—C16—S18—C18	1.6 (11)	C1—N1—C39—C37	178.9 (11)
C15—C16—S18—C18	−179.0 (12)	Cu1—N1—C39—C37	10.0 (15)
C18—C17—C19—O19	−2 (2)	C38—C37—C39—O39	−8 (2)
N17—C17—C19—O19	175.9 (13)	N37—C37—C39—O39	175.2 (12)
C18—C17—C19—N21	176.6 (14)	C38—C37—C39—N1	171.0 (14)
N17—C17—C19—N21	−5.2 (18)	N37—C37—C39—N1	−5.8 (17)
O19—C19—N21—C21	−7 (2)	O43—C40—O41—Cu1	25.4 (19)
C17—C19—N21—C21	173.9 (12)	O42—C40—O41—Cu1	−157.2 (9)
O19—C19—N21—Cu2	−177.2 (12)	Cu2—C40—O41—Cu1	−156.1 (8)
C17—C19—N21—Cu2	4.0 (16)	O43—C40—O41—Cu2	−178.5 (14)
C19—N21—C21—C26	−155.0 (13)	O42—C40—O41—Cu2	−1.1 (11)
Cu2—N21—C21—C26	15.1 (15)	O41—C40—O42—Cu2	1.5 (14)
C19—N21—C21—C22	79.7 (17)	O43—C40—O42—Cu2	178.9 (12)
Cu2—N21—C21—C22	−110.3 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O44^i	0.99	2.42	3.283 (16)	145
C7—H7···O39^ii	0.99	2.42	3.330 (17)	153
N11—H11···O41	0.87	2.24	3.090 (14)	166
C15—H15A···O42	0.98	2.40	3.289 (17)	150
C18—H18···O45^iii	0.94	2.42	3.30 (2)	155
C27—H27···O19^iv	0.99	2.52	3.472 (18)	161
N31—H31···O42	0.87	2.53	3.259 (17)	142
C31—H31A···S38	0.99	2.70	3.19 (2)	111
C35—H35A···O43	0.98	2.54	3.50 (2)	167
C35—H35A···O44	0.98	2.62	3.333 (16)	130
O44—H44A···O39^ii	0.811 (9)	1.872 (9)	2.633 (13)	155.9 (8)
O44—H44B···O41	0.863 (11)	2.492 (10)	2.913 (14)	110.8 (7)
O44—H44B···O43	0.863 (11)	1.739 (12)	2.527 (16)	150.7 (8)
O45—H45A···O10	0.905 (12)	1.965 (10)	2.870 (16)	179.1 (11)
O45—H45B···O19^v	0.871 (12)	2.024 (10)	2.890 (16)	171.9 (10)
C1—H1···O44^i	0.99	2.42	3.283 (16)	145
C2—H2···O39	0.99	2.66	3.256 (17)	119
C7—H7···O39^ii	0.99	2.42	3.330 (17)	153
N11—H11···O41	0.87	2.24	3.090 (14)	166
C15—H15A···O42	0.98	2.40	3.289 (17)	150
C18—H18···O45^iii	0.94	2.42	3.30 (2)	155
C27—H27···O19^iv	0.99	2.52	3.472 (18)	161
N31—H31···O42	0.87	2.53	3.259 (17)	142
C31—H31A···S38	0.99	2.70	3.19 (2)	111
C35—H35A···O43	0.98	2.54	3.50 (2)	167
C35—H35A···O44	0.98	2.62	3.333 (16)	130
O44—H44A···O39^ii	0.811 (9)	1.872 (9)	2.633 (13)	155.9 (8)
O44—H44B···O41	0.863 (11)	2.492 (10)	2.913 (14)	110.8 (7)
O44—H44B···O43	0.863 (11)	1.739 (12)	2.527 (16)	150.7 (8)
O45—H45A···O10	0.905 (12)	1.965 (10)	2.870 (16)	179.1 (11)
O45—H45B···O19^v	0.871 (12)	2.024 (10)	2.890 (16)	171.9 (10)

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