Crystal structure and bonding analysis of the first dinuclear calcium(II)–proton-pump inhibitor (PPI) `butterfly mol­ecule': a combined microcrystal synchrotron and DFT study

Proton-pump inhibitors (PPI) are prodrugs used widely to treat acid-related diseases since the late 1980s. After an extensive research effort it has become clear that the fundamental inter­actions between metal atoms and PPIs are of paramount importance for both drug release and long-term therapeutic safety. Unfortunately, until now, very little information has been available on this topic. In this paper, we report the crystal structure analysis of a novel calcium–PPI compound incorporating bridging and terminal deprotonated (R)-rabeprazole tricyclic ligands (L), namely bis­[μ-(R)-2-({[4-(3-meth­oxy­prop­oxy)-3-methyl­pyridin-2-yl]meth­yl}sulfin­yl)-6,7-di­hydro-3H-benzofuro[5,6-d]imidazol-1-ido]bis­{di­methanol[(R)-2-({[4-(3-meth­oxy­prop­oxy)-3-methyl­pyridin-2-yl]meth­yl}sulfin­yl)-6,7-di­hydro-3H-benzofuro[5,6-d]imidazol-1-ido]calcium(II)} methanol hexa­solvate, [Ca₂(C₂₀H₂₂N₃O₄S)₄(CH₃OH)₄]·6CH₃OH or [Ca₂(L)₄(CH₃OH)₄]·6CH₃OH, which crystallizes from methanol in the polar C2 space group. Using low-temperature microcrystal synchrotron radiation, we demonstrate that this compound is in the form of a beautiful `butterfly mol­ecule', consisting of a C₂-symmetric dinuclear (CH₃OH)₂LCa^II(μ₂-L)₂Ca^IIL(HOCH₃)₂ framework. A large amount of disorder is found within the bridging L ligand and the conformation of the fused tetra­hydro­furan ring exhibits great variety. All the sulfinyl groups remain intact and the nonbonded Ca...Ca distance is significantly longer than in other calcium dimers, indicating steric hindrance in the bridging ligands. Considerable hydrogen bonding and aromatic C—H...π inter­actions co-operate to stabilize the whole complex, as well as to facilitate supra­molecular assembly. Additional investigations into the bond nature were made using density functional theory (DFT) methods at the B3LYP/6-31G(d) level; geometry optimization, Mulliken atomic charges, MEP (molecular electrostatic potential), HOMO–LUMO (highest occupied molecular orbital–lowest unoccupied molecular orbital), TDOS (total density of states), PDOS (partial density of states), COOP (crystal orbital overlap population) and vibrational spectra were calculated/recorded and assessed carefully.

Computing details

Data collection: ADSC Quantum Q315r software; cell refinement: XDS (Kabsch, 2010); data reduction: XDS (Kabsch, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis[µ-(R)-2-({[4-(3-methoxypropoxy)-3-methylpyridin-2-yl]methyl}sulfinyl)-6,7-dihydro-3H-benzofuro[5,6-d]imidazol-1-ido]bis{dimethanol[(R)-2-({[4-(3-methoxypropoxy)-3-methylpyridin-2-yl]methyl}sulfinyl)-6,7-dihydro-3H-benzofuro[5,6-d]imidazol-1-ido]calcium(II)} methanol hexasolvate

Crystal data

[Ca2(C20H22N3SO4)4(CH4O)4]·6CH4O	F(000) = 2128
Mr = 2002.44	Dx = 1.327 Mg m^−3
Monoclinic, C2	Synchrotron radiation, λ = 0.79987 Å
a = 32.100 (6) Å	Cell parameters from 3062 reflections
b = 10.560 (2) Å	θ = 2.9–32.8°
c = 15.800 (3) Å	µ = 0.37 mm^−1
β = 110.70 (3)°	T = 100 K
V = 5010 (2) Å^3	Needle, yellow
Z = 2	0.05 × 0.03 × 0.01 mm

Data collection

ADSC Q315r CCD area-detector diffractometer	Rint = 0.028
φ scans	θmax = 32.8°, θmin = 2.9°
39409 measured reflections	h = −43→43
11723 independent reflections	k = −13→14
11544 reflections with I > 2σ(I)	l = −21→21

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) + (0.0536P)^2 + 2.6948P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.036	(Δ/σ)max = 0.001
wR(F^2) = 0.095	Δρmax = 0.54 e Å^−3
S = 1.08	Δρmin = −0.36 e Å^−3
11723 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
772 parameters	Extinction coefficient: 0.0096 (14)
171 restraints	Absolute structure: Flack x determined using 5262 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Hydrogen site location: mixed	Absolute structure parameter: 0.049 (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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ca1	0.06822 (2)	0.70157 (4)	1.04395 (3)	0.02369 (12)
S1	−0.00161 (2)	0.65606 (6)	0.82227 (4)	0.02588 (14)
S2	0.13937 (2)	0.78815 (6)	0.93215 (4)	0.02643 (14)
C22	0.22024 (8)	0.8284 (2)	1.17579 (17)	0.0296 (5)
C24	0.25831 (9)	0.8404 (3)	1.33317 (19)	0.0393 (6)
C29	0.18329 (8)	0.7725 (2)	1.19040 (16)	0.0282 (5)
O6	0.22814 (11)	0.7677 (4)	1.44084 (17)	0.0733 (8)
C28	0.18349 (9)	0.7484 (3)	1.27802 (17)	0.0356 (5)
C27	0.22172 (10)	0.7844 (3)	1.34751 (18)	0.0408 (6)
C23	0.25906 (9)	0.8629 (3)	1.2482 (2)	0.0355 (6)
N4	0.21012 (7)	0.8443 (2)	1.08363 (15)	0.0316 (4)
N5	0.15014 (7)	0.7512 (2)	1.10723 (14)	0.0284 (4)
C21	0.16912 (7)	0.7967 (2)	1.05042 (16)	0.0277 (4)
O5	0.09118 (5)	0.77251 (17)	0.92345 (11)	0.0280 (3)
N6	0.09664 (8)	0.5174 (2)	0.81720 (17)	0.0357 (5)
C35	0.14860 (8)	0.6063 (2)	0.75366 (17)	0.0289 (5)
C31	0.13428 (8)	0.5815 (2)	0.82573 (17)	0.0295 (5)
C30	0.15926 (9)	0.6294 (3)	0.91889 (18)	0.0319 (5)
C34	0.12140 (8)	0.5627 (2)	0.66782 (17)	0.0293 (5)
C32	0.07210 (10)	0.4776 (3)	0.7350 (2)	0.0399 (6)
C33	0.08258 (9)	0.4967 (3)	0.65823 (19)	0.0341 (5)
C36	0.19027 (9)	0.6806 (3)	0.76534 (18)	0.0383 (6)
H36A	0.1868	0.7672	0.7841	0.057*
H36B	0.1955	0.6827	0.7079	0.057*
H36C	0.2157	0.6402	0.8117	0.057*
O7	0.13589 (6)	0.5910 (2)	0.59946 (12)	0.0351 (4)
C39	0.12775 (10)	0.7728 (3)	0.46104 (19)	0.0393 (6)
C38	0.12635 (10)	0.6310 (3)	0.44593 (19)	0.0384 (6)
C37	0.10781 (10)	0.5600 (3)	0.50824 (18)	0.0370 (6)
O8	0.08504 (7)	0.8137 (2)	0.45738 (14)	0.0396 (4)
C40	0.08297 (15)	0.9461 (4)	0.4633 (3)	0.0652 (10)
H40A	0.1057	0.9751	0.5196	0.098*
H40B	0.0534	0.9709	0.4627	0.098*
H40C	0.0883	0.9848	0.4116	0.098*
C15	0.03251 (11)	0.9171 (3)	0.72652 (17)	0.0375 (6)
C18	0.13815 (12)	1.1694 (3)	0.6628 (2)	0.0449 (7)
C11	0.00030 (11)	0.8997 (3)	0.76606 (18)	0.0401 (6)
C19	0.17490 (12)	1.0734 (4)	0.6860 (3)	0.0603 (11)
H19A	0.1985	1.0965	0.7439	0.072*
H19B	0.1632	0.9890	0.6934	0.072*
O9	0.07459 (6)	0.50652 (18)	0.97169 (13)	0.0332 (4)
C41	0.05948 (10)	0.3819 (3)	0.9802 (2)	0.0379 (6)
H41A	0.0530	0.3759	1.0363	0.057*
H41B	0.0826	0.3205	0.9819	0.057*
H41C	0.0324	0.3637	0.9284	0.057*
C10	−0.02921 (9)	0.7841 (3)	0.74592 (16)	0.0333 (5)
C16	0.04041 (10)	0.8240 (3)	0.6626 (2)	0.0384 (6)
H16A	0.0547	0.7480	0.6960	0.058*
H16B	0.0599	0.8620	0.6337	0.058*
H16C	0.0119	0.8009	0.6162	0.058*
O11	0.15687 (10)	0.2604 (3)	0.9435 (2)	0.0703 (8)
C43	0.17391 (18)	0.1652 (5)	1.0055 (5)	0.0883 (16)
H43A	0.2057	0.1550	1.0164	0.132*
H43B	0.1583	0.0858	0.9819	0.132*
H43C	0.1698	0.1869	1.0624	0.132*
O1	−0.00056 (5)	0.70304 (19)	0.91445 (10)	0.0282 (3)
N1	−0.04585 (7)	0.4451 (2)	0.74046 (17)	0.0344 (5)
C1	−0.04603 (8)	0.5458 (2)	0.79054 (16)	0.0264 (4)
N2	−0.07982 (7)	0.5626 (2)	0.82100 (14)	0.0291 (4)
C9	−0.10572 (8)	0.4569 (2)	0.78553 (17)	0.0304 (5)
C2	−0.08507 (9)	0.3854 (2)	0.7362 (2)	0.0369 (6)
C8	−0.14608 (9)	0.4188 (3)	0.7945 (2)	0.0389 (6)
H8	−0.1605	0.4673	0.8267	0.047*
C3	−0.10333 (12)	0.2705 (3)	0.6944 (3)	0.0605 (10)
H3	−0.0897	0.2221	0.6606	0.073*
O2	−0.20248 (9)	0.2528 (3)	0.7528 (2)	0.0676 (8)
O13	0.22822 (7)	0.4258 (3)	−0.01411 (16)	0.0505 (6)
C45	0.24726 (13)	0.4639 (4)	0.0777 (2)	0.0591 (10)
H45A	0.2798	0.4650	0.0960	0.089*
H45B	0.2385	0.4042	0.1159	0.089*
H45C	0.2366	0.5489	0.0847	0.089*
C17	0.1194 (4)	1.1544 (10)	0.7346 (9)	0.041 (2)	0.52 (2)
H17A	0.1436	1.1506	0.7946	0.049*	0.52 (2)
H17B	0.0997	1.2266	0.7343	0.049*	0.52 (2)
O3	0.0944 (3)	1.0372 (10)	0.7161 (8)	0.0305 (16)	0.52 (2)
C14	0.0644 (4)	1.0180 (10)	0.7578 (7)	0.0286 (17)	0.52 (2)
C13	0.0610 (4)	1.0960 (9)	0.8256 (7)	0.038 (2)	0.52 (2)
H13	0.0799	1.1674	0.8463	0.046*	0.52 (2)
C12	0.0290 (4)	1.0657 (9)	0.8619 (7)	0.040 (2)	0.52 (2)
H12	0.0271	1.1173	0.9097	0.048*	0.52 (2)
N3	0.0004 (3)	0.9694 (9)	0.8349 (7)	0.0328 (16)	0.52 (2)
O3'	0.0810 (4)	1.0556 (11)	0.7031 (9)	0.0333 (17)	0.48 (2)
C17'	0.1026 (5)	1.1789 (12)	0.7143 (8)	0.043 (2)	0.48 (2)
H17C	0.1180	1.1982	0.7792	0.052*	0.48 (2)
H17D	0.0805	1.2463	0.6871	0.052*	0.48 (2)
C14'	0.0504 (4)	1.0412 (11)	0.7407 (8)	0.034 (2)	0.48 (2)
C13'	0.0405 (5)	1.1295 (8)	0.7968 (7)	0.042 (2)	0.48 (2)
H13'	0.0558	1.2081	0.8102	0.050*	0.48 (2)
C12'	0.0084 (5)	1.1008 (9)	0.8322 (7)	0.042 (2)	0.48 (2)
H12'	0.0025	1.1608	0.8714	0.050*	0.48 (2)
N3'	−0.0154 (4)	0.9926 (9)	0.8147 (7)	0.0370 (19)	0.48 (2)
C42	0.0897 (2)	1.0227 (7)	1.0804 (12)	0.057 (3)	0.73 (3)
H42A	0.0825	1.0957	1.1111	0.086*	0.73 (3)
H42B	0.0825	1.0425	1.0162	0.086*	0.73 (3)
H42C	0.1215	1.0033	1.1081	0.086*	0.73 (3)
C42'	0.0909 (5)	1.0093 (14)	1.1213 (15)	0.033 (4)	0.27 (3)
H42D	0.0979	1.0162	1.1867	0.050*	0.27 (3)
H42E	0.0767	1.0876	1.0918	0.050*	0.27 (3)
H42F	0.1185	0.9953	1.1091	0.050*	0.27 (3)
O10	0.06343 (7)	0.9126 (2)	1.08924 (14)	0.0382 (4)
H10O	0.0445	0.9325	1.1143	0.046*
C20	0.2312 (3)	0.9892 (9)	0.6666 (12)	0.059 (3)	0.52 (3)
H20A	0.2503	1.0343	0.7205	0.089*	0.52 (3)
H20B	0.2481	0.9703	0.6272	0.089*	0.52 (3)
H20C	0.2208	0.9100	0.6847	0.089*	0.52 (3)
C20'	0.2288 (3)	0.9920 (7)	0.6159 (14)	0.053 (4)	0.48 (3)
H20D	0.2561	1.0188	0.6643	0.079*	0.48 (3)
H20E	0.2325	1.0011	0.5573	0.079*	0.48 (3)
H20F	0.2226	0.9032	0.6252	0.079*	0.48 (3)
C25	0.29295 (11)	0.8709 (4)	1.4185 (3)	0.0615 (9)	0.575 (10)
H25A	0.2927	0.9620	1.4332	0.074*	0.575 (10)
H25B	0.3228	0.8472	1.4184	0.074*	0.575 (10)
C26	0.2786 (2)	0.7849 (8)	1.4866 (4)	0.0736 (16)	0.575 (10)
H26A	0.2940	0.7021	1.4959	0.088*	0.575 (10)
H26B	0.2858	0.8274	1.5459	0.088*	0.575 (10)
C25'	0.29295 (11)	0.8709 (4)	1.4185 (3)	0.0615 (9)	0.425 (10)
H25C	0.3063	0.9551	1.4175	0.074*	0.425 (10)
H25D	0.3166	0.8056	1.4372	0.074*	0.425 (10)
C26'	0.2624 (3)	0.8692 (11)	1.4801 (6)	0.0715 (18)	0.425 (10)
H26C	0.2806	0.8495	1.5438	0.086*	0.425 (10)
H26D	0.2479	0.9524	1.4781	0.086*	0.425 (10)
C7	−0.16295 (10)	0.3054 (3)	0.7528 (3)	0.0487 (7)
C4	−0.14233 (12)	0.2323 (3)	0.7053 (3)	0.0593 (9)
C6	−0.20737 (16)	0.1320 (4)	0.7060 (5)	0.0794 (12)
H6A	−0.2378	0.1246	0.6607	0.095*	0.575 (10)
H6B	−0.2028	0.0618	0.7499	0.095*	0.575 (10)
H6C	−0.2320	0.1364	0.6467	0.095*	0.425 (10)
H6D	−0.2142	0.0641	0.7423	0.095*	0.425 (10)
C5	−0.1726 (3)	0.1227 (8)	0.6580 (8)	0.0683 (17)	0.575 (10)
H5A	−0.1567	0.0407	0.6699	0.082*	0.575 (10)
H5B	−0.1864	0.1365	0.5920	0.082*	0.575 (10)
C5'	−0.1649 (4)	0.1052 (10)	0.6931 (11)	0.067 (2)	0.425 (10)
H5'1	−0.1701	0.0710	0.6318	0.081*	0.425 (10)
H5'2	−0.1468	0.0438	0.7386	0.081*	0.425 (10)
C44	0.0398 (5)	0.2588 (12)	0.4399 (7)	0.075 (4)	0.48 (2)
H44A	0.0722	0.2670	0.4676	0.112*	0.48 (2)
H44B	0.0324	0.2002	0.3886	0.112*	0.48 (2)
H44C	0.0279	0.2262	0.4847	0.112*	0.48 (2)
C44'	0.0101 (4)	0.2440 (10)	0.3988 (11)	0.087 (5)	0.52 (2)
H44D	0.0353	0.1954	0.3943	0.130*	0.52 (2)
H44E	−0.0159	0.2326	0.3434	0.130*	0.52 (2)
H44F	0.0031	0.2140	0.4509	0.130*	0.52 (2)
O12	0.02164 (11)	0.3745 (4)	0.4103 (2)	0.0729 (8)
H12O	0.029 (2)	0.407 (6)	0.360 (3)	0.087*
O4	0.19259 (8)	1.0688 (2)	0.6174 (2)	0.0621 (7)
H33	0.0637 (14)	0.462 (5)	0.605 (2)	0.075*
H10A	−0.0351 (17)	0.755 (5)	0.686 (2)	0.075*
H10B	−0.0571 (11)	0.803 (5)	0.754 (3)	0.075*
H30A	0.1535 (18)	0.575 (6)	0.964 (4)	0.075*
H30B	0.1883 (18)	0.634 (5)	0.927 (4)	0.075*
H28	0.1564 (17)	0.708 (6)	1.287 (3)	0.075*
H37A	0.0756 (10)	0.585 (5)	0.497 (3)	0.075*
H37B	0.1045 (17)	0.468 (6)	0.500 (4)	0.075*
H39A	0.1349 (17)	0.815 (6)	0.412 (4)	0.075*
H39B	0.1499 (17)	0.809 (5)	0.524 (3)	0.075*
H38A	0.1081 (18)	0.612 (5)	0.386 (4)	0.075*
H38B	0.1571 (18)	0.593 (6)	0.459 (4)	0.075*
H23	0.2841 (18)	0.901 (5)	1.239 (3)	0.075*
H32	0.0444 (18)	0.430 (5)	0.731 (4)	0.075*
H18A	0.1193 (15)	1.160 (6)	0.599 (2)	0.075*
H18B	0.1505 (9)	1.260 (2)	0.6666 (19)	0.075*
H9O	0.0820	0.5110	0.9233	0.075*
H13O	0.2505	0.3935	−0.0317	0.075*
H11O	0.1779	0.3194	0.9382	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.01931 (19)	0.0268 (2)	0.0233 (2)	0.00009 (16)	0.00540 (15)	−0.00255 (16)
S1	0.0235 (2)	0.0305 (3)	0.0230 (2)	−0.0076 (2)	0.00733 (19)	−0.0031 (2)
S2	0.0220 (2)	0.0288 (3)	0.0264 (3)	−0.00028 (19)	0.00589 (19)	0.0027 (2)
C22	0.0242 (10)	0.0261 (10)	0.0321 (11)	0.0036 (8)	0.0020 (9)	−0.0010 (9)
C24	0.0290 (11)	0.0355 (12)	0.0395 (13)	0.0081 (10)	−0.0049 (10)	−0.0137 (10)
C29	0.0237 (10)	0.0266 (11)	0.0304 (11)	0.0043 (8)	0.0049 (8)	−0.0030 (9)
O6	0.0779 (16)	0.103 (2)	0.0373 (11)	0.0177 (16)	0.0185 (11)	−0.0065 (13)
C28	0.0318 (12)	0.0430 (14)	0.0282 (11)	0.0078 (11)	0.0058 (9)	−0.0032 (10)
C27	0.0376 (12)	0.0494 (15)	0.0301 (11)	0.0125 (12)	0.0053 (10)	−0.0089 (11)
C23	0.0250 (11)	0.0272 (11)	0.0427 (14)	0.0037 (9)	−0.0025 (10)	−0.0046 (10)
N4	0.0239 (9)	0.0311 (10)	0.0346 (10)	−0.0013 (8)	0.0038 (8)	0.0028 (8)
N5	0.0235 (9)	0.0320 (10)	0.0267 (9)	0.0028 (8)	0.0051 (7)	0.0011 (8)
C21	0.0238 (10)	0.0273 (11)	0.0276 (10)	0.0007 (8)	0.0037 (8)	0.0013 (8)
O5	0.0229 (7)	0.0299 (8)	0.0277 (7)	0.0006 (6)	0.0046 (6)	−0.0017 (6)
N6	0.0393 (12)	0.0349 (11)	0.0398 (12)	−0.0025 (9)	0.0224 (10)	−0.0042 (9)
C35	0.0273 (10)	0.0258 (10)	0.0337 (12)	0.0052 (9)	0.0110 (9)	0.0034 (9)
C31	0.0310 (11)	0.0267 (11)	0.0324 (11)	0.0066 (9)	0.0131 (9)	0.0020 (9)
C30	0.0305 (11)	0.0331 (13)	0.0330 (12)	0.0082 (9)	0.0122 (10)	0.0043 (9)
C34	0.0305 (11)	0.0258 (11)	0.0342 (12)	0.0050 (9)	0.0148 (10)	0.0011 (9)
C32	0.0396 (14)	0.0366 (14)	0.0495 (16)	−0.0079 (11)	0.0231 (12)	−0.0099 (12)
C33	0.0339 (12)	0.0306 (12)	0.0397 (13)	−0.0001 (10)	0.0155 (10)	−0.0074 (10)
C36	0.0341 (12)	0.0487 (17)	0.0323 (11)	−0.0063 (11)	0.0120 (10)	−0.0004 (11)
O7	0.0332 (9)	0.0443 (11)	0.0277 (8)	−0.0024 (8)	0.0105 (7)	0.0003 (7)
C39	0.0407 (14)	0.0462 (16)	0.0291 (12)	−0.0025 (12)	0.0100 (10)	0.0004 (11)
C38	0.0401 (14)	0.0454 (16)	0.0293 (12)	0.0027 (12)	0.0117 (11)	−0.0020 (11)
C37	0.0399 (13)	0.0370 (14)	0.0314 (12)	−0.0026 (11)	0.0093 (11)	−0.0044 (10)
O8	0.0417 (10)	0.0387 (11)	0.0355 (9)	0.0009 (8)	0.0100 (8)	−0.0052 (8)
C40	0.065 (2)	0.0461 (19)	0.074 (3)	0.0002 (17)	0.0115 (19)	−0.0177 (18)
C15	0.0544 (16)	0.0290 (12)	0.0285 (12)	−0.0158 (11)	0.0138 (11)	−0.0032 (9)
C18	0.0569 (17)	0.0321 (14)	0.0485 (15)	−0.0184 (13)	0.0223 (14)	−0.0042 (12)
C11	0.0614 (17)	0.0306 (13)	0.0302 (12)	−0.0188 (12)	0.0187 (12)	−0.0033 (10)
C19	0.0478 (17)	0.0427 (17)	0.068 (2)	−0.0159 (14)	−0.0070 (16)	0.0184 (16)
O9	0.0407 (10)	0.0277 (8)	0.0368 (9)	−0.0049 (7)	0.0206 (8)	−0.0051 (7)
C41	0.0440 (14)	0.0292 (12)	0.0432 (14)	−0.0059 (11)	0.0188 (12)	−0.0051 (11)
C10	0.0406 (13)	0.0306 (12)	0.0235 (10)	−0.0100 (10)	0.0052 (9)	0.0014 (9)
C16	0.0440 (14)	0.0281 (12)	0.0449 (14)	−0.0094 (11)	0.0179 (12)	−0.0039 (11)
O11	0.0514 (14)	0.0664 (19)	0.082 (2)	−0.0008 (13)	0.0094 (14)	−0.0150 (15)
C43	0.071 (3)	0.057 (2)	0.125 (5)	−0.001 (2)	0.019 (3)	0.002 (3)
O1	0.0226 (7)	0.0383 (9)	0.0225 (7)	−0.0035 (7)	0.0064 (6)	−0.0020 (7)
N1	0.0301 (10)	0.0244 (10)	0.0479 (13)	−0.0038 (8)	0.0128 (9)	−0.0040 (9)
C1	0.0240 (10)	0.0254 (10)	0.0264 (10)	−0.0036 (8)	0.0048 (8)	0.0023 (8)
N2	0.0245 (9)	0.0320 (10)	0.0288 (9)	−0.0082 (8)	0.0070 (7)	−0.0006 (8)
C9	0.0274 (11)	0.0268 (11)	0.0319 (11)	−0.0048 (9)	0.0042 (9)	0.0048 (9)
C2	0.0318 (12)	0.0213 (11)	0.0527 (15)	−0.0025 (9)	0.0090 (11)	0.0011 (10)
C8	0.0294 (12)	0.0397 (14)	0.0454 (14)	−0.0088 (11)	0.0107 (11)	0.0031 (12)
C3	0.0461 (17)	0.0269 (14)	0.109 (3)	−0.0081 (12)	0.0287 (19)	−0.0197 (16)
O2	0.0447 (12)	0.0476 (13)	0.109 (2)	−0.0223 (11)	0.0254 (13)	−0.0009 (14)
O13	0.0382 (10)	0.0593 (14)	0.0489 (12)	0.0150 (10)	0.0092 (9)	−0.0146 (11)
C45	0.0547 (19)	0.069 (2)	0.0448 (17)	0.0287 (18)	0.0067 (15)	−0.0058 (16)
C17	0.042 (5)	0.032 (4)	0.056 (5)	−0.016 (4)	0.027 (4)	−0.013 (3)
O3	0.028 (4)	0.026 (3)	0.041 (4)	−0.009 (3)	0.017 (3)	−0.004 (2)
C14	0.033 (4)	0.023 (4)	0.029 (4)	−0.005 (3)	0.010 (3)	0.001 (3)
C13	0.044 (4)	0.031 (3)	0.046 (4)	−0.016 (3)	0.024 (4)	−0.014 (3)
C12	0.049 (5)	0.035 (3)	0.041 (4)	−0.011 (3)	0.024 (4)	−0.013 (3)
N3	0.035 (4)	0.031 (3)	0.036 (4)	−0.012 (3)	0.016 (3)	−0.005 (3)
O3'	0.032 (4)	0.027 (3)	0.042 (4)	−0.007 (3)	0.013 (4)	−0.005 (2)
C17'	0.048 (6)	0.040 (5)	0.046 (5)	−0.023 (4)	0.021 (4)	−0.007 (3)
C14'	0.039 (6)	0.027 (4)	0.034 (4)	−0.006 (4)	0.009 (4)	0.007 (3)
C13'	0.053 (6)	0.028 (3)	0.047 (4)	−0.014 (4)	0.023 (4)	−0.005 (3)
C12'	0.055 (6)	0.032 (3)	0.045 (4)	−0.012 (4)	0.027 (4)	−0.010 (3)
N3'	0.044 (5)	0.030 (3)	0.035 (4)	−0.010 (3)	0.012 (4)	−0.001 (3)
C42	0.053 (3)	0.033 (3)	0.087 (7)	−0.010 (2)	0.028 (4)	−0.019 (4)
C42'	0.029 (5)	0.033 (6)	0.036 (8)	0.000 (4)	0.008 (5)	−0.001 (5)
O10	0.0381 (9)	0.0338 (10)	0.0434 (10)	0.0013 (8)	0.0152 (8)	−0.0095 (8)
C20	0.049 (4)	0.060 (5)	0.067 (8)	−0.003 (3)	0.019 (4)	0.017 (4)
C20'	0.050 (4)	0.034 (3)	0.086 (10)	0.005 (3)	0.039 (5)	0.011 (4)
C25	0.0367 (13)	0.0509 (16)	0.0636 (17)	0.0134 (12)	−0.0236 (12)	−0.0291 (13)
C26	0.071 (3)	0.086 (3)	0.040 (2)	0.039 (3)	−0.009 (2)	−0.022 (2)
C25'	0.0367 (13)	0.0509 (16)	0.0636 (17)	0.0134 (12)	−0.0236 (12)	−0.0291 (13)
C26'	0.069 (3)	0.074 (3)	0.048 (3)	0.019 (3)	−0.010 (2)	−0.017 (3)
C7	0.0332 (12)	0.0318 (13)	0.076 (2)	−0.0101 (11)	0.0124 (13)	0.0104 (13)
C4	0.0421 (15)	0.0216 (12)	0.107 (3)	−0.0102 (11)	0.0180 (16)	−0.0034 (14)
C6	0.059 (2)	0.0428 (18)	0.131 (3)	−0.0227 (16)	0.026 (2)	−0.003 (2)
C5	0.053 (3)	0.025 (3)	0.121 (4)	−0.010 (2)	0.023 (3)	−0.005 (3)
C5'	0.049 (3)	0.026 (3)	0.113 (5)	−0.014 (3)	0.011 (3)	0.001 (3)
C44	0.072 (9)	0.085 (7)	0.061 (5)	−0.001 (5)	0.015 (5)	0.007 (5)
C44'	0.067 (7)	0.066 (6)	0.132 (11)	0.007 (5)	0.041 (7)	0.049 (6)
O12	0.0686 (18)	0.083 (2)	0.0690 (18)	−0.0034 (16)	0.0266 (15)	0.0075 (16)
O4	0.0377 (11)	0.0375 (12)	0.106 (2)	−0.0024 (10)	0.0192 (13)	−0.0023 (13)

Geometric parameters (Å, º)

Ca1—O10	2.362 (2)	C43—H43C	0.9800
Ca1—O5	2.3920 (18)	O1—Ca1^i	2.4814 (17)
Ca1—O9	2.3986 (19)	N1—C1	1.327 (3)
Ca1—O1	2.4225 (19)	N1—C2	1.388 (3)
Ca1—O1^i	2.4814 (17)	C1—N2	1.345 (3)
Ca1—N2^i	2.507 (2)	N2—C9	1.386 (3)
Ca1—N5	2.516 (2)	N2—Ca1^i	2.507 (2)
S1—O1	1.5277 (17)	C9—C2	1.409 (4)
S1—C1	1.771 (2)	C9—C8	1.411 (4)
S1—C10	1.820 (3)	C2—C3	1.406 (4)
S2—O5	1.5129 (17)	C8—C7	1.382 (4)
S2—C21	1.775 (2)	C8—H8	0.9500
S2—C30	1.832 (3)	C3—C4	1.383 (5)
C22—N4	1.385 (3)	C3—H3	0.9500
C22—C23	1.409 (3)	O2—C7	1.385 (4)
C22—C29	1.415 (4)	O2—C6	1.455 (6)
C24—C23	1.372 (5)	O13—C45	1.419 (4)
C24—C27	1.403 (5)	O13—H13O	0.9194
C24—C25'	1.448 (4)	C45—H45A	0.9800
C24—C25	1.448 (4)	C45—H45B	0.9800
C29—N5	1.386 (3)	C45—H45C	0.9800
C29—C28	1.405 (4)	C17—O3	1.448 (15)
O6—C27	1.426 (4)	C17—H17A	0.9900
O6—C26'	1.504 (11)	C17—H17B	0.9900
O6—C26	1.533 (8)	O3—C14	1.362 (14)
C28—C27	1.380 (4)	C14—C13	1.387 (12)
C28—H28	1.02 (5)	C13—C12	1.379 (9)
C23—H23	0.95 (5)	C13—H13	0.9500
N4—C21	1.331 (3)	C12—N3	1.334 (10)
N5—C21	1.339 (3)	C12—H12	0.9500
N6—C32	1.327 (4)	O3'—C14'	1.326 (17)
N6—C31	1.350 (3)	O3'—C17'	1.457 (16)
C35—C31	1.395 (3)	C17'—H17C	0.9900
C35—C34	1.406 (4)	C17'—H17D	0.9900
C35—C36	1.505 (4)	C14'—C13'	1.397 (15)
C31—C30	1.494 (4)	C13'—C12'	1.370 (10)
C30—H30A	0.98 (6)	C13'—H13'	0.9500
C30—H30B	0.90 (5)	C12'—N3'	1.347 (11)
C34—O7	1.352 (3)	C12'—H12'	0.9500
C34—C33	1.388 (4)	C42—O10	1.471 (9)
C32—C33	1.383 (4)	C42—H42A	0.9800
C32—H32	1.00 (5)	C42—H42B	0.9800
C33—H33	0.92 (3)	C42—H42C	0.9800
C36—H36A	0.9800	C42'—O10	1.327 (14)
C36—H36B	0.9800	C42'—H42D	0.9800
C36—H36C	0.9800	C42'—H42E	0.9800
O7—C37	1.442 (3)	C42'—H42F	0.9800
C39—O8	1.419 (4)	O10—H10O	0.8611
C39—C38	1.514 (4)	C20—O4	1.471 (9)
C39—H39A	0.98 (5)	C20—H20A	0.9800
C39—H39B	1.07 (5)	C20—H20B	0.9800
C38—C37	1.516 (4)	C20—H20C	0.9800
C38—H38A	0.94 (6)	C20'—O4	1.423 (8)
C38—H38B	1.02 (6)	C20'—H20D	0.9800
C37—H37A	1.02 (3)	C20'—H20E	0.9800
C37—H37B	0.98 (6)	C20'—H20F	0.9800
O8—C40	1.404 (5)	C25—C26	1.595 (11)
C40—H40A	0.9800	C25—H25A	0.9900
C40—H40B	0.9800	C25—H25B	0.9900
C40—H40C	0.9800	C26—H26A	0.9900
C15—C11	1.397 (4)	C26—H26B	0.9900
C15—C14'	1.416 (12)	C25'—C26'	1.608 (12)
C15—C14	1.438 (10)	C25'—H25C	0.9900
C15—C16	1.494 (4)	C25'—H25D	0.9900
C18—C17	1.468 (11)	C26'—H26C	0.9900
C18—C19	1.500 (6)	C26'—H26D	0.9900
C18—C17'	1.620 (13)	C7—C4	1.396 (6)
C18—H18A	0.98 (3)	C4—C5'	1.505 (11)
C18—H18B	1.03 (2)	C4—C5	1.526 (9)
C11—N3	1.313 (9)	C6—C5'	1.475 (14)
C11—N3'	1.443 (12)	C6—C5	1.558 (11)
C11—C10	1.508 (4)	C6—H6A	0.9900
C19—O4	1.391 (6)	C6—H6B	0.9900
C19—H19A	0.9900	C6—H6C	0.9900
C19—H19B	0.9900	C6—H6D	0.9900
O9—C41	1.425 (3)	C5—H5A	0.9900
O9—H9O	0.8781	C5—H5B	0.9900
C41—H41A	0.9800	C5'—H5'1	0.9900
C41—H41B	0.9800	C5'—H5'2	0.9900
C41—H41C	0.9800	C44—O12	1.363 (13)
C10—H10A	0.95 (3)	C44—H44A	0.9800
C10—H10B	0.97 (3)	C44—H44B	0.9800
C16—H16A	0.9800	C44—H44C	0.9800
C16—H16B	0.9800	C44'—O12	1.422 (12)
C16—H16C	0.9800	C44'—H44D	0.9800
O11—C43	1.375 (7)	C44'—H44E	0.9800
O11—H11O	0.9436	C44'—H44F	0.9800
C43—H43A	0.9800	O12—H12O	0.97 (3)
C43—H43B	0.9800
O10—Ca1—O5	90.98 (7)	S1—O1—Ca1^i	121.60 (9)
O10—Ca1—O9	168.52 (7)	Ca1—O1—Ca1^i	113.45 (6)
O5—Ca1—O9	77.75 (6)	C1—N1—C2	101.4 (2)
O10—Ca1—O1	96.45 (7)	N1—C1—N2	119.6 (2)
O5—Ca1—O1	76.76 (6)	N1—C1—S1	121.54 (19)
O9—Ca1—O1	78.99 (7)	N2—C1—S1	118.86 (18)
O10—Ca1—O1^i	75.94 (7)	C1—N2—C9	101.2 (2)
O5—Ca1—O1^i	138.91 (6)	C1—N2—Ca1^i	119.07 (15)
O9—Ca1—O1^i	111.19 (7)	C9—N2—Ca1^i	134.66 (17)
O1—Ca1—O1^i	66.55 (6)	N2—C9—C2	108.9 (2)
O10—Ca1—N2^i	107.48 (8)	N2—C9—C8	129.0 (3)
O5—Ca1—N2^i	150.00 (6)	C2—C9—C8	122.1 (2)
O9—Ca1—N2^i	83.71 (7)	N1—C2—C3	129.4 (3)
O1—Ca1—N2^i	122.66 (7)	N1—C2—C9	109.0 (2)
O1^i—Ca1—N2^i	70.05 (6)	C3—C2—C9	121.6 (3)
O10—Ca1—N5	81.59 (7)	C7—C8—C9	114.7 (3)
O5—Ca1—N5	71.23 (7)	C7—C8—H8	122.6
O9—Ca1—N5	96.61 (7)	C9—C8—H8	122.6
O1—Ca1—N5	147.87 (7)	C4—C3—C2	116.0 (3)
O1^i—Ca1—N5	141.54 (6)	C4—C3—H3	122.0
N2^i—Ca1—N5	87.92 (7)	C2—C3—H3	122.0
O1—S1—C1	103.16 (11)	C7—O2—C6	106.6 (3)
O1—S1—C10	103.43 (12)	C45—O13—H13O	108.3
C1—S1—C10	98.41 (12)	O13—C45—H45A	109.5
O5—S2—C21	104.69 (11)	O13—C45—H45B	109.5
O5—S2—C30	106.03 (12)	H45A—C45—H45B	109.5
C21—S2—C30	95.02 (12)	O13—C45—H45C	109.5
N4—C22—C23	129.3 (3)	H45A—C45—H45C	109.5
N4—C22—C29	108.8 (2)	H45B—C45—H45C	109.5
C23—C22—C29	121.8 (3)	O3—C17—C18	106.5 (8)
C23—C24—C27	122.4 (2)	O3—C17—H17A	110.4
C23—C24—C25'	126.8 (3)	C18—C17—H17A	110.4
C27—C24—C25'	110.7 (3)	O3—C17—H17B	110.4
C23—C24—C25	126.8 (3)	C18—C17—H17B	110.4
C27—C24—C25	110.7 (3)	H17A—C17—H17B	108.6
N5—C29—C28	129.7 (2)	C14—O3—C17	117.8 (10)
N5—C29—C22	108.7 (2)	O3—C14—C13	123.2 (9)
C28—C29—C22	121.6 (2)	O3—C14—C15	119.0 (9)
C27—O6—C26'	99.0 (5)	C13—C14—C15	117.7 (7)
C27—O6—C26	102.4 (4)	C12—C13—C14	117.2 (6)
C27—C28—C29	115.3 (3)	C12—C13—H13	121.4
C27—C28—H28	124 (3)	C14—C13—H13	121.4
C29—C28—H28	120 (3)	N3—C12—C13	125.0 (6)
C28—C27—C24	123.2 (3)	N3—C12—H12	117.5
C28—C27—O6	123.5 (3)	C13—C12—H12	117.5
C24—C27—O6	113.3 (3)	C11—N3—C12	119.5 (6)
C24—C23—C22	115.7 (3)	C14'—O3'—C17'	116.4 (11)
C24—C23—H23	122 (3)	O3'—C17'—C18	105.9 (8)
C22—C23—H23	123 (3)	O3'—C17'—H17C	110.6
C21—N4—C22	101.6 (2)	C18—C17'—H17C	110.6
C21—N5—C29	101.5 (2)	O3'—C17'—H17D	110.6
C21—N5—Ca1	117.86 (15)	C18—C17'—H17D	110.6
C29—N5—Ca1	139.01 (16)	H17C—C17'—H17D	108.7
N4—C21—N5	119.5 (2)	O3'—C14'—C13'	125.4 (10)
N4—C21—S2	121.55 (19)	O3'—C14'—C15	111.0 (10)
N5—C21—S2	118.98 (17)	C13'—C14'—C15	123.2 (9)
S2—O5—Ca1	123.69 (10)	C12'—C13'—C14'	119.0 (7)
C32—N6—C31	117.2 (2)	C12'—C13'—H13'	120.5
C31—C35—C34	117.0 (2)	C14'—C13'—H13'	120.5
C31—C35—C36	122.2 (2)	N3'—C12'—C13'	123.8 (7)
C34—C35—C36	120.7 (2)	N3'—C12'—H12'	118.1
N6—C31—C35	123.6 (2)	C13'—C12'—H12'	118.1
N6—C31—C30	114.7 (2)	C12'—N3'—C11	114.0 (8)
C35—C31—C30	121.6 (2)	O10—C42—H42A	109.5
C31—C30—S2	109.58 (17)	O10—C42—H42B	109.5
C31—C30—H30A	110 (3)	H42A—C42—H42B	109.5
S2—C30—H30A	107 (3)	O10—C42—H42C	109.5
C31—C30—H30B	109 (3)	H42A—C42—H42C	109.5
S2—C30—H30B	109 (4)	H42B—C42—H42C	109.5
H30A—C30—H30B	113 (5)	O10—C42'—H42D	109.5
O7—C34—C33	124.9 (2)	O10—C42'—H42E	109.5
O7—C34—C35	115.2 (2)	H42D—C42'—H42E	109.5
C33—C34—C35	119.8 (2)	O10—C42'—H42F	109.5
N6—C32—C33	124.6 (3)	H42D—C42'—H42F	109.5
N6—C32—H32	115 (3)	H42E—C42'—H42F	109.5
C33—C32—H32	120 (3)	C42'—O10—Ca1	137.4 (7)
C32—C33—C34	117.7 (3)	C42—O10—Ca1	128.0 (4)
C32—C33—H33	117 (3)	C42'—O10—H10O	96.8
C34—C33—H33	125 (3)	C42—O10—H10O	111.8
C35—C36—H36A	109.5	Ca1—O10—H10O	120.2
C35—C36—H36B	109.5	O4—C20—H20A	109.5
H36A—C36—H36B	109.5	O4—C20—H20B	109.5
C35—C36—H36C	109.5	H20A—C20—H20B	109.5
H36A—C36—H36C	109.5	O4—C20—H20C	109.5
H36B—C36—H36C	109.5	H20A—C20—H20C	109.5
C34—O7—C37	118.6 (2)	H20B—C20—H20C	109.5
O8—C39—C38	108.7 (3)	O4—C20'—H20D	109.5
O8—C39—H39A	109 (3)	O4—C20'—H20E	109.5
C38—C39—H39A	109 (3)	H20D—C20'—H20E	109.5
O8—C39—H39B	104 (3)	O4—C20'—H20F	109.5
C38—C39—H39B	118 (3)	H20D—C20'—H20F	109.5
H39A—C39—H39B	108 (4)	H20E—C20'—H20F	109.5
C39—C38—C37	112.5 (2)	C24—C25—C26	101.1 (4)
C39—C38—H38A	110 (3)	C24—C25—H25A	111.6
C37—C38—H38A	107 (3)	C26—C25—H25A	111.6
C39—C38—H38B	113 (3)	C24—C25—H25B	111.6
C37—C38—H38B	105 (3)	C26—C25—H25B	111.6
H38A—C38—H38B	109 (4)	H25A—C25—H25B	109.4
O7—C37—C38	106.7 (2)	O6—C26—C25	105.0 (4)
O7—C37—H37A	110 (3)	O6—C26—H26A	110.8
C38—C37—H37A	112 (3)	C25—C26—H26A	110.8
O7—C37—H37B	111 (3)	O6—C26—H26B	110.8
C38—C37—H37B	116 (3)	C25—C26—H26B	110.8
H37A—C37—H37B	100 (4)	H26A—C26—H26B	108.8
C40—O8—C39	111.6 (3)	C24—C25'—C26'	97.4 (4)
O8—C40—H40A	109.5	C24—C25'—H25C	112.3
O8—C40—H40B	109.5	C26'—C25'—H25C	112.3
H40A—C40—H40B	109.5	C24—C25'—H25D	112.3
O8—C40—H40C	109.5	C26'—C25'—H25D	112.3
H40A—C40—H40C	109.5	H25C—C25'—H25D	109.9
H40B—C40—H40C	109.5	O6—C26'—C25'	105.7 (6)
C11—C15—C14'	111.9 (6)	O6—C26'—H26C	110.6
C11—C15—C14	119.6 (5)	C25'—C26'—H26C	110.6
C11—C15—C16	123.0 (2)	O6—C26'—H26D	110.6
C14'—C15—C16	124.1 (6)	C25'—C26'—H26D	110.6
C14—C15—C16	116.7 (5)	H26C—C26'—H26D	108.7
C17—C18—C19	103.8 (6)	C8—C7—O2	123.5 (3)
C19—C18—C17'	123.5 (6)	C8—C7—C4	123.7 (3)
C17—C18—H18A	121 (3)	O2—C7—C4	112.7 (3)
C19—C18—H18A	109 (3)	C3—C4—C7	121.9 (3)
C17'—C18—H18A	104 (3)	C3—C4—C5'	131.3 (6)
C17—C18—H18B	108.1 (16)	C7—C4—C5'	105.3 (6)
C19—C18—H18B	111.0 (15)	C3—C4—C5	127.4 (5)
C17'—C18—H18B	103.9 (16)	C7—C4—C5	110.0 (4)
H18A—C18—H18B	104 (4)	O2—C6—C5'	107.4 (5)
N3—C11—C15	120.8 (4)	O2—C6—C5	109.6 (4)
C15—C11—N3'	127.0 (4)	O2—C6—H6A	109.8
N3—C11—C10	116.5 (4)	C5—C6—H6A	109.8
C15—C11—C10	121.4 (3)	O2—C6—H6B	109.8
N3'—C11—C10	110.6 (5)	C5—C6—H6B	109.8
O4—C19—C18	109.6 (3)	H6A—C6—H6B	108.2
O4—C19—H19A	109.8	O2—C6—H6C	110.2
C18—C19—H19A	109.8	C5'—C6—H6C	110.2
O4—C19—H19B	109.8	O2—C6—H6D	110.2
C18—C19—H19B	109.8	C5'—C6—H6D	110.2
H19A—C19—H19B	108.2	H6C—C6—H6D	108.5
C41—O9—Ca1	131.18 (16)	C4—C5—C6	99.0 (6)
C41—O9—H9O	109.8	C4—C5—H5A	112.0
Ca1—O9—H9O	117.6	C6—C5—H5A	112.0
O9—C41—H41A	109.5	C4—C5—H5B	112.0
O9—C41—H41B	109.5	C6—C5—H5B	112.0
H41A—C41—H41B	109.5	H5A—C5—H5B	109.7
O9—C41—H41C	109.5	C6—C5'—C4	103.7 (8)
H41A—C41—H41C	109.5	C6—C5'—H5'1	111.0
H41B—C41—H41C	109.5	C4—C5'—H5'1	111.0
C11—C10—S1	109.81 (19)	C6—C5'—H5'2	111.0
C11—C10—H10A	111 (3)	C4—C5'—H5'2	111.0
S1—C10—H10A	107 (3)	H5'1—C5'—H5'2	109.0
C11—C10—H10B	110 (3)	O12—C44—H44A	109.5
S1—C10—H10B	109 (3)	O12—C44—H44B	109.5
H10A—C10—H10B	109 (4)	H44A—C44—H44B	109.5
C15—C16—H16A	109.5	O12—C44—H44C	109.5
C15—C16—H16B	109.5	H44A—C44—H44C	109.5
H16A—C16—H16B	109.5	H44B—C44—H44C	109.5
C15—C16—H16C	109.5	O12—C44'—H44D	109.5
H16A—C16—H16C	109.5	O12—C44'—H44E	109.5
H16B—C16—H16C	109.5	H44D—C44'—H44E	109.5
C43—O11—H11O	115.4	O12—C44'—H44F	109.5
O11—C43—H43A	109.5	H44D—C44'—H44F	109.5
O11—C43—H43B	109.5	H44E—C44'—H44F	109.5
H43A—C43—H43B	109.5	C44—O12—H12O	114 (4)
O11—C43—H43C	109.5	C44'—O12—H12O	112 (4)
H43A—C43—H43C	109.5	C19—O4—C20'	126.3 (8)
H43B—C43—H43C	109.5	C19—O4—C20	96.2 (8)
S1—O1—Ca1	120.64 (9)
N4—C22—C29—N5	1.0 (3)	C2—N1—C1—N2	0.2 (3)
C23—C22—C29—N5	179.1 (2)	C2—N1—C1—S1	177.61 (19)
N4—C22—C29—C28	−178.2 (2)	O1—S1—C1—N1	−148.4 (2)
C23—C22—C29—C28	−0.1 (4)	C10—S1—C1—N1	105.6 (2)
N5—C29—C28—C27	−178.2 (3)	O1—S1—C1—N2	29.1 (2)
C22—C29—C28—C27	0.8 (4)	C10—S1—C1—N2	−76.9 (2)
C29—C28—C27—C24	−0.4 (4)	N1—C1—N2—C9	0.0 (3)
C29—C28—C27—O6	180.0 (3)	S1—C1—N2—C9	−177.53 (17)
C23—C24—C27—C28	−0.6 (5)	N1—C1—N2—Ca1^i	158.33 (18)
C25'—C24—C27—C28	178.4 (3)	S1—C1—N2—Ca1^i	−19.2 (2)
C25—C24—C27—C28	178.4 (3)	C1—N2—C9—C2	−0.1 (3)
C23—C24—C27—O6	179.0 (3)	Ca1^i—N2—C9—C2	−153.2 (2)
C25'—C24—C27—O6	−1.9 (4)	C1—N2—C9—C8	179.1 (3)
C25—C24—C27—O6	−1.9 (4)	Ca1^i—N2—C9—C8	26.1 (4)
C26'—O6—C27—C28	−156.2 (5)	C1—N1—C2—C3	−178.1 (4)
C26—O6—C27—C28	164.1 (4)	C1—N1—C2—C9	−0.2 (3)
C26'—O6—C27—C24	24.2 (5)	N2—C9—C2—N1	0.2 (3)
C26—O6—C27—C24	−15.5 (5)	C8—C9—C2—N1	−179.1 (2)
C27—C24—C23—C22	1.3 (4)	N2—C9—C2—C3	178.3 (3)
C25'—C24—C23—C22	−177.6 (3)	C8—C9—C2—C3	−1.1 (5)
C25—C24—C23—C22	−177.6 (3)	N2—C9—C8—C7	−178.0 (3)
N4—C22—C23—C24	176.8 (3)	C2—C9—C8—C7	1.2 (4)
C29—C22—C23—C24	−0.9 (4)	N1—C2—C3—C4	177.1 (3)
C23—C22—N4—C21	−178.6 (3)	C9—C2—C3—C4	−0.5 (6)
C29—C22—N4—C21	−0.6 (3)	C19—C18—C17—O3	−73.5 (7)
C28—C29—N5—C21	178.2 (3)	C18—C17—O3—C14	−162.9 (8)
C22—C29—N5—C21	−0.8 (3)	C17—O3—C14—C13	−9.1 (12)
C28—C29—N5—Ca1	14.5 (4)	C17—O3—C14—C15	166.7 (8)
C22—C29—N5—Ca1	−164.62 (19)	C11—C15—C14—O3	−177.3 (6)
C22—N4—C21—N5	0.1 (3)	C16—C15—C14—O3	12.0 (9)
C22—N4—C21—S2	−178.21 (18)	C11—C15—C14—C13	−1.3 (9)
C29—N5—C21—N4	0.5 (3)	C16—C15—C14—C13	−172.0 (6)
Ca1—N5—C21—N4	168.51 (18)	O3—C14—C13—C12	179.9 (8)
C29—N5—C21—S2	178.83 (18)	C15—C14—C13—C12	4.1 (12)
Ca1—N5—C21—S2	−13.1 (3)	C14—C13—C12—N3	−2.0 (14)
O5—S2—C21—N4	−161.4 (2)	C15—C11—N3—C12	6.3 (10)
C30—S2—C21—N4	90.6 (2)	C10—C11—N3—C12	173.4 (6)
O5—S2—C21—N5	20.3 (2)	C13—C12—N3—C11	−3.4 (13)
C30—S2—C21—N5	−87.7 (2)	C14'—O3'—C17'—C18	179.7 (8)
C21—S2—O5—Ca1	−19.16 (15)	C19—C18—C17'—O3'	−58.0 (9)
C30—S2—O5—Ca1	80.59 (13)	C17'—O3'—C14'—C13'	−6.5 (15)
C32—N6—C31—C35	−0.7 (4)	C17'—O3'—C14'—C15	−178.9 (8)
C32—N6—C31—C30	177.1 (2)	C11—C15—C14'—O3'	179.7 (7)
C34—C35—C31—N6	1.0 (4)	C16—C15—C14'—O3'	−11.3 (11)
C36—C35—C31—N6	178.6 (3)	C11—C15—C14'—C13'	7.1 (11)
C34—C35—C31—C30	−176.7 (2)	C16—C15—C14'—C13'	176.1 (7)
C36—C35—C31—C30	1.0 (4)	O3'—C14'—C13'—C12'	−179.0 (10)
N6—C31—C30—S2	−89.6 (2)	C15—C14'—C13'—C12'	−7.5 (14)
C35—C31—C30—S2	88.2 (3)	C14'—C13'—C12'—N3'	−1.5 (15)
O5—S2—C30—C31	64.2 (2)	C13'—C12'—N3'—C11	8.9 (13)
C21—S2—C30—C31	171.04 (19)	C15—C11—N3'—C12'	−9.1 (9)
C31—C35—C34—O7	178.5 (2)	C10—C11—N3'—C12'	−177.6 (6)
C36—C35—C34—O7	0.9 (3)	C23—C24—C25—C26	−163.4 (4)
C31—C35—C34—C33	−0.9 (4)	C27—C24—C25—C26	17.6 (4)
C36—C35—C34—C33	−178.6 (2)	C27—O6—C26—C25	25.3 (5)
C31—N6—C32—C33	0.3 (4)	C24—C25—C26—O6	−26.3 (5)
N6—C32—C33—C34	−0.3 (5)	C23—C24—C25'—C26'	159.3 (5)
O7—C34—C33—C32	−178.8 (3)	C27—C24—C25'—C26'	−19.7 (5)
C35—C34—C33—C32	0.6 (4)	C27—O6—C26'—C25'	−35.5 (6)
C33—C34—O7—C37	5.1 (4)	C24—C25'—C26'—O6	34.5 (6)
C35—C34—O7—C37	−174.3 (2)	C9—C8—C7—O2	−179.1 (3)
O8—C39—C38—C37	−51.8 (3)	C9—C8—C7—C4	0.2 (5)
C34—O7—C37—C38	165.9 (2)	C6—O2—C7—C8	−177.4 (4)
C39—C38—C37—O7	−58.3 (3)	C6—O2—C7—C4	3.3 (5)
C38—C39—O8—C40	−175.0 (3)	C2—C3—C4—C7	1.8 (6)
C14—C15—C11—N3	−4.0 (6)	C2—C3—C4—C5'	−162.0 (9)
C16—C15—C11—N3	166.1 (6)	C2—C3—C4—C5	171.2 (6)
C14'—C15—C11—N3'	1.3 (7)	C8—C7—C4—C3	−1.8 (6)
C16—C15—C11—N3'	−167.8 (6)	O2—C7—C4—C3	177.6 (4)
C14'—C15—C11—C10	168.8 (6)	C8—C7—C4—C5'	165.7 (7)
C14—C15—C11—C10	−170.5 (6)	O2—C7—C4—C5'	−15.0 (7)
C16—C15—C11—C10	−0.4 (5)	C8—C7—C4—C5	−172.8 (5)
C17—C18—C19—O4	173.9 (5)	O2—C7—C4—C5	6.5 (7)
C17'—C18—C19—O4	165.7 (5)	C7—O2—C6—C5'	10.2 (8)
N3—C11—C10—S1	−80.3 (6)	C7—O2—C6—C5	−11.6 (7)
C15—C11—C10—S1	86.7 (3)	C3—C4—C5—C6	177.2 (5)
N3'—C11—C10—S1	−104.0 (5)	C7—C4—C5—C6	−12.3 (7)
O1—S1—C10—C11	68.0 (2)	O2—C6—C5—C4	14.3 (8)
C1—S1—C10—C11	173.7 (2)	O2—C6—C5'—C4	−18.5 (11)
C1—S1—O1—Ca1	128.47 (12)	C3—C4—C5'—C6	−174.2 (6)
C10—S1—O1—Ca1	−129.39 (13)	C7—C4—C5'—C6	20.1 (10)
C1—S1—O1—Ca1^i	−26.68 (14)	C18—C19—O4—C20'	178.1 (6)
C10—S1—O1—Ca1^i	75.46 (14)	C18—C19—O4—C20	169.9 (5)

Symmetry code: (i) −x, y, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17A···O11^ii	0.99	2.52	3.285 (12)	134
C13—H13···O11^ii	0.95	2.60	3.451 (9)	150
C17′—H17C···O11^ii	0.99	2.54	3.527 (12)	177
O10—H10O···N3^i	0.86	1.92	2.780 (8)	176
O10—H10O···N3′^i	0.86	1.81	2.654 (10)	167
C26—H26A···O4^iii	0.99	2.43	3.137 (8)	128
C25′—H25C···O7^iv	0.99	2.43	3.341 (5)	152
C25′—H25D···O4^iii	0.99	2.63	3.301 (4)	125
O12—H12O···N1^v	0.97 (3)	1.89 (3)	2.853 (4)	171 (6)
C10—H10A···O8^v	0.95 (3)	2.35 (4)	3.092 (3)	135 (4)
C30—H30B···O13^vi	0.90 (5)	2.55 (6)	2.998 (3)	112 (4)
C32—H32···O12^v	1.00 (5)	2.54 (5)	3.260 (5)	128 (4)
O9—H9O···N6	0.88	1.90	2.774 (3)	178
O13—H13O···N4^vii	0.92	1.81	2.721 (3)	170
O11—H11O···O13^vi	0.94	1.89	2.767 (4)	153
C16—H16B···O3	0.98	2.31	2.785 (11)	109
C19—H19B···O3	0.99	2.41	2.813 (11)	104
C36—H36B···O7	0.98	2.28	2.753 (3)	108

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