A barium perchlorate complex with a lateral macrobicycle derived from 1,10-di­aza-15-crown-5 containing a phenol Schiff base spacer

In the crystal structure of (acetonitrile-κN)[13-methyl-39-oxido-1,17,25-tri­aza-9-azonia-28,31,36-trioxapentacyclo[23.8.5.1^11,15.0^3,8.0^18,23]nonatriaconta-3,5,7,9,11,13,15(39),16,18,20,22-un­decaene-κ⁷N¹,N¹⁷,N²⁵,O²⁸,O³¹,O³⁶,O³⁹](perchlorato-κ²O,O′)barium(II) perchlorate acetonitrile hemisolvate, [Ba(ClO₄)(C₂H₃N)(C₃₃H₄₀N₄O₄)]ClO₄·0.5CH₃CN, the barium(II) cation is asymmetrically situated in the macrobicyclic cavity and is bound to seven of the eight heteroatoms of the macrobicyclic ligand, to the N atom of an aceto­nitrile mol­ecule and to two O atoms of one perchlorate group. The azonia N atom is not coordinated to the barium(II) cation and is involved in an intramolecular hydrogen-bonding interaction with the oxido O atom.

S1. Comment

In a previous work (Esteban et al., 1999) we reported a novel family of Schiff base lateral macrobicycles that contain two different binding units, viz. a rigid and unsaturated N₂X set (X = N and O) and a flexible and cyclic N₂O_n set linked by aromatic bridges. These macrobicycles, which are the first examples of lateral macrobicycles containing imine groups, are structurally derived from bibracchial lariat ethers that incorporate pendant aniline moieties. We have found that ??the macrobicycles?? cannot be prepared by a direct reaction between the organic precursors; but barium can act as a template, thereby facilitating the formation of the desired macrobicycles in high yields. In all cases the barium(II) ion acts as a permanent template, remaining trapped in the macrobicyclic cavity. Herein we describe the X-ray crystal structure determination of one of these barium complexes, [Ba(L)(ClO₄)(CH₃CN)](ClO₄)0.5(CH₃CN), (I), where L is the macrobicycle formed by condensation of the bibracchial lariat ether N,N'-bis(2-aminobenzyl)-1,10-diaza-15-crown-5 and 2,6-diformyl-4-methylphenol.

The asymmetric unit of the crystals contains the cation [Ba(L)(ClO₄)(CH₃CN)]⁺, a well separated perchlorate anion and half a molecule of acetonitrile. Fig. 1 displays the structure of the cationic complex, while selected bond lengths and angles are given in Table 1. The barium(II) ion is bound to seven of the eight heteroatoms of L, to the N atom of an acetonitrile molecule and to two O atoms of one perchlorate group. The X-ray data suggest that the imine atom N1 and the phenol oxygen donor O4 are involved in an intramolecular hydrogen-bonding interaction [O4···N1 = 2.556 (4) Å;, O4···H1N—N1 = 1.72 Å; and O4···H1N—N1 = 141.7 °]. The relevant distances [N1—H1N = 0.97 and O4···H1N = 1.72 Å] also indicate that proton transfer from the phenol group to the imine atom N1 has occurred, as previously found in other related complexes (Esteban et al., 2002). As a result, N1 does not belong to the coordination sphere of the barium(II) ion, which consequently is situated asymmetrically in the macrobicyclic cavity. All the barium donor atom distances fall within the range found in the literature.

The dihedral angles N2—C7—C6—C1 [5.8 (6) °] and N1—C32—C2—C1 [−0.7 (6) °] indicate that the coordinated imine group is just slightly rotated from coplanarity with the phenol ring, whereas the uncoordinated imine group is rigorously coplanar with it. The phenol ring forms dihedral angles of 67.43 (11)° with the plane containing the benzyl ring attached to the coordinated imine atom N2 and of 32.31 (20)° with the plane containing the second aromatic ring. This difference in the fold of the receptor may be due to the coordination of the barium(II) ion, which, in order to maximize the interaction with the seven coordinated heteroatoms of the macrobicycle, forces the torsion and fold of this part of the receptor, so diminishing the degree of π conjugation and increasing the stress on this side of the receptor. In addition, the donor atoms O1, O3, N3 and N4 of the crown moiety are essentially coplanar (the mean deviation from the plane being 0.0044 Å), with the barium ion lying 1.5018 (18) Å above the plane.

The distance between the two imine N atoms (N1 and N2) is 5.376 (4) Å, which is 0.37 Å longer than the distance found in the analogous perchlorate complex in which the macrobicyclic receptor contains a pyridine Schiff base spacer (Esteban et al., 1999). The distance between the two pivotal N atoms (N3 and N4) is 5.169 (4) Å, which is some 0.22 Å shorter than the distance found in the analogous complex containing the pyridine spacer.

S2. Experimental

Single crystals of [Ba(L)(ClO₄)(CH₃CN)](ClO₄)0.5(CH₃CN) suitable for X-ray crystallography were grown by slow diffusion of diethyl ether into an acetonitrile solution of the previously reported complex Ba(L)(ClO₄)₂(EtOH) (Esteban et al., 1999).

S3. Refinement

The atoms O9, O10 and 012 of one perchlorate group are disordered [site occupancy factor 0.52 (2) for O9A, O10A and 012 A], as are the atoms C3S and N2S of an acetonitrile molecule [site occupancy factor 0.103 (13) for C3SA and N2SA], and 93 restraints were imposed. The site O11 is occupied by two non-separable, but not completely coincident, disordered atoms. The structure was solved by direct methods and refined by full matrix least-squares on F². The refinement converged with anisotropic displacement parameters for all non-H atoms, except for C3SA, C3SB, C4S, N2SA and N2SB, which were refined isotropically. The positions of all H atoms, except H1N, were calculated geometrically, and a riding model was used in their refinement. Atom H1N, which is involved in an intramolecular hydrogen bond, was found in a difference electron-density map and then refined riding on atom N1. The H atoms of the solvent (a non-coordinated acetonitrile) were not included. The minimum and maximum final electron density were −1.558 and 1.326 e Å⁻³ (0.86 and 0.89 Å from Ba, respectively).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures

Fig. 1. X-ray crystal structure of [Ba(L)(ClO4)(CH3CN)]^+, showing displacement ellipsoids at the 50% probability level. H atoms are omitted for clarity.

(I)

Crystal data

C33H40BaN4O4·ClO4·C2H3N·ClO4·CH1.5·N0.5	Z = 2
Mr = 954.51	F(000) = 970
Triclinic, P1	Dx = 1.489 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5691 (8) Å	Cell parameters from 14862 reflections
b = 14.8261 (13) Å	θ = 1.4–28.3°
c = 15.7110 (13) Å	µ = 1.12 mm^−1
α = 101.726 (2)°	T = 293 K
β = 101.994 (2)°	Block, orange
γ = 91.566 (2)°	0.55 × 0.40 × 0.40 mm
V = 2129.2 (3) Å^3

Data collection

Bruker CCD diffractometer	10257 independent reflections
Radiation source: fine-focus sealed tube	8410 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ϕ–ω scans	θmax = 28.3°, θmin = 1.4°
Absorption correction: empirical SADABS (Sheldrick, 1996)	h = −12→10
Tmin = 0.577, Tmax = 0.662	k = −19→16
14862 measured reflections	l = −19→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.087P)^2] where P = (Fo^2 + 2Fc^2)/3
10257 reflections	(Δ/σ)max = 0.001
547 parameters	Δρmax = 1.33 e Å^−3
93 restraints	Δρmin = −1.56 e Å^−3

Special details

Experimental. Data were collected using a Bruker SMART CCD based diffractometer operating at room temperature. Data were measured using phi–omega scans of 0.3 degrees per frame for 5 s. A total of 1321 frames were collected. The first 50 frames were recollected at the end of the measurement.

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ba1	0.35511 (2)	0.289037 (13)	0.307876 (12)	0.03199 (8)
Cl1	0.68248 (10)	0.39874 (8)	0.29505 (7)	0.0516 (2)
O1	0.1297 (3)	0.18848 (18)	0.18538 (16)	0.0443 (6)
N1	0.4385 (3)	0.2707 (2)	0.03617 (19)	0.0391 (6)
H1N	0.4153	0.2650	0.0923	0.047*
C1	0.5366 (4)	0.1432 (2)	0.1449 (2)	0.0345 (7)
N1S	0.4648 (4)	0.3458 (3)	0.5031 (3)	0.0626 (10)
C1S	0.4872 (7)	0.3577 (4)	0.6694 (3)	0.0753 (15)
H1S1	0.5036	0.4216	0.6992	0.113*
H1S2	0.5661	0.3244	0.6922	0.113*
H1S3	0.4004	0.3324	0.6797	0.113*
Cl2	0.20920 (15)	−0.21764 (12)	0.15003 (9)	0.0810 (4)
O2	0.1462 (3)	0.3405 (2)	0.40861 (19)	0.0502 (7)
N2	0.5074 (3)	0.1270 (2)	0.3288 (2)	0.0414 (7)
C2	0.5728 (4)	0.1415 (2)	0.0600 (2)	0.0378 (7)
C2S	0.4749 (5)	0.3499 (3)	0.5761 (3)	0.0515 (10)
O3	0.2523 (3)	0.46814 (18)	0.32520 (18)	0.0462 (6)
N3	0.1642 (3)	0.3634 (2)	0.14369 (19)	0.0374 (6)
C3	0.6614 (4)	0.0748 (3)	0.0257 (2)	0.0416 (8)
H3	0.6820	0.0745	−0.0297	0.050*
O4	0.4501 (3)	0.20102 (18)	0.17331 (16)	0.0422 (6)
N4	0.1716 (3)	0.1426 (2)	0.3601 (2)	0.0435 (7)
C4	0.7170 (4)	0.0111 (2)	0.0722 (3)	0.0415 (8)
O5	0.7602 (5)	0.4861 (3)	0.3326 (4)	0.1143 (17)
C5	0.6883 (4)	0.0149 (3)	0.1557 (3)	0.0427 (8)
H5	0.7287	−0.0277	0.1879	0.051*
O6	0.5408 (3)	0.4120 (2)	0.2481 (2)	0.0599 (8)
C6	0.6025 (4)	0.0787 (2)	0.1947 (2)	0.0387 (7)
O7	0.7576 (5)	0.3473 (4)	0.2378 (3)	0.1059 (15)
C7	0.5873 (4)	0.0778 (3)	0.2850 (2)	0.0423 (8)
H7	0.6413	0.0371	0.3137	0.051*
C8	0.5221 (4)	0.1241 (2)	0.4194 (2)	0.0408 (8)
O8	0.6658 (4)	0.3505 (4)	0.3621 (3)	0.1000 (15)
C9	0.6532 (5)	0.1495 (3)	0.4785 (3)	0.0502 (9)
H9	0.7328	0.1653	0.4578	0.060*
C10	0.6654 (6)	0.1514 (3)	0.5686 (3)	0.0599 (11)
H10	0.7532	0.1690	0.6082	0.072*
O11	0.2002 (9)	−0.2776 (5)	0.2030 (5)	0.181 (3)
O9A	0.2076 (15)	−0.2829 (15)	0.0700 (9)	0.138 (8)	0.52 (2)
O10A	0.0826 (15)	−0.1730 (12)	0.1309 (12)	0.142 (6)	0.52 (2)
O12A	0.327 (2)	−0.1488 (18)	0.1772 (14)	0.149 (8)	0.52 (2)
O9B	0.178 (2)	−0.2344 (19)	0.0600 (7)	0.160 (8)	0.48 (2)
O10B	0.145 (2)	−0.1440 (12)	0.1970 (19)	0.187 (9)	0.48 (2)
O12B	0.3581 (12)	−0.1901 (16)	0.1753 (10)	0.116 (7)	0.48 (2)
C11	0.5487 (6)	0.1275 (3)	0.5992 (3)	0.0572 (11)
H11	0.5572	0.1286	0.6594	0.069*
C12	0.4191 (5)	0.1018 (3)	0.5405 (3)	0.0528 (10)
H12	0.3408	0.0848	0.5618	0.063*
C13	0.4018 (4)	0.1006 (2)	0.4503 (2)	0.0408 (8)
C14	0.2605 (4)	0.0677 (3)	0.3868 (3)	0.0467 (9)
H14A	0.2788	0.0281	0.3336	0.056*
H14B	0.2058	0.0304	0.4143	0.056*
C15	0.1148 (5)	0.1891 (3)	0.4366 (3)	0.0579 (11)
H15A	0.1926	0.2035	0.4889	0.069*
H15B	0.0452	0.1466	0.4478	0.069*
C16	0.0437 (5)	0.2780 (4)	0.4237 (3)	0.0627 (12)
H16A	−0.0373	0.2645	0.3732	0.075*
H16B	0.0091	0.3052	0.4763	0.075*
C17	0.1104 (5)	0.4347 (3)	0.4273 (3)	0.0550 (11)
H17A	0.0997	0.4523	0.4884	0.066*
H17B	0.0204	0.4419	0.3883	0.066*
C18	0.2257 (5)	0.4943 (3)	0.4132 (3)	0.0530 (10)
H18A	0.1999	0.5577	0.4231	0.064*
H18B	0.3130	0.4910	0.4564	0.064*
C19	0.1578 (5)	0.5062 (3)	0.2602 (3)	0.0498 (9)
H19A	0.1770	0.5727	0.2728	0.060*
H19B	0.0592	0.4931	0.2632	0.060*
C20	0.1790 (5)	0.4650 (3)	0.1682 (3)	0.0465 (9)
H20A	0.1101	0.4888	0.1252	0.056*
H20B	0.2739	0.4858	0.1640	0.056*
C21	0.0301 (4)	0.3285 (3)	0.1624 (3)	0.0441 (8)
H21A	−0.0500	0.3541	0.1287	0.053*
H21B	0.0316	0.3506	0.2252	0.053*
C22	0.0058 (4)	0.2257 (3)	0.1404 (3)	0.0466 (9)
H22A	−0.0786	0.2072	0.1595	0.056*
H22B	−0.0091	0.2028	0.0765	0.056*
C23	0.1049 (5)	0.0958 (3)	0.1983 (3)	0.0531 (10)
H23A	0.1925	0.0641	0.2000	0.064*
H23B	0.0322	0.0614	0.1489	0.064*
C24	0.0571 (5)	0.1002 (3)	0.2831 (3)	0.0579 (11)
H24A	−0.0262	0.1360	0.2830	0.069*
H24B	0.0298	0.0383	0.2881	0.069*
C25	0.1537 (4)	0.3307 (3)	0.0459 (3)	0.0465 (9)
H25A	0.0568	0.3381	0.0158	0.056*
H25B	0.1666	0.2650	0.0350	0.056*
C26	0.2553 (4)	0.3753 (3)	0.0014 (2)	0.0445 (8)
C27	0.2112 (5)	0.4464 (3)	−0.0421 (3)	0.0587 (11)
H27	0.1259	0.4723	−0.0349	0.070*
C28	0.2884 (6)	0.4798 (3)	−0.0951 (3)	0.0650 (13)
H28	0.2543	0.5262	−0.1240	0.078*
C29	0.4158 (5)	0.4441 (3)	−0.1051 (3)	0.0558 (10)
H29	0.4681	0.4661	−0.1413	0.067*
C30	0.4673 (5)	0.3755 (3)	−0.0615 (3)	0.0481 (9)
H30	0.5550	0.3524	−0.0672	0.058*
C31	0.3870 (4)	0.3412 (3)	−0.0088 (2)	0.0393 (8)
C32	0.5209 (4)	0.2073 (3)	0.0094 (2)	0.0405 (8)
H32	0.5466	0.2051	−0.0449	0.049*
C33	0.8076 (5)	−0.0629 (3)	0.0334 (3)	0.0587 (11)
H33A	0.8522	−0.0938	0.0790	0.088*
H33B	0.8800	−0.0347	0.0112	0.088*
H33C	0.7474	−0.1070	−0.0144	0.088*
C4S	0.8699 (12)	−0.1853 (8)	0.2995 (7)	0.071 (3)*	0.50
N2SA	0.933 (3)	−0.1357 (19)	0.3587 (18)	0.072 (14)*	0.103 (13)
C3SA	0.834 (3)	−0.2487 (18)	0.2292 (12)	0.040 (10)*	0.103 (13)
N2SB	0.8708 (17)	−0.1133 (9)	0.3360 (9)	0.084 (4)*	0.397 (13)
C3SB	0.893 (2)	−0.2731 (11)	0.2742 (13)	0.095 (6)*	0.397 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ba1	0.02570 (11)	0.03960 (12)	0.03218 (11)	0.00565 (7)	0.00985 (7)	0.00709 (8)
Cl1	0.0318 (4)	0.0650 (6)	0.0654 (6)	0.0043 (4)	0.0163 (4)	0.0250 (5)
O1	0.0328 (13)	0.0516 (15)	0.0454 (15)	−0.0061 (11)	−0.0016 (11)	0.0146 (12)
N1	0.0376 (16)	0.0486 (17)	0.0350 (15)	0.0085 (13)	0.0128 (12)	0.0125 (12)
C1	0.0294 (16)	0.0358 (17)	0.0370 (17)	0.0048 (13)	0.0092 (13)	0.0029 (13)
N1S	0.060 (2)	0.072 (3)	0.050 (2)	0.0059 (19)	0.0031 (18)	0.0083 (18)
C1S	0.102 (4)	0.072 (3)	0.050 (3)	0.006 (3)	0.014 (3)	0.010 (2)
Cl2	0.0634 (8)	0.1310 (13)	0.0598 (7)	0.0176 (8)	0.0181 (6)	0.0401 (8)
O2	0.0391 (15)	0.0614 (17)	0.0582 (17)	0.0141 (12)	0.0248 (13)	0.0153 (13)
N2	0.0444 (17)	0.0451 (17)	0.0381 (16)	0.0097 (13)	0.0118 (13)	0.0133 (13)
C2	0.0309 (17)	0.0428 (19)	0.0388 (18)	0.0039 (14)	0.0098 (14)	0.0043 (14)
C2S	0.050 (2)	0.051 (2)	0.049 (2)	0.0045 (18)	0.0055 (18)	0.0040 (18)
O3	0.0457 (15)	0.0475 (15)	0.0480 (15)	0.0160 (12)	0.0143 (12)	0.0100 (12)
N3	0.0260 (14)	0.0490 (17)	0.0399 (15)	0.0055 (12)	0.0107 (11)	0.0116 (13)
C3	0.0309 (17)	0.048 (2)	0.0418 (19)	0.0034 (15)	0.0128 (14)	−0.0040 (15)
O4	0.0451 (15)	0.0488 (14)	0.0395 (13)	0.0206 (11)	0.0191 (11)	0.0127 (11)
N4	0.0376 (16)	0.0531 (19)	0.0429 (17)	0.0011 (14)	0.0074 (13)	0.0194 (14)
C4	0.0297 (17)	0.0404 (19)	0.047 (2)	0.0023 (14)	0.0074 (15)	−0.0067 (15)
O5	0.067 (3)	0.088 (3)	0.166 (5)	−0.022 (2)	−0.020 (3)	0.025 (3)
C5	0.0357 (19)	0.0381 (18)	0.051 (2)	0.0086 (15)	0.0069 (16)	0.0051 (15)
O6	0.0369 (15)	0.0601 (18)	0.084 (2)	0.0047 (13)	0.0055 (14)	0.0268 (16)
C6	0.0334 (18)	0.0412 (19)	0.0405 (18)	0.0073 (14)	0.0074 (14)	0.0066 (14)
O7	0.074 (3)	0.137 (4)	0.126 (4)	0.034 (3)	0.066 (3)	0.025 (3)
C7	0.041 (2)	0.0428 (19)	0.0434 (19)	0.0109 (15)	0.0058 (15)	0.0120 (15)
C8	0.046 (2)	0.0385 (18)	0.0377 (18)	0.0106 (15)	0.0063 (15)	0.0104 (14)
O8	0.059 (2)	0.169 (4)	0.089 (3)	−0.006 (3)	0.007 (2)	0.078 (3)
C9	0.045 (2)	0.052 (2)	0.054 (2)	0.0092 (17)	0.0062 (18)	0.0141 (18)
C10	0.064 (3)	0.058 (3)	0.051 (2)	0.013 (2)	−0.004 (2)	0.011 (2)
O11	0.191 (7)	0.185 (7)	0.197 (7)	0.002 (5)	0.023 (6)	0.132 (6)
O9A	0.043 (5)	0.235 (16)	0.102 (9)	0.032 (7)	0.003 (6)	−0.029 (9)
O10A	0.121 (9)	0.153 (12)	0.138 (12)	0.076 (8)	−0.011 (8)	0.032 (9)
O12A	0.140 (11)	0.212 (19)	0.088 (9)	−0.069 (13)	0.024 (9)	0.029 (9)
O9B	0.093 (13)	0.31 (2)	0.067 (5)	−0.076 (13)	−0.028 (6)	0.086 (8)
O10B	0.116 (13)	0.183 (14)	0.25 (2)	0.056 (11)	0.039 (15)	0.005 (13)
O12B	0.072 (5)	0.221 (18)	0.032 (5)	−0.004 (7)	0.013 (4)	−0.023 (8)
C11	0.078 (3)	0.055 (2)	0.038 (2)	0.015 (2)	0.006 (2)	0.0136 (18)
C12	0.067 (3)	0.054 (2)	0.046 (2)	0.017 (2)	0.018 (2)	0.0218 (18)
C13	0.048 (2)	0.0369 (18)	0.0394 (18)	0.0086 (15)	0.0097 (16)	0.0114 (14)
C14	0.047 (2)	0.047 (2)	0.049 (2)	0.0012 (17)	0.0092 (17)	0.0172 (17)
C15	0.050 (2)	0.079 (3)	0.061 (3)	0.012 (2)	0.029 (2)	0.032 (2)
C16	0.045 (2)	0.088 (3)	0.072 (3)	0.019 (2)	0.033 (2)	0.033 (3)
C17	0.055 (3)	0.067 (3)	0.050 (2)	0.028 (2)	0.024 (2)	0.011 (2)
C18	0.058 (3)	0.050 (2)	0.045 (2)	0.0186 (19)	0.0094 (18)	−0.0025 (17)
C19	0.050 (2)	0.048 (2)	0.054 (2)	0.0192 (18)	0.0124 (18)	0.0135 (18)
C20	0.046 (2)	0.046 (2)	0.052 (2)	0.0133 (17)	0.0120 (17)	0.0164 (17)
C21	0.0275 (17)	0.059 (2)	0.049 (2)	0.0071 (15)	0.0104 (15)	0.0155 (17)
C22	0.0274 (17)	0.069 (3)	0.044 (2)	−0.0019 (16)	0.0014 (15)	0.0201 (18)
C23	0.051 (2)	0.048 (2)	0.051 (2)	−0.0107 (18)	−0.0055 (18)	0.0092 (18)
C24	0.041 (2)	0.069 (3)	0.066 (3)	−0.009 (2)	0.004 (2)	0.031 (2)
C25	0.0337 (19)	0.061 (2)	0.044 (2)	0.0031 (17)	0.0103 (15)	0.0093 (17)
C26	0.041 (2)	0.057 (2)	0.0377 (19)	0.0072 (17)	0.0110 (15)	0.0138 (16)
C27	0.055 (3)	0.076 (3)	0.054 (2)	0.022 (2)	0.014 (2)	0.030 (2)
C28	0.080 (3)	0.070 (3)	0.054 (3)	0.021 (3)	0.014 (2)	0.033 (2)
C29	0.068 (3)	0.059 (3)	0.047 (2)	0.001 (2)	0.022 (2)	0.0200 (19)
C30	0.048 (2)	0.058 (2)	0.044 (2)	0.0048 (18)	0.0198 (17)	0.0139 (17)
C31	0.0412 (19)	0.048 (2)	0.0312 (16)	0.0064 (15)	0.0092 (14)	0.0132 (14)
C32	0.0366 (18)	0.051 (2)	0.0355 (17)	0.0035 (15)	0.0128 (14)	0.0074 (15)
C33	0.043 (2)	0.055 (2)	0.067 (3)	0.0084 (19)	0.014 (2)	−0.013 (2)

Geometric parameters (Å, º)

Ba1—O4	2.596 (2)	C9—C10	1.390 (6)
Ba1—O1	2.741 (2)	C9—H9	0.9300
Ba1—O2	2.827 (2)	C10—C11	1.370 (7)
Ba1—O3	2.838 (3)	C10—H10	0.9300
Ba1—N2	2.884 (3)	C11—C12	1.374 (7)
Ba1—O6	2.928 (3)	C11—H11	0.9300
Ba1—N1S	2.963 (4)	C12—C13	1.390 (5)
Ba1—O8	2.980 (4)	C12—H12	0.9300
Ba1—N4	3.096 (3)	C13—C14	1.505 (5)
Ba1—N3	3.243 (3)	C14—H14A	0.9700
Cl1—O7	1.388 (4)	C14—H14B	0.9700
Cl1—O8	1.420 (4)	C15—C16	1.531 (6)
Cl1—O5	1.425 (4)	C15—H15A	0.9700
Cl1—O6	1.441 (3)	C15—H15B	0.9700
O1—C22	1.434 (4)	C16—H16A	0.9700
O1—C23	1.449 (5)	C16—H16B	0.9700
N1—C32	1.304 (4)	C17—C18	1.474 (6)
N1—C31	1.421 (4)	C17—H17A	0.9700
N1—H1N	0.9708	C17—H17B	0.9700
C1—O4	1.287 (4)	C18—H18A	0.9700
C1—C6	1.434 (5)	C18—H18B	0.9700
C1—C2	1.441 (5)	C19—C20	1.508 (5)
N1S—C2S	1.120 (5)	C19—H19A	0.9700
C1S—C2S	1.426 (6)	C19—H19B	0.9700
C1S—H1S1	0.9600	C20—H20A	0.9700
C1S—H1S2	0.9600	C20—H20B	0.9700
C1S—H1S3	0.9600	C21—C22	1.493 (6)
Cl2—O11	1.347 (5)	C21—H21A	0.9700
Cl2—O9B	1.353 (10)	C21—H21B	0.9700
Cl2—O10A	1.404 (9)	C22—H22A	0.9700
Cl2—O10B	1.416 (11)	C22—H22B	0.9700
Cl2—O9A	1.419 (10)	C23—C24	1.487 (6)
Cl2—O12B	1.422 (10)	C23—H23A	0.9700
Cl2—O12A	1.437 (12)	C23—H23B	0.9700
O2—C16	1.419 (5)	C24—H24A	0.9700
O2—C17	1.433 (5)	C24—H24B	0.9700
N2—C7	1.279 (5)	C25—C26	1.518 (5)
N2—C8	1.412 (5)	C25—H25A	0.9700
C2—C32	1.417 (5)	C25—H25B	0.9700
C2—C3	1.417 (5)	C26—C31	1.399 (5)
O3—C19	1.434 (5)	C26—C27	1.399 (5)
O3—C18	1.435 (5)	C27—C28	1.374 (6)
N3—C20	1.472 (5)	C27—H27	0.9300
N3—C21	1.478 (4)	C28—C29	1.368 (7)
N3—C25	1.495 (5)	C28—H28	0.9300
C3—C4	1.361 (6)	C29—C30	1.384 (6)
C3—H3	0.9300	C29—H29	0.9300
N4—C24	1.470 (5)	C30—C31	1.396 (5)
N4—C15	1.474 (5)	C30—H30	0.9300
N4—C14	1.492 (5)	C32—H32	0.9300
C4—C5	1.386 (5)	C33—H33A	0.9600
C4—C33	1.526 (5)	C33—H33B	0.9600
C5—C6	1.400 (5)	C33—H33C	0.9600
C5—H5	0.9300	C4S—N2SB	1.103 (14)
C6—C7	1.460 (5)	C4S—N2SA	1.11 (2)
C7—H7	0.9300	C4S—C3SA	1.27 (2)
C8—C9	1.387 (6)	C4S—C3SB	1.321 (17)
C8—C13	1.400 (5)
O4—Ba1—O1	71.32 (8)	C6—C7—H7	116.6
O4—Ba1—O2	155.50 (9)	C9—C8—C13	120.3 (4)
O1—Ba1—O2	84.22 (8)	C9—C8—N2	120.1 (4)
O4—Ba1—O3	125.77 (8)	C13—C8—N2	119.5 (3)
O1—Ba1—O3	100.32 (8)	Cl1—O8—Ba1	101.73 (19)
O2—Ba1—O3	59.00 (8)	C10—C9—C8	119.9 (4)
O4—Ba1—N2	62.05 (8)	C10—C9—H9	120.0
O1—Ba1—N2	92.81 (9)	C8—C9—H9	120.0
O2—Ba1—N2	119.46 (8)	C11—C10—C9	120.2 (4)
O3—Ba1—N2	166.38 (9)	C11—C10—H10	119.9
O4—Ba1—O6	68.94 (9)	C9—C10—H10	119.9
O1—Ba1—O6	118.63 (8)	C10—C11—C12	119.8 (4)
O2—Ba1—O6	127.16 (9)	C10—C11—H11	120.1
O3—Ba1—O6	69.81 (8)	C12—C11—H11	120.1
N2—Ba1—O6	107.01 (9)	C11—C12—C13	121.8 (4)
O4—Ba1—N1S	136.23 (10)	C11—C12—H12	119.1
O1—Ba1—N1S	140.59 (10)	C13—C12—H12	119.1
O2—Ba1—N1S	64.51 (10)	C12—C13—C8	118.0 (4)
O3—Ba1—N1S	84.20 (10)	C12—C13—C14	120.7 (4)
N2—Ba1—N1S	83.34 (10)	C8—C13—C14	121.2 (3)
O6—Ba1—N1S	99.81 (11)	N4—C14—C13	114.9 (3)
O4—Ba1—O8	78.40 (12)	N4—C14—H14A	108.5
O1—Ba1—O8	149.71 (11)	C13—C14—H14A	108.5
O2—Ba1—O8	126.07 (12)	N4—C14—H14B	108.5
O3—Ba1—O8	96.58 (12)	C13—C14—H14B	108.5
N2—Ba1—O8	73.26 (12)	H14A—C14—H14B	107.5
O6—Ba1—O8	45.86 (9)	N4—C15—C16	114.1 (3)
N1S—Ba1—O8	65.86 (12)	N4—C15—H15A	108.7
O4—Ba1—N4	105.49 (9)	C16—C15—H15A	108.7
O1—Ba1—N4	59.46 (8)	N4—C15—H15B	108.7
O2—Ba1—N4	58.61 (9)	C16—C15—H15B	108.7
O3—Ba1—N4	115.63 (8)	H15A—C15—H15B	107.6
N2—Ba1—N4	68.21 (9)	O2—C16—C15	108.6 (3)
O6—Ba1—N4	174.20 (8)	O2—C16—H16A	110.0
N1S—Ba1—N4	83.11 (10)	C15—C16—H16A	110.0
O8—Ba1—N4	132.67 (10)	O2—C16—H16B	110.0
O4—Ba1—N3	78.10 (7)	C15—C16—H16B	110.0
O1—Ba1—N3	55.66 (8)	H16A—C16—H16B	108.3
O2—Ba1—N3	89.47 (8)	O2—C17—C18	108.9 (3)
O3—Ba1—N3	56.39 (8)	O2—C17—H17A	109.9
N2—Ba1—N3	136.21 (8)	C18—C17—H17A	109.9
O6—Ba1—N3	71.68 (8)	O2—C17—H17B	109.9
N1S—Ba1—N3	140.45 (10)	C18—C17—H17B	109.9
O8—Ba1—N3	117.52 (9)	H17A—C17—H17B	108.3
N4—Ba1—N3	109.25 (8)	O3—C18—C17	112.5 (3)
O7—Cl1—O8	109.6 (3)	O3—C18—H18A	109.1
O7—Cl1—O5	108.1 (3)	C17—C18—H18A	109.1
O8—Cl1—O5	111.3 (3)	O3—C18—H18B	109.1
O7—Cl1—O6	110.9 (3)	C17—C18—H18B	109.1
O8—Cl1—O6	107.2 (2)	H18A—C18—H18B	107.8
O5—Cl1—O6	109.8 (2)	O3—C19—C20	110.0 (3)
C22—O1—C23	114.7 (3)	O3—C19—H19A	109.7
C22—O1—Ba1	125.6 (2)	C20—C19—H19A	109.7
C23—O1—Ba1	113.7 (2)	O3—C19—H19B	109.7
C32—N1—C31	125.7 (3)	C20—C19—H19B	109.7
C32—N1—H1N	111.9	H19A—C19—H19B	108.2
C31—N1—H1N	122.3	N3—C20—C19	115.0 (3)
O4—C1—C6	122.9 (3)	N3—C20—H20A	108.5
O4—C1—C2	120.5 (3)	C19—C20—H20A	108.5
C6—C1—C2	116.6 (3)	N3—C20—H20B	108.5
C2S—N1S—Ba1	160.1 (4)	C19—C20—H20B	108.5
C2S—C1S—H1S1	109.5	H20A—C20—H20B	107.5
C2S—C1S—H1S2	109.5	N3—C21—C22	114.2 (3)
H1S1—C1S—H1S2	109.5	N3—C21—H21A	108.7
C2S—C1S—H1S3	109.5	C22—C21—H21A	108.7
H1S1—C1S—H1S3	109.5	N3—C21—H21B	108.7
H1S2—C1S—H1S3	109.5	C22—C21—H21B	108.7
O11—Cl2—O9B	128.1 (11)	H21A—C21—H21B	107.6
O11—Cl2—O10A	112.5 (8)	O1—C22—C21	108.1 (3)
O11—Cl2—O10B	97.5 (12)	O1—C22—H22A	110.1
O9B—Cl2—O10B	118.3 (12)	C21—C22—H22A	110.1
O11—Cl2—O9A	98.1 (11)	O1—C22—H22B	110.1
O10A—Cl2—O9A	104.1 (8)	C21—C22—H22B	110.1
O11—Cl2—O12B	100.7 (11)	H22A—C22—H22B	108.4
O9B—Cl2—O12B	105.0 (11)	O1—C23—C24	109.7 (4)
O10B—Cl2—O12B	103.9 (10)	O1—C23—H23A	109.7
O11—Cl2—O12A	117.8 (11)	C24—C23—H23A	109.7
O10A—Cl2—O12A	108.1 (12)	O1—C23—H23B	109.7
O9A—Cl2—O12A	115.3 (14)	C24—C23—H23B	109.7
C16—O2—C17	113.0 (3)	H23A—C23—H23B	108.2
C16—O2—Ba1	124.7 (2)	N4—C24—C23	111.0 (3)
C17—O2—Ba1	120.2 (2)	N4—C24—H24A	109.4
C7—N2—C8	117.6 (3)	C23—C24—H24A	109.4
C7—N2—Ba1	134.6 (2)	N4—C24—H24B	109.4
C8—N2—Ba1	104.9 (2)	C23—C24—H24B	109.4
C32—C2—C3	118.6 (3)	H24A—C24—H24B	108.0
C32—C2—C1	120.4 (3)	N3—C25—C26	119.1 (3)
C3—C2—C1	121.0 (3)	N3—C25—H25A	107.5
N1S—C2S—C1S	178.5 (5)	C26—C25—H25A	107.5
C19—O3—C18	113.5 (3)	N3—C25—H25B	107.5
C19—O3—Ba1	128.9 (2)	C26—C25—H25B	107.5
C18—O3—Ba1	107.3 (2)	H25A—C25—H25B	107.0
C20—N3—C21	110.2 (3)	C31—C26—C27	116.3 (4)
C20—N3—C25	110.5 (3)	C31—C26—C25	123.1 (3)
C21—N3—C25	106.5 (3)	C27—C26—C25	120.1 (4)
C20—N3—Ba1	107.1 (2)	C28—C27—C26	122.9 (4)
C21—N3—Ba1	91.34 (19)	C28—C27—H27	118.6
C25—N3—Ba1	128.8 (2)	C26—C27—H27	118.6
C4—C3—C2	121.3 (3)	C29—C28—C27	119.5 (4)
C4—C3—H3	119.4	C29—C28—H28	120.2
C2—C3—H3	119.4	C27—C28—H28	120.2
C1—O4—H1N	102.9	C28—C29—C30	120.3 (4)
C1—O4—Ba1	147.8 (2)	C28—C29—H29	119.8
H1N—O4—Ba1	106.7	C30—C29—H29	119.8
C24—N4—C15	112.2 (3)	C29—C30—C31	119.7 (4)
C24—N4—C14	107.8 (3)	C29—C30—H30	120.1
C15—N4—C14	108.8 (3)	C31—C30—H30	120.1
C24—N4—Ba1	109.5 (2)	C30—C31—C26	121.2 (3)
C15—N4—Ba1	107.8 (2)	C30—C31—N1	120.3 (3)
C14—N4—Ba1	110.8 (2)	C26—C31—N1	118.5 (3)
C3—C4—C5	118.2 (3)	N1—C32—C2	122.4 (3)
C3—C4—C33	121.1 (4)	N1—C32—H32	118.8
C5—C4—C33	120.7 (4)	C2—C32—H32	118.8
C4—C5—C6	124.1 (3)	C4—C33—H33A	109.5
C4—C5—H5	117.9	C4—C33—H33B	109.5
C6—C5—H5	117.9	H33A—C33—H33B	109.5
Cl1—O6—Ba1	103.45 (15)	C4—C33—H33C	109.5
C5—C6—C1	118.6 (3)	H33A—C33—H33C	109.5
C5—C6—C7	118.3 (3)	H33B—C33—H33C	109.5
C1—C6—C7	123.1 (3)	N2SA—C4S—C3SA	163 (2)
N2—C7—C6	126.8 (3)	N2SB—C4S—C3SB	165.3 (15)
N2—C7—H7	116.6
O4—Ba1—O1—C22	−119.0 (3)	N4—Ba1—O4—H1N	130.8
O2—Ba1—O1—C22	62.4 (3)	N3—Ba1—O4—H1N	23.9
O3—Ba1—O1—C22	5.4 (3)	O4—Ba1—N4—C24	−57.7 (3)
N2—Ba1—O1—C22	−178.2 (3)	O1—Ba1—N4—C24	−1.0 (3)
O6—Ba1—O1—C22	−67.1 (3)	O2—Ba1—N4—C24	101.9 (3)
N1S—Ba1—O1—C22	98.9 (3)	O3—Ba1—N4—C24	86.0 (3)
O8—Ba1—O1—C22	−117.4 (3)	N2—Ba1—N4—C24	−108.3 (3)
N4—Ba1—O1—C22	119.2 (3)	N1S—Ba1—N4—C24	166.2 (3)
N3—Ba1—O1—C22	−30.9 (2)	O8—Ba1—N4—C24	−146.0 (3)
Cl1—Ba1—O1—C22	−88.4 (3)	N3—Ba1—N4—C24	24.9 (3)
O4—Ba1—O1—C23	89.8 (3)	O4—Ba1—N4—C15	180.0 (2)
O2—Ba1—O1—C23	−88.8 (3)	O1—Ba1—N4—C15	−123.3 (3)
O3—Ba1—O1—C23	−145.8 (3)	O2—Ba1—N4—C15	−20.5 (2)
N2—Ba1—O1—C23	30.6 (3)	O3—Ba1—N4—C15	−36.3 (3)
O6—Ba1—O1—C23	141.7 (2)	N2—Ba1—N4—C15	129.4 (3)
N1S—Ba1—O1—C23	−52.3 (3)	N1S—Ba1—N4—C15	43.8 (2)
O8—Ba1—O1—C23	91.4 (3)	O8—Ba1—N4—C15	91.6 (3)
N4—Ba1—O1—C23	−32.0 (2)	N3—Ba1—N4—C15	−97.5 (2)
N3—Ba1—O1—C23	177.9 (3)	O4—Ba1—N4—C14	61.1 (2)
Cl1—Ba1—O1—C23	120.4 (2)	O1—Ba1—N4—C14	117.8 (3)
O4—Ba1—N1S—C2S	−114.5 (10)	O2—Ba1—N4—C14	−139.3 (3)
O1—Ba1—N1S—C2S	8.2 (11)	O3—Ba1—N4—C14	−155.2 (2)
O2—Ba1—N1S—C2S	49.1 (10)	N2—Ba1—N4—C14	10.5 (2)
O3—Ba1—N1S—C2S	107.4 (11)	N1S—Ba1—N4—C14	−75.1 (2)
N2—Ba1—N1S—C2S	−78.1 (11)	O8—Ba1—N4—C14	−27.3 (3)
O6—Ba1—N1S—C2S	175.8 (10)	N3—Ba1—N4—C14	143.6 (2)
O8—Ba1—N1S—C2S	−152.7 (11)	C2—C3—C4—C5	−2.0 (5)
N4—Ba1—N1S—C2S	−9.3 (10)	C2—C3—C4—C33	177.6 (4)
N3—Ba1—N1S—C2S	102.7 (10)	C3—C4—C5—C6	1.7 (6)
O4—Ba1—O2—C16	44.2 (4)	C33—C4—C5—C6	−177.8 (4)
O1—Ba1—O2—C16	47.6 (3)	O7—Cl1—O6—Ba1	106.6 (3)
O3—Ba1—O2—C16	153.3 (3)	O8—Cl1—O6—Ba1	−13.0 (3)
N2—Ba1—O2—C16	−42.4 (3)	O5—Cl1—O6—Ba1	−134.0 (3)
O6—Ba1—O2—C16	169.4 (3)	O4—Ba1—O6—Cl1	−86.02 (17)
N1S—Ba1—O2—C16	−107.8 (3)	O1—Ba1—O6—Cl1	−139.06 (15)
O8—Ba1—O2—C16	−132.5 (3)	O2—Ba1—O6—Cl1	115.29 (16)
N4—Ba1—O2—C16	−10.0 (3)	O3—Ba1—O6—Cl1	129.98 (19)
N3—Ba1—O2—C16	103.1 (3)	N2—Ba1—O6—Cl1	−36.04 (19)
O4—Ba1—O2—C17	−118.0 (3)	N1S—Ba1—O6—Cl1	49.93 (19)
O1—Ba1—O2—C17	−114.7 (3)	O8—Ba1—O6—Cl1	8.19 (18)
O3—Ba1—O2—C17	−8.9 (3)	N3—Ba1—O6—Cl1	−169.98 (19)
N2—Ba1—O2—C17	155.4 (3)	C4—C5—C6—C1	1.6 (6)
O6—Ba1—O2—C17	7.2 (3)	C4—C5—C6—C7	−177.0 (3)
N1S—Ba1—O2—C17	90.0 (3)	O4—C1—C6—C5	176.2 (3)
O8—Ba1—O2—C17	65.3 (3)	C2—C1—C6—C5	−4.4 (5)
N4—Ba1—O2—C17	−172.2 (3)	O4—C1—C6—C7	−5.3 (6)
N3—Ba1—O2—C17	−59.1 (3)	C2—C1—C6—C7	174.1 (3)
O4—Ba1—N2—C7	14.2 (4)	C8—N2—C7—C6	−172.1 (4)
O1—Ba1—N2—C7	81.3 (4)	Ba1—N2—C7—C6	−14.5 (6)
O2—Ba1—N2—C7	166.3 (4)	C5—C6—C7—N2	−175.7 (4)
O3—Ba1—N2—C7	−114.1 (4)	C1—C6—C7—N2	5.8 (6)
O6—Ba1—N2—C7	−39.8 (4)	C7—N2—C8—C9	59.2 (5)
N1S—Ba1—N2—C7	−138.0 (4)	Ba1—N2—C8—C9	−104.5 (3)
O8—Ba1—N2—C7	−71.3 (4)	C7—N2—C8—C13	−124.6 (4)
N4—Ba1—N2—C7	136.8 (4)	Ba1—N2—C8—C13	71.7 (3)
N3—Ba1—N2—C7	41.3 (4)	O7—Cl1—O8—Ba1	−107.8 (3)
O4—Ba1—N2—C8	173.8 (3)	O5—Cl1—O8—Ba1	132.7 (3)
O1—Ba1—N2—C8	−119.1 (2)	O6—Cl1—O8—Ba1	12.7 (3)
O2—Ba1—N2—C8	−34.2 (3)	O4—Ba1—O8—Cl1	63.6 (3)
O3—Ba1—N2—C8	45.4 (5)	O1—Ba1—O8—Cl1	62.0 (4)
O6—Ba1—N2—C8	119.8 (2)	O2—Ba1—O8—Cl1	−117.8 (2)
N1S—Ba1—N2—C8	21.5 (2)	O3—Ba1—O8—Cl1	−61.7 (3)
O8—Ba1—N2—C8	88.2 (2)	N2—Ba1—O8—Cl1	127.6 (3)
N4—Ba1—N2—C8	−63.7 (2)	O6—Ba1—O8—Cl1	−8.26 (18)
N3—Ba1—N2—C8	−159.2 (2)	N1S—Ba1—O8—Cl1	−142.3 (3)
O4—C1—C2—C32	4.0 (5)	N4—Ba1—O8—Cl1	164.02 (19)
C6—C1—C2—C32	−175.4 (3)	N3—Ba1—O8—Cl1	−6.3 (3)
O4—C1—C2—C3	−176.4 (3)	C13—C8—C9—C10	0.3 (6)
C6—C1—C2—C3	4.2 (5)	N2—C8—C9—C10	176.4 (4)
O4—Ba1—O3—C19	44.2 (3)	C8—C9—C10—C11	0.6 (6)
O1—Ba1—O3—C19	−30.1 (3)	C9—C10—C11—C12	−0.2 (7)
O2—Ba1—O3—C19	−106.9 (3)	C10—C11—C12—C13	−1.0 (7)
N2—Ba1—O3—C19	165.5 (4)	C11—C12—C13—C8	1.7 (6)
O6—Ba1—O3—C19	86.7 (3)	C11—C12—C13—C14	176.9 (4)
N1S—Ba1—O3—C19	−170.6 (3)	C9—C8—C13—C12	−1.4 (5)
O8—Ba1—O3—C19	124.6 (3)	N2—C8—C13—C12	−177.6 (3)
N4—Ba1—O3—C19	−91.1 (3)	C9—C8—C13—C14	−176.5 (3)
N3—Ba1—O3—C19	5.8 (3)	N2—C8—C13—C14	7.3 (5)
O4—Ba1—O3—C18	−173.7 (2)	C24—N4—C14—C13	166.4 (3)
O1—Ba1—O3—C18	111.9 (2)	C15—N4—C14—C13	−71.7 (4)
O2—Ba1—O3—C18	35.2 (2)	Ba1—N4—C14—C13	46.6 (4)
N2—Ba1—O3—C18	−52.4 (4)	C12—C13—C14—N4	101.8 (4)
O6—Ba1—O3—C18	−131.2 (3)	C8—C13—C14—N4	−83.2 (4)
N1S—Ba1—O3—C18	−28.5 (3)	C24—N4—C15—C16	−71.1 (5)
O8—Ba1—O3—C18	−93.3 (3)	C14—N4—C15—C16	169.8 (4)
N4—Ba1—O3—C18	51.0 (3)	Ba1—N4—C15—C16	49.6 (4)
N3—Ba1—O3—C18	147.9 (3)	C17—O2—C16—C15	−158.9 (4)
O4—Ba1—N3—C20	−127.5 (2)	Ba1—O2—C16—C15	37.8 (5)
O1—Ba1—N3—C20	157.1 (2)	N4—C15—C16—O2	−59.3 (6)
O2—Ba1—N3—C20	73.7 (2)	C16—O2—C17—C18	177.7 (4)
O3—Ba1—N3—C20	21.5 (2)	Ba1—O2—C17—C18	−18.1 (4)
N2—Ba1—N3—C20	−151.7 (2)	C19—O3—C18—C17	83.9 (4)
O6—Ba1—N3—C20	−56.0 (2)	Ba1—O3—C18—C17	−64.6 (4)
N1S—Ba1—N3—C20	27.1 (3)	O2—C17—C18—O3	56.2 (5)
O8—Ba1—N3—C20	−57.5 (2)	C18—O3—C19—C20	−172.1 (3)
N4—Ba1—N3—C20	130.0 (2)	Ba1—O3—C19—C20	−31.9 (5)
O4—Ba1—N3—C21	120.9 (2)	C21—N3—C20—C19	49.7 (4)
O1—Ba1—N3—C21	45.5 (2)	C25—N3—C20—C19	167.1 (3)
O2—Ba1—N3—C21	−37.8 (2)	Ba1—N3—C20—C19	−48.3 (4)
O3—Ba1—N3—C21	−90.1 (2)	O3—C19—C20—N3	54.7 (5)
N2—Ba1—N3—C21	96.7 (2)	C20—N3—C21—C22	−179.5 (3)
O6—Ba1—N3—C21	−167.6 (2)	C25—N3—C21—C22	60.6 (4)
N1S—Ba1—N3—C21	−84.4 (2)	Ba1—N3—C21—C22	−70.8 (3)
O8—Ba1—N3—C21	−169.1 (2)	C23—O1—C22—C21	158.4 (3)
N4—Ba1—N3—C21	18.5 (2)	Ba1—O1—C22—C21	7.5 (4)
O4—Ba1—N3—C25	8.4 (3)	N3—C21—C22—O1	54.1 (4)
O1—Ba1—N3—C25	−67.0 (3)	C22—O1—C23—C24	−88.0 (4)
O2—Ba1—N3—C25	−150.4 (3)	Ba1—O1—C23—C24	66.5 (4)
O3—Ba1—N3—C25	157.4 (3)	C15—N4—C24—C23	151.9 (4)
N2—Ba1—N3—C25	−15.9 (3)	C14—N4—C24—C23	−88.3 (4)
O6—Ba1—N3—C25	79.9 (3)	Ba1—N4—C24—C23	32.3 (4)
N1S—Ba1—N3—C25	163.0 (3)	O1—C23—C24—N4	−65.8 (5)
O8—Ba1—N3—C25	78.4 (3)	C20—N3—C25—C26	44.4 (4)
N4—Ba1—N3—C25	−94.1 (3)	C21—N3—C25—C26	164.0 (3)
C32—C2—C3—C4	178.6 (3)	Ba1—N3—C25—C26	−90.3 (4)
C1—C2—C3—C4	−1.0 (6)	N3—C25—C26—C31	91.9 (5)
C6—C1—O4—H1N	175.8	N3—C25—C26—C27	−96.6 (5)
C2—C1—O4—H1N	−3.5	C31—C26—C27—C28	2.4 (7)
C6—C1—O4—Ba1	19.4 (7)	C25—C26—C27—C28	−169.6 (4)
C2—C1—O4—Ba1	−159.9 (3)	C26—C27—C28—C29	−1.5 (8)
O1—Ba1—O4—C1	−122.7 (5)	C27—C28—C29—C30	−0.6 (8)
O2—Ba1—O4—C1	−119.2 (4)	C28—C29—C30—C31	1.5 (7)
O3—Ba1—O4—C1	147.9 (4)	C29—C30—C31—C26	−0.5 (6)
N2—Ba1—O4—C1	−18.9 (4)	C29—C30—C31—N1	179.9 (4)
O6—Ba1—O4—C1	105.1 (5)	C27—C26—C31—C30	−1.4 (6)
N1S—Ba1—O4—C1	23.0 (5)	C25—C26—C31—C30	170.3 (4)
O8—Ba1—O4—C1	58.2 (5)	C27—C26—C31—N1	178.2 (4)
N4—Ba1—O4—C1	−73.2 (5)	C25—C26—C31—N1	−10.0 (6)
N3—Ba1—O4—C1	179.8 (5)	C32—N1—C31—C30	−29.6 (6)
O1—Ba1—O4—H1N	81.4	C32—N1—C31—C26	150.7 (4)
O2—Ba1—O4—H1N	84.8	C31—N1—C32—C2	177.2 (3)
O3—Ba1—O4—H1N	−8.0	C3—C2—C32—N1	179.8 (3)
N2—Ba1—O4—H1N	−174.9	C1—C2—C32—N1	−0.7 (6)
O6—Ba1—O4—H1N	−50.9	N2—C7—C6—C1	5.8 (6)
N1S—Ba1—O4—H1N	−132.9	N1—C32—C2—C1	−0.7 (6)
O8—Ba1—O4—H1N	−97.8

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O4	0.97	1.72	2.556 (4)	142