Bis­[[mu]-2-(1,4,7,10-tetraoxa-13-aza­cyclo­pentadeca-13-yl)­cyclo­hepta-2,4,6-trien-1-one]­bis­[bis­(thio­cyanato)­barium(II)]

In the title complex, [Ba₂(NCS)₄(C₁₇H₂₅NO₅)₂], each Ba²⁺ cation is coordinated by one N atom, four O atoms of the macrocyclic unit, two N atoms of thio­cyanate unit and one O atom from each of the tropone units.

S1. Comment

Recently, we have prepared several aza-crown ethers having a tropone system and their guest cation complexes. By addition of metal thiocyanates, the original absorption bands of the organic molecule at 355 and 417 nm disappeared and a new absorption band appeared around 332 nm, suggesting that the conformation of the 2-aminotropone moiety changes (Takeshita et al., 1995). The X-ray crystallographic analysis of the Ca(NCS)₂ complex of N-(tropon-2-yl)-1,4,7,10-tetraoxa-13-azacyclopentadecane (ttapd) showed that the Ca²⁺ ion is eight-coordinated, which includes four ether O atoms, one azacrown N, two thiocyanate N atoms and one tropone O atom instead of an O atom from the solvent, such as methanol or water (Kubo et al., 1999b). From the results of the association constants determined by the absorption spectral changes of ttapd for various guest cations, ttapd showed Ba²⁺ ion selectivity (Takeshita et al., 1995). The stoichiometry of the complexation between ttapd and Ba²⁺ ion was confirmed as n:n (n = 1 or 2), at least in acetonitrile, by the molar-ratio method. However, the cavity of ttapd seems to be too small to accommodate a Ba²⁺ ion and ttapd also lacks one potential coordination site, if one assumes a normal Ba²⁺ ion coodination number of nine. In order to reveal the detailed structure of ttapd and the Ba²⁺ ion complex, the barium thiocyanate complex, (I), has been investigated by X-ray crystallographic analysis.

The title complex has 2:2 stoichiometry with C_i symmetry. The structure of (I) is distinct from those of 2,5,8,11,14-pentaoxapentadecane–Ba(NCS)₂–2H₂O (Wei et al., 1987), 1,4,7,10,13,16-hexaoxacyclooctadecane–Ba(NCS)₂–H₂O (Wei et al., 1988) and 10-methyl-9-[2-methyl-4-(1,4,7,10-tetraoxa-13-aza-13- cyclopentadecyl)phenyl]acridinium—Ba(ClO₄)₂—CH₃CN (Häming et al., 1990). Each Ba²⁺ ion of complex (I) has nine-coordination, which includes four ether O atoms (O1, O2, O3 and O4), one azacrown N1 atom, two thiocyanate N atoms (N2 and N3), one tropone O5 atom and one O atom from the other tropone, O5ⁱ [symmetry code: (i) 2 − x, −y, 1 − z]. One N atom (N1) and four O atoms (O1, O2, O3, and O4) of the azacrown are coordinated on one side of Ba1, and the two thiocyanate N atoms (N2 and N3) and the two tropone O atoms (O5 and O5ⁱ) on the opposite side. The dihedral angles between the least-squares azacrown plane defined by O1/O2/O3/O4/N1 and the tropone ring defined by C11–C17/O5 is 116.1 (1)°, while the two BaNCS planes intersect at 76.5 (5) and 50.6 (2)° to the azacrown plane, respectively.

The average value [2.846 (3) Å] of four Ba1—O ether distances is similar to those found in Ba(NCS)₂–2,5,8,11,14-pentaoxapentadecane [2.878 (3) Å; Wei et al., 1987], Ba(NCS)₂–1,4,7,10,13,16-hexaoxacyclooctadecane [2.835 (6) Å; Wei et al., 1988] and to the sum of the ionic and van der Waals radii (2.87 Å = 1.47 + 1.40 Å; Shannon, 1976; Lide, 1990). The Ba1—O5 distance [2.789 (2) Å] is significantly shorter than the Ba1—O ether distances and the Ba1—O5ⁱ distance [2.937 (2) Å]. The Ba1—N1 distance [3.096 (3) Å] is shorter than those of 10-methyl-9-[2-methyl-4-(1,4,7,10-tetraoxa-13-aza-13- cyclopentadecyl)phenyl]acridinium—Ba(ClO₄)₂—CH₃CN [3.260 (8) Å; Häming et al., 1990] and N,N'-bis(1-naphthylmethyl)-1,4,10,13-tetraoxa-7,16- diazacyclooctadecane-Ba(NCS)₂—H₂O [3.127 (5) Å; Kubo et al., 1999a] and is similar to the sum of the ionic and van der Waals radii (3.02 Å = 1.47 + 1.55 Å; Shannon, 1976; Lide, 1990), indicating fairly strong coordination of 2-aminotropone to the Ba²⁺ ion.

The tropone moiety of complex (I) shows pronounced bond alternation similar to those of ttapd–Ca(NCS)₂ (Kubo et al., 1999b) and tropone (Barrow & Mills, 1973) and its ring system deviates from planarity; the angle of the intersection between the least-squares planes A (defined by C11, C12, C17 and O5) and B (defined by C12, C13, C16 and C17) is 20.5 (2)°, while that between the least-squares planes B and C (defined by C13–C16) is 170.2 (3)°.

S2. Experimental

Ttapd was condensed with aza-15-crown-5 ether and 2-(p-toluenesulfonyloxy)tropone in toluene and EtOH (Takeshita et al., 1995). Single crystals of (I) were obtained by slow evaporation of an equimolar mixture of Ba(NCS)₂ and ttapd in CH₃CN.

S3. Refinement

All H atoms were placed at ideal positions and constrained to ride on the atom to which they are bonded. The H-atom isotropic displacement parameters were fixed to 1.2U_eq of the riding atoms.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software (Enraf-Nonius, 1989); data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Xtal_GX (Hall & du Boulay, 1995); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

(I)

Crystal data

[Ba2(NCS)4(C17H25NO5)2]	Z = 2
Mr = 576.88	F(000) = 576
Triclinic, P1	Dx = 1.646 Mg m^−3
a = 11.668 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.445 (5) Å	Cell parameters from 25 reflections
c = 8.918 (5) Å	θ = 10.7–18.1°
α = 96.697 (5)°	µ = 1.92 mm^−1
β = 106.143 (5)°	T = 296 K
γ = 106.720 (5)°	Prism, yellow
V = 1163.8 (9) Å^3	0.30 × 0.27 × 0.23 mm

Data collection

Enraf-Nonius FR590 diffractometer	4973 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.018
Graphite monochromator	θmax = 28.0°, θmin = 2.7°
ω–2θ scans	h = −14→15
Absorption correction: empirical (using intensity measurements) via ψ scans (North et al., 1968)	k = −16→0
Tmin = 0.570, Tmax = 0.643	l = −11→11
5850 measured reflections	3 standard reflections every 120 min
5597 independent reflections	intensity decay: 2.8%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.026	H-atom parameters constrained
wR(F^2) = 0.070	w = 1/[σ^2(Fo^2) + (0.0219P)^2 + 1.0237P] where P = (Fo^2 + 2Fc^2)/3
S = 1.15	(Δ/σ)max = 0.002
5597 reflections	Δρmax = 0.67 e Å^−3
272 parameters	Δρmin = −0.53 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0092 (5)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)

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

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
Ba1	0.958569 (15)	−0.197204 (14)	0.42676 (2)	0.03188 (7)
N1	0.6842 (2)	−0.2092 (2)	0.2528 (3)	0.0392 (5)
N2	0.8317 (4)	−0.2901 (4)	0.6257 (4)	0.0704 (10)
N3	1.1699 (3)	−0.1827 (3)	0.6796 (4)	0.0685 (10)
O1	0.7643 (2)	−0.41122 (18)	0.2474 (3)	0.0485 (5)
O2	1.0118 (3)	−0.4043 (2)	0.3731 (3)	0.0555 (6)
O3	1.0708 (2)	−0.2465 (2)	0.1917 (3)	0.0516 (6)
O4	0.8985 (2)	−0.1263 (3)	0.1362 (3)	0.0561 (6)
O5	0.85073 (19)	−0.03251 (18)	0.4955 (3)	0.0404 (5)
S1	0.66979 (13)	−0.43922 (10)	0.74368 (18)	0.0853 (4)
S2	1.34209 (10)	−0.18728 (11)	0.96152 (12)	0.0638 (3)
C1	0.7933 (4)	−0.5076 (3)	0.3017 (5)	0.0613 (10)
H1A	0.7257	−0.5785	0.2419	0.074*
H1B	0.8017	−0.5012	0.4140	0.074*
C2	0.9139 (4)	−0.5083 (3)	0.2774 (6)	0.0644 (11)
H2A	0.9342	−0.5743	0.3091	0.077*
H2B	0.9063	−0.5126	0.1656	0.077*
C3	1.1269 (4)	−0.3809 (4)	0.3368 (6)	0.0694 (12)
H3A	1.1497	−0.4499	0.3294	0.083*
H3B	1.1942	−0.3223	0.4226	0.083*
C4	1.1148 (5)	−0.3416 (4)	0.1848 (6)	0.0714 (12)
H4A	1.1963	−0.3192	0.1680	0.086*
H4B	1.0556	−0.4035	0.0964	0.086*
C5	1.0129 (5)	−0.2332 (6)	0.0352 (5)	0.0850 (16)
H5A	1.0710	−0.2288	−0.0251	0.102*
H5B	0.9375	−0.2994	−0.0194	0.102*
C6	0.9802 (5)	−0.1335 (5)	0.0427 (6)	0.0870 (17)
H6A	0.9387	−0.1282	−0.0653	0.104*
H6B	1.0575	−0.0677	0.0870	0.104*
C7	0.7745 (3)	−0.1334 (3)	0.0460 (4)	0.0537 (9)
H7A	0.7327	−0.2069	−0.0290	0.064*
H7B	0.7792	−0.0733	−0.0145	0.064*
C8	0.6992 (3)	−0.1209 (3)	0.1544 (4)	0.0468 (7)
H8A	0.7400	−0.0456	0.2253	0.056*
H8B	0.6157	−0.1241	0.0899	0.056*
C9	0.6101 (3)	−0.3250 (3)	0.1517 (4)	0.0504 (8)
H9A	0.6289	−0.3302	0.0523	0.060*
H9B	0.5206	−0.3355	0.1259	0.060*
C10	0.6364 (3)	−0.4200 (3)	0.2289 (4)	0.0502 (8)
H10A	0.6241	−0.4131	0.3323	0.060*
H10B	0.5793	−0.4939	0.1627	0.060*
C11	0.7390 (3)	−0.0687 (3)	0.4968 (4)	0.0388 (6)
C12	0.6481 (3)	−0.1753 (3)	0.3845 (4)	0.0395 (6)
C13	0.5436 (3)	−0.2441 (3)	0.4123 (5)	0.0563 (9)
H13	0.4986	−0.3115	0.3349	0.068*
C14	0.4926 (4)	−0.2315 (4)	0.5357 (6)	0.0709 (12)
H14	0.4322	−0.2974	0.5408	0.085*
C15	0.5185 (4)	−0.1375 (5)	0.6481 (6)	0.0781 (14)
H15	0.4722	−0.1446	0.7182	0.094*
C16	0.6088 (4)	−0.0304 (5)	0.6684 (5)	0.0748 (13)
H16	0.6040	0.0296	0.7362	0.090*
C17	0.7017 (3)	−0.0017 (4)	0.6039 (5)	0.0586 (10)
H17	0.7506	0.0758	0.6343	0.070*
C18	0.7639 (3)	−0.3515 (3)	0.6745 (4)	0.0473 (7)
C19	1.2409 (3)	−0.1843 (3)	0.7964 (4)	0.0439 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ba1	0.03061 (9)	0.03009 (9)	0.03254 (9)	0.00721 (6)	0.01006 (6)	0.00604 (6)
N1	0.0335 (12)	0.0337 (12)	0.0390 (13)	0.0017 (10)	0.0070 (10)	0.0013 (10)
N2	0.067 (2)	0.090 (3)	0.0562 (19)	0.0153 (19)	0.0298 (17)	0.0255 (19)
N3	0.0545 (19)	0.059 (2)	0.070 (2)	0.0104 (16)	−0.0053 (17)	0.0170 (17)
O1	0.0493 (13)	0.0313 (11)	0.0598 (14)	0.0043 (9)	0.0214 (11)	0.0058 (10)
O2	0.0632 (16)	0.0391 (12)	0.0725 (17)	0.0192 (11)	0.0320 (13)	0.0134 (12)
O3	0.0533 (14)	0.0620 (15)	0.0449 (13)	0.0217 (12)	0.0215 (11)	0.0123 (11)
O4	0.0539 (14)	0.0817 (18)	0.0482 (13)	0.0323 (13)	0.0238 (11)	0.0304 (13)
O5	0.0275 (9)	0.0334 (10)	0.0525 (12)	0.0039 (8)	0.0107 (9)	0.0021 (9)
S1	0.0828 (8)	0.0583 (6)	0.1126 (10)	−0.0057 (6)	0.0658 (8)	0.0019 (6)
S2	0.0500 (5)	0.0870 (7)	0.0475 (5)	0.0222 (5)	0.0079 (4)	0.0105 (5)
C1	0.074 (3)	0.0313 (16)	0.077 (3)	0.0106 (17)	0.031 (2)	0.0115 (17)
C2	0.083 (3)	0.0351 (18)	0.078 (3)	0.0223 (18)	0.031 (2)	0.0055 (17)
C3	0.069 (3)	0.063 (3)	0.100 (3)	0.037 (2)	0.045 (3)	0.025 (2)
C4	0.080 (3)	0.066 (3)	0.087 (3)	0.033 (2)	0.051 (3)	0.010 (2)
C5	0.077 (3)	0.157 (5)	0.051 (2)	0.064 (3)	0.035 (2)	0.038 (3)
C6	0.098 (4)	0.135 (5)	0.081 (3)	0.069 (4)	0.060 (3)	0.071 (3)
C7	0.0505 (19)	0.059 (2)	0.0420 (17)	0.0082 (16)	0.0069 (15)	0.0188 (16)
C8	0.0378 (16)	0.0469 (18)	0.0484 (18)	0.0114 (14)	0.0045 (13)	0.0136 (14)
C9	0.0419 (17)	0.0416 (17)	0.0468 (18)	0.0009 (14)	0.0016 (14)	−0.0037 (14)
C10	0.0440 (17)	0.0366 (16)	0.0522 (19)	−0.0069 (13)	0.0142 (15)	−0.0020 (14)
C11	0.0317 (14)	0.0389 (15)	0.0415 (15)	0.0099 (12)	0.0086 (12)	0.0055 (12)
C12	0.0279 (13)	0.0361 (15)	0.0491 (17)	0.0066 (11)	0.0097 (12)	0.0062 (13)
C13	0.0333 (16)	0.053 (2)	0.076 (3)	0.0034 (14)	0.0220 (16)	0.0060 (18)
C14	0.046 (2)	0.081 (3)	0.097 (3)	0.017 (2)	0.042 (2)	0.028 (3)
C15	0.053 (2)	0.121 (4)	0.071 (3)	0.029 (3)	0.037 (2)	0.020 (3)
C16	0.052 (2)	0.101 (4)	0.065 (3)	0.028 (2)	0.021 (2)	−0.015 (2)
C17	0.0436 (18)	0.057 (2)	0.065 (2)	0.0116 (16)	0.0169 (17)	−0.0112 (18)
C18	0.0417 (17)	0.0533 (19)	0.0426 (17)	0.0101 (15)	0.0160 (14)	0.0037 (14)
C19	0.0370 (15)	0.0349 (15)	0.0547 (19)	0.0078 (12)	0.0132 (14)	0.0052 (13)

Geometric parameters (Å, º)

Ba1—N2	2.762 (3)	O3—C5	1.423 (5)
Ba1—N3	2.784 (3)	O4—C7	1.418 (4)
Ba1—O5	2.789 (2)	O4—C6	1.444 (5)
Ba1—O4	2.804 (3)	O5—C11	1.255 (4)
Ba1—O2	2.838 (3)	O5—Ba1^i	2.937 (2)
Ba1—O3	2.858 (3)	S1—C18	1.619 (4)
Ba1—O1	2.882 (2)	S2—C19	1.623 (4)
Ba1—O5^i	2.937 (2)	C1—C2	1.485 (6)
Ba1—N1	3.096 (3)	C3—C4	1.478 (7)
Ba1—Ba1^i	4.6697 (19)	C5—C6	1.398 (7)
N1—C12	1.413 (4)	C7—C8	1.498 (5)
N1—C9	1.478 (4)	C9—C10	1.500 (5)
N1—C8	1.487 (4)	C11—C17	1.433 (5)
N2—C18	1.149 (5)	C11—C12	1.475 (4)
N3—C19	1.144 (5)	C12—C13	1.378 (4)
O1—C10	1.425 (4)	C13—C14	1.403 (6)
O1—C1	1.437 (4)	C14—C15	1.349 (7)
O2—C3	1.426 (5)	C15—C16	1.396 (7)
O2—C2	1.434 (5)	C16—C17	1.343 (6)
O3—C4	1.422 (5)
N2—Ba1—N3	82.41 (12)	C12—N1—C8	112.2 (3)
N2—Ba1—O5	78.26 (10)	C9—N1—C8	111.2 (3)
N3—Ba1—O5	112.09 (10)	C12—N1—Ba1	100.49 (17)
N2—Ba1—O4	137.27 (10)	C9—N1—Ba1	110.04 (19)
N3—Ba1—O4	139.77 (10)	C8—N1—Ba1	104.29 (17)
O5—Ba1—O4	78.18 (8)	C18—N2—Ba1	162.3 (3)
N2—Ba1—O2	87.92 (11)	C19—N3—Ba1	167.7 (3)
N3—Ba1—O2	72.26 (10)	C10—O1—C1	111.7 (3)
O5—Ba1—O2	164.57 (7)	C10—O1—Ba1	117.30 (18)
O4—Ba1—O2	108.47 (8)	C1—O1—Ba1	111.4 (2)
N2—Ba1—O3	144.62 (11)	C3—O2—C2	114.3 (3)
N3—Ba1—O3	93.03 (11)	C3—O2—Ba1	109.3 (2)
O5—Ba1—O3	134.57 (7)	C2—O2—Ba1	120.8 (2)
O4—Ba1—O3	59.38 (8)	C4—O3—C5	110.7 (4)
O2—Ba1—O3	57.58 (8)	C4—O3—Ba1	121.0 (2)
N2—Ba1—O1	71.66 (10)	C5—O3—Ba1	116.5 (2)
N3—Ba1—O1	123.40 (9)	C7—O4—C6	114.7 (3)
O5—Ba1—O1	110.51 (7)	C7—O4—Ba1	124.0 (2)
O4—Ba1—O1	84.07 (8)	C6—O4—Ba1	115.4 (2)
O2—Ba1—O1	57.77 (8)	C11—O5—Ba1	116.94 (19)
O3—Ba1—O1	82.20 (8)	C11—O5—Ba1^i	133.65 (19)
N2—Ba1—O5^i	125.60 (10)	Ba1—O5—Ba1^i	109.25 (7)
N3—Ba1—O5^i	70.08 (9)	O1—C1—C2	108.3 (3)
O5—Ba1—O5^i	70.75 (7)	O2—C2—C1	108.0 (3)
O4—Ba1—O5^i	78.01 (8)	O2—C3—C4	111.5 (4)
O2—Ba1—O5^i	123.78 (7)	O3—C4—C3	108.9 (3)
O3—Ba1—O5^i	84.43 (7)	C6—C5—O3	110.4 (4)
O1—Ba1—O5^i	161.41 (7)	C5—C6—O4	115.4 (4)
N2—Ba1—N1	77.88 (10)	O4—C7—C8	110.4 (3)
N3—Ba1—N1	158.17 (10)	N1—C8—C7	114.7 (3)
O5—Ba1—N1	54.71 (7)	N1—C9—C10	113.5 (3)
O4—Ba1—N1	59.41 (7)	O1—C10—C9	107.8 (3)
O2—Ba1—N1	115.91 (7)	O5—C11—C17	118.4 (3)
O3—Ba1—N1	108.48 (8)	O5—C11—C12	119.9 (3)
O1—Ba1—N1	58.42 (7)	C17—C11—C12	121.6 (3)
O5^i—Ba1—N1	114.64 (7)	C13—C12—N1	121.6 (3)
N2—Ba1—Ba1^i	104.16 (9)	C13—C12—C11	123.6 (3)
N3—Ba1—Ba1^i	90.59 (7)	N1—C12—C11	114.4 (3)
O5—Ba1—Ba1^i	36.42 (4)	C12—C13—C14	132.0 (4)
O4—Ba1—Ba1^i	75.35 (6)	C15—C14—C13	129.3 (4)
O2—Ba1—Ba1^i	157.74 (6)	C14—C15—C16	125.7 (4)
O3—Ba1—Ba1^i	110.98 (5)	C17—C16—C15	129.3 (4)
O1—Ba1—Ba1^i	143.64 (5)	C16—C17—C11	131.6 (4)
O5^i—Ba1—Ba1^i	34.33 (4)	N2—C18—S1	179.2 (4)
N1—Ba1—Ba1^i	85.25 (5)	N3—C19—S2	179.6 (4)
C12—N1—C9	117.2 (3)
N2—Ba1—N1—C12	40.08 (19)	O4—Ba1—O3—C5	−15.0 (3)
N3—Ba1—N1—C12	14.1 (3)	O2—Ba1—O3—C5	129.3 (4)
O5—Ba1—N1—C12	−44.00 (17)	O1—Ba1—O3—C5	72.7 (3)
O4—Ba1—N1—C12	−141.3 (2)	O5^i—Ba1—O3—C5	−94.4 (3)
O2—Ba1—N1—C12	121.71 (17)	N1—Ba1—O3—C5	19.8 (3)
O3—Ba1—N1—C12	−176.07 (17)	Ba1^i—Ba1—O3—C5	−72.2 (3)
O1—Ba1—N1—C12	115.86 (19)	N2—Ba1—O4—C7	−0.7 (3)
O5^i—Ba1—N1—C12	−83.74 (18)	N3—Ba1—O4—C7	−168.8 (3)
Ba1^i—Ba1—N1—C12	−65.51 (17)	O5—Ba1—O4—C7	−58.5 (3)
N2—Ba1—N1—C9	−84.1 (2)	O2—Ba1—O4—C7	107.1 (3)
N3—Ba1—N1—C9	−110.1 (3)	O3—Ba1—O4—C7	138.4 (3)
O5—Ba1—N1—C9	−168.2 (2)	O1—Ba1—O4—C7	54.0 (3)
O4—Ba1—N1—C9	94.5 (2)	O5^i—Ba1—O4—C7	−131.0 (3)
O2—Ba1—N1—C9	−2.5 (2)	N1—Ba1—O4—C7	−2.6 (3)
O3—Ba1—N1—C9	59.7 (2)	Ba1^i—Ba1—O4—C7	−95.8 (3)
O1—Ba1—N1—C9	−8.4 (2)	N2—Ba1—O4—C6	−152.0 (3)
O5^i—Ba1—N1—C9	152.0 (2)	N3—Ba1—O4—C6	39.9 (4)
Ba1^i—Ba1—N1—C9	170.3 (2)	O5—Ba1—O4—C6	150.2 (3)
N2—Ba1—N1—C8	156.5 (2)	O2—Ba1—O4—C6	−44.2 (4)
N3—Ba1—N1—C8	130.5 (3)	O3—Ba1—O4—C6	−12.9 (3)
O5—Ba1—N1—C8	72.38 (19)	O1—Ba1—O4—C6	−97.3 (3)
O4—Ba1—N1—C8	−24.91 (19)	O5^i—Ba1—O4—C6	77.7 (3)
O2—Ba1—N1—C8	−121.91 (19)	N1—Ba1—O4—C6	−153.9 (4)
O3—Ba1—N1—C8	−59.7 (2)	Ba1^i—Ba1—O4—C6	112.9 (3)
O1—Ba1—N1—C8	−127.8 (2)	N2—Ba1—O5—C11	−41.4 (2)
O5^i—Ba1—N1—C8	32.6 (2)	N3—Ba1—O5—C11	−118.1 (2)
Ba1^i—Ba1—N1—C8	50.87 (19)	O4—Ba1—O5—C11	102.7 (2)
N3—Ba1—N2—C18	−123.9 (11)	O2—Ba1—O5—C11	−14.6 (4)
O5—Ba1—N2—C18	121.6 (11)	O3—Ba1—O5—C11	123.2 (2)
O4—Ba1—N2—C18	63.9 (12)	O1—Ba1—O5—C11	23.7 (2)
O2—Ba1—N2—C18	−51.5 (11)	O5^i—Ba1—O5—C11	−176.0 (3)
O3—Ba1—N2—C18	−39.3 (12)	N1—Ba1—O5—C11	42.0 (2)
O1—Ba1—N2—C18	5.1 (11)	Ba1^i—Ba1—O5—C11	−176.0 (3)
O5^i—Ba1—N2—C18	177.4 (11)	N2—Ba1—O5—Ba1^i	134.62 (11)
N1—Ba1—N2—C18	65.6 (11)	N3—Ba1—O5—Ba1^i	57.91 (12)
Ba1^i—Ba1—N2—C18	147.5 (11)	O4—Ba1—O5—Ba1^i	−81.28 (9)
N2—Ba1—N3—C19	−2.9 (15)	O2—Ba1—O5—Ba1^i	161.5 (2)
O5—Ba1—N3—C19	71.1 (15)	O3—Ba1—O5—Ba1^i	−60.77 (12)
O4—Ba1—N3—C19	169.0 (14)	O1—Ba1—O5—Ba1^i	−160.26 (7)
O2—Ba1—N3—C19	−93.1 (15)	O5^i—Ba1—O5—Ba1^i	0.0
O3—Ba1—N3—C19	−147.6 (15)	N1—Ba1—O5—Ba1^i	−142.02 (11)
O1—Ba1—N3—C19	−65.0 (15)	C10—O1—C1—C2	165.4 (3)
O5^i—Ba1—N3—C19	129.4 (15)	Ba1—O1—C1—C2	−61.3 (4)
N1—Ba1—N3—C19	22.7 (16)	C3—O2—C2—C1	−167.2 (3)
Ba1^i—Ba1—N3—C19	101.3 (15)	Ba1—O2—C2—C1	−33.4 (4)
N2—Ba1—O1—C10	61.2 (2)	O1—C1—C2—O2	62.0 (4)
N3—Ba1—O1—C10	128.5 (2)	C2—O2—C3—C4	74.1 (4)
O5—Ba1—O1—C10	−8.2 (2)	Ba1—O2—C3—C4	−64.9 (4)
O4—Ba1—O1—C10	−83.2 (2)	C5—O3—C4—C3	−158.0 (4)
O2—Ba1—O1—C10	160.6 (2)	Ba1—O3—C4—C3	−16.4 (5)
O3—Ba1—O1—C10	−143.0 (2)	O2—C3—C4—O3	54.0 (5)
O5^i—Ba1—O1—C10	−98.6 (3)	C4—O3—C5—C6	−174.6 (4)
N1—Ba1—O1—C10	−25.6 (2)	Ba1—O3—C5—C6	42.0 (5)
Ba1^i—Ba1—O1—C10	−27.9 (3)	O3—C5—C6—O4	−56.4 (6)
N2—Ba1—O1—C1	−69.4 (2)	C7—O4—C6—C5	−111.6 (5)
N3—Ba1—O1—C1	−2.0 (3)	Ba1—O4—C6—C5	42.4 (6)
O5—Ba1—O1—C1	−138.7 (2)	C6—O4—C7—C8	−178.0 (4)
O4—Ba1—O1—C1	146.3 (2)	Ba1—O4—C7—C8	30.5 (4)
O2—Ba1—O1—C1	30.1 (2)	C12—N1—C8—C7	161.9 (3)
O3—Ba1—O1—C1	86.5 (2)	C9—N1—C8—C7	−64.6 (4)
O5^i—Ba1—O1—C1	130.9 (3)	Ba1—N1—C8—C7	54.0 (3)
N1—Ba1—O1—C1	−156.1 (2)	O4—C7—C8—N1	−59.8 (4)
Ba1^i—Ba1—O1—C1	−158.5 (2)	C12—N1—C9—C10	−73.4 (4)
N2—Ba1—O2—C3	−151.9 (3)	C8—N1—C9—C10	155.6 (3)
N3—Ba1—O2—C3	−69.2 (3)	Ba1—N1—C9—C10	40.5 (3)
O5—Ba1—O2—C3	−178.1 (3)	C1—O1—C10—C9	−172.5 (3)
O4—Ba1—O2—C3	68.4 (3)	Ba1—O1—C10—C9	57.1 (3)
O3—Ba1—O2—C3	36.4 (3)	N1—C9—C10—O1	−65.7 (4)
O1—Ba1—O2—C3	138.6 (3)	Ba1—O5—C11—C17	148.1 (3)
O5^i—Ba1—O2—C3	−19.3 (3)	Ba1^i—O5—C11—C17	−26.7 (5)
N1—Ba1—O2—C3	132.7 (3)	Ba1—O5—C11—C12	−34.6 (4)
Ba1^i—Ba1—O2—C3	−28.0 (4)	Ba1^i—O5—C11—C12	150.6 (2)
N2—Ba1—O2—C2	72.3 (3)	C9—N1—C12—C13	−3.8 (5)
N3—Ba1—O2—C2	155.0 (3)	C8—N1—C12—C13	126.8 (3)
O5—Ba1—O2—C2	46.0 (4)	Ba1—N1—C12—C13	−122.9 (3)
O4—Ba1—O2—C2	−67.4 (3)	C9—N1—C12—C11	169.4 (3)
O3—Ba1—O2—C2	−99.4 (3)	C8—N1—C12—C11	−60.1 (3)
O1—Ba1—O2—C2	2.7 (3)	Ba1—N1—C12—C11	50.2 (3)
O5^i—Ba1—O2—C2	−155.1 (3)	O5—C11—C12—C13	154.8 (3)
N1—Ba1—O2—C2	−3.2 (3)	C17—C11—C12—C13	−28.0 (5)
Ba1^i—Ba1—O2—C2	−163.8 (2)	O5—C11—C12—N1	−18.1 (4)
N2—Ba1—O3—C4	−24.6 (4)	C17—C11—C12—N1	159.0 (3)
N3—Ba1—O3—C4	56.5 (3)	N1—C12—C13—C14	177.2 (4)
O5—Ba1—O3—C4	−177.9 (3)	C11—C12—C13—C14	4.7 (7)
O4—Ba1—O3—C4	−154.5 (3)	C12—C13—C14—C15	13.7 (9)
O2—Ba1—O3—C4	−10.2 (3)	C13—C14—C15—C16	−2.7 (9)
O1—Ba1—O3—C4	−66.8 (3)	C14—C15—C16—C17	−12.5 (9)
O5^i—Ba1—O3—C4	126.2 (3)	C15—C16—C17—C11	−0.4 (9)
N1—Ba1—O3—C4	−119.7 (3)	O5—C11—C17—C16	−156.4 (5)
Ba1^i—Ba1—O3—C4	148.3 (3)	C12—C11—C17—C16	26.4 (7)
N2—Ba1—O3—C5	114.9 (4)	Ba1—N2—C18—S1	79 (26)
N3—Ba1—O3—C5	−164.0 (3)	Ba1—N3—C19—S2	119 (70)
O5—Ba1—O3—C5	−38.5 (4)

Symmetry code: (i) −x+2, −y, −z+1.