Barium bis­[6-amino-3-methyl-5-nitro­so­pyrimidine-2,4(1H,3H)-dionate] trihydrate: coordination polymer chains linked by hydrogen bonds

The title complex, catena-poly[[triaquabarium(II)]-di-[mu]-6-amino-3-methyl-5-nitro­so­pyrimidine-2,4(1H,3H)-dionato], [Ba(C₅H₅N₄O₃)₂(H₂O)₃]_n, forms a coordination polymer chain in which the two distinct anions use different ligating atoms to bridge pairs of cations. Adjacent pairs of cations are also linked by pairs of bridging water mol­ecules. The chains are linked into a single three-dimensional framework by an extensive series of hydrogen bonds.

S1. Comment

We have recently reported the molecular and supramolecular structures of the hydrated sodium and strontium salts derived from 6-amino-3-methyl-5-nitrosopyrimidine-2,4(1H,3H)-dione, (1). The cations and the (C₅H₅N₄O₃)⁻ anions [denoted L and shown as (2) in the Scheme] in the sodium salt, Na(L)·2H₂O, form a one-dimensional coordination polymer in the form of a molecular ladder, and the ladders are linked into a continuous three-dimensional framework by a combination of O—H···O and O—H···N hydrogen bonds (Cuesta et al., 2001). Within the ladder, the anion utilizes one amide O atom and the nitroso N atom to coordinate to a single Na atom, while the other amide O atom bridges a pair of cations, thus forming a centrosymmetric Na₂O₂ ring. By contrast, the Sr salt of composition Sr(L)₂·3H₂O forms a centrosymmetric dimer, in which the two L ligands adopt entirely different coordination modes: one water ligand bridges two Sr centres, and one of the anionic ligands is bidentate and bonded to just one Sr, while the other is tridentate and bridges the two Sr centres within the dimer. The dimeric units are linked by an extensive series of O—H···O, O—H···N and N—H···O hydrogen bonds to form a complex three-dimensional framework (Low et al., 2003).

Continuing this study, we report here the structure of the hydrated barium salt, (I), of L, whose composition, Ba(L)₂·3H₂O, is analogous to that of the Sr salt. While the structure of (I) (Fig. 1) is different from the structures of both the Na and the Sr complexes of L, it shares certain features with both of them. Complex (I) resembles Na(L)·2H₂O in that both form one-dimensional coordination polymers, but differs from it in containing two distinct anions exhibiting different coordination behaviour and in forming a chain of spiro-fused rings rather than edge-fused rings. Complex (I) resembles Sr(L)₂·3H₂O in forming centrosymmetric M₂(anion)₂ and M₂(H₂O)₂ rings, but differs from it in forming a coordination polymer containing ten-coordinate M (Fig. 2) rather than a finite centrosymmetric dimer containing nine-coordinate M.

The structures of the two independent anions are similar but not identical; each adopts the usual planar conformation with the nitroso group trans to the amide On4 atoms (n = 1 or 2), and each forms an intramolecular N—H···O hydrogen bond with the nitroso On5 atom as acceptor (Fig. 1). The anions show a number of the metrical features characteristic of 5-nitrosopyrimidines (Low et al., 2000, 2001a,b,c,d). In particular, the C4—C5 and C5—C6 distances are very similar, the difference between the C5—N5 and N5—O5 distances is less than 0.065 Å, and the C6—N6 bond is very short for a single C—N bond between three-connected atoms (Allen et al., 1987). While the similar C2—O2 and C4—O4 distances are both typical of those in neutral amides (Allen et al., 1987), the N1—C6 bond is somewhat shorter than the N1—C2 bond. These observations taken together indicate polarization of the electronic structure, so that (2a) is a significantly better representation than (2).

In forming the polymer chain in (I), the type 1 anion (containing N11, N13 etc.) uses two O atoms (O12 and O14) to coordinate to two different Ba atoms, reinforced by weak coordination of nitroso atom N15, while the type 2 anion (containing N21, N23 etc.) uses atom O22 and ring atom N21 to coordinate to a pair of Ba atoms different from those coordinated by the type 1 anion (Table 1). Thus, in the type 1 anion at (x, y, z), atoms O12 and O14 are bonded to Ba atoms at (x, y, z) and (1 − x, 1 − y, −z), respectively, while in the type 1 anion at (1 − x, 1 − y, −z), atoms O12 and O14 are bonded to Ba atoms at (1 − x, 1 − y, −z) and (x, y, z), respectively. In this manner, a centrosymmetric R²₄(12) ring (Starbuck et al., 1999) is formed, centred at (1/2, 1/2, 0). In the type 2 anion at (x, y, z), atoms N21 and O22 are bonded to Ba atoms at (x, y, z) and (1 − x, 1 − y, 1 − z), respectively, providing a centrosymmetric R²₄(8) ring centred at (1/2, 1/2, 1/2). Propagation by inversion of these two ring motifs thus generates a chain of spiro-fused rings running parallel to the [001] direction (Fig. 3), with R²₄(8) rings centred at (1/2, 1/2, 0.5 + n) (n = zero or integer) and R²₄(12) rings centred at (1/2, 1/2, n) (n = zero or integer). The chain is reinforced by two hydrogen bonds; atoms N26 and O2 at (x, y, z) act as hydrogen-bond donors, via atoms H26A and H2B, to atoms O14 and O15, respectively, both at (1 − x, 1 − y, −z).

Almost orthogonal to the R²₄(8) rings are centrosymmetric Ba₂O₂ rings containing water atom O1, where atom O1 at (x, y, z) is coordinated to Ba atoms at (x, y, z) and (1 − x, 1 − y, 1 − z). This feature thus resembles the Sr₂O₂ rings formed in the Sr(L)₂·3H₂O complex (Low et al., 2003). The coordination of the Ba cation at (x, y, z) is completed by the two water molecules containing atoms O2 and O3, both of which are bonded to a single cation, and by rather weak interactions with atom O22 in the type 2 cation at (x, y, z) and atom N15 in the type 1 cation at (1 − x, 1 − y, −z), so giving tenfold coordination (Fig. 2). This conformation may be contrasted with the near-octahedral six-coordination in Na(L)·2H₂O and the nine-coordination in Sr(L)₂·3H₂O.

There is just one coordination polymer chain running through each unit cell, and adjacent chains are linked by an extensive series of O—H···O, O—H···N and N—H···O hydrogen bonds (Table 2) to form a single three-dimensional framework. The formation of this framework is readily analyzed in terms of several one-dimensional substructures.

Water atom O1 at (x, y, z) lies in a Ba₂O₂ ring centred at (1/2, 1/2, 1/2) and acts as hydrogen-bond donor to both water atom O2 and water atom O3 at (-x, 1 − y, 1 − z). These water molecules are directly coordinated to the Ba cation at (-x, 1 − y, 1 − z), which itself lies in the Ba₂O₂ ring centred at (−0.5, 1/2, 1/2). Propagation of these hydrogen bonds by translation and inversion leads to the formation of a chain of rings running parallel to the [100] direction (Fig. 4). This chain contains Ba₂O₂ rings centred at (0.5 + n, 1/2, 1/2) (n = zero or integer), and rectangular prismatic cages built from two Ba cations and six water molecules centred at (n, 1/2, 1/2) (n = zero or integer). This [100] chain is reinforced by the single O—H···N hydrogen bond in the structure, in which water atom O3 at (x, y, z) acts as hydrogen-bond donor, via atom H3B, to pyrimidine atom? N11 in the type 1 anion at (−1 + x, y, z) (Fig. 4).

Water atom O3 at (x, y, z) is directly coordinated to the Ba atom at (x, y, z). This water molecule acts as donor, via atom H3A, to both atom O24 and atom N25 in the type 2 anion at (1 − x, 2 − y, 1 − z) in an effectively planar three-centre O—H···(N,O) hydrogen bond. This type 2 anion is directly coordinated to the Ba atom at (1 − x, 2 − y, 1 − z), which forms part of a Ba₂O₂ ring centred at (1/2, 1.5, 1/2). Propagation of this three-centre hydrogen bond thus generates a chain of rings running parallel to [010], containing Ba₂O₂ rings centred at (1/2, 0.5 + n, 1/2) (n = zero or integer) and R⁴₆(14) rings (Bernstein et al., 1995; Starbuck et al., 1999) centred at (1/2, n, 1/2) (n = zero or integer) (Fig. 5).

The chains along [100], [010] and [001] (Figs. 3–5) are sufficient to generate a single three-dimensional framework. However, the formation of these chains does not fully utilize all of the intermolecular hydrogen bonds, and the final two bonds serve to reinforce the framework by forming a chain running parallel to the [110] direction. Amino atom N16 in the type 1 anion at (x, y, z) acts as hydrogen-bond donor to atom O24 in the type 2 anion at (2 − x, 2 − y, 1 − z), so generating a chain containing Ba₂O₂ rings centred at (0.5 + n, 0.5 + n, 1/2) (n = zero or integer) and R⁴₆(24) rings centred at (n, n, 1/2) (n = zero or integer) (Fig. 6). This [110] chain is itself reinforced by an O—H···O hydrogen bond in which water atom O2 at (x, y, z) acts as donor, via atom H2A, to O25 in the type 2 anion at (−1 + x, −1 + y, z).

S2. Experimental

The title compound was obtained by adding barium chloride trihydrate (3 mmol) to a solution of the corresponding potassium uracilate K(L) (1 mmol) in methanol–water (40 cm³, 9:1% v/v). Slow evaporation of this solution gave crystals, which were dried over CaCl₂ for two weeks. Crystals suitable for single-crystal X-ray diffraction were selected directly from the prepared sample. Analysis found C 21.7, H 2.8, N 20.9%; C₁₀H₁₆BaN₈O₉ requires C 22.7, H 3.0, N 21.2%.

S3. Refinement

Crystals of (I) are triclinic, and the space group P-1 was chosen and confirmed by subsequent analysis. H atoms bonded to C or N atoms were treated as riding atoms, with C—H distances of 0.98 Å and N—H distances of 0.88 Å. H atoms bonded to O atoms were located from difference maps and refined initially using DFIX constraints (SHELXL97; Sheldrick, 1997), with O—H distances 0.90 (2) Å for atom O1 and 0.82 (2) Å for atoms O2 and O3, and finally as riding atoms with these distances. Although there are voids in the structure of ca 73 ų per unit cell, there is no evidence for the presence of any solvent molecules within the voids. Firstly, the only significant peaks in the difference map are clustered around the Ba atoms. In addition, the SQUEEZE option in PLATON (Spek, 2003) did not suggest that there was any significant electron density within the voids. Finally, when a supernumerary O atom was included in the void and refined with a fixed U_iso, its site-occupancy factor refined to a value of 0.036 (6), which is consistent with the absence of significant additional solvent in the void.

Computing details

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The asymmetric unit of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The ten-coordination of barium in (I). Atoms marked 'a' or 'b' are at the symmetry positions (1 − x, 1 − y, −z) and (1 − x, 1 − y, 1 − z), respectively.
	Fig. 3. Stereoview of part of the crystal structure of (I), showing the formation of the coordination polymer chain along (1/2, 1/2, z).
	Fig. 4. Stereoview of part of the crystal structure of (I), showing the formation of the hydrogen-bonded chain along (x, 1/2, 1/2).
	Fig. 5. Stereoview of part of the crystal structure of (I), showing the formation of the chain of rings along (1/2, y, 1/2).
	Fig. 6. Stereoview of part of the crystal structure of (I), showing the formation of the chain of rings parallel to [110].

Barium 6-amino-3-methyl-5-nitrosopyrimidine-2,4(1H,3H)-dionate trihydrate

Crystal data

[Ba(C5H5N4O3)2(H2O)3]	Z = 2
Mr = 529.65	F(000) = 520
Triclinic, P1	Dx = 1.953 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.7594 (1) Å	Cell parameters from 3946 reflections
b = 11.2513 (3) Å	θ = 2.9–27.5°
c = 12.6048 (2) Å	µ = 2.27 mm^−1
α = 106.467 (2)°	T = 120 K
β = 92.911 (1)°	Block, pink
γ = 99.935 (1)°	0.32 × 0.24 × 0.16 mm
V = 900.46 (3) Å^3

Data collection

Kappa-CCD diffractometer	3946 independent reflections
Radiation source: rotating anode	3892 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −8→8
Tmin = 0.519, Tmax = 0.699	k = −14→14
11514 measured reflections	l = −16→15

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.073	H-atom parameters constrained
S = 1.15	w = 1/[σ^2(Fo^2) + (0.0343P)^2 + 0.9783P] where P = (Fo^2 + 2Fc^2)/3
3946 reflections	(Δ/σ)max = 0.002
255 parameters	Δρmax = 0.71 e Å^−3
0 restraints	Δρmin = −1.22 e Å^−3

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

	x	y	z	Uiso*/Ueq
Ba1	0.369848 (18)	0.509100 (11)	0.351704 (10)	0.00851 (7)
O1	0.2337 (3)	0.49118 (18)	0.55253 (16)	0.0138 (4)
O2	−0.0037 (3)	0.32634 (19)	0.32702 (18)	0.0200 (4)
O3	0.0645 (3)	0.65064 (18)	0.37146 (17)	0.0152 (4)
N11	0.8127 (3)	0.5797 (2)	0.15918 (19)	0.0144 (5)
C13	0.5650 (4)	0.2546 (3)	−0.0094 (3)	0.0183 (6)
C12	0.7010 (4)	0.4606 (3)	0.1292 (2)	0.0136 (5)
O12	0.6292 (3)	0.4111 (2)	0.19801 (18)	0.0197 (4)
N13	0.6609 (3)	0.3878 (2)	0.01561 (19)	0.0124 (4)
C14	0.6967 (4)	0.4394 (2)	−0.0701 (2)	0.0111 (5)
O14	0.6357 (3)	0.37826 (18)	−0.16708 (16)	0.0146 (4)
C15	0.8093 (4)	0.5693 (3)	−0.0372 (2)	0.0120 (5)
N15	0.8521 (3)	0.6148 (2)	−0.1218 (2)	0.0141 (4)
O15	0.9579 (3)	0.72742 (19)	−0.10135 (18)	0.0199 (4)
C16	0.8658 (4)	0.6331 (3)	0.0807 (2)	0.0128 (5)
N16	0.9716 (4)	0.7505 (2)	0.1111 (2)	0.0171 (5)
N21	0.5886 (3)	0.7722 (2)	0.43837 (19)	0.0130 (4)
C22	0.5983 (4)	0.7828 (2)	0.5479 (2)	0.0121 (5)
O22	0.5342 (3)	0.68965 (18)	0.57903 (18)	0.0175 (4)
N23	0.6781 (4)	0.8980 (2)	0.6287 (2)	0.0149 (5)
C23	0.6800 (6)	0.9033 (3)	0.7461 (3)	0.0271 (7)
C24	0.7623 (4)	1.0050 (2)	0.6018 (2)	0.0146 (5)
O24	0.8411 (3)	1.10250 (19)	0.67474 (19)	0.0245 (5)
C25	0.7492 (4)	0.9940 (2)	0.4835 (2)	0.0123 (5)
N25	0.8242 (3)	1.1009 (2)	0.4611 (2)	0.0161 (5)
O25	0.8216 (3)	1.0996 (2)	0.35792 (19)	0.0231 (5)
C26	0.6595 (4)	0.8727 (2)	0.4049 (2)	0.0120 (5)
N26	0.6451 (4)	0.8600 (2)	0.2975 (2)	0.0205 (5)
H1A	0.1435	0.4273	0.5622	0.017*
H1B	0.2098	0.5641	0.5973	0.017*
H2A	−0.0439	0.2630	0.3457	0.024*
H2B	−0.0234	0.2970	0.2591	0.024*
H3A	0.1131	0.7261	0.3983	0.018*
H3B	−0.0040	0.6377	0.3123	0.018*
H13A	0.4183	0.2471	−0.0101	0.027*
H13B	0.6153	0.2201	0.0476	0.027*
H13C	0.5972	0.2073	−0.0824	0.027*
H16A	1.0053	0.7915	0.1820	0.021*
H16B	1.0081	0.7873	0.0602	0.021*
H21A	0.6780	0.9897	0.7911	0.041*
H21B	0.8025	0.8779	0.7697	0.041*
H21C	0.5608	0.8458	0.7562	0.041*
H26A	0.5898	0.7866	0.2496	0.025*
H26B	0.6908	0.9249	0.2737	0.025*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ba1	0.00978 (10)	0.00822 (10)	0.00699 (11)	0.00011 (6)	−0.00006 (6)	0.00254 (7)
O1	0.0118 (8)	0.0137 (9)	0.0145 (10)	−0.0002 (7)	0.0029 (7)	0.0033 (8)
O2	0.0264 (11)	0.0144 (9)	0.0169 (11)	−0.0049 (8)	−0.0005 (8)	0.0065 (8)
O3	0.0154 (9)	0.0103 (9)	0.0185 (10)	−0.0005 (7)	−0.0021 (7)	0.0043 (8)
N11	0.0135 (10)	0.0188 (11)	0.0093 (11)	0.0043 (9)	0.0001 (8)	0.0012 (9)
C13	0.0182 (13)	0.0148 (13)	0.0209 (15)	0.0021 (10)	0.0018 (11)	0.0044 (11)
C12	0.0122 (11)	0.0184 (13)	0.0109 (13)	0.0078 (10)	0.0020 (9)	0.0027 (10)
O12	0.0209 (10)	0.0267 (11)	0.0150 (10)	0.0066 (8)	0.0058 (8)	0.0100 (9)
N13	0.0114 (10)	0.0138 (11)	0.0114 (11)	0.0024 (8)	0.0008 (8)	0.0031 (9)
C14	0.0093 (11)	0.0137 (12)	0.0104 (12)	0.0045 (9)	0.0007 (9)	0.0025 (10)
O14	0.0173 (9)	0.0150 (9)	0.0089 (9)	0.0010 (7)	−0.0023 (7)	0.0017 (7)
C15	0.0088 (11)	0.0168 (12)	0.0097 (12)	0.0027 (9)	−0.0001 (9)	0.0029 (10)
N15	0.0122 (10)	0.0152 (11)	0.0142 (12)	0.0018 (8)	0.0008 (8)	0.0039 (9)
O15	0.0227 (10)	0.0171 (10)	0.0158 (10)	−0.0050 (8)	−0.0006 (8)	0.0038 (8)
C16	0.0090 (11)	0.0162 (13)	0.0116 (13)	0.0056 (10)	0.0003 (9)	0.0001 (10)
N16	0.0192 (11)	0.0181 (12)	0.0091 (11)	0.0001 (9)	−0.0022 (9)	−0.0012 (9)
N21	0.0159 (10)	0.0080 (10)	0.0124 (11)	−0.0016 (8)	−0.0009 (8)	0.0018 (8)
C22	0.0116 (11)	0.0085 (11)	0.0150 (13)	0.0023 (9)	−0.0006 (9)	0.0014 (10)
O22	0.0221 (10)	0.0121 (9)	0.0197 (11)	0.0020 (8)	0.0025 (8)	0.0074 (8)
N23	0.0213 (11)	0.0110 (10)	0.0110 (11)	0.0013 (9)	−0.0015 (9)	0.0026 (9)
C23	0.0482 (19)	0.0213 (15)	0.0120 (14)	0.0088 (14)	0.0011 (13)	0.0043 (12)
C24	0.0132 (12)	0.0104 (12)	0.0182 (14)	0.0038 (9)	−0.0016 (10)	0.0006 (10)
O24	0.0333 (12)	0.0119 (9)	0.0196 (11)	−0.0030 (8)	−0.0090 (9)	−0.0026 (8)
C25	0.0100 (11)	0.0093 (11)	0.0164 (13)	0.0005 (9)	−0.0004 (9)	0.0031 (10)
N25	0.0142 (10)	0.0123 (11)	0.0217 (13)	0.0017 (8)	0.0017 (9)	0.0054 (9)
O25	0.0298 (11)	0.0164 (10)	0.0245 (12)	0.0003 (8)	0.0060 (9)	0.0104 (9)
C26	0.0101 (11)	0.0094 (11)	0.0150 (13)	0.0012 (9)	0.0005 (9)	0.0017 (10)
N26	0.0292 (13)	0.0137 (11)	0.0147 (12)	−0.0040 (10)	0.0016 (10)	0.0031 (9)

Geometric parameters (Å, º)

Ba1—O1	2.7852 (19)	C13—H13C	0.98
Ba1—O2	2.910 (2)	N16—H16A	0.88
Ba1—O3	2.7966 (19)	N16—H16B	0.88
Ba1—O12	2.800 (2)	Ba1—N21	2.938 (2)
Ba1—O22	3.028 (2)	Ba1—N15^i	3.023 (2)
O1—H1A	0.90	Ba1—O1^ii	2.8836 (19)
O1—H1B	0.90	Ba1—O14^i	2.9501 (19)
O2—H2A	0.82	Ba1—O22^ii	2.7809 (19)
O2—H2B	0.82	N21—C22	1.349 (4)
O3—H3A	0.82	C22—N23	1.401 (3)
O3—H3B	0.82	N23—C24	1.379 (4)
N11—C12	1.358 (4)	C24—C25	1.457 (4)
C12—N13	1.419 (3)	C25—C26	1.449 (4)
N13—C14	1.377 (3)	C26—N21	1.338 (3)
C14—C15	1.459 (4)	C22—O22	1.239 (3)
C15—C16	1.453 (4)	N23—C23	1.464 (4)
C16—N11	1.329 (4)	C24—O24	1.228 (3)
C12—O12	1.234 (3)	C25—N25	1.335 (3)
C13—N13	1.464 (3)	N25—O25	1.295 (3)
C14—O14	1.230 (3)	C26—N26	1.316 (4)
C15—N15	1.332 (4)	C23—H21A	0.98
N15—O15	1.291 (3)	C23—H21B	0.98
C16—N16	1.328 (4)	C23—H21C	0.98
C13—H13A	0.98	N26—H26A	0.88
C13—H13B	0.98	N26—H26B	0.88
O22^ii—Ba1—O1	64.43 (6)	H3A—O3—H3B	110.7
O22^ii—Ba1—O3	138.34 (6)	C16—N11—C12	119.3 (2)
O1—Ba1—O3	78.61 (6)	N13—C13—H13A	109.5
O22^ii—Ba1—O12	77.08 (6)	N13—C13—H13B	109.5
O1—Ba1—O12	140.80 (6)	H13A—C13—H13B	109.5
O3—Ba1—O12	140.05 (6)	N13—C13—H13C	109.5
O22^ii—Ba1—O1^ii	56.37 (6)	H13A—C13—H13C	109.5
O1—Ba1—O1^ii	86.68 (5)	H13B—C13—H13C	109.5
O3—Ba1—O1^ii	142.83 (6)	O12—C12—N11	122.2 (3)
O12—Ba1—O1^ii	65.06 (6)	O12—C12—N13	117.1 (2)
O22^ii—Ba1—O2	72.90 (6)	N11—C12—N13	120.7 (2)
O1—Ba1—O2	65.94 (6)	C12—O12—Ba1	125.41 (17)
O3—Ba1—O2	75.00 (6)	C14—N13—C12	122.7 (2)
O12—Ba1—O2	110.56 (6)	C14—N13—C13	119.7 (2)
O1^ii—Ba1—O2	129.04 (6)	C12—N13—C13	117.5 (2)
O22^ii—Ba1—N21	124.34 (6)	O14—C14—N13	121.1 (2)
O1—Ba1—N21	96.11 (6)	O14—C14—C15	123.4 (2)
O3—Ba1—N21	76.09 (6)	N13—C14—C15	115.5 (2)
O12—Ba1—N21	99.70 (6)	C14—O14—Ba1^i	123.64 (17)
O1^ii—Ba1—N21	71.76 (6)	N15—C15—C16	127.4 (2)
O2—Ba1—N21	148.43 (6)	N15—C15—C14	114.4 (2)
O22^ii—Ba1—O14^i	145.45 (6)	C16—C15—C14	118.1 (2)
O1—Ba1—O14^i	149.21 (5)	O15—N15—C15	119.0 (2)
O3—Ba1—O14^i	70.93 (6)	O15—N15—Ba1^i	117.78 (16)
O12—Ba1—O14^i	69.99 (6)	C15—N15—Ba1^i	121.54 (17)
O1^ii—Ba1—O14^i	115.16 (5)	N16—C16—N11	118.8 (2)
O2—Ba1—O14^i	108.99 (6)	N16—C16—C15	118.4 (3)
N21—Ba1—O14^i	72.64 (6)	N11—C16—C15	122.8 (2)
O22^ii—Ba1—N15^i	104.74 (6)	C16—N16—H16A	120.0
O1—Ba1—N15^i	126.89 (6)	C16—N16—H16B	120.0
O3—Ba1—N15^i	81.88 (6)	H16A—N16—H16B	120.0
O12—Ba1—N15^i	68.56 (6)	C26—N21—C22	119.9 (2)
O1^ii—Ba1—N15^i	132.69 (6)	C26—N21—Ba1	141.34 (18)
O2—Ba1—N15^i	61.41 (6)	C22—N21—Ba1	98.61 (15)
N21—Ba1—N15^i	126.03 (6)	O22—C22—N21	120.0 (2)
O14^i—Ba1—N15^i	53.61 (6)	O22—C22—N23	118.5 (3)
O22^ii—Ba1—O22	89.65 (6)	N21—C22—N23	121.5 (2)
O1—Ba1—O22	54.65 (5)	O22—C22—Ba1	61.73 (14)
O3—Ba1—O22	83.74 (6)	N21—C22—Ba1	58.38 (13)
O12—Ba1—O22	121.11 (6)	N23—C22—Ba1	175.73 (17)
O1^ii—Ba1—O22	60.19 (5)	C22—O22—Ba1^ii	146.43 (17)
O2—Ba1—O22	119.66 (6)	C22—O22—Ba1	97.15 (17)
N21—Ba1—O22	44.09 (6)	Ba1^ii—O22—Ba1	90.35 (6)
O14^i—Ba1—O22	116.01 (5)	C24—N23—C22	122.6 (2)
N15^i—Ba1—O22	164.62 (6)	C24—N23—C23	118.8 (2)
O22^ii—Ba1—C22	107.29 (6)	C22—N23—C23	118.6 (2)
O1—Ba1—C22	74.06 (6)	N23—C23—H21A	109.5
O3—Ba1—C22	78.45 (6)	N23—C23—H21B	109.5
O12—Ba1—C22	112.92 (6)	H21A—C23—H21B	109.5
O1^ii—Ba1—C22	64.67 (6)	N23—C23—H21C	109.5
O2—Ba1—C22	135.31 (6)	H21A—C23—H21C	109.5
N21—Ba1—C22	23.01 (6)	H21B—C23—H21C	109.5
O14^i—Ba1—C22	95.11 (6)	O24—C24—N23	120.8 (3)
N15^i—Ba1—C22	147.37 (6)	O24—C24—C25	123.4 (3)
O22—Ba1—C22	21.12 (6)	N23—C24—C25	115.7 (2)
Ba1—O1—Ba1^ii	93.32 (5)	N25—C25—C26	127.5 (3)
Ba1—O1—H1A	126.4	N25—C25—C24	114.0 (2)
Ba1^ii—O1—H1A	109.9	C26—C25—C24	118.5 (2)
Ba1—O1—H1B	114.2	O25—N25—C25	118.4 (2)
Ba1^ii—O1—H1B	100.7	N26—C26—N21	118.5 (2)
H1A—O1—H1B	108.1	N26—C26—C25	119.8 (2)
Ba1—O2—H2A	138.0	N21—C26—C25	121.7 (2)
Ba1—O2—H2B	100.9	C26—N26—H26A	120.0
H2A—O2—H2B	100.5	C26—N26—H26B	120.0
Ba1—O3—H3A	110.1	H26A—N26—H26B	120.0
Ba1—O3—H3B	112.8
O22^ii—Ba1—O1—Ba1^ii	54.04 (6)	Ba1—N21—C22—O22	4.4 (3)
O3—Ba1—O1—Ba1^ii	−145.68 (6)	C26—N21—C22—N23	1.2 (4)
O12—Ba1—O1—Ba1^ii	42.31 (11)	Ba1—N21—C22—N23	−175.0 (2)
O2—Ba1—O1—Ba1^ii	135.81 (7)	C26—N21—C22—Ba1	176.2 (3)
N21—Ba1—O1—Ba1^ii	−71.24 (6)	O22^ii—Ba1—C22—O22	−34.56 (19)
O14^i—Ba1—O1—Ba1^ii	−137.25 (8)	O1—Ba1—C22—O22	21.44 (15)
N15^i—Ba1—O1—Ba1^ii	143.67 (6)	O3—Ba1—C22—O22	102.74 (16)
O22—Ba1—O1—Ba1^ii	−55.30 (6)	O12—Ba1—C22—O22	−117.52 (16)
C22—Ba1—O1—Ba1^ii	−64.59 (6)	O1^ii—Ba1—C22—O22	−72.48 (15)
C16—N11—C12—O12	−172.1 (2)	O2—Ba1—C22—O22	48.36 (18)
C16—N11—C12—N13	7.3 (4)	N21—Ba1—C22—O22	−175.7 (3)
N11—C12—O12—Ba1	56.9 (3)	O14^i—Ba1—C22—O22	172.07 (15)
N13—C12—O12—Ba1	−122.6 (2)	N15^i—Ba1—C22—O22	156.83 (15)
O22^ii—Ba1—O12—C12	−170.5 (2)	Ba1^ii—Ba1—C22—O22	−24.68 (14)
O1—Ba1—O12—C12	−159.64 (19)	O22^ii—Ba1—C22—N21	141.11 (15)
O3—Ba1—O12—C12	32.6 (3)	O1—Ba1—C22—N21	−162.88 (16)
O1^ii—Ba1—O12—C12	−111.8 (2)	O3—Ba1—C22—N21	−81.58 (16)
O2—Ba1—O12—C12	123.6 (2)	O12—Ba1—C22—N21	58.16 (16)
N21—Ba1—O12—C12	−47.3 (2)	O1^ii—Ba1—C22—N21	103.20 (16)
O14^i—Ba1—O12—C12	20.1 (2)	O2—Ba1—C22—N21	−135.97 (15)
N15^i—Ba1—O12—C12	77.8 (2)	O14^i—Ba1—C22—N21	−12.26 (16)
O22—Ba1—O12—C12	−88.9 (2)	N15^i—Ba1—C22—N21	−27.5 (2)
C22—Ba1—O12—C12	−67.0 (2)	O22—Ba1—C22—N21	175.7 (3)
Ba1^ii—Ba1—O12—C12	−130.8 (2)	Ba1^ii—Ba1—C22—N21	150.99 (17)
O12—C12—N13—C14	166.7 (2)	N21—C22—O22—Ba1^ii	97.3 (4)
N11—C12—N13—C14	−12.8 (4)	N23—C22—O22—Ba1^ii	−83.3 (4)
O12—C12—N13—C13	−9.1 (3)	Ba1—C22—O22—Ba1^ii	101.5 (3)
N11—C12—N13—C13	171.4 (2)	N21—C22—O22—Ba1	−4.2 (3)
C12—N13—C14—O14	−170.1 (2)	N23—C22—O22—Ba1	175.1 (2)
C13—N13—C14—O14	5.7 (4)	O22^ii—Ba1—O22—C22	147.20 (18)
C12—N13—C14—C15	9.6 (3)	O1—Ba1—O22—C22	−154.47 (18)
C13—N13—C14—C15	−174.6 (2)	O3—Ba1—O22—C22	−74.02 (16)
N13—C14—O14—Ba1^i	167.43 (16)	O12—Ba1—O22—C22	72.56 (17)
C15—C14—O14—Ba1^i	−12.3 (3)	O1^ii—Ba1—O22—C22	96.60 (16)
O14—C14—C15—N15	−3.9 (4)	O2—Ba1—O22—C22	−142.79 (15)
N13—C14—C15—N15	176.4 (2)	N21—Ba1—O22—C22	2.43 (15)
O14—C14—C15—C16	177.5 (2)	O14^i—Ba1—O22—C22	−8.80 (17)
N13—C14—C15—C16	−2.2 (3)	N15^i—Ba1—O22—C22	−53.1 (3)
C16—C15—N15—O15	1.0 (4)	Ba1^ii—Ba1—O22—C22	147.20 (18)
C14—C15—N15—O15	−177.4 (2)	O1—Ba1—O22—Ba1^ii	58.33 (6)
C16—C15—N15—Ba1^i	−164.07 (19)	O3—Ba1—O22—Ba1^ii	138.79 (6)
C14—C15—N15—Ba1^i	17.5 (3)	O12—Ba1—O22—Ba1^ii	−74.64 (7)
C12—N11—C16—N16	178.7 (2)	O1^ii—Ba1—O22—Ba1^ii	−50.60 (5)
C12—N11—C16—C15	0.0 (4)	O2—Ba1—O22—Ba1^ii	70.01 (7)
N15—C15—C16—N16	0.3 (4)	N21—Ba1—O22—Ba1^ii	−144.77 (10)
C14—C15—C16—N16	178.7 (2)	O14^i—Ba1—O22—Ba1^ii	−156.00 (5)
N15—C15—C16—N11	179.0 (2)	N15^i—Ba1—O22—Ba1^ii	159.65 (19)
C14—C15—C16—N11	−2.6 (4)	C22—Ba1—O22—Ba1^ii	−147.20 (18)
O22^ii—Ba1—N21—C26	138.8 (3)	O22—C22—N23—C24	176.6 (2)
O1—Ba1—N21—C26	−158.1 (3)	N21—C22—N23—C24	−4.0 (4)
O3—Ba1—N21—C26	−81.5 (3)	O22—C22—N23—C23	−0.7 (4)
O12—Ba1—N21—C26	57.9 (3)	N21—C22—N23—C23	178.7 (3)
O1^ii—Ba1—N21—C26	117.4 (3)	C22—N23—C24—O24	−175.9 (3)
O2—Ba1—N21—C26	−105.7 (3)	C23—N23—C24—O24	1.4 (4)
O14^i—Ba1—N21—C26	−7.5 (3)	C22—N23—C24—C25	4.6 (4)
N15^i—Ba1—N21—C26	−12.6 (3)	C23—N23—C24—C25	−178.1 (3)
O22—Ba1—N21—C26	−176.9 (3)	O24—C24—C25—N25	−2.3 (4)
C22—Ba1—N21—C26	−174.7 (4)	N23—C24—C25—N25	177.2 (2)
Ba1^ii—Ba1—N21—C26	159.9 (3)	O24—C24—C25—C26	177.7 (3)
O22^ii—Ba1—N21—C22	−46.54 (18)	N23—C24—C25—C26	−2.8 (3)
O1—Ba1—N21—C22	16.54 (16)	C26—C25—N25—O25	−0.9 (4)
O3—Ba1—N21—C22	93.18 (16)	C24—C25—N25—O25	179.1 (2)
O12—Ba1—N21—C22	−127.46 (15)	C22—N21—C26—N26	−179.0 (2)
O1^ii—Ba1—N21—C22	−67.91 (15)	Ba1—N21—C26—N26	−5.0 (4)
O2—Ba1—N21—C22	69.0 (2)	C22—N21—C26—C25	0.5 (4)
O14^i—Ba1—N21—C22	167.20 (16)	Ba1—N21—C26—C25	174.47 (18)
N15^i—Ba1—N21—C22	162.07 (14)	N25—C25—C26—N26	−0.2 (4)
O22—Ba1—N21—C22	−2.24 (13)	C24—C25—C26—N26	179.8 (2)
Ba1^ii—Ba1—N21—C22	−25.39 (15)	N25—C25—C26—N21	−179.7 (3)
C26—N21—C22—O22	−179.4 (2)	C24—C25—C26—N21	0.3 (4)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3^iii	0.90	1.88	2.735 (3)	157
O1—H1B···O2^iii	0.90	2.11	2.918 (3)	150
O2—H2A···O25^iv	0.82	1.96	2.761 (3)	167
O2—H2B···O15^i	0.82	2.01	2.781 (3)	156
O3—H3A···N25^v	0.82	2.19	2.934 (3)	151
O3—H3A···O24^v	0.82	2.34	2.967 (3)	133
O3—H3B···N11^vi	0.82	2.11	2.924 (3)	173
N16—H16A···O24^vii	0.88	1.98	2.833 (3)	163
N16—H16B···O15	0.88	1.95	2.611 (3)	131
N26—H26A···O14^i	0.88	2.15	2.987 (3)	159
N26—H26B···O25	0.88	1.97	2.628 (3)	130

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