Hexa­aqua­bis­[3,5-bis­(hy­droxy­imino)-1-methyl-2,4,6-trioxo­cyclo­hexa­nido-κ2N3,O4]barium tetrahydrate

Dinh Do, N.; Kovalchukova, O.; Stash, A.; Strashnova, S.

doi:10.1107/S1600536813027761

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 11| November 2013| Pages m602-m603

doi:10.1107/S1600536813027761

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Hexaaquabis[3,5-bis(hydroxyimino)-1-methyl-2,4,6-trioxocyclohexanido-κ²N³,O⁴]barium tetrahydrate

Nguyen Dinh Do,^a ^* Olga Kovalchukova,^b Adam Stash ^c and Svetlana Strashnova ^b

^aHanoi University of Mining and Geology, Dong Ngac, Tu Liem, Ha Noi, Vietnam, ^bPeoples' Friendship University of Russia, 6, Miklukho-Mallaya, 117198 Moscow, Russian Federation, and ^cKarpov Institute of Physical Chemistry, 10, Vorontsovo Pole, 105064 Moscow, Russian Federation
^*Correspondence e-mail: dondchem@gmail.com

(Received 3 August 2013; accepted 9 October 2013; online 16 October 2013)

In the title compound, [Ba(C₇H₅N₂O₅)₂(H₂O)₆]·4H₂O, the Ba²⁺ cation lies on a twofold rotation axis and is ten-coordinated by two 3,5-bis(hydroxyimino)-1-methyl-2,4,6-trioxocyclohexanide oxo O atoms [Ba—O = 2.8715 (17) Å], two hydroxyimino N atoms [Ba—N = 3.036 (2) Å], and six water molecules [Ba—O = 2.847 (2), 2.848 (2), and 2.880 (2) Å]. The 3,5-bis(hydroxyimino)-1-methyl-2,4,6-trioxocyclohexanide monoanions act in a bidentate chelating manner, coordinating through an N atom of the non-deprotonated hydroxyimino group and an O atom of the neighboring oxo group. Two lattice water molecules are located in the cavities of the framework and are involved in hydrogen bonding to O atoms of one of the coordinating water molecules and the O atom of a keto group of the ligand. As a result, a three-dimensional network is formed.

CCDC reference: 965674

Related literature

For the synthesis and crystal structure of sodium 3,5-bis(hydroxyimino)-1-methyl-2,4,6- trioxocyclohexanide, see: Kovalchukova et al. (2012 ). For related structures of metal complexes with 1,2-benzo(naphto)quinone-1-oximes, see: Chakravorty (1974 ); Charalambous et al. (1993 , 1995 , 1996 ); Adatia et al. (1996 ); Basu & Chakravorty (1992 ); McPartlin (1973 ); Djinovic et al. (1992 ); Liu et al. (2010 ). For applications of related complexes as catalysts, see: Gharah et al. (2009 ).

Experimental

Crystal data

[Ba(C₇H₅N₂O₅)₂(H₂O)₆]·4H₂O
M_r = 711.76
Monoclinic, C 2/c
a = 17.235 (3) Å
b = 6.736 (1) Å
c = 23.074 (5) Å
β = 108.61 (3)°
V = 2538.7 (9) Å³
Z = 4
Mo Kα radiation
μ = 1.66 mm⁻¹
T = 293 K
0.33 × 0.12 × 0.07 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983 ) T_min = 0.370, T_max = 0.780
2429 measured reflections
2346 independent reflections
1755 reflections with I > 2σ(I)
R_int = 0.019
3 standard reflections every 60 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.018
wR(F²) = 0.048
S = 0.98
2346 reflections
216 parameters
17 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.90 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O21—H21⋯O3	0.86 (3)	1.70 (3)	2.476 (3)	150 (4)
O61—H61⋯O5	0.86 (3)	1.64 (3)	2.469 (2)	160 (4)
O11—H111⋯O3ⁱ	0.85 (1)	1.99 (1)	2.827 (2)	167 (4)
O11—H112⋯O12ⁱⁱ	0.84 (1)	2.15 (3)	2.854 (3)	142 (4)
O12—H121⋯O14ⁱⁱⁱ	0.84 (1)	1.90 (1)	2.739 (3)	172 (4)
O12—H122⋯O11^iv	0.84 (1)	2.17 (3)	2.839 (3)	137 (3)
O13—H131⋯O14	0.85 (1)	2.13 (1)	2.957 (3)	165 (4)
O13—H132⋯O15^v	0.85 (1)	1.93 (1)	2.766 (3)	169 (4)
O14—H141⋯O13^vi	0.85 (1)	1.99 (1)	2.835 (3)	173 (4)
O15—H151⋯O5^vii	0.85 (1)	1.94 (1)	2.789 (3)	177 (4)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+1, y+1, -z+{\script{3\over 2}}]$ ; (iii) $[-x+1, y, -z+{\script{3\over 2}}]$ ; (iv) x, y-1, z; (v) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (vi) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vii) -x+1, -y, -z+1.

Data collection: CAD-4-PC (Enraf–Nonius, 1993 ); cell refinement: CAD-4-PC; data reduction: CAD-4-PC; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: CIFTAB97 (Sheldrick, 2008) and SHELXL97.

Supporting information

CCDC reference: 965674

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813027761/bv2225sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813027761/bv2225Isup2.hkl

checkCIF report

Comment top

1,2-Quinone monooximes (2-nitrosophenols) are good chelating agents which form stable colored complexes with a wide range of metal ions (Chakravorty, 1974; Charalambous et al., 1996; Djinovic et al., 1992; Liu et al., 2010). Increasing attention is also being devoted to these complexes in recent years because of their applications in organic synthesis (Gharah et al., 2009). Sodium 3,5-bis(hydroxyimino) -1-methyl-2,4,6-trioxocyclohexanide has been recently isolated as the only product of the reaction of nitrosation of methylphloroglucinol, and its crystal and molecular structure was reported (Kovalchukova et al., 2012). In the present paper we report the crystal and molecular structure of barium hexaaqua bis (3,5-bis(hydroxyimino)-1-methyl-2,4,6- trioxocyclohexanide) dihydrate, C₁₄H₃₀BaN₄O₂₀. The Ba cation of the reported structure lies on a center of inversion, and is ten-coordinated. It is surrounded by two oxo O atoms of 3,5-bis(hydroxyimino)-1-methyl-2,4,6- trioxocyclohexanide species [Ba—O = 2.8715 (17) Å], two hydroxyimino N atoms [Ba—N = 3.036 (2) Å], and six water molecules [Ba—O = 2.847 (2), 2.848 (2), and 2.880 (2) Å]. The 3,5-bis(hydroxyimino)-1-methyl-2,4,6- trioxocyclohexanide mono anions act as bidentate chelating coordinated through an N-atom of the non-deprotonated hydroxyimino group and an O-atom of the neighboring oxo-group. The conjugation in the chelate ring is observed in the equalizing of the chemical bonds [C1—O1 = 1.219 (3), C6—N6 = 1.299 (3), N6—O61 = 1.352, C1—C6 1.482 Å]. There are two intramolecular hydrogen bonds in the 3,5-bis(hydroxyimino)-1-methyl-2,4,6- trioxocyclohexanide anion adjusting the hydroxyimino H atoms with the neighboring O oxo atoms. The coordinated water molecules are involved in O—H···O hydrogen bonds with the O atoms of the organic anion. Two lattice water molecules are located in the cavities of the framework and involved in hydrogen bonding to O atoms of one of the coordinated H₂O and the O atom of an oxo group of the ligand. As a result, a three-dimensional network is formed. The described structure is in accordance with the other known structures of complexes of 1,2-benzo(naphto) quinone -1-oximes with the alkaline (Charalambous et al., 1993,1995; Adatia et al., 1996) and transition metals (Basu and Chakravorty, 1992; Charalambous et al., 1996; McPartlin, 1973) where the formation of monomeric complexes with the bidentate chelating coordination mode of the ligands was observed. The only one difference is in the nature of the hydroxyimino group which is not ionized in the structure reported here. From the other side, the 3,5-bis(hydroxyimino)- 1-methyl-2,4,6-trioxocyclohexanide anion in the sodium salt (Kovalchukova et al., 2012) acts as m-1,2,2,3 polydentate bridging ligands were both N and O hydroxyimino atoms take part in coordination, and one of the O oxo coordinated atoms forms a bifurcated bond.

Related literature top

For the synthesis and crystal structure of sodium 3,5-bis(hydroxyimino)-1-methyl-2,4,6- trioxocyclohexanide, see: Kovalchukova et al. (2012). For related structures of metal complexes with 1,2-benzo(naphto)quinone-1-oximes, see: Chakravorty (1974); Charalambous et al. (1993, 1995, 1996); Adatia et al. (1996); Basu & Chakravorty (1992); McPartlin (1973); Djinovic et al. (1992); Liu et al. (2010). For applications of related complexes as catalysts, see: Gharah et al. (2009).

Experimental top

Single crystals of C₁₄H₃₀BaN₄O₂₀ were grown by the slow evaporation of the ethanol solution of the 1-to-1 molar mixture of barium nitrate and sodium 3,5-bis(hydroxyimino)-1-methyl-2,4,6-trioxo cyclohexanide.

Computing details top

Data collection: CAD-4-PC (Enraf–Nonius, 1993); cell refinement: CAD-4-PC (Enraf–Nonius, 1993); data reduction: CAD-4-PC (Enraf–Nonius, 1993); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: CIFTAB97 (Sheldrick, 2008) and SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP view of C₁₄H₃₀BaN₄O₂₀ with atom labeling scheme (displacement ellipsoids are drawn at the 50% probability level for non-hydrogen atoms). Hydrogen bonds shown as dashed lines.
	Fig. 2. Molecular packing in the crystal of the complex along the crystallographic axis b. Hydrogen bonds shown as dashed lines.

Hexaaquabis[3,5-bis(hydroxyimino)-1-methyl-2,4,6-trioxocyclohexanido-κ²N³,O⁴]barium tetrahydrate top

Crystal data top

[Ba(C₇H₅N₂O₅)₂(H₂O)₆]·4H₂O	F(000) = 1432
M_r = 711.76	D_x = 1.862 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 17.235 (3) Å	θ = 9.2–11.7°
b = 6.736 (1) Å	µ = 1.66 mm⁻¹
c = 23.074 (5) Å	T = 293 K
β = 108.61 (3)°	Plate, red
V = 2538.7 (9) Å³	0.33 × 0.12 × 0.07 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1755 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.019
β-filter monochromator	θ_max = 25.5°, θ_min = 1.9°
ω/2θ scans	h = 0→20
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983)	k = −8→0
T_min = 0.370, T_max = 0.780	l = −27→26
2429 measured reflections	3 standard reflections every 60 min
2346 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.018	Hydrogen site location: difference Fourier map
wR(F²) = 0.048	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.0317P)²] where P = (F_o² + 2F_c²)/3
2346 reflections	(Δ/σ)_max = 0.001
216 parameters	Δρ_max = 0.47 e Å⁻³
17 restraints	Δρ_min = −0.90 e Å⁻³

Crystal data top

[Ba(C₇H₅N₂O₅)₂(H₂O)₆]·4H₂O	V = 2538.7 (9) Å³
M_r = 711.76	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 17.235 (3) Å	µ = 1.66 mm⁻¹
b = 6.736 (1) Å	T = 293 K
c = 23.074 (5) Å	0.33 × 0.12 × 0.07 mm
β = 108.61 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1755 reflections with I > 2σ(I)
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983)	R_int = 0.019
T_min = 0.370, T_max = 0.780	3 standard reflections every 60 min
2429 measured reflections	intensity decay: none
2346 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.018	17 restraints
wR(F²) = 0.048	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.47 e Å⁻³
2346 reflections	Δρ_min = −0.90 e Å⁻³
216 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Ba1	0.5000	0.24104 (3)	0.7500	0.02124 (7)
O1	0.56648 (10)	0.2550 (3)	0.65071 (7)	0.0332 (4)
O3	0.54847 (10)	0.3322 (3)	0.44397 (7)	0.0317 (4)
O5	0.32241 (10)	0.0962 (3)	0.49495 (7)	0.0349 (4)
O11	0.48141 (12)	0.6073 (3)	0.68255 (8)	0.0377 (4)
O12	0.59225 (10)	−0.1143 (3)	0.75770 (9)	0.0368 (4)
O13	0.32986 (11)	0.3326 (3)	0.70959 (8)	0.0371 (4)
O14	0.24224 (11)	−0.0492 (3)	0.70127 (9)	0.0447 (5)
O15	0.80288 (12)	0.0550 (3)	0.60419 (10)	0.0486 (5)
O21	0.67935 (10)	0.3795 (3)	0.52748 (8)	0.0335 (4)
O61	0.33722 (12)	0.0432 (3)	0.60383 (8)	0.0443 (5)
N2	0.64131 (11)	0.3306 (3)	0.56837 (9)	0.0259 (4)
N6	0.41475 (12)	0.1133 (3)	0.61886 (9)	0.0317 (4)
C1	0.52814 (12)	0.2383 (3)	0.59644 (9)	0.0226 (4)
C2	0.56427 (13)	0.2839 (3)	0.54772 (10)	0.0212 (4)
C3	0.51345 (14)	0.2780 (3)	0.48228 (10)	0.0214 (4)
C4	0.43167 (14)	0.2147 (3)	0.46508 (9)	0.0230 (4)
C5	0.39533 (13)	0.1576 (3)	0.50912 (10)	0.0235 (4)
C6	0.44222 (13)	0.1663 (3)	0.57513 (10)	0.0222 (4)
C7	0.38032 (15)	0.2124 (4)	0.39871 (10)	0.0314 (5)
H71	0.3245	0.2422	0.3951	0.038*
H72	0.3831	0.0834	0.3818	0.038*
H73	0.4005	0.3101	0.3769	0.038*
H21	0.646 (2)	0.360 (7)	0.4916 (14)	0.077 (4)*
H61	0.321 (2)	0.050 (6)	0.5645 (14)	0.077 (4)*
H111	0.470 (2)	0.606 (6)	0.6438 (5)	0.077 (4)*
H112	0.4404 (16)	0.664 (6)	0.6874 (16)	0.077 (4)*
H121	0.6431 (8)	−0.096 (6)	0.7668 (16)	0.077 (4)*
H122	0.582 (2)	−0.198 (5)	0.7293 (14)	0.077 (4)*
H131	0.302 (2)	0.228 (4)	0.7002 (17)	0.077 (4)*
H132	0.315 (2)	0.399 (5)	0.6766 (10)	0.077 (4)*
H141	0.217 (2)	−0.083 (6)	0.7256 (12)	0.077 (4)*
H142	0.2137 (19)	−0.102 (6)	0.6680 (9)	0.077 (4)*
H151	0.7660 (19)	0.008 (5)	0.5737 (12)	0.077 (4)*
H152	0.794 (3)	0.1784 (18)	0.6008 (18)	0.077 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ba1	0.02168 (10)	0.02131 (10)	0.02071 (9)	0.000	0.00676 (6)	0.000
O1	0.0286 (8)	0.0467 (10)	0.0227 (7)	−0.0042 (8)	0.0059 (6)	−0.0036 (8)
O3	0.0325 (9)	0.0387 (9)	0.0265 (8)	−0.0059 (8)	0.0131 (7)	0.0014 (7)
O5	0.0256 (8)	0.0448 (10)	0.0327 (9)	−0.0101 (8)	0.0070 (7)	−0.0014 (8)
O11	0.0491 (11)	0.0352 (10)	0.0281 (8)	0.0063 (8)	0.0116 (8)	0.0013 (7)
O12	0.0292 (8)	0.0334 (9)	0.0473 (10)	−0.0028 (8)	0.0114 (8)	−0.0080 (8)
O13	0.0344 (9)	0.0388 (10)	0.0347 (9)	0.0039 (8)	0.0062 (8)	0.0012 (8)
O14	0.0308 (9)	0.0582 (13)	0.0432 (10)	−0.0059 (9)	0.0092 (8)	0.0087 (10)
O15	0.0353 (10)	0.0522 (12)	0.0471 (11)	−0.0040 (10)	−0.0025 (8)	0.0100 (10)
O21	0.0273 (8)	0.0412 (10)	0.0351 (9)	−0.0068 (8)	0.0145 (7)	0.0002 (8)
O61	0.0343 (9)	0.0687 (14)	0.0310 (9)	−0.0242 (10)	0.0120 (8)	−0.0031 (9)
N2	0.0267 (10)	0.0223 (9)	0.0292 (10)	−0.0008 (8)	0.0097 (8)	−0.0012 (8)
N6	0.0294 (10)	0.0372 (12)	0.0293 (10)	−0.0115 (9)	0.0105 (8)	−0.0031 (9)
C1	0.0246 (10)	0.0187 (9)	0.0241 (9)	0.0008 (9)	0.0073 (8)	−0.0011 (9)
C2	0.0235 (10)	0.0137 (11)	0.0263 (10)	0.0013 (8)	0.0078 (8)	−0.0025 (8)
C3	0.0269 (10)	0.0138 (11)	0.0242 (9)	0.0021 (8)	0.0092 (8)	0.0000 (8)
C4	0.0293 (11)	0.0156 (11)	0.0226 (10)	0.0022 (8)	0.0064 (8)	0.0005 (8)
C5	0.0229 (11)	0.0180 (10)	0.0277 (11)	−0.0004 (9)	0.0054 (8)	−0.0018 (9)
C6	0.0250 (11)	0.0174 (9)	0.0244 (10)	0.0001 (9)	0.0082 (9)	−0.0011 (8)
C7	0.0352 (12)	0.0301 (13)	0.0245 (10)	−0.0031 (9)	0.0033 (9)	0.0003 (9)

Geometric parameters (Å, º) top

Ba1—O13	2.8467 (19)	O15—H151	0.846 (10)
Ba1—O13ⁱ	2.8467 (19)	O15—H152	0.845 (10)
Ba1—O12	2.8475 (19)	O21—N2	1.350 (3)
Ba1—O12ⁱ	2.8475 (19)	O21—H21	0.86 (3)
Ba1—O1ⁱ	2.8715 (17)	O61—N6	1.354 (3)
Ba1—O1	2.8715 (17)	O61—H61	0.86 (3)
Ba1—O11ⁱ	2.8799 (19)	N2—C2	1.298 (3)
Ba1—O11	2.8799 (19)	N6—C6	1.294 (3)
Ba1—N6	3.036 (2)	C1—C2	1.481 (3)
Ba1—N6ⁱ	3.036 (2)	C1—C6	1.485 (3)
O1—C1	1.220 (3)	C2—C3	1.485 (3)
O3—C3	1.273 (3)	C3—O3	1.273 (3)
O5—C5	1.263 (3)	C3—C4	1.403 (3)
O11—H111	0.851 (10)	C4—C5	1.407 (3)
O11—H112	0.841 (10)	C4—C7	1.504 (3)
O12—H121	0.842 (10)	C5—O5	1.263 (3)
O12—H122	0.841 (10)	C5—C6	1.480 (3)
O13—H131	0.847 (10)	C7—H71	0.9600
O13—H132	0.847 (10)	C7—H72	0.9600
O14—H141	0.851 (10)	C7—H73	0.9600
O14—H142	0.849 (10)

O13—Ba1—O13ⁱ	154.98 (9)	Ba1—O11—H111	121 (3)
O13—Ba1—O12	134.33 (6)	Ba1—O11—H112	106 (3)
O13ⁱ—Ba1—O12	70.45 (6)	H111—O11—H112	103 (2)
O13—Ba1—O12ⁱ	70.45 (6)	Ba1—O12—H121	114 (3)
O13ⁱ—Ba1—O12ⁱ	134.33 (5)	Ba1—O12—H122	123 (3)
O12—Ba1—O12ⁱ	65.59 (7)	H121—O12—H122	104 (2)
O13—Ba1—O1ⁱ	67.83 (5)	Ba1—O13—H131	111 (3)
O13ⁱ—Ba1—O1ⁱ	111.29 (5)	Ba1—O13—H132	113 (3)
O12—Ba1—O1ⁱ	109.55 (5)	H131—O13—H132	103 (2)
O12ⁱ—Ba1—O1ⁱ	73.76 (5)	H141—O14—H142	102 (2)
O13—Ba1—O1	111.30 (5)	H151—O15—H152	103 (2)
O13ⁱ—Ba1—O1	67.83 (5)	N2—O21—H21	108 (3)
O12—Ba1—O1	73.76 (5)	N6—O61—H61	102 (3)
O12ⁱ—Ba1—O1	109.55 (5)	C2—N2—O21	118.06 (19)
O1ⁱ—Ba1—O1	176.25 (8)	C6—N6—O61	118.25 (19)
O13—Ba1—O11ⁱ	85.23 (6)	C6—N6—Ba1	121.19 (14)
O13ⁱ—Ba1—O11ⁱ	73.27 (6)	O61—N6—Ba1	118.58 (13)
O12—Ba1—O11ⁱ	136.29 (6)	O1—C1—C2	122.60 (19)
O12ⁱ—Ba1—O11ⁱ	135.85 (5)	O1—C1—C6	121.73 (19)
O1ⁱ—Ba1—O11ⁱ	62.92 (5)	C2—C1—C6	115.65 (18)
O1—Ba1—O11ⁱ	113.53 (5)	N2—C2—C1	113.59 (19)
O13—Ba1—O11	73.27 (6)	N2—C2—C3	125.6 (2)
O13ⁱ—Ba1—O11	85.23 (6)	C1—C2—C3	120.79 (19)
O12—Ba1—O11	135.85 (5)	O3—C3—C4	123.2 (2)
O12ⁱ—Ba1—O11	136.29 (5)	O3—C3—C4	123.2 (2)
O1ⁱ—Ba1—O11	113.53 (5)	O3—C3—C2	116.23 (19)
O1—Ba1—O11	62.92 (5)	O3—C3—C2	116.23 (19)
O11ⁱ—Ba1—O11	62.11 (7)	C4—C3—C2	120.62 (19)
O13—Ba1—N6	67.33 (6)	C3—C4—C5	121.15 (19)
O13ⁱ—Ba1—N6	120.54 (6)	C3—C4—C7	120.2 (2)
O12—Ba1—N6	84.66 (6)	C5—C4—C7	118.7 (2)
O12ⁱ—Ba1—N6	67.46 (6)	O5—C5—C4	122.6 (2)
O1ⁱ—Ba1—N6	127.95 (5)	O5—C5—C4	122.6 (2)
O1—Ba1—N6	53.38 (5)	O5—C5—C6	116.8 (2)
O11ⁱ—Ba1—N6	135.75 (6)	O5—C5—C6	116.8 (2)
O11—Ba1—N6	76.65 (6)	C4—C5—C6	120.64 (19)
O13—Ba1—N6ⁱ	120.54 (6)	N6—C6—C5	125.2 (2)
O13ⁱ—Ba1—N6ⁱ	67.33 (6)	N6—C6—C1	113.97 (19)
O12—Ba1—N6ⁱ	67.46 (6)	C5—C6—C1	120.87 (19)
O12ⁱ—Ba1—N6ⁱ	84.66 (6)	C4—C7—H71	109.5
O1ⁱ—Ba1—N6ⁱ	53.38 (5)	C4—C7—H72	109.5
O1—Ba1—N6ⁱ	127.96 (5)	H71—C7—H72	109.5
O11ⁱ—Ba1—N6ⁱ	76.65 (6)	C4—C7—H73	109.5
O11—Ba1—N6ⁱ	135.76 (6)	H71—C7—H73	109.5
N6—Ba1—N6ⁱ	147.08 (8)	H72—C7—H73	109.5
C1—O1—Ba1	126.33 (14)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O21—H21···O3	0.86 (3)	1.70 (3)	2.476 (3)	150 (4)
O61—H61···O5	0.86 (3)	1.64 (3)	2.469 (2)	160 (4)
O11—H111···O3ⁱⁱ	0.85 (1)	1.99 (1)	2.827 (2)	167 (4)
O11—H112···O12ⁱⁱⁱ	0.84 (1)	2.15 (3)	2.854 (3)	142 (4)
O12—H121···O14ⁱ	0.84 (1)	1.90 (1)	2.739 (3)	172 (4)
O12—H122···O11^iv	0.84 (1)	2.17 (3)	2.839 (3)	137 (3)
O13—H131···O14	0.85 (1)	2.13 (1)	2.957 (3)	165 (4)
O13—H132···O15^v	0.85 (1)	1.93 (1)	2.766 (3)	169 (4)
O14—H141···O13^vi	0.85 (1)	1.99 (1)	2.835 (3)	173 (4)
O15—H151···O5^vii	0.85 (1)	1.94 (1)	2.789 (3)	177 (4)

Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, −y+1, −z+1; (iii) −x+1, y+1, −z+3/2; (iv) x, y−1, z; (v) x−1/2, y+1/2, z; (vi) −x+1/2, y−1/2, −z+3/2; (vii) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O21—H21···O3	0.86 (3)	1.70 (3)	2.476 (3)	150 (4)
O61—H61···O5	0.86 (3)	1.64 (3)	2.469 (2)	160 (4)
O11—H111···O3ⁱ	0.851 (10)	1.991 (14)	2.827 (2)	167 (4)
O11—H112···O12ⁱⁱ	0.841 (10)	2.15 (3)	2.854 (3)	142 (4)
O12—H121···O14ⁱⁱⁱ	0.842 (10)	1.902 (11)	2.739 (3)	172 (4)
O12—H122···O11^iv	0.841 (10)	2.17 (3)	2.839 (3)	137 (3)
O13—H131···O14	0.847 (10)	2.131 (13)	2.957 (3)	165 (4)
O13—H132···O15^v	0.847 (10)	1.931 (12)	2.766 (3)	169 (4)
O14—H141···O13^vi	0.851 (10)	1.989 (11)	2.835 (3)	173 (4)
O15—H151···O5^vii	0.846 (10)	1.944 (11)	2.789 (3)	177 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1, −z+3/2; (iii) −x+1, y, −z+3/2; (iv) x, y−1, z; (v) x−1/2, y+1/2, z; (vi) −x+1/2, y−1/2, −z+3/2; (vii) −x+1, −y, −z+1.

Acknowledgements

This research was supported by the Russian Foundation for Basic Research (grant 13–03–00079).

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