catena-Poly[barium(II)-μ2-(dimethyl sulfoxide)-κ2O:O-bis­(μ2-2,4,6-tri­nitro­phenolato-κ4O2,O1:O1,O6)]

Srinivasan, B.R.; Parsekar, N.U.; Narvekar, K.U.

doi:10.1107/S2414314620014984

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 11| November 2020| x201498

https://doi.org/10.1107/S2414314620014984

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catena-Poly[barium(II)-μ₂-(dimethyl sulfoxide)-κ²O:O-bis(μ₂-2,4,6-trinitrophenolato-κ⁴O²,O¹:O¹,O⁶)]

Bikshandarkoil R. Srinivasan,^a ^* Neha U. Parsekar ^a and Kedar U. Narvekar ^a

^aSchool of Chemical Sciences, Goa University, Goa 403206, India
^*Correspondence e-mail: srini@unigoa.ac.in

Edited by M. Weil, Vienna University of Technology, Austria (Received 29 October 2020; accepted 10 November 2020; online 13 November 2020)

The asymmetric unit of the title barium coordination polymer, [Ba(C₆H₂N₃O₇)₂(C₂H₆OS)]_n, consists of a barium cation (site symmetry m) and a dimethyl sulfoxide (DMSO) ligand (point group symmetry m) and a 2,4,6-trinitrophenolate anion located in general positions. The S atom and the methyl group of DMSO are disordered over two sets of sites. The DMSO ligand bridges a pair of Ba^II atoms resulting in a chain extending parallel to the a axis. The unique 2,4,6-trinitrophenolate anion also bridges a pair of Ba^II ions via the phenolic oxygen atom, with each Ba^II being additionally bonded to an oxygen atom of an adjacent nitro group. The μ₂-monoatomic bridging binding mode of both types of ligands results in the formation of an infinite chain of face-sharing {BaO₁₀} polyhedra flanked by the remaining parts of the 2,4,6-trinitrophenolato and DMSO ligands. In the one-dimensional coordination polymer, parallel chains are interlinked with the aid of C—H⋯O hydrogen bonds.

Keywords: crystal structure; barium; picrate anion; one-dimensional coordination polymer.

CCDC reference: 2043610

Structure description

As part of an ongoing research program, we were investigating the synthetic and structural aspects of bivalent metal salts of picric acid (also known as 2,4,6-trinitrophenol) containing zwitterionic glycine ligands (Srinivasan et al., 2019 ). During the course of these studies, the glycine-free title compound, [Ba(C₆H₂N₃O₇)₂(C₂H₆OS)] (1), was obtained serendipitously.

Compound (1) contains a coordinating DMSO molecule but no glycine. A perusal of the Cambridge Structural Database (CSD, version 5.41, update November 2019; Groom et al., 2016 ) reveals examples of structurally characterized Ba^II picrates devoid of DMSO (Hughes & Wingfield, 1977 ; Postma et al., 1983 ; Chandler et al., 1988 ; Harrowfield et al., 1995 ; Hong et al., 2007 ). In addition, Ba^II compounds containing DMSO as solvent molecules (Studebaker et al., 2000 ; Fichtel et al., 2004 ; Ferrando-Soria et al., 2012 ), and as monodentate and/or bridging bidentate ligands (Harrowfield et al., 2004 ; Pi et al., 2009 ; Gschwind & Jansen 2012 ) charge-balanced by anions other than picrate are also known. The title compound is a new example of a Ba^II compound in which both the DMSO and picrate ligands function as μ₂-bridges.

The asymmetric unit of (1) consists of a barium(II) cation and the S and O atom of a dimethyl sulfoxide (DMSO) ligand located on a mirror plane. The 2,4,6-trinitrophenolate anion is located in a general position (Fig. 1). Atom S11 of the DMSO ligand and the attached methyl group (C11) are disordered over two sets of sites. Bond lengths and angles of the picrate anion and the DMSO ligand are in agreement with reported data (Srinivasan et al., 2019, 2020 ). The central Ba^II atom exhibits ten-coordination and is bonded to eight oxygen atoms of four symmetry-related picrate anions and two oxygen atoms of two DMSO ligands resulting in a distorted {BaO₁₀} polyhedron (Fig. 2). The deviation of the {BaO₁₀} coordination polyhedron from a regular shape can be evidenced by the Ba—O bond lengths which range from 2.725 (2) to 2.970 (3) Å and the O—Ba—O bond angles which vary between 57.15 (12) and 151.94 (9)°. Both DMSO and picrate ligands exhibit an μ₂-monoatomic bridging binding mode resulting in chains extending parallel to the a axis with an identical Ba⋯Ba separation of 4.1933 (2) Å (Fig. 3). The oxygen O11 atom of DMSO binds with a Ba^II atom at a Ba1—O11 distance of 2.906 (4) Å and further coordinates with a symmetry-related Ba^iv [symmetry code: (iv) x + 1, y, z] atom at a shorter distance of 2.783 (4) Å.

Figure 1
The coordination environment of the Ba^II atom in the crystal structure of [Ba(C₆H₂N₃O₇)₂(C₂H₆OS)]. Displacement ellipsoids are drawn at the 50% probability level for non-hydrogen atoms. [Symmetry codes: (i) x, −y + $[{1\over 2}]$ , z; (ii) x − 1, y, z; (iii) x, −y + $[{1\over 2}]$ , z; (iv) x + 1, y, z.]

Figure 2
The distorted {BaO₁₀} coordination polyhedron in the crystal structure of [Ba(C₆H₂N₃O₇)₂(C₂H₆OS)]. Symmetry codes are as in Fig. 1

Figure 3
(Top) Ba^II cations bridged by O11 of DMSO, which results in the formation of chains extending along the a-axis direction. For clarity, the disordered S atom and the methyl group of the DMSO ligands as well as the picrate ligands are not displayed; (bottom) the chain showing the μ₂-monoatomic bridging binding of the picrate and DMSO ligands. For clarity, only the bridging O11 atom of the DMSO ligands are shown. Each Ba^II atom in the chain is bonded to ten O atoms (see Fig. 2

Binding of the nitro oxygen atom(s) of the picrate ligand is well documented in the literature for potassium picrate (Maartmann-Moe, 1969 ) and for many alkaline-earth picrates (Harrowfield et al., 1995). In the molecular compounds, [Ba(L)(pic)₂] (L = dibenzo-24-crown-8), [Ba(acetone)(pic)₂(phen)₂] (pic = picrate; phen = 1,10-phenanthroline) and [Ba(L′)(pic)₂] (L′ = diaza 21-crown-7 ether), the picrate anion functions as a bidentate and or monodentate ligand (Hughes & Wingfield, 1977; Postma et al., 1983; Chandler et al., 1988). In the water-rich coordination polymer [Ba(H₂O)₅(C₆H₂N₃O₇)₂]·H₂O, one picrate anion functions as a bidentate ligand via the phenolate oxygen and an adjacent nitro O atom, while the second independent picrate anion functions as a μ₂-bridging tridentate ligand (Harrowfield et al., 1995).

In the crystal structure of (1), the phenolate atom O1 makes a short Ba—O1 bond of 2.730 (2) Å and is further linked to a symmetry-related Baⁱⁱ [symmetry code: (ii) x − 1, y, z] atom accompanied by the shortest Ba—O bond of 2.725 (2) Å. Each of the Ba^II atoms bridged by O1 is further coordinated by an oxygen atom of the nitro group with longer bond lengths [Ba1—O7ⁱⁱ = 2.865 (2) Å; Ba1—O2 = 2.970 (3) Å]. Thus, the unique 2,4,6-trinitrophenolate anion bridges a pair of Ba^II ions via the phenolic oxygen atom, and each Ba^II atom is bonded to an oxygen atom of an adjacent nitro group resulting in a μ₂-monoatomic bridging bis-bidentate binding mode for this ligand. In the chain, each Ba^II atom is bonded to eight oxygen atoms of four symmetry-related picrate anions, and a pair of adjacent Ba^II atoms are bridged by two symmetry-related phenolate oxygen atoms (Fig. 3).

A polyhedral chain of face-sharing {BaO₉} units flanked by organic ligands was reported recently in the one-dimensional polymeric compound [Ba(H₂O)₂(NMF)₂(4-nba)₂] (NMF = N-methylformamide; 4-nba = 4-nitrobenzoate) due to a μ₂-binding aqua ligand and a pair of symmetry-related μ₂-monoatomic bridging 4-nba ligands (Bhargao & Srinivasan, 2019 ). Likewise, the monoatomic bridging binding modes of the unique DMSO and the phenolate oxygen atoms of the picrate ligands in the structure of (1) result in the formation of an infinite chain of face-sharing {BaO₁₀} polyhedra flanked by 2,4,6-trinitrophenolate and dimethyl sulfoxide ligands (Fig. 4). In the reported water-rich compound [Ba(H₂O)₅(C₆H₂N₃O₇)₂]·H₂O, however, the central Ba^II atom exhibits ten-coordination and is bonded to five monodentate aqua ligands and a bidentate picrate anion (Harrowfield et al., 1995). A second unique picrate anion is a μ₂-bridging tridentate ligand and binds to a Ba^II atom via a phenolate oxygen atom. The cation is also linked to an oxygen atom of an ortho nitro group and is bridged to a second Ba^II via an oxygen of the nitro group trans to the phenolate oxygen (Fig. 4). In this one-dimensional coordination polymer, discrete {BaO₁₀} polyhedra are bridged by a picrate anion due to the absence of any monoatomic bridge.

Figure 4
Face sharing {BaO₁₀} polyhedra in the crystal structure of (1) (top) versus discrete {BaO₁₀} polyhedra in the crystal structure of [Ba(H₂O)₅(C₆H₂N₃O₇)₂]·H₂O (bottom).

The aromatic hydrogen atoms H3 and H5 are attached to the C3 and C5 donor atoms while the nitro oxygen atoms O4 and O6 function as hydrogen acceptors, resulting in interchain C—H⋯O hydrogen bonding interactions. In this way, each chain is linked on either side to two other chains (Table 1, Fig. 5) into a three-dimensional network.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O4^v	0.93	2.43	3.283 (5)	153
C5—H5⋯O6^vi	0.90 (4)	2.63 (4)	3.492 (5)	159 (3)
Symmetry codes: (v) ; (vi) .

Figure 5
Interchain C—H⋯O hydrogen bonds, shown as broken pink lines for the C3—H3⋯O4^v interaction on the right and for the C5—H5⋯O6^vi interaction on the left, link adjacent polymeric chains. [Symmetry codes: (v) 1 − x, 1 − y, −z; (vi) 3 − x, 1 − y, 1 − z.]

Synthesis and crystallization

To a slurry of barium carbonate (0.395 g, 2 mmol) in water, picric acid (0.916 g, 4 mmol) in water (40 ml) was added and the reaction mixture was heated on a water bath. Brisk effervescence was observed resulting in dissolution of the insoluble carbonate. The reaction mixture was then filtered into a beaker containing glycine (4 mmol, 0.3002 g) in water. The filtrate was left aside for crystallization. A yellow precipitate was filtered off and subsequently dissolved in DMSO (10 ml); this solution was left undisturbed. The crystalline product, which separated after two days, was isolated by filtration, washed with dichloromethane and dried in air; yield 0.95 g. Compound (1) can also be obtained without addition of glycine in the reaction by dissolving barium carbonate in aqueous picric acid to obtain the dipicrate of barium in situ. Concentration of the reaction mixture to a small volume followed by addition of DMSO afforded (1) as above.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[Ba(C₆H₂N₃O₇)₂(C₂H₆OS)]
M_r	671.68
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	293
a, b, c (Å)	4.1933 (2), 24.1526 (13), 11.0917 (7)
β (°)	95.775 (2)
V (Å³)	1117.66 (11)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.96
Crystal size (mm)	0.23 × 0.16 × 0.05

Data collection
Diffractometer	Bruker D8 Quest Eco
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.537, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	15884, 2860, 2696
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.087, 1.09
No. of reflections	2860
No. of parameters	182
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.73, −1.10
Computer programs: APEX3 and SAINT (Bruker, 2019 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ), DIAMOND (Brandenburg, 1999 ), shelXle (Hübschle et al., 2011 ) and publCIF (Westrip, 2010 ).

The S11 atom of the DMSO ligand and the attached methyl group (C11—H11) are disordered over two positions in a 0.73:0.27 ratio.

Structural data

CCDC reference: 2043610

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314620014984/wm4142sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620014984/wm4142Isup3.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2019); cell refinement: SAINT (Bruker, 2019); data reduction: SAINT (Bruker, 2019); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009), DIAMOND (Brandenburg, 1999) and shelXle (Hübschle et al., 2011); software used to prepare material for publication: shelXle (Hübschle et al., 2011) and publCIF (Westrip, 2010).

catena-Poly[barium(II)-µ₂-(dimethyl sulfoxide)-κ²O:O-bis(µ₂-2,4,6-trinitrophenolato-κ⁴O²,O¹:O¹,O⁶)] top

Crystal data top

[Ba(C₆H₂N₃O₇)₂(C₂H₆OS)]	F(000) = 656
M_r = 671.68	D_x = 1.996 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
a = 4.1933 (2) Å	Cell parameters from 9959 reflections
b = 24.1526 (13) Å	θ = 3.4–28.3°
c = 11.0917 (7) Å	µ = 1.96 mm⁻¹
β = 95.775 (2)°	T = 293 K
V = 1117.66 (11) Å³	Plate, yellow
Z = 2	0.23 × 0.16 × 0.05 mm

Data collection top

Bruker D8 Quest Eco diffractometer	2696 reflections with I > 2σ(I)
Radiation source: Sealed Tube	R_int = 0.045
φ and ω scans	θ_max = 28.3°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −5→5
T_min = 0.537, T_max = 0.746	k = −32→32
15884 measured reflections	l = −14→14
2860 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.087	w = 1/[σ²(F_o²) + (0.055P)² + 0.7054P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
2860 reflections	Δρ_max = 1.73 e Å⁻³
182 parameters	Δρ_min = −1.10 e Å⁻³

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ba1	0.45109 (5)	0.250000	0.41165 (2)	0.02648 (9)
O1	0.9359 (5)	0.31686 (8)	0.3517 (2)	0.0342 (4)
O2	0.4249 (7)	0.30881 (12)	0.1757 (3)	0.0558 (7)
O3	0.6121 (10)	0.33930 (17)	0.0155 (3)	0.0842 (12)
O4	0.7913 (9)	0.54083 (14)	0.0692 (4)	0.0824 (11)
O5	1.1509 (12)	0.56275 (15)	0.2103 (4)	0.1123 (17)
O6	1.3008 (10)	0.44197 (13)	0.5598 (3)	0.0835 (12)
O7	1.4143 (7)	0.35863 (10)	0.5130 (2)	0.0522 (6)
O11	−0.0224 (9)	0.250000	0.5858 (3)	0.0470 (8)
N1	0.5951 (7)	0.33983 (13)	0.1240 (3)	0.0433 (6)
N2	0.9650 (10)	0.52998 (14)	0.1609 (4)	0.0628 (9)
N3	1.2850 (7)	0.40289 (11)	0.4887 (3)	0.0435 (6)
C1	0.9409 (7)	0.36577 (11)	0.3105 (3)	0.0312 (5)
C2	0.7786 (7)	0.38185 (13)	0.1958 (3)	0.0356 (6)
C3	0.7865 (9)	0.43382 (14)	0.1459 (3)	0.0435 (7)
H3	0.682230	0.441196	0.069627	0.052*
C4	0.9522 (9)	0.47457 (14)	0.2118 (4)	0.0465 (8)
C5	1.1114 (9)	0.46442 (14)	0.3244 (3)	0.0438 (7)
H5	1.219 (10)	0.4924 (19)	0.364 (4)	0.053*
C6	1.1081 (8)	0.41125 (12)	0.3708 (3)	0.0363 (6)
S11	0.1576 (5)	0.250000	0.70846 (17)	0.0577 (7)	0.729 (6)
C11	0.031 (2)	0.3077 (4)	0.7858 (7)	0.156 (4)	0.73
H11A	0.143280	0.308937	0.865642	0.187*	0.73
H11B	0.076199	0.340762	0.742520	0.187*	0.73
H11C	−0.195036	0.305151	0.791823	0.187*	0.73
S11'	−0.079 (3)	0.250000	0.7161 (8)	0.143 (6)	0.271 (6)
C11'	0.031 (2)	0.3077 (4)	0.7858 (7)	0.156 (4)	0.27
H11D	−0.010490	0.305316	0.869186	0.187*	0.27
H11E	0.256229	0.313593	0.781421	0.187*	0.27
H11F	−0.087455	0.338061	0.747709	0.187*	0.27

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ba1	0.02267 (13)	0.02134 (13)	0.03503 (14)	0.000	0.00095 (8)	0.000
O1	0.0308 (10)	0.0254 (9)	0.0463 (12)	0.0007 (8)	0.0035 (8)	0.0095 (8)
O2	0.0552 (16)	0.0523 (16)	0.0588 (15)	−0.0154 (12)	0.0002 (12)	0.0058 (12)
O3	0.125 (3)	0.088 (3)	0.0385 (14)	−0.033 (2)	0.0037 (17)	0.0009 (15)
O4	0.102 (3)	0.0507 (18)	0.092 (2)	0.0103 (17)	−0.003 (2)	0.0391 (17)
O5	0.153 (4)	0.0435 (19)	0.131 (4)	−0.034 (2)	−0.032 (3)	0.034 (2)
O6	0.138 (3)	0.0460 (17)	0.0609 (18)	0.0187 (19)	−0.0173 (19)	−0.0189 (14)
O7	0.0638 (16)	0.0344 (12)	0.0545 (14)	0.0111 (11)	−0.0133 (12)	−0.0060 (10)
O11	0.056 (2)	0.048 (2)	0.0360 (16)	0.000	−0.0012 (14)	0.000
N1	0.0485 (16)	0.0407 (15)	0.0395 (13)	0.0030 (12)	−0.0011 (11)	0.0068 (12)
N2	0.081 (3)	0.0332 (16)	0.076 (2)	0.0000 (16)	0.013 (2)	0.0194 (16)
N3	0.0575 (17)	0.0280 (13)	0.0444 (14)	0.0025 (12)	0.0019 (12)	−0.0029 (11)
C1	0.0303 (13)	0.0235 (12)	0.0408 (14)	0.0041 (10)	0.0086 (11)	0.0049 (10)
C2	0.0379 (15)	0.0301 (14)	0.0393 (14)	0.0025 (11)	0.0062 (11)	0.0070 (11)
C3	0.0506 (19)	0.0359 (16)	0.0447 (16)	0.0058 (14)	0.0078 (14)	0.0135 (13)
C4	0.056 (2)	0.0278 (15)	0.057 (2)	0.0052 (14)	0.0117 (16)	0.0147 (14)
C5	0.055 (2)	0.0252 (14)	0.0520 (18)	−0.0005 (13)	0.0081 (15)	0.0026 (13)
C6	0.0420 (16)	0.0259 (13)	0.0415 (15)	0.0033 (11)	0.0070 (12)	0.0023 (11)
S11	0.0417 (12)	0.0901 (16)	0.0403 (9)	0.000	−0.0005 (7)	0.000
C11	0.141 (7)	0.213 (10)	0.110 (5)	0.007 (7)	−0.005 (5)	−0.117 (7)
S11'	0.092 (9)	0.285 (19)	0.054 (4)	0.000	0.011 (4)	0.000
C11'	0.141 (7)	0.213 (10)	0.110 (5)	0.007 (7)	−0.005 (5)	−0.117 (7)

Geometric parameters (Å, º) top

Ba1—O1ⁱ	2.725 (2)	N1—C2	1.461 (4)
Ba1—O1ⁱⁱ	2.725 (2)	N2—C4	1.456 (4)
Ba1—O1	2.730 (2)	N3—C6	1.451 (4)
Ba1—O1ⁱⁱⁱ	2.730 (2)	C1—C6	1.432 (4)
Ba1—O11^iv	2.783 (4)	C1—C2	1.435 (4)
Ba1—O7ⁱⁱ	2.865 (2)	C2—C3	1.373 (4)
Ba1—O7ⁱ	2.865 (2)	C3—C4	1.372 (5)
Ba1—O11	2.906 (4)	C3—H3	0.9300
Ba1—O2ⁱⁱⁱ	2.970 (3)	C4—C5	1.379 (5)
Ba1—O2	2.970 (3)	C5—C6	1.384 (4)
Ba1—S11	3.629 (2)	C5—H5	0.90 (4)
Ba1—Ba1^iv	4.1933 (2)	S11—C11ⁱⁱⁱ	1.747 (7)
O1—C1	1.268 (3)	S11—C11	1.747 (7)
O2—N1	1.218 (4)	C11—H11A	0.9600
O3—N1	1.212 (4)	C11—H11B	0.9600
O4—N2	1.218 (5)	C11—H11C	0.9600
O5—N2	1.204 (6)	S11'—C11'	1.637 (9)
O6—N3	1.228 (4)	C11'—H11D	0.9600
O7—N3	1.217 (4)	C11'—H11E	0.9600
O11—S11	1.488 (4)	C11'—H11F	0.9600
O11—S11'	1.488 (9)

O1ⁱ—Ba1—O1ⁱⁱ	72.68 (9)	O7ⁱ—Ba1—Ba1^iv	95.35 (6)
O1ⁱ—Ba1—O1	151.94 (9)	O11—Ba1—Ba1^iv	138.60 (7)
O1ⁱⁱ—Ba1—O1	100.46 (6)	O2ⁱⁱⁱ—Ba1—Ba1^iv	87.04 (6)
O1ⁱ—Ba1—O1ⁱⁱⁱ	100.46 (6)	O2—Ba1—Ba1^iv	87.04 (6)
O1ⁱⁱ—Ba1—O1ⁱⁱⁱ	151.94 (9)	S11—Ba1—Ba1^iv	115.50 (3)
O1—Ba1—O1ⁱⁱⁱ	72.52 (9)	C1—O1—Ba1^iv	126.78 (18)
O1ⁱ—Ba1—O11^iv	136.32 (6)	C1—O1—Ba1	132.75 (18)
O1ⁱⁱ—Ba1—O11^iv	136.32 (6)	Ba1^iv—O1—Ba1	100.46 (6)
O1—Ba1—O11^iv	67.10 (7)	N1—O2—Ba1	137.6 (2)
O1ⁱⁱⁱ—Ba1—O11^iv	67.10 (7)	N3—O7—Ba1^iv	139.3 (2)
O1ⁱ—Ba1—O7ⁱⁱ	124.46 (7)	S11—O11—Ba1ⁱⁱ	158.2 (2)
O1ⁱⁱ—Ba1—O7ⁱⁱ	58.69 (7)	S11—O11—Ba1	106.9 (2)
O1—Ba1—O7ⁱⁱ	67.95 (8)	S11'—O11—Ba1	146.2 (5)
O1ⁱⁱⁱ—Ba1—O7ⁱⁱ	135.08 (7)	Ba1ⁱⁱ—O11—Ba1	94.94 (9)
O11^iv—Ba1—O7ⁱⁱ	78.34 (6)	O3—N1—O2	123.9 (3)
O1ⁱ—Ba1—O7ⁱ	58.69 (7)	O3—N1—C2	117.9 (3)
O1ⁱⁱ—Ba1—O7ⁱ	124.46 (7)	O2—N1—C2	118.2 (3)
O1—Ba1—O7ⁱ	135.08 (7)	O5—N2—O4	123.0 (4)
O1ⁱⁱⁱ—Ba1—O7ⁱ	67.95 (8)	O5—N2—C4	118.4 (4)
O11^iv—Ba1—O7ⁱ	78.34 (6)	O4—N2—C4	118.6 (4)
O7ⁱⁱ—Ba1—O7ⁱ	132.66 (11)	O7—N3—O6	122.6 (3)
O1ⁱ—Ba1—O11	65.44 (7)	O7—N3—C6	119.9 (3)
O1ⁱⁱ—Ba1—O11	65.44 (7)	O6—N3—C6	117.5 (3)
O1—Ba1—O11	137.49 (6)	O1—C1—C6	124.8 (3)
O1ⁱⁱⁱ—Ba1—O11	137.48 (6)	O1—C1—C2	123.3 (3)
O11^iv—Ba1—O11	94.94 (9)	C6—C1—C2	111.9 (3)
O7ⁱⁱ—Ba1—O11	70.84 (6)	C3—C2—C1	125.2 (3)
O7ⁱ—Ba1—O11	70.84 (6)	C3—C2—N1	116.6 (3)
O1ⁱ—Ba1—O2ⁱⁱⁱ	62.84 (7)	C1—C2—N1	118.2 (3)
O1ⁱⁱ—Ba1—O2ⁱⁱⁱ	96.33 (7)	C4—C3—C2	118.2 (3)
O1—Ba1—O2ⁱⁱⁱ	91.77 (8)	C4—C3—H3	120.9
O1ⁱⁱⁱ—Ba1—O2ⁱⁱⁱ	57.66 (7)	C2—C3—H3	120.9
O11^iv—Ba1—O2ⁱⁱⁱ	124.61 (8)	C3—C4—C5	121.9 (3)
O7ⁱⁱ—Ba1—O2ⁱⁱⁱ	141.74 (8)	C3—C4—N2	119.3 (3)
O7ⁱ—Ba1—O2ⁱⁱⁱ	84.78 (8)	C5—C4—N2	118.8 (4)
O11—Ba1—O2ⁱⁱⁱ	128.20 (8)	C4—C5—C6	118.7 (3)
O1ⁱ—Ba1—O2	96.33 (7)	C4—C5—H5	119 (3)
O1ⁱⁱ—Ba1—O2	62.84 (7)	C6—C5—H5	123 (3)
O1—Ba1—O2	57.66 (7)	C5—C6—C1	124.1 (3)
O1ⁱⁱⁱ—Ba1—O2	91.77 (8)	C5—C6—N3	116.1 (3)
O11^iv—Ba1—O2	124.61 (8)	C1—C6—N3	119.7 (3)
O7ⁱⁱ—Ba1—O2	84.78 (8)	O11—S11—C11ⁱⁱⁱ	107.4 (3)
O7ⁱ—Ba1—O2	141.74 (8)	O11—S11—C11	107.4 (3)
O11—Ba1—O2	128.20 (8)	C11ⁱⁱⁱ—S11—C11	105.9 (7)
O2ⁱⁱⁱ—Ba1—O2	57.15 (12)	O11—S11—Ba1	50.03 (16)
O1ⁱ—Ba1—S11	83.59 (5)	C11ⁱⁱⁱ—S11—Ba1	126.4 (4)
O1ⁱⁱ—Ba1—S11	83.59 (5)	C11—S11—Ba1	126.4 (4)
O1—Ba1—S11	123.35 (5)	S11—C11—H11A	109.5
O1ⁱⁱⁱ—Ba1—S11	123.35 (5)	S11—C11—H11B	109.5
O11^iv—Ba1—S11	71.83 (8)	H11A—C11—H11B	109.5
O7ⁱⁱ—Ba1—S11	66.89 (6)	S11—C11—H11C	109.5
O7ⁱ—Ba1—S11	66.89 (6)	H11A—C11—H11C	109.5
O11—Ba1—S11	23.10 (8)	H11B—C11—H11C	109.5
O2ⁱⁱⁱ—Ba1—S11	144.44 (6)	O11—S11'—C11'	113.2 (5)
O2—Ba1—S11	144.44 (6)	S11'—C11'—H11D	109.5
O1ⁱ—Ba1—Ba1^iv	140.18 (4)	S11'—C11'—H11E	109.5
O1ⁱⁱ—Ba1—Ba1^iv	140.18 (4)	H11D—C11'—H11E	109.5
O1—Ba1—Ba1^iv	39.73 (4)	S11'—C11'—H11F	109.5
O1ⁱⁱⁱ—Ba1—Ba1^iv	39.73 (4)	H11D—C11'—H11F	109.5
O11^iv—Ba1—Ba1^iv	43.66 (7)	H11E—C11'—H11F	109.5
O7ⁱⁱ—Ba1—Ba1^iv	95.35 (6)

Ba1—O2—N1—O3	144.7 (4)	O5—N2—C4—C5	10.7 (7)
Ba1—O2—N1—C2	−38.2 (5)	O4—N2—C4—C5	−170.5 (4)
Ba1^iv—O7—N3—O6	173.9 (3)	C3—C4—C5—C6	1.3 (6)
Ba1^iv—O7—N3—C6	−7.2 (6)	N2—C4—C5—C6	−177.8 (3)
Ba1^iv—O1—C1—C6	−58.8 (4)	C4—C5—C6—C1	−1.9 (5)
Ba1—O1—C1—C6	119.2 (3)	C4—C5—C6—N3	178.8 (3)
Ba1^iv—O1—C1—C2	120.7 (3)	O1—C1—C6—C5	179.9 (3)
Ba1—O1—C1—C2	−61.3 (4)	C2—C1—C6—C5	0.3 (4)
O1—C1—C2—C3	−177.7 (3)	O1—C1—C6—N3	−0.8 (5)
C6—C1—C2—C3	1.9 (4)	C2—C1—C6—N3	179.6 (3)
O1—C1—C2—N1	0.9 (4)	O7—N3—C6—C5	−147.6 (3)
C6—C1—C2—N1	−179.5 (3)	O6—N3—C6—C5	31.4 (5)
O3—N1—C2—C3	39.9 (5)	O7—N3—C6—C1	33.0 (5)
O2—N1—C2—C3	−137.3 (3)	O6—N3—C6—C1	−148.0 (4)
O3—N1—C2—C1	−138.8 (4)	Ba1ⁱⁱ—O11—S11—C11ⁱⁱⁱ	56.7 (4)
O2—N1—C2—C1	44.0 (4)	Ba1—O11—S11—C11ⁱⁱⁱ	−123.3 (4)
C1—C2—C3—C4	−2.5 (5)	Ba1ⁱⁱ—O11—S11—C11	−56.7 (4)
N1—C2—C3—C4	178.9 (3)	Ba1—O11—S11—C11	123.3 (4)
C2—C3—C4—C5	0.7 (6)	Ba1ⁱⁱ—O11—S11—Ba1	180.000 (2)
C2—C3—C4—N2	179.8 (3)	Ba1ⁱⁱ—O11—S11'—C11'	−112.1 (7)
O5—N2—C4—C3	−168.4 (5)	Ba1—O11—S11'—C11'	67.9 (7)
O4—N2—C4—C3	10.4 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O4^v	0.93	2.43	3.283 (5)	153
C5—H5···O6^vi	0.90 (4)	2.63 (4)	3.492 (5)	159 (3)

Symmetry codes: (v) −x+1, −y+1, −z; (vi) −x+3, −y+1, −z+1.

Acknowledgements

BRS acknowledges the Department of Science & Technology (DST) New Delhi, for the sanction of a Bruker D8 Quest Eco single crystal X-ray diffractometer under the DST–FIST program.

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