Dipotassium tetra­hydroxido­penta­oxido­tetra­borate monohydrate

Dhatchaiyini, M.K.; NizamMohideen, M.; Rajasekar, G.; Bhaskaran, A.

doi:10.1107/S2414314619001287

inorganic compounds

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ISSN: 2414-3146

Volume 4| Part 1| January 2019| x190128

https://doi.org/10.1107/S2414314619001287

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Dipotassium tetrahydroxidopentaoxidotetraborate monohydrate

M. K. Dhatchaiyini,^a M. NizamMohideen,^b ^* G. Rajasekar ^a and A. Bhaskaran ^a ^*

^aPG & Research Department of Physics, Presidency College (Autonomous), Chennai 600 005, Tamil Nadu, India, and ^bPG & Research Department of Physics, The New College (Autonomous), Chennai 600 014, Tamil Nadu, India
^*Correspondence e-mail: mnizam.new@gmail.com, abhaskaran_68@yahoo.co.in

Edited by M. Weil, Vienna University of Technology, Austria (Received 27 December 2018; accepted 23 January 2019; online 31 January 2019)

In the tetraborate anion of the title compound, K₂[B₄O₅(OH)₄]·H₂O, the bridging B—O bond lengths of the tetrahedral BO₄ and the trigonal-planar BO₃ units are slightly longer than the corresponding terminal B—OH bond lengths. The crystal structure is stabilized by intermolecular O—H⋯O, O—H⋯O_water and O_water—H⋯O hydrogen bonds, generating a three-dimensional network. The two potassium cations both show a coordination number of 9.

Keywords: crystal structure; potassium borate; hydrogen bonding.

CCDC reference: 1893090

Structure description

Inorganic borates exhibit promising applications as non-linear optical materials, birefringent materials, ferroelectric and piezoelectric materials, or host materials for luminescence (Berger, 1950 ; Heller et al., 1986 ; Becker, 1998 ; Chen et al., 1999 , 2007a ,b , 2010 , 2012 ; Yu et al., 2011 ; Wu et al., 2012 ; Strauss et al., 2016 ). In general, boron atoms in borates can be coordinated by either three or four oxygen atoms, forming trigonal–planar BO₃ or tetrahedral BO₄ groups, respectively. These groups may condense with each other through common oxygen atoms to give polyborate anionic groups that can adopt different coordination modes to bind to metal cations. The crystal chemistry of the resultant borates is rich, including rings, loops, infinite chains, sheets or three-dimensional networks (Burns et al., 1995 ). Against this background, we report herein on the crystal structure of K₂[B₄O₅(OH)₄]·H₂O, (I). This monohydrate is closely related to the corresponding dihydrate K₂[B₄O₅(OH)₄]·2H₂O (Marezio et al., 1963 ).

Fig. 1. shows the asymmetric unit of (I). It features two K⁺ cations, one [B₄O₅(OH)₄]^2– tetraborate anion and one water molecule of crystallization. The anion comprises of two tetrahedral BO₄ (B2, B4) and two trigonal–planar BO₃ (B1, B3) units, fused to a double ring via the central tetrahedra. Both BO₄ and BO₃ groups are rather regular; the O—B—O angles in the tetrahedra cover the range between 106.7 (2) and 111.51 (14)°, and those in the triangles between 116.26 (18) and 124.20 (17)°, with average O—B—O angles of 109.4 and 119.9°, respectively. The B—O bond lengths in the tetrahedra range from 1.441 (2) to 1.512 (2) Å, and those in the trigonal–planar units between 1.356 (2) and 1.390 (2) Å. The average B—O bond lengths (1.478 and 1.370 Å, respectively) are in good agreement with the data reviewed by Hawthorne et al. (1996 ), Chen et al. (2017 ) or Zobetz (1982 ).

Figure 1
View of the asymmetric unit of (I) with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

All terminal O atoms (O2, O4, O7, O9) in the anion carry an additional hydrogen atom, and are active in intermolecular O—H⋯O hydrogen bonding (Table 1, Fig. 2), generating centrosymmetric hydrogen-bonded dimers with a cyclic R₂²(8) ring motif. The crystal packing further comprises O—H⋯O_water and O_water—H⋯O hydrogen bonds whereby the water molecule (O10) interacts with O1 and O6 of the anion to form R₂²(12) ring motifs. Taking all the hydrogen-bonding interactions together, a three-dimensional network arises. The two unique potassium cations are situated in between the anionic network, with K—O distances ranging from 2.731 (2) to 3.269 (2) Å, and with a coordination number of 9 for both cations.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9⋯O8ⁱ	0.83 (2)	2.02 (2)	2.8385 (18)	173 (2)
O4—H4⋯O6ⁱⁱ	0.83 (2)	2.03 (2)	2.8338 (18)	164 (3)
O2—H2⋯O9ⁱⁱⁱ	0.80 (2)	2.19 (2)	2.957 (2)	161 (3)
O10—H10A⋯O6	0.86 (2)	1.82 (2)	2.6704 (18)	175 (3)
O10—H10B⋯O1^iv	0.85 (2)	2.10 (2)	2.850 (2)	146 (3)
O7—H7⋯O10^v	0.83 (2)	2.00 (2)	2.823 (2)	169 (3)
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x+1, -y+1, -z+2; (iii) x-1, y, z; (iv) -x+1, -y+1, -z+1; (v) x, y+1, z.

Figure 2
The crystal packing of the title compound, stabilized by medium–strong O—H⋯O, O—H⋯O_water and O_water—H⋯O hydrogen bonds (shown as dashed lines; see Table 1

for numerical details).

Synthesis and crystallization

Potassium carbonate (13.8 g) and boric acid (6.1 g) were mixed in the molar ratio 1:1 to prepare an aqueous solution of potassium borate. By continuous stirring, the solution achieved super saturation conditions. Crystallization from this solution yielded good-quality crystals. In order to ensure the purity of the product, recrystallization was carried out for several times by using double-distilled water to get high-quality crystals. The crystals were grown by slow and controlled evaporation of the solvent in a constant temperature bath at 313 K. The period of growth ranged from 30 to 40 days. In this way, crystals of K₂[B₄O₅(OH)₄]·H₂O with dimensions up to 7 × 9× 6 mm³ could be obtained.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	K₂[B₄O₅(OH)₄]·H₂O
M_r	287.49
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	7.1850 (6), 7.8479 (7), 8.9932 (8)
α, β, γ (°)	68.572 (1), 88.393 (2), 74.975 (1)
V (Å³)	454.66 (7)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	9.68
Crystal size (mm)	0.15 × 0.15 × 0.10

Data collection
Diffractometer	Bruker APEX3 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.428, 0.755
No. of measured, independent and observed [I > 2σ(I)] reflections	12205, 1782, 1685
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.073, 1.08
No. of reflections	1782
No. of parameters	169
No. of restraints	8
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.41
Computer programs: APEX3 and SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL2014/7 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1893090

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314619001287/wm5482sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619001287/wm5482Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314619001287/wm5482Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Dipotassium tetrahydroxidopentaoxidotetraborate monohydrate top

Crystal data top

K₂(B₄O₅(OH)₄)·H₂O	Z = 2
M_r = 287.49	F(000) = 288
Triclinic, P1	D_x = 2.100 Mg m⁻³
a = 7.1850 (6) Å	Cu Kα radiation, λ = 1.54178 Å
b = 7.8479 (7) Å	Cell parameters from 9535 reflections
c = 8.9932 (8) Å	θ = 5.3–72.9°
α = 68.572 (1)°	µ = 9.68 mm⁻¹
β = 88.393 (2)°	T = 296 K
γ = 74.975 (1)°	Block, colourless
V = 454.66 (7) Å³	0.15 × 0.15 × 0.10 mm

Data collection top

Bruker APEX3 CMOS diffractometer	1685 reflections with I > 2σ(I)
Radiation source: micro-focus sealed tube	R_int = 0.048
ω and φ scan	θ_max = 72.5°, θ_min = 5.3°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −8→8
T_min = 0.428, T_max = 0.755	k = −9→9
12205 measured reflections	l = −11→11
1782 independent reflections

Refinement top

Refinement on F²	8 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.029	All H-atom parameters refined
wR(F²) = 0.073	w = 1/[σ²(F_o²) + (0.0364P)² + 0.3324P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1782 reflections	Δρ_max = 0.26 e Å⁻³
169 parameters	Δρ_min = −0.41 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.

Refinement. The O-bound hydrogen atoms were located in a difference Fourier map and were refined with distance restraints of O—H = 0.85 (2) Å.

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

	x	y	z	U_iso*/U_eq
K1	−0.09251 (7)	0.38216 (6)	0.80053 (5)	0.02243 (14)
K2	0.20676 (6)	1.09022 (6)	0.19990 (5)	0.02022 (13)
O1	0.30645 (19)	0.80307 (18)	0.52405 (15)	0.0163 (3)
O2	0.0185 (2)	0.7652 (2)	0.44414 (18)	0.0278 (4)
O3	0.11229 (19)	0.64763 (19)	0.72235 (16)	0.0170 (3)
O4	0.2514 (2)	0.44850 (18)	0.98578 (16)	0.0165 (3)
O5	0.20264 (19)	0.78980 (17)	0.89638 (15)	0.0147 (3)
O6	0.45190 (18)	0.59912 (16)	0.78995 (15)	0.0118 (3)
O7	0.2574 (2)	1.07780 (19)	0.88399 (17)	0.0193 (3)
O8	0.40972 (19)	0.93391 (17)	0.70523 (15)	0.0148 (3)
O9	0.64504 (19)	0.74772 (18)	0.58708 (16)	0.0167 (3)
O10	0.5427 (3)	0.2666 (2)	0.75091 (19)	0.0276 (4)
B1	0.1486 (3)	0.7371 (3)	0.5679 (3)	0.0154 (4)
B2	0.2586 (3)	0.6167 (3)	0.8510 (2)	0.0125 (4)
B3	0.2906 (3)	0.9315 (3)	0.8275 (2)	0.0127 (4)
B4	0.4565 (3)	0.7673 (3)	0.6519 (2)	0.0111 (4)
H9	0.620 (3)	0.843 (3)	0.504 (2)	0.030 (7)*
H4	0.351 (3)	0.420 (4)	1.043 (3)	0.036 (8)*
H2	−0.076 (3)	0.735 (4)	0.482 (4)	0.049 (9)*
H10A	0.508 (5)	0.375 (3)	0.759 (3)	0.051 (9)*
H10B	0.547 (5)	0.285 (4)	0.652 (2)	0.049 (9)*
H7	0.329 (4)	1.148 (4)	0.842 (4)	0.050 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
K1	0.0295 (3)	0.0193 (2)	0.0218 (2)	−0.00895 (17)	0.00811 (18)	−0.01020 (17)
K2	0.0186 (2)	0.0179 (2)	0.0239 (2)	−0.00297 (16)	0.00074 (17)	−0.00873 (16)
O1	0.0168 (7)	0.0199 (6)	0.0121 (6)	−0.0072 (5)	0.0003 (5)	−0.0041 (5)
O2	0.0174 (8)	0.0495 (10)	0.0191 (8)	−0.0102 (7)	−0.0008 (6)	−0.0146 (7)
O3	0.0147 (6)	0.0228 (7)	0.0161 (6)	−0.0085 (5)	0.0008 (5)	−0.0077 (5)
O4	0.0201 (7)	0.0119 (6)	0.0162 (7)	−0.0069 (5)	0.0018 (6)	−0.0022 (5)
O5	0.0163 (6)	0.0130 (6)	0.0173 (6)	−0.0057 (5)	0.0063 (5)	−0.0078 (5)
O6	0.0130 (6)	0.0082 (5)	0.0137 (6)	−0.0025 (5)	0.0019 (5)	−0.0039 (5)
O7	0.0246 (7)	0.0152 (7)	0.0239 (7)	−0.0077 (6)	0.0081 (6)	−0.0125 (6)
O8	0.0194 (7)	0.0102 (6)	0.0169 (6)	−0.0060 (5)	0.0059 (5)	−0.0062 (5)
O9	0.0136 (7)	0.0144 (6)	0.0188 (7)	−0.0023 (5)	0.0055 (5)	−0.0037 (5)
O10	0.0435 (9)	0.0161 (7)	0.0268 (8)	−0.0075 (6)	0.0089 (7)	−0.0127 (6)
B1	0.0142 (10)	0.0179 (10)	0.0155 (10)	−0.0022 (8)	0.0007 (8)	−0.0091 (8)
B2	0.0131 (10)	0.0117 (9)	0.0127 (9)	−0.0040 (7)	0.0011 (8)	−0.0039 (7)
B3	0.0145 (10)	0.0107 (9)	0.0122 (9)	−0.0018 (7)	−0.0003 (8)	−0.0044 (7)
B4	0.0113 (9)	0.0105 (9)	0.0124 (9)	−0.0031 (7)	0.0023 (8)	−0.0051 (7)

Geometric parameters (Å, º) top

K1—O3	2.7315 (14)	O4—B2	1.441 (2)
K1—O5ⁱ	2.7608 (14)	O4—K1ⁱ	2.7783 (14)
K1—O4ⁱ	2.7782 (14)	O4—K2^x	2.8624 (13)
K1—O2ⁱⁱ	2.8174 (16)	O4—H4	0.825 (17)
K1—O7ⁱⁱⁱ	2.8759 (15)	O5—B3	1.363 (2)
K1—O9^iv	2.9741 (14)	O5—B2	1.512 (2)
K1—O10^iv	3.0799 (18)	O5—K1ⁱ	2.7608 (14)
K1—O6^iv	3.2608 (13)	O5—K2^ix	2.8982 (14)
K1—O4	3.2684 (14)	O6—B4	1.451 (2)
K2—O10^v	2.7938 (16)	O6—B2	1.471 (2)
K2—O8^vi	2.8461 (14)	O6—K1^xi	3.2608 (13)
K2—O4^vii	2.8624 (13)	O7—B3	1.383 (2)
K2—O7^viii	2.8877 (15)	O7—K1^xii	2.8759 (15)
K2—O5^ix	2.8982 (14)	O7—K2^xiii	2.8877 (15)
K2—O3^ix	2.9142 (15)	O7—H7	0.834 (18)
K2—O1	2.9274 (13)	O8—B3	1.372 (3)
K2—O9^vi	3.0031 (14)	O8—B4	1.508 (2)
K2—O2	3.2690 (18)	O8—K2^vi	2.8461 (14)
O1—B1	1.356 (3)	O9—B4	1.453 (2)
O1—B4	1.497 (2)	O9—K1^xi	2.9741 (14)
O2—B1	1.390 (2)	O9—K2^vi	3.0031 (14)
O2—K1ⁱⁱ	2.8174 (16)	O9—H9	0.825 (17)
O2—H2	0.804 (17)	O10—K2^v	2.7939 (16)
O3—B1	1.361 (3)	O10—K1^xi	3.0799 (18)
O3—B2	1.495 (2)	O10—H10A	0.856 (17)
O3—K2^ix	2.9142 (15)	O10—H10B	0.850 (17)

O3—K1—O5ⁱ	124.63 (4)	B1—O3—K2^ix	107.19 (11)
O3—K1—O4ⁱ	83.56 (4)	B2—O3—K2^ix	98.46 (10)
O5ⁱ—K1—O4ⁱ	52.02 (4)	K1—O3—K2^ix	90.33 (4)
O3—K1—O2ⁱⁱ	102.87 (5)	B2—O4—K1ⁱ	99.00 (10)
O5ⁱ—K1—O2ⁱⁱ	127.95 (5)	B2—O4—K2^x	167.17 (11)
O4ⁱ—K1—O2ⁱⁱ	167.06 (5)	K1ⁱ—O4—K2^x	90.48 (4)
O3—K1—O7ⁱⁱⁱ	91.40 (4)	B2—O4—K1	91.71 (10)
O5ⁱ—K1—O7ⁱⁱⁱ	87.71 (4)	K1ⁱ—O4—K1	109.46 (4)
O4ⁱ—K1—O7ⁱⁱⁱ	121.96 (4)	K2^x—O4—K1	76.91 (3)
O2ⁱⁱ—K1—O7ⁱⁱⁱ	69.61 (4)	B2—O4—H4	105 (2)
O3—K1—O9^iv	72.91 (4)	K1ⁱ—O4—H4	83 (2)
O5ⁱ—K1—O9^iv	117.88 (4)	K2^x—O4—H4	84 (2)
O4ⁱ—K1—O9^iv	77.28 (4)	K1—O4—H4	158 (2)
O2ⁱⁱ—K1—O9^iv	93.72 (4)	B3—O5—B2	118.48 (15)
O7ⁱⁱⁱ—K1—O9^iv	154.34 (4)	B3—O5—K1ⁱ	135.06 (11)
O3—K1—O10^iv	149.75 (4)	B2—O5—K1ⁱ	97.85 (10)
O5ⁱ—K1—O10^iv	74.23 (4)	B3—O5—K2^ix	112.27 (11)
O4ⁱ—K1—O10^iv	94.59 (4)	B2—O5—K2^ix	98.67 (9)
O2ⁱⁱ—K1—O10^iv	74.14 (4)	K1ⁱ—O5—K2^ix	85.04 (4)
O7ⁱⁱⁱ—K1—O10^iv	114.49 (4)	B4—O6—B2	111.10 (13)
O9^iv—K1—O10^iv	77.23 (4)	B4—O6—K1^xi	95.42 (10)
O3—K1—O6^iv	108.12 (4)	B2—O6—K1^xi	153.42 (10)
O5ⁱ—K1—O6^iv	75.04 (4)	B3—O7—K1^xii	122.95 (11)
O4ⁱ—K1—O6^iv	55.28 (4)	B3—O7—K2^xiii	132.83 (12)
O2ⁱⁱ—K1—O6^iv	111.80 (4)	K1^xii—O7—K2^xiii	83.18 (4)
O7ⁱⁱⁱ—K1—O6^iv	159.03 (4)	B3—O7—H7	110 (2)
O9^iv—K1—O6^iv	44.97 (3)	K1^xii—O7—H7	95 (2)
O10^iv—K1—O6^iv	49.71 (4)	K2^xiii—O7—H7	106 (2)
O3—K1—O4	45.69 (3)	B3—O8—B4	118.94 (14)
O5ⁱ—K1—O4	85.16 (4)	B3—O8—K2^vi	111.12 (11)
O4ⁱ—K1—O4	70.54 (5)	B4—O8—K2^vi	97.89 (10)
O2ⁱⁱ—K1—O4	121.96 (4)	B4—O9—K1^xi	108.04 (10)
O7ⁱⁱⁱ—K1—O4	65.58 (4)	B4—O9—K2^vi	92.77 (10)
O9^iv—K1—O4	111.87 (4)	K1^xi—O9—K2^vi	84.16 (4)
O10^iv—K1—O4	159.30 (4)	B4—O9—H9	99.7 (15)
O6^iv—K1—O4	123.31 (3)	K1^xi—O9—H9	152.0 (16)
O10^v—K2—O8^vi	68.19 (4)	K2^vi—O9—H9	98.6 (18)
O10^v—K2—O4^vii	126.34 (5)	K2^v—O10—K1^xi	85.71 (5)
O8^vi—K2—O4^vii	78.89 (4)	K2^v—O10—H10A	155 (2)
O10^v—K2—O7^viii	74.82 (4)	K1^xi—O10—H10A	72 (2)
O8^vi—K2—O7^viii	100.77 (4)	K2^v—O10—H10B	85 (2)
O4^vii—K2—O7^viii	71.12 (4)	K1^xi—O10—H10B	99 (2)
O10^v—K2—O5^ix	126.21 (4)	H10A—O10—H10B	108 (2)
O8^vi—K2—O5^ix	165.60 (4)	O1—B1—O3	124.20 (17)
O4^vii—K2—O5^ix	90.65 (4)	O1—B1—O2	116.26 (18)
O7^viii—K2—O5^ix	84.92 (4)	O3—B1—O2	119.54 (18)
O10^v—K2—O3^ix	154.22 (5)	O1—B1—K2	52.28 (9)
O8^vi—K2—O3^ix	118.33 (4)	O3—B1—K2	162.79 (13)
O4^vii—K2—O3^ix	78.91 (4)	O2—B1—K2	66.91 (11)
O7^viii—K2—O3^ix	124.27 (4)	O1—B1—K2^ix	123.52 (12)
O5^ix—K2—O3^ix	49.06 (3)	O3—B1—K2^ix	51.40 (9)
O10^v—K2—O1	59.69 (4)	O2—B1—K2^ix	95.47 (12)
O8^vi—K2—O1	71.95 (4)	K2—B1—K2^ix	114.13 (6)
O4^vii—K2—O1	144.45 (4)	O4—B2—O6	111.51 (14)
O7^viii—K2—O1	133.55 (4)	O4—B2—O3	108.42 (14)
O5^ix—K2—O1	113.64 (4)	O6—B2—O3	110.00 (15)
O3^ix—K2—O1	97.25 (4)	O4—B2—O5	110.66 (15)
O10^v—K2—O9^vi	108.20 (4)	O6—B2—O5	109.36 (14)
O8^vi—K2—O9^vi	48.87 (4)	O3—B2—O5	106.78 (14)
O4^vii—K2—O9^vi	75.56 (4)	O4—B2—K1ⁱ	55.65 (9)
O7^viii—K2—O9^vi	138.95 (4)	O6—B2—K1ⁱ	133.31 (11)
O5^ix—K2—O9^vi	119.08 (4)	O3—B2—K1ⁱ	116.64 (12)
O3^ix—K2—O9^vi	70.02 (4)	O5—B2—K1ⁱ	55.37 (8)
O1—K2—O9^vi	70.06 (4)	O4—B2—K2^ix	103.66 (11)
O10^v—K2—O2	71.45 (5)	O6—B2—K2^ix	144.84 (11)
O8^vi—K2—O2	115.02 (4)	O3—B2—K2^ix	56.29 (8)
O4^vii—K2—O2	161.79 (4)	O5—B2—K2^ix	55.77 (8)
O7^viii—K2—O2	115.01 (4)	K1ⁱ—B2—K2^ix	68.57 (4)
O5^ix—K2—O2	73.42 (4)	O5—B3—O8	122.62 (16)
O3^ix—K2—O2	83.88 (4)	O5—B3—O7	118.18 (18)
O1—K2—O2	43.80 (4)	O8—B3—O7	119.19 (17)
O9^vi—K2—O2	104.13 (4)	O5—B3—K2^vi	129.93 (12)
B1—O1—B4	118.49 (15)	O8—B3—K2^vi	47.92 (9)
B1—O1—K2	106.22 (11)	O7—B3—K2^vi	92.06 (11)
B4—O1—K2	132.16 (10)	O6—B4—O9	111.38 (14)
B1—O2—K1ⁱⁱ	126.73 (13)	O6—B4—O1	110.21 (14)
B1—O2—K2	90.06 (12)	O9—B4—O1	109.12 (15)
K1ⁱⁱ—O2—K2	81.83 (4)	O6—B4—O8	107.72 (14)
B1—O2—H2	109 (2)	O9—B4—O8	109.87 (14)
K1ⁱⁱ—O2—H2	105 (2)	O1—B4—O8	108.48 (14)
K2—O2—H2	149 (2)	O6—B4—K2^vi	99.24 (10)
B1—O3—B2	117.57 (15)	O9—B4—K2^vi	61.95 (9)
B1—O3—K1	121.32 (11)	O1—B4—K2^vi	150.20 (12)
B2—O3—K1	114.18 (10)	O8—B4—K2^vi	56.04 (8)

B4—O1—B1—O3	3.3 (3)	B3—O5—B2—O4	145.94 (16)
K2—O1—B1—O3	−159.13 (16)	K1ⁱ—O5—B2—O4	−6.65 (15)
B4—O1—B1—O2	−176.73 (16)	K2^ix—O5—B2—O4	−92.79 (13)
K2—O1—B1—O2	20.86 (19)	B3—O5—B2—O6	22.7 (2)
B4—O1—B1—K2	162.41 (17)	K1ⁱ—O5—B2—O6	−129.86 (12)
B4—O1—B1—K2^ix	66.24 (18)	K2^ix—O5—B2—O6	144.00 (11)
K2—O1—B1—K2^ix	−96.17 (11)	B3—O5—B2—O3	−96.26 (18)
B2—O3—B1—O1	−1.4 (3)	K1ⁱ—O5—B2—O3	111.15 (12)
K1—O3—B1—O1	−150.56 (14)	K2^ix—O5—B2—O3	25.01 (14)
K2^ix—O3—B1—O1	108.18 (18)	B3—O5—B2—K1ⁱ	152.59 (16)
B2—O3—B1—O2	178.60 (16)	K2^ix—O5—B2—K1ⁱ	−86.14 (5)
K1—O3—B1—O2	29.4 (2)	B3—O5—B2—K2^ix	−121.27 (15)
K2^ix—O3—B1—O2	−71.82 (19)	K1ⁱ—O5—B2—K2^ix	86.14 (5)
B2—O3—B1—K2	−73.6 (5)	B2—O5—B3—O8	8.0 (2)
K1—O3—B1—K2	137.3 (4)	K1ⁱ—O5—B3—O8	147.81 (13)
K2^ix—O3—B1—K2	36.0 (5)	K2^ix—O5—B3—O8	−106.03 (16)
B2—O3—B1—K2^ix	−109.58 (15)	B2—O5—B3—O7	−171.96 (15)
K1—O3—B1—K2^ix	101.26 (11)	K1ⁱ—O5—B3—O7	−32.2 (2)
K1ⁱⁱ—O2—B1—O1	62.0 (2)	K2^ix—O5—B3—O7	73.99 (17)
K2—O2—B1—O1	−17.83 (16)	B2—O5—B3—K2^vi	−51.8 (2)
K1ⁱⁱ—O2—B1—O3	−118.01 (17)	K1ⁱ—O5—B3—K2^vi	87.94 (18)
K2—O2—B1—O3	162.16 (16)	K2^ix—O5—B3—K2^vi	−165.90 (8)
K1ⁱⁱ—O2—B1—K2	79.83 (12)	B4—O8—B3—O5	−4.2 (2)
K1ⁱⁱ—O2—B1—K2^ix	−166.25 (9)	K2^vi—O8—B3—O5	−116.66 (16)
K2—O2—B1—K2^ix	113.93 (5)	B4—O8—B3—O7	175.75 (15)
K1ⁱ—O4—B2—O6	128.59 (12)	K2^vi—O8—B3—O7	63.32 (18)
K2^x—O4—B2—O6	−94.2 (5)	B4—O8—B3—K2^vi	112.44 (15)
K1—O4—B2—O6	−121.41 (13)	K1^xii—O7—B3—O5	−77.59 (19)
K1ⁱ—O4—B2—O3	−110.17 (13)	K2^xiii—O7—B3—O5	36.5 (2)
K2^x—O4—B2—O3	27.0 (6)	K1^xii—O7—B3—O8	102.43 (17)
K1—O4—B2—O3	−0.16 (13)	K2^xiii—O7—B3—O8	−143.50 (13)
K1ⁱ—O4—B2—O5	6.62 (14)	K1^xii—O7—B3—K2^vi	144.00 (8)
K2^x—O4—B2—O5	143.8 (5)	K2^xiii—O7—B3—K2^vi	−101.93 (13)
K1—O4—B2—O5	116.63 (12)	B2—O6—B4—O9	−177.72 (14)
K2^x—O4—B2—K1ⁱ	137.2 (5)	K1^xi—O6—B4—O9	3.91 (14)
K1—O4—B2—K1ⁱ	110.00 (6)	B2—O6—B4—O1	−56.45 (18)
K1ⁱ—O4—B2—K2^ix	−51.57 (8)	K1^xi—O6—B4—O1	125.17 (12)
K2^x—O4—B2—K2^ix	85.6 (5)	B2—O6—B4—O8	61.73 (17)
K1—O4—B2—K2^ix	58.43 (6)	K1^xi—O6—B4—O8	−116.65 (12)
B4—O6—B2—O4	178.63 (13)	B2—O6—B4—K2^vi	118.90 (12)
K1^xi—O6—B2—O4	−5.0 (3)	K1^xi—O6—B4—K2^vi	−59.48 (6)
B4—O6—B2—O3	58.31 (18)	K1^xi—O9—B4—O6	−4.49 (16)
K1^xi—O6—B2—O3	−125.31 (19)	K2^vi—O9—B4—O6	−89.24 (13)
B4—O6—B2—O5	−58.66 (18)	K1^xi—O9—B4—O1	−126.38 (11)
K1^xi—O6—B2—O5	117.7 (2)	K2^vi—O9—B4—O1	148.87 (11)
B4—O6—B2—K1ⁱ	−118.89 (15)	K1^xi—O9—B4—O8	114.80 (12)
K1^xi—O6—B2—K1ⁱ	57.5 (3)	K2^vi—O9—B4—O8	30.05 (13)
B4—O6—B2—K2^ix	−1.1 (3)	K1^xi—O9—B4—K2^vi	84.75 (6)
K1^xi—O6—B2—K2^ix	175.28 (8)	B1—O1—B4—O6	25.8 (2)
B1—O3—B2—O4	−151.09 (16)	K2—O1—B4—O6	−177.26 (9)
K1—O3—B2—O4	0.22 (18)	B1—O1—B4—O9	148.38 (15)
K2^ix—O3—B2—O4	94.41 (13)	K2—O1—B4—O9	−54.66 (19)
B1—O3—B2—O6	−28.9 (2)	B1—O1—B4—O8	−91.93 (18)
K1—O3—B2—O6	122.39 (12)	K2—O1—B4—O8	65.03 (19)
K2^ix—O3—B2—O6	−143.42 (11)	B1—O1—B4—K2^vi	−145.0 (2)
B1—O3—B2—O5	89.65 (19)	K2—O1—B4—K2^vi	12.0 (3)
K1—O3—B2—O5	−119.05 (12)	B3—O8—B4—O6	−30.2 (2)
K2^ix—O3—B2—O5	−24.85 (14)	K2^vi—O8—B4—O6	89.31 (12)
B1—O3—B2—K1ⁱ	148.80 (13)	B3—O8—B4—O9	−151.68 (15)
K1—O3—B2—K1ⁱ	−59.89 (12)	K2^vi—O8—B4—O9	−32.19 (14)
K2^ix—O3—B2—K1ⁱ	34.30 (10)	B3—O8—B4—O1	89.11 (18)
B1—O3—B2—K2^ix	114.50 (15)	K2^vi—O8—B4—O1	−151.40 (11)
K1—O3—B2—K2^ix	−94.20 (8)	B3—O8—B4—K2^vi	−119.49 (15)

Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x, −y+1, −z+1; (iii) x, y−1, z; (iv) x−1, y, z; (v) −x+1, −y+1, −z+1; (vi) −x+1, −y+2, −z+1; (vii) x, y+1, z−1; (viii) x, y, z−1; (ix) −x, −y+2, −z+1; (x) x, y−1, z+1; (xi) x+1, y, z; (xii) x, y+1, z; (xiii) x, y, z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9···O8^vi	0.83 (2)	2.02 (2)	2.8385 (18)	173 (2)
O4—H4···O6^xiv	0.83 (2)	2.03 (2)	2.8338 (18)	164 (3)
O2—H2···O9^iv	0.80 (2)	2.19 (2)	2.957 (2)	161 (3)
O10—H10A···O6	0.86 (2)	1.82 (2)	2.6704 (18)	175 (3)
O10—H10B···O1^v	0.85 (2)	2.10 (2)	2.850 (2)	146 (3)
O7—H7···O10^xii	0.83 (2)	2.00 (2)	2.823 (2)	169 (3)

Symmetry codes: (iv) x−1, y, z; (v) −x+1, −y+1, −z+1; (vi) −x+1, −y+2, −z+1; (xii) x, y+1, z; (xiv) −x+1, −y+1, −z+2.

Acknowledgements

The authors are thankful to the SAIF, IIT Madras, for the X-ray data collection.

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