Synthesis, crystal structure and Hirshfeld surface analysis of sodium bis­(malonato)borate monohydrate

Selvi, R.; Gokila, G.; Thiruvalluvar, A.A.; Sundararajan, R.S.

doi:10.1107/S2056989024000537

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 80| Part 2| February 2024| Pages 180-183

https://doi.org/10.1107/S2056989024000537

Open

access

Synthesis, crystal structure and Hirshfeld surface analysis of sodium bis(malonato)borate monohydrate

Ramalingam Selvi,^a Govindharajan Gokila,^a ^* Aravazhi Amalan Thiruvalluvar ^b ^* and Raju Sarangapani Sundararajan ^c

^aDepartment of Physics, Government College for Women (Autonomous), (affiliated to Bharathidasan University), Kumbakonam 612 001, Tamilnadu, India, ^bPrincipal (Retired), Kunthavai Naacchiyaar Government Arts College for Women (Autonomous), Thanjavur 613 007, Tamilnadu, India, and ^cDepartment of Physics, Government Arts College (Autonomous), (affiliated to Bharathidasan University), Kumbakonam 612 002, Tamilnadu, India
^*Correspondence e-mail: gokilaphy1981@gmail.com, thiruvalluvar.a@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 28 November 2023; accepted 14 January 2024; online 26 January 2024)

In the title salt, poly[aqua[μ₄-bis(malonato)borato]sodium], {[Na(C₆H₄BO₈)]·H₂O}_n or Na⁺·[B(C₃H₂O₄)₂]⁻·H₂O, the sodium cation exhibits fivefold coordination by four carbonyl O atoms of the bis(malonato)borate anions and a water O atom. The tetrahedral B atom at the centre of the anion leads to the formation of a polymeric three-dimensional framework, which is consolidated by C—H⋯O and O—H⋯O hydrogen bonds. A Hirshfeld surface analysis indicates that the most significant contacts in the crystal packing are H⋯O/O⋯H (49.7%), Na⋯O/O⋯Na (16.1%), O⋯O (12.6%), H⋯H (10.7%) and C⋯O/O⋯C (7.3%).

Keywords: synthesis; crystal structure; bis(malonato)borate anion; sodium; Hirshfeld surface analysis..

CCDC reference: 2325391

1. Chemical context

The review by Vaalma et al. (2018 ) provides a comprehensive overview of the cost and resource implications of sodium-ion batteries, which are a promising alternative to lithium-ion batteries for energy storage applications. The authors conclude that sodium-ion batteries have the potential to be significantly less expensive than lithium-ion batteries, due to the abundance of sodium and the lower cost of sodium-based materials. Allen et al. (2012 ) described the structure of lithium bis(2-methyllactato)borate monohydrate and there is a growing interest, as highlighted in various recent studies (Vaalma et al., 2018; Abraham, 2020 ; Li et al., 2019 ; Wang et al., 2018 ), in lithium bis(malonato)borate polymers as robust electrolytes.

The present study explores the substitution of 2-methyllactic acid and lithium carbonate with malonic acid and sodium carbonate, respectively, and presents the synthesis, crystal structure and Hirshfeld surface analysis of the title compound, Na⁺·[B(C₃H₂O₄)₂]⁻·H₂O, (I).

2. Structural commentary

The asymmetric unit of (I) comprises a sodium cation, a bis(malonato)borate anion and a coordinated water molecule (Fig. 1). The tetrahedral B atom is bonded to two malonate (C₃H₂O₄) ligands coordinated in an O,O′-bidentate mode.

Figure 1
View of the molecular structure of (I), showing 50% probability displacement ellipsoids (arbitrary spheres for the H atoms).

In the boron–oxygen tetrahedron, the mean B—O bond length of 1.4641 Å is in good agreement with the expected B(sp³)—O bond length of 1.468 Å (Allen et al., 1987 ). The largest O—B—O bond angles are the intracyclic angles: O1—B1—O3 = 112.92 (9)° and O5—B1—O7 = 112.21 (9)°. The six-membered boro–malonate rings O1/C1/C2/C3/O3/B1 and O5/C4/C5/C6/O7/B1 both adopt boat conformations [puckering parameters Q = 0.4082 (13) Å, θ = 87.85 (18)° and φ = 309.10 (18)° for the first ring, and Q = 0.4267 (13) Å, θ = 84.32 (16)° and φ = 317.00 (17)° for the second ring]. The `prow and stern' atoms in the first ring, B1 and C2, are displaced by 0.3680 (18) and 0.330 (2) Å, respectively, from C1/C3/O1/O3 (r.m.s. deviation = 0.0323 Å). In the second ring, the equivalent data are a B1 displacement of 0.4048 (17), a C5 displacement of 0.298 (2) Å and an r.m.s. deviation of 0.0621 Å. The dihedral angle between the O1/C1/C3/O3 and O5/C4/C6/O7 least-squares planes is 73.34 (4)°.

Na1 is surrounded by five O atoms [carbonyl O2 and O6 at (x − 1, y, z), water O9, carbonyl O8 at (x − $[{1\over 2}]$ , −y + $[{3\over 2}]$ , z + $[{1\over 2}]$ ) and O6 at (−x + $[{3\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{3\over 2}]$ )], forming a square-based pyramidal coordination polyhedron (Table 1). A possible sixth bond [Na1—O5 at (x − 1, y, z)], which would generate a distorted octahedron, is much longer at 3.0195 (10) Å and presumably only represents a marginal interaction in the structure.

Table 1
Selected geometric parameters (Å, °)

Na1—O9	2.3264 (12)	B1—O3	1.4508 (15)
Na1—O2	2.3402 (11)	B1—O7	1.4581 (16)
Na1—O6ⁱ	2.4032 (10)	B1—O1	1.4697 (15)
Na1—O8ⁱⁱ	2.4213 (12)	B1—O5	1.4779 (15)
Na1—O6ⁱⁱⁱ	2.4455 (11)

O9—Na1—O2	171.38 (5)	O6ⁱ—Na1—O8ⁱⁱ	80.15 (4)
O9—Na1—O6ⁱ	102.48 (4)	O9—Na1—O6ⁱⁱⁱ	84.03 (4)
O2—Na1—O6ⁱ	85.61 (4)	O2—Na1—O6ⁱⁱⁱ	88.60 (4)
O9—Na1—O8ⁱⁱ	88.27 (5)	O6ⁱ—Na1—O6ⁱⁱⁱ	167.40 (3)
O2—Na1—O8ⁱⁱ	90.22 (5)	O8ⁱⁱ—Na1—O6ⁱⁱⁱ	111.10 (5)
Symmetry codes: (i) ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

3. Supramolecular features and Hirshfeld surface analysis

The crystal structure of (I) is consolidated by two C—H⋯O links with the acceptors being one water O9 atom and one carbonyl O4 atom, and three O—H⋯O links, one of which is bifurcated, with the acceptors being one borate O1 atom and carbonyl atoms O4 and O2 (Table 2). The packing of the structure is shown in Fig. 2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2B⋯O9^iv	0.97	2.54	3.4247 (18)	151
C5—H5B⋯O4^v	0.97	2.46	3.2830 (18)	143
O9—H9A⋯O4^vi	0.85 (1)	2.23 (2)	2.9932 (17)	151 (3)
O9—H9B⋯O1^vii	0.84 (1)	2.46 (2)	3.1520 (14)	140 (3)
O9—H9B⋯O2^vii	0.84 (1)	2.39 (2)	3.1166 (17)	146 (3)
Symmetry codes: (iv) ; (v) ; (vi) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
A packing diagram of (I), viewed along the a-axis direction (projection onto the bc plane), showing the C—H⋯O and O—H⋯O hydrogen bonds as black dashed lines.

The Hirshfeld surface analysis of (I) was performed with CrystalExplorer (Version 21.5; Spackman et al., 2021 ). Fig. 3 shows the d_norm surface for the bis(malonato)borate anion plotted over the limits from −0.66 to +0.93 a.u. The intense red spots represent the shortest intermolecular contacts (attractive interactions like hydrogen bonds) and the blue regions denotes the longest (indicating possible repulsive interactions or regions with weak van der Waals interactions). Fig. 4 presents the two-dimensional fingerprint plots involving all the intermolecular interactions [Fig. 4(a)] and delineated into Na⋯O/O⋯Na = 16.1% [Fig. 4(b)], C⋯O/O⋯C = 7.3% [Fig. 4(c)], H⋯H = 10.7% [Fig. 4(d)], H⋯O/O⋯H = 49.7% [Fig. 4(e)] and O⋯O = 12.6% [Fig. 4(f)] interactions. The remaining interactions contribute less than 2.0%. The hydrogen bonds are indicated by pairs of characteristic wings in the fingerprint plot [Fig. 4(e)] representing H⋯O/O⋯H contacts. Pairs of scattered points of spikes are seen in the fingerprint plot delineated into H⋯O/O⋯H contacts (49.7% the maximum contribution to the Hirshfeld surface) [Fig. 4(e)].

Figure 3
The Hirshfeld surface for (I). The surface is drawn with transparency and simplified for clarity, and the regions with the strongest intermolecular interactions are shown in red. (d_norm range: −0.66 to +0.93 a.u.)

Figure 4
A view of the two-dimensional fingerprint plots for title compound (I), showing (a) all interactions, and those delineated into (b) Na⋯O/O⋯Na, (c) C⋯O/O⋯C, (d) H⋯H, (e) H⋯O/O⋯H and (f) O⋯O interactions. The d_i (x axis) and d_e (y axis) values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface.

4. Database survey

A search using CCDC ConQuest of the Cambridge Structural Database (CSD, Version 5.44, updated to June 2023; Groom et al., 2016 ) for the bis(malonato)borate anion gave one hit (CSD refcode PITQUF; Zviedre & Belyakov, 2007 ), in which the bis(malonato)borate unit is similar to that in (I) and is charge balanced by potassium cations. The K⁺ coordination geometry in PITQUF is an irregular nine-vertex polyhedron formed by the O atoms of seven complex anions.

5. Synthesis and crystallization

The title compound was synthesized by mixing malonic acid (C₃H₄O₄), boric acid (H₃BO₃) and sodium carbonate (Na₂CO₃) in a 4:2:1 molar ratio, using deionized water as the solvent. Initially, malonic acid (4.1264 g) was dissolved in deionized water. This was followed by the addition of a boric acid solution (1.236 g) and then a sodium carbonate solution (1.382 g) was added. The mixture was stirred thoroughly to ensure a uniform solution. The beaker containing the solution was then covered with a perforated sheet and left undisturbed. Over three months, due to slow evaporation of the solvent, small clear crystals of (I) formed at the bottom of the container [yield: 2.744 g, 40.6%; m.p. 527–529 K (decomposition)]. FT–IR (cm⁻¹): 3928, 3856, 3419, 3014, 2908, 2542, 2016, 1711, 1635, 1400, 1334, 1271, 1069, 1019, 958, 914, 859, 833, 657, 634, 561, 478, 457, 423.

6. Refinement

Crystal data and structure refinement details are summarized in Table 3. The H atoms attached to C atoms were placed in calculated positions (C—H = 0.97 Å) and refined as riding atoms with U_iso(H) = 1.2U_eq(C). The water H atoms were located in difference maps and refined with restraints (O—H = 0.84 ± 0.02 Å and H⋯H = 1.36 ± 0.02 Å) to ensure a realistic geometry.

Table 3
Experimental details

Crystal data
Chemical formula	[Na(C₆H₄BO₈)(H₂O)]
M_r	255.91
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	7.9058 (4), 8.2979 (5), 14.6473 (9)
β (°)	101.565 (2)
V (Å³)	941.38 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.21
Crystal size (mm)	0.35 × 0.27 × 0.27

Data collection
Diffractometer	Bruker D8 VENTURE diffractometer with a PHOTON II detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.917, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	32209, 2864, 2494
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.105, 1.08
No. of reflections	2864
No. of parameters	162
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.60
Computer programs: APEX4, SAINT and XPREP (Bruker, 2021 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), PLATON (Spek, 2020 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2325391

Crystal structure: contains datablock global. DOI: https://doi.org/10.1107/S2056989024000537/hb8086sup1.cif

checkCIF report

Computing details top

Poly[aqua[µ₄-bis(malonato)borato]sodium] top

Crystal data top

[Na(C₆H₄BO₈)(H₂O)]	F(000) = 520
M_r = 255.91	D_x = 1.806 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.9058 (4) Å	Cell parameters from 9951 reflections
b = 8.2979 (5) Å	θ = 2.8–30.5°
c = 14.6473 (9) Å	µ = 0.21 mm⁻¹
β = 101.565 (2)°	T = 298 K
V = 941.38 (9) Å³	Block, colourless
Z = 4	0.35 × 0.27 × 0.27 mm

Data collection top

Bruker D8 VENTURE diffractometer with a PHOTON II detector	2494 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.030
ω and φ scan	θ_max = 30.5°, θ_min = 3.6°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −10→11
T_min = 0.917, T_max = 0.958	k = −11→11
32209 measured reflections	l = −20→20
2864 independent reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: mixed
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0503P)² + 0.3262P] where P = (F_o² + 2F_c²)/3
2864 reflections	(Δ/σ)_max < 0.001
162 parameters	Δρ_max = 0.53 e Å⁻³
4 restraints	Δρ_min = −0.60 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
Na1	0.24488 (7)	0.47538 (7)	0.76584 (4)	0.03728 (15)
B1	0.76757 (17)	0.52073 (15)	0.55156 (9)	0.0271 (2)
C1	0.59169 (15)	0.47853 (15)	0.66789 (9)	0.0294 (2)
C2	0.64385 (17)	0.30481 (15)	0.66658 (9)	0.0331 (3)
H2A	0.551966	0.239128	0.681940	0.040*
H2B	0.745590	0.288268	0.715054	0.040*
C3	0.68228 (16)	0.24605 (14)	0.57587 (9)	0.0309 (2)
C4	1.01449 (13)	0.68524 (13)	0.61701 (7)	0.0235 (2)
C5	0.93606 (17)	0.81205 (14)	0.54883 (9)	0.0340 (3)
H5A	1.028548	0.875823	0.532601	0.041*
H5B	0.867448	0.883229	0.579401	0.041*
C6	0.82428 (16)	0.75128 (16)	0.46059 (9)	0.0331 (3)
O1	0.64336 (12)	0.57513 (11)	0.60743 (7)	0.0337 (2)
O2	0.50736 (14)	0.53111 (13)	0.72169 (8)	0.0451 (3)
O3	0.74511 (13)	0.35276 (11)	0.52435 (7)	0.0358 (2)
O4	0.66050 (17)	0.10738 (13)	0.55087 (9)	0.0518 (3)
O5	0.94362 (11)	0.54098 (10)	0.60778 (6)	0.02768 (18)
O6	1.13921 (12)	0.71217 (11)	0.67822 (6)	0.0329 (2)
O7	0.74022 (12)	0.61563 (12)	0.46608 (6)	0.0366 (2)
O8	0.80823 (17)	0.82359 (17)	0.38773 (8)	0.0577 (3)
O9	0.00848 (15)	0.39690 (13)	0.82757 (8)	0.0448 (3)
H9A	−0.008 (4)	0.443 (3)	0.8765 (14)	0.088 (9)*
H9B	0.019 (4)	0.2983 (16)	0.8397 (19)	0.100 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Na1	0.0334 (3)	0.0373 (3)	0.0430 (3)	0.0070 (2)	0.0124 (2)	0.0112 (2)
B1	0.0289 (6)	0.0257 (6)	0.0283 (6)	−0.0034 (4)	0.0090 (5)	−0.0002 (4)
C1	0.0242 (5)	0.0316 (6)	0.0337 (6)	−0.0052 (4)	0.0089 (4)	−0.0065 (4)
C2	0.0401 (6)	0.0291 (6)	0.0316 (6)	−0.0021 (5)	0.0107 (5)	0.0008 (4)
C3	0.0322 (5)	0.0252 (5)	0.0360 (6)	−0.0037 (4)	0.0086 (4)	−0.0039 (4)
C4	0.0255 (4)	0.0238 (5)	0.0219 (4)	0.0022 (4)	0.0062 (4)	0.0025 (4)
C5	0.0391 (6)	0.0234 (5)	0.0355 (6)	−0.0004 (4)	−0.0022 (5)	0.0087 (5)
C6	0.0310 (5)	0.0382 (6)	0.0286 (6)	0.0004 (5)	0.0025 (4)	0.0120 (5)
O1	0.0349 (4)	0.0249 (4)	0.0456 (5)	0.0004 (3)	0.0180 (4)	−0.0013 (4)
O2	0.0423 (5)	0.0478 (6)	0.0527 (6)	−0.0066 (4)	0.0272 (5)	−0.0150 (5)
O3	0.0458 (5)	0.0288 (4)	0.0375 (5)	−0.0077 (4)	0.0198 (4)	−0.0079 (4)
O4	0.0722 (8)	0.0270 (5)	0.0611 (7)	−0.0110 (5)	0.0249 (6)	−0.0122 (5)
O5	0.0295 (4)	0.0236 (4)	0.0292 (4)	−0.0007 (3)	0.0042 (3)	0.0075 (3)
O6	0.0332 (4)	0.0349 (4)	0.0274 (4)	−0.0009 (3)	−0.0016 (3)	0.0013 (3)
O7	0.0369 (4)	0.0411 (5)	0.0282 (4)	−0.0087 (4)	−0.0017 (3)	0.0066 (4)
O8	0.0601 (7)	0.0713 (8)	0.0370 (6)	−0.0081 (6)	−0.0020 (5)	0.0315 (6)
O9	0.0525 (6)	0.0366 (5)	0.0487 (6)	−0.0035 (4)	0.0181 (5)	0.0039 (5)

Geometric parameters (Å, º) top

Na1—O9	2.3264 (12)	C2—H2A	0.9700
Na1—O2	2.3402 (11)	C2—H2B	0.9700
Na1—O6ⁱ	2.4032 (10)	C3—O4	1.2094 (16)
Na1—O8ⁱⁱ	2.4213 (12)	C3—O3	1.3231 (15)
Na1—O6ⁱⁱⁱ	2.4455 (11)	C4—O6	1.2130 (14)
Na1—O5ⁱ	3.0195 (10)	C4—O5	1.3171 (13)
B1—O3	1.4508 (15)	C4—C5	1.4969 (15)
B1—O7	1.4581 (16)	C5—C6	1.4993 (18)
B1—O1	1.4697 (15)	C5—H5A	0.9700
B1—O5	1.4779 (15)	C5—H5B	0.9700
C1—O2	1.2109 (15)	C6—O8	1.2086 (15)
C1—O1	1.3186 (15)	C6—O7	1.3177 (16)
C1—C2	1.5005 (17)	O9—H9A	0.846 (13)
C2—C3	1.5024 (17)	O9—H9B	0.838 (13)

O9—Na1—O2	171.38 (5)	O4—C3—C2	122.33 (12)
O9—Na1—O6ⁱ	102.48 (4)	O3—C3—C2	116.93 (10)
O2—Na1—O6ⁱ	85.61 (4)	O6—C4—O5	120.62 (10)
O9—Na1—O8ⁱⁱ	88.27 (5)	O6—C4—C5	122.02 (10)
O2—Na1—O8ⁱⁱ	90.22 (5)	O5—C4—C5	117.36 (10)
O6ⁱ—Na1—O8ⁱⁱ	80.15 (4)	O6—C4—Na1^iv	45.91 (6)
O9—Na1—O6ⁱⁱⁱ	84.03 (4)	O5—C4—Na1^iv	74.82 (6)
O2—Na1—O6ⁱⁱⁱ	88.60 (4)	C5—C4—Na1^iv	167.29 (8)
O6ⁱ—Na1—O6ⁱⁱⁱ	167.40 (3)	C4—C5—C6	115.62 (10)
O8ⁱⁱ—Na1—O6ⁱⁱⁱ	111.10 (5)	C4—C5—H5A	108.4
O9—Na1—O5ⁱ	77.10 (4)	C6—C5—H5A	108.4
O2—Na1—O5ⁱ	111.06 (4)	C4—C5—H5B	108.4
O6ⁱ—Na1—O5ⁱ	46.12 (3)	C6—C5—H5B	108.4
O8ⁱⁱ—Na1—O5ⁱ	117.12 (4)	H5A—C5—H5B	107.4
O6ⁱⁱⁱ—Na1—O5ⁱ	127.08 (4)	O8—C6—O7	120.86 (13)
O3—B1—O7	107.10 (10)	O8—C6—C5	122.25 (13)
O3—B1—O1	112.92 (9)	O7—C6—C5	116.88 (10)
O7—B1—O1	108.16 (10)	C1—O1—B1	121.25 (10)
O3—B1—O5	108.18 (10)	C1—O2—Na1	137.99 (9)
O7—B1—O5	112.21 (9)	C3—O3—B1	121.70 (10)
O1—B1—O5	108.33 (10)	C4—O5—B1	119.62 (9)
O2—C1—O1	120.21 (12)	C4—O5—Na1^iv	80.28 (6)
O2—C1—C2	122.89 (12)	B1—O5—Na1^iv	156.45 (7)
O1—C1—C2	116.90 (10)	C4—O6—Na1^iv	112.84 (8)
C1—C2—C3	115.33 (11)	C4—O6—Na1^v	127.34 (8)
C1—C2—H2A	108.4	Na1^iv—O6—Na1^v	118.98 (3)
C3—C2—H2A	108.4	C6—O7—B1	121.60 (10)
C1—C2—H2B	108.4	C6—O8—Na1^vi	164.30 (13)
C3—C2—H2B	108.4	Na1—O9—H9A	118 (2)
H2A—C2—H2B	107.5	Na1—O9—H9B	108 (2)
O4—C3—O3	120.73 (12)	H9A—O9—H9B	107 (2)

O2—C1—C2—C3	156.38 (13)	C5—C4—O5—B1	−17.36 (15)
O1—C1—C2—C3	−24.22 (16)	Na1^iv—C4—O5—B1	166.54 (9)
C1—C2—C3—O4	−150.74 (13)	O6—C4—O5—Na1^iv	−3.33 (10)
C1—C2—C3—O3	30.58 (17)	C5—C4—O5—Na1^iv	176.10 (10)
O6—C4—C5—C6	160.61 (11)	O3—B1—O5—C4	159.43 (9)
O5—C4—C5—C6	−18.81 (16)	O7—B1—O5—C4	41.49 (14)
Na1^iv—C4—C5—C6	143.8 (3)	O1—B1—O5—C4	−77.85 (12)
C4—C5—C6—O8	−150.46 (14)	O3—B1—O5—Na1^iv	−55.6 (2)
C4—C5—C6—O7	30.90 (17)	O7—B1—O5—Na1^iv	−173.55 (12)
O2—C1—O1—B1	170.39 (12)	O1—B1—O5—Na1^iv	67.1 (2)
C2—C1—O1—B1	−9.02 (16)	O5—C4—O6—Na1^iv	4.47 (13)
O3—B1—O1—C1	35.76 (16)	C5—C4—O6—Na1^iv	−174.93 (9)
O7—B1—O1—C1	154.11 (10)	O5—C4—O6—Na1^v	−164.81 (7)
O5—B1—O1—C1	−84.03 (13)	C5—C4—O6—Na1^v	15.79 (16)
O1—C1—O2—Na1	126.39 (13)	Na1^iv—C4—O6—Na1^v	−169.29 (12)
C2—C1—O2—Na1	−54.2 (2)	O8—C6—O7—B1	175.44 (14)
O4—C3—O3—B1	178.15 (13)	C5—C6—O7—B1	−5.90 (18)
C2—C3—O3—B1	−3.14 (18)	O3—B1—O7—C6	−147.33 (11)
O7—B1—O3—C3	−147.88 (11)	O1—B1—O7—C6	90.69 (14)
O1—B1—O3—C3	−28.92 (17)	O5—B1—O7—C6	−28.75 (16)
O5—B1—O3—C3	90.96 (13)	O7—C6—O8—Na1^vi	117.5 (4)
O6—C4—O5—B1	163.22 (10)	C5—C6—O8—Na1^vi	−61.0 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···O9^iv	0.97	2.54	3.4247 (18)	151
C5—H5B···O4^vii	0.97	2.46	3.2830 (18)	143
O9—H9A···O4^viii	0.85 (1)	2.23 (2)	2.9932 (17)	151 (3)
O9—H9B···O1^ix	0.84 (1)	2.46 (2)	3.1520 (14)	140 (3)
O9—H9B···O2^ix	0.84 (1)	2.39 (2)	3.1166 (17)	146 (3)

Symmetry codes: (iv) x+1, y, z; (vii) x, y+1, z; (viii) −x+1/2, y+1/2, −z+3/2; (ix) −x+1/2, y−1/2, −z+3/2.

Acknowledgements

The authors thank the Sophisticated Analytical Instrument Facility (SAIF), Indian Institute of Technology Madras (IITM), Chennai, Tamilnadu, India, for the single-crystal X-ray diffraction data.

References

Abraham, K. M. (2020). ACS Energy Lett. 5, 3544–3547. CrossRef CAS Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Allen, J. L., Paillard, E., Boyle, P. D. & Henderson, W. A. (2012). Acta Cryst. E68, m749. CSD CrossRef IUCr Journals Google Scholar
Bruker (2021). APEX3, SAINT/XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Li, K., Zhang, J., Lin, D., Wang, D.-W., Li, B., Lv, W., Sun, S., He, Y.-B., Kang, F., Yang, Q.-H., Zhou, L. & Zhang, T.-Y. (2019). Nat. Commun. 10, 725. CrossRef PubMed Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst. 54, 1006–1011. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Vaalma, C., Buchholz, D., Weil, M. & Passerini, S. (2018). Nat. Rev. Mater. 3, 18013. CrossRef Google Scholar
Wang, T., Su, D., Shanmukaraj, D., Rojo, T., Armand, M. & Wang, G. (2018). Electrochem. Energy Rev. 1, 200–237. CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zviedre, I. I. & Belyakov, S. V. (2007). Russ. J. Inorg. Chem. 52, 686–690. CrossRef Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.