Crystal structure of Rb6[B12O18(OH)6]·2H2O

Qiu, Q.-M.; Yan, L.; Song, J.-B.

doi:10.1107/S2056989022008611

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Volume 78| Part 10| October 2022| Pages 971-973

https://doi.org/10.1107/S2056989022008611

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Crystal structure of Rb₆[B₁₂O₁₈(OH)₆]·2H₂O

Qi-Ming Qiu,^a ^* Li Yan ^b and Jian-Biao Song ^c

^aSchool of Science, China University of Geosciences, Beijing 100083, People's Republic of China, ^bAnalytical and Testing Centre, Beijing Institute of Technology, Beijing 100081, People's Republic of China, and ^cBeijing Chaoyang Foreign Language School, Beijing 100101, People's Republic of China
^*Correspondence e-mail: qiuqiming890521@163.com

Edited by B. Therrien, University of Neuchâtel, Switzerland (Received 18 August 2022; accepted 29 August 2022; online 2 September 2022)

The solvothermal reaction of H₃BO₃, sodium tert-butoxide, Rb₂CO₃ and pyridine led to a new alkaline metal borate hexarubidium hexahydroxydodecaborate dihydrate, Rb₆[B₁₂O₁₈(OH)₆]·2H₂O. Its structure contains a large cyclic dodecaoxoboron cluster, [B₁₂O₁₈(OH)₆]⁶⁻, formed by six {B₃O₃} rings. In the crystal, O—H⋯O hydrogen bonds between the components lead to the formation of a three-dimensional supramolecular framework.

Keywords: alkaline metal borate; solvothermal synthesis; hydrogen bond; supramolecular framework; crystal structure.

CCDC reference: 2192069

1. Chemical context

In recent years, borates have made excellent contributions to the development of nonlinear optical (NLO) materials and so they are the focus of material chemists (Bashir et al., 2018 ; Qiu et al., 2021a ; Wei et al., 2016 ). Scientists have found that alkali- and alkaline-earth–metal borates often exhibit a short ultraviolet cut-off edge due to no d–d and f–f electron transition in the ultraviolet region with wide transparency ranges (Shi et al., 2019 ; Tang et al., 2019 ). Generally, boron has two kinds of coordination modes: either BO₃ trigonal or BO₄ tetrahedral, and they further bond to each other through common O atoms forming different oxoboron clusters, which can further polymerize into isolated clusters, one-dimensional chains, two-dimensional layers or three-dimensional frameworks. Here, single crystals of Rb₆[B₁₂O₁₈(OH)₆]·2H₂O with alkali metal atoms and isolated oxoboron clusters have been obtained under solvothermal conditions.

2. Structural commentary

There are 13.5 independent atoms in the asymmetric unit of the title compound, including 3 B, 9/2 O, 3/2 OH, 3/2 Rb, and 1/2 H₂O. It should be noted that the Rb1, Rb2, B2, B4, O4, O6 and O8 atoms are located on special positions with occupancy of 0.25 or 0.5, while the remaining Rb, B and O atoms are located at general positions with an occupancy of 1. Bond-valence-sum calculations show that Rb and B are consistent with the expected oxidation states (Brown & Altermatt, 1985 ; Brese & O'Keeffe, 1991 ). Six trigonal BO₂(OH) units [B—O(av.) = 1.360 Å] and six tetrahedral BO₄ units [B—O(av.) = 1.474 Å] are linked by vertex sharing. Each BO₄ unit provides two terminal oxygen atoms to connect with two neighboring BO₄ units and shares the other two corners with the BO₂(OH) unit to form a [B₁₂O₁₈(OH)₆]⁶⁻ cluster (Fig. 1). Each Rb atom is six-coordinate, with Rb—O distances in the range of 2.793 (5)-3.359 (5) Å.

Figure 1
The asymmetric unit of the oxoboron cluster of [B₁₂O₁₈(OH)₆]⁶⁻ [symmetry codes: (i) 2 − x, 2 − y, z; (ii) x, y, 2 − z]. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

In the title compound, each [B₁₂O₁₈(OH)₆]⁶⁻ cluster is connected to other clusters by O1—H1⋯O6, and O6—H6⋯O1 hydrogen bonds, resulting in a three-dimensional supramolecular framework (Fig. 2, Table 1). Water molecules are also attached to supramolecular structure via O—H⋯O hydrogen bonds. The title structure is different from those of previously reported analogues K₇{(BO₃)Mn[B₁₂O₁₈(OH)₆]}·H₂O (Zhang et al., 2004 ), and Na₂Cs₄Ba₂[B₁₂O₁₈(OH)₆]·4OH (Zhang et al., 2016 ). Both compounds crystallize in the non-centrosymmetric Pmn2₁ space group and their supramolecular structures are different from that of the title compound. Therefore, the use of different alkali metals as templates may affect the crystallization of the oxoboron supramolecular structure.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H8B⋯O7ⁱ	0.85	2.25	3.046 (6)	155
O8—H8B⋯O4ⁱ	0.85	1.68	2.224 (7)	119
O8—H8A⋯O7ⁱⁱ	0.85	1.70	2.231 (5)	118
O8—H8A⋯O4ⁱⁱ	0.85	2.17	2.958 (7)	155
O6—H6⋯O1ⁱⁱⁱ	0.82	1.86	2.670 (5)	167
O1—H1⋯O6^iv	0.94	1.91	2.670 (5)	136
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
View of the three-dimensional supramolecular framework along the [010] direction. All of the Rb—O bonds are omitted for clarity and blue dashed lines represent O—H⋯O hydrogen bonds.

4. Database survey

A search of the Cambridge Structural Database (CSD, version 5.43, update June 2022; Groom et al., 2016 ) for the cyclic dodeca-oxoboron unit {B₁₂O₂₄} ring gave eight hits. In the crystals of Li₇Na₂KRb₂B₁₂O₂₄, Li_7.35Na_2.36K_1.50Cs_0.78B₁₂O₂₄, Li_6.97Na_2.63K_1.24Cs_1.15B₁₂O₂₄, and Li_7.27Na_2.67Rb_2.06B₁₂O₂₄ (refcodes: JOGBIT, JOGBOZ, JOFNEA, JOFNIE, trigonal, R $[\overline{3}]$ space group; Baiheti et al., 2019 ), the terminal oxygens of this type of the {B₁₂O₂₄} ring can be completely deprotonated [B₁₂O₂₄]¹²⁻ and fail to extend to high-dimensional structures through covalent bonds and hydrogen bonds. In the crystal of Na₈[B₁₂O₂₀(OH)₄] (refcode: ETIJAU, monoclinic, P2₁/c space group; Menchetti et al., 1979 ), the partially protonated [B₁₂O₂₀(OH)₄]⁸⁻ unit also fails to extend to a higher dimensional structure through O—B—O bonds. While KNa₈[Li@B₁₂O₁₈(OH)₆](CO₃)₂ (refcode: EBUCAJ, trigonal, R $[\overline{3}]$ space group; Qiu et al., 2021b ) is a borate carbonate with the isolated [Li@B₁₂O₁₈(OH)₆]⁵⁻ cluster and interesting layers formed by Na⁺ and CO₃²⁻ ions, thus forming a two-dimensional supramolecular structure. After changing the synthetic conditions, the isolated [Li@B₁₂O₁₈(OH)₆]⁵⁻ cluster was successfully extended to a layered structure via B—O—B bonds in Cs₅[Li@B₁₂O₂₀(OH)₂]·3H₂O (refcode: EBUCIR, monoclinic, Pc space group; Qiu et al., 2021b), by condensation reactions with the elimination of water molecules between oxoboron clusters.

5. Synthesis and crystallization

A mixture of H₃BO₃ (0.618 g, 10 mmol), sodium tert-butoxide (0.096 g, 1 mmol) and Rb₂CO₃ (0.231 g, 1 mmol) was added into pyridine (3.0 mL). After stirring for 15 min, the resulting mixture was sealed in a 25 mL Teflon-lined stainless steel autoclave, heated at 483 K for 7 days, and then slowly cooled to room temperature. Colorless block-shaped crystals of Rb₆[B₁₂O₁₈(OH)₆]·2H₂O were obtained (yield 51% based on H₃BO₃). Infrared (KBr pallet, cm⁻¹): 3445vs, 1639m, 1427s, 1320m, 1003m, 939w, 873m, 721m, 622w, 542m. The thermogravimetric curve of the title compound is shown in Fig. 3a. The weight loss of 8.6% (cal. 8.4%) in the temperature range 350–950 K for the compound is attributed to the loss of the water molecules and the removal of dehydration of the hydroxyl groups. The compound has almost no weight loss after 950 K. The ultraviolet visible diffuse reflectance spectrum of the title compound is shown in Fig. 3b. The band gap obtained by extrapolating the linear part of the rising curve to zero for the compound is 5.59 eV.

Figure 3
(a) Thermogravimetric curve and (b) ultraviolet visible diffuse reflectance spectrum of the title compound. Inset: plots of α/S versus E.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen-atom coordinates were refined without any constraints or restraints. Their U_iso values were set to 1.2U_eq of the parent atoms.

Table 2
Experimental details

Crystal data
Chemical formula	Rb₆[B₁₂O₁₈(OH)₆]·2H₂O
M_r	1068.62
Crystal system, space group	Orthorhombic, Pnnm
Temperature (K)	296
a, b, c (Å)	13.395 (4), 9.251 (2), 12.368 (4)
V (Å³)	1532.7 (7)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	9.60
Crystal size (mm)	0.08 × 0.07 × 0.07

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.452, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	17510, 1980, 1523
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.173, 1.07
No. of reflections	1980
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.57, −1.16
Computer programs: APEX2 and SAINT (Bruker, 2014 ), SHELXT2018/3 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 2192069

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989022008611/tx2056sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022008611/tx2056Isup3.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT2018/3 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

hexarubidium hexahydroxydodecaborate dihydrate, Rb₆[B₁₂O₁₈(OH)₆]·2H₂O top

Crystal data top

Rb₆[B₁₂O₁₈(OH)₆]·2H₂O	D_x = 2.316 Mg m⁻³
M_r = 1068.62	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnnm	Cell parameters from 3469 reflections
a = 13.395 (4) Å	θ = 2.7–26.1°
b = 9.251 (2) Å	µ = 9.60 mm⁻¹
c = 12.368 (4) Å	T = 296 K
V = 1532.7 (7) Å³	Block, colorless
Z = 2	0.08 × 0.07 × 0.07 mm
F(000) = 1000

Data collection top

Bruker APEXII CCD diffractometer	1523 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, Bruker (Mo) X-ray Source	R_int = 0.057
φ and ω scans	θ_max = 28.3°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −17→17
T_min = 0.452, T_max = 0.746	k = −12→12
17510 measured reflections	l = −16→16
1980 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.061	H-atom parameters constrained
wR(F²) = 0.173	w = 1/[σ²(F_o²) + (0.0825P)² + 9.4675P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1980 reflections	Δρ_max = 1.57 e Å⁻³
110 parameters	Δρ_min = −1.16 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)
Rb1	1.000000	1.000000	0.500000	0.0418 (4)
Rb2	1.000000	0.500000	1.000000	0.0529 (5)
Rb3	0.74535 (5)	1.03106 (9)	0.73060 (7)	0.0489 (3)
O1	1.0385 (4)	0.6325 (4)	0.6768 (4)	0.0397 (12)
H1	1.089080	0.687977	0.643718	0.048*
O2	0.9347 (3)	0.7048 (4)	0.8193 (3)	0.0191 (8)
O3	1.0311 (3)	0.8776 (4)	0.7204 (3)	0.0203 (8)
O4	0.9428 (4)	0.7903 (6)	1.000000	0.0204 (11)
O5	0.7857 (3)	0.7944 (4)	0.9032 (3)	0.0194 (8)
O6	0.6357 (4)	0.7801 (7)	1.000000	0.0270 (13)
H6	0.599457	0.797673	0.948224	0.032*	0.5
O7	0.9137 (3)	0.9603 (4)	0.8563 (3)	0.0224 (8)
O8	0.4074 (4)	0.3941 (5)	0.500000	0.0144 (9)
H8A	0.401585	0.483846	0.486660	0.017*	0.5
H8B	0.456785	0.383526	0.542470	0.017*	0.5
B1	0.9999 (4)	0.7413 (6)	0.7399 (4)	0.0193 (11)
B2	1.000000	1.000000	0.7919 (6)	0.0127 (14)
B3	0.8956 (4)	0.8163 (6)	0.8960 (4)	0.0114 (10)
B4	0.7386 (6)	0.7897 (9)	1.000000	0.0176 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Rb1	0.0586 (9)	0.0472 (8)	0.0196 (6)	0.0159 (6)	0.000	0.000
Rb2	0.0971 (13)	0.0268 (6)	0.0348 (7)	0.0271 (7)	0.000	0.000
Rb3	0.0324 (4)	0.0516 (5)	0.0628 (5)	0.0101 (3)	−0.0090 (3)	0.0248 (4)
O1	0.059 (3)	0.0192 (19)	0.041 (3)	−0.011 (2)	0.036 (2)	−0.0119 (18)
O2	0.0257 (18)	0.0140 (16)	0.0175 (18)	−0.0067 (14)	0.0084 (15)	−0.0047 (13)
O3	0.0296 (18)	0.0153 (16)	0.0158 (17)	−0.0080 (15)	0.0094 (15)	−0.0048 (14)
O4	0.010 (2)	0.036 (3)	0.015 (2)	0.007 (2)	0.000	0.000
O5	0.0110 (15)	0.036 (2)	0.0117 (16)	−0.0044 (15)	−0.0006 (13)	−0.0003 (14)
O6	0.013 (2)	0.052 (4)	0.016 (2)	−0.004 (2)	0.000	0.000
O7	0.0223 (19)	0.0154 (17)	0.029 (2)	0.0031 (14)	0.0108 (16)	0.0055 (15)
O8	0.017 (2)	0.012 (2)	0.013 (2)	0.0099 (18)	0.000	0.000
B1	0.025 (3)	0.018 (3)	0.014 (2)	−0.007 (2)	0.004 (2)	−0.007 (2)
B2	0.016 (3)	0.015 (3)	0.006 (3)	0.002 (3)	0.000	0.000
B3	0.008 (2)	0.014 (2)	0.012 (2)	−0.0031 (18)	−0.0010 (18)	−0.0018 (19)
B4	0.013 (4)	0.024 (4)	0.016 (4)	−0.004 (3)	0.000	0.000

Geometric parameters (Å, º) top

Rb1—O3	2.980 (4)	Rb3—O5	3.105 (4)
Rb1—O3ⁱ	2.980 (4)	Rb3—O3ⁱⁱ	3.114 (4)
Rb1—O3ⁱⁱ	2.980 (4)	Rb3—O1^xi	3.359 (5)
Rb1—O3ⁱⁱⁱ	2.980 (4)	Rb3—B3	3.491 (5)
Rb1—O6^iv	3.166 (6)	Rb3—B2	3.5061 (19)
Rb1—O6^v	3.166 (6)	Rb3—B3^v	3.603 (5)
Rb1—B2ⁱⁱⁱ	3.610 (7)	Rb3—B4^v	3.729 (5)
Rb1—B2	3.610 (7)	O1—B1	1.374 (7)
Rb1—Rb3	4.4556 (12)	O1—H1	0.9433
Rb1—Rb3ⁱ	4.4556 (12)	O2—B1	1.357 (6)
Rb1—Rb3ⁱⁱ	4.4556 (12)	O2—B3	1.495 (6)
Rb1—Rb3ⁱⁱⁱ	4.4556 (12)	O3—B1	1.350 (7)
Rb2—O4^vi	2.793 (5)	O3—B2	1.496 (5)
Rb2—O4	2.793 (5)	O4—B3^vii	1.453 (5)
Rb2—O2^vii	3.058 (4)	O4—B3	1.453 (5)
Rb2—O2^viii	3.058 (4)	O5—B4	1.354 (5)
Rb2—O2^vi	3.058 (4)	O5—B3	1.490 (6)
Rb2—O2	3.058 (4)	O6—B4	1.381 (9)
Rb2—B3	3.488 (5)	O6—H6	0.8200
Rb2—B3^vii	3.488 (5)	O6—H6^vii	0.8200
Rb2—B3^viii	3.488 (5)	O7—B3	1.441 (6)
Rb2—B3^vi	3.488 (5)	O7—B2	1.452 (5)
Rb2—Rb3^ix	4.3609 (11)	O8—H8A	0.8500
Rb2—Rb3^x	4.3609 (11)	O8—H8B	0.8500
Rb3—O7	2.816 (4)	O8—H8Aⁱ	0.8500
Rb3—O2^v	2.963 (4)	O8—H8Bⁱ	0.8500
Rb3—O5^v	2.974 (4)

O3—Rb1—O3ⁱ	132.24 (13)	O3ⁱⁱ—Rb3—O1^xi	158.35 (10)
O3—Rb1—O3ⁱⁱ	47.76 (13)	O7—Rb3—B3	23.42 (11)
O3ⁱ—Rb1—O3ⁱⁱ	180.00 (5)	O2^v—Rb3—B3	154.19 (11)
O3—Rb1—O3ⁱⁱⁱ	180.0	O5^v—Rb3—B3	150.79 (11)
O3ⁱ—Rb1—O3ⁱⁱⁱ	47.76 (13)	O5—Rb3—B3	25.25 (10)
O3ⁱⁱ—Rb1—O3ⁱⁱⁱ	132.24 (13)	O3ⁱⁱ—Rb3—B3	67.90 (10)
O3—Rb1—O6^iv	66.97 (7)	O1^xi—Rb3—B3	91.11 (11)
O3ⁱ—Rb1—O6^iv	66.97 (7)	O7—Rb3—B2	23.45 (12)
O3ⁱⁱ—Rb1—O6^iv	113.03 (7)	O2^v—Rb3—B2	151.80 (8)
O3ⁱⁱⁱ—Rb1—O6^iv	113.03 (7)	O5^v—Rb3—B2	108.86 (9)
O3—Rb1—O6^v	113.03 (7)	O5—Rb3—B2	67.94 (10)
O3ⁱ—Rb1—O6^v	113.03 (7)	O3ⁱⁱ—Rb3—B2	25.24 (9)
O3ⁱⁱ—Rb1—O6^v	66.97 (7)	O1^xi—Rb3—B2	133.79 (11)
O3ⁱⁱⁱ—Rb1—O6^v	66.97 (7)	B3—Rb3—B2	42.74 (11)
O6^iv—Rb1—O6^v	180.0	O7—Rb3—B3^v	146.09 (12)
O3—Rb1—B2ⁱⁱⁱ	156.12 (7)	O2^v—Rb3—B3^v	23.88 (10)
O3ⁱ—Rb1—B2ⁱⁱⁱ	23.88 (7)	O5^v—Rb3—B3^v	23.81 (10)
O3ⁱⁱ—Rb1—B2ⁱⁱⁱ	156.12 (7)	O5—Rb3—B3^v	155.00 (10)
O3ⁱⁱⁱ—Rb1—B2ⁱⁱⁱ	23.88 (7)	O3ⁱⁱ—Rb3—B3^v	106.72 (10)
O6^iv—Rb1—B2ⁱⁱⁱ	90.0	O1^xi—Rb3—B3^v	92.62 (11)
O6^v—Rb1—B2ⁱⁱⁱ	90.0	B3—Rb3—B3^v	166.87 (12)
O3—Rb1—B2	23.88 (7)	B2—Rb3—B3^v	131.60 (10)
O3ⁱ—Rb1—B2	156.12 (7)	O7—Rb3—B4^v	121.68 (14)
O3ⁱⁱ—Rb1—B2	23.88 (7)	O2^v—Rb3—B4^v	62.59 (13)
O3ⁱⁱⁱ—Rb1—B2	156.12 (7)	O5^v—Rb3—B4^v	19.43 (12)
O6^iv—Rb1—B2	90.0	O5—Rb3—B4^v	165.50 (14)
O6^v—Rb1—B2	90.0	O3ⁱⁱ—Rb3—B4^v	74.88 (13)
B2ⁱⁱⁱ—Rb1—B2	180.0	O1^xi—Rb3—B4^v	126.70 (14)
O3—Rb1—Rb3	63.01 (7)	B3—Rb3—B4^v	141.27 (14)
O3ⁱ—Rb1—Rb3	135.79 (7)	B2—Rb3—B4^v	99.31 (15)
O3ⁱⁱ—Rb1—Rb3	44.21 (7)	B3^v—Rb3—B4^v	39.47 (14)
O3ⁱⁱⁱ—Rb1—Rb3	116.99 (7)	O7—Rb3—Rb2^v	161.66 (8)
O6^iv—Rb1—Rb3	119.50 (7)	O2^v—Rb3—Rb2^v	44.45 (7)
O6^v—Rb1—Rb3	60.50 (7)	O5^v—Rb3—Rb2^v	65.47 (7)
B2ⁱⁱⁱ—Rb1—Rb3	129.799 (15)	O5—Rb3—Rb2^v	122.29 (7)
B2—Rb1—Rb3	50.201 (15)	O3ⁱⁱ—Rb3—Rb2^v	135.72 (7)
O3—Rb1—Rb3ⁱ	135.79 (7)	O1^xi—Rb3—Rb2^v	64.64 (7)
O3ⁱ—Rb1—Rb3ⁱ	63.01 (7)	B3—Rb3—Rb2^v	141.29 (9)
O3ⁱⁱ—Rb1—Rb3ⁱ	116.99 (7)	B2—Rb3—Rb2^v	150.36 (11)
O3ⁱⁱⁱ—Rb1—Rb3ⁱ	44.21 (7)	B3^v—Rb3—Rb2^v	50.87 (8)
O6^iv—Rb1—Rb3ⁱ	119.50 (7)	B4^v—Rb3—Rb2^v	65.52 (11)
O6^v—Rb1—Rb3ⁱ	60.50 (7)	O7—Rb3—Rb1	74.06 (8)
B2ⁱⁱⁱ—Rb1—Rb3ⁱ	50.202 (15)	O2^v—Rb3—Rb1	121.65 (7)
B2—Rb1—Rb3ⁱ	129.798 (15)	O5^v—Rb3—Rb1	78.67 (7)
Rb3—Rb1—Rb3ⁱ	79.60 (3)	O5—Rb3—Rb1	105.16 (7)
O3—Rb1—Rb3ⁱⁱ	44.21 (7)	O3ⁱⁱ—Rb3—Rb1	41.86 (7)
O3ⁱ—Rb1—Rb3ⁱⁱ	116.99 (7)	O1^xi—Rb3—Rb1	145.17 (7)
O3ⁱⁱ—Rb1—Rb3ⁱⁱ	63.01 (7)	B3—Rb3—Rb1	84.08 (9)
O3ⁱⁱⁱ—Rb1—Rb3ⁱⁱ	135.79 (7)	B2—Rb3—Rb1	52.28 (12)
O6^iv—Rb1—Rb3ⁱⁱ	60.50 (7)	B3^v—Rb3—Rb1	99.81 (8)
O6^v—Rb1—Rb3ⁱⁱ	119.50 (7)	B4^v—Rb3—Rb1	60.50 (11)
B2ⁱⁱⁱ—Rb1—Rb3ⁱⁱ	129.798 (14)	Rb2^v—Rb3—Rb1	98.86 (3)
B2—Rb1—Rb3ⁱⁱ	50.202 (14)	B1—O1—Rb3^xii	116.5 (4)
Rb3—Rb1—Rb3ⁱⁱ	100.40 (3)	B1—O1—H1	96.8
Rb3ⁱ—Rb1—Rb3ⁱⁱ	180.0	Rb3^xii—O1—H1	78.5
O3—Rb1—Rb3ⁱⁱⁱ	116.99 (7)	B1—O2—B3	120.9 (4)
O3ⁱ—Rb1—Rb3ⁱⁱⁱ	44.21 (7)	B1—O2—Rb3^x	120.5 (3)
O3ⁱⁱ—Rb1—Rb3ⁱⁱⁱ	135.79 (7)	B3—O2—Rb3^x	102.8 (2)
O3ⁱⁱⁱ—Rb1—Rb3ⁱⁱⁱ	63.01 (7)	B1—O2—Rb2	119.9 (3)
O6^iv—Rb1—Rb3ⁱⁱⁱ	60.50 (7)	B3—O2—Rb2	93.7 (3)
O6^v—Rb1—Rb3ⁱⁱⁱ	119.50 (7)	Rb3^x—O2—Rb2	92.81 (9)
B2ⁱⁱⁱ—Rb1—Rb3ⁱⁱⁱ	50.202 (14)	B1—O3—B2	121.0 (4)
B2—Rb1—Rb3ⁱⁱⁱ	129.798 (14)	B1—O3—Rb1	118.4 (3)
Rb3—Rb1—Rb3ⁱⁱⁱ	180.0	B2—O3—Rb1	102.4 (3)
Rb3ⁱ—Rb1—Rb3ⁱⁱⁱ	100.40 (3)	B1—O3—Rb3ⁱⁱ	122.9 (3)
Rb3ⁱⁱ—Rb1—Rb3ⁱⁱⁱ	79.60 (3)	B2—O3—Rb3ⁱⁱ	92.20 (15)
O4^vi—Rb2—O4	180.0	Rb1—O3—Rb3ⁱⁱ	93.93 (9)
O4^vi—Rb2—O2^vii	132.41 (6)	B3^vii—O4—B3	124.6 (5)
O4—Rb2—O2^vii	47.59 (6)	B3^vii—O4—Rb2	106.2 (3)
O4^vi—Rb2—O2^viii	47.59 (6)	B3—O4—Rb2	106.2 (3)
O4—Rb2—O2^viii	132.41 (6)	B4—O5—B3	121.2 (4)
O2^vii—Rb2—O2^viii	180.0	B4—O5—Rb3^x	113.6 (4)
O4^vi—Rb2—O2^vi	47.59 (6)	B3—O5—Rb3^x	102.5 (3)
O4—Rb2—O2^vi	132.41 (6)	B4—O5—Rb3	123.3 (4)
O2^vii—Rb2—O2^vi	86.08 (13)	B3—O5—Rb3	92.0 (3)
O2^viii—Rb2—O2^vi	93.92 (13)	Rb3^x—O5—Rb3	99.83 (10)
O4^vi—Rb2—O2	132.41 (6)	B4—O6—Rb1^x	128.7 (5)
O4—Rb2—O2	47.59 (6)	B4—O6—H6	125.4
O2^vii—Rb2—O2	93.92 (13)	Rb1^x—O6—H6	79.7
O2^viii—Rb2—O2	86.08 (13)	B4—O6—H6^vii	125.35 (13)
O2^vi—Rb2—O2	180.0	Rb1^x—O6—H6^vii	79.74 (6)
O4^vi—Rb2—B3	156.42 (9)	H6—O6—H6^vii	102.7
O4—Rb2—B3	23.58 (9)	B3—O7—B2	123.7 (3)
O2^vii—Rb2—B3	68.60 (11)	B3—O7—Rb3	105.6 (3)
O2^viii—Rb2—B3	111.40 (11)	B2—O7—Rb3	106.0 (3)
O2^vi—Rb2—B3	154.67 (10)	H8A—O8—H8B	107.7
O2—Rb2—B3	25.33 (10)	H8A—O8—H8Aⁱ	22.4
O4^vi—Rb2—B3^vii	156.42 (9)	H8B—O8—H8Aⁱ	93.7
O4—Rb2—B3^vii	23.58 (9)	H8A—O8—H8Bⁱ	93.7
O2^vii—Rb2—B3^vii	25.33 (10)	H8B—O8—H8Bⁱ	76.3
O2^viii—Rb2—B3^vii	154.67 (10)	H8Aⁱ—O8—H8Bⁱ	107.7
O2^vi—Rb2—B3^vii	111.40 (11)	O3—B1—O2	124.1 (5)
O2—Rb2—B3^vii	68.60 (11)	O3—B1—O1	117.8 (5)
B3—Rb2—B3^vii	43.27 (17)	O2—B1—O1	118.1 (5)
O4^vi—Rb2—B3^viii	23.58 (9)	O7ⁱⁱ—B2—O7	113.4 (6)
O4—Rb2—B3^viii	156.42 (9)	O7ⁱⁱ—B2—O3ⁱⁱ	110.79 (19)
O2^vii—Rb2—B3^viii	154.67 (10)	O7—B2—O3ⁱⁱ	107.1 (2)
O2^viii—Rb2—B3^viii	25.33 (10)	O7ⁱⁱ—B2—O3	107.1 (2)
O2^vi—Rb2—B3^viii	68.60 (11)	O7—B2—O3	110.79 (19)
O2—Rb2—B3^viii	111.40 (11)	O3ⁱⁱ—B2—O3	107.5 (5)
B3—Rb2—B3^viii	136.73 (17)	O7ⁱⁱ—B2—Rb3	150.8 (3)
B3^vii—Rb2—B3^viii	180.0	O7—B2—Rb3	50.53 (19)
O4^vi—Rb2—B3^vi	23.58 (9)	O3ⁱⁱ—B2—Rb3	62.57 (15)
O4—Rb2—B3^vi	156.42 (9)	O3—B2—Rb3	101.8 (2)
O2^vii—Rb2—B3^vi	111.40 (11)	O7ⁱⁱ—B2—Rb3ⁱⁱ	50.52 (19)
O2^viii—Rb2—B3^vi	68.60 (11)	O7—B2—Rb3ⁱⁱ	150.8 (3)
O2^vi—Rb2—B3^vi	25.33 (10)	O3ⁱⁱ—B2—Rb3ⁱⁱ	101.8 (2)
O2—Rb2—B3^vi	154.67 (10)	O3—B2—Rb3ⁱⁱ	62.57 (15)
B3—Rb2—B3^vi	180.00 (9)	Rb3—B2—Rb3ⁱⁱ	155.0 (2)
B3^vii—Rb2—B3^vi	136.73 (17)	O7ⁱⁱ—B2—Rb1	123.3 (3)
B3^viii—Rb2—B3^vi	43.27 (17)	O7—B2—Rb1	123.3 (3)
O4^vi—Rb2—Rb3^ix	74.33 (8)	O3ⁱⁱ—B2—Rb1	53.8 (3)
O4—Rb2—Rb3^ix	105.67 (8)	O3—B2—Rb1	53.8 (3)
O2^vii—Rb2—Rb3^ix	77.20 (7)	Rb3—B2—Rb1	77.52 (12)
O2^viii—Rb2—Rb3^ix	102.80 (7)	Rb3ⁱⁱ—B2—Rb1	77.52 (12)
O2^vi—Rb2—Rb3^ix	42.74 (7)	O7—B3—O4	112.5 (4)
O2—Rb2—Rb3^ix	137.26 (7)	O7—B3—O5	108.2 (4)
B3—Rb2—Rb3^ix	126.76 (8)	O4—B3—O5	110.8 (4)
B3^vii—Rb2—Rb3^ix	96.67 (8)	O7—B3—O2	111.3 (4)
B3^viii—Rb2—Rb3^ix	83.33 (8)	O4—B3—O2	107.2 (4)
B3^vi—Rb2—Rb3^ix	53.24 (8)	O5—B3—O2	106.9 (4)
O4^vi—Rb2—Rb3^x	105.67 (8)	O7—B3—Rb2	146.6 (3)
O4—Rb2—Rb3^x	74.33 (8)	O4—B3—Rb2	50.3 (3)
O2^vii—Rb2—Rb3^x	102.80 (7)	O5—B3—Rb2	105.1 (3)
O2^viii—Rb2—Rb3^x	77.20 (7)	O2—B3—Rb2	61.0 (2)
O2^vi—Rb2—Rb3^x	137.26 (7)	O7—B3—Rb3	51.0 (2)
O2—Rb2—Rb3^x	42.74 (7)	O4—B3—Rb3	149.7 (3)
B3—Rb2—Rb3^x	53.24 (8)	O5—B3—Rb3	62.7 (2)
B3^vii—Rb2—Rb3^x	83.33 (8)	O2—B3—Rb3	102.9 (3)
B3^viii—Rb2—Rb3^x	96.67 (8)	Rb2—B3—Rb3	157.61 (16)
B3^vi—Rb2—Rb3^x	126.76 (8)	O7—B3—Rb3^x	128.1 (3)
Rb3^ix—Rb2—Rb3^x	180.0	O4—B3—Rb3^x	119.4 (3)
O7—Rb3—O2^v	153.22 (11)	O5—B3—Rb3^x	53.7 (2)
O7—Rb3—O5^v	127.55 (10)	O2—B3—Rb3^x	53.3 (2)
O2^v—Rb3—O5^v	47.64 (10)	Rb2—B3—Rb3^x	75.88 (10)
O7—Rb3—O5	46.94 (10)	Rb3—B3—Rb3^x	81.95 (10)
O2^v—Rb3—O5	131.85 (10)	O5—B4—O5^vii	124.3 (6)
O5^v—Rb3—O5	169.84 (10)	O5—B4—O6	117.8 (3)
O7—Rb3—O3ⁱⁱ	46.81 (9)	O5^vii—B4—O6	117.8 (3)
O2^v—Rb3—O3ⁱⁱ	128.83 (9)	O5—B4—Rb3^x	47.0 (3)
O5^v—Rb3—O3ⁱⁱ	83.65 (10)	O5^vii—B4—Rb3^x	132.1 (5)
O5—Rb3—O3ⁱⁱ	92.98 (9)	O6—B4—Rb3^x	90.9 (3)
O7—Rb3—O1^xi	111.56 (10)	O5—B4—Rb3^xiii	132.1 (5)
O2^v—Rb3—O1^xi	69.14 (10)	O5^vii—B4—Rb3^xiii	47.0 (3)
O5^v—Rb3—O1^xi	116.34 (10)	O6—B4—Rb3^xiii	90.9 (3)
O5—Rb3—O1^xi	65.88 (10)	Rb3^x—B4—Rb3^xiii	99.8 (2)

B2—O3—B1—O2	4.2 (8)	Rb2—O4—B3—O5	92.7 (4)
Rb1—O3—B1—O2	−123.3 (5)	B3^vii—O4—B3—O2	−147.0 (4)
Rb3ⁱⁱ—O3—B1—O2	120.5 (5)	Rb2—O4—B3—O2	−23.6 (4)
B2—O3—B1—O1	−174.3 (5)	B3^vii—O4—B3—Rb2	−123.5 (7)
Rb1—O3—B1—O1	58.2 (6)	B3^vii—O4—B3—Rb3	40.4 (11)
Rb3ⁱⁱ—O3—B1—O1	−58.1 (6)	Rb2—O4—B3—Rb3	163.9 (5)
B3—O2—B1—O3	−3.0 (8)	B3^vii—O4—B3—Rb3^x	−89.9 (6)
Rb3^x—O2—B1—O3	127.7 (5)	Rb2—O4—B3—Rb3^x	33.5 (3)
Rb2—O2—B1—O3	−118.4 (5)	B4—O5—B3—O7	−107.7 (6)
B3—O2—B1—O1	175.6 (5)	Rb3^x—O5—B3—O7	124.4 (3)
Rb3^x—O2—B1—O1	−53.8 (6)	Rb3—O5—B3—O7	23.9 (3)
Rb2—O2—B1—O1	60.1 (6)	B4—O5—B3—O4	15.9 (7)
Rb3^xii—O1—B1—O3	91.4 (5)	Rb3^x—O5—B3—O4	−111.9 (4)
Rb3^xii—O1—B1—O2	−87.2 (5)	Rb3—O5—B3—O4	147.5 (4)
B3—O7—B2—O7ⁱⁱ	−87.0 (4)	B4—O5—B3—O2	132.3 (5)
Rb3—O7—B2—O7ⁱⁱ	151.1 (2)	Rb3^x—O5—B3—O2	4.5 (4)
B3—O7—B2—O3ⁱⁱ	150.5 (4)	Rb3—O5—B3—O2	−96.0 (3)
Rb3—O7—B2—O3ⁱⁱ	28.6 (4)	B4—O5—B3—Rb2	68.6 (6)
B3—O7—B2—O3	33.5 (6)	Rb3^x—O5—B3—Rb2	−59.2 (2)
Rb3—O7—B2—O3	−88.4 (3)	Rb3—O5—B3—Rb2	−159.77 (14)
B3—O7—B2—Rb3	121.9 (5)	B4—O5—B3—Rb3	−131.6 (6)
B3—O7—B2—Rb3ⁱⁱ	−37.2 (9)	Rb3^x—O5—B3—Rb3	100.53 (14)
Rb3—O7—B2—Rb3ⁱⁱ	−159.0 (5)	B4—O5—B3—Rb3^x	127.9 (6)
B3—O7—B2—Rb1	93.0 (4)	Rb3—O5—B3—Rb3^x	−100.53 (14)
Rb3—O7—B2—Rb1	−28.9 (2)	B1—O2—B3—O7	15.5 (6)
B1—O3—B2—O7ⁱⁱ	106.5 (5)	Rb3^x—O2—B3—O7	−122.4 (3)
Rb1—O3—B2—O7ⁱⁱ	−119.1 (3)	Rb2—O2—B3—O7	143.9 (3)
Rb3ⁱⁱ—O3—B2—O7ⁱⁱ	−24.6 (3)	B1—O2—B3—O4	−107.8 (5)
B1—O3—B2—O7	−17.7 (6)	Rb3^x—O2—B3—O4	114.3 (3)
Rb1—O3—B2—O7	116.7 (4)	Rb2—O2—B3—O4	20.6 (4)
Rb3ⁱⁱ—O3—B2—O7	−148.8 (3)	B1—O2—B3—O5	133.4 (5)
B1—O3—B2—O3ⁱⁱ	−134.4 (5)	Rb3^x—O2—B3—O5	−4.5 (4)
Rb1—O3—B2—O3ⁱⁱ	0.000 (2)	Rb2—O2—B3—O5	−98.2 (3)
Rb3ⁱⁱ—O3—B2—O3ⁱⁱ	94.51 (12)	B1—O2—B3—Rb2	−128.3 (5)
B1—O3—B2—Rb3	−69.7 (5)	Rb3^x—O2—B3—Rb2	93.72 (13)
Rb1—O3—B2—Rb3	64.69 (18)	B1—O2—B3—Rb3	68.4 (5)
Rb3ⁱⁱ—O3—B2—Rb3	159.20 (13)	Rb3^x—O2—B3—Rb3	−69.56 (19)
B1—O3—B2—Rb3ⁱⁱ	131.1 (5)	Rb2—O2—B3—Rb3	−163.28 (12)
Rb1—O3—B2—Rb3ⁱⁱ	−94.51 (12)	B1—O2—B3—Rb3^x	137.9 (5)
B1—O3—B2—Rb1	−134.4 (5)	Rb2—O2—B3—Rb3^x	−93.72 (13)
Rb3ⁱⁱ—O3—B2—Rb1	94.51 (12)	B3—O5—B4—O5^vii	−4.5 (11)
B2—O7—B3—O4	87.7 (6)	Rb3^x—O5—B4—O5^vii	118.2 (7)
Rb3—O7—B3—O4	−150.2 (3)	Rb3—O5—B4—O5^vii	−121.1 (6)
B2—O7—B3—O5	−149.6 (4)	B3—O5—B4—O6	175.2 (6)
Rb3—O7—B3—O5	−27.6 (4)	Rb3^x—O5—B4—O6	−62.1 (8)
B2—O7—B3—O2	−32.5 (6)	Rb3—O5—B4—O6	58.6 (8)
Rb3—O7—B3—O2	89.5 (3)	B3—O5—B4—Rb3^x	−122.7 (6)
B2—O7—B3—Rb2	36.8 (8)	Rb3—O5—B4—Rb3^x	120.7 (4)
Rb3—O7—B3—Rb2	158.8 (4)	B3—O5—B4—Rb3^xiii	−64.7 (7)
B2—O7—B3—Rb3	−122.0 (5)	Rb3^x—O5—B4—Rb3^xiii	58.0 (5)
B2—O7—B3—Rb3^x	−91.9 (5)	Rb3—O5—B4—Rb3^xiii	178.7 (2)
Rb3—O7—B3—Rb3^x	30.1 (4)	Rb1^x—O6—B4—O5	90.1 (6)
B3^vii—O4—B3—O7	90.4 (7)	Rb1^x—O6—B4—O5^vii	−90.1 (6)
Rb2—O4—B3—O7	−146.2 (3)	Rb1^x—O6—B4—Rb3^x	49.90 (10)
B3^vii—O4—B3—O5	−30.8 (8)	Rb1^x—O6—B4—Rb3^xiii	−49.90 (10)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8B···O7^x	0.85	2.25	3.046 (6)	155
O8—H8B···O4^x	0.85	1.68	2.224 (7)	119
O8—H8A···O7^xiv	0.85	1.70	2.231 (5)	118
O8—H8A···O4^xiv	0.85	2.17	2.958 (7)	155
O6—H6···O1^xi	0.82	1.86	2.670 (5)	167
O1—H1···O6^iv	0.94	1.91	2.670 (5)	136

Symmetry codes: (iv) x+1/2, −y+3/2, z−1/2; (x) −x+3/2, y−1/2, −z+3/2; (xi) x−1/2, −y+3/2, −z+3/2; (xiv) x−1/2, −y+3/2, z−1/2.

Funding information

We gratefully acknowledge support by the Fundamental Research Funds for the Central Universities (grant No. 2–9-2021–008).

References

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