Flux-growth method for the targeted synthesis of the salt-inclusion copper(II) phosphate Rb9Na2Cu6(P2O7)4Cl7

Luviano, K.; Williams, E.D.; Liurukara, D.S.; Dayeh, Y.; Cox, J.; Ranmohotti, K.G.S.

doi:10.1107/S2056989026004287

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ISSN: 2056-9890

Volume 82| Part 6| June 2026|

https://doi.org/10.1107/S2056989026004287

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Flux-growth method for the targeted synthesis of the salt-inclusion copper(II) phosphate Rb₉Na₂Cu₆(P₂O₇)₄Cl₇

Karla Luviano,^a Emily D. Williams,^b Duminda S. Liurukara,^c Yasmin Dayeh,^a Julia Cox ^a and Kulugammana G. S. Ranmohotti ^a ^*

^aDivision of Science, Mathematics, and Technology, Governors State University, 1 University Parkway, University Park, IL 60484-0975, USA, ^bDepartment of Chemistry and Center for Optical Materials Science and Engineering Technologies (COMSET), Clemson University, Clemson, SC 29634-0973, USA, and ^cUniversity of Missouri Research Reactor (MURR), University of Missouri, Columbia, MO 65211, USA
^*Correspondence e-mail: [email protected]

Edited by M. Weil, Vienna University of Technology, Austria (Received 22 December 2025; accepted 22 April 2026; online 7 May 2026)

There is a great deal of interest in the synthesis and structural features of a newly emerged class of salt-inclusion solids (SISs), which are made of a hybrid framework exhibiting integrated covalent (metal oxides) and ionic (metal halides) structural units. In general, we explored the conditions under which desired phase formation occurs and, for this study, we selected one of the compounds in the series of salt-templated phosphates and arsenates, A₂M₃(X₂O₇)₂·(salt) [where A = K, Rb, Cs; M = Mn, Cu; X = P, As] commonly known as CU-2 materials, which crystallize in two different space groups (I4/mcm and P4/nbm) due to the variation of the structural units. In our attempt to incorporate mixed Rb⁺/Na⁺ cations along with Cl⁻ anions into the negatively charged framework, Cu₃(P₂O₇)₂²⁻, the title compound, Rb₉Na₂Cu₆(P₂O₇)₄Cl₇, nonarubidium disodium hexacopper(II) tetrakis(pyrophosphate) heptachloride, has been synthesized by employing a high-temperature RbCl/NaCl eutectic flux and structurally characterized by single-crystal X-ray diffraction, revealing I4/mcm as the space group. In the title compound, the same negatively charged framework, Cu₃(P₂O₇)₂^2–, characteristic of the CU-2 materials, is retained, while the extended salt-like part of the structure, composed of mixed alkali metal chloride fragments, is different from the known CU-2 materials, and includes rarely seen corner-sharing {Na₄Cl₈} units.

Keywords: crystal structure; salt-inclusion solids; eutectic flux; molten-salt approach; open framework; salt structure; bond-valence-sum calculations.

CCDC reference: 2548269

1. Chemical context

Exploratory synthesis has been a vital aspect of solid-state chemistry, where the discovery of new compounds and structure types leads to new systems that can be optimized for a desired property and even to the discovery of new unexpected properties. These unprecedented discoveries have opened doors to novel materials synthesis via the utilities of salt-inclusion chemistry (SIC) that are otherwise known as the molten-salt approach (West & Hwu, 2012 ). The solubility of metal oxides in molten salts facilitates the synthesis of complex oxide compounds, such as transition-metal phosphates, arsenates, and silicates (Hwu, 1998 ). Although occasional salt inclusion is inevitable, this approach provides added variety in structural features of the resulting solids. These solids display an integrated structure between chemically dissimilar structures of a more covalent metal oxide and a more ionic halide salt.

By a broad definition, this class of materials is called salt-inclusion solids (SISs). Alternatively, the SISs are viewed as a metal oxide covalent framework templated by an extended structural unit made of an ionic salt (Hwu et al., 2002 ). The characteristic feature of SISs is that the more covalent metal oxide framework consists of voids filled by ionic salt-like structural units exhibiting 0-periodicity (Tang et al., 2008 ), 1-periodicity (Yu et al., 2013 ), or 2-periodicity (Queen et al., 2008 ). These salt-like units usually have complimentary structural features with respect to the negatively charged metal oxide framework (Hwu & Mo, 2001 ). It is intriguing to notice that the shape of the pore windows can be varied by altering the identity and relative concentration of the incorporated salt (Huang & Hwu, 2003 ). Recent reports of SISs have highlighted a correlation between the incorporation of ionic salts and the formation of special frameworks that would otherwise not be isolated without the aid of molten salt as a reactive solvent in the synthesis of metal oxide frameworks with low periodicity (Morrison et al., 2016a ). Many of the SISs adopt new structure types, whereby the incorporated salts play an essential role in bulk structural and chemical/physical properties. Most of the fascinating physical properties exhibited in SISs are associated with features like porous frameworks (Ulutagay et al., 1998 ), non-centrosymmetric structures (Etheredge & Hwu, 1995 ), or magnetic nanostructures (Stern et al., 2006 ). Interestingly, in some cases, SISs exhibit intense luminescence (Morrison et al., 2016b ) and can have important applications as new waste forms for the safe long-term storage of radio isotopes (Morrison & zur Loye, 2016 ).

With increasing interest, the above findings convey the fact that salt inclusion is a valid tool for a broad range of synthetic chemistry, and the SISs represent a newly emerging class of solids. However, SISs have remained a challenge to synthesize as their synthesis is largely serendipitous (Gao et al., 2015 ). Therefore, it is important to shift the focus of this exploration toward the development of new synthesis routes that allow for the targeted growth of new compounds within already explored phase and compositional space. Inspired by the study of salt-templated phosphates and arsenates of the type A₂M₃(X₂O₇)₂·(salt) (where A is K, Rb, Cs; M is Mn, Cu; X is P, As), commonly known as CU-2 materials (Huang et al., 1999 ), K_1.23Cs_3.60Mn₃(P₂O₇)₂Cl_3.74, K_2.12Cs_2.76Mn_0.76Cu_2.24(P₂O₇)₂Cl_2.87, K_3.81Cs_1.44Cu₃(P₂O₇)₂Cl_3.25, and Rb_1.14Cs_4.15Cu₃(As₂O₇)₂Cl_3.19, designated as CU-2-MnPO, CU-2-MnCuPO, CU-2-CuPO, and CU-2-CuAsO, respectively, we have undertaken an investigation of the salt-inclusion type CU-2-CuPO phase. The aim of this work is to design a reaction taking place by the careful selection of a metal oxide mixture aiming at the Rb₂Cu₃(P₂O₇)₂ composition and the use of a mixed RbCl/NaCl eutectic flux to isolate salt-inclusion compounds of the form Rb_2–xNa_xCu₃(P₂O₇)₂·y(RbCl). Here we report a second member of CU-2-CuPO materials of which the idealized formula can be written as Rb₂Na₂Cu₆(P₂O₇)₄·7(RbCl), where the open framework is conceptually templated by extended (Rb/Na)Cl units.

2. Structural commentary

Rb₉Na₂Cu₆(P₂O₇)₄Cl₇ crystallizes with four formula units in the space group I4/mcm. To the best of our knowledge, Rb₉Na₂Cu₆(P₂O₇)₄Cl₇ represents the fourth member structurally characterized in the CU-2-MXO system (Huang et al., 1999). The crystal structure of Rb₉Na₂Cu₆(P₂O₇)₄Cl₇ can be described as having a tri-periodic framework containing channels. As shown in Fig. 1, the corner-sharing PO₄ tetrahedra and CuO₄ square-planar units form two types of such channels ca 5.4 and 11.9 Å in diameter. This is where Rb2 (located at a site with multiplicity 16, Wyckoff letter l, symmetry m), Rb3 (16k, m) and Na1 (16l, m) cations link together with Cl2, Cl3A–D, and Cl4 anions to reside in the larger channels, while Rb1 (4c, 4/m) cations and Cl1 (4a, 422) anions occupy the smaller channels. As shown in Fig. 2(a), each smaller channel is surrounded by four larger channels and vice versa. The square-planar CuO₄ units and Cl⁻ ions form CuO₄Cl square pyramids [Fig. 2(b)]. The open framework is made of the Cu—O—P—O—Cu covalent linkages, leading to alternating CuO₄Cl units and pyrophosphate [P₂O₇] units with a shared vertex O atom O1. It shows that this bridging O1 atom occupies a special site (16l, m). There are two crystallographically distinct Cu²⁺ sites in the open framework. Cu1 and Cu2 are situated at special sites, 16j and 8h, with symmetry 2 and m2m, respectively. The Cl1 atom is common for all the Cu1O₄Cl units and is occupying the center of the smaller channel, whereas Cl2 (8h, m2m) in Cu2O₄Cl units face the center of the large channel [Fig. 2(b)].

Figure 1
Perspective view of the crystal structure of Rb₉Na₂Cu₆(P₂O₇)₄Cl₇ along [001]. The alternating P₂O₇ and CuO₄Cl units (given in polyhedral representation; Cu—Cl bonds have been omitted for clarity) are interlinked through corner-sharing O atoms. The larger channel is occupied by Rb⁺ and Na⁺ cations and Cl⁻ anions, whereas the smaller is occupied by Rb⁺ cations and Cl⁻ anions.

Figure 2
(a) The channel structure of Rb₉Na₂Cu₆(P₂O₇)₄Cl₇ in a view along [001], with the Cu–P–O framework outlined by CuO₄ and P₂O₇ units. The channels are formed by eight (8-ring) or sixteen (16-ring) alternating cations of Cu and P. To indicate the apparent disorder of some atoms (Na, Rb, and Cl), their arrangement is highlighted in two of the large channels. (b) Projection of one large and small channel onto (001), with some Cl and all Rb and Na sites are omitted for clarity. Cl atoms occupy the apical position of the Cu²⁺-centered square-pyramidal CuO₄Cl units (ball-and-stick drawing), with Cu—O bonds as solid lines and Cu—Cl bonds in dotted lines. The polyhedral units represent PO₄ tetrahedra.

The oxidation state of the copper cations in the CuO₄Cl square-pyramidal environment is supported through bond valence sum calculations (Brese & O'Keefe, 1991 ), with 2.09 valence units for Cu1 and 2.06 valence units for Cu2. Moreover, all the Cu—O bond lengths (Table 1) are consistent with what is expected from the sum of the Shannon crystal radii (Shannon, 1976 ) for five-coordinate Cu²⁺ and two-coordinate O²⁻ (2.00 Å), whereas the Cu—Cl bond lengths (Table 1) are somewhat longer than the sum of the Shannon crystal radii (2.46 Å) of five-coordinate Cu²⁺ (0.79 Å) and Cl⁻ (1.67).

Table 1
Selected bond lengths (Å)

Cu1—O4ⁱ	1.947 (7)	Cu2—O3^vi	1.938 (7)
Cu1—O4ⁱⁱ	1.947 (7)	Cu2—O3^vii	1.938 (7)
Cu1—O2ⁱⁱⁱ	1.950 (7)	Cu2—Cl2^viii	2.797 (9)
Cu1—O2^iv	1.950 (7)	P1—O2	1.507 (7)
Cu1—Cl1	2.7281 (19)	P1—O4	1.516 (7)
Cu2—O3	1.938 (7)	P1—O3^ix	1.520 (7)
Cu2—O3^v	1.938 (7)	P1—O1	1.616 (4)
Symmetry codes: (i) $[-x, y, -z+{\script{1\over 2}}]$ ; (ii) ; (iii) ; (iv) $[y, x, -z+{\script{1\over 2}}]$ ; (v) $[y-{\script{1\over 2}}, x+{\script{1\over 2}}, z]$ ; (vi) $[y-{\script{1\over 2}}, x+{\script{1\over 2}}, -z]$ ; (vii) ; (viii) $[-x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ix) $[-y, -x, -z+{\script{1\over 2}}]$ .

The P atom is surrounded by four O atoms to form an almost regular tetrahedron. The terminal P—O bond lengths average to about 1.52 Å, the sum of the Shannon crystal radii (Shannon, 1976) for P⁵⁺ (0.31 Å) and O²⁻ (1.21 Å). As expected for a condensed pyrophosphate group (Durif, 1995 ), the bond length to the bridging O1 atom is longer (Table 1). The calculated bond valence sum confirms the oxidation state of P⁵⁺, i.e. 4.79 valence units for P1. Fig. 3(a) shows how the salt-like parts of the structure, Rb⁺, Na⁺, and Cl⁻ ions are linked to the negatively charged wall of the Cu₃(P₂O₇)₂²⁻ framework. The three crystallographically different rubidium cations form significantly different polyhedra with oxygen and chlorine, as shown in Fig. 3(b).

Figure 3
(a) Partial structure of Rb₉Na₂Cu₆(P₂O₇)₄Cl₇ viewed along [001], showing the building blocks of the Rb–O–Cl and NaCl fragments. A portion of the Cu–P–O framework is included to show the location of one large and one small channel. All the Rb₂O₆Cl₃ polyhedra are included, while others are omitted for clarity. The bottom right section shows the actual arrangement of all the Rb–O–Cl polyhedral units and NaCl units. (b) The polyhedra representing the coordination around Rb1 (pink), Rb2 (green), and Rb3 (orange).

In CU-2-MXO materials (Huang et al.., 1999), the smaller channel is centered by a linear chain-like fragment of alternating A–Cl–A units (A = K, Rb, Cs), while the large channel is stuffed with mixed KCl/CsCl salt-like structure units, which adopt features characteristic for the crystal structures of NaCl and CsCl. Another series of materials adopting the framework of CU-2 topology with general formula A_xCu₆(P₂O₇)₄Cl_(x-6) (Williams et al., 2013 ) exhibits a wide variety of complex inorganic anions trapped in the large channels, with anions including chloride, bromide, phosphate and the complex metal halogenido anions [PtCl₄]²⁻, [PdBr₄]²⁻, [CuCl₄]²⁻, or [AuCl₄]⁻. Fig. 4(a) shows a perspective view of the Rb–Cl and Rb–Na–Cl salt structural units along [001], and Figs. 4(b)–(e) illustrate details of these units in side views. Fig. 5(a) shows the partial structure of the Rb–Na–Cl salt structural unit occupying the larger channel and running along [001]. There is disorder found at the central part of the Rb–Na–Cl salt structure creating partially occupied Na and Cl sites that form corner-sharing {Na₄Cl₈} units [Figs. 5(b)–(d) and 6)]. Four split sites for Cl3 are present within the {Na₄Cl₈} units, Cl3A (8g, 2mm), Cl3B (8g, 2mm), Cl3C (4d, mmm), and Cl3D (8g, 2mm), as well as one Cl4 (16j, 2) and one Na1(16l, m) site with an occupancy of 0.5 each. Cl3A, Cl3B, Cl3D, and Cl4 form an octahedron with respect to one another, shown in Fig. 6(b), where half of Cl4 would be in the axial position and the other half of the Cl4, Cl3A, and Cl3B would be in the four equatorial positions. It is intriguing to recognize the formation of structurally isolated corner-sharing {Na₄Cl₈} units that are `embedded' in the extended rubidium chloride salt structure.

Figure 4
(a) Perspective view of the Rb–Cl and Rb–Na–Cl salt-like structural units in a view along [001] (color codes: Rb1 pink, Rb2 dark green, Rb3 orange, Na1 gold, and Cl light green). (b) Ball-and-stick drawing of the extended salt structure occupying the larger channel. One Na–Cl unit (see the one in yellow) is highlighted as a polyhedral unit. (c) Extended Rb2–Cl salt structural unit forming NaCl-type fragments (top); `cubane'-like fragments formed together with Rb3 (bottom), whereby Rb2 occupies all the corners, Rb3 occupies four of the six faces, while Cl3D occupies the other two faces, and Cl4 occupies eight of the twelve edges. (d) Salt stucture extending along [001], showing the corner-sharing {Na₄Cl₈} units (Rb2 excluded for clarity). (e) Alternating Rb1 and Cl1 sites in the smaller channel.

Figure 5
(a) Partial structure showing the Rb–Na–Cl salt structure along [001], occupying the larger channel. (b) Extended salt structural unit in the larger channel with polyhedral representation showing the corner-sharing {Na₄Cl₈} units. (c) The arrangement of two corner-sharing {Na₄Cl₈} units centered in the faces of a `cubane'-like fragment. (d) Fragment of the Rb–Na–Cl salt structure, showing the polyhedral arrangement of Cl and Na. Displacement ellipsoids are presented at the 90% probability level.

Figure 6
(a) Projected view of a {Na₄Cl₈} unit [displacement ellipsoids as in Fig. 5

(d)]. (b) The octahedral arrangement of Cl3A, Cl3B, Cl3D, and Cl4 in an {Na₄Cl₈} unit. (c) Partial structure showing the lengths between some Cl sites. (d) μ₄-Cl3D-centered Na4 unit with distorted tetrahedral shape.

Transition metals and main-group elements form especially robust clusters and their investigation provides valuable insight into how physicochemical properties evolve going from molecular systems to the solid state (Berry, 1993 ). Much attention has been paid to studies on sodium chloride clusters using theoretical approaches, especially on the structural shapes and relative stabilities in neutral and charged clusters (Zhang & Chen, 2003 ). We hope that the structurally isolated {Na₄Cl₈} units in the title compound can be relevant for the discussion of the nature of chemical bonding for the theoreticians to apply a simple electrostatic model to describe the energies and stabilities of this sodium chloride unit based on inversion pair potentials. Furthermore, controlling the interaction between the two chemically dissimilar structural units (halides and oxides) may give rise to new material design by placing efforts on the targeted growth of salt-inclusion compounds via the careful selection of systems and the use of a mixed alkali halide eutectic flux.

3. Synthesis and crystallization

Single crystals of Rb₉Na₂Cu₆(P₂O₇)₄Cl₇ were grown using a eutectic RbCl/NaCl flux in a fused-silica ampoule. The eutectic flux used was 53% RbCl (Alfa, 99.8%) and 47% NaCl (Strem, 99.999%) by moles (melting point 823.4 K). The reactants were ground and loaded in a nitrogen-blanketed dry box and then sealed under vacuum prior to heating. Crystals were grown by introducing the reactants, i.e. P₄O₁₀ (2.1 mmol, Aldrich, 98+%), Rb₂O (2.1 mmol, Aldrich, 99+%), and CuO (6.3 mmol, Alfa, 99.7%), to the eutectic RbCl/NaCl flux with a flux-to-charge ratio of 3:1. The resulting mixture was loaded into a silica ampoule and the reaction mixture was heated to 923 K at a rate of 2 K min⁻¹, dwelled for 2 d and then cooled slowly to 573 K at a rate of 0.1 K min⁻¹, followed by cooling to room temperature at a rate of 3 K min⁻¹. Irregular-shaped light-green crystals of Rb₉Na₂Cu₆(P₂O₇)₄Cl₇ (Fig. 7) were isolated manually and washed with deionized water using suction filtration methods.

Figure 7
Crystal aggregates of Rb₉Na₂Cu₆(P₂O₇)₄Cl₇ obtained from a RbCl/NaCl eutectic flux.

4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The final Fourier difference synthesis showed the maximum residual electron density of 2.37 e Å⁻³ located at 1.82 Å from Na1 and the minimum of −4.12 e Å⁻³ directly at the Cl3C position. Refinements were carried out in comparison with the parent structure of Rb₉Cu₆(P₂O₇)₄(CuCl₇) (Williams et al., 2013). All positions remained the same up to the point of Cu being exchanged for Na, which, in turn, alters the sites of some Cl atoms as well. The parent structure has the Cu3 atom position at Wyckoff site 4b and is fully occupied. When Cu is exchanged by Na on this site, the Na position changes to Wyckoff site 16l and becomes half-occupied to maintain charge neutrality. This can be attributed to the larger size of sodium needing to shift slightly off the special position into a general position, which disturbs the channel that contains the chloride anions. In the parent structure, Cl1 is positioned at Wyckoff site 16j and corresponds to the disordered Cl3 and Cl4 sites reported herein. Cl3 was split into four sites, Cl3A, Cl3B, Cl3C, and Cl3D, with site occupation factors of 0.167, 0.333, 0.667, and 0.167, adding up to half-occupancy for Cl3, which is half of what is reported in the parent structure. To maintain charge neutrality, Cl4 was added at Wyckoff site 16j with half-occupancy to obtain charge neutrality. It is important to note that in comparison to the parent structure, Cl2 and Cl3 correspond to Cl1 and Cl2 within the structure presented herein. The observed minimum electron density noted above indicates that another spliting of the Cl3C site might be necessary, but the refinement in this case resulted in models that were not meaningful.

Table 2
Experimental details

Crystal data
Chemical formula	Rb₉Na₂Cu₆(P₂O₇)₄Cl₇
M_r	2140.36
Crystal system, space group	Tetragonal, I4/mcm
Temperature (K)	298
a, c (Å)	17.840 (3), 13.483 (3)
V (Å³)	4291.2 (15)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	13.90
Crystal size (mm)	0.09 × 0.07 × 0.05

Data collection
Diffractometer	Bruker D8 Quest Photon 3 CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.849, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	18814, 1105, 1048
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.164, 1.12
No. of reflections	1105
No. of parameters	98
No. of restraints	30
Δρ_max, Δρ_min (e Å⁻³)	2.37, −4.12
Computer programs: APEX3 and SAINT (Bruker, 2017 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), CrystalMaker (Palmer, 2014 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2548269

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989026004287/wm5786sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989026004287/wm5786Isup2.hkl

checkCIF report

Computing details top

Nonarubidium disodium hexacopper(II) tetrakis(pyrophosphate) heptachloride top

Crystal data top

Rb₉Na₂Cu₆(P₂O₇)₄Cl₇	D_x = 3.313 Mg m⁻³
M_r = 2140.36	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4/mcm	Cell parameters from 6572 reflections
a = 17.840 (3) Å	θ = 3.2–26.9°
c = 13.483 (3) Å	µ = 13.90 mm⁻¹
V = 4291.2 (15) Å³	T = 298 K
Z = 4	Block, green
F(000) = 3968	0.09 × 0.07 × 0.05 mm

Data collection top

Bruker D8 Quest Photon 3 CCD diffractometer	1048 reflections with I > 2σ(I)
Radiation source: Incoatec IµS	R_int = 0.058
φ and ω scans	θ_max = 25.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −21→21
T_min = 0.849, T_max = 1.000	k = −21→21
18814 measured reflections	l = −16→16
1105 independent reflections

Refinement top

Refinement on F²	98 parameters
Least-squares matrix: full	30 restraints
R[F² > 2σ(F²)] = 0.063	w = 1/[σ²(F_o²) + (0.0661P)² + 335.4492P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.164	(Δ/σ)_max < 0.001
S = 1.12	Δρ_max = 2.37 e Å⁻³
1105 reflections	Δρ_min = −4.12 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	0.000000	0.000000	0.000000	0.0186 (6)
Rb2	−0.17521 (7)	0.32479 (7)	0.26679 (11)	0.0245 (4)
Rb3	0.00646 (12)	0.27062 (11)	0.500000	0.0417 (6)
Cu1	0.15292 (11)	0.000000	0.250000	0.0137 (4)
Cu2	−0.23588 (10)	0.26412 (10)	0.000000	0.0119 (6)
P1	−0.14115 (13)	0.13979 (13)	0.39130 (16)	0.0065 (5)
O1	−0.1038 (5)	0.1476 (5)	0.500000	0.0084 (18)
O2	−0.0891 (4)	0.1826 (4)	0.3239 (5)	0.0121 (14)
O3	−0.1760 (4)	0.2182 (4)	0.1034 (5)	0.0164 (16)
O4	−0.1452 (4)	0.0559 (4)	0.3735 (5)	0.0151 (15)
Cl1	0.000000	0.000000	0.250000	0.0250 (16)
Cl2	−0.1533 (4)	0.3467 (4)	0.500000	0.0455 (18)
Cl3A	0.500000	0.000000	0.118 (11)	0.107 (8)	0.1667
Cl3D	0.500000	0.000000	0.275 (6)	0.110 (8)	0.1667
Cl3B	0.500000	0.000000	0.388 (6)	0.108 (8)	0.3333
Cl3C	0.500000	0.000000	0.500000	0.118 (8)	0.6666
Cl4	0.3563 (17)	0.000000	0.250000	0.135 (10)	0.5
Na1	0.5772 (9)	0.0772 (9)	0.399 (3)	0.102 (11)	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Rb1	0.0196 (9)	0.0196 (9)	0.0166 (13)	0.000	0.000	0.000
Rb2	0.0275 (6)	0.0275 (6)	0.0186 (8)	0.0074 (6)	−0.0047 (5)	−0.0047 (5)
Rb3	0.0376 (11)	0.0346 (10)	0.0528 (12)	0.0058 (8)	0.000	0.000
Cu1	0.0295 (10)	0.0083 (8)	0.0033 (7)	0.000	0.000	0.0002 (6)
Cu2	0.0168 (8)	0.0168 (8)	0.0020 (10)	0.0113 (10)	0.000	0.000
P1	0.0089 (12)	0.0081 (12)	0.0024 (10)	0.0024 (8)	0.0001 (9)	−0.0002 (9)
O1	0.010 (5)	0.013 (5)	0.002 (4)	0.002 (4)	0.000	0.000
O2	0.014 (3)	0.013 (3)	0.009 (3)	0.004 (3)	0.001 (3)	0.003 (3)
O3	0.033 (4)	0.011 (3)	0.005 (3)	0.010 (3)	−0.001 (3)	−0.002 (3)
O4	0.027 (4)	0.011 (3)	0.007 (3)	−0.002 (3)	−0.004 (3)	−0.003 (3)
Cl1	0.024 (2)	0.024 (2)	0.027 (4)	0.000	0.000	0.000
Cl2	0.058 (3)	0.058 (3)	0.020 (3)	0.014 (4)	0.000	0.000
Cl3A	0.107 (10)	0.107 (10)	0.106 (16)	−0.082 (16)	0.000	0.000
Cl3D	0.110 (10)	0.110 (10)	0.109 (15)	−0.080 (15)	0.000	0.000
Cl3B	0.108 (10)	0.108 (10)	0.106 (15)	−0.083 (14)	0.000	0.000
Cl3C	0.120 (10)	0.120 (10)	0.115 (15)	−0.072 (14)	0.000	0.000
Cl4	0.25 (3)	0.025 (6)	0.130 (17)	0.000	0.000	−0.021 (9)
Na1	0.047 (7)	0.047 (7)	0.21 (3)	0.006 (9)	0.006 (12)	0.006 (12)

Geometric parameters (Å, º) top

Rb1—O1ⁱ	3.220 (9)	Cu1—O4^xx	1.947 (7)
Rb1—O1ⁱⁱ	3.220 (9)	Cu1—O2^xiv	1.950 (7)
Rb1—O1ⁱⁱⁱ	3.220 (9)	Cu1—O2^iv	1.950 (7)
Rb1—O1^iv	3.220 (9)	Cu1—Cl1	2.7281 (19)
Rb1—O4ⁱ	3.257 (7)	Cu2—O3	1.938 (7)
Rb1—O4ⁱⁱ	3.257 (7)	Cu2—O3^ix	1.938 (7)
Rb1—O4^v	3.257 (7)	Cu2—O3^xxi	1.938 (7)
Rb1—O4^vi	3.257 (7)	Cu2—O3^xxii	1.938 (7)
Rb1—O4^vii	3.257 (7)	Cu2—Cl2^xii	2.797 (9)
Rb1—O4^viii	3.257 (7)	P1—O2	1.507 (7)
Rb1—O4ⁱⁱⁱ	3.257 (7)	P1—O4	1.516 (7)
Rb1—O4^iv	3.257 (7)	P1—O3^vi	1.520 (7)
Rb2—O3	2.911 (7)	P1—O1	1.616 (4)
Rb2—O3^ix	2.911 (7)	Cl3A—Cl3B^xxiii	0.1 (2)
Rb2—O2	3.064 (6)	Cl3A—Cl3D^xxiii	1.43 (17)
Rb2—O2^ix	3.064 (6)	Cl3A—Cl3C^xxiv	1.60 (15)
Rb2—Cl4^x	3.184 (6)	Cl3A—Na1^xxv	1.96 (3)
Rb2—Cl4^xi	3.184 (6)	Cl3A—Na1^xxiii	1.96 (3)
Rb2—Cl2	3.193 (2)	Cl3A—Cl3D	2.12 (17)
Rb2—O3^vi	3.271 (8)	Cl3D—Cl3D^xxiii	0.69 (16)
Rb2—O3^xii	3.271 (8)	Cl3D—Cl3B	1.52 (11)
Rb2—Na1^xiii	3.33 (3)	Cl3D—Cl3B^xxiii	2.21 (11)
Rb2—P1	3.752 (3)	Cl3D—Na1^xxvi	2.56 (6)
Rb2—P1^ix	3.752 (3)	Cl3D—Na1	2.56 (6)
Rb3—O1	2.947 (10)	Cl3D—Na1^xxv	3.05 (7)
Rb3—O4^xiv	2.949 (7)	Cl3D—Na1^xxiii	3.05 (7)
Rb3—O4^xv	2.949 (7)	Cl3B—Cl3C	1.51 (7)
Rb3—Cl2	3.156 (4)	Cl3B—Na1^xxvi	1.95 (2)
Rb3—Na1^xvi	3.289 (18)	Cl3B—Na1	1.95 (2)
Rb3—Na1^xvii	3.289 (18)	Cl3C—Na1^xviii	2.38 (3)
Rb3—O2^xviii	3.318 (7)	Cl3C—Na1^xxvi	2.38 (3)
Rb3—O2	3.318 (7)	Cl3C—Na1^xxvii	2.38 (3)
Rb3—O3^xix	3.459 (8)	Cl3C—Na1	2.38 (3)
Rb3—O3ⁱⁱ	3.459 (8)	Cl4—Na1^xxvi	2.71 (3)
Rb3—P1^xv	3.625 (3)	Cl4—Na1^xxv	2.71 (3)
Rb3—P1^xiv	3.625 (3)	Na1—Na1^xviii	2.72 (8)
Cu1—O4ⁱⁱ	1.947 (7)	Na1—Na1^xxvi	3.90 (5)

O1ⁱ—Rb1—O1ⁱⁱ	180.0 (3)	O3^vi—P1—Rb2	60.1 (3)
O1ⁱ—Rb1—O1ⁱⁱⁱ	90.0	O1—P1—Rb2	113.3 (3)
O1ⁱⁱ—Rb1—O1ⁱⁱⁱ	90.0	Rb3^x—P1—Rb2	130.91 (8)
O1ⁱ—Rb1—O1^iv	90.0	O2—P1—Rb3	59.7 (3)
O1ⁱⁱ—Rb1—O1^iv	90.0	O4—P1—Rb3	134.2 (3)
O1ⁱⁱⁱ—Rb1—O1^iv	180.0 (3)	O3^vi—P1—Rb3	110.2 (3)
O1ⁱ—Rb1—O4ⁱ	44.93 (16)	O1—P1—Rb3	46.6 (3)
O1ⁱⁱ—Rb1—O4ⁱ	135.07 (16)	Rb3^x—P1—Rb3	133.35 (7)
O1ⁱⁱⁱ—Rb1—O4ⁱ	61.70 (18)	Rb2—P1—Rb3	75.25 (6)
O1^iv—Rb1—O4ⁱ	118.30 (18)	O2—P1—Rb1ⁱⁱ	99.0 (3)
O1ⁱ—Rb1—O4ⁱⁱ	135.07 (16)	O4—P1—Rb1ⁱⁱ	56.6 (3)
O1ⁱⁱ—Rb1—O4ⁱⁱ	44.93 (16)	O3^vi—P1—Rb1ⁱⁱ	148.4 (3)
O1ⁱⁱⁱ—Rb1—O4ⁱⁱ	118.30 (18)	O1—P1—Rb1ⁱⁱ	55.9 (3)
O1^iv—Rb1—O4ⁱⁱ	61.70 (18)	Rb3^x—P1—Rb1ⁱⁱ	80.63 (5)
O4ⁱ—Rb1—O4ⁱⁱ	180.0 (3)	Rb2—P1—Rb1ⁱⁱ	148.13 (8)
O1ⁱ—Rb1—O4^v	61.70 (18)	Rb3—P1—Rb1ⁱⁱ	78.33 (5)
O1ⁱⁱ—Rb1—O4^v	118.30 (18)	O2—P1—Rb2^xii	96.0 (3)
O1ⁱⁱⁱ—Rb1—O4^v	135.07 (16)	O4—P1—Rb2^xii	91.9 (3)
O1^iv—Rb1—O4^v	44.93 (16)	O3^vi—P1—Rb2^xii	37.8 (3)
O4ⁱ—Rb1—O4^v	74.10 (11)	O1—P1—Rb2^xii	144.6 (3)
O4ⁱⁱ—Rb1—O4^v	105.90 (11)	Rb3^x—P1—Rb2^xii	78.18 (6)
O1ⁱ—Rb1—O4^vi	118.30 (18)	Rb2—P1—Rb2^xii	58.99 (5)
O1ⁱⁱ—Rb1—O4^vi	61.70 (18)	Rb3—P1—Rb2^xii	132.91 (7)
O1ⁱⁱⁱ—Rb1—O4^vi	44.93 (16)	Rb1ⁱⁱ—P1—Rb2^xii	148.52 (7)
O1^iv—Rb1—O4^vi	135.07 (16)	P1^xviii—O1—P1	130.2 (6)
O4ⁱ—Rb1—O4^vi	105.90 (11)	P1^xviii—O1—Rb3	109.9 (3)
O4ⁱⁱ—Rb1—O4^vi	74.10 (11)	P1—O1—Rb3	109.9 (3)
O4^v—Rb1—O4^vi	180.0 (3)	P1^xviii—O1—Rb1ⁱⁱ	99.6 (3)
O1ⁱ—Rb1—O4^vii	135.07 (16)	P1—O1—Rb1ⁱⁱ	99.6 (3)
O1ⁱⁱ—Rb1—O4^vii	44.93 (16)	Rb3—O1—Rb1ⁱⁱ	103.0 (3)
O1ⁱⁱⁱ—Rb1—O4^vii	118.30 (18)	P1—O2—Cu1^x	132.3 (4)
O1^iv—Rb1—O4^vii	61.70 (18)	P1—O2—Rb2	105.2 (3)
O4ⁱ—Rb1—O4^vii	116.9 (2)	Cu1^x—O2—Rb2	120.3 (3)
O4ⁱⁱ—Rb1—O4^vii	63.1 (2)	P1—O2—Rb3	97.2 (3)
O4^v—Rb1—O4^vii	74.10 (11)	Cu1^x—O2—Rb3	94.3 (2)
O4^vi—Rb1—O4^vii	105.90 (11)	Rb2—O2—Rb3	92.62 (18)
O1ⁱ—Rb1—O4^viii	44.93 (16)	P1^vi—O3—Cu2	130.6 (4)
O1ⁱⁱ—Rb1—O4^viii	135.07 (16)	P1^vi—O3—Rb2	123.6 (4)
O1ⁱⁱⁱ—Rb1—O4^viii	61.70 (18)	Cu2—O3—Rb2	105.7 (3)
O1^iv—Rb1—O4^viii	118.30 (18)	P1^vi—O3—Rb2^xii	96.2 (3)
O4ⁱ—Rb1—O4^viii	63.1 (2)	Cu2—O3—Rb2^xii	92.1 (3)
O4ⁱⁱ—Rb1—O4^viii	116.9 (2)	Rb2—O3—Rb2^xii	75.63 (17)
O4^v—Rb1—O4^viii	105.90 (11)	P1^vi—O3—Rb3ⁱⁱ	83.8 (3)
O4^vi—Rb1—O4^viii	74.10 (11)	Cu2—O3—Rb3ⁱⁱ	94.5 (3)
O4^vii—Rb1—O4^viii	180.0 (3)	Rb2—O3—Rb3ⁱⁱ	97.1 (2)
O1ⁱ—Rb1—O4ⁱⁱⁱ	118.30 (18)	Rb2^xii—O3—Rb3ⁱⁱ	171.3 (2)
O1ⁱⁱ—Rb1—O4ⁱⁱⁱ	61.70 (18)	P1—O4—Cu1^xx	130.1 (4)
O1ⁱⁱⁱ—Rb1—O4ⁱⁱⁱ	44.93 (16)	P1—O4—Rb3^x	103.9 (4)
O1^iv—Rb1—O4ⁱⁱⁱ	135.07 (16)	Cu1^xx—O4—Rb3^x	106.7 (3)
O4ⁱ—Rb1—O4ⁱⁱⁱ	74.10 (11)	P1—O4—Rb1ⁱⁱ	100.5 (3)
O4ⁱⁱ—Rb1—O4ⁱⁱⁱ	105.90 (11)	Cu1^xx—O4—Rb1ⁱⁱ	110.3 (3)
O4^v—Rb1—O4ⁱⁱⁱ	116.9 (2)	Rb3^x—O4—Rb1ⁱⁱ	102.07 (19)
O4^vi—Rb1—O4ⁱⁱⁱ	63.1 (2)	Cu1—Cl1—Cu1^xiv	90.0
O4^vii—Rb1—O4ⁱⁱⁱ	74.10 (11)	Cu1—Cl1—Cu1^x	90.0
O4^viii—Rb1—O4ⁱⁱⁱ	105.90 (11)	Cu1^xiv—Cl1—Cu1^x	180.0
O1ⁱ—Rb1—O4^iv	61.70 (18)	Cu1—Cl1—Cu1^xx	180.0
O1ⁱⁱ—Rb1—O4^iv	118.30 (18)	Cu1^xiv—Cl1—Cu1^xx	90.0
O1ⁱⁱⁱ—Rb1—O4^iv	135.07 (16)	Cu1^x—Cl1—Cu1^xx	90.0
O1^iv—Rb1—O4^iv	44.93 (16)	Cu1—Cl1—Rb1	90.0
O4ⁱ—Rb1—O4^iv	105.90 (11)	Cu1^xiv—Cl1—Rb1	90.0
O4ⁱⁱ—Rb1—O4^iv	74.10 (11)	Cu1^x—Cl1—Rb1	90.0
O4^v—Rb1—O4^iv	63.1 (2)	Cu1^xx—Cl1—Rb1	90.0
O4^vi—Rb1—O4^iv	116.9 (2)	Cu1—Cl1—Rb1ⁱⁱ	90.0
O4^vii—Rb1—O4^iv	105.90 (11)	Cu1^xiv—Cl1—Rb1ⁱⁱ	90.0
O4^viii—Rb1—O4^iv	74.10 (11)	Cu1^x—Cl1—Rb1ⁱⁱ	90.0
O4ⁱⁱⁱ—Rb1—O4^iv	180.0 (3)	Cu1^xx—Cl1—Rb1ⁱⁱ	90.0
O3—Rb2—O3^ix	54.6 (3)	Rb1—Cl1—Rb1ⁱⁱ	180.0
O3—Rb2—O2	69.62 (18)	Rb3^xxviii—Cl2—Rb3	141.0 (3)
O3^ix—Rb2—O2	120.9 (2)	Rb3^xxviii—Cl2—Rb2	93.32 (3)
O3—Rb2—O2^ix	120.9 (2)	Rb3—Cl2—Rb2	93.32 (3)
O3^ix—Rb2—O2^ix	69.62 (18)	Rb3^xxviii—Cl2—Rb2^xviii	93.32 (3)
O2—Rb2—O2^ix	140.1 (3)	Rb3—Cl2—Rb2^xviii	93.32 (3)
O3—Rb2—Cl4^x	93.8 (4)	Rb2—Cl2—Rb2^xviii	160.0 (3)
O3^ix—Rb2—Cl4^x	126.05 (16)	Cl3B^xxiii—Cl3A—Cl3D^xxiii	180.00 (4)
O2—Rb2—Cl4^x	70.8 (5)	Cl3B^xxiii—Cl3A—Cl3C^xxiv	0.00 (2)
O2^ix—Rb2—Cl4^x	137.9 (5)	Cl3D^xxiii—Cl3A—Cl3C^xxiv	180.0
O3—Rb2—Cl4^xi	126.05 (16)	Cl3B^xxiii—Cl3A—Na1^xxv	83 (4)
O3^ix—Rb2—Cl4^xi	93.8 (4)	Cl3D^xxiii—Cl3A—Na1^xxv	97 (4)
O2—Rb2—Cl4^xi	137.9 (5)	Cl3C^xxiv—Cl3A—Na1^xxv	83 (4)
O2^ix—Rb2—Cl4^xi	70.8 (5)	Cl3B^xxiii—Cl3A—Na1^xxiii	83 (4)
Cl4^x—Rb2—Cl4^xi	69.4 (11)	Cl3D^xxiii—Cl3A—Na1^xxiii	97 (4)
O3—Rb2—Cl2	145.72 (17)	Cl3C^xxiv—Cl3A—Na1^xxiii	83 (4)
O3^ix—Rb2—Cl2	145.71 (17)	Na1^xxv—Cl3A—Na1^xxiii	166 (9)
O2—Rb2—Cl2	78.02 (13)	Cl3B^xxiii—Cl3A—Cl3D	180.00 (3)
O2^ix—Rb2—Cl2	78.02 (13)	Cl3D^xxiii—Cl3A—Cl3D	0.000 (3)
Cl4^x—Rb2—Cl2	85.87 (15)	Cl3C^xxiv—Cl3A—Cl3D	180.0
Cl4^xi—Rb2—Cl2	85.87 (15)	Na1^xxv—Cl3A—Cl3D	97 (4)
O3—Rb2—O3^vi	82.8 (2)	Na1^xxiii—Cl3A—Cl3D	97 (4)
O3^ix—Rb2—O3^vi	104.37 (17)	Cl3D^xxiii—Cl3D—Cl3A^xxiii	180.00 (2)
O2—Rb2—O3^vi	46.45 (17)	Cl3D^xxiii—Cl3D—Cl3B	180.000 (12)
O2^ix—Rb2—O3^vi	94.48 (18)	Cl3A^xxiii—Cl3D—Cl3B	0.000 (11)
Cl4^x—Rb2—O3^vi	114.3 (5)	Cl3D^xxiii—Cl3D—Cl3A	0.000 (13)
Cl4^xi—Rb2—O3^vi	151.18 (16)	Cl3A^xxiii—Cl3D—Cl3A	180.0
Cl2—Rb2—O3^vi	66.49 (19)	Cl3B—Cl3D—Cl3A	180.000 (16)
O3—Rb2—O3^xii	104.37 (17)	Cl3D^xxiii—Cl3D—Cl3B^xxiii	0.000 (10)
O3^ix—Rb2—O3^xii	82.8 (2)	Cl3A^xxiii—Cl3D—Cl3B^xxiii	180.000 (16)
O2—Rb2—O3^xii	94.48 (18)	Cl3B—Cl3D—Cl3B^xxiii	180.0
O2^ix—Rb2—O3^xii	46.45 (17)	Cl3A—Cl3D—Cl3B^xxiii	0.000 (3)
Cl4^x—Rb2—O3^xii	151.18 (16)	Cl3D^xxiii—Cl3D—Na1^xxvi	130.5 (16)
Cl4^xi—Rb2—O3^xii	114.3 (5)	Cl3A^xxiii—Cl3D—Na1^xxvi	49.5 (16)
Cl2—Rb2—O3^xii	66.49 (19)	Cl3B—Cl3D—Na1^xxvi	49.5 (16)
O3^vi—Rb2—O3^xii	48.2 (2)	Cl3A—Cl3D—Na1^xxvi	130.5 (16)
O3—Rb2—Na1^xiii	80.6 (5)	Cl3B^xxiii—Cl3D—Na1^xxvi	130.5 (16)
O3^ix—Rb2—Na1^xiii	80.6 (5)	Cl3D^xxiii—Cl3D—Na1	130.5 (16)
O2—Rb2—Na1^xiii	109.88 (13)	Cl3A^xxiii—Cl3D—Na1	49.5 (16)
O2^ix—Rb2—Na1^xiii	109.88 (13)	Cl3B—Cl3D—Na1	49.5 (16)
Cl4^x—Rb2—Na1^xiii	49.1 (5)	Cl3A—Cl3D—Na1	130.5 (16)
Cl4^xi—Rb2—Na1^xiii	49.1 (5)	Cl3B^xxiii—Cl3D—Na1	130.5 (16)
Cl2—Rb2—Na1^xiii	122.1 (6)	Na1^xxvi—Cl3D—Na1	99 (3)
O3^vi—Rb2—Na1^xiii	155.17 (18)	Cl3D^xxiii—Cl3D—Na1^xxv	39.6 (11)
O3^xii—Rb2—Na1^xiii	155.17 (18)	Cl3A^xxiii—Cl3D—Na1^xxv	140.4 (11)
O3—Rb2—P1	76.40 (14)	Cl3B—Cl3D—Na1^xxv	140.4 (11)
O3^ix—Rb2—P1	116.12 (17)	Cl3A—Cl3D—Na1^xxv	39.6 (11)
O2—Rb2—P1	22.79 (13)	Cl3B^xxiii—Cl3D—Na1^xxv	39.6 (11)
O2^ix—Rb2—P1	117.55 (14)	Na1^xxvi—Cl3D—Na1^xxv	120.0 (9)
Cl4^x—Rb2—P1	91.6 (5)	Na1—Cl3D—Na1^xxv	120.0 (9)
Cl4^xi—Rb2—P1	150.1 (3)	Cl3D^xxiii—Cl3D—Na1^xxiii	39.6 (11)
Cl2—Rb2—P1	69.35 (11)	Cl3A^xxiii—Cl3D—Na1^xxiii	140.4 (11)
O3^vi—Rb2—P1	23.75 (12)	Cl3B—Cl3D—Na1^xxiii	140.4 (11)
O3^xii—Rb2—P1	71.69 (13)	Cl3A—Cl3D—Na1^xxiii	39.6 (11)
Na1^xiii—Rb2—P1	132.57 (4)	Cl3B^xxiii—Cl3D—Na1^xxiii	39.6 (11)
O3—Rb2—P1^ix	116.12 (17)	Na1^xxvi—Cl3D—Na1^xxiii	120.0 (9)
O3^ix—Rb2—P1^ix	76.40 (14)	Na1—Cl3D—Na1^xxiii	120.0 (9)
O2—Rb2—P1^ix	117.55 (14)	Na1^xxv—Cl3D—Na1^xxiii	79 (2)
O2^ix—Rb2—P1^ix	22.79 (13)	Cl3A^xxiii—Cl3B—Cl3C	180.00 (19)
Cl4^x—Rb2—P1^ix	150.1 (3)	Cl3A^xxiii—Cl3B—Cl3D	0.0 (2)
Cl4^xi—Rb2—P1^ix	91.6 (5)	Cl3C—Cl3B—Cl3D	180.000 (12)
Cl2—Rb2—P1^ix	69.35 (11)	Cl3A^xxiii—Cl3B—Na1^xxvi	94 (3)
O3^vi—Rb2—P1^ix	71.69 (13)	Cl3C—Cl3B—Na1^xxvi	86 (2)
O3^xii—Rb2—P1^ix	23.75 (12)	Cl3D—Cl3B—Na1^xxvi	94 (2)
Na1^xiii—Rb2—P1^ix	132.57 (4)	Cl3A^xxiii—Cl3B—Na1	94 (2)
P1—Rb2—P1^ix	94.86 (8)	Cl3C—Cl3B—Na1	86 (2)
O1—Rb3—O4^xiv	68.6 (2)	Cl3D—Cl3B—Na1	94 (2)
O1—Rb3—O4^xv	68.6 (2)	Na1^xxvi—Cl3B—Na1	172 (5)
O4^xiv—Rb3—O4^xv	70.6 (3)	Cl3A^xxiii—Cl3B—Cl3D^xxiii	0.0 (2)
O1—Rb3—Cl2	73.6 (2)	Cl3C—Cl3B—Cl3D^xxiii	180.000 (11)
O4^xiv—Rb3—Cl2	126.64 (18)	Cl3D—Cl3B—Cl3D^xxiii	0.000 (3)
O4^xv—Rb3—Cl2	126.64 (18)	Na1^xxvi—Cl3B—Cl3D^xxiii	94 (2)
O1—Rb3—Na1^xvi	150.6 (5)	Na1—Cl3B—Cl3D^xxiii	94 (2)
O4^xiv—Rb3—Na1^xvi	138.7 (4)	Cl3B—Cl3C—Cl3A^xxiii	0.000 (6)
O4^xv—Rb3—Na1^xvi	105.8 (6)	Cl3B—Cl3C—Cl3A^xxix	180.00 (3)
Cl2—Rb3—Na1^xvi	89.5 (4)	Cl3A^xxiii—Cl3C—Cl3A^xxix	180.000 (16)
O1—Rb3—Na1^xvii	150.6 (5)	Cl3B—Cl3C—Na1^xviii	124.9 (8)
O4^xiv—Rb3—Na1^xvii	105.8 (6)	Cl3A^xxiii—Cl3C—Na1^xviii	124.9 (8)
O4^xv—Rb3—Na1^xvii	138.7 (4)	Cl3A^xxix—Cl3C—Na1^xviii	55.1 (8)
Cl2—Rb3—Na1^xvii	89.5 (4)	Cl3B—Cl3C—Na1^xxvi	55.1 (8)
Na1^xvi—Rb3—Na1^xvii	48.9 (12)	Cl3A^xxiii—Cl3C—Na1^xxvi	55.1 (8)
O1—Rb3—O2^xviii	45.94 (12)	Cl3A^xxix—Cl3C—Na1^xxvi	124.9 (8)
O4^xiv—Rb3—O2^xviii	102.02 (18)	Na1^xviii—Cl3C—Na1^xxvi	180.0 (6)
O4^xv—Rb3—O2^xviii	51.76 (18)	Cl3B—Cl3C—Na1^xxvii	124.9 (8)
Cl2—Rb3—O2^xviii	74.91 (16)	Cl3A^xxiii—Cl3C—Na1^xxvii	124.9 (8)
Na1^xvi—Rb3—O2^xviii	107.0 (6)	Cl3A^xxix—Cl3C—Na1^xxvii	55.1 (8)
Na1^xvii—Rb3—O2^xviii	152.2 (6)	Na1^xviii—Cl3C—Na1^xxvii	110.1 (17)
O1—Rb3—O2	45.94 (12)	Na1^xxvi—Cl3C—Na1^xxvii	69.9 (17)
O4^xiv—Rb3—O2	51.76 (18)	Cl3B—Cl3C—Na1	55.1 (8)
O4^xv—Rb3—O2	102.03 (18)	Cl3A^xxiii—Cl3C—Na1	55.1 (8)
Cl2—Rb3—O2	74.91 (16)	Cl3A^xxix—Cl3C—Na1	124.9 (8)
Na1^xvi—Rb3—O2	152.1 (6)	Na1^xviii—Cl3C—Na1	69.9 (17)
Na1^xvii—Rb3—O2	107.0 (6)	Na1^xxvi—Cl3C—Na1	110.1 (17)
O2^xviii—Rb3—O2	91.4 (2)	Na1^xxvii—Cl3C—Na1	180.0
O1—Rb3—O3^xix	112.5 (2)	Na1^xxvi—Cl4—Na1^xxv	128.1 (15)
O4^xiv—Rb3—O3^xix	76.46 (18)	Na1^xxvi—Cl4—Rb2^xxx	68.3 (5)
O4^xv—Rb3—O3^xix	45.57 (18)	Na1^xxv—Cl4—Rb2^xxx	121.6 (6)
Cl2—Rb3—O3^xix	154.91 (12)	Na1^xxvi—Cl4—Rb2^xiv	121.6 (6)
Na1^xvi—Rb3—O3^xix	73.8 (4)	Na1^xxv—Cl4—Rb2^xiv	68.3 (5)
Na1^xvii—Rb3—O3^xix	93.1 (4)	Rb2^xxx—Cl4—Rb2^xiv	159.7 (11)
O2^xviii—Rb3—O3^xix	91.89 (17)	Na1^xxvi—Cl4—Rb3^iv	150.6 (5)
O2—Rb3—O3^xix	127.56 (17)	Na1^xxv—Cl4—Rb3^iv	59.3 (5)
O1—Rb3—O3ⁱⁱ	112.5 (2)	Rb2^xxx—Cl4—Rb3^iv	83.9 (3)
O4^xiv—Rb3—O3ⁱⁱ	45.57 (18)	Rb2^xiv—Cl4—Rb3^iv	87.8 (3)
O4^xv—Rb3—O3ⁱⁱ	76.46 (18)	Na1^xxvi—Cl4—Rb3^xv	59.3 (5)
Cl2—Rb3—O3ⁱⁱ	154.91 (13)	Na1^xxv—Cl4—Rb3^xv	150.6 (5)
Na1^xvi—Rb3—O3ⁱⁱ	93.1 (4)	Rb2^xxx—Cl4—Rb3^xv	87.8 (3)
Na1^xvii—Rb3—O3ⁱⁱ	73.8 (4)	Rb2^xiv—Cl4—Rb3^xv	83.9 (3)
O2^xviii—Rb3—O3ⁱⁱ	127.56 (17)	Rb3^iv—Cl4—Rb3^xv	131.2 (8)
O2—Rb3—O3ⁱⁱ	91.89 (17)	Cl3B—Na1—Cl3A^xxiii	3 (6)
O3^xix—Rb3—O3ⁱⁱ	47.5 (2)	Cl3B—Na1—Cl3C	39 (2)
O1—Rb3—P1^xv	87.92 (17)	Cl3A^xxiii—Na1—Cl3C	42 (4)
O4^xiv—Rb3—P1^xv	63.49 (14)	Cl3B—Na1—Cl3D	36 (3)
O4^xv—Rb3—P1^xv	23.96 (14)	Cl3A^xxiii—Na1—Cl3D	34 (5)
Cl2—Rb3—P1^xv	150.05 (11)	Cl3C—Na1—Cl3D	75.5 (15)
Na1^xvi—Rb3—P1^xv	96.1 (5)	Cl3B—Na1—Cl4^xxvi	84 (2)
Na1^xvii—Rb3—P1^xv	116.2 (4)	Cl3A^xxiii—Na1—Cl4^xxvi	82 (3)
O2^xviii—Rb3—P1^xv	75.31 (12)	Cl3C—Na1—Cl4^xxvi	112.6 (8)
O2—Rb3—P1^xv	108.96 (12)	Cl3D—Na1—Cl4^xxvi	58.7 (12)
O3^xix—Rb3—P1^xv	24.64 (12)	Cl3B—Na1—Cl4^xxiii	84 (2)
O3ⁱⁱ—Rb3—P1^xv	54.33 (12)	Cl3A^xxiii—Na1—Cl4^xxiii	82 (3)
O1—Rb3—P1^xiv	87.92 (17)	Cl3C—Na1—Cl4^xxiii	112.6 (8)
O4^xiv—Rb3—P1^xiv	23.96 (14)	Cl3D—Na1—Cl4^xxiii	58.7 (12)
O4^xv—Rb3—P1^xiv	63.49 (14)	Cl4^xxvi—Na1—Cl4^xxiii	84.0 (13)
Cl2—Rb3—P1^xiv	150.05 (11)	Cl3B—Na1—Na1^xviii	94 (2)
Na1^xvi—Rb3—P1^xiv	116.2 (4)	Cl3A^xxiii—Na1—Na1^xviii	97 (4)
Na1^xvii—Rb3—P1^xiv	96.1 (5)	Cl3C—Na1—Na1^xviii	55.1 (8)
O2^xviii—Rb3—P1^xiv	108.96 (12)	Cl3D—Na1—Na1^xviii	130.5 (16)
O2—Rb3—P1^xiv	75.31 (12)	Cl4^xxvi—Na1—Na1^xviii	137.9 (6)
O3^xix—Rb3—P1^xiv	54.33 (12)	Cl4^xxiii—Na1—Na1^xviii	137.9 (6)
O3ⁱⁱ—Rb3—P1^xiv	24.64 (12)	Cl3B—Na1—Cl3D^xxiii	46 (3)
P1^xv—Rb3—P1^xiv	47.69 (8)	Cl3A^xxiii—Na1—Cl3D^xxiii	43 (4)
O4ⁱⁱ—Cu1—O4^xx	171.8 (5)	Cl3C—Na1—Cl3D^xxiii	85.3 (12)
O4ⁱⁱ—Cu1—O2^xiv	92.2 (3)	Cl3D—Na1—Cl3D^xxiii	10 (2)
O4^xx—Cu1—O2^xiv	90.0 (3)	Cl4^xxvi—Na1—Cl3D^xxiii	52.9 (10)
O4ⁱⁱ—Cu1—O2^iv	90.0 (3)	Cl4^xxiii—Na1—Cl3D^xxiii	52.9 (10)
O4^xx—Cu1—O2^iv	92.2 (3)	Na1^xviii—Na1—Cl3D^xxiii	140.4 (11)
O2^xiv—Cu1—O2^iv	148.5 (4)	Cl3B—Na1—Rb3^xxxi	110.0 (11)
O4ⁱⁱ—Cu1—Cl1	85.9 (2)	Cl3A^xxiii—Na1—Rb3^xxxi	111.1 (18)
O4^xx—Cu1—Cl1	85.9 (2)	Cl3C—Na1—Rb3^xxxi	91.1 (8)
O2^xiv—Cu1—Cl1	105.8 (2)	Cl3D—Na1—Rb3^xxxi	120.4 (5)
O2^iv—Cu1—Cl1	105.8 (2)	Cl4^xxvi—Na1—Rb3^xxxi	153.5 (11)
O4ⁱⁱ—Cu1—Rb3^xv	141.1 (2)	Cl4^xxiii—Na1—Rb3^xxxi	75.6 (5)
O4^xx—Cu1—Rb3^xv	45.3 (2)	Na1^xviii—Na1—Rb3^xxxi	65.5 (6)
O2^xiv—Cu1—Rb3^xv	56.4 (2)	Cl3D^xxiii—Na1—Rb3^xxxi	121.2 (5)
O2^iv—Cu1—Rb3^xv	105.5 (2)	Cl3B—Na1—Rb3^xxxii	110.0 (11)
Cl1—Cu1—Rb3^xv	121.90 (3)	Cl3A^xxiii—Na1—Rb3^xxxii	111.1 (18)
O4ⁱⁱ—Cu1—Rb3^iv	45.3 (2)	Cl3C—Na1—Rb3^xxxii	91.1 (8)
O4^xx—Cu1—Rb3^iv	141.1 (2)	Cl3D—Na1—Rb3^xxxii	120.4 (5)
O2^xiv—Cu1—Rb3^iv	105.5 (2)	Cl4^xxvi—Na1—Rb3^xxxii	75.6 (5)
O2^iv—Cu1—Rb3^iv	56.4 (2)	Cl4^xxiii—Na1—Rb3^xxxii	153.5 (11)
Cl1—Cu1—Rb3^iv	121.90 (3)	Na1^xviii—Na1—Rb3^xxxii	65.5 (6)
Rb3^xv—Cu1—Rb3^iv	116.19 (7)	Cl3D^xxiii—Na1—Rb3^xxxii	121.2 (5)
O3—Cu2—O3^ix	87.1 (4)	Rb3^xxxi—Na1—Rb3^xxxii	117.5 (10)
O3—Cu2—O3^xxi	169.6 (5)	Cl3B—Na1—Rb2^xiii	134 (3)
O3^ix—Cu2—O3^xxi	92.0 (4)	Cl3A^xxiii—Na1—Rb2^xiii	131 (5)
O3—Cu2—O3^xxii	92.0 (4)	Cl3C—Na1—Rb2^xiii	172.8 (14)
O3^ix—Cu2—O3^xxii	169.6 (5)	Cl3D—Na1—Rb2^xiii	97.3 (18)
O3^xxi—Cu2—O3^xxii	87.1 (4)	Cl4^xxvi—Na1—Rb2^xiii	62.6 (7)
O3—Cu2—Cl2^xii	95.2 (2)	Cl4^xxiii—Na1—Rb2^xiii	62.6 (7)
O3^ix—Cu2—Cl2^xii	95.2 (2)	Na1^xviii—Na1—Rb2^xiii	132.1 (6)
O3^xxi—Cu2—Cl2^xii	95.2 (2)	Cl3D^xxiii—Na1—Rb2^xiii	87.5 (14)
O3^xxii—Cu2—Cl2^xii	95.2 (2)	Rb3^xxxi—Na1—Rb2^xiii	92.7 (5)
O2—P1—O4	115.7 (4)	Rb3^xxxii—Na1—Rb2^xiii	92.7 (5)
O2—P1—O3^vi	111.7 (4)	Cl3B—Na1—Na1^xxvi	4 (2)
O4—P1—O3^vi	112.6 (4)	Cl3A^xxiii—Na1—Na1^xxvi	7 (4)
O2—P1—O1	104.4 (4)	Cl3C—Na1—Na1^xxvi	34.9 (8)
O4—P1—O1	104.4 (4)	Cl3D—Na1—Na1^xxvi	40.5 (16)
O3^vi—P1—O1	107.0 (4)	Cl4^xxvi—Na1—Na1^xxvi	87.1 (7)
O2—P1—Rb3^x	165.7 (3)	Cl4^xxiii—Na1—Na1^xxvi	87.1 (7)
O4—P1—Rb3^x	52.2 (3)	Na1^xviii—Na1—Na1^xxvi	89.998 (3)
O3^vi—P1—Rb3^x	71.6 (3)	Cl3D^xxiii—Na1—Na1^xxvi	50.4 (11)
O1—P1—Rb3^x	87.3 (3)	Rb3^xxxi—Na1—Na1^xxvi	108.2 (4)
O2—P1—Rb2	52.0 (3)	Rb3^xxxii—Na1—Na1^xxvi	108.2 (4)
O4—P1—Rb2	142.1 (3)	Rb2^xiii—Na1—Na1^xxvi	137.9 (6)

Symmetry codes: (i) x, −y, z−1/2; (ii) −x, y, −z+1/2; (iii) −y, −x, z−1/2; (iv) y, x, −z+1/2; (v) y, x, z−1/2; (vi) −y, −x, −z+1/2; (vii) −x, y, z−1/2; (viii) x, −y, −z+1/2; (ix) y−1/2, x+1/2, z; (x) −y, x, z; (xi) x−1/2, y+1/2, −z+1/2; (xii) −x−1/2, −y+1/2, −z+1/2; (xiii) −x+1/2, −y+1/2, −z+1/2; (xiv) y, −x, z; (xv) y, −x, −z+1; (xvi) y, −x+1, −z+1; (xvii) y, −x+1, z; (xviii) x, y, −z+1; (xix) −x, y, z+1/2; (xx) −x, −y, z; (xxi) y−1/2, x+1/2, −z; (xxii) x, y, −z; (xxiii) y+1/2, −x+1/2, −z+1/2; (xxiv) −y+1/2, x−1/2, z−1/2; (xxv) −y+1/2, x−1/2, −z+1/2; (xxvi) −x+1, −y, z; (xxvii) −x+1, −y, −z+1; (xxviii) y−1/2, x+1/2, −z+1; (xxix) −y+1/2, x−1/2, z+1/2; (xxx) x+1/2, y−1/2, −z+1/2; (xxxi) x+1/2, −y+1/2, z; (xxxii) −y+1, x, z.

Acknowledgements

The Division of Science, Mathematics and Technology at Governors State University and the Illinois Louis Stokes Alliance for Minority Participation (ILSAMP) program are gratefully acknowledged for their support. Special thanks are due to Dr. Colin D. McMillen at Clemson University for X-ray crystallography expertise.

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