K(Na,K)Na₂[Cu₂(SO₄)₄]: a new highly porous anhydrous sulfate and evaluation of possible ion migration pathways

Alkali copper sulfates form a rapidly developing family of inorganics. Herein, we report synthesis and crystal structure, and evaluate possible ion migration pathways for a novel Na-K-Cu anhydrous sulfate, K(Na,K)Na₂[Cu₂(SO₄)₄]. The CuO₇ and SO₄ polyhedra share common vertices and edges to form [Cu₂(SO₄)₄]⁴⁻ wide ribbons, which link to each other via common oxygen atoms forming the host part of the structure. Four guest alkali sites are occupied by solely K⁺, mixture of K⁺ and Na⁺, and solely Na⁺, which agrees well with the size of the cavities. The crystal structure of K(Na,K)Na₂[Cu₂(SO₄)₄] contains two symmetry-independent Cu sites with [4+1+(2)] coordination environments. The overall coordination polyhedra of Cu²⁺ can be considered as `octahedra with one split vertex'. A similar coordination mode was observed also in some other multinary copper sulfates, mostly of the mineral world. These coordination modes were reviewed and five types of CuO₇ polyhedra are identified. CuO₇ polyhedra are almost restricted to copper sulfates and phosphates. It was found that a larger amount of the smaller SO₄²⁻ and PO₄³⁻ anions can cluster around a single Cu²⁺ cation; in addition, for such relatively small anions, both mono (κ¹) and bidentate (κ²) coordination modes to the Cu²⁺ are possible. The correlation between crystallographic characteristics and bond valence energies showed that the new copper sulfate framework, [Cu₂(SO₄)₄]⁴⁻, contains one interconnected path suitable for Na⁺ mobility at tolerable activation energies and that K(Na,K)Na₂[Cu₂(SO₄)₄] can be considered as a potential candidate for novel Na-ion conductors.

Computing details

Program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2018).

(I)

Crystal data

Cu8K5.13Na10.87O64S16	F(000) = 1217
Mr = 2495.76	Dx = 2.920 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.5085 (9) Å	Cell parameters from 1760 reflections
b = 9.3166 (7) Å	θ = 2.8–28.0°
c = 12.7894 (10) Å	µ = 4.13 mm^−1
β = 107.775 (2)°	T = 296 K
V = 1419.28 (19) Å^3	Prism
Z = 1	0.10 × 0.10 × 0.05 mm

Data collection

Bruker Apex II Duo diffractometer	Rint = 0.041
Absorption correction: multi-scan	θmax = 28.0°, θmin = 2.8°
	h = −16→16
13295 measured reflections	k = −12→12
3393 independent reflections	l = −16→13
2656 reflections with I > 2σ(I)

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0358P)^2 + 1.0736P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.030	(Δ/σ)max = 0.001
wR(F^2) = 0.077	Δρmax = 0.54 e Å^−3
S = 1.02	Δρmin = −0.65 e Å^−3
3393 reflections	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
237 parameters	Extinction coefficient: 0.00090 (19)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.43543 (3)	0.59355 (4)	0.81573 (3)	0.01214 (11)
Cu2	0.18205 (3)	0.89881 (4)	0.55924 (3)	0.01240 (11)
K1	0.29227 (6)	0.25219 (8)	0.70496 (6)	0.02114 (18)
Na1	−0.08168 (10)	0.76871 (15)	0.08627 (11)	0.0204 (3)
Na2	0.43127 (10)	0.77780 (15)	0.06462 (11)	0.0192 (3)
Na3	0.15076 (11)	0.6620 (2)	0.33753 (13)	0.0590 (8)	0.718 (11)
K2	0.15076 (11)	0.6620 (2)	0.33753 (13)	0.0590 (8)	0.282 (11)
S1	0.38967 (6)	0.90637 (8)	0.79088 (6)	0.01092 (16)
S2	0.64429 (5)	0.59305 (8)	0.03189 (6)	0.01061 (16)
S3	0.19659 (6)	0.58760 (8)	0.61760 (7)	0.01284 (17)
S4	−0.03802 (6)	0.91496 (9)	0.35754 (7)	0.01321 (17)
O1	−0.11108 (17)	0.9147 (2)	0.43257 (18)	0.0152 (5)
O2	0.57170 (16)	0.5868 (2)	0.10673 (18)	0.0130 (5)
O3	0.67918 (18)	0.4464 (3)	0.0165 (2)	0.0194 (5)
O4	0.44032 (17)	0.7839 (2)	0.74766 (18)	0.0138 (5)
O5	0.73711 (18)	0.6891 (3)	0.0775 (2)	0.0202 (5)
O6	0.23987 (17)	0.7019 (2)	0.55722 (19)	0.0163 (5)
O7	0.28093 (18)	0.9451 (3)	0.7094 (2)	0.0216 (5)
O8	−0.08985 (18)	0.8266 (3)	0.2628 (2)	0.0220 (5)
O9	0.07051 (18)	0.8473 (3)	0.4202 (2)	0.0234 (6)
O10	0.57326 (18)	0.6548 (3)	0.92613 (19)	0.0184 (5)
O11	0.3676 (2)	0.8640 (3)	0.8916 (2)	0.0236 (6)
O12	0.46516 (19)	1.0300 (3)	0.8061 (2)	0.0199 (5)
O13	−0.0224 (2)	1.0626 (3)	0.3289 (2)	0.0268 (6)
O14	0.1579 (2)	0.4664 (3)	0.5457 (2)	0.0288 (6)
O15	0.29260 (19)	0.5395 (3)	0.7116 (2)	0.0270 (6)
O16	0.1112 (2)	0.6511 (3)	0.6580 (2)	0.0298 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01297 (17)	0.0105 (2)	0.0118 (2)	−0.00037 (13)	0.00202 (14)	0.00210 (15)
Cu2	0.01131 (17)	0.0111 (2)	0.0138 (2)	0.00183 (13)	0.00241 (14)	−0.00013 (16)
K1	0.0225 (3)	0.0141 (4)	0.0247 (4)	−0.0003 (3)	0.0041 (3)	−0.0026 (3)
Na1	0.0178 (6)	0.0240 (8)	0.0185 (7)	−0.0012 (5)	0.0044 (5)	−0.0026 (6)
Na2	0.0188 (6)	0.0233 (8)	0.0146 (7)	0.0026 (5)	0.0038 (5)	0.0028 (6)
Na3	0.0324 (8)	0.0979 (16)	0.0397 (10)	0.0199 (8)	0.0005 (6)	−0.0420 (10)
K2	0.0324 (8)	0.0979 (16)	0.0397 (10)	0.0199 (8)	0.0005 (6)	−0.0420 (10)
S1	0.0132 (3)	0.0100 (4)	0.0093 (4)	−0.0002 (3)	0.0030 (3)	0.0008 (3)
S2	0.0104 (3)	0.0112 (4)	0.0101 (4)	−0.0005 (3)	0.0029 (3)	0.0000 (3)
S3	0.0115 (3)	0.0093 (4)	0.0159 (4)	0.0003 (3)	0.0015 (3)	0.0011 (3)
S4	0.0111 (3)	0.0132 (4)	0.0135 (4)	0.0013 (3)	0.0011 (3)	−0.0025 (3)
O1	0.0175 (10)	0.0146 (12)	0.0133 (12)	0.0045 (8)	0.0043 (9)	−0.0005 (9)
O2	0.0151 (9)	0.0128 (12)	0.0130 (11)	0.0011 (8)	0.0072 (9)	0.0001 (9)
O3	0.0199 (11)	0.0165 (13)	0.0239 (13)	0.0018 (9)	0.0098 (9)	−0.0030 (10)
O4	0.0181 (10)	0.0099 (11)	0.0142 (11)	0.0022 (8)	0.0061 (8)	0.0021 (9)
O5	0.0150 (10)	0.0236 (14)	0.0198 (13)	−0.0082 (9)	0.0022 (9)	−0.0018 (11)
O6	0.0175 (10)	0.0117 (12)	0.0205 (13)	0.0023 (8)	0.0071 (9)	0.0039 (10)
O7	0.0179 (10)	0.0217 (14)	0.0201 (13)	0.0079 (9)	−0.0018 (9)	−0.0048 (11)
O8	0.0193 (11)	0.0294 (15)	0.0162 (13)	−0.0020 (10)	0.0035 (9)	−0.0103 (11)
O9	0.0151 (10)	0.0251 (14)	0.0235 (14)	0.0080 (9)	−0.0037 (9)	−0.0075 (11)
O10	0.0206 (10)	0.0170 (13)	0.0131 (12)	−0.0044 (9)	−0.0015 (9)	0.0058 (10)
O11	0.0325 (13)	0.0258 (15)	0.0174 (13)	0.0046 (10)	0.0150 (11)	0.0063 (11)
O12	0.0233 (11)	0.0136 (13)	0.0229 (13)	−0.0070 (9)	0.0071 (9)	−0.0035 (10)
O13	0.0272 (12)	0.0164 (14)	0.0391 (17)	−0.0024 (10)	0.0133 (11)	0.0041 (12)
O14	0.0339 (13)	0.0184 (14)	0.0279 (15)	−0.0068 (11)	0.0002 (11)	−0.0078 (12)
O15	0.0231 (11)	0.0181 (13)	0.0300 (15)	−0.0057 (10)	−0.0063 (10)	0.0108 (12)
O16	0.0291 (13)	0.0257 (15)	0.0435 (18)	0.0059 (11)	0.0241 (12)	0.0031 (13)

Geometric parameters (Å, º)

Cu1—O15	1.941 (2)	Na1—S4^ix	3.6005 (16)
Cu1—O10	1.951 (2)	Na1—S4	3.6103 (16)
Cu1—O2^i	1.967 (2)	Na1—S3^x	3.6354 (14)
Cu1—O4	1.985 (2)	Na1—S2^viii	3.6682 (14)
Cu1—O12^ii	2.347 (2)	Na1—Na3	3.750 (2)
Cu1—O11	2.918 (3)	Na2—O11^xii	2.258 (3)
Cu1—O3^i	2.946 (2)	Na2—O6^x	2.374 (2)
Cu1—S1	2.9684 (9)	Na2—O4^x	2.379 (3)
Cu1—S2^i	3.0002 (9)	Na2—O2	2.442 (2)
Cu1—S2^iii	3.1715 (8)	Na2—O12^xiii	2.512 (3)
Cu1—S3	3.2753 (8)	Na2—O3^xiv	2.544 (3)
Cu1—S1^ii	3.3923 (8)	Na2—O10^xii	3.086 (3)
Cu2—O9	1.956 (2)	Na2—S2	3.3044 (15)
Cu2—O1^iv	1.969 (2)	Na2—O15^x	3.381 (3)
Cu2—O6	1.975 (2)	Na2—S3^x	3.4443 (15)
Cu2—O7	1.989 (2)	Na2—S1^x	3.5366 (16)
Cu2—O3^v	2.274 (2)	Na2—S1^xii	3.5846 (16)
Cu2—O13^iv	2.813 (3)	Na3—O9	2.398 (3)
Cu2—O16	2.897 (3)	Na3—O13^ix	2.425 (3)
Cu2—S4^iv	2.9257 (9)	Na3—O11^x	2.598 (3)
Cu2—S3	2.9856 (9)	Na3—O6	2.714 (3)
Cu2—S4	3.1495 (8)	Na3—O16^x	2.802 (4)
Cu2—S1	3.2907 (8)	Na3—O7^x	2.821 (3)
Cu2—S2^v	3.3012 (9)	Na3—O14	3.204 (4)
K1—O15	2.678 (3)	Na3—O8	3.251 (3)
K1—O8^vi	2.785 (2)	Na3—S1^x	3.2836 (16)
K1—O10^ii	2.861 (2)	Na3—S4^ix	3.3710 (17)
K1—O1^vi	2.866 (2)	Na3—O8^ix	3.376 (3)
K1—O7^vii	2.866 (3)	Na3—S4	3.4004 (17)
K1—O2^i	2.906 (2)	Na3—S3	3.519 (2)
K1—O5^i	2.967 (3)	S1—O11	1.452 (3)
K1—O14	2.978 (3)	S1—O12	1.464 (2)
K1—O12^vii	2.988 (3)	S1—O7	1.483 (2)
K1—O4^ii	3.226 (2)	S1—O4	1.491 (2)
K1—S4^vi	3.4097 (10)	S2—O5	1.441 (2)
K1—S3	3.4102 (11)	S2—O3	1.466 (2)
K1—S1^vii	3.5007 (11)	S2—O10^xii	1.489 (2)
K1—S2^i	3.5220 (11)	S2—O2	1.508 (2)
Na1—O8	2.354 (3)	S3—O14	1.443 (3)
Na1—O5^viii	2.355 (2)	S3—O16	1.447 (3)
Na1—O13^ix	2.387 (3)	S3—O15	1.486 (2)
Na1—O16^x	2.423 (3)	S3—O6	1.510 (2)
Na1—O14^xi	2.483 (3)	S4—O8	1.444 (2)
Na1—O1^x	2.545 (3)	S4—O13	1.452 (3)
Na1—O9^x	3.431 (3)	S4—O9	1.489 (2)
Na1—S4^x	3.5720 (16)	S4—O1	1.514 (2)
O15—Cu1—O10	176.08 (12)	S4^ix—Na3—S4	112.69 (4)
O15—Cu1—O2^i	87.15 (10)	O8^ix—Na3—S4	126.07 (6)
O10—Cu1—O2^i	92.93 (9)	O9—Na3—Cu2	32.03 (6)
O15—Cu1—O4	94.37 (10)	O13^ix—Na3—Cu2	145.87 (8)
O10—Cu1—O4	85.26 (9)	O11^x—Na3—Cu2	89.64 (7)
O2^i—Cu1—O4	175.34 (9)	O6—Na3—Cu2	33.92 (5)
O15—Cu1—O12^ii	92.41 (11)	O16^x—Na3—Cu2	102.66 (8)
O10—Cu1—O12^ii	91.38 (9)	O7^x—Na3—Cu2	138.39 (7)
O2^i—Cu1—O12^ii	103.53 (9)	O14—Na3—Cu2	73.68 (6)
O4—Cu1—O12^ii	80.84 (9)	O8—Na3—Cu2	78.84 (5)
O15—Cu1—O11	98.76 (10)	S1^x—Na3—Cu2	112.62 (4)
O10—Cu1—O11	77.83 (9)	S4^ix—Na3—Cu2	160.56 (6)
O2^i—Cu1—O11	120.50 (8)	O8^ix—Na3—Cu2	147.50 (8)
O4—Cu1—O11	54.92 (8)	S4—Na3—Cu2	54.12 (3)
O12^ii—Cu1—O11	134.88 (8)	O9—Na3—S3	69.72 (7)
O15—Cu1—O3^i	85.21 (10)	O13^ix—Na3—S3	132.57 (10)
O10—Cu1—O3^i	91.65 (8)	O11^x—Na3—S3	83.01 (7)
O2^i—Cu1—O3^i	54.39 (8)	O6—Na3—S3	23.84 (5)
O4—Cu1—O3^i	121.29 (8)	O16^x—Na3—S3	152.80 (8)
O12^ii—Cu1—O3^i	157.84 (8)	O7^x—Na3—S3	125.29 (7)
O11—Cu1—O3^i	67.12 (7)	O14—Na3—S3	24.21 (5)
O15—Cu1—S1	94.27 (8)	O8—Na3—S3	103.92 (6)
O10—Cu1—S1	83.64 (7)	S1^x—Na3—S3	105.79 (4)
O2^i—Cu1—S1	148.85 (7)	S4^ix—Na3—S3	121.33 (7)
O4—Cu1—S1	26.68 (7)	O8^ix—Na3—S3	98.76 (7)
O12^ii—Cu1—S1	107.49 (6)	S4—Na3—S3	87.77 (4)
O11—Cu1—S1	28.55 (5)	Cu2—Na3—S3	50.20 (3)
O3^i—Cu1—S1	94.66 (5)	O11—S1—O12	112.66 (15)
O15—Cu1—S2^i	82.91 (8)	O11—S1—O7	107.88 (15)
O10—Cu1—S2^i	95.45 (7)	O12—S1—O7	108.56 (15)
O2^i—Cu1—S2^i	26.14 (6)	O11—S1—O4	109.76 (14)
O4—Cu1—S2^i	149.72 (7)	O12—S1—O4	108.76 (13)
O12^ii—Cu1—S2^i	129.31 (6)	O7—S1—O4	109.16 (13)
O11—Cu1—S2^i	95.53 (5)	O11—S1—Cu1	73.78 (11)
O3^i—Cu1—S2^i	28.53 (5)	O12—S1—Cu1	131.49 (10)
S1—Cu1—S2^i	123.16 (3)	O7—S1—Cu1	114.80 (11)
O15—Cu1—S2^iii	159.81 (8)	O4—S1—Cu1	36.71 (9)
O10—Cu1—S2^iii	19.72 (7)	O11—S1—Na3^xv	49.91 (10)
O2^i—Cu1—S2^iii	73.22 (6)	O12—S1—Na3^xv	135.58 (11)
O4—Cu1—S2^iii	104.84 (6)	O7—S1—Na3^xv	58.96 (11)
O12^ii—Cu1—S2^iii	96.66 (6)	O4—S1—Na3^xv	115.60 (10)
O11—Cu1—S2^iii	87.54 (5)	Cu1—S1—Na3^xv	86.93 (4)
O3^i—Cu1—S2^iii	79.59 (5)	O11—S1—Cu2	118.77 (10)
S1—Cu1—S2^iii	100.10 (2)	O12—S1—Cu2	115.88 (10)
S2^i—Cu1—S2^iii	77.38 (2)	O7—S1—Cu2	21.65 (10)
O15—Cu1—S3	14.88 (8)	O4—S1—Cu2	87.58 (9)
O10—Cu1—S3	163.91 (7)	Cu1—S1—Cu2	98.56 (2)
O2^i—Cu1—S3	101.80 (6)	Na3^xv—S1—Cu2	69.36 (3)
O4—Cu1—S3	79.56 (6)	O11—S1—Cu1^xvi	144.77 (11)
O12^ii—Cu1—S3	91.44 (6)	O12—S1—Cu1^xvi	34.94 (10)
O11—Cu1—S3	89.01 (5)	O7—S1—Cu1^xvi	99.12 (11)
O3^i—Cu1—S3	91.70 (5)	O4—S1—Cu1^xvi	81.10 (9)
S1—Cu1—S3	80.40 (2)	Cu1—S1—Cu1^xvi	114.89 (2)
S2^i—Cu1—S3	95.00 (2)	Na3^xv—S1—Cu1^xvi	155.12 (4)
S2^iii—Cu1—S3	171.29 (2)	Cu2—S1—Cu1^xvi	94.46 (2)
O15—Cu1—S1^ii	99.33 (9)	O11—S1—K1^xvii	112.74 (11)
O10—Cu1—S1^ii	84.57 (8)	O12—S1—K1^xvii	57.75 (10)
O2^i—Cu1—S1^ii	84.12 (6)	O7—S1—K1^xvii	53.07 (10)
O4—Cu1—S1^ii	99.96 (7)	O4—S1—K1^xvii	137.28 (9)
O12^ii—Cu1—S1^ii	20.93 (6)	Cu1—S1—K1^xvii	167.03 (3)
O11—Cu1—S1^ii	150.03 (5)	Na3^xv—S1—K1^xvii	89.24 (4)
O3^i—Cu1—S1^ii	138.15 (5)	Cu2—S1—K1^xvii	68.515 (19)
S1—Cu1—S1^ii	126.060 (19)	Cu1^xvi—S1—K1^xvii	66.80 (2)
S2^i—Cu1—S1^ii	110.26 (2)	O11—S1—Na2^xv	135.17 (12)
S2^iii—Cu1—S1^ii	83.62 (2)	O12—S1—Na2^xv	103.92 (11)
S3—Cu1—S1^ii	103.19 (2)	O7—S1—Na2^xv	82.87 (10)
O9—Cu2—O1^iv	93.25 (9)	O4—S1—Na2^xv	30.69 (9)
O9—Cu2—O6	85.57 (10)	Cu1—S1—Na2^xv	62.58 (3)
O1^iv—Cu2—O6	173.47 (9)	Na3^xv—S1—Na2^xv	115.08 (5)
O9—Cu2—O7	172.86 (11)	Cu2—S1—Na2^xv	61.69 (3)
O1^iv—Cu2—O7	85.12 (9)	Cu1^xvi—S1—Na2^xv	69.30 (3)
O6—Cu2—O7	95.26 (10)	K1^xvii—S1—Na2^xv	108.28 (3)
O9—Cu2—O3^v	94.93 (10)	O11—S1—Na2^iii	18.73 (10)
O1^iv—Cu2—O3^v	105.41 (9)	O12—S1—Na2^iii	103.73 (11)
O6—Cu2—O3^v	81.10 (9)	O7—S1—Na2^iii	126.56 (11)
O7—Cu2—O3^v	92.21 (10)	O4—S1—Na2^iii	98.91 (9)
O9—Cu2—O13^iv	94.24 (9)	Cu1—S1—Na2^iii	66.52 (3)
O1^iv—Cu2—O13^iv	57.20 (8)	Na3^xv—S1—Na2^iii	68.07 (4)
O6—Cu2—O13^iv	116.44 (9)	Cu2—S1—Na2^iii	135.35 (3)
O7—Cu2—O13^iv	79.02 (9)	Cu1^xvi—S1—Na2^iii	130.18 (3)
O3^v—Cu2—O13^iv	160.80 (8)	K1^xvii—S1—Na2^iii	123.16 (3)
O9—Cu2—O16	88.46 (10)	Na2^xv—S1—Na2^iii	128.55 (3)
O1^iv—Cu2—O16	118.50 (8)	O11—S1—Na2^xiii	91.28 (11)
O6—Cu2—O16	55.09 (8)	O12—S1—Na2^xiii	21.51 (10)
O7—Cu2—O16	86.23 (10)	O7—S1—Na2^xiii	115.43 (11)
O3^v—Cu2—O16	135.70 (8)	O4—S1—Na2^xiii	121.11 (9)
O13^iv—Cu2—O16	61.36 (7)	Cu1—S1—Na2^xiii	129.77 (3)
O9—Cu2—S4^iv	97.40 (7)	Na3^xv—S1—Na2^xiii	119.59 (5)
O1^iv—Cu2—S4^iv	28.29 (7)	Cu2—S1—Na2^xiii	129.62 (3)
O6—Cu2—S4^iv	145.52 (7)	Cu1^xvi—S1—Na2^xiii	56.16 (2)
O7—Cu2—S4^iv	77.91 (7)	K1^xvii—S1—Na2^xiii	62.54 (3)
O3^v—Cu2—S4^iv	132.38 (7)	Na2^xv—S1—Na2^xiii	124.00 (3)
O13^iv—Cu2—S4^iv	29.23 (5)	Na2^iii—S1—Na2^xiii	84.02 (4)
O16—Cu2—S4^iv	90.55 (5)	O5—S2—O3	113.40 (14)
O9—Cu2—S3	87.79 (8)	O5—S2—O10^xii	108.13 (14)
O1^iv—Cu2—S3	146.93 (7)	O3—S2—O10^xii	110.94 (15)
O6—Cu2—S3	26.70 (7)	O5—S2—O2	109.52 (14)
O7—Cu2—S3	89.80 (8)	O3—S2—O2	108.13 (13)
O3^v—Cu2—S3	107.43 (6)	O10^xii—S2—O2	106.48 (13)
O13^iv—Cu2—S3	89.74 (6)	O5—S2—Cu1^i	118.93 (11)
O16—Cu2—S3	28.43 (5)	O3—S2—Cu1^i	73.68 (10)
S4^iv—Cu2—S3	118.83 (3)	O10^xii—S2—Cu1^i	126.13 (9)
O9—Cu2—S4	20.66 (7)	O2—S2—Cu1^i	35.07 (8)
O1^iv—Cu2—S4	72.89 (6)	O5—S2—Cu1^xii	134.38 (11)
O6—Cu2—S4	105.41 (7)	O3—S2—Cu1^xii	94.81 (10)
O7—Cu2—S4	155.66 (7)	O10^xii—S2—Cu1^xii	26.25 (9)
O3^v—Cu2—S4	103.41 (6)	O2—S2—Cu1^xii	93.33 (8)
O13^iv—Cu2—S4	80.32 (6)	Cu1^i—S2—Cu1^xii	102.62 (2)
O16—Cu2—S4	95.06 (6)	O5—S2—Cu2^xviii	86.99 (10)
S4^iv—Cu2—S4	77.78 (3)	O3—S2—Cu2^xviii	35.56 (9)
S3—Cu2—S4	102.85 (2)	O10^xii—S2—Cu2^xviii	99.53 (10)
O9—Cu2—S1	166.37 (7)	O2—S2—Cu2^xviii	142.32 (9)
O1^iv—Cu2—S1	100.25 (7)	Cu1^i—S2—Cu2^xviii	107.26 (2)
O6—Cu2—S1	80.80 (7)	Cu1^xii—S2—Cu2^xviii	98.56 (2)
O7—Cu2—S1	15.97 (7)	O5—S2—Na2	101.92 (11)
O3^v—Cu2—S1	83.33 (6)	O3—S2—Na2	141.94 (10)
O13^iv—Cu2—S1	91.54 (6)	O10^xii—S2—Na2	68.48 (10)
O16—Cu2—S1	83.50 (6)	O2—S2—Na2	43.51 (9)
S4^iv—Cu2—S1	93.68 (2)	Cu1^i—S2—Na2	77.22 (3)
S3—Cu2—S1	79.90 (2)	Cu1^xii—S2—Na2	68.17 (3)
S4—Cu2—S1	171.34 (2)	Cu2^xviii—S2—Na2	166.72 (3)
O9—Cu2—S2^v	100.19 (8)	O5—S2—K1^i	55.97 (10)
O1^iv—Cu2—S2^v	83.74 (7)	O3—S2—K1^i	121.38 (11)
O6—Cu2—S2^v	102.79 (7)	O10^xii—S2—K1^i	127.44 (10)
O7—Cu2—S2^v	86.56 (8)	O2—S2—K1^i	54.06 (8)
O3^v—Cu2—S2^v	22.01 (6)	Cu1^i—S2—K1^i	68.84 (2)
O13^iv—Cu2—S2^v	139.07 (6)	Cu1^xii—S2—K1^i	135.86 (3)
O16—Cu2—S2^v	155.86 (5)	Cu2^xviii—S2—K1^i	125.53 (2)
S4^iv—Cu2—S2^v	110.36 (2)	Na2—S2—K1^i	67.72 (3)
S3—Cu2—S2^v	128.62 (2)	O5—S2—Na1^xix	19.11 (10)
S4—Cu2—S2^v	100.92 (2)	O3—S2—Na1^xix	98.16 (9)
S1—Cu2—S2^v	83.26 (2)	O10^xii—S2—Na1^xix	105.29 (9)
O15—K1—O8^vi	104.57 (8)	O2—S2—Na1^xix	127.27 (9)
O15—K1—O10^ii	109.88 (9)	Cu1^i—S2—Na1^xix	127.73 (3)
O8^vi—K1—O10^ii	136.61 (7)	Cu1^xii—S2—Na1^xix	129.64 (3)
O15—K1—O1^vi	123.70 (7)	Cu2^xviii—S2—Na1^xix	68.53 (3)
O8^vi—K1—O1^vi	50.47 (7)	Na2—S2—Na1^xix	119.11 (4)
O10^ii—K1—O1^vi	87.97 (7)	K1^i—S2—Na1^xix	73.22 (3)
O15—K1—O7^vii	175.39 (9)	O5—S2—K1^v	74.48 (10)
O8^vi—K1—O7^vii	71.40 (7)	O3—S2—K1^v	96.72 (11)
O10^ii—K1—O7^vii	74.73 (7)	O10^xii—S2—K1^v	46.64 (9)
O1^vi—K1—O7^vii	55.67 (6)	O2—S2—K1^v	149.67 (9)
O15—K1—O2^i	57.52 (7)	Cu1^i—S2—K1^v	165.61 (3)
O8^vi—K1—O2^i	110.01 (7)	Cu1^xii—S2—K1^v	66.93 (2)
O10^ii—K1—O2^i	110.44 (6)	Cu2^xviii—S2—K1^v	66.34 (2)
O1^vi—K1—O2^i	160.39 (7)	Na2—S2—K1^v	106.26 (3)
O7^vii—K1—O2^i	121.25 (7)	K1^i—S2—K1^v	125.51 (2)
O15—K1—O5^i	77.61 (8)	Na1^xix—S2—K1^v	63.34 (3)
O8^vi—K1—O5^i	62.05 (6)	O5—S2—Na2^xiv	143.97 (11)
O10^ii—K1—O5^i	150.63 (7)	O3—S2—Na2^xiv	30.62 (9)
O1^vi—K1—O5^i	111.99 (7)	O10^xii—S2—Na2^xiv	92.12 (10)
O7^vii—K1—O5^i	98.29 (7)	O2—S2—Na2^xiv	91.94 (9)
O2^i—K1—O5^i	48.42 (6)	Cu1^i—S2—Na2^xiv	64.73 (3)
O15—K1—O14	49.22 (7)	Cu1^xii—S2—Na2^xiv	69.60 (3)
O8^vi—K1—O14	85.94 (8)	Cu2^xviii—S2—Na2^xiv	59.87 (2)
O10^ii—K1—O14	96.99 (8)	Na2—S2—Na2^xiv	113.31 (3)
O1^vi—K1—O14	76.60 (7)	K1^i—S2—Na2^xiv	131.48 (3)
O7^vii—K1—O14	131.43 (7)	Na1^xix—S2—Na2^xiv	127.57 (4)
O2^i—K1—O14	106.64 (7)	K1^v—S2—Na2^xiv	101.53 (3)
O5^i—K1—O14	108.20 (8)	O14—S3—O16	114.02 (16)
O15—K1—O12^vii	133.23 (7)	O14—S3—O15	108.10 (16)
O8^vi—K1—O12^vii	108.89 (7)	O16—S3—O15	109.68 (17)
O10^ii—K1—O12^vii	63.69 (7)	O14—S3—O6	109.18 (15)
O1^vi—K1—O12^vii	102.84 (6)	O16—S3—O6	108.25 (14)
O7^vii—K1—O12^vii	48.19 (6)	O15—S3—O6	107.41 (13)
O2^i—K1—O12^vii	80.53 (6)	O14—S3—Cu2	128.11 (12)
O5^i—K1—O12^vii	90.12 (7)	O16—S3—Cu2	72.37 (11)
O14—K1—O12^vii	160.61 (8)	O15—S3—Cu2	117.90 (10)
O15—K1—O4^ii	84.90 (7)	O6—S3—Cu2	35.99 (9)
O8^vi—K1—O4^ii	159.03 (7)	O14—S3—Cu1	123.75 (11)
O10^ii—K1—O4^ii	51.51 (6)	O16—S3—Cu1	108.35 (12)
O1^vi—K1—O4^ii	138.19 (6)	O15—S3—Cu1	19.60 (10)
O7^vii—K1—O4^ii	98.19 (6)	O6—S3—Cu1	89.94 (9)
O2^i—K1—O4^ii	59.06 (6)	Cu2—S3—Cu1	98.54 (2)
O5^i—K1—O4^ii	103.02 (6)	O14—S3—K1	60.53 (11)
O14—K1—O4^ii	113.79 (7)	O16—S3—K1	118.75 (12)
O12^vii—K1—O4^ii	53.86 (6)	O15—S3—K1	48.86 (10)
O15—K1—S4^vi	117.14 (6)	O6—S3—K1	132.02 (9)
O8^vi—K1—S4^vi	24.39 (5)	Cu2—S3—K1	163.80 (3)
O10^ii—K1—S4^vi	113.01 (5)	Cu1—S3—K1	67.419 (19)
O1^vi—K1—S4^vi	26.12 (5)	O14—S3—Na2^xv	107.42 (12)
O7^vii—K1—S4^vi	60.03 (5)	O16—S3—Na2^xv	133.44 (12)
O2^i—K1—S4^vi	134.29 (5)	O15—S3—Na2^xv	75.05 (11)
O5^i—K1—S4^vi	86.01 (5)	O6—S3—Na2^xv	35.14 (8)
O14—K1—S4^vi	81.63 (5)	Cu2—S3—Na2^xv	65.66 (3)
O12^vii—K1—S4^vi	106.56 (5)	Cu1—S3—Na2^xv	61.00 (3)
O4^ii—K1—S4^vi	157.72 (5)	K1—S3—Na2^xv	99.39 (3)
O15—K1—S3	24.70 (5)	O14—S3—Na3	65.58 (12)
O8^vi—K1—S3	92.64 (6)	O16—S3—Na3	111.99 (12)
O10^ii—K1—S3	108.00 (6)	O15—S3—Na3	136.32 (12)
O1^vi—K1—S3	99.39 (5)	O6—S3—Na3	46.59 (10)
O7^vii—K1—S3	155.06 (5)	Cu2—S3—Na3	64.89 (4)
O2^i—K1—S3	81.76 (5)	Cu1—S3—Na3	127.65 (3)
O5^i—K1—S3	90.39 (5)	K1—S3—Na3	116.48 (4)
O14—K1—S3	24.96 (5)	Na2^xv—S3—Na3	67.16 (4)
O12^vii—K1—S3	155.78 (5)	O14—S3—Na1^xv	95.41 (11)
O4^ii—K1—S3	102.58 (5)	O16—S3—Na1^xv	26.22 (12)
S4^vi—K1—S3	97.63 (2)	O15—S3—Na1^xv	135.29 (13)
O15—K1—S1^vii	155.92 (6)	O6—S3—Na1^xv	99.47 (9)
O8^vi—K1—S1^vii	87.47 (6)	Cu2—S3—Na1^xv	68.39 (3)
O10^ii—K1—S1^vii	71.43 (5)	Cu1—S3—Na1^xv	134.07 (3)
O1^vi—K1—S1^vii	80.08 (5)	K1—S3—Na1^xv	127.01 (3)
O7^vii—K1—S1^vii	24.43 (4)	Na2^xv—S3—Na1^xv	133.56 (4)
O2^i—K1—S1^vii	98.94 (5)	Na3—S3—Na1^xv	87.84 (3)
O5^i—K1—S1^vii	90.35 (5)	O14—S3—Na3^xv	148.03 (12)
O14—K1—S1^vii	154.32 (6)	O16—S3—Na3^xv	36.53 (12)
O12^vii—K1—S1^vii	24.48 (4)	O15—S3—Na3^xv	81.66 (12)
O4^ii—K1—S1^vii	77.51 (4)	O6—S3—Na3^xv	95.93 (10)
S4^vi—K1—S1^vii	82.16 (2)	Cu2—S3—Na3^xv	65.21 (3)
S3—K1—S1^vii	179.21 (3)	Cu1—S3—Na3^xv	74.17 (3)
O15—K1—S2^i	64.08 (6)	K1—S3—Na3^xv	115.71 (4)
O8^vi—K1—S2^i	85.20 (5)	Na2^xv—S3—Na3^xv	104.50 (4)
O10^ii—K1—S2^i	133.52 (5)	Na3—S3—Na3^xv	127.82 (3)
O1^vi—K1—S2^i	135.55 (5)	Na1^xv—S3—Na3^xv	60.25 (3)
O7^vii—K1—S2^i	112.81 (6)	O8—S4—O13	112.86 (16)
O2^i—K1—S2^i	24.85 (4)	O8—S4—O9	108.19 (15)
O5^i—K1—S2^i	23.73 (4)	O13—S4—O9	111.45 (15)
O14—K1—S2^i	107.14 (6)	O8—S4—O1	109.11 (14)
O12^vii—K1—S2^i	87.01 (5)	O13—S4—O1	108.40 (15)
O4^ii—K1—S2^i	82.23 (4)	O9—S4—O1	106.61 (14)
S4^vi—K1—S2^i	109.45 (3)	O8—S4—Cu2^iv	118.33 (10)
S3—K1—S2^i	83.80 (3)	O13—S4—Cu2^iv	71.06 (11)
S1^vii—K1—S2^i	96.98 (3)	O9—S4—Cu2^iv	128.07 (11)
O8—Na1—O5^viii	78.17 (9)	O1—S4—Cu2^iv	38.05 (9)
O8—Na1—O13^ix	85.73 (10)	O8—S4—Cu2	135.73 (10)
O5^viii—Na1—O13^ix	98.73 (10)	O13—S4—Cu2	95.78 (11)
O8—Na1—O16^x	84.02 (9)	O9—S4—Cu2	27.61 (10)
O5^viii—Na1—O16^x	161.45 (11)	O1—S4—Cu2	91.52 (9)
O13^ix—Na1—O16^x	74.57 (10)	Cu2^iv—S4—Cu2	102.22 (3)
O8—Na1—O14^xi	111.20 (11)	O8—S4—Na3^xi	77.83 (12)
O5^viii—Na1—O14^xi	92.11 (10)	O13—S4—Na3^xi	39.13 (11)
O13^ix—Na1—O14^xi	161.57 (11)	O9—S4—Na3^xi	142.53 (12)
O16^x—Na1—O14^xi	99.20 (10)	O1—S4—Na3^xi	105.86 (9)
O8—Na1—O1^x	148.92 (10)	Cu2^iv—S4—Na3^xi	72.50 (4)
O5^viii—Na1—O1^x	80.89 (9)	Cu2—S4—Na3^xi	134.62 (4)
O13^ix—Na1—O1^x	75.01 (9)	O8—S4—Na3	71.71 (10)
O16^x—Na1—O1^x	113.07 (9)	O13—S4—Na3	119.17 (11)
O14^xi—Na1—O1^x	92.19 (10)	O9—S4—Na3	37.57 (10)
O8—Na1—O9^x	149.41 (8)	O1—S4—Na3	127.87 (10)
O5^viii—Na1—O9^x	125.38 (9)	Cu2^iv—S4—Na3	163.18 (4)
O13^ix—Na1—O9^x	72.51 (8)	Cu2—S4—Na3	64.86 (3)
O16^x—Na1—O9^x	69.82 (8)	Na3^xi—S4—Na3	124.11 (3)
O14^xi—Na1—O9^x	89.06 (9)	O8—S4—K1^vi	52.80 (10)
O1^x—Na1—O9^x	44.52 (6)	O13—S4—K1^vi	124.14 (10)
O8—Na1—S4^x	163.26 (9)	O9—S4—K1^vi	124.39 (11)
O5^viii—Na1—S4^x	101.28 (7)	O1—S4—K1^vi	56.45 (9)
O13^ix—Na1—S4^x	77.79 (8)	Cu2^iv—S4—K1^vi	73.88 (2)
O16^x—Na1—S4^x	94.26 (8)	Cu2—S4—K1^vi	133.60 (3)
O14^xi—Na1—S4^x	85.52 (8)	Na3^xi—S4—K1^vi	89.36 (3)
O1^x—Na1—S4^x	21.25 (5)	Na3—S4—K1^vi	106.58 (4)
O9^x—Na1—S4^x	24.45 (4)	O8—S4—Na1^xv	105.80 (12)
O8—Na1—S4^ix	98.95 (8)	O13—S4—Na1^xv	136.61 (12)
O5^viii—Na1—S4^ix	93.26 (7)	O9—S4—Na1^xv	72.48 (11)
O13^ix—Na1—S4^ix	15.63 (7)	O1—S4—Na1^xv	37.54 (9)
O16^x—Na1—S4^ix	84.33 (8)	Cu2^iv—S4—Na1^xv	73.80 (3)
O14^xi—Na1—S4^ix	149.84 (9)	Cu2—S4—Na1^xv	67.68 (3)
O1^x—Na1—S4^ix	59.53 (6)	Na3^xi—S4—Na1^xv	143.05 (4)
O9^x—Na1—S4^ix	63.88 (5)	Na3—S4—Na1^xv	90.74 (5)
S4^x—Na1—S4^ix	64.33 (3)	K1^vi—S4—Na1^xv	66.94 (3)
O8—Na1—S4	14.03 (6)	O8—S4—Na1^xi	137.90 (12)
O5^viii—Na1—S4	91.48 (7)	O13—S4—Na1^xi	26.30 (11)
O13^ix—Na1—S4	88.00 (8)	O9—S4—Na1^xi	91.41 (11)
O16^x—Na1—S4	71.26 (7)	O1—S4—Na1^xi	99.78 (10)
O14^xi—Na1—S4	106.68 (8)	Cu2^iv—S4—Na1^xi	69.47 (3)
O1^x—Na1—S4	159.95 (8)	Cu2—S4—Na1^xi	70.97 (3)
O9^x—Na1—S4	139.82 (5)	Na3^xi—S4—Na1^xi	64.99 (4)
S4^x—Na1—S4	162.12 (4)	Na3—S4—Na1^xi	113.16 (4)
S4^ix—Na1—S4	102.82 (4)	K1^vi—S4—Na1^xi	140.01 (3)
O8—Na1—S3^x	97.49 (7)	Na1^xv—S4—Na1^xi	115.67 (3)
O5^viii—Na1—S3^x	175.22 (8)	S4—O1—Cu2^iv	113.67 (13)
O13^ix—Na1—S3^x	82.83 (7)	S4—O1—Na1^xv	121.20 (12)
O16^x—Na1—S3^x	15.30 (7)	Cu2^iv—O1—Na1^xv	120.84 (11)
O14^xi—Na1—S3^x	87.58 (7)	S4—O1—K1^vi	97.43 (11)
O1^x—Na1—S3^x	103.89 (6)	Cu2^iv—O1—K1^vi	103.09 (8)
O9^x—Na1—S3^x	59.39 (5)	Na1^xv—O1—K1^vi	90.61 (8)
S4^x—Na1—S3^x	83.46 (3)	S4—O1—Na3^xi	53.09 (8)
S4^ix—Na1—S3^x	89.38 (3)	Cu2^iv—O1—Na3^xi	66.66 (7)
S4—Na1—S3^x	84.04 (3)	Na1^xv—O1—Na3^xi	172.21 (9)
O8—Na1—S2^viii	88.42 (7)	K1^vi—O1—Na3^xi	85.25 (6)
O5^viii—Na1—S2^viii	11.56 (6)	S4—O1—Na1^xi	59.08 (8)
O13^ix—Na1—S2^viii	94.34 (7)	Cu2^iv—O1—Na1^xi	65.13 (6)
O16^x—Na1—S2^viii	166.98 (9)	Na1^xv—O1—Na1^xi	129.13 (7)
O14^xi—Na1—S2^viii	93.41 (7)	K1^vi—O1—Na1^xi	139.70 (8)
O1^x—Na1—S2^viii	69.38 (6)	Na3^xi—O1—Na1^xi	54.48 (4)
O9^x—Na1—S2^viii	113.89 (5)	S2—O2—Cu1^i	118.79 (13)
S4^x—Na1—S2^viii	89.92 (3)	S2—O2—Na2	111.33 (12)
S4^ix—Na1—S2^viii	86.39 (3)	Cu1^i—O2—Na2	126.40 (10)
S4—Na1—S2^viii	102.06 (4)	S2—O2—K1^i	101.10 (10)
S3^x—Na1—S2^viii	173.21 (5)	Cu1^i—O2—K1^i	97.37 (8)
O8—Na1—Na3	59.21 (7)	Na2—O2—K1^i	90.37 (8)
O5^viii—Na1—Na3	116.15 (8)	S2—O2—Na2^xiv	66.13 (8)
O13^ix—Na1—Na3	39.16 (7)	Cu1^i—O2—Na2^xiv	63.93 (6)
O16^x—Na1—Na3	48.33 (8)	Na2—O2—Na2^xiv	127.35 (8)
O14^xi—Na1—Na3	144.60 (8)	K1^i—O2—Na2^xiv	142.22 (7)
O1^x—Na1—Na3	112.05 (7)	S2—O3—Cu2^xviii	122.43 (14)
O9^x—Na1—Na3	90.89 (5)	S2—O3—Na2^xiv	132.31 (13)
S4^x—Na1—Na3	107.61 (4)	Cu2^xviii—O3—Na2^xiv	93.25 (9)
S4^ix—Na1—Na3	54.55 (4)	S2—O3—Cu1^i	77.79 (10)
S4—Na1—Na3	54.99 (3)	Cu2^xviii—O3—Cu1^i	152.86 (11)
S3^x—Na1—Na3	62.44 (4)	Na2^xiv—O3—Cu1^i	82.46 (7)
S2^viii—Na1—Na3	118.64 (5)	S2—O3—Na3^xviii	141.25 (14)
O11^xii—Na2—O6^x	83.29 (9)	Cu2^xviii—O3—Na3^xviii	70.48 (6)
O11^xii—Na2—O4^x	161.19 (10)	Na2^xiv—O3—Na3^xviii	76.43 (7)
O6^x—Na2—O4^x	78.64 (9)	Cu1^i—O3—Na3^xviii	82.49 (7)
O11^xii—Na2—O2	119.34 (10)	S2—O3—K1^v	62.52 (9)
O6^x—Na2—O2	135.66 (10)	Cu2^xviii—O3—K1^v	66.65 (6)
O4^x—Na2—O2	78.00 (8)	Na2^xiv—O3—K1^v	116.05 (8)
O11^xii—Na2—O12^xiii	110.37 (10)	Cu1^i—O3—K1^v	138.91 (7)
O6^x—Na2—O12^xiii	106.30 (9)	Na3^xviii—O3—K1^v	135.71 (7)
O4^x—Na2—O12^xiii	70.41 (9)	S2—O3—Na1^xix	61.31 (9)
O2—Na2—O12^xiii	100.52 (8)	Cu2^xviii—O3—Na1^xix	68.78 (6)
O11^xii—Na2—O3^xiv	84.69 (10)	Na2^xiv—O3—Na1^xix	161.88 (9)
O6^x—Na2—O3^xiv	68.50 (8)	Cu1^i—O3—Na1^xix	114.51 (7)
O4^x—Na2—O3^xiv	93.41 (9)	Na3^xviii—O3—Na1^xix	98.65 (6)
O2—Na2—O3^xiv	75.89 (8)	K1^v—O3—Na1^xix	55.70 (4)
O12^xiii—Na2—O3^xiv	163.80 (10)	S1—O4—Cu1	116.60 (13)
O11^xii—Na2—O10^xii	70.26 (8)	S1—O4—Na2^xv	130.66 (13)
O6^x—Na2—O10^xii	139.16 (9)	Cu1—O4—Na2^xv	102.54 (10)
O4^x—Na2—O10^xii	127.74 (8)	S1—O4—K1^xvi	122.28 (11)
O2—Na2—O10^xii	49.82 (7)	Cu1—O4—K1^xvi	90.28 (7)
O12^xiii—Na2—O10^xii	111.77 (8)	Na2^xv—O4—K1^xvi	84.14 (7)
O3^xiv—Na2—O10^xii	78.31 (8)	S1—O4—Na2^iii	59.98 (8)
O11^xii—Na2—S2	96.77 (8)	Cu1—O4—Na2^iii	62.55 (6)
O6^x—Na2—S2	151.47 (8)	Na2^xv—O4—Na2^iii	164.66 (8)
O4^x—Na2—S2	101.58 (7)	K1^xvi—O4—Na2^iii	98.83 (6)
O2—Na2—S2	25.16 (5)	S1—O4—Na3^xv	45.50 (7)
O12^xiii—Na2—S2	100.42 (7)	Cu1—O4—Na3^xv	80.83 (7)
O3^xiv—Na2—S2	83.07 (6)	Na2^xv—O4—Na3^xv	121.21 (8)
O10^xii—Na2—S2	26.66 (4)	K1^xvi—O4—Na3^xv	154.34 (7)
O11^xii—Na2—O15^x	106.17 (9)	Na2^iii—O4—Na3^xv	55.73 (4)
O6^x—Na2—O15^x	45.57 (7)	S2—O5—Na1^xix	149.33 (16)
O4^x—Na2—O15^x	56.84 (7)	S2—O5—K1^i	100.29 (12)
O2—Na2—O15^x	134.49 (8)	Na1^xix—O5—K1^i	106.87 (9)
O12^xiii—Na2—O15^x	61.59 (7)	S2—O5—K1^v	82.61 (11)
O3^xiv—Na2—O15^x	109.45 (8)	Na1^xix—O5—K1^v	78.26 (7)
O10^xii—Na2—O15^x	171.42 (8)	K1^i—O5—K1^v	156.30 (9)
S2—Na2—O15^x	154.57 (6)	S2—O5—Na2	56.71 (9)
O11^xii—Na2—Cu1^x	134.16 (8)	Na1^xix—O5—Na2	149.30 (10)
O6^x—Na2—Cu1^x	74.64 (7)	K1^i—O5—Na2	66.19 (5)
O4^x—Na2—Cu1^x	34.58 (6)	K1^v—O5—Na2	97.30 (6)
O2—Na2—Cu1^x	104.18 (7)	S3—O6—Cu2	117.30 (13)
O12^xiii—Na2—Cu1^x	43.43 (6)	S3—O6—Na2^xv	123.39 (12)
O3^xiv—Na2—Cu1^x	121.48 (7)	Cu2—O6—Na2^xv	107.13 (10)
O10^xii—Na2—Cu1^x	145.50 (6)	S3—O6—Na3	109.56 (12)
S2—Na2—Cu1^x	121.39 (4)	Cu2—O6—Na3	96.00 (9)
O15^x—Na2—Cu1^x	33.19 (4)	Na2^xv—O6—Na3	98.20 (9)
O11^xii—Na2—S3^x	89.80 (7)	S3—O6—Na1^xv	59.55 (8)
O6^x—Na2—S3^x	21.47 (6)	Cu2—O6—Na1^xv	64.52 (6)
O4^x—Na2—S3^x	71.45 (6)	Na2^xv—O6—Na1^xv	169.08 (10)
O2—Na2—S3^x	145.15 (7)	Na3—O6—Na1^xv	89.93 (6)
O12^xiii—Na2—S3^x	84.85 (7)	S1—O7—Cu2	142.39 (16)
O3^xiv—Na2—S3^x	89.41 (6)	S1—O7—Na3^xv	94.27 (13)
O10^xii—Na2—S3^x	157.28 (6)	Cu2—O7—Na3^xv	100.67 (10)
S2—Na2—S3^x	169.49 (5)	S1—O7—K1^xvii	102.50 (12)
O15^x—Na2—S3^x	25.12 (4)	Cu2—O7—K1^xvii	102.54 (10)
Cu1^x—Na2—S3^x	57.06 (3)	Na3^xv—O7—K1^xvii	113.93 (10)
O11^xii—Na2—Cu2^x	95.86 (7)	S1—O7—Na2^xv	73.43 (10)
O6^x—Na2—Cu2^x	32.55 (6)	Cu2—O7—Na2^xv	69.66 (7)
O4^x—Na2—Cu2^x	71.40 (6)	Na3^xv—O7—Na2^xv	124.73 (10)
O2—Na2—Cu2^x	103.75 (7)	K1^xvii—O7—Na2^xv	121.32 (9)
O12^xiii—Na2—Cu2^x	128.62 (7)	S4—O8—Na1	142.69 (16)
O3^xiv—Na2—Cu2^x	40.35 (6)	S4—O8—K1^vi	102.81 (12)
O10^xii—Na2—Cu2^x	118.58 (6)	Na1—O8—K1^vi	112.90 (9)
S2—Na2—Cu2^x	119.96 (4)	S4—O8—Na3	83.34 (10)
O15^x—Na2—Cu2^x	69.10 (5)	Na1—O8—Na3	82.32 (8)
Cu1^x—Na2—Cu2^x	86.64 (3)	K1^vi—O8—Na3	129.36 (10)
S3^x—Na2—Cu2^x	50.86 (2)	S4—O8—Na3^xi	77.45 (11)
O11^xii—Na2—S1^x	151.44 (8)	Na1—O8—Na3^xi	85.32 (9)
O6^x—Na2—S1^x	70.90 (7)	K1^vi—O8—Na3^xi	100.98 (7)
O4^x—Na2—S1^x	18.65 (5)	Na3—O8—Na3^xi	129.03 (8)
O2—Na2—S1^x	75.03 (6)	S4—O9—Cu2	131.73 (16)
O12^xiii—Na2—S1^x	89.00 (7)	S4—O9—Na3	120.19 (14)
O3^xiv—Na2—S1^x	74.80 (7)	Cu2—O9—Na3	107.39 (10)
O10^xii—Na2—S1^x	122.93 (6)	S4—O9—Na1^xv	83.07 (11)
S2—Na2—S1^x	100.18 (4)	Cu2—O9—Na1^xv	83.73 (9)
O15^x—Na2—S1^x	63.95 (5)	Na3—O9—Na1^xv	115.59 (11)
Cu1^x—Na2—S1^x	50.53 (2)	S4—O9—Na1^xi	66.33 (10)
S3^x—Na2—S1^x	70.64 (3)	Cu2—O9—Na1^xi	75.76 (8)
Cu2^x—Na2—S1^x	55.70 (2)	Na3—O9—Na1^xi	133.43 (11)
O11^xii—Na2—S1^xii	11.92 (6)	Na1^xv—O9—Na1^xi	110.96 (7)
O6^x—Na2—S1^xii	95.20 (7)	S2^iii—O10—Cu1	134.03 (15)
O4^x—Na2—S1^xii	172.19 (7)	S2^iii—O10—K1^xvi	111.13 (11)
O2—Na2—S1^xii	109.82 (7)	Cu1—O10—K1^xvi	102.50 (9)
O12^xiii—Na2—S1^xii	107.24 (7)	S2^iii—O10—Na2^iii	84.86 (11)
O3^xiv—Na2—S1^xii	88.71 (7)	Cu1—O10—Na2^iii	89.29 (8)
O10^xii—Na2—S1^xii	60.06 (5)	K1^xvi—O10—Na2^iii	139.71 (9)
S2—Na2—S1^xii	86.13 (4)	S2^iii—O10—Na2^i	66.23 (9)
O15^x—Na2—S1^xii	115.38 (6)	Cu1—O10—Na2^i	73.24 (7)
Cu1^x—Na2—S1^xii	139.25 (4)	K1^xvi—O10—Na2^i	110.50 (8)
S3^x—Na2—S1^xii	101.08 (4)	Na2^iii—O10—Na2^i	109.79 (7)
Cu2^x—Na2—S1^xii	105.93 (3)	S1—O11—Na2^iii	149.35 (15)
S1^x—Na2—S1^xii	161.35 (4)	S1—O11—Na3^xv	104.77 (13)
O9—Na3—O13^ix	114.06 (10)	Na2^iii—O11—Na3^xv	104.77 (10)
O9—Na3—O11^x	119.56 (10)	S1—O11—Cu1	77.67 (11)
O13^ix—Na3—O11^x	123.76 (10)	Na2^iii—O11—Cu1	88.14 (9)
O9—Na3—O6	62.61 (8)	Na3^xv—O11—Cu1	102.52 (10)
O13^ix—Na3—O6	156.04 (12)	S1—O11—Na2^xiii	68.05 (10)
O11^x—Na3—O6	70.83 (8)	Na2^iii—O11—Na2^xiii	97.88 (9)
O9—Na3—O16^x	85.46 (10)	Na3^xv—O11—Na2^xiii	131.10 (10)
O13^ix—Na3—O16^x	67.32 (10)	Cu1—O11—Na2^xiii	121.20 (7)
O11^x—Na3—O16^x	100.65 (10)	S1—O12—Cu1^xvi	124.12 (14)
O6—Na3—O16^x	132.62 (11)	S1—O12—Na2^xiii	146.15 (16)
O9—Na3—O7^x	154.67 (13)	Cu1^xvi—O12—Na2^xiii	89.18 (8)
O13^ix—Na3—O7^x	72.55 (8)	S1—O12—K1^xvii	97.77 (11)
O11^x—Na3—O7^x	51.74 (7)	Cu1^xvi—O12—K1^xvii	89.87 (8)
O6—Na3—O7^x	121.48 (8)	Na2^xiii—O12—K1^xvii	87.17 (8)
O16^x—Na3—O7^x	74.50 (9)	S1—O12—K1^xvi	87.25 (11)
O9—Na3—O14	87.28 (10)	Cu1^xvi—O12—K1^xvi	65.22 (6)
O13^ix—Na3—O14	110.78 (11)	Na2^xiii—O12—K1^xvi	103.82 (7)
O11^x—Na3—O14	87.92 (9)	K1^xvii—O12—K1^xvi	152.17 (8)
O6—Na3—O14	47.11 (7)	S1—O12—Na2^xv	56.01 (9)
O16^x—Na3—O14	170.75 (9)	Cu1^xvi—O12—Na2^xv	68.52 (6)
O7^x—Na3—O14	113.99 (9)	Na2^xiii—O12—Na2^xv	154.08 (8)
O9—Na3—O8	46.81 (7)	K1^xvii—O12—Na2^xv	105.13 (7)
O13^ix—Na3—O8	67.46 (8)	K1^xvi—O12—Na2^xv	55.58 (4)
O11^x—Na3—O8	156.93 (11)	S4—O13—Na1^xi	138.07 (17)
O6—Na3—O8	106.89 (8)	S4—O13—Na3^xi	118.66 (15)
O16^x—Na3—O8	63.27 (8)	Na1^xi—O13—Na3^xi	102.40 (11)
O7^x—Na3—O8	130.01 (9)	S4—O13—Cu2^iv	79.71 (11)
O14—Na3—O8	107.51 (8)	Na1^xi—O13—Cu2^iv	92.24 (10)
O9—Na3—S1^x	138.27 (9)	Na3^xi—O13—Cu2^iv	90.86 (9)
O13^ix—Na3—S1^x	99.32 (8)	S4—O13—Na1	62.87 (11)
O11^x—Na3—S1^x	25.32 (6)	Na1^xi—O13—Na1	147.41 (10)
O6—Na3—S1^x	96.07 (6)	Na3^xi—O13—Na1	70.57 (9)
O16^x—Na3—S1^x	85.09 (7)	Cu2^iv—O13—Na1	119.07 (8)
O7^x—Na3—S1^x	26.77 (5)	S3—O14—Na1^ix	176.16 (18)
O14—Na3—S1^x	104.15 (7)	S3—O14—K1	94.51 (12)
O8—Na3—S1^x	148.27 (8)	Na1^ix—O14—K1	89.25 (9)
O9—Na3—S4^ix	132.91 (7)	S3—O14—Na3	90.21 (13)
O13^ix—Na3—S4^ix	22.21 (6)	Na1^ix—O14—Na3	87.13 (9)
O11^x—Na3—S4^ix	107.47 (7)	K1—O14—Na3	144.70 (10)
O6—Na3—S4^ix	143.77 (10)	S3—O14—Na1^xv	63.74 (10)
O16^x—Na3—S4^ix	83.61 (7)	Na1^ix—O14—Na1^xv	113.26 (8)
O7^x—Na3—S4^ix	60.92 (5)	K1—O14—Na1^xv	127.44 (9)
O14—Na3—S4^ix	97.22 (7)	Na3—O14—Na1^xv	85.74 (7)
O8—Na3—S4^ix	87.94 (5)	S3—O14—Na2^xv	53.02 (10)
S1^x—Na3—S4^ix	86.06 (4)	Na1^ix—O14—Na2^xv	127.55 (10)
O9—Na3—O8^ix	139.25 (10)	K1—O14—Na2^xv	93.58 (6)
O13^ix—Na3—O8^ix	45.61 (8)	Na3—O14—Na2^xv	62.06 (6)
O11^x—Na3—O8^ix	96.37 (8)	Na1^xv—O14—Na2^xv	105.95 (7)
O6—Na3—O8^ix	119.62 (10)	S3—O15—Cu1	145.52 (17)
O16^x—Na3—O8^ix	107.50 (8)	S3—O15—K1	106.45 (13)
O7^x—Na3—O8^ix	63.58 (7)	Cu1—O15—K1	105.87 (10)
O14—Na3—O8^ix	74.65 (8)	S3—O15—Na2^xv	79.83 (11)
O8—Na3—O8^ix	104.10 (5)	Cu1—O15—Na2^xv	74.32 (8)
S1^x—Na3—O8^ix	82.16 (5)	K1—O15—Na2^xv	118.80 (10)
S4^ix—Na3—O8^ix	24.72 (4)	S3—O15—Na3^xv	76.21 (11)
O9—Na3—S4	22.24 (6)	Cu1—O15—Na3^xv	88.34 (10)
O13^ix—Na3—S4	92.40 (7)	K1—O15—Na3^xv	136.81 (10)
O11^x—Na3—S4	137.50 (9)	Na2^xv—O15—Na3^xv	104.23 (7)
O6—Na3—S4	84.39 (6)	S3—O16—Na1^xv	138.48 (18)
O16^x—Na3—S4	71.23 (7)	S3—O16—Na3^xv	125.57 (15)
O7^x—Na3—S4	145.69 (9)	Na1^xv—O16—Na3^xv	91.43 (9)
O14—Na3—S4	100.10 (7)	S3—O16—Cu2	79.20 (11)
O8—Na3—S4	24.95 (4)	Na1^xv—O16—Cu2	89.48 (9)
S1^x—Na3—S4	147.10 (8)	Na3^xv—O16—Cu2	82.03 (8)

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