Expanding the family of mineral-like anhydrous alkali copper sulfate framework structures: new phases, topological analysis and evaluation of ion migration potentialities

Two novel compounds, K₂Cu₃(SO₄)₄ and KNaCu(SO₄)₂, were synthesized. The crystal structure of K₂Cu₃(SO₄)₄ is based on a [Cu₃(SO₄)₄]²⁻ framework with relatively simple bond topology, but with four different CuO_n polyhedron geometries. The K⁺ cations reside in the pores of the framework. The [Cu(SO₄)₂]²⁻ framework in KNaCu(SO₄)₂ encloses large elliptical channels running along [001]. Larger channels are occupied by K⁺, whereas smaller ones are filled by Na⁺. The bond-valence energy landscape (BVEL) approach has been demonstrated to be a useful method for the prediction of the mobility of alkali metal ions in various structures. By means of this approach, the threshold energies at which isosurfaces begin to percolate as well as the directions of possible ion migration in the structures were determined. The modelling of ion migration maps by the analysis of the procrystal electron-density distribution was used to rapidly identify ion migration pathways and limiting barriers between particular crystallographic sites in the structures under consideration. Its consistency and complementarity with the BVEL method have been demonstrated. Both approaches revealed a relatively low ion threshold percolation and migration barriers in the cryptochalcite-type structures [cryptochalcite: K₂Cu₅O(SO₄)₅]. Hence, one may assume that its 3D framework type is suited for ion transport applications. The review of all known members of the groups of anhydrous copper sulfates did not reveal a correlation between the porosity of the framework structures and a manifestation of ion conduction properties.

Computing details

For both structures, program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2018).

(K2Cu3SO44)

Crystal data

CuK0.67O5.33S1.33	F(000) = 2536
Mr = 217.69	Dx = 3.376 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.6088 (5) Å	Cell parameters from 2344 reflections
b = 11.9627 (5) Å	θ = 2.6–28.0°
c = 17.0791 (7) Å	µ = 6.32 mm^−1
β = 112.450 (1)°	T = 296 K
V = 2569.72 (18) Å^3	Prism
Z = 24

Data collection

Bruker APEX 2 Duo diffractometer	θmax = 28.0°, θmin = 2.6°
12218 measured reflections	h = −17→17
3093 independent reflections	k = −15→15
2746 reflections with I > 2σ(I)	l = −22→21
Rint = 0.028

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0307P)^2 + 6.8205P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.023	(Δ/σ)max < 0.001
wR(F^2) = 0.061	Δρmax = 1.40 e Å^−3
S = 1.03	Δρmin = −1.33 e Å^−3
3093 reflections	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
231 parameters	Extinction coefficient: 0.00040 (4)

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
Cu1	0.18027 (3)	0.37478 (2)	0.37549 (2)	0.01083 (9)
Cu2	0.000000	0.000000	0.500000	0.01035 (11)
Cu3	0.21091 (3)	−0.11938 (2)	0.38223 (2)	0.01233 (9)
Cu4	0.500000	0.17223 (4)	0.250000	0.02095 (13)
S1	0.15707 (5)	0.12584 (5)	0.43030 (4)	0.00891 (13)
S2	0.25976 (5)	0.62829 (5)	0.42973 (4)	0.00921 (13)
S3	0.39868 (5)	0.35893 (5)	0.32593 (4)	0.01143 (13)
S4	0.07333 (5)	0.45584 (5)	0.17289 (4)	0.01247 (14)
K1	0.48159 (6)	0.16244 (5)	0.47511 (4)	0.02471 (15)
K2	0.32922 (9)	0.63841 (6)	0.26592 (6)	0.0442 (2)
O1	0.44236 (14)	0.45639 (15)	0.38073 (11)	0.0130 (4)
O2	0.13143 (15)	0.21999 (15)	0.36936 (12)	0.0145 (4)
O3	0.32584 (16)	0.29510 (16)	0.35344 (13)	0.0205 (4)
O4	0.23614 (15)	0.52527 (15)	0.37897 (12)	0.0139 (4)
O5	0.07879 (16)	0.12492 (14)	0.47042 (13)	0.0153 (4)
O6	0.21119 (16)	0.62686 (15)	0.49384 (13)	0.0148 (4)
O7	0.20966 (16)	0.71908 (15)	0.36657 (12)	0.0163 (4)
O8	0.14523 (15)	0.02496 (15)	0.37808 (13)	0.0162 (4)
O9	0.48903 (17)	0.28597 (16)	0.32932 (13)	0.0199 (4)
O10	0.11225 (17)	0.37378 (16)	0.24151 (14)	0.0209 (5)
O11	0.26564 (15)	0.13447 (15)	0.49377 (13)	0.0165 (4)
O12	0.34385 (18)	0.40389 (16)	0.24056 (13)	0.0206 (4)
O13	0.13710 (17)	0.45542 (19)	0.12049 (14)	0.0256 (5)
O14	0.37427 (15)	0.64563 (16)	0.46935 (14)	0.0193 (4)
O15	−0.03675 (16)	0.43245 (19)	0.11633 (14)	0.0260 (5)
O16	0.07908 (19)	0.57047 (16)	0.20782 (14)	0.0252 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01413 (16)	0.00772 (15)	0.01048 (17)	−0.00134 (11)	0.00450 (13)	0.00070 (11)
Cu2	0.0139 (2)	0.0104 (2)	0.0073 (2)	−0.00380 (16)	0.00475 (17)	−0.00205 (16)
Cu3	0.02120 (17)	0.00811 (15)	0.00734 (17)	0.00284 (12)	0.00507 (13)	0.00014 (11)
Cu4	0.0423 (3)	0.0084 (2)	0.0185 (3)	0.000	0.0187 (2)	0.000
S1	0.0122 (3)	0.0062 (3)	0.0090 (3)	0.0000 (2)	0.0048 (2)	0.0004 (2)
S2	0.0128 (3)	0.0072 (3)	0.0081 (3)	0.0006 (2)	0.0045 (2)	−0.0001 (2)
S3	0.0180 (3)	0.0088 (3)	0.0068 (3)	−0.0030 (2)	0.0040 (2)	−0.0008 (2)
S4	0.0155 (3)	0.0104 (3)	0.0129 (3)	0.0012 (2)	0.0070 (3)	−0.0006 (2)
K1	0.0364 (4)	0.0189 (3)	0.0179 (3)	0.0024 (3)	0.0093 (3)	0.0045 (2)
K2	0.0934 (7)	0.0227 (3)	0.0372 (5)	0.0136 (4)	0.0480 (5)	0.0092 (3)
O1	0.0190 (9)	0.0122 (8)	0.0071 (9)	−0.0034 (7)	0.0043 (7)	−0.0031 (7)
O2	0.0198 (9)	0.0100 (8)	0.0130 (10)	−0.0017 (7)	0.0055 (8)	0.0029 (7)
O3	0.0242 (10)	0.0179 (10)	0.0177 (11)	−0.0091 (8)	0.0060 (9)	0.0025 (8)
O4	0.0218 (9)	0.0090 (8)	0.0127 (10)	−0.0015 (7)	0.0084 (8)	−0.0020 (7)
O5	0.0218 (10)	0.0131 (9)	0.0157 (10)	−0.0039 (7)	0.0124 (8)	−0.0028 (7)
O6	0.0195 (9)	0.0166 (9)	0.0092 (10)	0.0012 (7)	0.0066 (8)	0.0004 (7)
O7	0.0291 (11)	0.0092 (8)	0.0098 (10)	0.0039 (8)	0.0066 (8)	0.0018 (7)
O8	0.0203 (9)	0.0112 (8)	0.0164 (11)	0.0016 (7)	0.0062 (8)	−0.0041 (7)
O9	0.0312 (11)	0.0126 (9)	0.0167 (11)	0.0045 (8)	0.0100 (9)	−0.0022 (8)
O10	0.0253 (11)	0.0146 (9)	0.0233 (12)	0.0021 (8)	0.0100 (9)	0.0049 (8)
O11	0.0138 (9)	0.0159 (9)	0.0168 (11)	−0.0007 (7)	0.0024 (8)	0.0005 (8)
O12	0.0357 (12)	0.0153 (9)	0.0072 (10)	0.0000 (9)	0.0042 (9)	0.0002 (8)
O13	0.0249 (11)	0.0346 (12)	0.0230 (12)	0.0078 (9)	0.0154 (10)	0.0045 (10)
O14	0.0125 (9)	0.0178 (9)	0.0253 (12)	−0.0005 (7)	0.0047 (8)	−0.0041 (8)
O15	0.0188 (10)	0.0371 (13)	0.0203 (12)	−0.0044 (9)	0.0052 (9)	−0.0031 (10)
O16	0.0409 (13)	0.0120 (9)	0.0224 (12)	0.0030 (9)	0.0118 (10)	−0.0036 (8)

Geometric parameters (Å, º)

Cu1—O4	1.9463 (18)	S2—O7	1.4989 (19)
Cu1—O2	1.9566 (18)	S2—K2	3.2796 (10)
Cu1—O11^i	2.070 (2)	S3—O12	1.463 (2)
Cu1—O10	2.116 (2)	S3—O3	1.463 (2)
Cu1—O15^ii	2.126 (2)	S3—O1	1.4709 (18)
Cu1—O3	2.355 (2)	S3—O9	1.491 (2)
Cu1—K2^iii	3.6887 (8)	S3—K1	3.3307 (9)
Cu1—K1^i	3.9817 (8)	S3—K2	3.5189 (10)
Cu2—O1^i	1.9536 (18)	S4—O10	1.464 (2)
Cu2—O1^iv	1.9536 (18)	S4—O15	1.466 (2)
Cu2—O5^v	2.0129 (18)	S4—O13	1.465 (2)
Cu2—O5	2.0129 (18)	S4—O16	1.486 (2)
Cu2—O14^i	2.3564 (19)	S4—K1^x	3.4078 (10)
Cu2—O14^iv	2.3564 (19)	S4—K1^xi	3.4279 (9)
Cu3—O8	1.9331 (18)	K1—O15^xii	2.762 (2)
Cu3—O7^vi	1.9500 (18)	K1—O3	2.822 (2)
Cu3—O12^iii	1.959 (2)	K1—O9	2.930 (2)
Cu3—O6^i	1.974 (2)	K1—O5^i	2.9319 (19)
Cu3—O13^iii	2.270 (2)	K1—O14^xiii	2.932 (2)
Cu3—K2^iii	3.8930 (9)	K1—O13^xii	2.936 (2)
Cu3—K1^vii	3.9908 (8)	K1—O6^viii	3.047 (2)
Cu4—O16^iii	1.937 (2)	K1—O13^iii	3.065 (2)
Cu4—O16^viii	1.937 (2)	K1—O11	3.093 (2)
Cu4—O9	1.9655 (19)	K1—O16^iii	3.112 (2)
Cu4—O9^ix	1.9656 (19)	K1—O15^iii	3.386 (2)
Cu4—K1	3.9488 (7)	K2—O2^x	2.743 (2)
Cu4—K1^ix	3.9488 (7)	K2—O12	2.857 (2)
S1—O11	1.465 (2)	K2—O1	2.941 (2)
S1—O5	1.470 (2)	K2—O8^x	2.944 (2)
S1—O8	1.4724 (19)	K2—O10^x	2.942 (2)
S1—O2	1.4821 (18)	K2—O7	2.945 (2)
S1—K2^iii	3.4301 (10)	K2—O3^x	2.973 (2)
S2—O14	1.457 (2)	K2—O4	3.005 (2)
S2—O4	1.4701 (18)	K2—O16	3.264 (3)
S2—O6	1.479 (2)	K2—O14	3.291 (2)
O4—Cu1—O2	176.17 (8)	O13^xii—K1—O11	105.50 (6)
O4—Cu1—O11^i	92.45 (8)	O6^viii—K1—O11	161.95 (6)
O2—Cu1—O11^i	88.90 (8)	O13^iii—K1—O11	68.86 (6)
O4—Cu1—O10	92.45 (8)	O15^xii—K1—O16^iii	130.82 (6)
O2—Cu1—O10	86.41 (8)	O3—K1—O16^iii	67.84 (6)
O11^i—Cu1—O10	174.25 (8)	O9—K1—O16^iii	53.64 (5)
O4—Cu1—O15^ii	93.20 (8)	O5^i—K1—O16^iii	128.78 (6)
O2—Cu1—O15^ii	90.50 (8)	O14^xiii—K1—O16^iii	119.33 (6)
O11^i—Cu1—O15^ii	84.47 (8)	O13^xii—K1—O16^iii	120.57 (6)
O10—Cu1—O15^ii	92.26 (8)	O6^viii—K1—O16^iii	85.66 (6)
O4—Cu1—O3	92.10 (7)	O13^iii—K1—O16^iii	45.23 (6)
O2—Cu1—O3	84.13 (7)	O11—K1—O16^iii	99.61 (6)
O11^i—Cu1—O3	100.17 (7)	O15^xii—K1—S3	147.23 (5)
O10—Cu1—O3	82.65 (8)	O3—K1—S3	25.86 (4)
O15^ii—Cu1—O3	172.80 (8)	O9—K1—S3	26.57 (4)
O4—Cu1—K2^iii	130.14 (6)	O5^i—K1—S3	64.93 (4)
O2—Cu1—K2^iii	46.63 (6)	O14^xiii—K1—S3	71.59 (5)
O11^i—Cu1—K2^iii	125.06 (5)	O13^xii—K1—S3	155.52 (5)
O10—Cu1—K2^iii	52.84 (5)	O6^viii—K1—S3	102.31 (4)
O15^ii—Cu1—K2^iii	119.24 (7)	O13^iii—K1—S3	101.95 (5)
O3—Cu1—K2^iii	53.57 (5)	O11—K1—S3	95.60 (4)
O4—Cu1—K1^i	112.90 (6)	O16^iii—K1—S3	66.36 (4)
O2—Cu1—K1^i	70.65 (6)	O15^xii—K1—O15^iii	100.29 (6)
O11^i—Cu1—K1^i	50.10 (5)	O3—K1—O15^iii	110.71 (6)
O10—Cu1—K1^i	124.88 (6)	O9—K1—O15^iii	86.11 (6)
O15^ii—Cu1—K1^i	41.16 (6)	O5^i—K1—O15^iii	171.74 (6)
O3—Cu1—K1^i	139.67 (5)	O14^xiii—K1—O15^iii	123.14 (6)
K2^iii—Cu1—K1^i	116.375 (18)	O13^xii—K1—O15^iii	77.57 (6)
O1^i—Cu2—O1^iv	180.0	O6^viii—K1—O15^iii	62.35 (5)
O1^i—Cu2—O5^v	88.67 (8)	O13^iii—K1—O15^iii	42.47 (6)
O1^iv—Cu2—O5^v	91.33 (8)	O11—K1—O15^iii	110.26 (5)
O1^i—Cu2—O5	91.33 (8)	O16^iii—K1—O15^iii	43.14 (5)
O1^iv—Cu2—O5	88.67 (8)	S3—K1—O15^iii	106.90 (4)
O5^v—Cu2—O5	180.0	O2^x—K2—O12	100.04 (6)
O1^i—Cu2—O14^i	89.85 (7)	O2^x—K2—O1	127.17 (6)
O1^iv—Cu2—O14^i	90.15 (7)	O12—K2—O1	47.55 (5)
O5^v—Cu2—O14^i	78.85 (7)	O2^x—K2—O8^x	48.46 (5)
O5—Cu2—O14^i	101.15 (7)	O12—K2—O8^x	51.93 (6)
O1^i—Cu2—O14^iv	90.15 (7)	O1—K2—O8^x	90.97 (5)
O1^iv—Cu2—O14^iv	89.85 (7)	O2^x—K2—O10^x	58.67 (6)
O5^v—Cu2—O14^iv	101.15 (7)	O12—K2—O10^x	153.83 (7)
O5—Cu2—O14^iv	78.85 (7)	O1—K2—O10^x	130.98 (7)
O14^i—Cu2—O14^iv	180.00 (12)	O8^x—K2—O10^x	106.56 (6)
O8—Cu3—O7^vi	154.22 (8)	O2^x—K2—O7	134.78 (6)
O8—Cu3—O12^iii	81.51 (9)	O12—K2—O7	119.76 (6)
O7^vi—Cu3—O12^iii	90.81 (8)	O1—K2—O7	96.82 (5)
O8—Cu3—O6^i	97.54 (8)	O8^x—K2—O7	155.07 (7)
O7^vi—Cu3—O6^i	94.31 (8)	O10^x—K2—O7	86.02 (6)
O12^iii—Cu3—O6^i	169.46 (9)	O2^x—K2—O3^x	60.91 (6)
O8—Cu3—O13^iii	93.40 (8)	O12—K2—O3^x	125.98 (7)
O7^vi—Cu3—O13^iii	110.36 (9)	O1—K2—O3^x	167.90 (7)
O12^iii—Cu3—O13^iii	84.21 (9)	O8^x—K2—O3^x	89.84 (6)
O6^i—Cu3—O13^iii	85.38 (8)	O10^x—K2—O3^x	60.00 (6)
O8—Cu3—K2^iii	47.19 (6)	O7—K2—O3^x	77.75 (6)
O7^vi—Cu3—K2^iii	134.76 (6)	O2^x—K2—O4	165.29 (7)
O12^iii—Cu3—K2^iii	44.77 (6)	O12—K2—O4	74.10 (6)
O6^i—Cu3—K2^iii	128.12 (5)	O1—K2—O4	58.67 (5)
O13^iii—Cu3—K2^iii	64.99 (6)	O8^x—K2—O4	122.85 (6)
O8—Cu3—K1^vii	120.00 (6)	O10^x—K2—O4	130.25 (6)
O7^vi—Cu3—K1^vii	84.72 (6)	O7—K2—O4	46.38 (5)
O12^iii—Cu3—K1^vii	123.60 (7)	O3^x—K2—O4	111.20 (6)
O6^i—Cu3—K1^vii	48.01 (6)	O2^x—K2—O16	110.43 (7)
O13^iii—Cu3—K1^vii	46.55 (6)	O12—K2—O16	80.47 (6)
K2^iii—Cu3—K1^vii	110.68 (2)	O1—K2—O16	103.77 (6)
O16^iii—Cu4—O16^viii	102.11 (13)	O8^x—K2—O16	94.21 (6)
O16^iii—Cu4—O9	88.82 (9)	O10^x—K2—O16	119.56 (6)
O16^viii—Cu4—O9	152.96 (9)	O7—K2—O16	60.95 (6)
O16^iii—Cu4—O9^ix	152.96 (9)	O3^x—K2—O16	64.13 (6)
O16^viii—Cu4—O9^ix	88.82 (9)	O4—K2—O16	55.71 (6)
O9—Cu4—O9^ix	92.39 (12)	O2^x—K2—S2	160.80 (5)
O16^iii—Cu4—K1	50.83 (7)	O12—K2—S2	98.77 (5)
O16^viii—Cu4—K1	126.46 (7)	O1—K2—S2	69.63 (4)
O9—Cu4—K1	45.55 (6)	O8^x—K2—S2	149.34 (5)
O9^ix—Cu4—K1	137.85 (6)	O10^x—K2—S2	104.07 (5)
O16^iii—Cu4—K1^ix	126.46 (7)	O7—K2—S2	27.19 (4)
O16^viii—Cu4—K1^ix	50.83 (7)	O3^x—K2—S2	104.35 (5)
O9—Cu4—K1^ix	137.85 (6)	O4—K2—S2	26.60 (4)
O9^ix—Cu4—K1^ix	45.55 (6)	O16—K2—S2	69.10 (4)
K1—Cu4—K1^ix	176.60 (2)	O2^x—K2—O14	149.60 (6)
O11—S1—O5	111.18 (12)	O12—K2—O14	100.96 (6)
O11—S1—O8	110.62 (11)	O1—K2—O14	58.43 (5)
O5—S1—O8	110.18 (11)	O8^x—K2—O14	149.37 (6)
O11—S1—O2	111.51 (11)	O10^x—K2—O14	94.36 (6)
O5—S1—O2	108.35 (11)	O7—K2—O14	45.30 (5)
O8—S1—O2	104.80 (12)	O3^x—K2—O14	120.31 (6)
O11—S1—K2^iii	107.70 (9)	O4—K2—O14	44.58 (5)
O5—S1—K2^iii	140.80 (9)	O16—K2—O14	94.57 (6)
O8—S1—K2^iii	58.56 (8)	S2—K2—O14	25.63 (4)
O2—S1—K2^iii	50.70 (8)	O2^x—K2—S1^x	24.72 (4)
O14—S2—O4	110.33 (11)	O12—K2—S1^x	77.05 (5)
O14—S2—O6	111.03 (12)	O1—K2—S1^x	114.14 (4)
O4—S2—O6	111.59 (11)	O8^x—K2—S1^x	25.26 (4)
O14—S2—O7	110.06 (12)	O10^x—K2—S1^x	83.29 (5)
O4—S2—O7	104.24 (11)	O7—K2—S1^x	146.42 (5)
O6—S2—O7	109.39 (11)	O3^x—K2—S1^x	69.32 (4)
O14—S2—K2	77.61 (9)	O4—K2—S1^x	143.27 (5)
O4—S2—K2	66.24 (8)	O16—K2—S1^x	97.56 (5)
O6—S2—K2	170.95 (9)	S2—K2—S1^x	166.60 (4)
O7—S2—K2	63.85 (8)	O14—K2—S1^x	167.17 (5)
O12—S3—O3	111.19 (12)	S3—O1—Cu2^xiv	141.16 (12)
O12—S3—O1	105.73 (11)	S3—O1—K2	100.43 (9)
O3—S3—O1	111.59 (12)	Cu2^xiv—O1—K2	113.39 (8)
O12—S3—O9	110.67 (12)	S1—O2—Cu1	134.23 (12)
O3—S3—O9	109.38 (12)	S1—O2—K2^iii	104.59 (9)
O1—S3—O9	108.21 (12)	Cu1—O2—K2^iii	102.14 (8)
O12—S3—K1	156.42 (9)	S3—O3—Cu1	123.67 (12)
O3—S3—K1	57.28 (8)	S3—O3—K1	96.86 (10)
O1—S3—K1	97.82 (8)	Cu1—O3—K1	123.44 (8)
O9—S3—K1	61.55 (8)	S3—O3—K2^iii	119.96 (11)
O12—S3—K2	51.86 (8)	Cu1—O3—K2^iii	86.83 (6)
O3—S3—K2	116.72 (9)	K1—O3—K2^iii	106.69 (7)
O1—S3—K2	55.29 (8)	S2—O4—Cu1	142.03 (13)
O9—S3—K2	133.90 (9)	S2—O4—K2	87.16 (8)
K1—S3—K2	150.25 (3)	Cu1—O4—K2	130.73 (8)
O10—S4—O15	111.45 (13)	S1—O5—Cu2	132.28 (11)
O10—S4—O13	111.65 (13)	S1—O5—K1^i	118.82 (9)
O15—S4—O13	106.94 (13)	Cu2—O5—K1^i	108.89 (8)
O10—S4—O16	110.49 (13)	S2—O6—Cu3^i	125.81 (12)
O15—S4—O16	108.94 (13)	S2—O6—K1^xv	130.60 (11)
O13—S4—O16	107.20 (13)	Cu3^i—O6—K1^xv	103.19 (8)
O10—S4—K1^x	171.82 (9)	S2—O7—Cu3^xvi	129.91 (12)
O15—S4—K1^x	76.72 (9)	S2—O7—K2	88.96 (9)
O13—S4—K1^x	64.07 (9)	Cu3^xvi—O7—K2	115.28 (8)
O16—S4—K1^x	65.88 (9)	S1—O8—Cu3	140.15 (13)
O10—S4—K1^xi	113.35 (9)	S1—O8—K2^iii	96.18 (9)
O15—S4—K1^xi	51.40 (9)	Cu3—O8—K2^iii	104.00 (8)
O13—S4—K1^xi	58.30 (9)	S3—O9—Cu4	131.08 (13)
O16—S4—K1^xi	136.08 (9)	S3—O9—K1	91.87 (10)
K1^x—S4—K1^xi	70.99 (2)	Cu4—O9—K1	105.84 (8)
O15^xii—K1—O3	125.53 (7)	S4—O10—Cu1	137.49 (12)
O15^xii—K1—O9	173.37 (7)	S4—O10—K2^iii	128.93 (12)
O3—K1—O9	49.51 (6)	Cu1—O10—K2^iii	92.19 (7)
O15^xii—K1—O5^i	87.12 (6)	S1—O11—Cu1^i	129.59 (13)
O3—K1—O5^i	61.51 (6)	S1—O11—K1	131.37 (12)
O9—K1—O5^i	86.38 (6)	Cu1^i—O11—K1	99.00 (7)
O15^xii—K1—O14^xiii	108.16 (7)	S3—O12—Cu3^x	148.79 (14)
O3—K1—O14^xiii	91.11 (6)	S3—O12—K2	104.38 (10)
O9—K1—O14^xiii	69.15 (6)	Cu3^x—O12—K2	106.36 (8)
O5^i—K1—O14^xiii	56.76 (6)	S4—O13—Cu3^x	140.40 (14)
O15^xii—K1—O13^xii	48.73 (6)	S4—O13—K1^xi	96.57 (11)
O3—K1—O13^xii	171.46 (7)	Cu3^x—O13—K1^xi	99.30 (8)
O9—K1—O13^xii	135.50 (6)	S4—O13—K1^x	90.46 (10)
O5^i—K1—O13^xii	110.31 (6)	Cu3^x—O13—K1^x	127.34 (9)
O14^xiii—K1—O13^xii	85.72 (6)	K1^xi—O13—K1^x	82.79 (6)
O15^xii—K1—O6^viii	106.37 (6)	S2—O14—Cu2^xiv	123.71 (11)
O3—K1—O6^viii	127.42 (6)	S2—O14—K1^xiii	136.57 (11)
O9—K1—O6^viii	78.05 (6)	Cu2^xiv—O14—K1^xiii	99.65 (7)
O5^i—K1—O6^viii	119.23 (6)	S2—O14—K2	76.76 (9)
O14^xiii—K1—O6^viii	62.80 (5)	Cu2^xiv—O14—K2	92.40 (7)
O13^xii—K1—O6^viii	57.65 (6)	K1^xiii—O14—K2	101.19 (7)
O15^xii—K1—O13^iii	85.88 (7)	S4—O15—Cu1^ii	138.74 (14)
O3—K1—O13^iii	88.13 (6)	S4—O15—K1^xi	104.09 (11)
O9—K1—O13^iii	97.88 (6)	Cu1^ii—O15—K1^xi	108.40 (9)
O5^i—K1—O13^iii	135.69 (6)	S4—O15—K1^x	78.36 (9)
O14^xiii—K1—O13^iii	163.02 (6)	Cu1^ii—O15—K1^x	131.68 (9)
O13^xii—K1—O13^iii	97.21 (6)	K1^xi—O15—K1^x	79.71 (6)
O6^viii—K1—O13^iii	104.70 (6)	S4—O16—Cu4^xv	141.08 (15)
O15^xii—K1—O11	57.26 (6)	S4—O16—K1^x	88.29 (10)
O3—K1—O11	70.17 (6)	Cu4^xv—O16—K1^x	100.32 (8)
O9—K1—O11	118.99 (6)	S4—O16—K2	103.94 (11)
O5^i—K1—O11	70.65 (5)	Cu4^xv—O16—K2	113.18 (8)
O14^xiii—K1—O11	126.58 (6)	K1^x—O16—K2	93.63 (6)

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

(KNaCuSO42)

Crystal data

CuKNaO8S2	F(000) = 1240
Mr = 317.75	Dx = 3.088 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.9721 (10) Å	Cell parameters from 1256 reflections
b = 9.4576 (6) Å	θ = 2.5–28.0°
c = 9.0679 (6) Å	µ = 4.49 mm^−1
β = 93.635 (1)°	T = 296 K
V = 1367.02 (15) Å^3	Prism
Z = 8

Data collection

Bruker APEX 2 Duo diffractometer	θmax = 28.0°, θmin = 2.5°
6732 measured reflections	h = −21→21
1655 independent reflections	k = −12→12
1452 reflections with I > 2σ(I)	l = −6→11
Rint = 0.028

Refinement

Refinement on F^2	120 parameters
Least-squares matrix: full	0 restraints
R[F^2 > 2σ(F^2)] = 0.029	w = 1/[σ^2(Fo^2) + (0.0372P)^2 + 5.925P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.085	(Δ/σ)max = 0.001
S = 1.19	Δρmax = 0.69 e Å^−3
1655 reflections	Δρmin = −0.81 e Å^−3

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
Cu1	0.13626 (3)	0.69568 (5)	0.16921 (5)	0.01462 (14)
S1	0.28562 (5)	0.90211 (9)	0.14187 (9)	0.01156 (18)
S2	−0.02639 (5)	0.75891 (9)	0.05052 (9)	0.01176 (18)
K1	0.11238 (5)	0.93846 (8)	−0.18306 (9)	0.02035 (19)
Na1	0.250000	0.750000	0.500000	0.0164 (4)
Na2	0.000000	0.5682 (2)	−0.250000	0.0236 (5)
O1	0.02206 (15)	0.6307 (3)	0.1012 (3)	0.0157 (5)
O2	0.22461 (17)	0.9931 (3)	0.0629 (3)	0.0262 (6)
O3	0.33740 (17)	0.8228 (3)	0.0412 (3)	0.0239 (6)
O4	0.24175 (17)	0.7929 (3)	0.2289 (3)	0.0244 (6)
O5	−0.10725 (15)	0.7605 (3)	0.1253 (3)	0.0182 (5)
O6	−0.04543 (17)	0.7551 (3)	−0.1080 (3)	0.0207 (6)
O7	0.34103 (18)	0.9811 (3)	0.2465 (3)	0.0268 (6)
O8	0.02487 (18)	0.8821 (3)	0.0935 (3)	0.0231 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0130 (2)	0.0163 (2)	0.0148 (2)	−0.00076 (16)	0.00308 (16)	0.00030 (16)
S1	0.0097 (4)	0.0128 (4)	0.0123 (4)	−0.0008 (3)	0.0017 (3)	−0.0014 (3)
S2	0.0121 (4)	0.0146 (4)	0.0087 (4)	0.0008 (3)	0.0022 (3)	0.0004 (3)
K1	0.0242 (4)	0.0180 (4)	0.0185 (4)	0.0004 (3)	−0.0012 (3)	−0.0014 (3)
Na1	0.0181 (10)	0.0177 (10)	0.0123 (9)	0.0049 (8)	−0.0073 (7)	−0.0033 (8)
Na2	0.0305 (12)	0.0114 (10)	0.0301 (12)	0.000	0.0110 (10)	0.000
O1	0.0145 (12)	0.0171 (12)	0.0158 (12)	0.0046 (10)	0.0035 (9)	0.0023 (10)
O2	0.0225 (14)	0.0250 (14)	0.0298 (15)	0.0102 (12)	−0.0079 (12)	−0.0002 (12)
O3	0.0220 (14)	0.0331 (16)	0.0181 (13)	0.0100 (12)	0.0122 (11)	0.0031 (11)
O4	0.0175 (13)	0.0359 (16)	0.0202 (14)	−0.0129 (12)	0.0032 (11)	0.0068 (12)
O5	0.0109 (12)	0.0253 (14)	0.0191 (13)	0.0059 (10)	0.0053 (10)	0.0035 (11)
O6	0.0269 (14)	0.0252 (14)	0.0099 (12)	0.0060 (11)	−0.0004 (10)	−0.0009 (10)
O7	0.0313 (16)	0.0173 (13)	0.0296 (15)	−0.0028 (12)	−0.0154 (12)	−0.0057 (11)
O8	0.0287 (15)	0.0212 (14)	0.0195 (13)	−0.0115 (11)	0.0036 (11)	−0.0003 (11)

Geometric parameters (Å, º)

Cu1—O4	1.965 (3)	K1—O2	2.819 (3)
Cu1—O1	1.986 (3)	K1—O3^i	2.876 (3)
Cu1—O3^i	1.987 (3)	K1—O5^vi	2.897 (3)
Cu1—O5^ii	2.042 (3)	K1—O8^vi	2.927 (3)
Cu1—O7^iii	2.191 (3)	K1—O8^viii	2.929 (3)
Cu1—Na2^iv	3.4210 (16)	K1—O8	2.995 (3)
Cu1—Na1	3.4454 (5)	K1—O2^viii	3.076 (3)
Cu1—K1^v	3.7386 (9)	K1—O6	3.169 (3)
Cu1—K1	3.9328 (9)	K1—O4^i	3.242 (3)
S1—O2	1.454 (3)	K1—O4^viii	3.401 (3)
S1—O7	1.461 (3)	Na1—O5^ix	2.484 (3)
S1—O3	1.475 (3)	Na1—O5^ii	2.484 (3)
S1—O4	1.500 (3)	Na1—O4	2.486 (3)
S1—K1^v	3.6065 (12)	Na1—O4^x	2.486 (3)
S1—K1^i	3.6182 (12)	Na1—O2^v	2.534 (3)
S2—O6	1.451 (3)	Na1—O2^iii	2.534 (3)
S2—O8	1.463 (3)	Na2—O6	2.330 (3)
S2—O1	1.495 (3)	Na2—O6^vii	2.330 (3)
S2—O5	1.497 (2)	Na2—O1^xi	2.354 (3)
S2—Na2	3.3171 (14)	Na2—O1^iv	2.354 (3)
S2—K1^vi	3.4253 (11)	Na2—O7^xii	2.580 (3)
S2—K1	3.5885 (11)	Na2—O7^i	2.580 (3)
K1—O6^vii	2.735 (3)
O4—Cu1—O1	170.09 (12)	O2^v—Na1—Cu1	104.82 (6)
O4—Cu1—O3^i	94.35 (12)	O2^iii—Na1—Cu1	75.18 (6)
O1—Cu1—O3^i	85.46 (11)	O5^ix—Na1—Cu1^x	35.87 (6)
O4—Cu1—O5^ii	81.27 (11)	O5^ii—Na1—Cu1^x	144.13 (6)
O1—Cu1—O5^ii	96.84 (10)	O4—Na1—Cu1^x	145.92 (6)
O3^i—Cu1—O5^ii	167.48 (11)	O4^x—Na1—Cu1^x	34.08 (6)
O4—Cu1—O7^iii	102.55 (12)	O2^v—Na1—Cu1^x	75.18 (6)
O1—Cu1—O7^iii	87.13 (10)	O2^iii—Na1—Cu1^x	104.82 (6)
O3^i—Cu1—O7^iii	102.30 (12)	Cu1—Na1—Cu1^x	180.0
O5^ii—Cu1—O7^iii	90.12 (11)	O5^ix—Na1—K1^v	133.46 (6)
O4—Cu1—Na2^iv	145.93 (8)	O5^ii—Na1—K1^v	46.54 (6)
O1—Cu1—Na2^iv	41.95 (7)	O4—Na1—K1^v	58.20 (7)
O3^i—Cu1—Na2^iv	108.52 (9)	O4^x—Na1—K1^v	121.80 (7)
O5^ii—Cu1—Na2^iv	80.76 (7)	O2^v—Na1—K1^v	44.87 (7)
O7^iii—Cu1—Na2^iv	48.93 (8)	O2^iii—Na1—K1^v	135.13 (7)
O4—Cu1—Na1	45.15 (8)	Cu1—Na1—K1^v	59.997 (14)
O1—Cu1—Na1	137.71 (7)	Cu1^x—Na1—K1^v	120.003 (14)
O3^i—Cu1—Na1	135.80 (8)	O5^ix—Na1—K1^iii	46.54 (6)
O5^ii—Cu1—Na1	45.47 (7)	O5^ii—Na1—K1^iii	133.46 (6)
O7^iii—Cu1—Na1	76.58 (7)	O4—Na1—K1^iii	121.80 (7)
Na2^iv—Cu1—Na1	103.287 (11)	O4^x—Na1—K1^iii	58.20 (7)
O4—Cu1—K1^v	64.74 (9)	O2^v—Na1—K1^iii	135.13 (7)
O1—Cu1—K1^v	106.57 (7)	O2^iii—Na1—K1^iii	44.87 (7)
O3^i—Cu1—K1^v	117.26 (9)	Cu1—Na1—K1^iii	120.003 (14)
O5^ii—Cu1—K1^v	50.28 (8)	Cu1^x—Na1—K1^iii	59.997 (14)
O7^iii—Cu1—K1^v	138.66 (8)	K1^v—Na1—K1^iii	180.0
Na2^iv—Cu1—K1^v	121.18 (3)	O5^ix—Na1—K1^i	77.74 (6)
Na1—Cu1—K1^v	67.057 (15)	O5^ii—Na1—K1^i	102.26 (6)
O4—Cu1—K1	89.31 (8)	O4—Na1—K1^i	51.68 (7)
O1—Cu1—K1	83.61 (7)	O4^x—Na1—K1^i	128.32 (7)
O3^i—Cu1—K1	44.53 (8)	O2^v—Na1—K1^i	132.06 (7)
O5^ii—Cu1—K1	123.34 (8)	O2^iii—Na1—K1^i	47.94 (7)
O7^iii—Cu1—K1	146.06 (8)	Cu1—Na1—K1^i	66.700 (14)
Na2^iv—Cu1—K1	124.720 (19)	Cu1^x—Na1—K1^i	113.299 (14)
Na1—Cu1—K1	129.696 (17)	K1^v—Na1—K1^i	109.495 (11)
K1^v—Cu1—K1	75.157 (11)	K1^iii—Na1—K1^i	70.505 (11)
O2—S1—O7	112.14 (17)	O5^ix—Na1—K1^xiii	102.26 (6)
O2—S1—O3	112.37 (17)	O5^ii—Na1—K1^xiii	77.74 (6)
O7—S1—O3	108.76 (18)	O4—Na1—K1^xiii	128.32 (7)
O2—S1—O4	110.23 (17)	O4^x—Na1—K1^xiii	51.68 (7)
O7—S1—O4	107.10 (17)	O2^v—Na1—K1^xiii	47.94 (7)
O3—S1—O4	105.94 (17)	O2^iii—Na1—K1^xiii	132.06 (7)
O2—S1—K1^v	57.36 (12)	Cu1—Na1—K1^xiii	113.300 (14)
O7—S1—K1^v	87.16 (13)	Cu1^x—Na1—K1^xiii	66.701 (14)
O3—S1—K1^v	163.93 (12)	K1^v—Na1—K1^xiii	70.505 (11)
O4—S1—K1^v	70.07 (12)	K1^iii—Na1—K1^xiii	109.495 (11)
O2—S1—K1^i	149.42 (12)	K1^i—Na1—K1^xiii	180.0
O7—S1—K1^i	97.92 (12)	O6—Na2—O6^vii	81.27 (15)
O3—S1—K1^i	49.06 (11)	O6—Na2—O1^xi	170.44 (9)
O4—S1—K1^i	63.59 (12)	O6^vii—Na2—O1^xi	103.09 (9)
K1^v—S1—K1^i	132.82 (3)	O6—Na2—O1^iv	103.09 (9)
O6—S2—O8	111.23 (16)	O6^vii—Na2—O1^iv	170.44 (9)
O6—S2—O1	110.90 (15)	O1^xi—Na2—O1^iv	73.94 (13)
O8—S2—O1	107.12 (16)	O6—Na2—O7^xii	78.64 (10)
O6—S2—O5	108.46 (16)	O6^vii—Na2—O7^xii	118.10 (10)
O8—S2—O5	110.82 (16)	O1^xi—Na2—O7^xii	91.81 (10)
O1—S2—O5	108.27 (14)	O1^iv—Na2—O7^xii	71.32 (9)
O6—S2—Na2	37.08 (11)	O6—Na2—O7^i	118.10 (10)
O8—S2—Na2	123.64 (11)	O6^vii—Na2—O7^i	78.65 (10)
O1—S2—Na2	73.82 (10)	O1^xi—Na2—O7^i	71.32 (9)
O5—S2—Na2	122.43 (11)	O1^iv—Na2—O7^i	91.81 (10)
O6—S2—K1^vi	107.73 (11)	O7^xii—Na2—O7^i	159.19 (15)
O8—S2—K1^vi	58.05 (12)	O6—Na2—S2^vii	95.82 (9)
O1—S2—K1^vi	141.35 (10)	O6^vii—Na2—S2^vii	22.05 (6)
O5—S2—K1^vi	57.01 (11)	O1^xi—Na2—S2^vii	86.12 (6)
Na2—S2—K1^vi	144.82 (4)	O1^iv—Na2—S2^vii	159.50 (9)
O6—S2—K1	61.66 (11)	O7^xii—Na2—S2^vii	105.33 (7)
O8—S2—K1	54.83 (11)	O7^i—Na2—S2^vii	86.11 (7)
O1—S2—K1	103.79 (10)	O6—Na2—S2	22.05 (6)
O5—S2—K1	147.75 (11)	O6^vii—Na2—S2	95.83 (9)
Na2—S2—K1	69.94 (3)	O1^xi—Na2—S2	159.50 (9)
K1^vi—S2—K1	95.05 (3)	O1^iv—Na2—S2	86.12 (6)
O6^vii—K1—O2	149.91 (9)	O7^xii—Na2—S2	86.11 (7)
O6^vii—K1—O3^i	81.43 (8)	O7^i—Na2—S2	105.33 (7)
O2—K1—O3^i	70.02 (9)	S2^vii—Na2—S2	114.11 (7)
O6^vii—K1—O5^vi	137.20 (8)	O6—Na2—Cu1^iv	102.16 (7)
O2—K1—O5^vi	72.59 (8)	O6^vii—Na2—Cu1^iv	153.71 (6)
O3^i—K1—O5^vi	140.69 (8)	O1^xi—Na2—Cu1^iv	70.14 (7)
O6^vii—K1—O8^vi	107.02 (8)	O1^iv—Na2—Cu1^iv	34.32 (6)
O2—K1—O8^vi	97.13 (8)	O7^xii—Na2—Cu1^iv	39.81 (6)
O3^i—K1—O8^vi	124.49 (8)	O7^i—Na2—Cu1^iv	120.31 (9)
O5^vi—K1—O8^vi	49.46 (7)	S2^vii—Na2—Cu1^iv	133.50 (2)
O6^vii—K1—O8^viii	74.90 (8)	S2—Na2—Cu1^iv	96.031 (18)
O2—K1—O8^viii	133.84 (9)	O6—Na2—Cu1^xi	153.71 (6)
O3^i—K1—O8^viii	156.12 (9)	O6^vii—Na2—Cu1^xi	102.16 (7)
O5^vi—K1—O8^viii	62.48 (8)	O1^xi—Na2—Cu1^xi	34.32 (6)
O8^vi—K1—O8^viii	61.53 (10)	O1^iv—Na2—Cu1^xi	70.14 (7)
O6^vii—K1—O8	106.53 (8)	O7^xii—Na2—Cu1^xi	120.31 (9)
O2—K1—O8	71.18 (8)	O7^i—Na2—Cu1^xi	39.81 (6)
O3^i—K1—O8	66.70 (8)	S2^vii—Na2—Cu1^xi	96.032 (18)
O5^vi—K1—O8	90.20 (7)	S2—Na2—Cu1^xi	133.50 (2)
O8^vi—K1—O8	58.22 (10)	Cu1^iv—Na2—Cu1^xi	86.32 (5)
O8^viii—K1—O8	117.04 (10)	O6—Na2—K1	53.05 (8)
O6^vii—K1—O2^viii	80.53 (8)	O6^vii—Na2—K1	42.30 (7)
O2—K1—O2^viii	100.51 (8)	O1^xi—Na2—K1	135.30 (6)
O3^i—K1—O2^viii	110.88 (8)	O1^iv—Na2—K1	134.49 (7)
O5^vi—K1—O2^viii	87.31 (8)	O7^xii—Na2—K1	126.67 (9)
O8^vi—K1—O2^viii	124.61 (8)	O7^i—Na2—K1	73.86 (7)
O8^viii—K1—O2^viii	68.60 (8)	S2^vii—Na2—K1	64.25 (4)
O8—K1—O2^viii	171.69 (8)	S2—Na2—K1	58.24 (3)
O6^vii—K1—O6	61.35 (9)	Cu1^iv—Na2—K1	154.11 (3)
O2—K1—O6	113.89 (8)	Cu1^xi—Na2—K1	112.902 (17)
O3^i—K1—O6	68.71 (8)	O6—Na2—K1^vii	42.30 (7)
O5^vi—K1—O6	117.84 (7)	O6^vii—Na2—K1^vii	53.05 (8)
O8^vi—K1—O6	68.75 (7)	O1^xi—Na2—K1^vii	134.49 (7)
O8^viii—K1—O6	96.56 (8)	O1^iv—Na2—K1^vii	135.30 (6)
O8—K1—O6	45.82 (7)	O7^xii—Na2—K1^vii	73.86 (7)
O2^viii—K1—O6	141.74 (7)	O7^i—Na2—K1^vii	126.67 (9)
O6^vii—K1—O4^i	74.68 (8)	S2^vii—Na2—K1^vii	58.24 (3)
O2—K1—O4^i	78.41 (8)	S2—Na2—K1^vii	64.25 (4)
O3^i—K1—O4^i	45.20 (7)	Cu1^iv—Na2—K1^vii	112.902 (17)
O5^vi—K1—O4^i	135.67 (7)	Cu1^xi—Na2—K1^vii	154.11 (3)
O8^vi—K1—O4^i	169.61 (8)	K1—Na2—K1^vii	55.90 (4)
O8^viii—K1—O4^i	128.13 (7)	S2—O1—Cu1	106.96 (14)
O8—K1—O4^i	111.39 (8)	S2—O1—Na2^iv	136.96 (14)
O2^viii—K1—O4^i	65.69 (7)	Cu1—O1—Na2^iv	103.73 (10)
O6—K1—O4^i	104.25 (7)	S1—O2—Na1^xiv	124.50 (16)
O6^vii—K1—O4^viii	121.84 (7)	S1—O2—K1	130.83 (16)
O2—K1—O4^viii	71.54 (8)	Na1^xiv—O2—K1	95.77 (9)
O3^i—K1—O4^viii	126.17 (8)	S1—O2—K1^v	99.18 (14)
O5^vi—K1—O4^viii	48.16 (7)	Na1^xiv—O2—K1^v	94.35 (9)
O8^vi—K1—O4^viii	96.25 (7)	K1—O2—K1^v	105.04 (9)
O8^viii—K1—O4^viii	71.06 (8)	S1—O3—Cu1^i	143.13 (18)
O8—K1—O4^viii	130.69 (7)	S1—O3—K1^i	108.15 (14)
O2^viii—K1—O4^viii	43.59 (7)	Cu1^i—O3—K1^i	106.49 (11)
O6—K1—O4^viii	164.24 (7)	S1—O4—Cu1	126.72 (17)
O4^i—K1—O4^viii	91.25 (2)	S1—O4—Na1	129.44 (16)
O6^vii—K1—S2^vi	128.67 (7)	Cu1—O4—Na1	100.77 (10)
O2—K1—S2^vi	79.53 (6)	S1—O4—K1^i	91.92 (13)
O3^i—K1—S2^vi	131.88 (6)	Cu1—O4—K1^i	105.02 (12)
O5^vi—K1—S2^vi	25.68 (5)	Na1—O4—K1^i	91.33 (9)
O8^vi—K1—S2^vi	25.09 (5)	S1—O4—K1^v	85.43 (13)
O8^viii—K1—S2^vi	64.81 (6)	Cu1—O4—K1^v	83.76 (10)
O8—K1—S2^vi	68.65 (6)	Na1—O4—K1^v	83.40 (8)
O2^viii—K1—S2^vi	110.65 (6)	K1^i—O4—K1^v	170.52 (10)
O6—K1—S2^vi	92.27 (5)	S2—O5—Cu1^ii	131.51 (16)
O4^i—K1—S2^vi	156.40 (6)	S2—O5—Na1^ii	125.84 (15)
O4^viii—K1—S2^vi	73.82 (5)	Cu1^ii—O5—Na1^ii	98.66 (9)
O5^ix—Na1—O5^ii	180.0	S2—O5—K1^vi	97.31 (13)
O5^ix—Na1—O4	116.64 (9)	Cu1^ii—O5—K1^vi	96.87 (10)
O5^ii—Na1—O4	63.36 (8)	Na1^ii—O5—K1^vi	94.96 (8)
O5^ix—Na1—O4^x	63.36 (9)	S2—O6—Na2	120.86 (15)
O5^ii—Na1—O4^x	116.64 (9)	S2—O6—K1^vii	135.97 (15)
O4—Na1—O4^x	180.0	Na2—O6—K1^vii	102.71 (9)
O5^ix—Na1—O2^v	95.21 (9)	S2—O6—K1	94.57 (13)
O5^ii—Na1—O2^v	84.79 (9)	Na2—O6—K1	90.96 (9)
O4—Na1—O2^v	93.82 (10)	K1^vii—O6—K1	77.63 (7)
O4^x—Na1—O2^v	86.18 (10)	S1—O7—Cu1^xiv	141.27 (18)
O5^ix—Na1—O2^iii	84.79 (9)	S1—O7—Na2^i	118.09 (17)
O5^ii—Na1—O2^iii	95.21 (9)	Cu1^xiv—O7—Na2^i	91.26 (11)
O4—Na1—O2^iii	86.18 (10)	S2—O8—K1^vi	96.86 (14)
O4^x—Na1—O2^iii	93.82 (10)	S2—O8—K1^v	151.67 (15)
O2^v—Na1—O2^iii	180.0	K1^vi—O8—K1^v	78.77 (7)
O5^ix—Na1—Cu1	144.12 (6)	S2—O8—K1	101.63 (13)
O5^ii—Na1—Cu1	35.88 (6)	K1^vi—O8—K1	121.78 (10)
O4—Na1—Cu1	34.08 (6)	K1^v—O8—K1	104.40 (8)
O4^x—Na1—Cu1	145.92 (6)

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