Joint crystallization of KCuAl[PO₄]₂ and K(Al,Zn)₂[(P,Si)O₄]₂: crystal chemistry and mechanism of formation of phosphate-silicate epitaxial heterostructure

Two novel phases, potassium copper aluminium bis­(phosphate), KCuAl[PO₄]₂ (I), and potassium zinc aluminium bis­(phosphate-silicate), K(Al,Zn)₂[(P,Si)O₄]₂ (II), were obtained in one hydro­thermal synthesis experiment at 553 K. Their crystal structures have been studied using single-crystal X-ray diffraction. (I) is a new member of the A⁺M²⁺M³⁺[PO₄]₂ family. Its open 3D framework built by AlO₅ and PO₄ polyhedra includes small channels populated by columns of CuO₆ octahedra sharing edges, and large channels where K⁺ ions are deposited. It is assumed that the stability of this structure type is due to the pair substitution of Cu/Al with Ni/Fe, Co/Fe or Mg/Fe in different representatives of the series. From the KCuAl[PO₄]₂ structural features, one may suppose it is a potentially electrochemically active material and/or possible low-temperature antiferromagnet. In accordance with results obtained from X-ray diffraction data, using scanning electron microscopy, microprobe analysis and detailed crystal chemical observation, (II) is considered as a product of epitaxial intergrowth of phosphate KAlZn[PO₄]₂ and silicate KAlSi[SiO₄]₂ components having closely similar crystal structures. The assembly of `coherent intergrowth' is described in the framework of a single diffraction pattern.

Computing details

For both structures, data collection: CrysAlis PRO, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01); cell refinement: CrysAlis PRO, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01); data reduction: CrysAlis PRO, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01); program(s) used to solve structure: SHELXT (Sheldrick, 2015); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2016); molecular graphics: DIAMOND (Brandenburg, 2006).

potassium copper aluminium bis(phosphate) (I)

Crystal data

AlCuKO8P2	F(000) = 620
Mr = 319.56	Dx = 3.321 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.0270 (8) Å	Cell parameters from 3068 reflections
b = 14.047 (2) Å	θ = 3.7–30.1°
c = 9.263 (1) Å	µ = 4.72 mm^−1
β = 102.29 (1)°	T = 293 K
V = 639.11 (15) Å^3	Isometric, light green
Z = 4	0.07 × 0.06 × 0.06 mm

Data collection

Xcalibur, Sapphire3 diffractometer	1469 independent reflections
Radiation source: Enhance(Mo)X-ray Source	1360 reflections with I > 2σ(I)
Detector resolution: 16.0630 pixels mm^-1	Rint = 0.057
ω scans	θmax = 27.5°, θmin = 2.7°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −6→6
Tmin = 0.957, Tmax = 1.000	k = −18→18
9355 measured reflections	l = −12→12

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.049	Secondary atom site location: difference Fourier map
wR(F^2) = 0.093	w = 1/[σ^2(Fo^2) + (0.014P)^2 + 5.5P] where P = (Fo^2 + 2Fc^2)/3
S = 1.23	(Δ/σ)max < 0.001
1469 reflections	Δρmax = 0.63 e Å^−3
122 parameters	Δρmin = −1.02 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	Occ. (<1)
Cu1	0.74086 (14)	0.95540 (5)	0.45632 (8)	0.01199 (19)
K1	0.6843 (18)	0.8279 (4)	0.8045 (11)	0.0185 (12)	0.80 (5)
K2	0.726 (5)	0.8224 (14)	0.777 (3)	0.0185 (12)	0.20 (5)
P1	0.2358 (3)	0.82680 (9)	0.45459 (15)	0.0072 (3)
P2	0.7890 (3)	0.50961 (10)	0.66871 (15)	0.0076 (3)
Al1	0.2585 (3)	0.62940 (10)	0.61265 (17)	0.0049 (3)
O1	0.4104 (7)	0.9137 (3)	0.5232 (4)	0.0088 (7)
O2	−0.0620 (8)	0.8359 (3)	0.4655 (4)	0.0120 (8)
O3	0.9125 (8)	0.5881 (3)	0.5893 (4)	0.0118 (8)
O4	0.3612 (8)	0.7412 (3)	0.5468 (4)	0.0107 (8)
O5	0.7449 (8)	0.4182 (3)	0.5807 (4)	0.0147 (8)
O6	0.2641 (8)	0.8119 (3)	0.2962 (4)	0.0129 (8)
O7	0.5145 (8)	0.5458 (3)	0.6968 (5)	0.0152 (8)
O8	0.9667 (8)	0.4907 (3)	0.8211 (4)	0.0131 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0122 (3)	0.0097 (3)	0.0158 (4)	0.0007 (3)	0.0068 (3)	0.0005 (3)
K1	0.0204 (18)	0.0185 (9)	0.015 (2)	0.0001 (10)	0.0014 (15)	−0.0011 (11)
K2	0.0204 (18)	0.0185 (9)	0.015 (2)	0.0001 (10)	0.0014 (15)	−0.0011 (11)
P1	0.0093 (6)	0.0049 (6)	0.0080 (7)	−0.0008 (5)	0.0032 (5)	0.0003 (5)
P2	0.0092 (7)	0.0064 (6)	0.0082 (6)	−0.0004 (5)	0.0039 (5)	−0.0017 (5)
Al1	0.0067 (7)	0.0030 (7)	0.0050 (7)	−0.0003 (6)	0.0017 (6)	−0.0009 (6)
O1	0.0096 (18)	0.0045 (17)	0.0128 (19)	−0.0019 (14)	0.0037 (14)	−0.0010 (15)
O2	0.0092 (18)	0.0080 (18)	0.019 (2)	−0.0011 (14)	0.0035 (15)	−0.0008 (15)
O3	0.0108 (19)	0.0111 (19)	0.014 (2)	−0.0021 (15)	0.0042 (15)	0.0016 (15)
O4	0.017 (2)	0.0055 (17)	0.0098 (19)	−0.0003 (15)	0.0028 (15)	0.0032 (14)
O5	0.025 (2)	0.0081 (18)	0.014 (2)	−0.0031 (16)	0.0102 (17)	−0.0028 (16)
O6	0.019 (2)	0.0101 (19)	0.010 (2)	−0.0003 (16)	0.0039 (16)	−0.0004 (15)
O7	0.0120 (19)	0.017 (2)	0.019 (2)	0.0055 (16)	0.0092 (16)	0.0044 (17)
O8	0.0117 (19)	0.016 (2)	0.0114 (19)	0.0018 (16)	0.0034 (15)	0.0025 (16)

Geometric parameters (Å, º)

Cu1—O2^i	1.942 (4)	K2—O1	2.85 (2)
Cu1—O1	1.981 (4)	K2—O2^vii	2.886 (19)
Cu1—O8^ii	2.010 (4)	K2—O5^iv	3.02 (2)
Cu1—O1^iii	2.014 (4)	K2—O6^vi	3.03 (2)
Cu1—O8^iv	2.317 (4)	K2—O8^iv	3.07 (2)
Cu1—O7^ii	2.431 (4)	K2—O3^vi	3.11 (2)
Cu1—P2^ii	2.7698 (15)	K2—O5^viii	3.24 (3)
Cu1—Cu1^v	2.8488 (14)	K2—O6^vii	3.27 (3)
Cu1—Cu1^iii	2.9872 (14)	K2—O2^i	3.29 (3)
Cu1—K2	3.53 (2)	K2—O7^viii	3.39 (2)
Cu1—K1	3.752 (10)	K2—P1^vii	3.44 (2)
K1—O4	2.858 (8)	P1—O6	1.519 (4)
K1—O6^vi	2.873 (7)	P1—O2	1.527 (4)
K1—O2^vii	2.887 (6)	P1—O4	1.530 (4)
K1—O5^viii	2.893 (14)	P1—O1	1.558 (4)
K1—O3^vi	2.894 (9)	P2—O5	1.512 (4)
K1—O1	2.935 (7)	P2—O8	1.525 (4)
K1—O5^iv	3.110 (7)	P2—O3	1.529 (4)
K1—O4^vi	3.189 (14)	P2—O7	1.543 (4)
K1—O7^viii	3.219 (8)	Al1—O7	1.794 (4)
K1—O8^iv	3.244 (9)	Al1—O4	1.800 (4)
K1—P1	3.532 (6)	Al1—O3^ix	1.802 (4)
K1—P2^viii	3.534 (11)	Al1—O6^vi	1.884 (4)
K2—O4	2.75 (2)	Al1—O5^x	1.908 (4)
O2^i—Cu1—O1	100.66 (15)	O6—P1—K2	129.7 (6)
O2^i—Cu1—O8^ii	90.13 (16)	O2—P1—K2	118.3 (5)
O1—Cu1—O8^ii	158.29 (16)	O4—P1—K2	50.8 (3)
O2^i—Cu1—O1^iii	169.84 (16)	O1—P1—K2	54.8 (3)
O1—Cu1—O1^iii	83.22 (15)	K2^xi—P1—K2	136.4 (5)
O8^ii—Cu1—O1^iii	89.38 (15)	O6—P1—K1	135.6 (3)
O2^i—Cu1—O8^iv	85.67 (15)	O2—P1—K1	112.5 (3)
O1—Cu1—O8^iv	101.56 (15)	O4—P1—K1	52.04 (17)
O8^ii—Cu1—O8^iv	97.97 (14)	O1—P1—K1	55.12 (16)
O1^iii—Cu1—O8^iv	84.35 (15)	K2^xi—P1—K1	134.8 (5)
O2^i—Cu1—O7^ii	99.48 (15)	K2—P1—K1	5.9 (3)
O1—Cu1—O7^ii	93.44 (14)	O6—P1—K1^xi	76.3 (3)
O8^ii—Cu1—O7^ii	66.03 (14)	O2—P1—K1^xi	52.0 (2)
O1^iii—Cu1—O7^ii	89.58 (15)	O4—P1—K1^xi	86.14 (18)
O8^iv—Cu1—O7^ii	163.00 (14)	O1—P1—K1^xi	163.92 (19)
O2^i—Cu1—P2^ii	92.71 (12)	K2^xi—P1—K1^xi	5.7 (3)
O1—Cu1—P2^ii	127.15 (12)	K2—P1—K1^xi	132.9 (5)
O8^ii—Cu1—P2^ii	32.53 (11)	K1—P1—K1^xi	130.7 (3)
O1^iii—Cu1—P2^ii	92.33 (11)	O6—P1—K1^ii	49.5 (2)
O8^iv—Cu1—P2^ii	130.49 (10)	O2—P1—K1^ii	140.92 (19)
O7^ii—Cu1—P2^ii	33.73 (9)	O4—P1—K1^ii	61.7 (2)
O2^i—Cu1—Cu1^v	86.57 (12)	O1—P1—K1^ii	106.53 (19)
O1—Cu1—Cu1^v	144.92 (12)	K2^xi—P1—K1^ii	85.0 (4)
O8^ii—Cu1—Cu1^v	53.65 (11)	K2—P1—K1^ii	86.2 (4)
O1^iii—Cu1—Cu1^v	84.97 (11)	K1—P1—K1^ii	91.55 (18)
O8^iv—Cu1—Cu1^v	44.32 (10)	K1^xi—P1—K1^ii	88.88 (11)
O7^ii—Cu1—Cu1^v	119.41 (10)	O6—P1—K2^ii	46.7 (4)
P2^ii—Cu1—Cu1^v	86.18 (4)	O2—P1—K2^ii	142.9 (4)
O2^i—Cu1—Cu1^iii	141.85 (12)	O4—P1—K2^ii	65.6 (4)
O1—Cu1—Cu1^iii	42.03 (10)	O1—P1—K2^ii	104.1 (4)
O8^ii—Cu1—Cu1^iii	127.51 (12)	K2^xi—P1—K2^ii	86.8 (4)
O1^iii—Cu1—Cu1^iii	41.19 (10)	K2—P1—K2^ii	87.5 (5)
O8^iv—Cu1—Cu1^iii	93.81 (10)	K1—P1—K2^ii	93.0 (3)
O7^ii—Cu1—Cu1^iii	92.00 (10)	K1^xi—P1—K2^ii	91.0 (3)
P2^ii—Cu1—Cu1^iii	115.34 (5)	K1^ii—P1—K2^ii	4.3 (3)
Cu1^v—Cu1—Cu1^iii	118.92 (5)	O5—P2—O8	109.9 (2)
O2^i—Cu1—K2	66.9 (5)	O5—P2—O3	112.4 (2)
O1—Cu1—K2	53.8 (4)	O8—P2—O3	110.7 (2)
O8^ii—Cu1—K2	147.3 (4)	O5—P2—O7	109.7 (2)
O1^iii—Cu1—K2	109.2 (5)	O8—P2—O7	105.7 (2)
O8^iv—Cu1—K2	59.1 (3)	O3—P2—O7	108.2 (2)
O7^ii—Cu1—K2	137.8 (3)	O5—P2—Cu1^vi	129.53 (16)
P2^ii—Cu1—K2	158.0 (4)	O8—P2—Cu1^vi	45.14 (15)
Cu1^v—Cu1—K2	100.1 (3)	O3—P2—Cu1^vi	117.54 (16)
Cu1^iii—Cu1—K2	80.2 (5)	O7—P2—Cu1^vi	60.99 (16)
O2^i—Cu1—K1	71.4 (2)	O5—P2—K1^xii	53.2 (2)
O1—Cu1—K1	50.82 (17)	O8—P2—K1^xii	94.56 (19)
O8^ii—Cu1—K1	150.69 (18)	O3—P2—K1^xii	154.6 (2)
O1^iii—Cu1—K1	104.8 (2)	O7—P2—K1^xii	65.6 (2)
O8^iv—Cu1—K1	59.13 (11)	Cu1^vi—P2—K1^xii	82.11 (18)
O7^ii—Cu1—K1	137.87 (11)	O5—P2—K2^xiii	57.6 (4)
P2^ii—Cu1—K1	161.71 (15)	O8—P2—K2^xiii	59.4 (4)
Cu1^v—Cu1—K1	101.41 (8)	O3—P2—K2^xiii	105.4 (5)
Cu1^iii—Cu1—K1	75.72 (18)	O7—P2—K2^xiii	146.3 (5)
K2—Cu1—K1	4.6 (3)	Cu1^vi—P2—K2^xiii	101.2 (4)
O4—K1—O6^vi	53.32 (13)	K1^xii—P2—K2^xiii	84.7 (4)
O4—K1—O2^vii	101.7 (2)	O5—P2—K1^xiii	57.55 (18)
O6^vi—K1—O2^vii	73.19 (15)	O8—P2—K1^xiii	62.7 (2)
O4—K1—O5^viii	99.1 (3)	O3—P2—K1^xiii	100.0 (3)
O6^vi—K1—O5^viii	73.0 (3)	O7—P2—K1^xiii	151.7 (3)
O2^vii—K1—O5^viii	116.2 (4)	Cu1^vi—P2—K1^xiii	105.63 (18)
O4—K1—O3^vi	168.3 (5)	K1^xii—P2—K1^xiii	88.83 (12)
O6^vi—K1—O3^vi	116.7 (4)	K2^xiii—P2—K1^xiii	5.7 (3)
O2^vii—K1—O3^vi	78.94 (18)	O5—P2—K2^xii	57.1 (4)
O5^viii—K1—O3^vi	70.6 (3)	O8—P2—K2^xii	92.2 (4)
O4—K1—O1	50.01 (15)	O3—P2—K2^xii	157.1 (4)
O6^vi—K1—O1	93.06 (16)	O7—P2—K2^xii	63.0 (4)
O2^vii—K1—O1	149.1 (4)	Cu1^vi—P2—K2^xii	78.2 (4)
O5^viii—K1—O1	84.3 (2)	K1^xii—P2—K2^xii	4.0 (3)
O3^vi—K1—O1	131.4 (2)	K2^xiii—P2—K2^xii	86.3 (4)
O4—K1—O5^iv	141.1 (5)	K1^xiii—P2—K2^xii	90.7 (3)
O6^vi—K1—O5^iv	155.2 (2)	O7—Al1—O4	119.21 (19)
O2^vii—K1—O5^iv	82.78 (17)	O7—Al1—O3^ix	115.24 (19)
O5^viii—K1—O5^iv	113.7 (3)	O4—Al1—O3^ix	125.37 (19)
O3^vi—K1—O5^iv	50.54 (12)	O7—Al1—O6^vi	91.33 (19)
O1—K1—O5^iv	111.1 (3)	O4—Al1—O6^vi	88.48 (18)
O4—K1—O4^vi	100.0 (2)	O3^ix—Al1—O6^vi	94.46 (19)
O6^vi—K1—O4^vi	47.9 (2)	O7—Al1—O5^x	92.34 (19)
O2^vii—K1—O4^vi	68.2 (2)	O4—Al1—O5^x	86.18 (18)
O5^viii—K1—O4^vi	49.0 (2)	O3^ix—Al1—O5^x	87.65 (18)
O3^vi—K1—O4^vi	69.2 (3)	O6^vi—Al1—O5^x	174.52 (18)
O1—K1—O4^vi	122.5 (3)	O7—Al1—K1^xi	145.29 (17)
O5^iv—K1—O4^vi	117.0 (3)	O4—Al1—K1^xi	80.1 (2)
O4—K1—O7^viii	106.32 (16)	O3^ix—Al1—K1^xi	51.4 (3)
O6^vi—K1—O7^viii	115.1 (4)	O6^vi—Al1—K1^xi	119.4 (2)
O2^vii—K1—O7^viii	149.6 (4)	O5^x—Al1—K1^xi	58.4 (2)
O5^viii—K1—O7^viii	47.88 (18)	O7—Al1—K2	88.1 (4)
O3^vi—K1—O7^viii	71.2 (2)	O4—Al1—K2	45.4 (4)
O1—K1—O7^viii	61.28 (13)	O3^ix—Al1—K2	142.9 (5)
O5^iv—K1—O7^viii	82.92 (14)	O6^vi—Al1—K2	54.6 (5)
O4^vi—K1—O7^viii	95.0 (4)	O5^x—Al1—K2	121.5 (5)
O4—K1—O8^iv	104.8 (3)	K1^xi—Al1—K2	122.0 (4)
O6^vi—K1—O8^iv	157.3 (3)	O7—Al1—K2^xi	143.9 (3)
O2^vii—K1—O8^iv	122.3 (3)	O4—Al1—K2^xi	76.4 (4)
O5^viii—K1—O8^iv	109.0 (2)	O3^ix—Al1—K2^xi	56.7 (5)
O3^vi—K1—O8^iv	84.26 (14)	O6^vi—Al1—K2^xi	123.0 (4)
O1—K1—O8^iv	65.14 (19)	O5^x—Al1—K2^xi	54.3 (4)
O5^iv—K1—O8^iv	46.00 (15)	K1^xi—Al1—K2^xi	5.7 (3)
O4^vi—K1—O8^iv	149.6 (4)	K2—Al1—K2^xi	119.6 (3)
O7^viii—K1—O8^iv	61.30 (12)	O7—Al1—K1	89.81 (17)
O4—K1—P1	24.97 (9)	O4—Al1—K1	48.08 (18)
O6^vi—K1—P1	69.53 (12)	O3^ix—Al1—K1	137.7 (3)
O2^vii—K1—P1	126.6 (2)	O6^vi—Al1—K1	49.1 (3)
O5^viii—K1—P1	87.64 (18)	O5^x—Al1—K1	126.8 (3)
O3^vi—K1—P1	152.8 (3)	K1^xi—Al1—K1	121.87 (8)
O1—K1—P1	25.82 (9)	K2—Al1—K1	5.7 (3)
O5^iv—K1—P1	132.7 (4)	K2^xi—Al1—K1	120.1 (4)
O4^vi—K1—P1	108.9 (2)	O7—Al1—K1^ii	87.98 (14)
O7^viii—K1—P1	82.16 (12)	O4—Al1—K1^ii	52.10 (14)
O8^iv—K1—P1	87.8 (2)	O3^ix—Al1—K1^ii	128.16 (15)
O4—K1—P2^viii	95.44 (18)	O6^vi—Al1—K1^ii	132.63 (15)
O6^vi—K1—P2^viii	89.6 (3)	O5^x—Al1—K1^ii	43.53 (14)
O2^vii—K1—P2^viii	140.3 (5)	K1^xi—Al1—K1^ii	82.5 (2)
O5^viii—K1—P2^viii	24.73 (11)	K2—Al1—K1^ii	78.0 (5)
O3^vi—K1—P2^viii	77.5 (3)	K2^xi—Al1—K1^ii	76.9 (5)
O1—K1—P2^viii	64.53 (15)	K1—Al1—K1^ii	83.5 (2)
O5^iv—K1—P2^viii	105.51 (19)	P1—O1—Cu1	122.8 (2)
O4^vi—K1—P2^viii	73.7 (3)	P1—O1—Cu1^iii	124.2 (2)
O7^viii—K1—P2^viii	25.89 (11)	Cu1—O1—Cu1^iii	96.78 (15)
O8^iv—K1—P2^viii	86.54 (13)	P1—O1—K2	98.7 (4)
P1—K1—P2^viii	76.10 (11)	Cu1—O1—K2	92.0 (6)
O4—K2—O1	51.9 (4)	Cu1^iii—O1—K2	119.2 (5)
O4—K2—O2^vii	104.4 (6)	P1—O1—K1	99.06 (18)
O1—K2—O2^vii	156.2 (8)	Cu1—O1—K1	97.6 (3)
O4—K2—O5^iv	154.5 (12)	Cu1^iii—O1—K1	114.0 (3)
O1—K2—O5^iv	116.3 (7)	K2—O1—K1	7.1 (4)
O2^vii—K2—O5^iv	84.4 (5)	P1—O2—Cu1^ix	124.6 (2)
O4—K2—O6^vi	52.6 (4)	P1—O2—K2^xi	97.8 (6)
O1—K2—O6^vi	91.7 (6)	Cu1^ix—O2—K2^xi	121.3 (4)
O2^vii—K2—O6^vi	71.0 (5)	P1—O2—K1^xi	103.3 (3)
O5^iv—K2—O6^vi	150.2 (9)	Cu1^ix—O2—K1^xi	120.06 (19)
O4—K2—O8^iv	112.6 (8)	K2^xi—O2—K1^xi	7.3 (4)
O1—K2—O8^iv	68.6 (5)	P1—O2—K2^ix	124.0 (4)
O2^vii—K2—O8^iv	129.0 (8)	Cu1^ix—O2—K2^ix	80.3 (4)
O5^iv—K2—O8^iv	48.2 (3)	K2^xi—O2—K2^ix	109.8 (6)
O6^vi—K2—O8^iv	159.9 (7)	K1^xi—O2—K2^ix	102.6 (4)
O4—K2—O3^vi	155.4 (11)	P2—O3—Al1^i	130.9 (3)
O1—K2—O3^vi	126.2 (8)	P2—O3—K1^ii	127.6 (3)
O2^vii—K2—O3^vi	75.5 (5)	Al1^i—O3—K1^ii	99.4 (3)
O5^iv—K2—O3^vi	49.6 (3)	P2—O3—K2^ii	131.8 (5)
O6^vi—K2—O3^vi	106.4 (9)	Al1^i—O3—K2^ii	94.2 (5)
O8^iv—K2—O3^vi	83.9 (5)	K1^ii—O3—K2^ii	5.7 (4)
O4—K2—O5^viii	93.6 (7)	P1—O4—Al1	139.5 (3)
O1—K2—O5^viii	79.7 (6)	P1—O4—K2	103.6 (4)
O2^vii—K2—O5^viii	106.4 (9)	Al1—O4—K2	106.9 (5)
O5^iv—K2—O5^viii	106.9 (7)	P1—O4—K1	103.0 (2)
O6^vi—K2—O5^viii	66.3 (6)	Al1—O4—K1	104.0 (2)
O8^iv—K2—O5^viii	105.0 (6)	K2—O4—K1	7.2 (4)
O3^vi—K2—O5^viii	63.6 (6)	P1—O4—K1^ii	93.3 (2)
O4—K2—O6^vii	102.1 (8)	Al1—O4—K1^ii	101.5 (2)
O1—K2—O6^vii	127.8 (10)	K2—O4—K1^ii	108.5 (7)
O2^vii—K2—O6^vii	47.8 (4)	K1—O4—K1^ii	115.7 (4)
O5^iv—K2—O6^vii	65.9 (5)	P2—O5—Al1^x	140.8 (3)
O6^vi—K2—O6^vii	105.9 (6)	P2—O5—K1^xii	102.1 (2)
O8^iv—K2—O6^vii	89.8 (7)	Al1^x—O5—K1^xii	109.4 (2)
O3^vi—K2—O6^vii	95.8 (5)	P2—O5—K2^xiii	97.4 (4)
O5^viii—K2—O6^vii	152.4 (8)	Al1^x—O5—K2^xiii	94.8 (5)
O4—K2—O2^i	68.2 (6)	K1^xii—O5—K2^xiii	107.5 (6)
O1—K2—O2^i	58.4 (5)	P2—O5—K1^xiii	98.2 (2)
O2^vii—K2—O2^i	115.3 (9)	Al1^x—O5—K1^xiii	90.1 (2)
O5^iv—K2—O2^i	86.4 (7)	K1^xii—O5—K1^xiii	113.7 (3)
O6^vi—K2—O2^i	118.9 (7)	K2^xiii—O5—K1^xiii	6.7 (4)
O8^iv—K2—O2^i	54.3 (5)	P2—O5—K2^xii	99.8 (4)
O3^vi—K2—O2^i	134.7 (7)	Al1^x—O5—K2^xii	112.0 (4)
O5^viii—K2—O2^i	137.3 (6)	K1^xii—O5—K2^xii	2.5 (4)
O6^vii—K2—O2^i	70.2 (6)	K2^xiii—O5—K2^xii	106.9 (7)
O4—K2—O7^viii	104.5 (6)	K1^xiii—O5—K2^xii	113.1 (4)
O1—K2—O7^viii	59.8 (4)	P1—O6—Al1^ii	145.6 (3)
O2^vii—K2—O7^viii	139.6 (10)	P1—O6—K1^ii	106.7 (3)
O5^iv—K2—O7^viii	81.4 (5)	Al1^ii—O6—K1^ii	101.1 (3)
O6^vi—K2—O7^viii	106.4 (8)	P1—O6—K2^ii	111.9 (5)
O8^iv—K2—O7^viii	61.1 (4)	Al1^ii—O6—K2^ii	94.9 (6)
O3^vi—K2—O7^viii	66.5 (5)	K1^ii—O6—K2^ii	6.5 (4)
O5^viii—K2—O7^viii	44.2 (4)	P1—O6—K2^xi	83.4 (5)
O6^vii—K2—O7^viii	146.4 (7)	Al1^ii—O6—K2^xi	110.5 (5)
O2^i—K2—O7^viii	101.3 (5)	K1^ii—O6—K2^xi	101.7 (3)
O4—K2—P1^vii	115.1 (7)	K2^ii—O6—K2^xi	105.9 (6)
O1—K2—P1^vii	153.5 (11)	P2—O7—Al1	136.6 (3)
O2^vii—K2—P1^vii	26.1 (2)	P2—O7—Cu1^vi	85.27 (18)
O5^iv—K2—P1^vii	64.3 (4)	Al1—O7—Cu1^vi	125.2 (2)
O6^vi—K2—P1^vii	95.5 (5)	P2—O7—K1^xii	88.5 (3)
O8^iv—K2—P1^vii	103.9 (7)	Al1—O7—K1^xii	115.3 (2)
O3^vi—K2—P1^vii	75.9 (4)	Cu1^vi—O7—K1^xii	94.41 (19)
O5^viii—K2—P1^vii	126.4 (8)	P2—O7—K2^xii	93.0 (5)
O6^vii—K2—P1^vii	25.98 (18)	Al1—O7—K2^xii	113.8 (4)
O2^i—K2—P1^vii	96.1 (7)	Cu1^vi—O7—K2^xii	91.3 (4)
O7^viii—K2—P1^vii	140.4 (7)	K1^xii—O7—K2^xii	5.7 (3)
O6—P1—O2	111.7 (2)	P2—O8—Cu1^vi	102.3 (2)
O6—P1—O4	108.6 (2)	P2—O8—Cu1^xiii	175.6 (2)
O2—P1—O4	108.8 (2)	Cu1^vi—O8—Cu1^xiii	82.03 (14)
O6—P1—O1	110.0 (2)	P2—O8—K2^xiii	95.3 (4)
O2—P1—O1	112.5 (2)	Cu1^vi—O8—K2^xiii	149.7 (6)
O4—P1—O1	105.0 (2)	Cu1^xiii—O8—K2^xiii	80.5 (4)
O6—P1—K2^xi	70.6 (5)	P2—O8—K1^xiii	92.7 (2)
O2—P1—K2^xi	56.1 (5)	Cu1^vi—O8—K1^xiii	155.4 (3)
O4—P1—K2^xi	88.0 (4)	Cu1^xiii—O8—K1^xiii	83.07 (16)
O1—P1—K2^xi	165.6 (4)	K2^xiii—O8—K1^xiii	5.9 (4)

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

potassium zinc aluminium bis(phosphate-silicate) (II)

Crystal data

Al3K2O16P3SiZn	F(000) = 1176
Mr = 601.51	Dx = 2.700 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.234 (1) Å	Cell parameters from 2260 reflections
b = 13.121 (1) Å	θ = 3.0–29.9°
c = 8.6581 (8) Å	µ = 2.89 mm^−1
β = 100.14 (1)°	T = 293 K
V = 1479.9 (2) Å^3	Plate, blue
Z = 4	0.06 × 0.06 × 0.05 mm

Data collection

Xcalibur, Sapphire3 diffractometer	1303 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1176 reflections with I > 2σ(I)
Detector resolution: 16.0630 pixels mm^-1	Rint = 0.060
/w scans	θmax = 25.0°, θmin = 3.0°
Absorption correction: gaussian CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) Numerical absorption correction based on gaussian integration over a multifaceted crystal model	h = −15→15
Tmin = 0.800, Tmax = 0.856	k = −15→15
8821 measured reflections	l = −10→10

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.059	Secondary atom site location: difference Fourier map
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.014P)^2 + 13.2P] where P = (Fo^2 + 2Fc^2)/3
S = 1.29	(Δ/σ)max < 0.001
1303 reflections	Δρmax = 0.42 e Å^−3
118 parameters	Δρmin = −0.42 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	Occ. (<1)
Al1	0.36768 (9)	0.93751 (10)	0.11136 (13)	0.0135 (3)	0.75
Al2	0.42151 (9)	0.37427 (9)	−0.04604 (14)	0.0142 (3)	0.75
P1	0.35517 (11)	0.43393 (12)	0.59287 (17)	0.0160 (4)	0.75
P2	0.42386 (12)	0.13702 (11)	−0.03024 (18)	0.0151 (4)	0.75
Si1	0.35517 (11)	0.43393 (12)	0.59287 (17)	0.0160 (4)	0.25
Si2	0.42386 (12)	0.13702 (11)	−0.03024 (18)	0.0151 (4)	0.25
Zn1	0.36768 (9)	0.93751 (10)	0.11136 (13)	0.0135 (3)	0.25
Zn2	0.42151 (9)	0.37427 (9)	−0.04604 (14)	0.0142 (3)	0.25
K1	0.18167 (11)	0.75169 (14)	0.21957 (17)	0.0348 (4)
O1	0.3901 (3)	0.0698 (4)	0.0976 (5)	0.0293 (11)
O2	0.3689 (3)	0.8973 (4)	0.3057 (5)	0.0363 (12)
O3	0.3577 (4)	0.6042 (4)	0.2615 (5)	0.0397 (13)
O4	0.4432 (3)	0.3850 (4)	0.5205 (5)	0.0320 (11)
O5	0.2534 (3)	0.3957 (3)	0.4942 (5)	0.0273 (10)
O6	0.4582 (3)	0.8675 (3)	0.0208 (5)	0.0252 (11)
O7	0.3917 (3)	0.2469 (4)	0.0026 (5)	0.0326 (11)
O8	0.3662 (3)	0.4486 (3)	0.0887 (5)	0.0278 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Al1	0.0109 (6)	0.0153 (7)	0.0140 (6)	−0.0009 (5)	0.0014 (5)	0.0033 (5)
Al2	0.0145 (7)	0.0124 (7)	0.0160 (6)	0.0005 (5)	0.0033 (5)	0.0022 (5)
P1	0.0156 (8)	0.0156 (9)	0.0162 (8)	−0.0023 (7)	0.0012 (6)	0.0025 (6)
P2	0.0163 (8)	0.0136 (9)	0.0161 (8)	0.0005 (6)	0.0044 (6)	−0.0007 (6)
Si1	0.0156 (8)	0.0156 (9)	0.0162 (8)	−0.0023 (7)	0.0012 (6)	0.0025 (6)
Si2	0.0163 (8)	0.0136 (9)	0.0161 (8)	0.0005 (6)	0.0044 (6)	−0.0007 (6)
Zn1	0.0109 (6)	0.0153 (7)	0.0140 (6)	−0.0009 (5)	0.0014 (5)	0.0033 (5)
Zn2	0.0145 (7)	0.0124 (7)	0.0160 (6)	0.0005 (5)	0.0033 (5)	0.0022 (5)
K1	0.0360 (9)	0.0432 (9)	0.0283 (8)	0.0008 (8)	0.0139 (6)	0.0059 (8)
O1	0.036 (3)	0.030 (3)	0.024 (2)	−0.002 (2)	0.010 (2)	0.005 (2)
O2	0.029 (3)	0.052 (3)	0.026 (3)	0.006 (2)	0.001 (2)	0.002 (2)
O3	0.047 (3)	0.048 (3)	0.025 (3)	0.000 (3)	0.009 (2)	−0.012 (2)
O4	0.025 (2)	0.033 (3)	0.040 (3)	0.002 (2)	0.012 (2)	−0.004 (2)
O5	0.021 (2)	0.026 (2)	0.033 (2)	−0.003 (2)	−0.0004 (18)	−0.004 (2)
O6	0.017 (2)	0.025 (3)	0.034 (3)	−0.0005 (18)	0.005 (2)	−0.002 (2)
O7	0.038 (3)	0.024 (2)	0.042 (3)	0.010 (2)	0.026 (2)	0.003 (2)
O8	0.032 (3)	0.016 (2)	0.035 (3)	0.0001 (19)	0.003 (2)	0.002 (2)

Geometric parameters (Å, º)

Al1—O2	1.760 (5)	P1—K1^vii	3.646 (2)
Al1—O1^i	1.769 (5)	P2—O1	1.541 (5)
Al1—O5^ii	1.785 (4)	P2—O7	1.543 (5)
Al1—O6	1.796 (4)	P2—O2^iv	1.545 (5)
Al1—K1	3.701 (2)	P2—O6^viii	1.549 (4)
Al1—K1^iii	3.760 (2)	P2—K1^vi	3.574 (2)
Al2—O3^iv	1.753 (5)	P2—K1^iv	3.828 (2)
Al2—O4^v	1.771 (5)	K1—O7^ii	2.749 (4)
Al2—O8	1.774 (5)	K1—O5^ii	2.880 (5)
Al2—O7	1.785 (5)	K1—O6^iii	2.974 (4)
Al2—K1^vi	3.7149 (19)	K1—O4^ii	2.983 (5)
Al2—K1^iv	3.828 (2)	K1—O3	3.000 (5)
P1—O3^vii	1.539 (5)	K1—O5^iv	3.017 (5)
P1—O5	1.546 (4)	K1—O1^ii	3.104 (5)
P1—O8^vii	1.550 (5)	K1—O2	3.114 (5)
P1—O4	1.555 (5)	K1—O8^ii	3.194 (5)
P1—K1^vi	3.579 (2)	K1—O7^vii	3.366 (5)
O2—Al1—O1^i	112.7 (2)	O4^ii—K1—O1^ii	128.64 (13)
O2—Al1—O5^ii	104.7 (2)	O3—K1—O1^ii	75.12 (13)
O1^i—Al1—O5^ii	114.4 (2)	O5^iv—K1—O1^ii	89.79 (13)
O2—Al1—O6	111.7 (2)	O7^ii—K1—O2	101.15 (14)
O1^i—Al1—O6	109.9 (2)	O5^ii—K1—O2	55.69 (12)
O5^ii—Al1—O6	103.1 (2)	O6^iii—K1—O2	149.44 (13)
O2—Al1—K1	57.00 (16)	O4^ii—K1—O2	97.29 (13)
O1^i—Al1—K1	142.25 (16)	O3—K1—O2	78.38 (13)
O5^ii—Al1—K1	49.48 (15)	O5^iv—K1—O2	102.75 (13)
O6—Al1—K1	107.34 (15)	O1^ii—K1—O2	130.67 (12)
O2—Al1—K1^iii	120.10 (18)	O7^ii—K1—O8^ii	55.30 (13)
O1^i—Al1—K1^iii	127.24 (15)	O5^ii—K1—O8^ii	84.97 (13)
O5^ii—Al1—K1^iii	52.22 (15)	O6^iii—K1—O8^ii	129.26 (12)
O6—Al1—K1^iii	50.90 (13)	O4^ii—K1—O8^ii	75.61 (13)
K1—Al1—K1^iii	73.97 (4)	O3—K1—O8^ii	132.80 (12)
O3^iv—Al2—O4^v	114.4 (2)	O5^iv—K1—O8^ii	165.60 (13)
O3^iv—Al2—O8	110.6 (2)	O1^ii—K1—O8^ii	104.48 (12)
O4^v—Al2—O8	113.5 (2)	O2—K1—O8^ii	66.53 (12)
O3^iv—Al2—O7	106.6 (2)	O7^ii—K1—O7^vii	74.72 (13)
O4^v—Al2—O7	107.8 (2)	O5^ii—K1—O7^vii	99.35 (12)
O8—Al2—O7	103.0 (2)	O6^iii—K1—O7^vii	147.65 (13)
O3^iv—Al2—K1^vi	127.77 (17)	O4^ii—K1—O7^vii	142.08 (14)
O4^v—Al2—K1^vi	116.00 (16)	O3—K1—O7^vii	52.53 (12)
O8—Al2—K1^vi	59.21 (15)	O5^iv—K1—O7^vii	99.26 (12)
O7—Al2—K1^vi	44.68 (14)	O1^ii—K1—O7^vii	85.44 (12)
O3^iv—Al2—K1^iv	49.45 (17)	O2—K1—O7^vii	45.73 (12)
O4^v—Al2—K1^iv	145.73 (17)	O8^ii—K1—O7^vii	80.28 (12)
O8—Al2—K1^iv	100.74 (14)	O7^ii—K1—P2^ii	24.02 (10)
O7—Al2—K1^iv	61.54 (16)	O5^ii—K1—P2^ii	163.79 (11)
K1^vi—Al2—K1^iv	80.50 (4)	O6^iii—K1—P2^ii	91.60 (10)
O3^vii—P1—O5	106.9 (3)	O4^ii—K1—P2^ii	121.95 (10)
O3^vii—P1—O8^vii	111.1 (3)	O3—K1—P2^ii	92.02 (11)
O5—P1—O8^vii	112.7 (2)	O5^iv—K1—P2^ii	115.21 (10)
O3^vii—P1—O4	110.8 (3)	O1^ii—K1—P2^ii	25.46 (8)
O5—P1—O4	106.6 (3)	O2—K1—P2^ii	118.56 (10)
O8^vii—P1—O4	108.7 (3)	O8^ii—K1—P2^ii	79.03 (9)
O3^vii—P1—K1^vi	118.5 (2)	O7^vii—K1—P2^ii	80.59 (8)
O5—P1—K1^vi	51.42 (18)	O7^ii—K1—P1^ii	130.91 (12)
O8^vii—P1—K1^vi	130.39 (18)	O5^ii—K1—P1^ii	24.81 (9)
O4—P1—K1^vi	55.37 (17)	O6^iii—K1—P1^ii	80.62 (9)
O3^vii—P1—K1^vii	53.6 (2)	O4^ii—K1—P1^ii	25.40 (9)
O5—P1—K1^vii	54.28 (18)	O3—K1—P1^ii	121.46 (10)
O8^vii—P1—K1^vii	137.62 (19)	O5^iv—K1—P1^ii	87.48 (9)
O4—P1—K1^vii	113.68 (19)	O1^ii—K1—P1^ii	152.39 (10)
K1^vi—P1—K1^vii	76.81 (5)	O2—K1—P1^ii	76.57 (9)
O1—P2—O7	106.1 (2)	O8^ii—K1—P1^ii	80.76 (9)
O1—P2—O2^iv	110.1 (3)	O7^vii—K1—P1^ii	122.11 (9)
O7—P2—O2^iv	109.9 (3)	P2^ii—K1—P1^ii	146.19 (6)
O1—P2—O6^viii	110.9 (2)	P2—O1—Al1^ix	133.1 (3)
O7—P2—O6^viii	109.5 (3)	P2—O1—K1^vi	94.6 (2)
O2^iv—P2—O6^viii	110.1 (3)	Al1^ix—O1—K1^vi	130.5 (2)
O1—P2—K1^vi	59.95 (18)	P2^vii—O2—Al1	152.9 (3)
O7—P2—K1^vi	46.46 (17)	P2^vii—O2—K1	105.5 (2)
O2^iv—P2—K1^vi	129.19 (19)	Al1—O2—K1	94.70 (18)
O6^viii—P2—K1^vi	119.99 (18)	P1^iv—O3—Al2^vii	151.7 (3)
O1—P2—K1^iv	107.74 (18)	P1^iv—O3—K1	102.0 (2)
O7—P2—K1^iv	61.13 (19)	Al2^vii—O3—K1	104.2 (2)
O2^iv—P2—K1^iv	51.62 (19)	P1—O4—Al2^v	142.7 (3)
O6^viii—P2—K1^iv	141.21 (18)	P1—O4—K1^vi	99.2 (2)
K1^vi—P2—K1^iv	82.30 (5)	Al2^v—O4—K1^vi	117.7 (2)
O7^ii—K1—O5^ii	140.25 (15)	P1—O5—Al1^vi	143.1 (3)
O7^ii—K1—O6^iii	109.16 (14)	P1—O5—K1^vi	103.8 (2)
O5^ii—K1—O6^iii	96.58 (13)	Al1^vi—O5—K1^vi	102.41 (18)
O7^ii—K1—O4^ii	112.68 (14)	P1—O5—K1^vii	101.1 (2)
O5^ii—K1—O4^ii	50.13 (12)	Al1^vi—O5—K1^vii	99.89 (19)
O6^iii—K1—O4^ii	67.70 (12)	K1^vi—O5—K1^vii	99.10 (13)
O7^ii—K1—O3	105.38 (14)	P2^viii—O6—Al1	137.7 (3)
O5^ii—K1—O3	100.83 (14)	P2^viii—O6—K1^iii	120.9 (2)
O6^iii—K1—O3	96.89 (13)	Al1—O6—K1^iii	101.16 (17)
O4^ii—K1—O3	141.76 (13)	P2—O7—Al2	138.7 (3)
O7^ii—K1—O5^iv	138.67 (14)	P2—O7—K1^vi	109.5 (2)
O5^ii—K1—O5^iv	80.89 (13)	Al2—O7—K1^vi	108.2 (2)
O6^iii—K1—O5^iv	55.82 (12)	P2—O7—K1^iv	95.2 (2)
O4^ii—K1—O5^iv	97.13 (13)	Al2—O7—K1^iv	90.67 (18)
O3—K1—O5^iv	48.62 (12)	K1^vi—O7—K1^iv	105.28 (13)
O7^ii—K1—O1^ii	49.37 (13)	P1^iv—O8—Al2	127.8 (3)
O5^ii—K1—O1^ii	170.08 (13)	P1^iv—O8—K1^vi	139.9 (2)
O6^iii—K1—O1^ii	75.18 (12)	Al2—O8—K1^vi	92.30 (17)

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