The crystal structure of the first synthetic copper(II) tellurite arsenate, Cu^II₅(Te^IVO₃)₂(As^VO₄)₂

Crystals of the first synthetic copper tellurite arsenate, Cu^II₅(Te^IVO₃)₂(As^VO₄)₂ [systematic name pentacopper(II) bis-oxotellurate(IV) bis-oxoarsenate(V)], were grown by the chemical vapour transport method and structurally determined using single-crystal X-ray diffraction. Cu^II₅(Te^IVO₃)₂(As^VO₄)₂ possesses a novel structure type including a new topological arrangement of Cu^II and O atoms. Cu^II₅(Te^IVO₃)₂(As^VO₄)₂ is formed from a framework of two types of Jahn–Teller distorted [Cu^IIO₆] octahedra (one of which is considerably elongated) and [Cu^IIO₅] square pyramids, which are linked by edge-sharing to form chains and dimers and by corner-sharing to complete a three-dimensional framework. [As^VO₄] tetrahedra and [Te^IVO₅] polyhedra bridge the edges of channels along the a-axis direction, with void space remaining for the Te^IV stereoactive 5s² lone pairs. A comparison is made between the crystal structure of Cu^II₅(Te^IVO₃)₂(As^VO₄)₂ and those of known compounds and minerals, in particular fumarolitic Cu minerals.

Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: CrystalMaker (Palmer, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

pentacopper(II) bis-oxotellurate(IV) bis-oxoarsenate(V)

Crystal data

As2Cu5O14Te2	Z = 1
Mr = 946.74	F(000) = 427
Triclinic, P1	Dx = 5.337 Mg m^−3
a = 4.9929 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.8796 (12) Å	Cell parameters from 4198 reflections
c = 8.1428 (12) Å	θ = 2.5–30.0°
α = 77.333 (3)°	µ = 19.39 mm^−1
β = 79.233 (3)°	T = 100 K
γ = 71.862 (3)°	Fragment, dark green
V = 294.59 (8) Å^3	0.08 × 0.07 × 0.06 mm

Data collection

Bruker APEX-II CCD diffractometer	2347 reflections with I > 2σ(I)
ω– and φ–scans	Rint = 0.038
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 35.0°, θmin = 2.6°
Tmin = 0.449, Tmax = 0.747	h = −8→8
7545 measured reflections	k = −12→12
2581 independent reflections	l = −13→13

Refinement

Refinement on F^2	106 parameters
Least-squares matrix: full	0 restraints
R[F^2 > 2σ(F^2)] = 0.025	w = 1/[σ^2(Fo^2) + (0.025P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.062	(Δ/σ)max = 0.001
S = 1.10	Δρmax = 1.26 e Å^−3
2581 reflections	Δρmin = −2.92 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	1.23462 (8)	0.99911 (5)	0.11680 (5)	0.00313 (7)
Cu2	0.89747 (8)	0.82328 (5)	0.49911 (5)	0.00314 (7)
Cu3	0.500000	0.500000	0.500000	0.00292 (9)
Te1	0.92519 (4)	0.66465 (2)	0.19225 (2)	0.00232 (5)
As1	0.37274 (6)	0.76681 (4)	0.74042 (4)	0.00213 (6)
O1	0.6356 (5)	0.8501 (3)	0.0918 (3)	0.0050 (4)
O2	1.0984 (5)	0.8112 (3)	0.2695 (3)	0.0043 (4)
O3	0.7491 (5)	0.6495 (3)	0.4229 (3)	0.0047 (4)
O4	0.2158 (5)	0.8841 (3)	0.5684 (3)	0.0044 (4)
O5	0.6879 (5)	0.8115 (3)	0.7257 (3)	0.0052 (4)
O6	0.1514 (5)	0.8242 (3)	0.9175 (3)	0.0037 (4)
O7	0.4350 (5)	0.5424 (3)	0.7362 (3)	0.0047 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.00209 (15)	0.00302 (15)	0.00338 (16)	−0.00055 (12)	0.00034 (11)	0.00048 (12)
Cu2	0.00355 (15)	0.00413 (15)	0.00223 (16)	−0.00218 (12)	0.00071 (12)	−0.00086 (12)
Cu3	0.0036 (2)	0.0029 (2)	0.0026 (2)	−0.00185 (16)	0.00071 (16)	−0.00065 (16)
Te1	0.00240 (8)	0.00206 (8)	0.00223 (9)	−0.00041 (6)	−0.00012 (6)	−0.00028 (6)
As1	0.00195 (12)	0.00217 (12)	0.00213 (13)	−0.00060 (9)	0.00014 (9)	−0.00038 (9)
O1	0.0031 (9)	0.0053 (9)	0.0052 (10)	−0.0011 (7)	−0.0003 (7)	0.0016 (7)
O2	0.0056 (9)	0.0054 (9)	0.0026 (9)	−0.0029 (7)	0.0006 (7)	−0.0010 (7)
O3	0.0060 (9)	0.0063 (9)	0.0030 (9)	−0.0040 (8)	0.0010 (7)	−0.0012 (7)
O4	0.0046 (9)	0.0047 (9)	0.0038 (9)	−0.0010 (7)	−0.0024 (7)	0.0008 (7)
O5	0.0042 (9)	0.0090 (10)	0.0040 (9)	−0.0043 (8)	0.0012 (7)	−0.0021 (7)
O6	0.0045 (9)	0.0043 (9)	0.0022 (9)	−0.0016 (7)	0.0003 (7)	−0.0001 (7)
O7	0.0071 (10)	0.0021 (8)	0.0040 (9)	−0.0009 (7)	0.0005 (7)	−0.0003 (7)

Geometric parameters (Å, º)

Cu1—O2	1.925 (2)	Cu3—O7	1.975 (2)
Cu1—O1^i	1.975 (2)	Cu3—O4^vi	3.042 (2)
Cu1—O1^ii	1.979 (2)	Cu3—O4	3.042 (2)
Cu1—O6^iii	2.023 (2)	Te1—O1	1.870 (2)
Cu1—O5^iv	2.325 (2)	Te1—O2	1.902 (2)
Cu1—O6^v	2.509 (2)	Te1—O3	1.914 (2)
Cu2—O5	1.942 (2)	Te1—O6^v	2.563 (2)
Cu2—O2	1.957 (2)	Te1—O7^vi	2.693 (2)
Cu2—O3	1.996 (2)	Te1—O7^vii	3.200 (2)
Cu2—O4^ii	2.001 (2)	As1—O4	1.680 (2)
Cu2—O4^iii	2.165 (2)	As1—O5	1.694 (2)
Cu3—O3	1.904 (2)	As1—O6	1.698 (2)
Cu3—O3^vi	1.904 (2)	As1—O7	1.704 (2)
Cu3—O7^vi	1.975 (2)
O2—Cu1—O1^i	162.28 (9)	Cu2—O3—Cu3^ii	62.27 (6)
O2—Cu1—O1^ii	94.72 (9)	Cu2^vii—O3—Cu3^ii	60.97 (4)
O1^i—Cu1—O1^ii	83.00 (10)	Cu3—O3—Cu1^viii	93.38 (8)
O2—Cu1—O6^iii	96.58 (9)	Te1—O3—Cu1^viii	68.91 (7)
O1^i—Cu1—O6^iii	83.76 (9)	Cu2—O3—Cu1^viii	98.48 (8)
O1^ii—Cu1—O6^iii	166.08 (9)	Cu2^vii—O3—Cu1^viii	139.34 (6)
O2—Cu1—O5^iv	108.98 (8)	Cu3^ii—O3—Cu1^viii	141.33 (6)
O1^i—Cu1—O5^iv	88.74 (8)	Cu3—O3—Cu2^viii	54.11 (6)
O1^ii—Cu1—O5^iv	94.77 (8)	Te1—O3—Cu2^viii	116.93 (9)
O6^iii—Cu1—O5^iv	89.22 (8)	Cu2—O3—Cu2^viii	107.60 (8)
O2—Cu1—O6^v	77.44 (8)	Cu2^vii—O3—Cu2^viii	119.99 (5)
O1^i—Cu1—O6^v	84.87 (8)	Cu3^ii—O3—Cu2^viii	161.35 (6)
O1^ii—Cu1—O6^v	86.54 (8)	Cu1^viii—O3—Cu2^viii	51.87 (3)
O6^iii—Cu1—O6^v	88.00 (8)	Cu3—O3—Cu1	164.22 (9)
O5^iv—Cu1—O6^v	173.28 (8)	Te1—O3—Cu1	47.95 (5)
O5—Cu2—O2	173.75 (8)	Cu2—O3—Cu1	52.37 (5)
O5—Cu2—O3	96.68 (9)	Cu2^vii—O3—Cu1	117.05 (6)
O2—Cu2—O3	77.29 (9)	Cu3^ii—O3—Cu1	67.20 (3)
O5—Cu2—O4^ii	93.67 (9)	Cu1^viii—O3—Cu1	74.54 (4)
O2—Cu2—O4^ii	90.90 (9)	Cu2^viii—O3—Cu1	120.63 (6)
O3—Cu2—O4^ii	150.30 (10)	As1—O4—Cu2^viii	122.06 (12)
O5—Cu2—O4^iii	97.02 (9)	As1—O4—Cu2^iii	123.88 (11)
O2—Cu2—O4^iii	88.14 (9)	Cu2^viii—O4—Cu2^iii	102.76 (9)
O3—Cu2—O4^iii	128.57 (9)	As1—O4—Cu3	73.46 (8)
O4^ii—Cu2—O4^iii	77.24 (10)	Cu2^viii—O4—Cu3	78.21 (7)
O3—Cu3—O3^vi	180.0	Cu2^iii—O4—Cu3	154.16 (10)
O3—Cu3—O7^vi	85.85 (9)	As1—O4—Cu1^iii	74.77 (8)
O3^vi—Cu3—O7^vi	94.15 (9)	Cu2^viii—O4—Cu1^iii	84.03 (7)
O3—Cu3—O7	94.15 (9)	Cu2^iii—O4—Cu1^iii	78.63 (7)
O3^vi—Cu3—O7	85.85 (9)	Cu3—O4—Cu1^iii	126.78 (7)
O7^vi—Cu3—O7	180.0	As1—O4—Cu2	68.48 (7)
O3—Cu3—O4^vi	111.53 (8)	Cu2^viii—O4—Cu2	143.35 (10)
O3^vi—Cu3—O4^vi	68.47 (8)	Cu2^iii—O4—Cu2	95.80 (7)
O7^vi—Cu3—O4^vi	61.52 (8)	Cu3—O4—Cu2	71.66 (5)
O7—Cu3—O4^vi	118.48 (8)	Cu1^iii—O4—Cu2	130.97 (7)
O3—Cu3—O4	68.47 (8)	As1—O4—Cu1^viii	150.07 (11)
O3^vi—Cu3—O4	111.53 (8)	Cu2^viii—O4—Cu1^viii	70.55 (6)
O7^vi—Cu3—O4	118.48 (8)	Cu2^iii—O4—Cu1^viii	72.15 (6)
O7—Cu3—O4	61.52 (8)	Cu3—O4—Cu1^viii	84.23 (5)
O4^vi—Cu3—O4	180.00 (9)	Cu1^iii—O4—Cu1^viii	135.15 (7)
O1—Te1—O2	98.28 (10)	Cu2—O4—Cu1^viii	85.89 (5)
O1—Te1—O3	98.60 (10)	As1—O5—Cu2	114.22 (12)
O2—Te1—O3	80.60 (9)	As1—O5—Cu1^iv	123.65 (12)
O1—Te1—O6^v	72.13 (8)	Cu2—O5—Cu1^iv	113.30 (9)
O2—Te1—O6^v	76.44 (8)	As1—O5—Cu3	51.17 (6)
O3—Te1—O6^v	153.50 (8)	Cu2—O5—Cu3	71.98 (6)
O1—Te1—O7^vi	87.12 (8)	Cu1^iv—O5—Cu3	174.51 (9)
O2—Te1—O7^vi	148.15 (8)	As1—O5—Cu2^iii	62.76 (7)
O3—Te1—O7^vi	67.55 (8)	Cu2—O5—Cu2^iii	83.14 (8)
O6^v—Te1—O7^vi	134.38 (7)	Cu1^iv—O5—Cu2^iii	95.28 (7)
O1—Te1—O7^vii	155.80 (8)	Cu3—O5—Cu2^iii	83.72 (5)
O2—Te1—O7^vii	67.34 (8)	As1—O5—Cu1^ix	74.37 (8)
O3—Te1—O7^vii	98.03 (8)	Cu2—O5—Cu1^ix	156.20 (10)
O6^v—Te1—O7^vii	85.24 (6)	Cu1^iv—O5—Cu1^ix	50.42 (5)
O7^vi—Te1—O7^vii	115.55 (7)	Cu3—O5—Cu1^ix	124.11 (6)
O4—As1—O5	108.42 (11)	Cu2^iii—O5—Cu1^ix	81.71 (5)
O4—As1—O6	109.10 (11)	As1—O5—Cu2^iv	142.03 (11)
O5—As1—O6	112.56 (10)	Cu2—O5—Cu2^iv	54.16 (5)
O4—As1—O7	107.25 (11)	Cu1^iv—O5—Cu2^iv	60.04 (5)
O5—As1—O7	108.90 (11)	Cu3—O5—Cu2^iv	124.85 (6)
O6—As1—O7	110.45 (10)	Cu2^iii—O5—Cu2^iv	79.42 (5)
Te1—O1—Cu1^i	114.83 (11)	Cu1^ix—O5—Cu2^iv	104.82 (5)
Te1—O1—Cu1^viii	147.17 (13)	As1—O5—Cu3^ii	125.49 (10)
Cu1^i—O1—Cu1^viii	97.00 (10)	Cu2—O5—Cu3^ii	45.37 (5)
Te1—O1—Cu1	67.20 (6)	Cu1^iv—O5—Cu3^ii	109.18 (7)
Cu1^i—O1—Cu1	64.76 (6)	Cu3—O5—Cu3^ii	75.46 (4)
Cu1^viii—O1—Cu1	124.88 (9)	Cu2^iii—O5—Cu3^ii	128.09 (6)
Te1—O1—Cu2	52.76 (5)	Cu1^ix—O5—Cu3^ii	148.33 (6)
Cu1^i—O1—Cu2	119.86 (8)	Cu2^iv—O5—Cu3^ii	75.02 (4)
Cu1^viii—O1—Cu2	105.13 (8)	As1—O6—Cu1^iii	116.95 (12)
Cu1—O1—Cu2	56.59 (3)	As1—O6—Cu1^ix	125.30 (10)
Te1—O1—Cu3	56.32 (6)	Cu1^iii—O6—Cu1^ix	91.99 (8)
Cu1^i—O1—Cu3	171.00 (10)	As1—O6—Cu1^iv	72.21 (7)
Cu1^viii—O1—Cu3	92.00 (7)	Cu1^iii—O6—Cu1^iv	119.12 (8)
Cu1—O1—Cu3	110.07 (6)	Cu1^ix—O6—Cu1^iv	53.09 (4)
Cu2—O1—Cu3	57.44 (3)	As1—O6—Cu2^viii	55.89 (6)
Te1—O2—Cu1	121.75 (12)	Cu1^iii—O6—Cu2^viii	66.61 (6)
Te1—O2—Cu2	101.70 (10)	Cu1^ix—O6—Cu2^viii	149.05 (8)
Cu1—O2—Cu2	126.80 (11)	Cu1^iv—O6—Cu2^viii	116.91 (6)
Te1—O2—Cu3^ii	97.89 (8)	As1—O6—Cu2^iii	61.13 (7)
Cu1—O2—Cu3^ii	121.31 (9)	Cu1^iii—O6—Cu2^iii	63.15 (6)
Cu2—O2—Cu3^ii	76.16 (7)	Cu1^ix—O6—Cu2^iii	101.24 (6)
Te1—O2—Cu1^i	62.66 (6)	Cu1^iv—O6—Cu2^iii	75.92 (4)
Cu1—O2—Cu1^i	63.71 (6)	Cu2^viii—O6—Cu2^iii	49.82 (3)
Cu2—O2—Cu1^i	124.49 (9)	As1—O7—Cu3	110.54 (11)
Cu3^ii—O2—Cu1^i	152.61 (7)	As1—O7—Cu2^viii	66.71 (7)
Te1—O2—Cu2^iv	154.57 (10)	Cu3—O7—Cu2^viii	67.29 (6)
Cu1—O2—Cu2^iv	68.91 (6)	As1—O7—Cu2	55.26 (6)
Cu2—O2—Cu2^iv	59.50 (5)	Cu3—O7—Cu2	74.31 (6)
Cu3^ii—O2—Cu2^iv	93.94 (5)	Cu2^viii—O7—Cu2	88.08 (5)
Cu1^i—O2—Cu2^iv	111.78 (6)	As1—O7—Cu1^vii	156.06 (10)
Te1—O2—Cu3	44.72 (5)	Cu3—O7—Cu1^vii	88.22 (7)
Cu1—O2—Cu3	156.62 (9)	Cu2^viii—O7—Cu1^vii	136.54 (6)
Cu2—O2—Cu3	57.37 (5)	Cu2—O7—Cu1^vii	120.36 (6)
Cu3^ii—O2—Cu3	81.88 (5)	As1—O7—Cu2^vii	131.93 (10)
Cu1^i—O2—Cu3	94.51 (4)	Cu3—O7—Cu2^vii	51.08 (5)
Cu2^iv—O2—Cu3	115.82 (5)	Cu2^viii—O7—Cu2^vii	118.37 (6)
Cu3—O3—Te1	118.53 (11)	Cu2—O7—Cu2^vii	76.72 (4)
Cu3—O3—Cu2	141.53 (12)	Cu1^vii—O7—Cu2^vii	50.08 (3)
Te1—O3—Cu2	99.86 (9)	As1—O7—Cu1^iii	39.31 (6)
Cu3—O3—Cu2^vii	65.88 (6)	Cu3—O7—Cu1^iii	119.75 (8)
Te1—O3—Cu2^vii	90.03 (8)	Cu2^viii—O7—Cu1^iii	53.27 (3)
Cu2—O3—Cu2^vii	119.76 (9)	Cu2—O7—Cu1^iii	93.50 (5)
Cu3—O3—Cu3^ii	122.99 (9)	Cu1^vii—O7—Cu1^iii	141.89 (6)
Te1—O3—Cu3^ii	81.19 (7)	Cu2^vii—O7—Cu1^iii	167.90 (6)

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