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The crystal structure of a new arsenide, Rb3Cu3As2 (trirubidium tricopper diarsenide), has been established from single-crystal X-ray diffraction data. This compound crystallizes in the K3Cu3P2 type, with layers of inter­linked CuAs2 units. The partitioning of the available valence electrons yields the charge-balanced composition (Rb+)3(Cu+)3(As3–)2, placing this phase in a broad field of transition-metal-containing Zintl phases. First-principles calculations confirm a semiconducting ground state, in accordance with electron-counting considerations. Chemical bonding analysis reveals strong covalent Cu—As bonds and ionic Rb...As inter­actions. In addition, a weak attraction is found between the Cu atoms, possibly pointing toward cuprophilic inter­actions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229618014341/fn3276sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229618014341/fn3276Isup2.hkl
Contains datablock I

CCDC reference: 1872662

Computing details top

Data collection: SMART (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010) and STRUCTURE TIDY (Gelato & Parthé, 1987).

Trirubidium tricopper diarsenide top
Crystal data top
Rb3Cu3As2Dx = 4.586 Mg m3
Mr = 596.87Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3mCell parameters from 508 reflections
a = 6.020 (4) Åθ = 3.0–27.3°
c = 20.663 (12) ŵ = 31.59 mm1
V = 648.4 (9) Å3T = 200 K
Z = 3Block, red
F(000) = 7920.06 × 0.06 × 0.04 mm
Data collection top
Bruker SMART APEXII DUO CCD
diffractometer
229 reflections with I > 2σ(I)
Radiation source: sealed tubeRint = 0.055
phi and ω scansθmax = 29.5°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2014)
h = 88
Tmin = 0.129, Tmax = 0.264k = 88
2941 measured reflectionsl = 2828
261 independent reflections
Refinement top
Refinement on F213 parameters
Least-squares matrix: full0 restraints
R[F2 > 2σ(F2)] = 0.025 w = 1/[σ2(Fo2) + (0.0268P)2 + 1.0297P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.056(Δ/σ)max < 0.001
S = 1.10Δρmax = 1.05 e Å3
261 reflectionsΔρmin = 0.74 e Å3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Rb10.00000.00000.09011 (4)0.0189 (2)
Rb20.00000.00000.50000.0296 (4)
Cu0.50000.00000.00000.0200 (3)
As0.00000.00000.25740 (4)0.0175 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Rb10.0185 (3)0.0185 (3)0.0198 (5)0.00927 (16)0.0000.000
Rb20.0275 (5)0.0275 (5)0.0336 (8)0.0138 (3)0.0000.000
Cu0.0199 (4)0.0229 (5)0.0183 (5)0.0115 (3)0.00161 (19)0.0032 (4)
As0.0182 (3)0.0182 (3)0.0161 (5)0.00909 (17)0.0000.000
Geometric parameters (Å, º) top
Rb1—As3.457 (2)Rb2—Cuxv3.8574 (18)
Rb1—Asi3.4877 (1)Rb2—Cuxxi3.8574 (18)
Rb1—Asii3.488 (2)Cu—Asii2.3413 (9)
Rb1—Asiii3.4877 (10)Cu—Asxxii2.3413 (9)
Rb1—Cuiv3.5392 (11)Cu—Cuxxiii3.0098 (9)
Rb1—Cuv3.5392 (7)Cu—Cuv3.0098 (9)
Rb1—Cuvi3.5392 (17)Cu—Cuvii3.0098
Rb1—Cuvii3.5392 (11)Cu—Cuxxiv3.0098
Rb1—Cu3.5392 (17)Cu—Rb1xxv3.5392 (17)
Rb1—Cuviii3.5392 (7)Cu—Rb1ix3.5392 (17)
Rb1—Rb1ix3.724 (3)Cu—Rb1xxvi3.5392 (17)
Rb1—Rb2x3.8184 (5)Cu—Rb2xxvii3.8574 (18)
Rb2—Rb1xi3.8184 (5)Cu—Rb2xxii3.8574 (18)
Rb2—Rb1xii3.8184 (5)As—Cuxviii2.3413 (10)
Rb2—Rb1xiii3.818 (2)As—Cuxv2.3413 (9)
Rb2—Rb1xiv3.818 (2)As—Cuxx2.3413 (12)
Rb2—Rb1xv3.8185 (11)As—Rb1i3.4877 (1)
Rb2—Rb1xvi3.8185 (11)As—Rb1ii3.488 (2)
Rb2—Cuxvii3.8574 (18)As—Rb1iii3.4877 (10)
Rb2—Cuxviii3.8574 (18)As—Rb2xxviii3.949 (2)
Rb2—Cuxix3.8574 (19)As—Rb2x3.9489 (7)
Rb2—Cuxx3.8574 (19)As—Rb2xxii3.9489 (11)
As—Rb1—Asi94.82 (2)Rb1xii—Rb2—Cuxxi87.70 (3)
As—Rb1—Asii94.82 (2)Rb1xiii—Rb2—Cuxxi54.910 (17)
Asi—Rb1—Asii119.303 (7)Rb1xiv—Rb2—Cuxxi125.090 (17)
As—Rb1—Asiii94.82 (2)Rb1xv—Rb2—Cuxxi125.09 (2)
Asi—Rb1—Asiii119.30 (3)Rb1xvi—Rb2—Cuxxi54.91 (2)
Asii—Rb1—Asiii119.30 (3)Cuxvii—Rb2—Cuxxi45.92 (2)
As—Rb1—Cuiv121.74 (2)Cuxviii—Rb2—Cuxxi134.08 (2)
Asi—Rb1—Cuiv38.916 (14)Cuxix—Rb2—Cuxxi45.92 (3)
Asii—Rb1—Cuiv133.61 (3)Cuxx—Rb2—Cuxxi134.08 (3)
Asiii—Rb1—Cuiv87.47 (3)Cuxv—Rb2—Cuxxi180.0
As—Rb1—Cuv121.744 (19)Asii—Cu—Asxxii180.00 (3)
Asi—Rb1—Cuv38.917 (19)Asii—Cu—Cuxxiii50.002 (19)
Asii—Rb1—Cuv87.468 (19)Asxxii—Cu—Cuxxiii129.998 (19)
Asiii—Rb1—Cuv133.60 (3)Asii—Cu—Cuv129.998 (19)
Cuiv—Rb1—Cuv50.33 (3)Asxxii—Cu—Cuv50.002 (19)
As—Rb1—Cuvi121.74 (2)Cuxxiii—Cu—Cuv180.0
Asi—Rb1—Cuvi87.47 (2)Asii—Cu—Cuvii50.00 (2)
Asii—Rb1—Cuvi133.60 (4)Asxxii—Cu—Cuvii130.00 (2)
Asiii—Rb1—Cuvi38.92 (2)Cuxxiii—Cu—Cuvii60.00 (3)
Cuiv—Rb1—Cuvi50.33 (2)Cuv—Cu—Cuvii120.00 (3)
Cuv—Rb1—Cuvi94.86 (3)Asii—Cu—Cuxxiv130.00 (2)
As—Rb1—Cuvii121.74 (2)Asxxii—Cu—Cuxxiv50.00 (2)
Asi—Rb1—Cuvii133.61 (3)Cuxxiii—Cu—Cuxxiv120.00 (3)
Asii—Rb1—Cuvii38.916 (17)Cuv—Cu—Cuxxiv60.00 (3)
Asiii—Rb1—Cuvii87.47 (4)Cuvii—Cu—Cuxxiv180.0
Cuiv—Rb1—Cuvii116.51 (4)Asii—Cu—Rb1xxv69.355 (19)
Cuv—Rb1—Cuvii94.86 (3)Asxxii—Cu—Rb1xxv110.645 (19)
Cuvi—Rb1—Cuvii94.86 (4)Cuxxiii—Cu—Rb1xxv64.84 (3)
As—Rb1—Cu121.74 (2)Cuv—Cu—Rb1xxv115.16 (3)
Asi—Rb1—Cu87.47 (2)Cuvii—Cu—Rb1xxv115.164 (7)
Asii—Rb1—Cu38.92 (2)Cuxxiv—Cu—Rb1xxv64.836 (7)
Asiii—Rb1—Cu133.60 (3)Asii—Cu—Rb1ix110.645 (19)
Cuiv—Rb1—Cu94.86 (4)Asxxii—Cu—Rb1ix69.355 (19)
Cuv—Rb1—Cu50.327 (12)Cuxxiii—Cu—Rb1ix115.16 (3)
Cuvi—Rb1—Cu116.51 (5)Cuv—Cu—Rb1ix64.84 (3)
Cuvii—Rb1—Cu50.33 (2)Cuvii—Cu—Rb1ix64.836 (7)
As—Rb1—Cuviii121.74 (2)Cuxxiv—Cu—Rb1ix115.164 (7)
Asi—Rb1—Cuviii133.60 (3)Rb1xxv—Cu—Rb1ix180.00 (2)
Asii—Rb1—Cuviii87.47 (2)Asii—Cu—Rb1xxvi110.65 (3)
Asiii—Rb1—Cuviii38.916 (16)Asxxii—Cu—Rb1xxvi69.35 (3)
Cuiv—Rb1—Cuviii94.86 (3)Cuxxiii—Cu—Rb1xxvi64.84 (3)
Cuv—Rb1—Cuviii116.51 (4)Cuv—Cu—Rb1xxvi115.16 (3)
Cuvi—Rb1—Cuviii50.327 (12)Cuvii—Cu—Rb1xxvi115.164 (7)
Cuvii—Rb1—Cuviii50.33 (3)Cuxxiv—Cu—Rb1xxvi64.836 (7)
Cu—Rb1—Cuviii94.86 (3)Rb1xxv—Cu—Rb1xxvi63.49 (5)
As—Rb1—Rb1ix180.0Rb1ix—Cu—Rb1xxvi116.51 (5)
Asi—Rb1—Rb1ix85.18 (2)Asii—Cu—Rb169.35 (3)
Asii—Rb1—Rb1ix85.18 (2)Asxxii—Cu—Rb1110.65 (3)
Asiii—Rb1—Rb1ix85.18 (2)Cuxxiii—Cu—Rb1115.16 (3)
Cuiv—Rb1—Rb1ix58.26 (2)Cuv—Cu—Rb164.84 (3)
Cuv—Rb1—Rb1ix58.256 (19)Cuvii—Cu—Rb164.836 (7)
Cuvi—Rb1—Rb1ix58.26 (2)Cuxxiv—Cu—Rb1115.164 (7)
Cuvii—Rb1—Rb1ix58.26 (2)Rb1xxv—Cu—Rb1116.51 (5)
Cu—Rb1—Rb1ix58.26 (2)Rb1ix—Cu—Rb163.49 (5)
Cuviii—Rb1—Rb1ix58.26 (2)Rb1xxvi—Cu—Rb1180.0
As—Rb1—Rb2x65.527 (18)Asii—Cu—Rb2xxvii105.31 (3)
Asi—Rb1—Rb2x160.35 (3)Asxxii—Cu—Rb2xxvii74.69 (3)
Asii—Rb1—Rb2x65.248 (10)Cuxxiii—Cu—Rb2xxvii67.038 (11)
Asiii—Rb1—Rb2x65.25 (3)Cuv—Cu—Rb2xxvii112.962 (11)
Cuiv—Rb1—Rb2x152.656 (10)Cuvii—Cu—Rb2xxvii67.037 (13)
Cuv—Rb1—Rb2x152.655 (18)Cuxxiv—Cu—Rb2xxvii112.963 (13)
Cuvi—Rb1—Rb2x102.589 (15)Rb1xxv—Cu—Rb2xxvii118.02 (3)
Cuvii—Rb1—Rb2x63.10 (2)Rb1ix—Cu—Rb2xxvii61.98 (3)
Cu—Rb1—Rb2x102.59 (2)Rb1xxvi—Cu—Rb2xxvii61.985 (19)
Cuviii—Rb1—Rb2x63.11 (3)Rb1—Cu—Rb2xxvii118.02 (2)
Rb1ix—Rb1—Rb2x114.473 (18)Asii—Cu—Rb2xxii74.69 (3)
Rb1xi—Rb2—Rb1xii180.0Asxxii—Cu—Rb2xxii105.31 (3)
Rb1xi—Rb2—Rb1xiii104.04 (2)Cuxxiii—Cu—Rb2xxii112.962 (11)
Rb1xii—Rb2—Rb1xiii75.96 (2)Cuv—Cu—Rb2xxii67.038 (11)
Rb1xi—Rb2—Rb1xiv75.96 (2)Cuvii—Cu—Rb2xxii112.963 (13)
Rb1xii—Rb2—Rb1xiv104.04 (2)Cuxxiv—Cu—Rb2xxii67.037 (13)
Rb1xiii—Rb2—Rb1xiv180.0Rb1xxv—Cu—Rb2xxii61.98 (3)
Rb1xi—Rb2—Rb1xv75.96 (3)Rb1ix—Cu—Rb2xxii118.02 (3)
Rb1xii—Rb2—Rb1xv104.04 (3)Rb1xxvi—Cu—Rb2xxii118.015 (19)
Rb1xiii—Rb2—Rb1xv75.96 (4)Rb1—Cu—Rb2xxii61.98 (2)
Rb1xiv—Rb2—Rb1xv104.04 (4)Rb2xxvii—Cu—Rb2xxii180.0
Rb1xi—Rb2—Rb1xvi104.04 (3)Cuxviii—As—Cuxv80.00 (4)
Rb1xii—Rb2—Rb1xvi75.96 (3)Cuxviii—As—Cuxx80.00 (5)
Rb1xiii—Rb2—Rb1xvi104.04 (4)Cuxv—As—Cuxx80.00 (4)
Rb1xiv—Rb2—Rb1xvi75.96 (4)Cuxviii—As—Rb1132.08 (2)
Rb1xv—Rb2—Rb1xvi180.00 (2)Cuxv—As—Rb1132.08 (2)
Rb1xi—Rb2—Cuxvii54.910 (17)Cuxx—As—Rb1132.08 (3)
Rb1xii—Rb2—Cuxvii125.090 (17)Cuxviii—As—Rb1i71.73 (2)
Rb1xiii—Rb2—Cuxvii54.910 (13)Cuxv—As—Rb1i142.74 (4)
Rb1xiv—Rb2—Cuxvii125.090 (14)Cuxx—As—Rb1i71.730 (17)
Rb1xv—Rb2—Cuxvii87.70 (3)Rb1—As—Rb1i85.18 (2)
Rb1xvi—Rb2—Cuxvii92.30 (3)Cuxviii—As—Rb1ii71.73 (3)
Rb1xi—Rb2—Cuxviii125.090 (17)Cuxv—As—Rb1ii71.730 (15)
Rb1xii—Rb2—Cuxviii54.910 (17)Cuxx—As—Rb1ii142.74 (4)
Rb1xiii—Rb2—Cuxviii125.090 (13)Rb1—As—Rb1ii85.18 (2)
Rb1xiv—Rb2—Cuxviii54.910 (14)Rb1i—As—Rb1ii119.303 (7)
Rb1xv—Rb2—Cuxviii92.30 (3)Cuxviii—As—Rb1iii142.74 (4)
Rb1xvi—Rb2—Cuxviii87.70 (3)Cuxv—As—Rb1iii71.73 (2)
Cuxvii—Rb2—Cuxviii180.0Cuxx—As—Rb1iii71.73 (3)
Rb1xi—Rb2—Cuxix54.910 (14)Rb1—As—Rb1iii85.18 (2)
Rb1xii—Rb2—Cuxix125.090 (14)Rb1i—As—Rb1iii119.30 (3)
Rb1xiii—Rb2—Cuxix92.30 (4)Rb1ii—As—Rb1iii119.30 (3)
Rb1xiv—Rb2—Cuxix87.70 (4)Cuxviii—As—Rb2xxviii130.151 (17)
Rb1xv—Rb2—Cuxix125.090 (18)Cuxv—As—Rb2xxviii130.151 (13)
Rb1xvi—Rb2—Cuxix54.910 (17)Cuxx—As—Rb2xxviii70.43 (4)
Cuxvii—Rb2—Cuxix45.92 (3)Rb1—As—Rb2xxviii61.65 (2)
Cuxviii—Rb2—Cuxix134.08 (3)Rb1i—As—Rb2xxviii61.421 (10)
Rb1xi—Rb2—Cuxx125.090 (14)Rb1ii—As—Rb2xxviii146.84 (4)
Rb1xii—Rb2—Cuxx54.910 (14)Rb1iii—As—Rb2xxviii61.42 (3)
Rb1xiii—Rb2—Cuxx87.70 (4)Cuxviii—As—Rb2x130.15 (2)
Rb1xiv—Rb2—Cuxx92.30 (4)Cuxv—As—Rb2x70.43 (3)
Rb1xv—Rb2—Cuxx54.910 (17)Cuxx—As—Rb2x130.151 (10)
Rb1xvi—Rb2—Cuxx125.090 (17)Rb1—As—Rb2x61.653 (18)
Cuxvii—Rb2—Cuxx134.08 (3)Rb1i—As—Rb2x146.84 (4)
Cuxviii—Rb2—Cuxx45.92 (3)Rb1ii—As—Rb2x61.421 (10)
Cuxix—Rb2—Cuxx180.0Rb1iii—As—Rb2x61.42 (3)
Rb1xi—Rb2—Cuxv87.70 (3)Rb2xxviii—As—Rb2x99.31 (3)
Rb1xii—Rb2—Cuxv92.30 (3)Cuxviii—As—Rb2xxii70.43 (3)
Rb1xiii—Rb2—Cuxv125.090 (17)Cuxv—As—Rb2xxii130.15 (3)
Rb1xiv—Rb2—Cuxv54.910 (17)Cuxx—As—Rb2xxii130.152 (19)
Rb1xv—Rb2—Cuxv54.91 (2)Rb1—As—Rb2xxii61.65 (2)
Rb1xvi—Rb2—Cuxv125.09 (2)Rb1i—As—Rb2xxii61.42 (3)
Cuxvii—Rb2—Cuxv134.08 (2)Rb1ii—As—Rb2xxii61.42 (3)
Cuxviii—Rb2—Cuxv45.92 (2)Rb1iii—As—Rb2xxii146.84 (4)
Cuxix—Rb2—Cuxv134.08 (3)Rb2xxviii—As—Rb2xxii99.31 (4)
Cuxx—Rb2—Cuxv45.92 (3)Rb2x—As—Rb2xxii99.31 (3)
Rb1xi—Rb2—Cuxxi92.30 (3)
Symmetry codes: (i) x1/3, y2/3, z+1/3; (ii) x+2/3, y+1/3, z+1/3; (iii) x1/3, y+1/3, z+1/3; (iv) x+y, x, z; (v) y, xy1, z; (vi) x1, y, z; (vii) x+y+1, x+1, z; (viii) y, xy, z; (ix) x, y, z; (x) x+1/3, y+2/3, z1/3; (xi) x+1/3, y+2/3, z+2/3; (xii) x1/3, y2/3, z+1/3; (xiii) x2/3, y1/3, z+2/3; (xiv) x+2/3, y+1/3, z+1/3; (xv) x1/3, y+1/3, z+1/3; (xvi) x+1/3, y1/3, z+2/3; (xvii) x+y+1/3, x+2/3, z+2/3; (xviii) x+y+2/3, x+1/3, z+1/3; (xix) y+1/3, xy1/3, z+2/3; (xx) y1/3, xy2/3, z+1/3; (xxi) x2/3, y1/3, z+2/3; (xxii) x+1/3, y1/3, z1/3; (xxiii) y+1, xy, z; (xxiv) x+y+1, x, z; (xxv) x+1, y, z; (xxvi) x+1, y, z; (xxvii) x+2/3, y+1/3, z2/3; (xxviii) x2/3, y1/3, z1/3.
 

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