Buy article online - an online subscription or single-article purchase is required to access this article.
The crystal structure of a new arsenide, Rb
3Cu
3As
2 (trirubidium tricopper diarsenide), has been established from single-crystal X-ray diffraction data. This compound crystallizes in the K
3Cu
3P
2 type, with layers of interlinked CuAs
2 units. The partitioning of the available valence electrons yields the charge-balanced composition (Rb
+)
3(Cu
+)
3(As
3–)
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
CCDC reference: 1872662
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
Rb3Cu3As2 | Dx = 4.586 Mg m−3 |
Mr = 596.87 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3m | Cell parameters from 508 reflections |
a = 6.020 (4) Å | θ = 3.0–27.3° |
c = 20.663 (12) Å | µ = 31.59 mm−1 |
V = 648.4 (9) Å3 | T = 200 K |
Z = 3 | Block, red |
F(000) = 792 | 0.06 × 0.06 × 0.04 mm |
Data collection top
Bruker SMART APEXII DUO CCD diffractometer | 229 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.055 |
phi and ω scans | θmax = 29.5°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −8→8 |
Tmin = 0.129, Tmax = 0.264 | k = −8→8 |
2941 measured reflections | l = −28→28 |
261 independent reflections | |
Refinement top
Refinement on F2 | 13 parameters |
Least-squares matrix: full | 0 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 = 1.10 | Δρmax = 1.05 e Å−3 |
261 reflections | Δρmin = −0.74 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Rb1 | 0.0000 | 0.0000 | 0.09011 (4) | 0.0189 (2) | |
Rb2 | 0.0000 | 0.0000 | 0.5000 | 0.0296 (4) | |
Cu | 0.5000 | 0.0000 | 0.0000 | 0.0200 (3) | |
As | 0.0000 | 0.0000 | 0.25740 (4) | 0.0175 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Rb1 | 0.0185 (3) | 0.0185 (3) | 0.0198 (5) | 0.00927 (16) | 0.000 | 0.000 |
Rb2 | 0.0275 (5) | 0.0275 (5) | 0.0336 (8) | 0.0138 (3) | 0.000 | 0.000 |
Cu | 0.0199 (4) | 0.0229 (5) | 0.0183 (5) | 0.0115 (3) | −0.00161 (19) | −0.0032 (4) |
As | 0.0182 (3) | 0.0182 (3) | 0.0161 (5) | 0.00909 (17) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
Rb1—As | 3.457 (2) | Rb2—Cuxv | 3.8574 (18) |
Rb1—Asi | 3.4877 (1) | Rb2—Cuxxi | 3.8574 (18) |
Rb1—Asii | 3.488 (2) | Cu—Asii | 2.3413 (9) |
Rb1—Asiii | 3.4877 (10) | Cu—Asxxii | 2.3413 (9) |
Rb1—Cuiv | 3.5392 (11) | Cu—Cuxxiii | 3.0098 (9) |
Rb1—Cuv | 3.5392 (7) | Cu—Cuv | 3.0098 (9) |
Rb1—Cuvi | 3.5392 (17) | Cu—Cuvii | 3.0098 |
Rb1—Cuvii | 3.5392 (11) | Cu—Cuxxiv | 3.0098 |
Rb1—Cu | 3.5392 (17) | Cu—Rb1xxv | 3.5392 (17) |
Rb1—Cuviii | 3.5392 (7) | Cu—Rb1ix | 3.5392 (17) |
Rb1—Rb1ix | 3.724 (3) | Cu—Rb1xxvi | 3.5392 (17) |
Rb1—Rb2x | 3.8184 (5) | Cu—Rb2xxvii | 3.8574 (18) |
Rb2—Rb1xi | 3.8184 (5) | Cu—Rb2xxii | 3.8574 (18) |
Rb2—Rb1xii | 3.8184 (5) | As—Cuxviii | 2.3413 (10) |
Rb2—Rb1xiii | 3.818 (2) | As—Cuxv | 2.3413 (9) |
Rb2—Rb1xiv | 3.818 (2) | As—Cuxx | 2.3413 (12) |
Rb2—Rb1xv | 3.8185 (11) | As—Rb1i | 3.4877 (1) |
Rb2—Rb1xvi | 3.8185 (11) | As—Rb1ii | 3.488 (2) |
Rb2—Cuxvii | 3.8574 (18) | As—Rb1iii | 3.4877 (10) |
Rb2—Cuxviii | 3.8574 (18) | As—Rb2xxviii | 3.949 (2) |
Rb2—Cuxix | 3.8574 (19) | As—Rb2x | 3.9489 (7) |
Rb2—Cuxx | 3.8574 (19) | As—Rb2xxii | 3.9489 (11) |
| | | |
As—Rb1—Asi | 94.82 (2) | Rb1xii—Rb2—Cuxxi | 87.70 (3) |
As—Rb1—Asii | 94.82 (2) | Rb1xiii—Rb2—Cuxxi | 54.910 (17) |
Asi—Rb1—Asii | 119.303 (7) | Rb1xiv—Rb2—Cuxxi | 125.090 (17) |
As—Rb1—Asiii | 94.82 (2) | Rb1xv—Rb2—Cuxxi | 125.09 (2) |
Asi—Rb1—Asiii | 119.30 (3) | Rb1xvi—Rb2—Cuxxi | 54.91 (2) |
Asii—Rb1—Asiii | 119.30 (3) | Cuxvii—Rb2—Cuxxi | 45.92 (2) |
As—Rb1—Cuiv | 121.74 (2) | Cuxviii—Rb2—Cuxxi | 134.08 (2) |
Asi—Rb1—Cuiv | 38.916 (14) | Cuxix—Rb2—Cuxxi | 45.92 (3) |
Asii—Rb1—Cuiv | 133.61 (3) | Cuxx—Rb2—Cuxxi | 134.08 (3) |
Asiii—Rb1—Cuiv | 87.47 (3) | Cuxv—Rb2—Cuxxi | 180.0 |
As—Rb1—Cuv | 121.744 (19) | Asii—Cu—Asxxii | 180.00 (3) |
Asi—Rb1—Cuv | 38.917 (19) | Asii—Cu—Cuxxiii | 50.002 (19) |
Asii—Rb1—Cuv | 87.468 (19) | Asxxii—Cu—Cuxxiii | 129.998 (19) |
Asiii—Rb1—Cuv | 133.60 (3) | Asii—Cu—Cuv | 129.998 (19) |
Cuiv—Rb1—Cuv | 50.33 (3) | Asxxii—Cu—Cuv | 50.002 (19) |
As—Rb1—Cuvi | 121.74 (2) | Cuxxiii—Cu—Cuv | 180.0 |
Asi—Rb1—Cuvi | 87.47 (2) | Asii—Cu—Cuvii | 50.00 (2) |
Asii—Rb1—Cuvi | 133.60 (4) | Asxxii—Cu—Cuvii | 130.00 (2) |
Asiii—Rb1—Cuvi | 38.92 (2) | Cuxxiii—Cu—Cuvii | 60.00 (3) |
Cuiv—Rb1—Cuvi | 50.33 (2) | Cuv—Cu—Cuvii | 120.00 (3) |
Cuv—Rb1—Cuvi | 94.86 (3) | Asii—Cu—Cuxxiv | 130.00 (2) |
As—Rb1—Cuvii | 121.74 (2) | Asxxii—Cu—Cuxxiv | 50.00 (2) |
Asi—Rb1—Cuvii | 133.61 (3) | Cuxxiii—Cu—Cuxxiv | 120.00 (3) |
Asii—Rb1—Cuvii | 38.916 (17) | Cuv—Cu—Cuxxiv | 60.00 (3) |
Asiii—Rb1—Cuvii | 87.47 (4) | Cuvii—Cu—Cuxxiv | 180.0 |
Cuiv—Rb1—Cuvii | 116.51 (4) | Asii—Cu—Rb1xxv | 69.355 (19) |
Cuv—Rb1—Cuvii | 94.86 (3) | Asxxii—Cu—Rb1xxv | 110.645 (19) |
Cuvi—Rb1—Cuvii | 94.86 (4) | Cuxxiii—Cu—Rb1xxv | 64.84 (3) |
As—Rb1—Cu | 121.74 (2) | Cuv—Cu—Rb1xxv | 115.16 (3) |
Asi—Rb1—Cu | 87.47 (2) | Cuvii—Cu—Rb1xxv | 115.164 (7) |
Asii—Rb1—Cu | 38.92 (2) | Cuxxiv—Cu—Rb1xxv | 64.836 (7) |
Asiii—Rb1—Cu | 133.60 (3) | Asii—Cu—Rb1ix | 110.645 (19) |
Cuiv—Rb1—Cu | 94.86 (4) | Asxxii—Cu—Rb1ix | 69.355 (19) |
Cuv—Rb1—Cu | 50.327 (12) | Cuxxiii—Cu—Rb1ix | 115.16 (3) |
Cuvi—Rb1—Cu | 116.51 (5) | Cuv—Cu—Rb1ix | 64.84 (3) |
Cuvii—Rb1—Cu | 50.33 (2) | Cuvii—Cu—Rb1ix | 64.836 (7) |
As—Rb1—Cuviii | 121.74 (2) | Cuxxiv—Cu—Rb1ix | 115.164 (7) |
Asi—Rb1—Cuviii | 133.60 (3) | Rb1xxv—Cu—Rb1ix | 180.00 (2) |
Asii—Rb1—Cuviii | 87.47 (2) | Asii—Cu—Rb1xxvi | 110.65 (3) |
Asiii—Rb1—Cuviii | 38.916 (16) | Asxxii—Cu—Rb1xxvi | 69.35 (3) |
Cuiv—Rb1—Cuviii | 94.86 (3) | Cuxxiii—Cu—Rb1xxvi | 64.84 (3) |
Cuv—Rb1—Cuviii | 116.51 (4) | Cuv—Cu—Rb1xxvi | 115.16 (3) |
Cuvi—Rb1—Cuviii | 50.327 (12) | Cuvii—Cu—Rb1xxvi | 115.164 (7) |
Cuvii—Rb1—Cuviii | 50.33 (3) | Cuxxiv—Cu—Rb1xxvi | 64.836 (7) |
Cu—Rb1—Cuviii | 94.86 (3) | Rb1xxv—Cu—Rb1xxvi | 63.49 (5) |
As—Rb1—Rb1ix | 180.0 | Rb1ix—Cu—Rb1xxvi | 116.51 (5) |
Asi—Rb1—Rb1ix | 85.18 (2) | Asii—Cu—Rb1 | 69.35 (3) |
Asii—Rb1—Rb1ix | 85.18 (2) | Asxxii—Cu—Rb1 | 110.65 (3) |
Asiii—Rb1—Rb1ix | 85.18 (2) | Cuxxiii—Cu—Rb1 | 115.16 (3) |
Cuiv—Rb1—Rb1ix | 58.26 (2) | Cuv—Cu—Rb1 | 64.84 (3) |
Cuv—Rb1—Rb1ix | 58.256 (19) | Cuvii—Cu—Rb1 | 64.836 (7) |
Cuvi—Rb1—Rb1ix | 58.26 (2) | Cuxxiv—Cu—Rb1 | 115.164 (7) |
Cuvii—Rb1—Rb1ix | 58.26 (2) | Rb1xxv—Cu—Rb1 | 116.51 (5) |
Cu—Rb1—Rb1ix | 58.26 (2) | Rb1ix—Cu—Rb1 | 63.49 (5) |
Cuviii—Rb1—Rb1ix | 58.26 (2) | Rb1xxvi—Cu—Rb1 | 180.0 |
As—Rb1—Rb2x | 65.527 (18) | Asii—Cu—Rb2xxvii | 105.31 (3) |
Asi—Rb1—Rb2x | 160.35 (3) | Asxxii—Cu—Rb2xxvii | 74.69 (3) |
Asii—Rb1—Rb2x | 65.248 (10) | Cuxxiii—Cu—Rb2xxvii | 67.038 (11) |
Asiii—Rb1—Rb2x | 65.25 (3) | Cuv—Cu—Rb2xxvii | 112.962 (11) |
Cuiv—Rb1—Rb2x | 152.656 (10) | Cuvii—Cu—Rb2xxvii | 67.037 (13) |
Cuv—Rb1—Rb2x | 152.655 (18) | Cuxxiv—Cu—Rb2xxvii | 112.963 (13) |
Cuvi—Rb1—Rb2x | 102.589 (15) | Rb1xxv—Cu—Rb2xxvii | 118.02 (3) |
Cuvii—Rb1—Rb2x | 63.10 (2) | Rb1ix—Cu—Rb2xxvii | 61.98 (3) |
Cu—Rb1—Rb2x | 102.59 (2) | Rb1xxvi—Cu—Rb2xxvii | 61.985 (19) |
Cuviii—Rb1—Rb2x | 63.11 (3) | Rb1—Cu—Rb2xxvii | 118.02 (2) |
Rb1ix—Rb1—Rb2x | 114.473 (18) | Asii—Cu—Rb2xxii | 74.69 (3) |
Rb1xi—Rb2—Rb1xii | 180.0 | Asxxii—Cu—Rb2xxii | 105.31 (3) |
Rb1xi—Rb2—Rb1xiii | 104.04 (2) | Cuxxiii—Cu—Rb2xxii | 112.962 (11) |
Rb1xii—Rb2—Rb1xiii | 75.96 (2) | Cuv—Cu—Rb2xxii | 67.038 (11) |
Rb1xi—Rb2—Rb1xiv | 75.96 (2) | Cuvii—Cu—Rb2xxii | 112.963 (13) |
Rb1xii—Rb2—Rb1xiv | 104.04 (2) | Cuxxiv—Cu—Rb2xxii | 67.037 (13) |
Rb1xiii—Rb2—Rb1xiv | 180.0 | Rb1xxv—Cu—Rb2xxii | 61.98 (3) |
Rb1xi—Rb2—Rb1xv | 75.96 (3) | Rb1ix—Cu—Rb2xxii | 118.02 (3) |
Rb1xii—Rb2—Rb1xv | 104.04 (3) | Rb1xxvi—Cu—Rb2xxii | 118.015 (19) |
Rb1xiii—Rb2—Rb1xv | 75.96 (4) | Rb1—Cu—Rb2xxii | 61.98 (2) |
Rb1xiv—Rb2—Rb1xv | 104.04 (4) | Rb2xxvii—Cu—Rb2xxii | 180.0 |
Rb1xi—Rb2—Rb1xvi | 104.04 (3) | Cuxviii—As—Cuxv | 80.00 (4) |
Rb1xii—Rb2—Rb1xvi | 75.96 (3) | Cuxviii—As—Cuxx | 80.00 (5) |
Rb1xiii—Rb2—Rb1xvi | 104.04 (4) | Cuxv—As—Cuxx | 80.00 (4) |
Rb1xiv—Rb2—Rb1xvi | 75.96 (4) | Cuxviii—As—Rb1 | 132.08 (2) |
Rb1xv—Rb2—Rb1xvi | 180.00 (2) | Cuxv—As—Rb1 | 132.08 (2) |
Rb1xi—Rb2—Cuxvii | 54.910 (17) | Cuxx—As—Rb1 | 132.08 (3) |
Rb1xii—Rb2—Cuxvii | 125.090 (17) | Cuxviii—As—Rb1i | 71.73 (2) |
Rb1xiii—Rb2—Cuxvii | 54.910 (13) | Cuxv—As—Rb1i | 142.74 (4) |
Rb1xiv—Rb2—Cuxvii | 125.090 (14) | Cuxx—As—Rb1i | 71.730 (17) |
Rb1xv—Rb2—Cuxvii | 87.70 (3) | Rb1—As—Rb1i | 85.18 (2) |
Rb1xvi—Rb2—Cuxvii | 92.30 (3) | Cuxviii—As—Rb1ii | 71.73 (3) |
Rb1xi—Rb2—Cuxviii | 125.090 (17) | Cuxv—As—Rb1ii | 71.730 (15) |
Rb1xii—Rb2—Cuxviii | 54.910 (17) | Cuxx—As—Rb1ii | 142.74 (4) |
Rb1xiii—Rb2—Cuxviii | 125.090 (13) | Rb1—As—Rb1ii | 85.18 (2) |
Rb1xiv—Rb2—Cuxviii | 54.910 (14) | Rb1i—As—Rb1ii | 119.303 (7) |
Rb1xv—Rb2—Cuxviii | 92.30 (3) | Cuxviii—As—Rb1iii | 142.74 (4) |
Rb1xvi—Rb2—Cuxviii | 87.70 (3) | Cuxv—As—Rb1iii | 71.73 (2) |
Cuxvii—Rb2—Cuxviii | 180.0 | Cuxx—As—Rb1iii | 71.73 (3) |
Rb1xi—Rb2—Cuxix | 54.910 (14) | Rb1—As—Rb1iii | 85.18 (2) |
Rb1xii—Rb2—Cuxix | 125.090 (14) | Rb1i—As—Rb1iii | 119.30 (3) |
Rb1xiii—Rb2—Cuxix | 92.30 (4) | Rb1ii—As—Rb1iii | 119.30 (3) |
Rb1xiv—Rb2—Cuxix | 87.70 (4) | Cuxviii—As—Rb2xxviii | 130.151 (17) |
Rb1xv—Rb2—Cuxix | 125.090 (18) | Cuxv—As—Rb2xxviii | 130.151 (13) |
Rb1xvi—Rb2—Cuxix | 54.910 (17) | Cuxx—As—Rb2xxviii | 70.43 (4) |
Cuxvii—Rb2—Cuxix | 45.92 (3) | Rb1—As—Rb2xxviii | 61.65 (2) |
Cuxviii—Rb2—Cuxix | 134.08 (3) | Rb1i—As—Rb2xxviii | 61.421 (10) |
Rb1xi—Rb2—Cuxx | 125.090 (14) | Rb1ii—As—Rb2xxviii | 146.84 (4) |
Rb1xii—Rb2—Cuxx | 54.910 (14) | Rb1iii—As—Rb2xxviii | 61.42 (3) |
Rb1xiii—Rb2—Cuxx | 87.70 (4) | Cuxviii—As—Rb2x | 130.15 (2) |
Rb1xiv—Rb2—Cuxx | 92.30 (4) | Cuxv—As—Rb2x | 70.43 (3) |
Rb1xv—Rb2—Cuxx | 54.910 (17) | Cuxx—As—Rb2x | 130.151 (10) |
Rb1xvi—Rb2—Cuxx | 125.090 (17) | Rb1—As—Rb2x | 61.653 (18) |
Cuxvii—Rb2—Cuxx | 134.08 (3) | Rb1i—As—Rb2x | 146.84 (4) |
Cuxviii—Rb2—Cuxx | 45.92 (3) | Rb1ii—As—Rb2x | 61.421 (10) |
Cuxix—Rb2—Cuxx | 180.0 | Rb1iii—As—Rb2x | 61.42 (3) |
Rb1xi—Rb2—Cuxv | 87.70 (3) | Rb2xxviii—As—Rb2x | 99.31 (3) |
Rb1xii—Rb2—Cuxv | 92.30 (3) | Cuxviii—As—Rb2xxii | 70.43 (3) |
Rb1xiii—Rb2—Cuxv | 125.090 (17) | Cuxv—As—Rb2xxii | 130.15 (3) |
Rb1xiv—Rb2—Cuxv | 54.910 (17) | Cuxx—As—Rb2xxii | 130.152 (19) |
Rb1xv—Rb2—Cuxv | 54.91 (2) | Rb1—As—Rb2xxii | 61.65 (2) |
Rb1xvi—Rb2—Cuxv | 125.09 (2) | Rb1i—As—Rb2xxii | 61.42 (3) |
Cuxvii—Rb2—Cuxv | 134.08 (2) | Rb1ii—As—Rb2xxii | 61.42 (3) |
Cuxviii—Rb2—Cuxv | 45.92 (2) | Rb1iii—As—Rb2xxii | 146.84 (4) |
Cuxix—Rb2—Cuxv | 134.08 (3) | Rb2xxviii—As—Rb2xxii | 99.31 (4) |
Cuxx—Rb2—Cuxv | 45.92 (3) | Rb2x—As—Rb2xxii | 99.31 (3) |
Rb1xi—Rb2—Cuxxi | 92.30 (3) | | |
Symmetry codes: (i) −x−1/3, −y−2/3, −z+1/3; (ii) −x+2/3, −y+1/3, −z+1/3; (iii) −x−1/3, −y+1/3, −z+1/3; (iv) −x+y, −x, z; (v) −y, x−y−1, z; (vi) x−1, y, z; (vii) −x+y+1, −x+1, z; (viii) −y, x−y, z; (ix) −x, −y, −z; (x) x+1/3, y+2/3, z−1/3; (xi) −x+1/3, −y+2/3, −z+2/3; (xii) x−1/3, y−2/3, z+1/3; (xiii) −x−2/3, −y−1/3, −z+2/3; (xiv) x+2/3, y+1/3, z+1/3; (xv) x−1/3, y+1/3, z+1/3; (xvi) −x+1/3, −y−1/3, −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, x−y−1/3, z+2/3; (xx) −y−1/3, x−y−2/3, z+1/3; (xxi) x−2/3, y−1/3, z+2/3; (xxii) x+1/3, y−1/3, z−1/3; (xxiii) −y+1, x−y, z; (xxiv) −x+y+1, −x, z; (xxv) x+1, y, z; (xxvi) −x+1, −y, −z; (xxvii) x+2/3, y+1/3, z−2/3; (xxviii) x−2/3, y−1/3, z−1/3. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.