A novel polymorph of RbCuCl
3 (rubidium copper trichloride), denoted
-RbCuCl
3, has been prepared by chemical vapour transport (CVT) from a mixture of CuO, CuCl
2, SeO
2 and RbCl. The new polymorph crystallizes in the orthorhombic space group
C222
1. The crystal structure is based on an octahedral framework of the 4
H perovskite type. The Rb
+ and Cl
− ions form a four-layer closest-packing array with an
ABCB sequence. The Cu
2+ cations reside in octahedral cavities with a typical [4 + 2]-Jahn–Teller-distorted coordination, forming four short and two long Cu—Cl bonds.
-RbCuCl
3 is the most structurally complex and most dense among all currently known RbCuCl
3 polymorphs, which allows us to suggest that it is a high-pressure phase, which is unstable under ambient conditions.
Supporting information
CCDC reference: 1830660
Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009) and
DIAMOND (Brandenburg & Putz, 1999); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
Rubidium copper trichloride
top
Crystal data top
RbCuCl3 | Dx = 3.440 Mg m−3 |
Mr = 255.36 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, C2221 | Cell parameters from 1041 reflections |
a = 7.053 (3) Å | θ = 3.4–33.6° |
b = 11.864 (5) Å | µ = 15.67 mm−1 |
c = 11.785 (6) Å | T = 100 K |
V = 986.1 (8) Å3 | Prism, red |
Z = 8 | 0.08 × 0.05 × 0.03 mm |
F(000) = 936 | |
Data collection top
Bruker APEXII CCD diffractometer | 1042 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
φ and ω scans | θmax = 28.0°, θmin = 3.4° |
Absorption correction: multi-scan | h = −9→9 |
| k = −15→15 |
4745 measured reflections | l = −8→15 |
1184 independent reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.012P)2] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.028 | (Δ/σ)max < 0.001 |
wR(F2) = 0.044 | Δρmax = 0.60 e Å−3 |
S = 1.02 | Δρmin = −0.70 e Å−3 |
1184 reflections | Absolute structure: Refined as an inversion twin |
49 parameters | Absolute structure parameter: 0.495 (19) |
0 restraints | |
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. |
Refinement. Refined as a 2-component inversion twin. Data were collected using Bruker Kappa Duo diffractometer
equipped with an APEX II CCD detector operated with monochromated MoKα
radiation at 50 kV and 40 mA. Diffraction data were collected at 100 K with
the frame width of 0.5o in ω and φ, and exposure of 60 s spent per each
frame. Data were integrated and corrected for background, Lorentz, and
polarization effects using an empirical spherical model by means of the Bruker
programs APEX2 and XPREP. Absorption correction was applied
using SADABS program. The unit-cell parameters were refined by the
least-squares techniques. The structure was solved by direct methods and
refined using the SHELX program (Sheldrick, 2008)
incorporated in the
OLEX2 program package (Dolomanov et al., 2009). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Rb1 | 0.0000 | 0.32138 (6) | 0.2500 | 0.0105 (2) | |
Rb2 | 0.01172 (15) | 0.0000 | 0.0000 | 0.0111 (2) | |
Cu1 | 0.51064 (15) | 0.15615 (6) | 0.11987 (7) | 0.00720 (18) | |
Cl1 | 0.5000 | 0.30598 (14) | 0.2500 | 0.0089 (4) | |
Cl2 | 0.2142 (2) | 0.26279 (13) | 0.51375 (15) | 0.0108 (4) | |
Cl3 | 0.2555 (2) | 0.07319 (11) | 0.27800 (13) | 0.0089 (3) | |
Cl4 | 0.0034 (4) | 0.5000 | 0.0000 | 0.0123 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Rb1 | 0.0105 (4) | 0.0090 (4) | 0.0119 (5) | 0.000 | −0.0003 (6) | 0.000 |
Rb2 | 0.0094 (4) | 0.0099 (4) | 0.0141 (5) | 0.000 | 0.000 | −0.0020 (4) |
Cu1 | 0.0086 (4) | 0.0061 (3) | 0.0069 (4) | 0.0010 (4) | −0.0018 (4) | −0.0008 (3) |
Cl1 | 0.0115 (10) | 0.0067 (8) | 0.0085 (11) | 0.000 | 0.0000 (14) | 0.000 |
Cl2 | 0.0111 (8) | 0.0109 (8) | 0.0105 (9) | 0.0022 (7) | 0.0043 (7) | −0.0016 (7) |
Cl3 | 0.0083 (6) | 0.0090 (6) | 0.0094 (9) | −0.0018 (6) | 0.0001 (8) | −0.0011 (6) |
Cl4 | 0.0139 (9) | 0.0105 (9) | 0.0125 (12) | 0.000 | 0.000 | −0.0061 (9) |
Geometric parameters (Å, º) top
Rb1—Cl1 | 3.5313 (15) | Cu1—Rb1xiii | 4.2554 (17) |
Rb1—Cl1i | 3.5313 (15) | Cu1—Rb1xii | 4.2581 (19) |
Rb1—Cl2ii | 3.579 (2) | Cu1—Rb2xiii | 4.2330 (19) |
Rb1—Cl2iii | 3.525 (2) | Cu1—Cl1 | 2.3489 (16) |
Rb1—Cl2iv | 3.579 (2) | Cu1—Cl2iv | 2.2372 (19) |
Rb1—Cl2 | 3.525 (2) | Cu1—Cl3xiv | 2.2667 (19) |
Rb1—Cl3v | 3.4651 (19) | Cu1—Cl4xii | 2.3303 (11) |
Rb1—Cl3vi | 3.4651 (19) | Cl1—Rb1xiii | 3.5313 (16) |
Rb1—Cl3 | 3.4680 (19) | Cl1—Rb2xv | 3.7397 (17) |
Rb1—Cl3iii | 3.4680 (19) | Cl1—Rb2xvi | 3.7397 (17) |
Rb1—Cl4 | 3.6292 (14) | Cl1—Cu1xiv | 2.3489 (16) |
Rb1—Cl4vii | 3.6292 (14) | Cl2—Rb1xv | 3.579 (2) |
Rb2—Cl1viii | 3.7397 (17) | Cl2—Rb2xv | 3.418 (2) |
Rb2—Cl1iv | 3.7397 (17) | Cl2—Rb2xvii | 3.505 (2) |
Rb2—Cl2iv | 3.418 (2) | Cl2—Cu1xv | 2.2372 (19) |
Rb2—Cl2ix | 3.418 (2) | Cl3—Rb1xii | 3.4651 (19) |
Rb2—Cl2iii | 3.505 (2) | Cl3—Rb2xvii | 3.339 (2) |
Rb2—Cl2x | 3.505 (2) | Cl3—Cu1xiv | 2.2666 (19) |
Rb2—Cl3iii | 3.339 (2) | Cl4—Rb1xviii | 3.6292 (14) |
Rb2—Cl3x | 3.339 (2) | Cl4—Rb2v | 3.468 (4) |
Rb2—Cl3xi | 3.800 (2) | Cl4—Rb2xvi | 3.585 (4) |
Rb2—Cl3 | 3.800 (2) | Cl4—Cu1xix | 2.3303 (11) |
Rb2—Cl4xii | 3.468 (4) | Cl4—Cu1v | 2.3303 (11) |
Rb2—Cl4viii | 3.585 (4) | | |
| | | |
Cl1—Rb1—Cl1i | 174.07 (6) | Cl3x—Rb2—Cl2ix | 93.90 (4) |
Cl1i—Rb1—Cl2iv | 123.22 (3) | Cl3x—Rb2—Cl2iv | 124.78 (4) |
Cl1—Rb1—Cl2ii | 123.22 (3) | Cl3iii—Rb2—Cl2x | 86.47 (4) |
Cl1—Rb1—Cl2iv | 54.77 (3) | Cl3iii—Rb2—Cl2ix | 124.78 (4) |
Cl1i—Rb1—Cl2ii | 54.77 (3) | Cl3x—Rb2—Cl2iii | 86.47 (4) |
Cl1i—Rb1—Cl4vii | 91.35 (5) | Cl3x—Rb2—Cl2x | 63.15 (4) |
Cl1i—Rb1—Cl4 | 92.11 (5) | Cl3iii—Rb2—Cl3xi | 171.95 (4) |
Cl1—Rb1—Cl4 | 91.35 (5) | Cl3xi—Rb2—Cl3 | 126.20 (6) |
Cl1—Rb1—Cl4vii | 92.11 (5) | Cl3x—Rb2—Cl3iii | 111.27 (7) |
Cl2—Rb1—Cl1 | 64.01 (3) | Cl3x—Rb2—Cl3 | 171.95 (4) |
Cl2iii—Rb1—Cl1 | 114.70 (3) | Cl3iii—Rb2—Cl3 | 61.35 (5) |
Cl2iii—Rb1—Cl1i | 64.01 (3) | Cl3x—Rb2—Cl3xi | 61.35 (5) |
Cl2—Rb1—Cl1i | 114.70 (3) | Cl3iii—Rb2—Cl4viii | 55.64 (3) |
Cl2iv—Rb1—Cl2ii | 147.60 (6) | Cl3x—Rb2—Cl4xii | 124.36 (3) |
Cl2iii—Rb1—Cl2 | 157.25 (6) | Cl3iii—Rb2—Cl4xii | 124.36 (3) |
Cl2—Rb1—Cl2ii | 60.03 (3) | Cl3x—Rb2—Cl4viii | 55.64 (3) |
Cl2iii—Rb1—Cl2iv | 60.03 (3) | Cl4xii—Rb2—Cl1viii | 91.267 (16) |
Cl2—Rb1—Cl2iv | 112.92 (3) | Cl4viii—Rb2—Cl1viii | 88.733 (16) |
Cl2iii—Rb1—Cl2ii | 112.92 (3) | Cl4xii—Rb2—Cl1iv | 91.267 (16) |
Cl2iv—Rb1—Cl4 | 61.82 (5) | Cl4viii—Rb2—Cl1iv | 88.733 (16) |
Cl2iii—Rb1—Cl4 | 53.29 (4) | Cl4xii—Rb2—Cl2x | 117.04 (3) |
Cl2ii—Rb1—Cl4vii | 61.82 (5) | Cl4xii—Rb2—Cl2iii | 117.04 (3) |
Cl2ii—Rb1—Cl4 | 142.95 (6) | Cl4xii—Rb2—Cl3 | 63.10 (3) |
Cl2iv—Rb1—Cl4vii | 142.95 (6) | Cl4viii—Rb2—Cl3 | 116.90 (3) |
Cl2—Rb1—Cl4 | 145.90 (5) | Cl4xii—Rb2—Cl3xi | 63.10 (3) |
Cl2iii—Rb1—Cl4vii | 145.90 (5) | Cl4viii—Rb2—Cl3xi | 116.90 (3) |
Cl2—Rb1—Cl4vii | 53.29 (4) | Cl4xii—Rb2—Cl4viii | 180.0 |
Cl3vi—Rb1—Cl1i | 122.79 (4) | Rb1xiii—Cu1—Rb1xii | 108.31 (3) |
Cl3v—Rb1—Cl1 | 122.79 (4) | Rb2xiii—Cu1—Rb1xii | 74.14 (2) |
Cl3iii—Rb1—Cl1 | 118.36 (4) | Rb2—Cu1—Rb1xii | 72.33 (2) |
Cl3—Rb1—Cl1i | 118.36 (4) | Rb2xiii—Cu1—Rb1xiii | 69.19 (4) |
Cl3vi—Rb1—Cl1 | 63.10 (4) | Rb2—Cu1—Rb1xiii | 177.68 (3) |
Cl3iii—Rb1—Cl1i | 55.74 (4) | Rb2—Cu1—Rb2xiii | 113.10 (3) |
Cl3—Rb1—Cl1 | 55.74 (4) | Cl1—Cu1—Rb1xii | 118.05 (5) |
Cl3v—Rb1—Cl1i | 63.10 (4) | Cl1—Cu1—Rb1xiii | 56.08 (3) |
Cl3iii—Rb1—Cl2iii | 61.70 (4) | Cl1—Cu1—Rb2xiii | 125.15 (4) |
Cl3v—Rb1—Cl2iii | 92.33 (4) | Cl1—Cu1—Rb2 | 121.61 (4) |
Cl3iii—Rb1—Cl2ii | 62.90 (4) | Cl2iv—Cu1—Rb1xii | 126.15 (6) |
Cl3vi—Rb1—Cl2iii | 107.42 (4) | Cl2iv—Cu1—Rb1xiii | 125.34 (6) |
Cl3vi—Rb1—Cl2ii | 126.50 (4) | Cl2iv—Cu1—Rb2xiii | 126.41 (6) |
Cl3vi—Rb1—Cl2iv | 83.47 (4) | Cl2iv—Cu1—Rb2 | 53.87 (5) |
Cl3vi—Rb1—Cl2 | 92.33 (4) | Cl2iv—Cu1—Cl1 | 90.97 (6) |
Cl3v—Rb1—Cl2iv | 126.50 (4) | Cl2iv—Cu1—Cl3xiv | 178.05 (8) |
Cl3—Rb1—Cl2iii | 98.00 (4) | Cl2iv—Cu1—Cl4xii | 89.27 (8) |
Cl3—Rb1—Cl2iv | 62.90 (4) | Cl3xiv—Cu1—Rb1xii | 54.31 (4) |
Cl3v—Rb1—Cl2ii | 83.47 (4) | Cl3xiv—Cu1—Rb1xiii | 54.44 (5) |
Cl3iii—Rb1—Cl2iv | 88.95 (4) | Cl3xiv—Cu1—Rb2xiii | 51.66 (5) |
Cl3—Rb1—Cl2 | 61.70 (4) | Cl3xiv—Cu1—Rb2 | 126.43 (5) |
Cl3iii—Rb1—Cl2 | 98.00 (4) | Cl3xiv—Cu1—Cl1 | 90.30 (6) |
Cl3v—Rb1—Cl2 | 107.42 (4) | Cl3xiv—Cu1—Cl4xii | 89.58 (7) |
Cl3—Rb1—Cl2ii | 88.95 (4) | Cl4xii—Cu1—Rb1xii | 58.43 (4) |
Cl3vi—Rb1—Cl3iii | 168.98 (5) | Cl4xii—Cu1—Rb1xiii | 127.05 (8) |
Cl3vi—Rb1—Cl3 | 118.85 (3) | Cl4xii—Cu1—Rb2 | 55.24 (7) |
Cl3vi—Rb1—Cl3v | 60.89 (6) | Cl4xii—Cu1—Rb2xiii | 57.87 (8) |
Cl3v—Rb1—Cl3iii | 118.85 (3) | Cl4xii—Cu1—Cl1 | 175.37 (6) |
Cl3—Rb1—Cl3iii | 63.78 (6) | Rb1—Cl1—Rb1xiii | 174.07 (6) |
Cl3v—Rb1—Cl3 | 168.98 (5) | Rb1xiii—Cl1—Rb2xv | 89.44 (2) |
Cl3v—Rb1—Cl4vii | 54.27 (4) | Rb1—Cl1—Rb2xv | 86.91 (3) |
Cl3vi—Rb1—Cl4 | 54.27 (4) | Rb1—Cl1—Rb2xvi | 89.44 (2) |
Cl3—Rb1—Cl4vii | 114.96 (4) | Rb1xiii—Cl1—Rb2xvi | 86.91 (3) |
Cl3iii—Rb1—Cl4 | 114.96 (4) | Rb2xv—Cl1—Rb2xvi | 104.02 (5) |
Cl3iii—Rb1—Cl4vii | 124.72 (4) | Cu1xiv—Cl1—Rb1xiii | 94.08 (3) |
Cl3v—Rb1—Cl4 | 64.99 (4) | Cu1—Cl1—Rb1 | 94.08 (3) |
Cl3—Rb1—Cl4 | 124.72 (4) | Cu1xiv—Cl1—Rb1 | 90.42 (3) |
Cl3vi—Rb1—Cl4vii | 64.99 (4) | Cu1—Cl1—Rb1xiii | 90.42 (3) |
Cl4vii—Rb1—Cl4 | 108.55 (4) | Cu1—Cl1—Rb2xvi | 87.18 (4) |
Cl1iv—Rb2—Cl1viii | 177.47 (3) | Cu1—Cl1—Rb2xv | 168.77 (5) |
Cl1iv—Rb2—Cl3 | 123.26 (4) | Cu1xiv—Cl1—Rb2xvi | 168.77 (5) |
Cl1viii—Rb2—Cl3xi | 123.26 (4) | Cu1xiv—Cl1—Rb2xv | 87.18 (4) |
Cl1iv—Rb2—Cl3xi | 58.10 (4) | Cu1xiv—Cl1—Cu1 | 81.64 (7) |
Cl1viii—Rb2—Cl3 | 58.10 (4) | Rb1—Cl2—Rb1xv | 169.18 (5) |
Cl2x—Rb2—Cl1viii | 53.56 (4) | Rb2xv—Cl2—Rb1 | 92.19 (5) |
Cl2x—Rb2—Cl1iv | 125.02 (4) | Rb2xvii—Cl2—Rb1xv | 92.51 (5) |
Cl2ix—Rb2—Cl1viii | 62.81 (4) | Rb2xvii—Cl2—Rb1 | 86.55 (4) |
Cl2iii—Rb2—Cl1viii | 125.02 (4) | Rb2xv—Cl2—Rb1xv | 87.03 (4) |
Cl2iii—Rb2—Cl1iv | 53.56 (4) | Rb2xv—Cl2—Rb2xvii | 170.86 (6) |
Cl2iv—Rb2—Cl1iv | 62.81 (4) | Cu1xv—Cl2—Rb1 | 95.98 (6) |
Cl2ix—Rb2—Cl1iv | 118.82 (4) | Cu1xv—Cl2—Rb1xv | 94.84 (7) |
Cl2iv—Rb2—Cl1viii | 118.82 (4) | Cu1xv—Cl2—Rb2xvii | 94.93 (6) |
Cl2ix—Rb2—Cl2x | 61.77 (3) | Cu1xv—Cl2—Rb2xv | 94.21 (6) |
Cl2iv—Rb2—Cl2ix | 111.13 (7) | Rb1xii—Cl3—Rb1 | 168.98 (5) |
Cl2x—Rb2—Cl2iii | 125.91 (6) | Rb1—Cl3—Rb2 | 82.93 (4) |
Cl2iv—Rb2—Cl2iii | 61.77 (3) | Rb1xii—Cl3—Rb2 | 86.91 (4) |
Cl2ix—Rb2—Cl2iii | 170.86 (5) | Rb2xvii—Cl3—Rb1 | 90.11 (4) |
Cl2iv—Rb2—Cl2x | 170.86 (5) | Rb2xvii—Cl3—Rb1xii | 97.55 (4) |
Cl2iii—Rb2—Cl3 | 92.43 (4) | Rb2xvii—Cl3—Rb2 | 111.14 (5) |
Cl2ix—Rb2—Cl3 | 88.46 (4) | Cu1xiv—Cl3—Rb1xii | 93.60 (6) |
Cl2iv—Rb2—Cl3 | 61.00 (4) | Cu1xiv—Cl3—Rb1 | 93.44 (5) |
Cl2x—Rb2—Cl3xi | 92.43 (4) | Cu1xiv—Cl3—Rb2 | 152.40 (6) |
Cl2x—Rb2—Cl3 | 111.66 (4) | Cu1xiv—Cl3—Rb2xvii | 96.18 (7) |
Cl2iii—Rb2—Cl3xi | 111.66 (4) | Rb1xviii—Cl4—Rb1 | 179.24 (10) |
Cl2ix—Rb2—Cl3xi | 61.00 (4) | Rb2v—Cl4—Rb1xviii | 89.62 (5) |
Cl2iv—Rb2—Cl3xi | 88.46 (4) | Rb2v—Cl4—Rb1 | 89.62 (5) |
Cl2ix—Rb2—Cl4viii | 124.44 (3) | Rb2xvi—Cl4—Rb1xviii | 90.38 (5) |
Cl2ix—Rb2—Cl4xii | 55.56 (3) | Rb2xvi—Cl4—Rb1 | 90.38 (5) |
Cl2iv—Rb2—Cl4viii | 124.44 (3) | Rb2v—Cl4—Rb2xvi | 180.0 |
Cl2x—Rb2—Cl4viii | 62.96 (3) | Cu1xix—Cl4—Rb1xviii | 88.41 (4) |
Cl2iii—Rb2—Cl4viii | 62.96 (3) | Cu1v—Cl4—Rb1 | 88.41 (4) |
Cl2iv—Rb2—Cl4xii | 55.56 (3) | Cu1v—Cl4—Rb1xviii | 91.61 (4) |
Cl3x—Rb2—Cl1viii | 116.40 (4) | Cu1xix—Cl4—Rb1 | 91.61 (4) |
Cl3iii—Rb2—Cl1iv | 116.40 (4) | Cu1xix—Cl4—Rb2v | 91.26 (7) |
Cl3x—Rb2—Cl1iv | 61.99 (4) | Cu1v—Cl4—Rb2xvi | 88.74 (7) |
Cl3iii—Rb2—Cl1viii | 61.99 (4) | Cu1v—Cl4—Rb2v | 91.26 (7) |
Cl3iii—Rb2—Cl2iv | 93.90 (4) | Cu1xix—Cl4—Rb2xvi | 88.74 (7) |
Cl3iii—Rb2—Cl2iii | 63.15 (4) | Cu1xix—Cl4—Cu1v | 177.49 (14) |
Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+1/2, −z+1; (iii) −x, y, −z+1/2; (iv) −x+1/2, −y+1/2, z−1/2; (v) x−1/2, y+1/2, z; (vi) −x+1/2, y+1/2, −z+1/2; (vii) −x, −y+1, z+1/2; (viii) x−1/2, y−1/2, z; (ix) −x+1/2, y−1/2, −z+1/2; (x) −x, −y, z−1/2; (xi) x, −y, −z; (xii) x+1/2, y−1/2, z; (xiii) x+1, y, z; (xiv) −x+1, y, −z+1/2; (xv) −x+1/2, −y+1/2, z+1/2; (xvi) x+1/2, y+1/2, z; (xvii) −x, −y, z+1/2; (xviii) −x, −y+1, z−1/2; (xix) x−1/2, −y+1/2, −z. |
Complexity, density and average <Rb—Cl> bond lengths in the RbCuCl3
polymorphs topPolymorph | Space group | IG (bits per atom) | IG,total (bits per unit cell) | Density (Mg m-3) | <Rb—Cl> (Å) |
α | P63/mmc | 1.371 | 13.710 | 3.27 | 3.619 |
β | Pbcn | 1.922 | 38.439 | 3.29 | 3.610 |
γ | C2/c | 2.522 | 50.439 | 3.39 | 3.567 |
ε | C2221 | 2.722 | 54.439 | 3.44 | 3.508, 3.555 |