Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199014997/gs1065sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199014997/gs1065Isup2.hkl |
Single crystals of FeZn13 were obtained by using a flux method. A mixture Fe/Zn containing 98 at.% Zn was melted at 1000 K in a silica tube, homogenized for 10 d and then air quenched. The resulting ingot (2.9 g) was inserted with dried ZnCl2 (5 g) in a silica tube, flame sealed, heated to 973 K for a week and then was cooled at the rate of 3 K h- to room temperature for crystal growth. The nearly spherical ingot obtained displayed on its surface, at the interface with ZnCl2, some small flat needles. Chemical analysis, FeZn13.08 (6), indicated the ζ phase, which has a very narrow range in the phase diagram (Bastin et al., 1974, 1977).
Refinement with a Zn atom at 2(a) position and a Fe atom at the 2(c) position gives R(F) = 0.0417 while the opposite [Fe at 2(a) and Zn at 2(c)] leads to R(F)=0.534. Refinement of Fe/Zn statistical site occupation would give 86 (2)% Zn on 2(a) site and 91 (5)% Fe on 2(c) site with R(F) = 0.0415. Within the 3σ limits, we consider 2(a) and 2(c) sites fully occupied by Zn and Fe, respectively
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: local program; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ATOMS (Dowty, 1993).
FeZn13 | F(000) = 832 |
Mr = 905.66 | Dx = 7.327 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71069 Å |
a = 13.394 (3) Å | Cell parameters from 25 reflections |
b = 7.5980 (9) Å | θ = 9.4–20.6° |
c = 5.066 (2) Å | µ = 38.82 mm−1 |
β = 127.23 (2)° | T = 293 K |
V = 410.49 (19) Å3 | Triangular platelet, metallic grey |
Z = 2 | 0.10 × 0.05 × 0.02 mm |
Nonius CAD-4 diffractometer | 439 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.059 |
Graphite monochromator | θmax = 29.9°, θmin = 3.3° |
ω–2θ scans | h = −18→18 |
Absorption correction: numerical (The absorption effects have been corrected using the numerical procedure provided by SHELX76; Sheldrick, 1976) | k = 0→10 |
Tmin = 0.118, Tmax = 0.462 | l = −7→7 |
1091 measured reflections | 3 standard reflections every 100 reflections |
604 independent reflections | intensity decay: none |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.042 | Calculated w = 1/[σ2(Fo2) + (0.0521P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.109 | (Δ/σ)max < 0.001 |
S = 1.03 | Δρmax = 2.15 e Å−3 |
604 reflections | Δρmin = −1.50 e Å−3 |
40 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0019 (5) |
FeZn13 | V = 410.49 (19) Å3 |
Mr = 905.66 | Z = 2 |
Monoclinic, C2/m | Mo Kα radiation |
a = 13.394 (3) Å | µ = 38.82 mm−1 |
b = 7.5980 (9) Å | T = 293 K |
c = 5.066 (2) Å | 0.10 × 0.05 × 0.02 mm |
β = 127.23 (2)° |
Nonius CAD-4 diffractometer | 439 reflections with I > 2σ(I) |
Absorption correction: numerical (The absorption effects have been corrected using the numerical procedure provided by SHELX76; Sheldrick, 1976) | Rint = 0.059 |
Tmin = 0.118, Tmax = 0.462 | 3 standard reflections every 100 reflections |
1091 measured reflections | intensity decay: none |
604 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 40 parameters |
wR(F2) = 0.109 | 0 restraints |
S = 1.03 | Δρmax = 2.15 e Å−3 |
604 reflections | Δρmin = −1.50 e Å−3 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.0000 | 0.0000 | 0.0000 | 0.0134 (5) | |
Fe2 | 0.0000 | 0.0000 | 0.5000 | 0.0045 (5) | |
Zn3 | 0.11406 (12) | 0.5000 | 0.2942 (3) | 0.0109 (4) | |
Zn4 | 0.22002 (13) | 0.0000 | 0.0693 (4) | 0.0148 (4) | |
Zn5 | 0.07635 (9) | 0.29477 (17) | 0.8340 (3) | 0.0172 (3) | |
Zn6 | 0.17545 (9) | 0.17895 (15) | 0.5486 (3) | 0.0114 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0125 (9) | 0.0216 (12) | 0.0057 (9) | 0.000 | 0.0052 (8) | 0.000 |
Fe2 | 0.0058 (10) | 0.0051 (11) | 0.0014 (9) | 0.000 | 0.0015 (8) | 0.000 |
Zn3 | 0.0105 (7) | 0.0086 (8) | 0.0065 (6) | 0.000 | 0.0013 (6) | 0.000 |
Zn4 | 0.0122 (7) | 0.0182 (9) | 0.0063 (7) | 0.000 | 0.0015 (6) | 0.000 |
Zn5 | 0.0149 (5) | 0.0156 (6) | 0.0171 (6) | −0.0013 (4) | 0.0076 (4) | −0.0092 (4) |
Zn6 | 0.0114 (5) | 0.0098 (5) | 0.0129 (5) | −0.0010 (4) | 0.0074 (4) | 0.0015 (4) |
Zn1—Fe2i | 2.5330 (10) | Zn3—Zn6xiv | 2.7775 (16) |
Zn1—Fe2 | 2.5330 (10) | Zn3—Zn6ix | 2.7775 (16) |
Zn1—Zn6 | 2.6819 (14) | Zn4—Zn3ix | 2.582 (2) |
Zn1—Zn6ii | 2.6819 (14) | Zn4—Fe2i | 2.5919 (17) |
Zn1—Zn6iii | 2.6819 (14) | Zn4—Zn6v | 2.6939 (19) |
Zn1—Zn6iv | 2.6819 (14) | Zn4—Zn6i | 2.6939 (19) |
Zn1—Zn4 | 2.7488 (17) | Zn4—Zn5v | 2.7137 (15) |
Zn1—Zn4ii | 2.7488 (17) | Zn4—Zn5i | 2.7137 (15) |
Zn1—Zn5i | 2.7946 (14) | Zn4—Zn6ix | 2.8945 (14) |
Zn1—Zn5v | 2.7946 (14) | Zn4—Zn6xv | 2.8945 (14) |
Zn1—Zn5vi | 2.7946 (14) | Zn4—Zn5ix | 2.9143 (18) |
Zn1—Zn5vii | 2.7946 (14) | Zn4—Zn5xv | 2.9143 (18) |
Fe2—Zn1 | 2.5330 (10) | Zn4—Zn6 | 3.139 (2) |
Fe2—Zn1viii | 2.5330 (10) | Zn5—Zn3viii | 2.5878 (17) |
Fe2—Zn4ii | 2.5919 (17) | Zn5—Zn6 | 2.6358 (17) |
Fe2—Zn4viii | 2.5919 (17) | Zn5—Zn5vii | 2.694 (3) |
Fe2—Zn6 | 2.5945 (11) | Zn5—Zn3xiii | 2.7119 (16) |
Fe2—Zn6vi | 2.5945 (11) | Zn5—Zn4viii | 2.7137 (15) |
Fe2—Zn6iv | 2.5945 (11) | Zn5—Zn1viii | 2.7946 (14) |
Fe2—Zn6vii | 2.5945 (11) | Zn5—Zn6vii | 2.8277 (17) |
Fe2—Zn5vi | 2.6136 (12) | Zn5—Zn6xvi | 2.8797 (18) |
Fe2—Zn5 | 2.6136 (12) | Zn5—Zn4ix | 2.9143 (18) |
Fe2—Zn5vii | 2.6136 (12) | Zn5—Zn5xi | 3.119 (3) |
Fe2—Zn5iv | 2.6136 (12) | Zn5—Zn6viii | 3.135 (2) |
Zn3—Zn4ix | 2.582 (2) | Zn6—Zn6ix | 2.567 (2) |
Zn3—Zn5i | 2.5878 (17) | Zn6—Zn4viii | 2.6939 (19) |
Zn3—Zn5x | 2.5878 (17) | Zn6—Zn6iv | 2.719 (2) |
Zn3—Zn6xi | 2.6468 (13) | Zn6—Zn3ix | 2.7775 (16) |
Zn3—Zn6 | 2.6468 (13) | Zn6—Zn5vii | 2.8277 (17) |
Zn3—Zn3xii | 2.683 (3) | Zn6—Zn5xvi | 2.8797 (18) |
Zn3—Zn5vii | 2.7119 (16) | Zn6—Zn4ix | 2.8945 (14) |
Zn3—Zn5xiii | 2.7119 (16) | Zn6—Zn5i | 3.135 (2) |
Fe2i—Zn1—Fe2 | 180.0 | Fe2i—Zn4—Zn5i | 58.97 (4) |
Fe2i—Zn1—Zn6 | 120.41 (3) | Zn6v—Zn4—Zn5i | 107.95 (6) |
Fe2—Zn1—Zn6 | 59.59 (3) | Zn6i—Zn4—Zn5i | 58.34 (4) |
Fe2i—Zn1—Zn6ii | 59.59 (3) | Zn5v—Zn4—Zn5i | 111.24 (7) |
Fe2—Zn1—Zn6ii | 120.41 (3) | Zn3ix—Zn4—Zn1 | 101.86 (7) |
Zn6—Zn1—Zn6ii | 180.0 | Fe2i—Zn4—Zn1 | 56.53 (4) |
Fe2i—Zn1—Zn6iii | 59.59 (3) | Zn6v—Zn4—Zn1 | 106.83 (5) |
Fe2—Zn1—Zn6iii | 120.41 (3) | Zn6i—Zn4—Zn1 | 106.83 (5) |
Zn6—Zn1—Zn6iii | 119.07 (5) | Zn5v—Zn4—Zn1 | 61.54 (4) |
Zn6ii—Zn1—Zn6iii | 60.93 (5) | Zn5i—Zn4—Zn1 | 61.54 (4) |
Fe2i—Zn1—Zn6iv | 120.41 (3) | Zn3ix—Zn4—Zn6ix | 57.46 (3) |
Fe2—Zn1—Zn6iv | 59.59 (3) | Fe2i—Zn4—Zn6ix | 120.56 (4) |
Zn6—Zn1—Zn6iv | 60.93 (5) | Zn6v—Zn4—Zn6ix | 144.21 (6) |
Zn6ii—Zn1—Zn6iv | 119.07 (5) | Zn6i—Zn4—Zn6ix | 87.73 (4) |
Zn6iii—Zn1—Zn6iv | 180.0 | Zn5v—Zn4—Zn6ix | 156.47 (7) |
Fe2i—Zn1—Zn4 | 58.60 (4) | Zn5i—Zn4—Zn6ix | 61.69 (4) |
Fe2—Zn1—Zn4 | 121.40 (4) | Zn1—Zn4—Zn6ix | 97.63 (4) |
Zn6—Zn1—Zn4 | 70.62 (4) | Zn3ix—Zn4—Zn6xv | 57.46 (4) |
Zn6ii—Zn1—Zn4 | 109.38 (4) | Fe2i—Zn4—Zn6xv | 120.56 (4) |
Zn6iii—Zn1—Zn4 | 109.38 (4) | Zn6v—Zn4—Zn6xv | 87.73 (4) |
Zn6iv—Zn1—Zn4 | 70.62 (4) | Zn6i—Zn4—Zn6xv | 144.21 (6) |
Fe2i—Zn1—Zn4ii | 121.40 (4) | Zn5v—Zn4—Zn6xv | 61.69 (4) |
Fe2—Zn1—Zn4ii | 58.60 (4) | Zn5i—Zn4—Zn6xv | 156.47 (7) |
Zn6—Zn1—Zn4ii | 109.38 (4) | Zn1—Zn4—Zn6xv | 97.63 (4) |
Zn6ii—Zn1—Zn4ii | 70.62 (4) | Zn6ix—Zn4—Zn6xv | 114.86 (7) |
Zn6iii—Zn1—Zn4ii | 70.62 (4) | Zn3ix—Zn4—Zn5ix | 77.25 (5) |
Zn6iv—Zn1—Zn4ii | 109.38 (4) | Fe2i—Zn4—Zn5ix | 120.36 (5) |
Zn4—Zn1—Zn4ii | 180.0 | Zn6v—Zn4—Zn5ix | 93.74 (6) |
Fe2i—Zn1—Zn5i | 58.51 (2) | Zn6i—Zn4—Zn5ix | 61.64 (4) |
Fe2—Zn1—Zn5i | 121.49 (2) | Zn5v—Zn4—Zn5ix | 149.12 (6) |
Zn6—Zn1—Zn5i | 69.81 (4) | Zn5i—Zn4—Zn5ix | 88.57 (4) |
Zn6ii—Zn1—Zn5i | 110.19 (4) | Zn1—Zn4—Zn5ix | 147.50 (3) |
Zn6iii—Zn1—Zn5i | 62.13 (3) | Zn6ix—Zn4—Zn5ix | 53.97 (4) |
Zn6iv—Zn1—Zn5i | 117.87 (3) | Zn6xv—Zn4—Zn5ix | 108.28 (5) |
Zn4—Zn1—Zn5i | 58.61 (3) | Zn3ix—Zn4—Zn5xv | 77.25 (5) |
Zn4ii—Zn1—Zn5i | 121.39 (3) | Fe2i—Zn4—Zn5xv | 120.36 (5) |
Fe2i—Zn1—Zn5v | 58.51 (2) | Zn6v—Zn4—Zn5xv | 61.64 (4) |
Fe2—Zn1—Zn5v | 121.49 (2) | Zn6i—Zn4—Zn5xv | 93.74 (6) |
Zn6—Zn1—Zn5v | 117.87 (3) | Zn5v—Zn4—Zn5xv | 88.57 (4) |
Zn6ii—Zn1—Zn5v | 62.13 (3) | Zn5i—Zn4—Zn5xv | 149.12 (6) |
Zn6iii—Zn1—Zn5v | 110.19 (4) | Zn1—Zn4—Zn5xv | 147.50 (3) |
Zn6iv—Zn1—Zn5v | 69.81 (4) | Zn6ix—Zn4—Zn5xv | 108.28 (5) |
Zn4—Zn1—Zn5v | 58.61 (3) | Zn6xv—Zn4—Zn5xv | 53.97 (4) |
Zn4ii—Zn1—Zn5v | 121.39 (3) | Zn5ix—Zn4—Zn5xv | 64.70 (6) |
Zn5i—Zn1—Zn5v | 106.53 (5) | Zn3ix—Zn4—Zn6 | 57.09 (5) |
Fe2i—Zn1—Zn5vi | 121.49 (2) | Fe2i—Zn4—Zn6 | 103.91 (6) |
Fe2—Zn1—Zn5vi | 58.51 (2) | Zn6v—Zn4—Zn6 | 160.52 (7) |
Zn6—Zn1—Zn5vi | 110.19 (4) | Zn6i—Zn4—Zn6 | 120.37 (5) |
Zn6ii—Zn1—Zn5vi | 69.81 (4) | Zn5v—Zn4—Zn6 | 106.32 (6) |
Zn6iii—Zn1—Zn5vi | 117.87 (3) | Zn5i—Zn4—Zn6 | 64.29 (5) |
Zn6iv—Zn1—Zn5vi | 62.13 (3) | Zn1—Zn4—Zn6 | 53.69 (4) |
Zn4—Zn1—Zn5vi | 121.39 (3) | Zn6ix—Zn4—Zn6 | 50.14 (4) |
Zn4ii—Zn1—Zn5vi | 58.61 (3) | Zn6xv—Zn4—Zn6 | 95.11 (5) |
Zn5i—Zn1—Zn5vi | 180.0 | Zn5ix—Zn4—Zn6 | 103.58 (4) |
Zn5v—Zn1—Zn5vi | 73.47 (5) | Zn5xv—Zn4—Zn6 | 134.29 (6) |
Fe2i—Zn1—Zn5vii | 121.49 (2) | Zn3viii—Zn5—Fe2 | 152.40 (6) |
Fe2—Zn1—Zn5vii | 58.51 (2) | Zn3viii—Zn5—Zn6 | 143.77 (6) |
Zn6—Zn1—Zn5vii | 62.13 (3) | Fe2—Zn5—Zn6 | 59.24 (4) |
Zn6ii—Zn1—Zn5vii | 117.87 (3) | Zn3viii—Zn5—Zn5vii | 135.85 (5) |
Zn6iii—Zn1—Zn5vii | 69.81 (4) | Fe2—Zn5—Zn5vii | 58.97 (3) |
Zn6iv—Zn1—Zn5vii | 110.19 (4) | Zn6—Zn5—Zn5vii | 64.07 (6) |
Zn4—Zn1—Zn5vii | 121.39 (3) | Zn3viii—Zn5—Zn3xiii | 60.78 (6) |
Zn4ii—Zn1—Zn5vii | 58.61 (3) | Fe2—Zn5—Zn3xiii | 113.25 (5) |
Zn5i—Zn1—Zn5vii | 73.47 (5) | Zn6—Zn5—Zn3xiii | 140.66 (6) |
Zn5v—Zn1—Zn5vii | 180.0 | Zn5vii—Zn5—Zn3xiii | 79.05 (5) |
Zn5vi—Zn1—Zn5vii | 106.53 (5) | Zn3viii—Zn5—Zn4viii | 113.67 (6) |
Zn1viii—Fe2—Zn1 | 180.0 | Fe2—Zn5—Zn4viii | 58.19 (4) |
Zn1viii—Fe2—Zn4ii | 115.14 (5) | Zn6—Zn5—Zn4viii | 60.45 (5) |
Zn1—Fe2—Zn4ii | 64.86 (5) | Zn5vii—Zn5—Zn4viii | 110.45 (5) |
Zn1viii—Fe2—Zn4viii | 64.86 (5) | Zn3xiii—Zn5—Zn4viii | 153.37 (7) |
Zn1—Fe2—Zn4viii | 115.14 (5) | Zn3viii—Zn5—Zn1viii | 96.85 (5) |
Zn4ii—Fe2—Zn4viii | 180.0 | Fe2—Zn5—Zn1viii | 55.73 (3) |
Zn1viii—Fe2—Zn6 | 116.94 (3) | Zn6—Zn5—Zn1viii | 107.15 (5) |
Zn1—Fe2—Zn6 | 63.06 (3) | Zn5vii—Zn5—Zn1viii | 103.89 (4) |
Zn4ii—Fe2—Zn6 | 117.41 (4) | Zn3xiii—Zn5—Zn1viii | 94.04 (4) |
Zn4viii—Fe2—Zn6 | 62.59 (4) | Zn4viii—Zn5—Zn1viii | 59.85 (4) |
Zn1viii—Fe2—Zn6vi | 63.06 (3) | Zn3viii—Zn5—Zn6vii | 107.87 (6) |
Zn1—Fe2—Zn6vi | 116.94 (3) | Fe2—Zn5—Zn6vii | 56.79 (3) |
Zn4ii—Fe2—Zn6vi | 62.59 (4) | Zn6—Zn5—Zn6vii | 107.92 (5) |
Zn4viii—Fe2—Zn6vi | 117.41 (4) | Zn5vii—Zn5—Zn6vii | 56.96 (5) |
Zn6—Fe2—Zn6vi | 180.0 | Zn3xiii—Zn5—Zn6vii | 57.04 (4) |
Zn1viii—Fe2—Zn6iv | 116.94 (3) | Zn4viii—Zn5—Zn6vii | 106.20 (6) |
Zn1—Fe2—Zn6iv | 63.06 (3) | Zn1viii—Zn5—Zn6vii | 56.98 (4) |
Zn4ii—Fe2—Zn6iv | 117.41 (4) | Zn3viii—Zn5—Zn6xvi | 60.78 (5) |
Zn4viii—Fe2—Zn6iv | 62.59 (4) | Fe2—Zn5—Zn6xvi | 120.33 (5) |
Zn6—Fe2—Zn6iv | 63.21 (5) | Zn6—Zn5—Zn6xvi | 89.16 (5) |
Zn6vi—Fe2—Zn6iv | 116.79 (5) | Zn5vii—Zn5—Zn6xvi | 149.82 (7) |
Zn1viii—Fe2—Zn6vii | 63.06 (3) | Zn3xiii—Zn5—Zn6xvi | 121.37 (6) |
Zn1—Fe2—Zn6vii | 116.94 (3) | Zn4viii—Zn5—Zn6xvi | 62.24 (4) |
Zn4ii—Fe2—Zn6vii | 62.59 (4) | Zn1viii—Zn5—Zn6xvi | 96.94 (5) |
Zn4viii—Fe2—Zn6vii | 117.41 (4) | Zn6vii—Zn5—Zn6xvi | 151.70 (6) |
Zn6—Fe2—Zn6vii | 116.79 (5) | Zn3viii—Zn5—Zn4ix | 82.72 (5) |
Zn6vi—Fe2—Zn6vii | 63.21 (5) | Fe2—Zn5—Zn4ix | 121.82 (5) |
Zn6iv—Fe2—Zn6vii | 180.0 | Zn6—Zn5—Zn4ix | 62.63 (4) |
Zn1viii—Fe2—Zn5vi | 114.24 (3) | Zn5vii—Zn5—Zn4ix | 97.66 (6) |
Zn1—Fe2—Zn5vi | 65.76 (3) | Zn3xiii—Zn5—Zn4ix | 112.43 (5) |
Zn4ii—Fe2—Zn5vi | 62.84 (3) | Zn4viii—Zn5—Zn4ix | 91.43 (4) |
Zn4viii—Fe2—Zn5vi | 117.16 (3) | Zn1viii—Zn5—Zn4ix | 148.63 (5) |
Zn6—Fe2—Zn5vi | 119.19 (4) | Zn6vii—Zn5—Zn4ix | 152.69 (6) |
Zn6vi—Fe2—Zn5vi | 60.81 (4) | Zn6xvi—Zn5—Zn4ix | 55.41 (4) |
Zn6iv—Fe2—Zn5vi | 65.77 (4) | Zn3viii—Zn5—Zn5xi | 52.94 (4) |
Zn6vii—Fe2—Zn5vi | 114.23 (4) | Fe2—Zn5—Zn5xi | 148.97 (3) |
Zn1viii—Fe2—Zn5 | 65.76 (3) | Zn6—Zn5—Zn5xi | 109.50 (4) |
Zn1—Fe2—Zn5 | 114.24 (3) | Zn5vii—Zn5—Zn5xi | 90.0 |
Zn4ii—Fe2—Zn5 | 117.16 (3) | Zn3xiii—Zn5—Zn5xi | 54.90 (3) |
Zn4viii—Fe2—Zn5 | 62.84 (3) | Zn4viii—Zn5—Zn5xi | 145.62 (4) |
Zn6—Fe2—Zn5 | 60.81 (4) | Zn1viii—Zn5—Zn5xi | 143.26 (2) |
Zn6vi—Fe2—Zn5 | 119.19 (4) | Zn6vii—Zn5—Zn5xi | 108.13 (4) |
Zn6iv—Fe2—Zn5 | 114.23 (4) | Zn6xvi—Zn5—Zn5xi | 86.02 (3) |
Zn6vii—Fe2—Zn5 | 65.77 (4) | Zn4ix—Zn5—Zn5xi | 57.65 (3) |
Zn5vi—Fe2—Zn5 | 180.0 | Zn3viii—Zn5—Zn6viii | 54.08 (4) |
Zn1viii—Fe2—Zn5vii | 114.24 (3) | Fe2—Zn5—Zn6viii | 103.50 (5) |
Zn1—Fe2—Zn5vii | 65.76 (3) | Zn6—Zn5—Zn6viii | 122.53 (6) |
Zn4ii—Fe2—Zn5vii | 62.84 (3) | Zn5vii—Zn5—Zn6viii | 156.88 (5) |
Zn4viii—Fe2—Zn5vii | 117.16 (3) | Zn3xiii—Zn5—Zn6viii | 96.75 (5) |
Zn6—Fe2—Zn5vii | 65.77 (4) | Zn4viii—Zn5—Zn6viii | 64.46 (5) |
Zn6vi—Fe2—Zn5vii | 114.23 (4) | Zn1viii—Zn5—Zn6viii | 53.41 (3) |
Zn6iv—Fe2—Zn5vii | 119.19 (4) | Zn6vii—Zn5—Zn6viii | 101.55 (5) |
Zn6vii—Fe2—Zn5vii | 60.81 (4) | Zn6xvi—Zn5—Zn6viii | 50.30 (4) |
Zn5vi—Fe2—Zn5vii | 117.95 (6) | Zn4ix—Zn5—Zn6viii | 104.87 (5) |
Zn5—Fe2—Zn5vii | 62.05 (6) | Zn5xi—Zn5—Zn6viii | 106.30 (3) |
Zn1viii—Fe2—Zn5iv | 65.76 (3) | Zn6ix—Zn6—Fe2 | 165.36 (8) |
Zn1—Fe2—Zn5iv | 114.24 (3) | Zn6ix—Zn6—Zn5 | 132.33 (8) |
Zn4ii—Fe2—Zn5iv | 117.16 (3) | Fe2—Zn6—Zn5 | 59.95 (4) |
Zn4viii—Fe2—Zn5iv | 62.84 (3) | Zn6ix—Zn6—Zn3 | 64.36 (6) |
Zn6—Fe2—Zn5iv | 114.23 (4) | Fe2—Zn6—Zn3 | 116.11 (5) |
Zn6vi—Fe2—Zn5iv | 65.77 (4) | Zn5—Zn6—Zn3 | 81.28 (6) |
Zn6iv—Fe2—Zn5iv | 60.81 (4) | Zn6ix—Zn6—Zn1 | 108.06 (7) |
Zn6vii—Fe2—Zn5iv | 119.19 (4) | Fe2—Zn6—Zn1 | 57.35 (3) |
Zn5vi—Fe2—Zn5iv | 62.05 (6) | Zn5—Zn6—Zn1 | 108.75 (5) |
Zn5—Fe2—Zn5iv | 117.95 (6) | Zn3—Zn6—Zn1 | 98.24 (5) |
Zn5vii—Fe2—Zn5iv | 180.0 | Zn6ix—Zn6—Zn4viii | 131.53 (7) |
Zn4ix—Zn3—Zn5i | 132.58 (5) | Fe2—Zn6—Zn4viii | 58.66 (4) |
Zn4ix—Zn3—Zn5x | 132.58 (5) | Zn5—Zn6—Zn4viii | 61.20 (5) |
Zn5i—Zn3—Zn5x | 74.11 (8) | Zn3—Zn6—Zn4viii | 139.60 (6) |
Zn4ix—Zn3—Zn6xi | 67.21 (4) | Zn1—Zn6—Zn4viii | 107.16 (5) |
Zn5i—Zn3—Zn6xi | 145.89 (7) | Zn6ix—Zn6—Zn6iv | 114.88 (5) |
Zn5x—Zn3—Zn6xi | 73.57 (5) | Fe2—Zn6—Zn6iv | 58.39 (3) |
Zn4ix—Zn3—Zn6 | 67.21 (4) | Zn5—Zn6—Zn6iv | 109.50 (4) |
Zn5i—Zn3—Zn6 | 73.57 (5) | Zn3—Zn6—Zn6iv | 157.16 (4) |
Zn5x—Zn3—Zn6 | 145.89 (7) | Zn1—Zn6—Zn6iv | 59.54 (3) |
Zn6xi—Zn3—Zn6 | 134.32 (7) | Zn4viii—Zn6—Zn6iv | 59.69 (3) |
Zn4ix—Zn3—Zn3xii | 158.21 (10) | Zn6ix—Zn6—Zn3ix | 59.22 (4) |
Zn5i—Zn3—Zn3xii | 61.90 (5) | Fe2—Zn6—Zn3ix | 118.33 (5) |
Zn5x—Zn3—Zn3xii | 61.90 (5) | Zn5—Zn6—Zn3ix | 140.06 (6) |
Zn6xi—Zn3—Zn3xii | 110.51 (4) | Zn3—Zn6—Zn3ix | 123.58 (4) |
Zn6—Zn3—Zn3xii | 110.51 (4) | Zn1—Zn6—Zn3ix | 98.62 (5) |
Zn4ix—Zn3—Zn5vii | 105.85 (6) | Zn4viii—Zn6—Zn3ix | 83.51 (5) |
Zn5i—Zn3—Zn5vii | 78.18 (6) | Zn6iv—Zn6—Zn3ix | 60.69 (3) |
Zn5x—Zn3—Zn5vii | 119.22 (6) | Zn6ix—Zn6—Zn5vii | 118.78 (7) |
Zn6xi—Zn3—Zn5vii | 128.06 (6) | Fe2—Zn6—Zn5vii | 57.44 (3) |
Zn6—Zn3—Zn5vii | 63.68 (4) | Zn5—Zn6—Zn5vii | 58.97 (5) |
Zn3xii—Zn3—Zn5vii | 57.32 (5) | Zn3—Zn6—Zn5vii | 59.28 (4) |
Zn4ix—Zn3—Zn5xiii | 105.85 (6) | Zn1—Zn6—Zn5vii | 60.89 (4) |
Zn5i—Zn3—Zn5xiii | 119.22 (6) | Zn4viii—Zn6—Zn5vii | 107.10 (5) |
Zn5x—Zn3—Zn5xiii | 78.18 (6) | Zn6iv—Zn6—Zn5vii | 108.13 (4) |
Zn6xi—Zn3—Zn5xiii | 63.68 (4) | Zn3ix—Zn6—Zn5vii | 158.70 (6) |
Zn6—Zn3—Zn5xiii | 128.06 (6) | Zn6ix—Zn6—Zn5xvi | 70.02 (6) |
Zn3xii—Zn3—Zn5xiii | 57.32 (5) | Fe2—Zn6—Zn5xvi | 121.57 (5) |
Zn5vii—Zn3—Zn5xiii | 70.20 (6) | Zn5—Zn6—Zn5xvi | 90.84 (5) |
Zn4ix—Zn3—Zn6xiv | 71.61 (5) | Zn3—Zn6—Zn5xvi | 106.22 (5) |
Zn5i—Zn3—Zn6xiv | 99.46 (6) | Zn1—Zn6—Zn5xvi | 150.77 (5) |
Zn5x—Zn3—Zn6xiv | 64.81 (5) | Zn4viii—Zn6—Zn5xvi | 62.95 (5) |
Zn6xi—Zn3—Zn6xiv | 56.42 (4) | Zn6iv—Zn6—Zn5xvi | 93.98 (3) |
Zn6—Zn3—Zn6xiv | 110.44 (5) | Zn3ix—Zn6—Zn5xvi | 54.41 (4) |
Zn3xii—Zn3—Zn6xiv | 126.49 (7) | Zn5vii—Zn6—Zn5xvi | 146.86 (6) |
Zn5vii—Zn3—Zn6xiv | 174.03 (5) | Zn6ix—Zn6—Zn4ix | 69.89 (6) |
Zn5xiii—Zn3—Zn6xiv | 115.57 (4) | Fe2—Zn6—Zn4ix | 123.30 (5) |
Zn4ix—Zn3—Zn6ix | 71.61 (5) | Zn5—Zn6—Zn4ix | 63.40 (5) |
Zn5i—Zn3—Zn6ix | 64.81 (5) | Zn3—Zn6—Zn4ix | 55.32 (5) |
Zn5x—Zn3—Zn6ix | 99.46 (6) | Zn1—Zn6—Zn4ix | 152.42 (5) |
Zn6xi—Zn3—Zn6ix | 110.44 (5) | Zn4viii—Zn6—Zn4ix | 92.27 (4) |
Zn6—Zn3—Zn6ix | 56.42 (4) | Zn6iv—Zn6—Zn4ix | 147.43 (3) |
Zn3xii—Zn3—Zn6ix | 126.49 (7) | Zn3ix—Zn6—Zn4ix | 102.97 (5) |
Zn5vii—Zn3—Zn6ix | 115.57 (4) | Zn5vii—Zn6—Zn4ix | 95.16 (6) |
Zn5xiii—Zn3—Zn6ix | 174.03 (5) | Zn5xvi—Zn6—Zn4ix | 56.06 (4) |
Zn6xiv—Zn3—Zn6ix | 58.62 (5) | Zn6ix—Zn6—Zn5i | 59.68 (5) |
Zn3ix—Zn4—Fe2i | 158.40 (8) | Fe2—Zn6—Zn5i | 108.13 (5) |
Zn3ix—Zn4—Zn6v | 137.42 (6) | Zn5—Zn6—Zn5i | 122.53 (6) |
Fe2i—Zn4—Zn6v | 58.75 (4) | Zn3—Zn6—Zn5i | 52.35 (4) |
Zn3ix—Zn4—Zn6i | 137.42 (6) | Zn1—Zn6—Zn5i | 56.79 (4) |
Fe2i—Zn4—Zn6i | 58.75 (4) | Zn4viii—Zn6—Zn5i | 163.86 (5) |
Zn6v—Zn4—Zn6i | 60.63 (7) | Zn6iv—Zn6—Zn5i | 106.30 (3) |
Zn3ix—Zn4—Zn5v | 113.23 (5) | Zn3ix—Zn6—Zn5i | 96.64 (5) |
Fe2i—Zn4—Zn5v | 58.97 (4) | Zn5vii—Zn6—Zn5i | 67.98 (5) |
Zn6v—Zn4—Zn5v | 58.34 (4) | Zn5xvi—Zn6—Zn5i | 129.70 (4) |
Zn6i—Zn4—Zn5v | 107.95 (6) | Zn4ix—Zn6—Zn5i | 103.37 (5) |
Zn3ix—Zn4—Zn5i | 113.23 (5) |
Symmetry codes: (i) x, y, z−1; (ii) −x, −y, −z; (iii) −x, y, −z; (iv) x, −y, z; (v) x, −y, z−1; (vi) −x, −y, −z+1; (vii) −x, y, −z+1; (viii) x, y, z+1; (ix) −x+1/2, −y+1/2, −z+1; (x) x, −y+1, z−1; (xi) x, −y+1, z; (xii) −x, −y+1, −z; (xiii) −x, −y+1, −z+1; (xiv) −x+1/2, y+1/2, −z+1; (xv) −x+1/2, y−1/2, −z+1; (xvi) −x+1/2, −y+1/2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | FeZn13 |
Mr | 905.66 |
Crystal system, space group | Monoclinic, C2/m |
Temperature (K) | 293 |
a, b, c (Å) | 13.394 (3), 7.5980 (9), 5.066 (2) |
β (°) | 127.23 (2) |
V (Å3) | 410.49 (19) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 38.82 |
Crystal size (mm) | 0.10 × 0.05 × 0.02 |
Data collection | |
Diffractometer | Nonius CAD-4 diffractometer |
Absorption correction | Numerical (The absorption effects have been corrected using the numerical procedure provided by SHELX76; Sheldrick, 1976) |
Tmin, Tmax | 0.118, 0.462 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1091, 604, 439 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.702 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.109, 1.03 |
No. of reflections | 604 |
No. of parameters | 40 |
Δρmax, Δρmin (e Å−3) | 2.15, −1.50 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, local program, SHELXL97 (Sheldrick, 1997), ATOMS (Dowty, 1993).
Zn1—Fe2 | 2.5330 (10) | Zn4—Zn6i | 2.6939 (19) |
Zn1—Zn6 | 2.6819 (14) | Zn4—Zn5i | 2.7137 (15) |
Zn1—Zn4 | 2.7488 (17) | Zn4—Zn6iii | 2.8945 (14) |
Zn1—Zn5i | 2.7946 (14) | Zn4—Zn5iii | 2.9143 (18) |
Fe2—Zn4ii | 2.5919 (17) | Zn4—Zn6 | 3.139 (2) |
Fe2—Zn6 | 2.5945 (11) | Zn5—Zn6 | 2.6358 (17) |
Fe2—Zn5 | 2.6136 (12) | Zn5—Zn5v | 2.694 (3) |
Zn3—Zn4iii | 2.582 (2) | Zn5—Zn6v | 2.8277 (17) |
Zn3—Zn5i | 2.5878 (17) | Zn5—Zn6vii | 2.8797 (18) |
Zn3—Zn6 | 2.6468 (13) | Zn5—Zn5viii | 3.119 (3) |
Zn3—Zn3iv | 2.683 (3) | Zn5—Zn6ix | 3.135 (2) |
Zn3—Zn5v | 2.7119 (16) | Zn6—Zn6iii | 2.567 (2) |
Zn3—Zn6vi | 2.7775 (16) | Zn6—Zn6x | 2.719 (2) |
Symmetry codes: (i) x, y, z−1; (ii) −x, −y, −z; (iii) −x+1/2, −y+1/2, −z+1; (iv) −x, −y+1, −z; (v) −x, y, −z+1; (vi) −x+1/2, y+1/2, −z+1; (vii) −x+1/2, −y+1/2, −z+2; (viii) x, −y+1, z; (ix) x, y, z+1; (x) x, −y, z. |
In our general study of icosahedron-based intermetallic phases, we have reinvestigated the Fe—Zn binary system. Several phases, cubic γ-Fe3Zn10 (Brandon et al., 1974) and monoclinic ζ-FeZn13 (Brown, 1962), were known but their structures poorly determined while hexagonal δ-FeZn10 was not yet structurally characterized. For FeZn13, intensities have been determined visually from Weissenberg photographs and the structure refined in the monoclinic space group C2/m with reflections from the [010] and [001] projections. Agreement factors R(F) were 0.121 ([010] projection) and 0.098 ([001] projection). Such refinements based on a restricted number of intensities led to an incomplete description of the structure. Since the limited quality of data did not allow any atomic differentiation, positions 2(a) and 2(c) were ambiguously assigned to iron and/or zinc atoms. Difficulty in obtaining good quality single crystals (having sharp reflections) was underlined by Brown (1962) who prepared FeZn13 by an electrochemical process. With a flux method, we have obtained needles which display satisfactory diffraction spots. Structural refinement has allowed location of iron atoms at only the 2(c) position, the centre of zinc icosahedron. In the structure, icosahedra are packed in chains along the c axis by sharing opposite vertices. Furthermore, their linking is achieved by octahedra sharing in planes parallel to (402) and by vertex to vertex bonding in planes parallel to (001). Each icosahedron is then surrounded by 12 alike units. Zn3 atoms form dumbbells which complement the metallic bonding.