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In the title 2212-type superconductor (thallium mercury calcium barium strontium copper oxide), which contains both Tl and Hg in the charge reservoir (CR), Sr is located at both alkali-earth (AE) metal sites. Ca enters the CR at the same time as Tl shares the smaller AE site, which increases the apical Cu-Cu distance significantly. The structure causes the superconducting Cu-O layers to become significantly puckered.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102013148/br1382sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102013148/br1382Isup2.hkl
Contains datablock I

Comment top

Ever since the 2212-type superconductors were discovered, originating from Tl2Ba2CaCu2O8, which is as abbreviated 2212 (Subramanian et al., 1988), several closely related compounds have been prepared, differing in their chemical substitutions. Hg was tried at the Tl site (Bryntse, 1994) and Sr was introduced at both the Ba and the Ca site in different amounts (Maignan et al., 1995; Valldor et al., 2000). Single crystals of (Tl,Hg)2Sr2CaCu2O8 - d were obtained using a high-pressure–high-temperature technique (Valldor et al., 1999). The starting composition Tl1.3Hg0.7BaSr1.5Ca0.5Cu2O8 - d was also tried for a single-crystal growth and this structural study will be presented below. To insure that the analysed crystal was a representative of the whole sample, unit-cell parameters were also calculated from powder diffraction using a Guinier–Hägg camera on ground single crystals [a = 3.8353 (5) Å and c = 29.138 (6) Å]. The unit-cell parameters obtained from the single-crystal diffractometer data were a = 3.8380 (6) Å and c = 29.145 (7) Å. Ten elemental analyses (EDS) were performed on the single-crystal after diffraction data had been collected and the resulting stoichiometry [Tl1.22 (4)Hg0.79 (4)Ba0.86 (3)Sr1.48 (4)Ca0.63 (2)Cu2.03 (6)Ox] agreed with the starting composition (Tl1.3Hg0.7BaSr1.5Ca0.5Cu2Ox). The only significant difference was the lower Ba content in the product balanced by a higher presence of Ca.

The results from EDS were used to generate the occupancies at the different sites in the structure, as illustrated in Fig. 1. The starting point of the fractional coordinates for all atoms was taken from the work of Subramanian et al. (1988). The reason for atoms O2 and O3 only being refined isotropically was the limited number of observed reflections with an intensity/background ratio greater than 3. The first model obtained with only (Tl,Hg) in the charge reservoir (CR) and (Ca,Sr) at the smaller alkali-earth (AE1) metal site between the Cu–O layers, resulted in unfavourable atomic displacement parameters at both sites: a large U value for (Tl,Hg) and a negative U value for (Ca,Sr). Both Tl and Hg were earlier observed at the AE1 site in a high-pressure synthesized 2212-type phase (Wu et al., 1998), however, they reported it as a new stacking order. The CR on the other hand was occupied by both Ca and Cu in another superconducting material, also formed under high-pressure conditions (Chu et al., 1997). Since our crystal was synthesized under pressure as well, Ca was introduced at the CR site at the same time as a minor amount of Tl was placed at the AE1 site. When refining the occupancies, all sites were assumed fully occupied, except for the O3 site, which ended up 78 (5)% occupied after refining it. Ba, Hg, Cu and O were all placed at their presumed sites, while Sr was placed at both AE sites with fixed values taken from EDS results. Tl and Ca are placed in the CR and at the AE1 site. The total amounts of each of the two metals were kept constant, according to EDS results, and only their relative occupations at both sites were refined, using one parameter. The metal distribution according to the refinement was (Tl0.582 (2)Hg0.395Ca0.023 (2))2(Ba0.435Sr0.565)2(Sr0.36Ca0.594 (5)Tl0.046 (5))Cu2.

This caused both atomic displacement parameters to end up positive and reasonable. In the final model, only atom O3 had a large atomic displacement, however, in many papers, this O atom is displaced from the high-symmetry position (0, 0, z) to (x, x, z) (see, for example, Subramanian et al., 1988), which could be a reason for this relatively high value. Calculated bond lengths and angles are reasonable (Table 1). The CR metal atoms (Tl,Hg,Ca) are situated in distorted octahedra with shorter apical distances that suit the Hg2+ (40%), for which linear coordination is common.

From bond lengths between Cu and O, the bond-valence sum of Cu is calculated as BVS(Cu) = 2.195 (9). Assuming nominal oxidation states of all metal atoms, the calculated oxygen content would be 7.62, which agrees well with the refined value of 7.6 (2). The measured crystal was too small for resistivity of susceptibility measurements, however if the BVS of Cu is the main property connected to Tc in this system, the BVS–Tc comparison (Valldor et al., 2000) could be used to conclude that Tc should be within the range 75–90 K. From the same report, it is possible to conclude that both cell parameters and EDS analyses agree well with a Tc of about 80 K. When comparing interatomic distances in Tl2Ba2CaCu2O8 (Table 2; B, Subramanian et al., 1988) with those presented here (Table 2, A), several things are made clear. The CR in A is larger than in B, which also could be an indication of a minor Ca content at this site in A, since Ca2+ has a larger ionic radius compared with Tl3+ and Hg2+. The larger AE site (AE2) has shorter metal-to-oxygen bonds in A, as expected, since the site is partially occupied by Sr. An important observation is the size difference of the AE1 site, where A has longer metal-to-oxygen bonds, also due to presence of Sr. When comparing the O—Cu—O angles, it is obvious that A is more puckered than B. The puckering of the Cu–O layers and the presence of Sr at the AE1 site cause the apical Cu—Cu distance across the AE1 layer to be almost 0.2 Å longer in A than in B. A difference Fourier analysis was carried out and the maxima of 1.39 and -2.74 e Å-3, respectively, were both found close to the AE2 site. The maxima are tolerable considering the high electron densities already present at the AE2 site. This high-pressure synthesis study agrees with previous reports concerning mixed sites (Chu et al., 1997; Wu et al., 1998), i.e. Cu as well as Ca enter the CR and Tl can be found at the AE1 site.

Experimental top

In order to obtain high purity starting materials, Tl2O3, HgO, and CuO were heated at 420 K overnight to remove moisture, while CaCO3 was decomposed into CaO at 1270 K for 20 h. SrO and BaO, respectively, were prepared by heating their carbonates at 1320 K under dynamic vacuum (<6.0 × 10-6 mbar; 1 mbar = 100 Pa) and the oxides formed were subsequently transported to a glove-box. All metal oxides were weighted, mixed in an agate mortar, and pelletized under inert conditions inside a glove-box. The metal-to-metal ratios were chosen to reach the nominal composition Tl1.3Hg0.7BaSr1.5Ca0.5Cu2O8 - d, aiming at placing Sr at two crystallographic sites in the 2212 structure. The pellets were placed in a BaZrO3 crucible and placed inside a high-pressure chamber, which is further described by Morawski et al. (1997). 0.9 GPa of Ar pressure was applied before the heat treatment began. The reaction progressed in several steps; the pre-reaction heating (1190 K, 1 h), the melting (1410 K, 2 min), and the crystal growth (-24 K h-1 to 1230 K), after which the heating was shut off to let the sample cool to room temperature. The crystals, found inside the crucible after the reaction, were all black, opaque and plate-like. Elemental analyses (EDS) of the crystals were performed inside a scanning electron microscope Jeol SEM 820 attached with a LINK AN10000 system. When refining the unit-cell parameters, X-ray powder diffraction was performed using elemental Si as internal standard in a Guinier–Hägg focusing camera (Cu Kα1, λ = 1.5405 Å).

Refinement top

The reflection-to-parameter ratio was low, at 6.3 (138/22). This problem was not discovered until the crystal had been covered with gold for elemental analyses. The goodness-of-fit is slightly too high, which might be due to the problem with correctly weighting the weak reflections against the strong.

Computing details top

Data collection: IPDS (Stoe, 1996); cell refinement: IPDS; data reduction: X-RED and X-SHAPE (Stoe, 1996); program(s) used to solve structure: JANA98 (Petricek & Dusek, 1997); program(s) used to refine structure: JANA98.

Figures top
[Figure 1] Fig. 1. The 2212 structure explaining the elemental distribution.
(I) top
Crystal data top
Ba0.87Ca0.64Cu2Hg0.79O7.56Sr1.49Tl1.21Dx = 7.194 Mg m3
Mr = 930.2Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4/mmmCell parameters from 121 reflections
Hall symbol: -I 4 2θ = 2.8–23.9°
a = 3.8380 (6) ŵ = 55.06 mm1
c = 29.145 (7) ÅT = 293 K
V = 429.3 (1) Å3Plate, black
Z = 20.10 × 0.05 × 0.01 mm
F(000) = 796
Data collection top
Stoe IPDS
diffractometer
138 independent reflections
Radiation source: fine-focus sealed tube121 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.046
Detector resolution: 6.0 pixels mm-1θmax = 23.9°, θmin = 2.8°
area detector scansh = 44
Absorption correction: numerical
X-RED version 1.09 (Stoe, 1997)
k = 44
Tmin = 0.057, Tmax = 0.210l = 3231
1228 measured reflections
Refinement top
Refinement on F22 parameters
R[F2 > 2σ(F2)] = 0.020 w = 1/[σ2(F) + 0.000036F2]
wR(F2) = 0.021(Δ/σ)max = 0.002
S = 2.41Δρmax = 1.39 e Å3
138 reflectionsΔρmin = 2.74 e Å3
Crystal data top
Ba0.87Ca0.64Cu2Hg0.79O7.56Sr1.49Tl1.21Z = 2
Mr = 930.2Mo Kα radiation
Tetragonal, I4/mmmµ = 55.06 mm1
a = 3.8380 (6) ÅT = 293 K
c = 29.145 (7) Å0.10 × 0.05 × 0.01 mm
V = 429.3 (1) Å3
Data collection top
Stoe IPDS
diffractometer
138 independent reflections
Absorption correction: numerical
X-RED version 1.09 (Stoe, 1997)
121 reflections with I > 3σ(I)
Tmin = 0.057, Tmax = 0.210Rint = 0.046
1228 measured reflectionsθmax = 23.9°
Refinement top
R[F2 > 2σ(F2)] = 0.02022 parameters
wR(F2) = 0.021Δρmax = 1.39 e Å3
S = 2.41Δρmin = 2.74 e Å3
138 reflections
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Tl0.50.50.21267 (2)0.0152 (2)0.582 (2)
Hg0.50.50.21267 (2)0.0152 (2)0.395
Ca0.50.50.21267 (2)0.0152 (2)0.023 (2)
Ba0.00.00.12228 (3)0.0102 (3)0.435
Sr10.00.00.12228 (3)0.0102 (3)0.565
Sr20.00.00.00.0060 (7)0.36
Tl20.00.00.00.0060 (7)0.046 (5)
Ca20.00.00.000.0060 (7)0.594 (5)
Cu0.50.50.05775 (5)0.0073 (4)
O10.00.50.0558 (2)0.012 (2)
O20.50.50.1435 (4)0.017 (2)
O30.00.00.2180 (5)0.040 (7)0.78 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Tl0.0169 (3)0.0169 (3)0.0118 (3)0.000.000.00
Hg0.0169 (3)0.0169 (3)0.0118 (3)0.000.000.00
Ca0.0169 (3)0.0169 (3)0.0118 (3)0.000.000.00
Ba0.0060 (4)0.0060 (4)0.0186 (6)0.000.000.00
Sr10.0060 (4)0.0060 (4)0.0186 (6)0.000.000.00
Sr20.003 (1)0.003 (1)0.011 (1)0.000.000.00
Tl20.003 (1)0.003 (1)0.011 (1)0.000.000.00
Ca20.003 (1)0.003 (1)0.011 (1)0.000.000.00
Cu0.0021 (6)0.0021 (6)0.0178 (9)0.000.000.00
O10.005 (4)0.013 (4)0.020 (3)0.000.000.00
Geometric parameters (Å, º) top
Tl—O22.01 (1)Ba—O32.79 (2)
Tl—O32.7183 (9)Sr2—O1v2.514 (4)
Tl—O3i2.7183 (9)Sr2—O12.514 (4)
Tl—O3ii2.7183 (9)Sr2—O1x2.514 (4)
Tl—O3iii2.7183 (9)Sr2—O1xi2.514 (4)
Tl—O3iv2.02 (2)Sr2—O1vi2.514 (4)
Ba—O1v2.729 (5)Sr2—O1vii2.514 (4)
Ba—O12.729 (5)Sr2—O1xii2.514 (4)
Ba—O1vi2.729 (5)Sr2—O1xiii2.514 (4)
Ba—O1vii2.729 (5)Cu—O11.9199 (2)
Ba—O2viii2.784 (2)Cu—O1ii1.9199 (2)
Ba—O2ix2.784 (2)Cu—O1vii1.9199 (2)
Ba—O2v2.784 (2)Cu—O1xiv1.9199 (2)
Ba—O22.784 (2)Cu—O22.50 (1)
O2—Tl—O393.2 (4)O1v—Sr2—O199.4 (2)
O2—Tl—O3i93.2 (4)O1v—Sr2—O1x80.6 (2)
O2—Tl—O3ii93.2 (4)O1v—Sr2—O1xi180
O2—Tl—O3iii93.2 (4)O1v—Sr2—O1vi65.27 (11)
O2—Tl—O3iv180O1v—Sr2—O1vii65.27 (11)
O3—Tl—O3i89.82 (4)O1v—Sr2—O1xii114.73 (11)
O3—Tl—O3ii89.82 (4)O1v—Sr2—O1xiii114.73 (11)
O3—Tl—O3iii173.5 (6)O1—Sr2—O1v99.4 (2)
O3—Tl—O3iv86.8 (4)O1—Sr2—O1x180
O3i—Tl—O389.82 (4)O1—Sr2—O1xi80.6 (2)
O3i—Tl—O3ii173.5 (6)O1—Sr2—O1vi65.27 (11)
O3i—Tl—O3iii89.82 (4)O1—Sr2—O1vii65.27 (11)
O3i—Tl—O3iv86.8 (4)O1—Sr2—O1xii114.73 (11)
O3ii—Tl—O389.82 (4)O1—Sr2—O1xiii114.73 (11)
O3ii—Tl—O3i173.5 (6)O1x—Sr2—O1v80.6 (2)
O3ii—Tl—O3iii89.82 (4)O1x—Sr2—O1180
O3ii—Tl—O3iv86.8 (4)O1x—Sr2—O1xi99.4 (2)
O3iii—Tl—O3173.5 (6)O1x—Sr2—O1vi114.73 (11)
O3iii—Tl—O3i89.82 (4)O1x—Sr2—O1vii114.73 (11)
O3iii—Tl—O3ii89.82 (4)O1x—Sr2—O1xii65.27 (11)
O3iii—Tl—O3iv86.8 (4)O1x—Sr2—O1xiii65.27 (11)
O3iv—Tl—O386.8 (4)O1xi—Sr2—O1v180
O3iv—Tl—O3i86.8 (4)O1xi—Sr2—O180.6 (2)
O3iv—Tl—O3ii86.8 (4)O1xi—Sr2—O1x99.4 (2)
O3iv—Tl—O3iii86.8 (4)O1xi—Sr2—O1vi114.73 (11)
O1v—Ba—O189.48 (17)O1xi—Sr2—O1vii114.73 (11)
O1v—Ba—O1vi59.70 (10)O1xi—Sr2—O1xii65.27 (11)
O1v—Ba—O1vii59.70 (10)O1xi—Sr2—O1xiii65.27 (11)
O1v—Ba—O2viii70.9 (2)O1vi—Sr2—O1v65.27 (11)
O1v—Ba—O2ix130.0 (2)O1vi—Sr2—O165.27 (11)
O1v—Ba—O2v70.9 (2)O1vi—Sr2—O1x114.73 (11)
O1v—Ba—O2130.0 (2)O1vi—Sr2—O1xi114.73 (11)
O1v—Ba—O3135.26 (12)O1vi—Sr2—O1vii99.4 (2)
O1—Ba—O1v89.48 (17)O1vi—Sr2—O1xii80.6 (2)
O1—Ba—O1vi59.70 (10)O1vi—Sr2—O1xiii180
O1—Ba—O1vii59.70 (10)O1vii—Sr2—O1v65.27 (11)
O1—Ba—O2viii130.0 (2)O1vii—Sr2—O165.27 (11)
O1—Ba—O2ix70.9 (2)O1vii—Sr2—O1x114.73 (11)
O1—Ba—O2v130.0 (2)O1vii—Sr2—O1xi114.73 (11)
O1—Ba—O270.9 (2)O1vii—Sr2—O1vi99.4 (2)
O1—Ba—O3135.26 (12)O1vii—Sr2—O1xii180
O1vi—Ba—O1v59.70 (10)O1vii—Sr2—O1xiii80.6 (2)
O1vi—Ba—O159.70 (10)O1xii—Sr2—O1v114.73 (11)
O1vi—Ba—O1vii89.48 (17)O1xii—Sr2—O1114.73 (11)
O1vi—Ba—O2viii70.9 (2)O1xii—Sr2—O1x65.27 (11)
O1vi—Ba—O2ix70.9 (2)O1xii—Sr2—O1xi65.27 (11)
O1vi—Ba—O2v130.0 (2)O1xii—Sr2—O1vi80.6 (2)
O1vi—Ba—O2130.0 (2)O1xii—Sr2—O1vii180
O1vi—Ba—O3135.26 (12)O1xii—Sr2—O1xiii99.4 (2)
O1vii—Ba—O1v59.70 (10)O1xiii—Sr2—O1v114.73 (11)
O1vii—Ba—O159.70 (10)O1xiii—Sr2—O1114.73 (11)
O1vii—Ba—O1vi89.48 (17)O1xiii—Sr2—O1x65.27 (11)
O1vii—Ba—O2viii130.0 (2)O1xiii—Sr2—O1xi65.27 (11)
O1vii—Ba—O2ix130.0 (2)O1xiii—Sr2—O1vi180
O1vii—Ba—O2v70.9 (2)O1xiii—Sr2—O1vii80.6 (2)
O1vii—Ba—O270.9 (2)O1xiii—Sr2—O1xii99.4 (2)
O1vii—Ba—O3135.26 (12)O1—Cu—O1ii176.7 (4)
O2viii—Ba—O2ix87.18 (8)O1—Cu—O1vii89.952 (11)
O2viii—Ba—O2v87.18 (8)O1—Cu—O1xiv89.952 (11)
O2viii—Ba—O2154.4 (4)O1—Cu—O291.7 (2)
O2viii—Ba—O377.2 (3)O1ii—Cu—O1176.7 (4)
O2ix—Ba—O2viii87.18 (8)O1ii—Cu—O1vii89.952 (11)
O2ix—Ba—O2v154.4 (4)O1ii—Cu—O1xiv89.952 (11)
O2ix—Ba—O287.18 (8)O1ii—Cu—O291.7 (2)
O2ix—Ba—O377.2 (3)O1vii—Cu—O189.952 (11)
O2v—Ba—O2viii87.18 (8)O1vii—Cu—O1ii89.952 (11)
O2v—Ba—O2ix154.4 (4)O1vii—Cu—O1xiv176.7 (4)
O2v—Ba—O287.18 (8)O1vii—Cu—O291.7 (2)
O2v—Ba—O377.2 (3)O1xiv—Cu—O189.952 (11)
O2—Ba—O2viii154.4 (4)O1xiv—Cu—O1ii89.952 (11)
O2—Ba—O2ix87.18 (8)O1xiv—Cu—O1vii176.7 (4)
O2—Ba—O2v87.18 (8)O1xiv—Cu—O291.7 (2)
O2—Ba—O377.2 (3)
Symmetry codes: (i) x, y+1, z; (ii) x+1, y, z; (iii) x+1, y+1, z; (iv) x+1/2, y+1/2, z+1/2; (v) x, y1, z; (vi) y, x, z; (vii) y+1, x, z; (viii) x1, y1, z; (ix) x1, y, z; (x) x, y, z; (xi) x, y+1, z; (xii) y1, x, z; (xiii) y, x, z; (xiv) y+1, x+1, z.

Experimental details

Crystal data
Chemical formulaBa0.87Ca0.64Cu2Hg0.79O7.56Sr1.49Tl1.21
Mr930.2
Crystal system, space groupTetragonal, I4/mmm
Temperature (K)293
a, c (Å)3.8380 (6), 29.145 (7)
V3)429.3 (1)
Z2
Radiation typeMo Kα
µ (mm1)55.06
Crystal size (mm)0.10 × 0.05 × 0.01
Data collection
DiffractometerStoe IPDS
diffractometer
Absorption correctionNumerical
X-RED version 1.09 (Stoe, 1997)
Tmin, Tmax0.057, 0.210
No. of measured, independent and
observed [I > 3σ(I)] reflections
1228, 138, 121
Rint0.046
θmax (°)23.9
(sin θ/λ)max1)0.570
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.020, 0.021, 2.41
No. of reflections138
No. of parameters22
No. of restraints?
Δρmax, Δρmin (e Å3)1.39, 2.74

Computer programs: IPDS (Stoe, 1996), IPDS, X-RED and X-SHAPE (Stoe, 1996), JANA98 (Petricek & Dusek, 1997), JANA98.

Selected bond lengths (Å) top
Tl—O22.01 (1)Ba—O32.79 (2)
Tl—O32.7183 (9)Sr2—O1ii2.514 (4)
Tl—O3i2.02 (2)Cu—O11.9199 (2)
Ba—O1ii2.729 (5)Cu—O22.50 (1)
Ba—O2iii2.784 (2)
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x, y1, z; (iii) x1, y1, z.
Interatomic distances and angles in the 2212 structure (A) compared with Tl2Ba2CaCu2O8 (B; Subramanian et al., 1988). top
Parameter in AValue in ANumberValue in BParameter in B
(TlHg,Ca)—O22.01 (1)11.979 (9)Tl—O2
(TlHg,Ca)—O32.02 (2)11.99 (2)Tl—O3
(TlHg,Ca)—O32.718 (1)42.46 (2)Tl—O3
(Sr,Ba)—O32.79 (2)12.86 (2)Ba—O3
(Sr,Ba)—O22.784 (2)42.818 (2)Ba—O2
(Sr,Ba)—O12.729 (5)42.788 (4)Ba—O1
(Ca,Sr,Tl)—O12.514 (4)82.478 (4)Ca—O1
Cu—O22.50 (1)12.700 (9)Cu—O2
Cu—O11.9199 (2)41.928 (0)Cu—O1
Cu—Cu3.366 (2)13.166 (4)Cu—Cu(apical)
O1—Cu—O1176.7 (4)2178.43 (0)O1—Cu—O1
O1—Cu—O291.7 (2)490.78 (9)O1—Cu—O2
 

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