data_COSB2O6_VAR3_1_publ

_publ_section_keywords
;
antimonate, rosiaite, trirutile, magnetic properties, antiferromagnetic
ordering, short-range correlations, layered structure, Rietveld method
;

#Added by publCIF

_publcif_datablock.id '{ebe13885-f400-446a-b4a9-14a26dccd99a}'



_publ_manuscript_text
;
(type here to add)
;

_pd_block_id
  2015-12-23T11:22|COSB2O6_VAR3_1|ils|arl

_audit_creation_method  "from EXP file using GSAS2CIF"
_audit_creation_date                   2015-12-23T11:22

loop_
_audit_author_name
;
I.L.Shukaev
;

_audit_update_record
;
2015-12-23T11:22  Initial CIF as created by GSAS2CIF
2016-12-20 # Formatted by publCIF
;

# SUBMISSION DETAILS

_publ_section_title
;
Preparation and characterization of metastable trigonal layered MSb2O6 phases'
(M= Co, Ni, Cu, Zn) and considerations on FeSb2O6
;
_publ_contact_author_name            'Nalbandyan, Vladimir'
_publ_contact_author_address         '7 ul.Zorge, Rostov-na-Donu,344090 Russia'
_publ_contact_author_email           vbn@sfedu.ru
_publ_requested_journal              'Dalton Transaction'
_publ_requested_category             ?   # Acta C: one of CI/CM/CO/FI/FM/FO
_publ_section_abstract
;
MSb2O6 compounds (M = Co, Ni, Cu, Zn) are known in the tetragonal trirutile
forms, slightly distorted monoclinically with M=Cu due to the Jahn-Teller
effect. In this work, using low-temperature exchange reaction between
ilmenite-type NaSbO3 and molten MSO4-KCl mixtures, these four compositions
were prepared for the first time as trigonal layered PbSb2O6-type phases. On
heating, they irreversibly transform to the known phases via amorphous
intermediates, in contrast to previously studied isostructural MnSb2O6, where
the stable phase is structurally related to the metastable one. The formula
volumes of the new phases show a reasonable correlation with the ionic radii
and are 2-3 % larger than those for the known forms, although all coordination
numbers are the same. Crystal structure of CoSb2O6 has been refined by the
Rietveld method: P-31m, a=5.1318(3) Å, c=4.5520(3) Å. Compounds with M =
Co and Ni order antiferromagnetically at ca. 11 and 15 K, respectively, but
the copper compound does not show long-range magnetic order down to 1.5 K.
FeSb2O6 could not be prepared because of the 2Fe2+ + Sb5+ = 2Fe3+ + Sb3+ redox
reaction. This electron transfer creates an additional 5s2 shell for Sb and
results in volume increase. Comparison of the formula volume for the stable
mixture FeSbO4+0.5Sb2O4 with that extrapolated for FeSb2O6 predicts that the
trirutile-type FeSb2O6 may be stabilized at high pressures.
;

loop_
_publ_author_name
_publ_author_address
_publ_author_footnote
_publ_author_email
;
'A.Yu. Nikulin'
;
;
'7 ul.Zorge, Rostov-na-Donu,344090, Russia'
;
;
'Chemistry Faculty, Southern Federal University'
;
;
chemistnik@yandex.ru
;
;
'V.B. Nalbandyan'
;
;
'7 ul.Zorge, Rostov-na-Donu,344090, Russia'
;
;
'Chemistry Faculty, Southern Federal University'
;
;
vbn@sfedu.ru
;
;
'I.L. Shukaev'
;
;
'7 ul.Zorge, Rostov-na-Donu,344090, Russia'
;
;
'Chemistry Faculty, Southern Federal University'
;
;
ishukaev@sfedu.ru
;


# INSTRUMENT CHARACTERIZATION

_exptl_special_details           ?
_pd_proc_info_excluded_regions   ?

_diffrn_ambient_temperature       298
_diffrn_measurement_device_type   ARL'Xtra

_pd_meas_scan_method              cont
_pd_meas_special_details          ?

_computing_data_collection        WinXRD
_computing_data_reduction         ?

_pd_spec_mount_mode               reflection

_refine_ls_shift/su_max                0.08
_refine_ls_shift/su_mean               0.01
_computing_structure_refinement        GSAS
_refine_ls_number_parameters           44
_refine_ls_goodness_of_fit_all         1.47
_refine_ls_number_restraints           0
_refine_ls_matrix_type                 full

_pd_phase_name
    "from E:/SHUKAEV/SCIENTIA/Struct_Analysis/CoSb2O6/Fit/Var1/1.cif"
_pd_char_colour                        violet
_cell_length_a                         5.13183(25)
_cell_length_b                         5.13183
_cell_length_c                         4.55202(34)
_cell_angle_alpha                      90.0
_cell_angle_beta                       90.0
_cell_angle_gamma                      120.0
_cell_volume                           103.820(11)
_cell_measurement_temperature          298
_symmetry_cell_setting                 trigonal
_symmetry_space_group_name_H-M         'P -3 1 m'
_symmetry_space_group_name_Hall        '-P 3 2'
_exptl_crystal_density_diffrn          6.373


loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz
       1 +x,+y,+z 
       2 -y,x-y,+z 
       3 y-x,-x,+z 
       4 +y,+x,+z 
       5 -x,y-x,+z 
       6 x-y,-y,+z 
      -1 -x,-y,-z 
      -2 +y,y-x,-z 
      -3 x-y,+x,-z 
      -4 -y,-x,-z 
      -5 +x,x-y,-z 
      -6 y-x,+y,-z 

# ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS


loop_
      _atom_site_type_symbol
      _atom_site_label
      _atom_site_fract_x
      _atom_site_fract_y
      _atom_site_fract_z
      _atom_site_occupancy
      _atom_site_thermal_displace_type
      _atom_site_U_iso_or_equiv
      _atom_site_symmetry_multiplicity
Co
Co1     0.0          0.0          0.0          1.0        Uiso   0.01          1
Sb
Sb1     0.33333      0.66667      0.5          1.0        Uani   0.01958       2
O 
O1      0.3721(18)   0.0          0.2518(13)   1.0        Uiso   0.03          6

loop_ _atom_site_aniso_label
      _atom_site_aniso_U_11
      _atom_site_aniso_U_12
      _atom_site_aniso_U_13
      _atom_site_aniso_U_22
      _atom_site_aniso_U_23
      _atom_site_aniso_U_33
Sb1     0.0156(4)   0.00779(19  0.0         0.0156(4)   0.0         0.0276(8) 
 
# If you change Z, be sure to change all 3 of the following
_chemical_formula_sum                  "Co O6 Sb2"
_chemical_formula_weight               398.43
_cell_formula_units_Z                  1

# MOLECULAR GEOMETRY

loop_
      _geom_bond_atom_site_label_1
      _geom_bond_atom_site_label_2
      _geom_bond_distance
      _geom_bond_site_symmetry_1
      _geom_bond_site_symmetry_2
      _geom_bond_publ_flag
  Co1       O1                2.227(8)  .      1_555  n
  Co1       O1                2.227(8)  .      2_555  n
  Co1       O1                2.227(8)  .      3_555  n
  Co1       O1                2.227(8)  .     -1_555  n
  Co1       O1                2.227(8)  .     -2_555  n
  Co1       O1                2.227(8)  .     -3_555  n
  Sb1       O1                1.975(4)  .      1_565  n
  Sb1       O1                1.975(4)  .      2_555  n
  Sb1       O1                1.975(4)  .      3_665  n
  Sb1       O1                1.975(4)  .     -1_666  n
  Sb1       O1                1.975(4)  .     -2_566  n
  Sb1       O1                1.975(4)  .     -3_556  n

loop_
      _geom_angle_atom_site_label_1
      _geom_angle_atom_site_label_2
      _geom_angle_atom_site_label_3
      _geom_angle
      _geom_angle_site_symmetry_1
      _geom_angle_site_symmetry_2
      _geom_angle_site_symmetry_3
      _geom_angle_publ_flag
  O1        Sb1       O1               90.54(21)      1_565  .      2_555  n
  O1        Sb1       O1               90.54(21)      1_565  .      3_665  n
  O1        Sb1       O1               82.82(29)      1_565  .     -1_666  n
  O1        Sb1       O1                 97.0(5)      1_565  .     -2_566  n
  O1        Sb1       O1                170.0(5)      1_565  .     -3_556  n
  O1        Sb1       O1               90.54(21)      2_555  .      3_665  n
  O1        Sb1       O1                170.0(5)      2_555  .     -1_666  n
  O1        Sb1       O1               82.82(29)      2_555  .     -2_566  n
  O1        Sb1       O1                 97.0(5)      2_555  .     -3_556  n
  O1        Sb1       O1                 97.0(5)      3_665  .     -1_666  n
  O1        Sb1       O1                170.0(5)      3_665  .     -2_566  n
  O1        Sb1       O1               82.82(29)      3_665  .     -3_556  n
  O1        Sb1       O1               90.54(21)     -1_666  .     -2_566  n
  O1        Sb1       O1               90.54(21)     -1_666  .     -3_556  n
  O1        Sb1       O1               90.54(21)     -2_566  .     -3_556  n
  Sb1       O1        Sb1              97.18(29)      1_545  .      4_555  n
  

loop_ _atom_type_symbol
      _atom_type_number_in_cell
      _atom_type_scat_dispersion_real
      _atom_type_scat_dispersion_imag
      _atom_type_scat_Cromer_Mann_a1
      _atom_type_scat_Cromer_Mann_a2
      _atom_type_scat_Cromer_Mann_a3
      _atom_type_scat_Cromer_Mann_a4
      _atom_type_scat_Cromer_Mann_b1
      _atom_type_scat_Cromer_Mann_b2
      _atom_type_scat_Cromer_Mann_b3
      _atom_type_scat_Cromer_Mann_b4
      _atom_type_scat_Cromer_Mann_c
      _atom_type_scat_source
  Co         1.0    0.000    0.000
 12.2841 4.27910 7.34090 0.27840 4.00340 13.5359 2.34880 71.1692 1.01180 
  International_Tables_Vol_C
  Sb         2.0    0.000    0.000
 19.6418 5.30340 19.0455 0.46070 5.03710 27.9074 2.68270 75.2825 4.59090 
  International_Tables_Vol_C
  O          6.0    0.000    0.000
 3.04850 13.2771 2.28680 5.70110 1.54630 0.32390 0.86700 32.9089 0.25080 
  International_Tables_Vol_C
_diffrn_radiation_probe                x-ray
_diffrn_radiation_polarisn_ratio       0.7

loop_
      _diffrn_radiation_wavelength
      _diffrn_radiation_wavelength_wt
      _diffrn_radiation_type
      _diffrn_radiation_wavelength_id
                      1.540600      1.000   'Cu K\a'  1
                      1.544400      0.500   'Cu K\a'  2
_pd_proc_ls_prof_R_factor              0.0611
_pd_proc_ls_prof_wR_factor             0.0776
_pd_proc_ls_prof_wR_expected           0.0531
_refine_ls_R_Fsqd_factor               0.05085

_pd_proc_ls_background_function
;   GSAS Background function number 1 with 16 terms.
 Shifted Chebyshev function of 1st kind
      1:    257.262     2:   -169.017     3:    55.2171     4:    8.65470    
      5:   -15.7118     6:    17.5577     7:   -1.10343     8:   -9.37983    
      9:    4.25022    10:   -4.01858    11:    5.50104    12:   -10.7930    
     13:    19.1438    14:   -5.98680    15:   -8.21721    16:    1.30827    
;

_exptl_absorpt_process_details
;   GSAS Absorption/surface roughness correction: function number 2
 Surface roughness abs. correction (Pitschke, et al.)
Terms =     0.19199        0.88620E-01
Correction is refined.
;
_exptl_absorpt_correction_T_min        0.57981
_exptl_absorpt_correction_T_max        1.00299
# Extinction correction
_gsas_exptl_extinct_corr_T_min         1.00000
_gsas_exptl_extinct_corr_T_max         1.00000
_pd_proc_ls_pref_orient_corr
;   March-Dollase
 AXIS  1 Ratio=   0.98733  h= 0.000  k= 0.000  l= 1.000
 Prefered orientation correction range: Min=   0.98102, Max=   1.03907
;

_pd_proc_ls_profile_function
;
 CW Profile function number 3 with  19 terms
 Pseudovoigt profile coefficients as parameterized in
 P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83.
 Asymmetry correction of L.W. Finger, D.E. Cox & A. P. Jephcoat (1994).
 J. Appl. Cryst.,27,892-900.
 #1(GU)   = ******** #2(GV)   = ******** #3(GW)   =  206.303
 #4(GP)   =  170.940 #5(LX)   =    0.000 #6(LY)   =   25.509
 #7(S/L)  =   0.0250 #8(H/L)  =   0.0232
 #9(trns) =   -10.54 #10(shft)=  -6.2499
 #11(stec)=    11.67 #12(ptec)=     9.89 #13(sfec)=     0.00
 #14(L11) =    1.928 #15(L22) =  -20.283 #16(L33) =    3.984
 #17(L12) =   12.324 #18(L13) =    0.120 #19(L23) =   13.987
 Peak tails are ignored  where the intensity is below 0.0004 times the peak
   Aniso. broadening axis   0.0   0.0   1.0
;
_pd_proc_ls_peak_cutoff 0.00040
_pd_proc_info_datetime                 2015-12-23T11:22:35
_pd_calc_method                        "Rietveld Refinement"

#---- raw/calc data loop -----
_pd_meas_2theta_range_min              15.0
_pd_meas_2theta_range_max              89.96
_pd_meas_2theta_range_inc              0.02
_pd_proc_2theta_range_min              15.0
_pd_proc_2theta_range_max              89.96
_pd_proc_2theta_range_inc              0.02
_pd_meas_number_of_points              3749
_pd_proc_number_of_points              3749

loop_
      _refln_index_h
      _refln_index_k
      _refln_index_l
_pd_refln_wavelength_id
      _refln_observed_status
      _refln_F_squared_meas
      _refln_F_squared_calc
      _refln_phase_calc
      _refln_d_spacing
      _gsas_i100_meas
   0   0   1  1 o  4594.119  4511.341  180.00   4.55202  42.19
   0   0   1  2 o  4575.378  4511.341  180.00   4.55202  20.90
   1   1   2  1 o  8436.456  7798.249   0.00    1.70269  37.79
   1   1   2  2 o  8547.162  7798.249   0.00    1.70269  19.07
   1   1   3  1 o  554.318   542.401   180.00   1.30607   2.02
   1   1   3  2 o  548.686   542.401   180.00   1.30607   1.00
   1   1   1  1 o  5803.410  5866.403  180.00   2.23525  44.43
   1   1   1  2 o  5716.090  5866.403  180.00   2.23525  21.82
   2   1   3  1 o  857.132   833.438    0.00    1.12598   3.88
   1   0   0  2 o  756.932   730.232   180.00   4.44429  10.17
   2   1   3  2 o  853.986   833.438    0.00    1.12598   1.93
   1   0   0  1 o  760.452   730.232   180.00   4.44429  20.52
   1   0   1  1 o  4110.305  4101.713   0.00    3.17999 100.00
   1   0   1  2 o  4128.069  4101.713   0.00    3.17999  50.03
   2   1   2  1 o  222.073   146.924   180.00   1.35155   1.72
   2   1   2  2 o  223.092   146.924   180.00   1.35155   0.86
   2   2   2  1 o  3411.396  3342.812   0.00    1.11763   7.94
   2   2   2  2 o  3407.025  3342.812   0.00    1.11763   3.96
   0   0   2  2 o  4281.778  3967.386   0.00    2.27601   5.29
   0   0   2  1 o  4363.370  3967.386   0.00    2.27601  10.83
   2   1   1  1 o  2528.414  2687.220   0.00    1.57591  18.67
   2   1   1  2 o  2510.017  2687.220   0.00    1.57591   9.22
   1   0   2  1 o  201.055   146.287   180.00   2.02581   3.27
   1   0   2  2 o  187.054   146.287   180.00   2.02581   1.54
   1   1   0  1 o  7556.377  7146.301   0.00    2.56591  64.78
   1   1   0  2 o  7627.762  7146.301   0.00    2.56591  32.57
   3   1   1  1 o  981.408   973.229    0.00    1.18978   4.61
   2   0   0  1 o  72.755    83.230    180.00   2.22215   0.84
   2   0   0  2 o  68.282    83.230    180.00   2.22215   0.40
   3   1   1  2 o  971.102   973.229    0.00    1.18978   2.27
   2   1   0  1 o  298.574   231.710   180.00   1.67978   3.23
   2   1   0  2 o  305.752   231.710   180.00   1.67978   1.64
   2   0   1  1 o  2717.721  2829.103   0.00    1.99691  30.12
   2   0   1  2 o  2652.897  2829.103   0.00    1.99691  14.61
   0   0   3  1 o  1414.713  1419.446  180.00   1.51734   2.08
   0   0   3  2 o  1446.871  1419.446  180.00   1.51734   1.05
   1   0   3  1 o  1765.780  1629.830   0.00    1.43596  11.61
   2   2   1  1 o  825.873   794.542   180.00   1.23485   2.58
   1   0   3  2 o  1750.769  1629.830   0.00    1.43596   5.73
   2   2   1  2 o  824.256   794.542   180.00   1.23485   1.29
   2   0   2  1 o  335.059   366.707   180.00   1.59000   3.47
   2   0   2  2 o  337.032   366.707   180.00   1.59000   1.74
   3   1   0  1 o  263.878   254.370   180.00   1.23263   1.78
   3   1   0  2 o  263.606   254.370   180.00   1.23263   0.89
   0   0   4  1 o  3891.177  3620.639   0.00    1.13801   3.21
   0   0   4  2 o  3817.284  3620.639   0.00    1.13801   1.57
   1   1  -1  1 o  984.346   979.401   180.00   2.23525   8.30
   1   1  -1  2 o  944.241   979.401   180.00   2.23525   3.99
   1   0   4  1 o  70.926    70.438    180.00   1.10244   0.54
   2   0   3  1 o  1334.825  1292.087   0.00    1.25308   6.98
   2   0   3  2 o  1339.687  1292.087   0.00    1.25308   3.49
   1   0   4  2 o  70.783    70.438    180.00   1.10244   0.27
   2   1  -1  1 o  1528.124  1623.821   0.00    1.57591  11.12
   2   1  -1  2 o  1511.826  1623.821   0.00    1.57591   5.47
   3   0   1  1 o  1517.438  1695.955  180.00   1.40871  11.27
   3   0   1  2 o  1471.600  1695.955  180.00   1.40871   5.46
   3   0   0  1 o  8290.612  7625.376   0.00    1.48143  28.48
   3   0   0  2 o  8309.985  7625.376   0.00    1.48143  14.22
   3   0   2  1 o  2671.950  2568.563   0.00    1.24159  14.05
   3   0   2  2 o  2658.450  2568.563   0.00    1.24159   6.97
   3   1  -1  1 o  1680.121  1683.315   0.00    1.18978   8.01
   3   1  -1  2 o  1650.658  1683.315   0.00    1.18978   3.92
   2   2   0  1 o  3678.961  3650.882   0.00    1.28296   9.99
   2   2   0  2 o  3715.179  3650.882   0.00    1.28296   5.03
   1   1  -2  1 o  7821.524  7664.068   0.00    1.70269  34.98
   1   1  -2  2 o  7939.348  7664.068   0.00    1.70269  17.69
   2   1  -2  1 o  266.722   141.958   180.00   1.35155   1.99
   2   1  -2  2 o  270.719   141.958   180.00   1.35155   1.00
   4   0   0  1 o  204.976   201.262   180.00   1.11107   0.63
   4   0   0  2 o  203.862   201.262   180.00   1.11107   0.31
   2   1  -3  1 o  1224.497  1239.031   0.00    1.12598   5.59
   2   1  -3  2 o  1230.067  1239.031   0.00    1.12598   2.80
   1   1  -3  1 o  1637.063  2030.511  180.00   1.30607   5.60
   1   1  -3  2 o  1683.760  2030.511  180.00   1.30607   2.86
   2   2  -1  1 o  2049.419  2011.270  180.00   1.23485   6.07
   2   2  -1  2 o  2007.966  2011.270  180.00   1.23485   2.97
   2   2  -2  2 o  3504.536  3379.172   0.00    1.11763   4.07
   2   2  -2  1 o  3462.790  3379.172   0.00    1.11763   8.06
_reflns_number_total                   78
_reflns_limit_h_min                    0
_reflns_limit_h_max                    4
_reflns_limit_k_min                    0
_reflns_limit_k_max                    2
_reflns_limit_l_min                    -4
_reflns_limit_l_max                    4
_reflns_d_resolution_high              1.102
_reflns_d_resolution_low               4.552
#--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--eof--#

_publcif_info_exptl_table_max_cols 4
_publcif_info_exptl_table_use_headnotes n

loop_
_publcif_info_datablock.id
_publcif_info_datablock.publ_exptl
_publcif_info_datablock.publ_geom
_publcif_info_datablock.structure

 {ebe13885-f400-446a-b4a9-14a26dccd99a} y y y
loop_
_publcif_info_exptl_table_extra_item

 ?
loop_
_publcif_info_exptl_table_header_item

 ?
loop_
_publcif_info_tables.block_id
_publcif_info_tables.reference_item
"{ebe13885-f400-446a-b4a9-14a26dccd99a}" "_publcif_info_datablock.publ_exptl"
loop_
_publcif_info_cif.paper_type
 ?

