Unexpected hydrolytic transformation of new type hybrid bromobismuthates with methylpyrazinium dications.
Kotov, Vitalii Yu; Ilyukhin, Andrey B.; Buikin, Petr A.; Simonenko, Nikolay P.; Korlyukov, Alexander A.; Smol'yakov, Alexander F.; Yorov, Khursand E.; Gavrikov, Andrey V.; Dalton transactions (Cambridge, England : 2003) 48 (2019) 7602–7611; doi:10.1039/c9dt01019j

data_7049907
_publ_section_title
;
 Unexpected hydrolytic transformation of new type hybrid bromobismuthates
 with methylpyrazinium dications.
;
_journal_issue                   22
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              7602
_journal_page_last               7611
_journal_paper_doi               10.1039/c9dt01019j
_journal_volume                  48
_journal_year                    2019
_chemical_formula_moiety         'Bi Br6, 2(C4 H5 N2), H3 O, H2 O'
_chemical_formula_sum            'C8 H15 Bi Br6 N4 O2'
_chemical_formula_weight         887.68
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_cell_setting           triclinic
_symmetry_Int_Tables_number      2
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_conform_dict_location     ftp://ftp.iucr.org/pub/cif_core.dic
_audit_conform_dict_name         cif_core.dic
_audit_conform_dict_version      2.4.3
_audit_creation_date             2018-04-13T14:57:44-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_audit_update_record
;
2019-04-25 deposited with the CCDC.    2019-04-29 downloaded from the CCDC.
;
_cell_angle_alpha                77.477(2)
_cell_angle_beta                 86.384(2)
_cell_angle_gamma                65.451(2)
_cell_formula_units_Z            2
_cell_length_a                   8.9423(6)
_cell_length_b                   9.2461(6)
_cell_length_c                   14.0873(8)
_cell_measurement_reflns_used    5081
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      29.97
_cell_measurement_theta_min      2.48
_cell_measurement_wavelength     0.71073
_cell_volume                     1033.79(11)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'WinGX publication routines (Farrugia, 2012)'
_computing_structure_refinement  'SHELXL-2018 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-2018 (Sheldrick, 2015)'
_diffrn_ambient_temperature      120(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0258
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            27294
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.414
_diffrn_reflns_theta_min         2.477
_exptl_absorpt_coefficient_mu    20.129
_exptl_absorpt_correction_T_max  0.0299
_exptl_absorpt_correction_T_min  0.0060
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   TWINABS
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    2.852
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             800
_exptl_crystal_size_max          .24
_exptl_crystal_size_mid          .20
_exptl_crystal_size_min          .14
_refine_diff_density_max         3.879
_refine_diff_density_min         -0.986
_refine_diff_density_rms         0.264
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.149
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     193
_refine_ls_number_reflns         3806
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.149
_refine_ls_R_factor_all          0.0472
_refine_ls_R_factor_gt           0.043
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0500P)^2^+20.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1155
_refine_ls_wR_factor_ref         0.1177
_reflns_Friedel_coverage         0
_reflns_number_gt                3528
_reflns_number_total             3806
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt01019j2.cif
_cod_data_source_block           5
_cod_depositor_comments
'Adding full bibliography for 7049900--7049908.cif.'
_cod_database_code               7049907
_twin_special_details
;
To collect experimental data for 5, the spliced crystals have been 
investigated. The main domain made up \\sim 70% of the volume and the latter 
part contained more than 5 domains thus not allowing one to take absorbance 
into account correctly.

 TWINABS - Bruker AXS scaling for twinned crystals - Version 2012/1
 ------------------------------------------------------------------

 Equivalent reflections defined according to point group -1    

 Reading batch  1 from file 11_24_4_01.mul
 Reading batch  2 from file 11_24_4_02.mul
 Reading batch  3 from file 11_24_4_03.mul
 Reading batch  4 from file 11_24_4_04.mul

  2 twin components present

 Mean and maximum errors in direction cosine check function =   0.001   0.009
 The mean error should not exceed 0.008, and is usually caused by matrix
 changes during data processing.

 Maximum 2-theta =  55.35 deg.   Approximate wavelength = 0.71069 Angstroms
 Approximate highest resolution = 0.765 Angstroms
 Approximate unit-cell:   8.937   9.240  14.081   77.49   86.35   65.46

 ==============================================================================

 PART 1 - Refinement of parameters to model systematic errors

    10199 data (   3556 unique ) involve domain  1 only,  mean I/sigma   8.8
    10178 data (   3546 unique ) involve domain  2 only,  mean I/sigma   6.5
     7029 data (   2526 unique ) involve   2 domains,  mean I/sigma  10.1

 Settings for parameter refinement:

 Maximum resolution =  0.1000 A
 (Intensity/sigma) threshold = 3.000
 Restraint esd for equal adjacent scale factors =  0.0050
 Maximum odd and even orders for spherical harmonics =   3   6

 Parameter refinement for twin component  1
 ------------------------------------------

    7136 single and      0 composite reflections used for parameter fitting
 Effective data to parameter ratio =    3.37

 wR2(int) =  0.0872 (selected reflections only, before parameter refinement)

 Cycle wR2(incid) wR2(diffr) Mean wt.
    1    0.0636    0.0511    0.9495
    2    0.0469    0.0452    0.9570
    3    0.0444    0.0439    0.9579
    4    0.0436    0.0434    0.9581
    5    0.0433    0.0432    0.9582
    6    0.0431    0.0431    0.9583
    7    0.0430    0.0430    0.9583
    8    0.0430    0.0430    0.9583
    9    0.0429    0.0429    0.9583
   10    0.0429    0.0429    0.9583
   11    0.0429    0.0429    0.9583
   12    0.0428    0.0429    0.9583
   13    0.0428    0.0428    0.9583
   14    0.0428    0.0428    0.9584
   15    0.0428    0.0428    0.9584
   16    0.0428    0.0428    0.9584
   17    0.0428    0.0428    0.9584
   18    0.0428    0.0428    0.9584
   19    0.0428    0.0428    0.9584
   20    0.0428    0.0428    0.9584
   21    0.0428    0.0428    0.9584
   22    0.0428    0.0428    0.9584
   23    0.0428    0.0428    0.9584
   24    0.0427    0.0428    0.9584
   25    0.0427    0.0428    0.9584
   26    0.0427    0.0428    0.9584
   27    0.0427    0.0428    0.9584
   28    0.0427    0.0427    0.9584
   29    0.0427    0.0427    0.9584
   30    0.0427    0.0427    0.9584
   31    0.0427    0.0427    0.9585
   32    0.0427    0.0427    0.9585
   33    0.0427    0.0427    0.9585
   34    0.0427    0.0427    0.9585
   35    0.0427    0.0427    0.9585
   36    0.0427    0.0427    0.9585
   37    0.0427    0.0427    0.9585
   38    0.0427    0.0427    0.9585
   39    0.0427    0.0427    0.9585
   40    0.0427    0.0427    0.9585

 wR2(int) =  0.0427 (selected reflections only, after parameter refinement)

 Parameter refinement for twin component  2
 ------------------------------------------

    6374 single and      0 composite reflections used for parameter fitting
 Effective data to parameter ratio =    3.02

 wR2(int) =  0.0953 (selected reflections only, before parameter refinement)

 Cycle wR2(incid) wR2(diffr) Mean wt.
    1    0.0707    0.0578    0.9345
    2    0.0533    0.0516    0.9424
    3    0.0507    0.0502    0.9433
    4    0.0498    0.0496    0.9437
    5    0.0493    0.0492    0.9439
    6    0.0491    0.0490    0.9442
    7    0.0489    0.0488    0.9444
    8    0.0488    0.0487    0.9445
    9    0.0486    0.0486    0.9447
   10    0.0486    0.0486    0.9448
   11    0.0485    0.0485    0.9450
   12    0.0485    0.0484    0.9451
   13    0.0484    0.0484    0.9452
   14    0.0484    0.0484    0.9453
   15    0.0483    0.0483    0.9453
   16    0.0483    0.0483    0.9454
   17    0.0483    0.0483    0.9455
   18    0.0483    0.0483    0.9455
   19    0.0482    0.0482    0.9456
   20    0.0482    0.0482    0.9456
   21    0.0482    0.0482    0.9457
   22    0.0482    0.0482    0.9457
   23    0.0482    0.0482    0.9457
   24    0.0481    0.0482    0.9458
   25    0.0481    0.0481    0.9458
   26    0.0481    0.0481    0.9458
   27    0.0481    0.0481    0.9458
   28    0.0481    0.0481    0.9458
   29    0.0481    0.0481    0.9459
   30    0.0481    0.0481    0.9459
   31    0.0480    0.0480    0.9459
   32    0.0480    0.0480    0.9459
   33    0.0480    0.0480    0.9459
   34    0.0480    0.0480    0.9459
   35    0.0480    0.0480    0.9459
   36    0.0480    0.0480    0.9459
   37    0.0480    0.0480    0.9459
   38    0.0480    0.0480    0.9460
   39    0.0480    0.0480    0.9460
   40    0.0480    0.0480    0.9460

 wR2(int) =  0.0480 (selected reflections only, after parameter refinement)

 ==============================================================================

 PART 2 - Reject outliers and establish error model

 Rejected reflections are ignored in the statistics and Postscript plots
 (except the detector diagnostics) and in the output .hkl files. All statistics
 and error estimates refer to total intensities (of single or composite
 reflections) only. Before applying rejections there are:

   27406 total and   9628 unique reflections assuming Friedel's law.

   27394 total and   9626 unique reflections after rejecting pathological cases 

   27306 total and   9624 unique reflections left after |I-<I>|/su test

 g = 0.0259 gave best error model; g set to 0.0259 for further calculations

 Statistics for singles of twin component  1
 -------------------------------------------

 Scan 2-theta  R(int)  Incid. factors  Diffr. factors    K     Total I>2sig(I)
    1  -22.5  0.0367   0.852 - 1.142   0.943 - 1.138   0.765    2903    2448
    2  -22.5  0.0420   0.963 - 1.238   0.953 - 1.144   0.848    2834    2359
    3  -22.5  0.0453   0.683 - 0.966   0.943 - 1.144   0.786    2281    1892
    4  -22.5  0.0435   0.699 - 1.008   0.943 - 1.144   0.752    2168    1798

   All scans  0.0417   0.683 - 1.238   0.943 - 1.144   0.788   10186    8497

 Statistics for singles of twin component  2
 -------------------------------------------

 Scan 2-theta  R(int)  Incid. factors  Diffr. factors    K     Total I>2sig(I)
    1  -22.5  0.0505   0.848 - 1.160   0.926 - 1.206   0.765    2887    2309
    2  -22.5  0.0532   0.905 - 1.170   0.927 - 1.203   0.848    2820    2182
    3  -22.5  0.0616   0.607 - 0.979   0.915 - 1.193   0.786    2293    1810
    4  -22.5  0.0583   0.661 - 0.996   0.915 - 1.192   0.752    2165    1714

   All scans  0.0556   0.607 - 1.170   0.915 - 1.206   0.788   10165    8015

 Statistics for all composite reflections
 ----------------------------------------

 Scan 2-theta  R(int)  Incid. factors  Diffr. factors    K     Total I>2sig(I)
    1  -22.5  0.0502   0.852 - 1.135   0.930 - 1.145   0.765    1668    1544
    2  -22.5  0.0522   0.921 - 1.224   0.949 - 1.149   0.848    1567    1432
    3  -22.5  0.0593   0.642 - 0.976   0.925 - 1.105   0.786    1904    1686
    4  -22.5  0.0576   0.680 - 1.002   0.925 - 1.115   0.752    1816    1619

   All scans  0.0550   0.642 - 1.224   0.925 - 1.149   0.788    6955    6281

 Statistics for all single and composite reflections
 ---------------------------------------------------

 Scan 2-theta  R(int)  Incid. factors  Diffr. factors    K     Total I>2sig(I)
    1  -22.5  0.0451   0.848 - 1.160   0.926 - 1.206   0.765    7458    6301
    2  -22.5  0.0485   0.905 - 1.238   0.927 - 1.203   0.848    7221    5973
    3  -22.5  0.0549   0.607 - 0.979   0.915 - 1.193   0.786    6478    5388
    4  -22.5  0.0529   0.661 - 1.008   0.915 - 1.192   0.752    6149    5131

   All scans  0.0502   0.607 - 1.238   0.915 - 1.206   0.788   27306   22793

 su = K * Sqrt[ sigma^2(I) + (g<I>)^2 ]  where sigma(I) is estimated by SAINT

 The above statistics are based on all non-rejected data, ignoring
 reflections without equivalents when estimating R(int) and K.

 ==============================================================================

 PART 3 - Output Postscript diagnostics and corrected data

 Unique HKLF 4 data extracted from all observed data

 Cycle   N(1) Rint(1)  N(all) Rint(all) Twin fractions
    1   17100  0.0866   27233  0.0891   0.6248  0.3752
    2   17129  0.0771   27294  0.0772   0.6228  0.3772
    3   17129  0.0577   27294  0.0610   0.6235  0.3765
    4   17129  0.0574   27294  0.0608   0.6235  0.3765
    5   17129  0.0573   27294  0.0607   0.6235  0.3765
    6   17129  0.0572   27294  0.0606   0.6235  0.3765
    7   17129  0.0571   27294  0.0606   0.6235  0.3765
    8   17129  0.0570   27294  0.0605   0.6235  0.3765
    9   17129  0.0570   27294  0.0605   0.6235  0.3765
   10   17129  0.0569   27294  0.0604   0.6234  0.3766
   11   17129  0.0569   27294  0.0604   0.6234  0.3766
   12   17129  0.0569   27294  0.0604   0.6234  0.3766
   13   17129  0.0568   27294  0.0604   0.6234  0.3766
   14   17129  0.0568   27294  0.0604   0.6234  0.3766
   15   17129  0.0568   27294  0.0603   0.6234  0.3766
   16   17129  0.0568   27294  0.0603   0.6234  0.3766
   17   17129  0.0568   27294  0.0603   0.6234  0.3766
   18   17129  0.0568   27294  0.0603   0.6234  0.3766
   19   17129  0.0568   27294  0.0603   0.6234  0.3766
   20   17129  0.0568   27294  0.0603   0.6234  0.3766

 N(1) and Rint(1) refer to singles and composites that include domain 1.

 Rint = 0.0603  for all   27294  observations and
 Rint = 0.0480  for all   16729  observations with I > 3sigma(I)

 Rint is based on agreement between observed single and composite intensities
 and those calculated from refined unique intensities and twin fractions.

    4027 Corrected reflections written to file twin4.hkl
 Reflections merged according to point-group -1    
 Minimum and maximum apparent transmission:  0.005917  0.029912
 Additional spherical absorption correction applied with mu*r =  4.0000

 HKLF 5 dataset constructed from all observations involving domain 1
    5100 Corrected reflections written to file twin5.hkl
 Reflections merged according to point-group -1    
 Single reflections that also occur in composites omitted
 Minimum and maximum apparent transmission:  0.006201  0.029912
 Additional spherical absorption correction applied with mu*r =  4.0000

;
_shelx_res_checksum              25831