Aromatic sulfonium polyoxomolybdates: tuning the photochromic properties through substitutions on the counter ion moiety
Kumar, Ashwani; Pradeep, Chullikkattil P.; CrystEngComm  (2018) –; doi:10.1039/C8CE00345A

data_7230397
_publ_section_title
;
 Aromatic sulfonium polyoxomolybdates: tuning the photochromic properties
 through substitutions on the counter ion moiety
;
_journal_name_full               CrystEngComm
_journal_paper_doi               10.1039/C8CE00345A
_journal_year                    2018
_chemical_formula_moiety         'Mo12 O40 P, 3(C12 H19 O S)'
_chemical_formula_sum            'C36 H57 Mo12 O43 P S3'
_chemical_formula_weight         2456.25
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-01-22
_audit_creation_method
;
  Olex2 1.2-ac2
  (compiled 2012.03.27 svn.r2268, GUI svn.r4156)
;
_audit_update_record
;
2018-03-01 deposited with the CCDC.
2018-04-02 downloaded from the CCDC.
;
_cell_angle_alpha                95.806(4)
_cell_angle_beta                 95.886(4)
_cell_angle_gamma                115.353(5)
_cell_formula_units_Z            2
_cell_length_a                   12.4149(7)
_cell_length_b                   12.6395(6)
_cell_length_c                   23.2868(9)
_cell_measurement_reflns_used    8268
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      66.8960
_cell_measurement_theta_min      3.9400
_cell_volume                     3241.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122

Alert level B

PLAT430_ALERT_2_B Short Inter D...A Contact O12 ..O12 2.81 Ang.

discussion: Short Inter D...A Contact might have arisen due to less intensely scattered oxygen atoms of cluster
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9974
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w      5.00 102.00   1.00    1.00    --   25.51  57.00  60.00   97
  2  \w    100.00 149.00   1.00    1.00    --   66.75 111.00 120.00   49
  3  \w    114.00 147.00   1.00    1.00    --   66.75 111.00  30.00   33
  4  \w    110.00 150.00   1.00    1.00    --   66.75 111.00 -30.00   40
  5  \w    110.00 176.00   1.00    2.50    --  108.00 104.00 -60.00   66
  6  \w    153.00 178.00   1.00    2.50    --  108.00  32.00 -30.00   25
  7  \w    116.00 143.00   1.00    2.50    --  108.00  32.00 -30.00   27
  8  \w    102.00 178.00   1.00    2.50    --  108.00 104.00-120.00   76
  9  \w    102.00 174.00   1.00    2.50    --  108.00 104.00   0.00   72
 10  \w    103.00 142.00   1.00    1.00    --   66.75 121.00  73.00   39
 11  \w     99.00 178.00   1.00    2.50    --  108.00 138.00 120.00   79
 12  \w     95.00 171.00   1.00    2.50    --  108.00  32.00  90.00   76
 13  \w     87.00 154.00   1.00    2.50    --  108.00 -89.00 -60.00   67
 14  \w    103.00 157.00   1.00    2.50    --  108.00 -89.00-150.00   54
 15  \w     75.00 111.00   1.00    2.50    --  108.00-104.00-180.00   36
 16  \w     67.00 122.00   1.00    2.50    --  108.00-128.00 -48.26   55
 17  \w     43.00 111.00   1.00    1.00    --   66.75 -45.00   0.00   68
 18  \w     74.00 108.00   1.00    2.50    --  108.00-104.00 120.00   34
 19  \w     40.00  98.00   1.00    2.50    --  108.00-104.00  90.00   58
 20  \w     29.00  68.00   1.00    2.50    --  108.00-104.00 120.00   39
 21  \w    -11.00  16.00   1.00    1.00    --   66.75 -45.00   0.00   27
 22  \w     34.00  70.00   1.00    2.50    --  108.00 -89.00 -60.00   36
 23  \w     29.00  56.00   1.00    2.50    --  108.00-128.00 -48.26   27
 24  \w     25.00  91.00   1.00    2.50    --  108.00 -89.00-150.00   66
 25  \w     24.00  58.00   1.00    2.50    --  108.00-104.00-180.00   34
 26  \w     12.00 112.00   1.00    1.00    --   66.75-111.00-180.00  100
 27  \w     50.00  88.00   1.00    2.50    --  108.00  32.00 -30.00   38
 28  \w     66.00 175.00   1.00    2.50    --  108.00  32.00   0.00  109
 29  \w    102.00 177.00   1.00    2.50    --  108.00 104.00 -90.00   75
 30  \w     62.00 112.00   1.00    1.00    --   66.75  61.00-180.00   50
 31  \w     57.00 149.00   1.00    1.00    --   66.75 178.00-150.00   92
 32  \w     65.00 178.00   1.00    2.50    --  108.00  77.00  30.00  113
 33  \w     44.00  80.00   1.00    2.50    --  108.00  32.00  90.00   36
 34  \w     33.00 112.00   1.00    1.00    --   66.75  61.00  60.00   79
 35  \w    -12.00  81.00   1.00    1.00    --   25.51  77.00 -60.00   93
 36  \w     -7.00 150.00   1.00    1.00    --   66.75  15.00 -30.00  157
 37  \w    -16.00  79.00   1.00    1.00    --   25.51  77.00-180.00   95
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0905917000
_diffrn_orient_matrix_UB_12      0.0340580000
_diffrn_orient_matrix_UB_13      0.0569529000
_diffrn_orient_matrix_UB_21      -0.1051174000
_diffrn_orient_matrix_UB_22      -0.0383785000
_diffrn_orient_matrix_UB_23      0.0353072000
_diffrn_orient_matrix_UB_31      -0.0102824000
_diffrn_orient_matrix_UB_32      -0.1266549000
_diffrn_orient_matrix_UB_33      -0.0071504000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0443
_diffrn_reflns_av_unetI/netI     0.0550
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            21623
_diffrn_reflns_theta_full        66.98
_diffrn_reflns_theta_max         66.98
_diffrn_reflns_theta_min         3.87
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    20.380
_exptl_absorpt_correction_T_max  0.489
_exptl_absorpt_correction_T_min  0.139
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    2.516
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       triclinic
_exptl_crystal_F_000             2368
_exptl_crystal_size_max          0.165
_exptl_crystal_size_mid          0.127
_exptl_crystal_size_min          0.072
_refine_diff_density_max         4.066
_refine_diff_density_min         -1.215
_refine_diff_density_rms         0.198
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     865
_refine_ls_number_reflns         11367
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0500
_refine_ls_R_factor_gt           0.0420
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0594P)^2^+6.6345P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1072
_refine_ls_wR_factor_ref         0.1141
_reflns_number_gt                9819
_reflns_number_total             11367
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c8ce00345a2.cif
_cod_data_source_block           h4_lt_cu
_cod_database_code               7230397
_chemical_oxdiff_formula         'C72 H114 Mo24 O86 P2 S6 '
_reflns_odcompleteness_completeness 98.24
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_date_sample_data_collection 2018-01-02
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C0AA(H0Aa,H0Ab), C11(H11a,H11b), C17(H17a,H17b), C1BA(H1Ba,H1Bb), C6(H6a,H6b),
  C5BA(H5Ba,H5Bb), C4BA(H4Ba,H4Bb), C6BA(H6Ba,H6Bb), C1(H1a,H1b)
2.b Aromatic/amide H refined with riding coordinates:
 C57(H57), C85(H85), C19(H19), C9AA(H9AA), C6AA(H6AA), C10(H10), C2AA(H2AA),
 C20(H20), C8AA(H8AA), C4AA(H4AA), C14(H14), C5(H5)
2.c Idealised Me refined as rotating group:
 C1AA(H1Aa,H1Ab,H1Ac), C13(H13a,H13b,H13c), C0BA(H0Ba,H0Bb,H0Bc), C4(H4a,H4b,
 H4c), C7AA(H7Aa,H7Ab,H7Ac), C3BA(H3Ba,H3Bb,H3Bc), C2BA(H2Ba,H2Bb,H2Bc), C2(H2a,
 H2b,H2c), C3(H3a,H3b,H3c)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.903
_oxdiff_exptl_absorpt_empirical_full_min 0.699