Frontier orbitals of photosubstitutionally active ruthenium complexes: an experimental study of the spectator ligands’ electronic properties influence on photoreactivity
Jang, Hyo Jin; Hopkins, Samantha L.; Siegler, Maxime A.; Bonnet, Sylvestre; Dalton Trans.  (2017) –; doi:10.1039/C7DT01540B

data_7043729
_publ_section_title
;
 Frontier orbitals of photosubstitutionally active ruthenium complexes: an
 experimental study of the spectator ligands&#x2019; electronic properties
 influence on photoreactivity
;
_journal_name_full               'Dalton Trans.'
_journal_paper_doi               10.1039/C7DT01540B
_journal_year                    2017
_chemical_formula_sum            'C29 H29 Cl2 N5 O Ru'
_chemical_formula_weight         635.54
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014/7
_audit_update_record
;
2017-04-19 deposited with the CCDC.
2017-07-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.737(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1750(5)
_cell_length_b                   14.2168(5)
_cell_length_c                   15.7813(7)
_cell_measurement_reflns_used    6562
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      72.03
_cell_measurement_theta_min      4.16
_cell_volume                     2717.90(19)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'SHELXTL v6.10 (Sheldrick, 2008)'
_computing_publication_material  'SHELXTL v6.10 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-2014/7 (Sheldrick, 2015)'
_diffrn_ambient_temperature      110(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_source         'SuperNova (Cu) X-ray Source'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0368
_diffrn_reflns_av_unetI/netI     0.0538
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            15180
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         71.873
_diffrn_reflns_theta_min         3.649
_exptl_absorpt_coefficient_mu    6.737
_exptl_absorpt_correction_T_max  0.746
_exptl_absorpt_correction_T_min  0.102
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_diffrn    1.553
_exptl_crystal_description       plate
_exptl_crystal_F_000             1296
_exptl_crystal_size_max          0.63
_exptl_crystal_size_mid          0.48
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.288
_refine_diff_density_min         -0.934
_refine_diff_density_rms         0.149
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.980
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     348
_refine_ls_number_reflns         5956
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.980
_refine_ls_R_factor_all          0.0512
_refine_ls_R_factor_gt           0.0461
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0963P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1215
_refine_ls_wR_factor_ref         0.1250
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5156
_reflns_number_total             5956
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt01540b2.cif
_cod_data_source_block           1_Cl
_cod_database_code               7043729
_shelx_shelxl_version_number     2014/7
_twin_information
;
 * * * CRYSALIS TWIN DATA REDUCTION FINALIZING (Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)) * * *
Laue class: 2/m (b-unique) - Friedel mate is equivalent
Lattice type: P-lattice 
DC PROFFITRRPTWIN INFO: Step 1 - Loading orientation matrices (UB) of 2 components
 
DC PROFFITRRPTWIN INFO: Loading UB component 1
 
DC PROFFITRRPTWIN INFO: Loading UB component 2
 
DC PROFFITRRPTWIN INFO: Step 2 - Computing crossed twin laws
 
Twin law determination (relative to component 1)
Matrix 1 is taken from component 1 (  12.175   14.208   15.777    89.96    95.71    89.96)
Matrix 2 is taken from component 2 (  12.169   14.217   15.791    90.07    95.82    89.98)
Twin analysis: Component 1 with component 2
TL  =UB[1]-1*UB[2]:  -1.0004  -0.0017  -0.1569     0.0017  -0.9994   0.0002    -0.0033   0.0005   0.9988   det 0.999142
TL-1=UB[2]*UB[1]-1:  -0.9991   0.0017  -0.1569    -0.0017  -1.0006  -0.0001    -0.0033   0.0005   1.0006   det 1.000859
Rot= 179.9188 deg around the following vectors: 
Reciprocal space (hkl): -0.0776 0.0009 0.9970
Direct space (uvw)    : -0.0017 0.0003 1.0000
 
DC PROFFITRRPTWIN INFO: Step 3 - Loading reflections of 2 components
 
DC PROFFITRRPTWIN ALL INFO: Component 1
DC PROFFITRRPTWIN INFO: Face list of component 1 
  1:   7.8474  -0.0126   1.0278  d=   0.0402
  2:  -7.8474   0.0126  -1.0278  d=   0.0135
  3:   1.7752  -7.9954  -4.9904  d=   0.3287
  4:   0.3616  -7.9951   3.9998  d=   0.1343
  5:   0.2640   5.9966  -7.9953  d=   0.3492
  6:   1.5706  -0.0002  -9.9891  d=   0.2640
  7:  -1.6182   7.9953   3.9915  d=   0.1525
  8:  -7.8487  -0.9866  -1.0278  d=   0.0022
  9:  -1.7752   7.9954   4.9904  d=   0.1481
DC PROFFITRRPTWIN ALL INFO: Component 2
DC PROFFITRRPTWIN INFO: Face list of component 2 
  1:  -8.0015  -0.0005   1.0023  d=   0.0402
  2:   8.0015   0.0005  -1.0023  d=   0.0135
  3:  -1.0039   7.9976  -5.0036  d=   0.3287
  4:  -1.0022   7.9992   3.9970  d=   0.1343
  5:   1.0008  -6.0003  -7.9981  d=   0.3492
  6:  -0.0019  -0.0018 -10.0007  d=   0.2640
  7:   1.0037  -7.9978   4.0036  d=   0.1525
  8:   8.0011   1.0004  -1.0028  d=   0.0022
  9:   1.0039  -7.9976   5.0036  d=   0.1481
 
DC PROFFITRRPTWIN INFO: Step 4 - Analysing composite reflections of 2 components
 
Component 1: 18548 observations read
Component 2: 18581 observations read

27879 composite observations collected (18816 fully isolated, 9063 overlapped), 36 skipped due to one or more missing parts and 68 skipped due to I/sig<-3.0

OVERLAP STATISTICS

2 COMPONENTS

COMPONENTS 1, 2
 Overlap factor | # in range | % of all obs 
 -------------- | ---------- | ------------ 
   0.00 - 0.20  |       3071 |    11.0 <--- ALMOST SEPARATED
   0.20 - 0.40  |       1603 |     5.7
   0.40 - 0.60  |       1759 |     6.3
   0.60 - 0.80  |       1193 |     4.3
   0.80 - 1.00  |       1437 |     5.2 <--- FULLY OVERLAPPED
 -------------- | ---------- | ------------ 
      Total     |       9063 |    32.5

 
DC PROFFITRRPTWIN INFO: Step 5 - Scaling data & analysing twin ratios of 2 components
 
Computed twin ratios:
Twin 1: 73.06% (12613 common observations, 3829 merged)
Twin 2: 26.94% (11558 common observations, 3829 merged)

Preparing data for SCALE3 ABSPACK...

SCALING COMPONENT 1

14482 of 18455 reflections used for ABSPACK refinement
PROFFIT INFO: Inet (after scale3 abspack): min=-7906501.0000 max=23924008.0000
PROFFIT INFO: sig(Inet) (after scale3 abspack): min=667.7054 max=80605.3672

SCALING COMPONENT 2

14072 of 18487 reflections used for ABSPACK refinement
PROFFIT INFO: Inet (after scale3 abspack): min=-12799096.0000 max=23924008.0000
PROFFIT INFO: sig(Inet) (after scale3 abspack): min=667.7054 max=91375.6328

Computed twin ratios:
Twin 1: 72.32% (12613 common observations, 3829 merged)
Twin 2: 27.68% (11558 common observations, 3829 merged)

DC PROFFITRRPTWIN INFO: Determining HKLF4 overlap threshold for completeness requirement (>=80.0%)
DC PROFFITRRPTWIN INFO: HKLF4 overlap threshold kept - 0.40

DC PROFFITRRPTWIN INFO: Step 6 - Decomposed intensities statistics (HKLF4)
 
COMPONENT 1

 
Note: The Rint, Rsigma and RsigmaB values are computed for redundant data only!
    Mean F2 and F2/sig(F2) are given for all measured values!
Note: The RsigmaA values are computed for all measured values!

Help: For more information about computations of rint and rsigma please look into Crysalis help: 
 file:__#HELP_DTheoryAlgorithm_DataReductionOutput.html
 

Statistics vs intensity - point group symmetry: P2/m (b-unique)
                      #        #        #      average    mean      mean        
         intensity measured   kept    unique  redundancy   F2     F2/sig(F2)   Rint   Rsigma
 15654001- 1140959     1594     1594      464    3.4   2145542.52    75.80    0.072    0.079
  1140784-  683962     1528     1528      464    3.3    881757.62    45.03    0.076    0.086
   683764-  431338     1489     1489      464    3.2    551178.54    34.02    0.083    0.090
   430813-  279601     1488     1488      464    3.2    349921.10    25.50    0.088    0.101
   279501-  164709     1476     1476      464    3.2    217910.45    18.56    0.088    0.098
   164687-   93962     1433     1433      464    3.1    127614.18    12.23    0.104    0.115
    93741-   46468     1453     1453      464    3.1     68420.96     7.24    0.118    0.132
    46454-   18102     1429     1429      464    3.1     31217.17     3.56    0.176    0.192
    18094-    4105     1375     1375      464    3.0     10415.19     1.26    0.374    0.413
     4091-  -27033     1217     1217      464    2.6       353.61     0.08    0.888    1.511
 15654001-  -27033    14482    14482     4640    3.1    467614.35    23.52    0.080    0.088
 

Statistics vs resolution - point group symmetry: P2/m (b-unique)
resolu-      #        #        #               average    mean      mean          
tion(A)   measured   kept    unique           redundancy   F2     F2/sig(F2)   Rint   Rsigma   RsigmaA
 inf-1.73     1671     1671      464             3.6   1168730.42    53.33    0.072    0.079     0.014
1.73-1.38     1295     1295      464             2.8    707789.62    25.89    0.066    0.074     0.027
1.38-1.21     1763     1763      464             3.8    553470.67    22.19    0.096    0.111     0.035
1.21-1.10     1719     1719      464             3.7    425337.63    19.93    0.090    0.104     0.039
1.10-1.02     1540     1540      464             3.3    365417.65    18.84    0.084    0.094     0.041
1.02-0.96     1480     1480      464             3.2    304605.00    17.33    0.080    0.092     0.045
0.96-0.91     1431     1431      464             3.1    282151.83    17.71    0.078    0.088     0.045
0.91-0.87     1352     1352      464             2.9    261483.48    18.43    0.089    0.098     0.043
0.87-0.84     1212     1212      464             2.6    209296.39    17.63    0.071    0.076     0.045
0.84-0.81     1019     1019      464             2.2    167831.22    17.97    0.085    0.088     0.045
 inf-0.81    14482    14482     4640             3.1    467614.35    23.52    0.080    0.088     0.031
 

Statistics vs resolution (taking redundancy into account) - point group symmetry: P2/m (b-unique)
resolu-      #        #        #       %       average    mean      mean          
tion(A)    kept     theory   unique complete  redundancy   F2     F2/sig(F2)   Rint  RsigmaB
 inf-1.73     1671      596      464   77.9      3.6   1168730.42   101.81    0.072    0.008
1.73-1.38     1295      563      464   82.4      2.8    707789.62    46.32    0.066    0.017
1.38-1.21     1763      543      464   85.5      3.8    553470.67    46.87    0.096    0.019
1.21-1.10     1719      588      464   78.9      3.7    425337.63    40.23    0.090    0.021
1.10-1.02     1540      568      464   81.7      3.3    365417.65    35.61    0.084    0.023
1.02-0.96     1480      550      464   84.4      3.2    304605.00    31.81    0.080    0.026
0.96-0.91     1431      553      464   83.9      3.1    282151.83    32.20    0.078    0.026
0.91-0.87     1352      541      464   85.8      2.9    261483.48    32.45    0.089    0.026
0.87-0.84     1212      539      464   86.1      2.6    209296.39    30.15    0.071    0.028
0.84-0.81     1019      557      464   83.3      2.2    167831.22    27.96    0.085    0.030
 inf-0.81    14482     5600     4640   82.9      3.1    467614.35    44.11    0.080    0.018
DC PROFFITRRPTWIN INFO: Step 7 - Generating output files
 
HKLF 4
Reflections read=18455, from those 14482 with overlapping factor < 0.400 written to file D:\Data\xs0876a\test_twin1_hklf4.hkl, 3973 skipped
Use the HKLF 4 file(s) for structure solution.

HKLF 5 merged
RINT ANALYSIS FOR ALL HKLF5 REFLECTIONS
 Components measured    kept     unique redundancy F2/sig(F2) Rint      Rsigma
1,2          18455     15180      6222     2.44     23.86     0.037     0.034

RINT ANALYSIS FOR OVERLAPPED REFLECTIONS
 Components measured    kept     unique redundancy F2/sig(F2) Rint      Rsigma
1,2           9063      7255      3050     2.38     24.65     0.039     0.032

RINT ANALYSIS FOR ISOLATED REFLECTIONS
 Component measured     kept     unique redundancy F2/sig(F2) Rint      Rsigma
     1        9392      7925      3172     2.50     23.18     0.034     0.035
     2           0         0         0     0.00      0.00     0.000     0.000

6222 merged reflections saved into file: D:\Data\xs0876a\test_twin1_hklf5.hkl

Use this hkl file in SHELXL with BASF instruction, which has (components minus 1) entries, and HKLF 5 instruction.
E.g. Two component twin: 'BASF n2' in .ins file, BASF n1 can be computed as n1 = 1.0 - n2.
E.g. Three component twin: 'BASF n2 n3' in .ins file, BASF n1 can be computed as n1 = 1.0 - (n2 + n3).

BASF 0.27677 
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_shelx_res_checksum              9347