Intramolecular Hydrogen Bonding Enhances Stability and Reactivity of Mononuclear Cupric Superoxide Complexes.
Bhadra, Mayukh; Lee, Jung Yoon C.; Cowley, Ryan E.; Kim, Sunghee; Siegler, Maxime A.; Solomon, Edward I.; Karlin, Kenneth D.; Journal of the American Chemical Society 140 (2018) 9042–9045; doi:10.1021/jacs.8b04671

data_4132528
_publ_section_title
;
 Intramolecular Hydrogen Bonding Enhances Stability and Reactivity of
 Mononuclear Cupric Superoxide Complexes.
;
_journal_issue                   29
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9042
_journal_page_last               9045
_journal_paper_doi               10.1021/jacs.8b04671
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety
'C50 H40 Cu2 F10 N10, 2(F6 Sb), 0.583(C4 H10 O)'
_chemical_formula_sum            'C52.33 H45.83 Cu2 F22 N10 O0.58 Sb2'
_chemical_formula_weight         1612.69
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014
_cell_angle_alpha                112.2691(15)
_cell_angle_beta                 106.5181(13)
_cell_angle_gamma                102.1115(14)
_cell_formula_units_Z            6
_cell_length_a                   19.8184(3)
_cell_length_b                   23.5255(4)
_cell_length_c                   23.9366(3)
_cell_measurement_reflns_used    42947
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      72.07
_cell_measurement_theta_min      4.68
_cell_volume                     9245.6(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_molecular_graphics    'SHELXTL v6.10 (Sheldrick, 2008)'
_computing_publication_material  'SHELXTL v6.10 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXS-2014/7 (Sheldrick, 2014)'
_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  0.0322
_diffrn_reflns_av_unetI/netI     0.0548
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            105437
_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         71.898
_diffrn_reflns_theta_min         3.426
_exptl_absorpt_coefficient_mu    8.666
_exptl_absorpt_correction_T_max  0.504
_exptl_absorpt_correction_T_min  0.232
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
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            orange-yellow
_exptl_crystal_density_diffrn    1.738
_exptl_crystal_description       'small block'
_exptl_crystal_F_000             4755
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.450
_refine_diff_density_min         -1.002
_refine_diff_density_rms         0.102
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.986
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3039
_refine_ls_number_reflns         42032
_refine_ls_number_restraints     2918
_refine_ls_restrained_S_all      1.006
_refine_ls_R_factor_all          0.0505
_refine_ls_R_factor_gt           0.0433
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0691P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1087
_refine_ls_wR_factor_ref         0.1117
_reflns_Friedel_coverage         0.000
_reflns_number_gt                34974
_reflns_number_total             42032
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b04671_si_003.cif
_cod_data_source_block           F5BA_Cu_I_2
_cod_original_cell_volume        9245.5(3)
_cod_database_code               4132528
_twin_info
;

 * * * CRYSALIS TWIN DATA REDUCTION FINALIZING (Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)) * * *
Laue class: 1bar - 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 (  19.814   23.512   23.925   112.26   106.54   102.11)
Matrix 2 is taken from component 2 (  19.813   23.489   23.914   112.23   106.61   102.07)
Twin analysis: Component 1 with component 2
TL  =UB[1]-1*UB[2]:  -1.0000   0.0009  -0.0003    -0.0979  -0.0046  -1.0051     0.0971  -0.9965   0.0051   det 1.001493
TL-1=UB[2]*UB[1]-1:  -1.0002   0.0003  -0.0009    -0.0969  -0.0050  -1.0036     0.0978  -0.9949   0.0047   det 0.998509
Rot= -179.9694 deg around the following vectors: 
Reciprocal space (hkl): 0.0000 -0.7071 0.7071
Direct space (uvw)    : 0.0687 -0.7022 0.7086
 
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:  -0.0129  -1.9453  13.9612  d=   0.0430
  2:  -1.9875   2.7594 -12.7756  d=   0.0691
  3:  -0.9914  14.9607  -3.9650  d=   0.0581
  4:  -3.0095 -13.3326   6.3362  d=   0.0724
  5:   4.9930 -14.5785   1.5837  d=   0.0759
  6:   4.0104  13.4258  -7.4298  d=   0.0701
  7: -12.0028   4.8844   7.1135  d=   0.1148
  8:  -0.0094 -15.0539   5.0586  d=   0.0669
  9:  12.0024  -5.8895  -7.1084  d=   0.1330
 10:   8.9970 -12.1954  -2.8007  d=   0.1000
 11:  -3.9855  13.6295 -10.6443  d=   0.0708
 12:  -0.9842  12.9086 -12.9234  d=   0.0639
 13:   2.0159  11.1873 -14.2010  d=   0.0672
 14:   4.9863 -13.5363   9.5507  d=   0.0777
 15:  -1.0154 -12.0992  13.1125  d=   0.0644
 16:  10.9938 -10.9759   0.9861  d=   0.1168
 17:  -7.9904   3.1959  -8.2122  d=   0.0892
 18:  -2.9882   0.6512 -12.6684  d=   0.0677
 19:   3.0109  -0.7719 -13.2407  d=   0.0742
 20:  12.9983  -4.7633  -2.2280  d=   0.1365
 21:  -5.0028  -9.5356   0.5310  d=   0.0760
 22:  -0.0011 -11.0705  -2.9337  d=   0.0664
 23:   4.0002 -11.6934  -5.3100  d=   0.0747
 24:   4.0023  10.4475   0.5575  d=   0.0771
 25:   1.0010  11.1683   2.8366  d=   0.0676
 26:  12.0037   3.1661  -5.1611  d=   0.1326
DC PROFFITRRPTWIN ALL INFO: Component 2
DC PROFFITRRPTWIN INFO: Face list of component 2 
  1:   0.0000 -14.0000   2.0000  d=   0.0430
  2:   2.0000  13.0000  -3.0000  d=   0.0691
  3:   1.0000   4.0000 -15.0000  d=   0.0581
  4:   3.0000  -6.0000  13.0000  d=   0.0724
  5:  -5.0000  -2.0000  15.0000  d=   0.0759
  6:  -4.0000   7.0000 -13.0000  d=   0.0701
  7:  12.0000  -6.0000  -6.0000  d=   0.1148
  8:   0.0000  -5.0000  15.0000  d=   0.0669
  9: -12.0000   6.0000   7.0000  d=   0.1330
 10:  -9.0000   2.0000  13.0000  d=   0.1000
 11:   4.0000  11.0000 -14.0000  d=   0.0708
 12:   1.0000  13.0000 -13.0000  d=   0.0639
 13:  -2.0000  14.0000 -11.0000  d=   0.0672
 14:  -5.0000 -10.0000  14.0000  d=   0.0777
 15:   1.0000 -13.0000  12.0000  d=   0.0644
 16: -11.0000  -2.0000  12.0000  d=   0.1168
 17:   8.0000   9.0000  -4.0000  d=   0.0892
 18:   3.0000  13.0000  -1.0000  d=   0.0677
 19:  -3.0000  13.0000   1.0000  d=   0.0742
 20: -13.0000   1.0000   6.0000  d=   0.1365
 21:   5.0000  -0.0000   9.0000  d=   0.0760
 22:  -0.0000   3.0000  11.0000  d=   0.0664
 23:  -4.0000   5.0000  12.0000  d=   0.0747
 24:  -4.0000  -1.0000 -10.0000  d=   0.0771
 25:  -1.0000  -3.0000 -11.0000  d=   0.0676
 26: -12.0000   4.0000  -2.0000  d=   0.1326
 
DC PROFFITRRPTWIN INFO: Step 4 - Analysing composite reflections of 2 components
 
Component 1: 118382 observations read
Component 2: 118167 observations read

165052 composite observations collected (93777 fully isolated, 71275 overlapped), 128 skipped due to one or more missing parts and 32 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  |      22854 |    13.8 <--- ALMOST SEPARATED
   0.20 - 0.40  |      14640 |     8.9
   0.40 - 0.60  |      12463 |     7.6
   0.60 - 0.80  |      11554 |     7.0
   0.80 - 1.00  |       9764 |     5.9 <--- FULLY OVERLAPPED
 -------------- | ---------- | ------------ 
      Total     |      71275 |    43.2

 
DC PROFFITRRPTWIN INFO: Step 5 - Scaling data & analysing twin ratios of 2 components
 
Computed twin ratios:
Twin 1: 67.55% (71053 common observations, 21515 merged)
Twin 2: 32.45% (61621 common observations, 21515 merged)

Preparing data for SCALE3 ABSPACK...

SCALING COMPONENT 1

84584 of 118277 reflections used for ABSPACK refinement
PROFFIT INFO: Inet (after scale3 abspack): min=-1810069.2500 max=7502704.0000
PROFFIT INFO: sig(Inet) (after scale3 abspack): min=394.1218 max=59654.4688

SCALING COMPONENT 2

85495 of 118050 reflections used for ABSPACK refinement
PROFFIT INFO: Inet (after scale3 abspack): min=-3332303.2500 max=7502704.0000
PROFFIT INFO: sig(Inet) (after scale3 abspack): min=369.4233 max=59654.4688

Computed twin ratios:
Twin 1: 68.82% (71053 common observations, 21515 merged)
Twin 2: 31.18% (61621 common observations, 21515 merged)

DC PROFFITRRPTWIN INFO: Determining HKLF4 overlap threshold for completeness requirement (>=80.0%)
DC PROFFITRRPTWIN INFO: New HKLF4 overlap threshold - 0.47

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: P-1
                      #        #        #      average    mean      mean        
         intensity measured   kept    unique  redundancy   F2     F2/sig(F2)   Rint   Rsigma
--------------------------------------------------------------------------------------------
  5735335-  152322    12616    12616     2910    4.3    412273.19    51.15    0.054    0.065
   152273-   74209    10627    10627     2910    3.7    106211.94    25.55    0.074    0.079
    74167-   43706     9587     9587     2910    3.3     57142.26    18.64    0.084    0.087
    43692-   27065     8745     8745     2910    3.0     34723.67    13.35    0.101    0.101
    27045-   17106     8427     8427     2910    2.9     21776.70     9.46    0.121    0.120
    17101-   10474     8024     8024     2910    2.8     13585.08     6.47    0.148    0.143
    10473-    6052     7986     7986     2910    2.7      8159.67     4.02    0.203    0.198
     6051-    3092     8015     8015     2910    2.8      4469.53     2.28    0.276    0.277
     3092-    1239     7712     7712     2910    2.7      2105.27     1.14    0.412    0.431
     1239- -244365     7188     7188     2916    2.5       187.79     0.26    0.830    1.363
------------------------------------------------------------------------------------------
  5735335- -244365    88927    88927    29106    3.1     85379.30    15.80    0.068    0.079
 

Statistics vs resolution - point group symmetry: P-1
resolu-      #        #        #               average    mean      mean          
tion(A)   measured   kept    unique           redundancy   F2     F2/sig(F2)   Rint   Rsigma   RsigmaA
------------------------------------------------------------------------------------------------------
 inf-1.83    14881    14881     2910             5.1    245068.59    34.20    0.063    0.076     0.022
1.83-1.42    11279    11279     2910             3.9    130467.75    14.93    0.075    0.087     0.051
1.42-1.24    11614    11614     2910             4.0     80884.00    12.58    0.082    0.098     0.074
1.24-1.12    11524    11524     2910             4.0     49935.62    13.38    0.076    0.086     0.077
1.12-1.04     8199     8199     2910             2.8     36274.08    13.15    0.053    0.057     0.065
1.04-0.97     7436     7436     2910             2.6     30815.44    11.93    0.055    0.058     0.073
0.97-0.92     6884     6884     2910             2.4     23243.81    10.06    0.059    0.063     0.088
0.92-0.88     6282     6282     2910             2.2     18825.77     9.48    0.060    0.063     0.095
0.88-0.84     5847     5847     2910             2.0     15838.28     9.59    0.065    0.068     0.095
0.84-0.81     4981     4981     2916             1.7     12413.95     9.23    0.067    0.068     0.099
------------------------------------------------------------------------------------------------------
 inf-0.81    88927    88927    29106             3.1     85379.30    15.80    0.068    0.079     0.046
 

Statistics vs resolution (taking redundancy into account) - point group symmetry: P-1
resolu-      #        #        #       %       average    mean      mean          
tion(A)    kept     theory   unique complete  redundancy   F2     F2/sig(F2)   Rint  RsigmaB
--------------------------------------------------------------------------------------------
 inf-1.83    14881     3125     2910   93.1      5.1    245068.59    75.99    0.063    0.010
1.83-1.42    11279     3606     2910   80.7      3.9    130467.75    30.12    0.075    0.027
1.42-1.24    11614     3476     2910   83.7      4.0     80884.00    22.20    0.082    0.042
1.24-1.12    11524     3566     2910   81.6      4.0     49935.62    23.35    0.076    0.041
1.12-1.04     8199     3670     2910   79.3      2.8     36274.08    23.42    0.053    0.039
1.04-0.97     7436     3639     2910   80.0      2.6     30815.44    19.95    0.055    0.045
0.97-0.92     6884     3827     2910   76.0      2.4     23243.81    16.22    0.059    0.055
0.92-0.88     6282     3910     2910   74.4      2.2     18825.77    14.59    0.060    0.062
0.88-0.84     5847     3800     2910   76.6      2.0     15838.28    14.21    0.065    0.063
0.84-0.81     4981     3761     2916   77.5      1.7     12413.95    12.63    0.067    0.066
--------------------------------------------------------------------------------------------
 inf-0.81    88927    36382    29106   80.0      3.1     85379.30    30.22    0.068    0.027
DC PROFFITRRPTWIN INFO: Step 7 - Generating output files
 
HKLF 4
Reflections read=118277, from those 88927 with overlapping factor < 0.466 written to file D:\Data\xs0367a\xs0367a_max3_twin1_hklf4.hkl, 29350 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         118277    105437     42116     2.50     16.16     0.032     0.054

RINT ANALYSIS FOR OVERLAPPED REFLECTIONS
 Components measured    kept     unique redundancy F2/sig(F2) Rint      Rsigma
------------------------------------------------------------------------------
1,2          71275     63287     25645     2.47     16.03     0.034     0.056

RINT ANALYSIS FOR ISOLATED REFLECTIONS
 Component measured     kept     unique redundancy F2/sig(F2) Rint      Rsigma
------------------------------------------------------------------------------
     1       47002     42150     16471     2.56     16.43     0.028     0.051
     2           0         0         0     0.00      0.00     0.000     0.000

42116 merged reflections saved into file: D:\Data\xs0367a\xs0367a_max3_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 0.31179 
;
_shelxl_version_number           2014-3
_shelx_res_checksum              78999
_shelx_hkl_checksum              53645
_shelx_fab_checksum              57011