Metal-Ligand Covalency Enables Room Temperature Molecular Qubit Candidates
Fataftah, Majed S.; Krzyaniak, Matthew D.; Vlaisavljevich, Bess; Wasielewski, Michael R.; Zadrozny, Joseph; Freedman, Danna; Chemical Science  (2019) –; doi:10.1039/C9SC00074G

data_1551187
_publ_section_title
;
 Metal-Ligand Covalency Enables Room Temperature Molecular Qubit
 Candidates
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC00074G
_journal_year                    2019
_chemical_formula_moiety         'C18 H12 S6 Ti, 2(C24 H20 P)'
_chemical_formula_sum            'C66 H52 P2 S6 Ti'
_chemical_formula_weight         1147.27
_chemical_name_systematic
'tetraphenyl phosphonium titanium tris(dithiocatecholate)'
_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
_audit_block_doi                 10.5517/ccdc.csd.cc210d7q
_audit_creation_date             2018-03-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-11-05 deposited with the CCDC.    2019-05-28 downloaded from the CCDC.
;
_cell_angle_alpha                100.250(5)
_cell_angle_beta                 91.957(5)
_cell_angle_gamma                119.364(5)
_cell_formula_units_Z            4
_cell_length_a                   13.870(4)
_cell_length_b                   14.040(4)
_cell_length_c                   33.318(10)
_cell_measurement_reflns_used    9947
_cell_measurement_temperature    100
_cell_measurement_theta_max      24.74
_cell_measurement_theta_min      2.33
_cell_volume                     5508(3)
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 V2014.11-0 (Bruker, 2014)'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      99.99
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.964
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'MX optics'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0631
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            22936
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.941
_diffrn_reflns_theta_min         0.627
_diffrn_source                   microsource
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.484
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6330
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0810 before and 0.0729 after correction. The Ratio of minimum to maximum transmission is 0.8492. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'dull dark red'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.383
_exptl_crystal_description       block
_exptl_crystal_F_000             2384
_exptl_crystal_preparation
'prepared from dithiocatechole and tetrakis(dimethylamido)titanium(IV) in THF'
_exptl_crystal_recrystallization_method
'Crystallized from DMF solution layered under diethyl ether'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.575
_refine_diff_density_min         -0.920
_refine_diff_density_rms         0.213
_refine_ls_extinction_coef       0.097(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.176
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1353
_refine_ls_number_reflns         22936
_refine_ls_number_restraints     2286
_refine_ls_restrained_S_all      1.120
_refine_ls_R_factor_all          0.1401
_refine_ls_R_factor_gt           0.1259
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1347P)^2^+58.3364P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3289
_refine_ls_wR_factor_ref         0.3370
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19146
_reflns_number_total             22936
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc00074g2.cif
_cod_data_source_block           mo_msf5_149_2_0m_tw
_cod_original_cell_volume        5509(3)
_cod_database_code               1551187
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.953
_shelx_estimated_absorpt_t_min   0.944
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.741(2)
 0.259(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.1 and sigma
for terminal atoms of 0.2
5.a Aromatic/amide H refined with riding coordinates:
 C00K(H00K), C00N(H00N), C00O(H00O), C00Q(H00Q), C00R(H00R), C00T(H00T),
 C00U(H00U), C00W(H00W), C00X(H00X), C00Z(H00Z), C010(H010), C013(H013),
 C014(H014), C015(H015), C018(H018), C019(H019), C01A(H01A), C01B(H01B),
 C01C(H01C), C01E(H01E), C01J(H01J), C01K(H01K), C01L(H01L), C01M(H01M),
 C01N(H01N), C01O(H01O), C01P(H01P), C01Q(H01Q), C01R(H01R), C01T(H01T),
 C01V(H01V), C01W(H01W), C01X(H01X), C01Y(H01Y), C01Z(H01Z), C020(H020),
 C021(H021), C022(H022), C023(H023), C024(H024), C025(H025), C026(H026),
 C028(H028), C02A(H02A), C02B(H02B), C02D(H02D), C02E(H02E), C02G(H02G),
 C02J(H02J), C02K(H02K), C02L(H02L), C02M(H02M), C02N(H02N), C02O(H02O),
 C02P(H02P), C02Q(H02Q), C02R(H02R), C02S(H02S), C02T(H02T), C02U(H02U),
 C02V(H02V), C02W(H02W), C02X(H02X), C02Y(H02Y), C030(H030), C031(H031),
 C032(H032), C033(H033), C034(H034), C035(H035), C037(H037), C038(H038),
 C039(H039), C03A(H03A), C03B(H03B), C03C(H03C), C03D(H03D), C03E(H03E),
 C03F(H03F), C03G(H03G), C03H(H03H), C03I(H03I), C03J(H03J), C03K(H03K),
 C03L(H03L), C03M(H03M), C03N(H03N), C03O(H03O), C03P(H03P), C03R(H03R),
 C03S(H03S), C03T(H03T), C03U(H03U), C03W(H03W), C03X(H03X), C03Y(H03Y),
 C03Z(H03Z), C040(H040), C041(H041), C042(H042), C043(H043), C044(H044),
 C045(H045), C046(H046)
;
_shelx_res_checksum              37167
_olex2_exptl_crystal_mounting_method 'Mounted under paratone oil'
_olex2_submission_original_sample_id 'Compound 5'
_olex2_submission_special_instructions 'No special instructions were received'