Combatting AMR: photoactivatable ruthenium(ii)-isoniazid complex exhibits rapid selective antimycobacterial activity.
Smith, Nichola A.; Zhang, Pingyu; Greenough, Simon E.; Horbury, Michael D.; Clarkson, Guy J.; McFeely, Daniel; Habtemariam, Abraha; Salassa, Luca; Stavros, Vasilios G.; Dowson, Christopher G.; Sadler, Peter J.; Chemical science 8 (2017) 395–404; doi:10.1039/c6sc03028a

data_1544969
_publ_section_title
;
 Combatting AMR: photoactivatable ruthenium(ii)-isoniazid complex exhibits
 rapid selective antimycobacterial activity.
;
_journal_issue                   1
_journal_name_full               'Chemical science'
_journal_page_first              395
_journal_page_last               404
_journal_paper_doi               10.1039/c6sc03028a
_journal_volume                  8
_journal_year                    2017
_chemical_formula_moiety         'C32 H30 N10 O2 Ru, 2(F6 P), 2.5(C4 H8 O2)'
_chemical_formula_sum            'C42 H50 F12 N10 O7 P2 Ru'
_chemical_formula_weight         1197.93
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-04-15
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.16 svn.r3265 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2016-04-15 deposited with the CCDC.
2016-08-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 130.884(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.9093(7)
_cell_length_b                   15.8193(3)
_cell_length_c                   19.1282(12)
_cell_measurement_reflns_used    2830
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.06
_cell_measurement_theta_min      3.76
_cell_volume                     5012.2(4)
_computing_cell_refinement       'CrysAlis RED, Oxford Diffraction Ltd'
_computing_data_collection       'CrysAlis CCD, Oxford Diffraction Ltd'
_computing_data_reduction        'CrysAlis RED, Oxford Diffraction Ltd'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS-1997 (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 10.2833
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Oxford Diffraction Gemini R'
_diffrn_measurement_method       '\f & \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0328
_diffrn_reflns_av_unetI/netI     0.0317
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            14904
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.681
_diffrn_reflns_theta_min         3.687
_diffrn_standards_decay_%        nil
_exptl_absorpt_coefficient_mu    4.062
_exptl_absorpt_correction_T_max  1.00
_exptl_absorpt_correction_T_min  0.56
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'ABSPACK(CrysAlis, Oxford Diffraction)'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.587
_exptl_crystal_description       block
_exptl_crystal_F_000             2440
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.315
_refine_diff_density_min         -0.695
_refine_diff_density_rms         0.153
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     384
_refine_ls_number_reflns         4794
_refine_ls_number_restraints     92
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0854
_refine_ls_R_factor_gt           0.0787
_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^)+(0.1725P)^2^+10.8258P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2222
_refine_ls_wR_factor_ref         0.2336
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4245
_reflns_number_total             4794
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6sc03028a2.cif
_cod_data_source_block           ns1
_cod_depositor_comments          'Adding full bibliography for 1544969.cif.'
_cod_database_code               1544969
_olex2_refinement_description
;

The hydrazide group on the pyridyl was modelled as disordered over two positions.
The occupancy was originally linked to a free variable  but this settled at 50: 50
and was fixed at this for the rest of the refinement.
The amide hydrogen of these hydrazide groups was placed at a calculated position
using AFIX 43. The two hydrogens on the terminal NH2 were locate in a difference
map and refined with DFIX and DANG restraints and given thermal parameters of
1.2 times the equivalent isotropic displacement parameter of the nitrogen to which 
they are attached. 

The PF6 was modelled as disordered about the central meridian and refined to 
an occupancy of 65:35 major to minor.

There were several molecules of dioxane in the crystal. These were very disordered.
Dioxane O20-C25 was modelled at half occupancy. Dioxane O20A-C25A was modelled 
at 0.25 occupancy and was situated roughly on the same position as dioxane O20-C25.
Dioxane O20B-C25B was disordered about a two fold axis and so was refined at half 
occupancy under a PART -1 in Shelxl.
No hydrogens were placed on the minor component dioxane O20A-C25A but these 
were included in the formula for completeness.

Many DFIX, DANG and SIMU restraints were used to give these disordered 
components reasonable bond lengths, bond angles and thermal parameters.
All the disordered dioxanes were refined isotropically.

1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
2. Restrained distances
 O20B-C21B = C21B-C22B = C22B-O23B = O23B-C24B = C24B-C25B = C25B-O20B
 1.35 with sigma of 0.02
 O20-C21 = C21-C22 = C22-O23 = O23-C24 = C24-C25 = C25-O20
 1.35 with sigma of 0.02
 P10-F13A = P10-F14A = P10-F15A = P10-F16A
 1.6 with sigma of 0.02
 C25A-C24A = C24A-O23A = O23A-C22A = C22A-C21A = C21A-O20A = O20A-C25A
 1.35 with sigma of 0.02
 O23A-C21A
 -2.1 with sigma of 0.02
 N21A-H21D = N21A-H21C = N21-H21A = N21-H21B
 1 with sigma of 0.008
 H21C-H21D = H21A-H21B
 1.6 with sigma of 0.04
 N20-H21B = N20-H21A
 1.9 with sigma of 0.04
 F11-F13A = F11-F14A = F11-F15A = F11-F16A
 2.26 with sigma of 0.04
 F12-F13A = F12-F14A = F12-F15A = F12-F16A
 2.26 with sigma of 0.04
3. Rigid bond restraints
 F11, F12, F13, F14, F15, F16, F13A, F14A, F15A, F16A
 with sigma for 1-2 distances of 0.0008 and sigma for 1-3 distances of 0.0008
4. Uiso/Uaniso restraints and constraints
C25A \\sim C24A \\sim O23A \\sim C22A \\sim C21A \\sim O20A: within 1.7A with
sigma of 0.02 and sigma for terminal atoms of 0.016
O20B \\sim C21B \\sim C22B \\sim O23B \\sim C24B \\sim C25B: within 1.7A with
sigma of 0.002 and sigma for terminal atoms of 0.016
F11 \\sim F12 \\sim F13 \\sim F14 \\sim F15 \\sim F16 \\sim F13A \\sim F14A
\\sim F15A \\sim F16A: within 1.7A with sigma of 0.008 and sigma for terminal
atoms of 0.016
5. Others
 Sof(F13A)=Sof(F14A)=Sof(F15A)=Sof(F16A)=1-FVAR(1)
 Sof(F13)=Sof(F14)=Sof(F15)=Sof(F16)=FVAR(1)
 Fixed Sof: O19(0.5) C19(0.5) N20(0.5) H20(0.5) N21(0.5) H21A(0.5) H21B(0.5)
 O19A(0.5) C19A(0.5) N20A(0.5) H20A(0.5) N21A(0.5) H21C(0.5) H21D(0.5) O20(0.5)
 C21(0.5) H21E(0.5) H21F(0.5) C22(0.5) H22A(0.5) H22B(0.5) O23(0.5) C24(0.5)
 H24A(0.5) H24B(0.5) C25(0.5) H25A(0.5) H25B(0.5) C25A(0.25) H25C(0.25)
 H25D(0.25) C24A(0.25) H24C(0.25) H24D(0.25) O23A(0.25) C22A(0.25) H22C(0.25)
 H22D(0.25) C21A(0.25) H21G(0.25) H21H(0.25) O20A(0.25) O20B(0.5) C21B(0.5)
 H21I(0.5) H21J(0.5) C22B(0.5) H22E(0.5) H22F(0.5) O23B(0.5) C24B(0.5)
 H24E(0.5) H24F(0.5) C25B(0.5) H25E(0.5) H25F(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C21(H21E,H21F), C22(H22A,H22B), C24(H24A,H24B), C25(H25A,H25B), C25A(H25C,
 H25D), C24A(H24C,H24D), C22A(H22C,H22D), C21A(H21G,H21H), C21B(H21I,H21J),
 C22B(H22E,H22F), C24B(H24E,H24F), C25B(H25E,H25F)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11), C14(H14),
 C15(H15), C17(H17), C18(H18), N20(H20), N20A(H20A)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'