Pyridine dicarbanion-bonded Ag<sub>13</sub> organometallic nanoclusters: synthesis and on-surface oxidative coupling reaction.
Li, Cui-Cui; Zhang, Siqi; Tang, Jian; Jian, Ruijun; Xia, Yu; Zhao, Liang; Chemical science 13 (2022) 8095–8103; doi:10.1039/d2sc00989g

data_1567112
_publ_section_title
;
 Pyridine dicarbanion-bonded Ag<sub>13</sub> organometallic nanoclusters:
 synthesis and on-surface oxidative coupling reaction.
;
_journal_issue                   27
_journal_name_full               'Chemical science'
_journal_page_first              8095
_journal_page_last               8103
_journal_paper_doi               10.1039/d2sc00989g
_journal_volume                  13
_journal_year                    2022
_chemical_formula_moiety
'0.5(C57 H58 Ag5 F3 N17 O3 S), 0.5(C57 H56 Ag5 F3 N17 O3 S), 2(C F3 O3 S)'
_chemical_formula_sum            'C59 H57 Ag5 F9 N17 O9 S3'
_chemical_formula_weight         1954.74
_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
_audit_creation_date             2021-01-04
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2021-02-10 deposited with the CCDC.	2022-06-13 downloaded from the CCDC.
;
_cell_angle_alpha                84.932(2)
_cell_angle_beta                 76.949(2)
_cell_angle_gamma                73.121(2)
_cell_formula_units_Z            4
_cell_length_a                   14.8014(4)
_cell_length_b                   22.3158(5)
_cell_length_c                   24.8300(6)
_cell_measurement_reflns_used    12185
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      69.2180
_cell_measurement_theta_min      3.6470
_cell_volume                     7643.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2137
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.970
_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    -92.00 -10.00   1.00   15.00    --  -40.81 125.00 120.00   82
  2  \w     -8.00  27.00   1.00   15.00    --  -40.81  38.00-180.00   35
  3  \w    -64.00 -38.00   1.00   15.00    --  -40.81  38.00-180.00   26
  4  \w   -106.00 -16.00   1.00   15.00    --  -40.81 -38.00-120.00   90
  5  \w    -65.00  33.00   1.00   15.00    --  -40.81  38.00  60.00   98
  6  \w     81.00 114.00   1.00   30.00    --   96.56-125.00  60.00   33
  7  \w     46.00 104.00   1.00   30.00    --   96.56 -95.00 120.00   58
  8  \w     27.00 116.00   1.00   30.00    --   96.56-125.00 -90.00   89
  9  \w    103.00 162.00   1.00   30.00    --   96.56  77.00 -30.00   59
 10  \w     67.00  92.00   1.00   30.00    --   96.56  77.00 -30.00   25
 11  \w    117.00 150.00   1.00   30.00    --   96.56 125.00  30.00   33
 12  \w     75.00 169.00   1.00   30.00    --   96.56  30.00  60.00   94
 13  \w     71.00 168.00   1.00   30.00    --   96.56  45.00 120.00   97
 14  \w     25.00 119.00   1.00   30.00    --   96.56 -61.00 -30.00   94
 15  \w    118.00 160.00   1.00   30.00    --   96.56 125.00 -60.00   42
 16  \w     24.00  99.00   1.00   30.00    --   96.56-126.00 -21.00   75
 17  \w    106.00 146.00   1.00   30.00    --   96.56 125.00 -90.00   40
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0466771000
_diffrn_orient_matrix_UB_12      0.0112916000
_diffrn_orient_matrix_UB_13      -0.0606579000
_diffrn_orient_matrix_UB_21      -0.0839250000
_diffrn_orient_matrix_UB_22      -0.0138503000
_diffrn_orient_matrix_UB_23      -0.0189676000
_diffrn_orient_matrix_UB_31      -0.0561612000
_diffrn_orient_matrix_UB_32      0.0699164000
_diffrn_orient_matrix_UB_33      0.0044326000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0571
_diffrn_reflns_av_unetI/netI     0.0831
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            52675
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.344
_diffrn_reflns_theta_min         3.656
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.587
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71634
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_density_diffrn    1.699
_exptl_crystal_description       block
_exptl_crystal_F_000             3864
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.295
_refine_diff_density_min         -1.862
_refine_diff_density_rms         0.121
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1936
_refine_ls_number_reflns         27744
_refine_ls_number_restraints     127
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0878
_refine_ls_R_factor_gt           0.0591
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0402P)^2^+21.4544P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1229
_refine_ls_wR_factor_ref         0.1376
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19864
_reflns_number_total             27744
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00989g2.cif
_cod_data_source_block           ca-49_sq
_cod_depositor_comments
'Adding full bibliography for 1567108--1567115.cif.'
_cod_database_code               1567112
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H O N Ag S F'
_shelx_estimated_absorpt_t_max   0.801
_shelx_estimated_absorpt_t_min   0.595
_reflns_odcompleteness_completeness 99.79
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C52-N5
 1.38 with sigma of 0.02
 C05C-C29 = C27-C99 = C29-C27
 1.5 with sigma of 0.02
 C05C-C27 = C29-C99
 2.2 with sigma of 0.02
 S1-O4 \\sim S1-O2 \\sim S1-O1 \\sim S1-O9 \\sim S1-O3
 with sigma of 0.02
 O1-O3 \\sim O2-O1 \\sim O3-O2 \\sim O1-O9 \\sim O4-O1 \\sim O9-O4
 with sigma of 0.02
 C7-O3 \\sim C7-O2 \\sim C7-O1
 with sigma of 0.02
 C20-O4 \\sim C20-O9 \\sim C20-O1
 with sigma of 0.02
 C20-F2 \\sim C20-F3 \\sim C20-F4 \\sim C7-F1 \\sim C7-F2 \\sim C7-F3
 with sigma of 0.02
 F2-F3 \\sim F4-F2 \\sim F3-F4 \\sim F1-F2 \\sim F3-F1 \\sim F2-F3
 with sigma of 0.02
 S1-F1 \\sim S1-F2 \\sim S1-F3 \\sim S1-F4
 with sigma of 0.02
3. Rigid bond restraints
 C99, C27, C29, C05C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O05S, S01T, O05F, O7
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C99 \\sim C27 \\sim C29 \\sim C05C: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
O05S \\sim S01T \\sim O05F \\sim O7: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Uanis(O4) \\sim Ueq, Uanis(O9) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
5. Others
 Sof(N03O)=Sof(C0)=Sof(C05V)=Sof(H05V)=Sof(C04Y)=Sof(H04Y)=Sof(C18A)=Sof(H18A)=
 Sof(C52A)=Sof(N5A)=Sof(C0AB)=Sof(H0AD)=Sof(H0AE)=Sof(H0AF)=1-FVAR(1)
 Sof(N03N)=Sof(C057)=Sof(C05U)=Sof(H05U)=Sof(C04X)=Sof(H04X)=Sof(C18)=Sof(H18)=
 Sof(C52)=Sof(N5)=Sof(C0AA)=Sof(H0AA)=Sof(H0AB)=Sof(H0AC)=FVAR(1)
 Fixed Sof: C7(0.66667) F1(0.66667) F4(0.33333) C20(0.33333) O3(0.66667)
 O2(0.66667) O4(0.33333) O9(0.33333)
6.a Secondary CH2 refined with riding coordinates:
 C058(H05D,H05E), C05P(H05F,H05G), C27(H27A,H27B), C29(H29A,H29B)
6.b Aromatic/amide H refined with riding coordinates:
 N01E(H01E), C020(H020), C021(H021), C027(H027), C02A(H02A), C02C(H02C),
 C02E(H02E), C02I(H02I), C02K(H02K), C02O(H02O), C02P(H02P), C02Q(H02Q),
 C02R(H02R), C02S(H02S), C02T(H02T), C02U(H02U), C02V(H02V), C02W(H02W),
 C031(H031), C032(H032), C037(H037), C038(H038), C03E(H03E), C03I(H03I),
 C03K(H03K), C03L(H03L), C03M(H03M), C05U(H05U), C04X(H04X), C18(H18),
 C03P(H03P), C03R(H03R), C03U(H03U), C03V(H03V), C03W(H03W), C03Z(H03Z),
 C044(H044), C048(H048), C049(H049), C04B(H04V), C04H(H04Z), C04K(H04K),
 C04L(H04L), C04P(H04P), C04R(H2), C04W(H04W), C04Z(H3), C05H(H05H), C05J(H05J),
  C05M(H05M), C05N(H05N), C12(H12), C05V(H05V), C04Y(H04Y), C18A(H18A)
6.c Fitted hexagon refined as free rotating group:
 N03N(C057,C05U,C04X,C18,C52), N03O(C0,C05V,C04Y,C18A,C52A)
6.d Idealised Me refined as rotating group:
 C02J(H02B,H02D,H02F), C02M(H02G,H02H,H02J), C02Z(H02L,H02M,H02N), C039(H03A,
 H03B,H03C), C03H(H03D,H03F,H03G), C03O(H03H,H03J,H03N), C042(H04A,H04B,H04C),
 C045(H04D,H04E,H04F), C04A(H04S,H04T,H04U), C04I(H04G,H04H,H04I), C04J(H04,H,
 HA), C04N(H04J,H04M,H04N), C04O(H1,HB,HC), C04S(H04O,H04Q,H04R), C05B(H05A,
 H05B,H05C), C05R(H05I,H05K,H05L), C0AA(H0AA,H0AB,H0AC), C99(H99A,H99B,H99C),
 C0AB(H0AD,H0AE,H0AF)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              41220
_shelx_fab_checksum              34756
_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 2.134
_oxdiff_exptl_absorpt_empirical_full_min 0.755