Structural characterization and gas-phase studies of the [Ag10H8(L)6]2+ nanocluster dication
Ma, Howard Z.; McKay, Alasdair I.; Mravak, Antonija; Scholz, Michael S.; White, Jonathan M.; Mulder, Roger J.; Bieske, Evan J.; Bonačić-Koutecký, Vlasta; O'Hair, Richard A. J.; Nanoscale  (2019) –; doi:10.1039/C9NR08321A

data_1556090
_publ_section_title
;
 Structural characterization and gas-phase studies of the [Ag10H8(L)6]2+
 nanocluster dication
;
_journal_name_full               Nanoscale
_journal_paper_doi               10.1039/C9NR08321A
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety
'C144 H126 Ag10 N6 P12, 2(C2 H3 N), C4 H10 O, C2 N, 2(N O3), 2.5(O)'
_chemical_formula_sum            'C154 H142 Ag10 N11 O9.5 P12'
_chemical_formula_weight         3749.12
_chemical_name_systematic        '[Ag10H8(dppa)6](NO3)2'
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Heat-sensitive,Oxygen-sensitive,Photo-sensitive
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-05-29 deposited with the CCDC.	2019-11-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.53950(10)
_cell_length_b                   24.44690(10)
_cell_length_c                   38.1398(2)
_cell_measurement_reflns_used    65220
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.7560
_cell_measurement_theta_min      3.2290
_cell_volume                     15421.43(14)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.984
_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     49.00  74.00   0.50    0.50    --   48.30  79.00 -17.00   50
  2  \w     89.00 154.00   0.50    2.00    --  107.75  79.00 -17.00  130
  3  \w    153.00 178.00   0.50    2.00    --  107.75  45.00 -90.00   50
  4  \w    100.00 162.00   0.50    2.00    --  107.75  45.00 -60.00  124
  5  \w    107.00 139.00   0.50    2.00    --  107.75  45.00 -90.00   64
  6  \w     98.00 177.00   0.50    2.00    --  107.75  15.00 -90.00  158
  7  \w     70.00 129.00   0.50    2.00    --  107.75 -79.00-142.00  118
  8  \w     50.00  76.00   0.50    2.00    --  107.75 -45.00-150.00   52
  9  \w     36.00  77.00   0.50    2.00    --  107.75 -45.00-120.00   82
 10  \w     39.00  77.00   0.50    2.00    --  107.75 -45.00 -90.00   76
 11  \w     46.00 100.00   0.50    2.00    --  107.75 -94.00 -30.00  108
 12  \w     48.00  77.00   0.50    2.00    --  107.75 -45.00  30.00   58
 13  \w     68.00  93.00   0.50    2.00    --  107.75 -61.00  60.00   50
 14  \w    120.00 173.00   0.50    2.00    --  107.75  15.00 150.00  106
 15  \w     46.00  93.00   0.50    2.00    --  107.75 -61.00  90.00   94
 16  \w     39.00  96.00   0.50    2.00    --  107.75 -61.00   0.00  114
 17  \w     42.00  68.00   0.50    2.00    --  107.75 -30.00   0.00   52
 18  \w     39.00  65.00   0.50    2.00    --  107.75 -30.00 -60.00   52
 19  \w     36.00  73.00   0.50    2.00    --  107.75 -45.00   0.00   74
 20  \w     35.00  66.00   0.50    2.00    --  107.75 -30.00  60.00   62
 21  \w     -4.00  37.00   0.50    0.50    --   48.30 -79.00-142.00   82
 22  \w     37.00  63.00   0.50    2.00    --  107.75 -30.00-180.00   52
 23  \w     45.00  70.00   0.50    2.00    --  107.75 -45.00-180.00   50
 24  \w    -70.00  24.00   0.50    0.50    --  -48.30  79.00 -17.00  188
 25  \w    -59.00 -16.00   0.50    2.00    --  -86.25  45.00-180.00   86
 26  \w    -86.00 -61.00   0.50    2.00    --  -86.25  79.00 -17.00   50
 27  \w    -99.00 -67.00   0.50    0.50    --  -48.30 -79.00-142.00   64
 28  \w   -119.00 -87.00   0.50    0.50    --  -48.30-125.00-180.00   64
 29  \w   -135.00-110.00   0.50    2.00    --  -86.25 -79.00-142.00   50
 30  \w   -119.00 -83.00   0.50    0.50    --  -48.30-125.00  30.00   72
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0695
_diffrn_reflns_av_unetI/netI     0.0465
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       48
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            133405
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.454
_diffrn_reflns_theta_min         3.226
_exptl_absorpt_coefficient_mu    11.602
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.16830
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.615
_exptl_crystal_description       prism
_exptl_crystal_F_000             7476
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile and diethyl ether'
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.04
_refine_diff_density_max         2.195
_refine_diff_density_min         -1.471
_refine_diff_density_rms         0.142
_refine_ls_abs_structure_details
;
 Flack x determined using 12742 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.017(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1940
_refine_ls_number_reflns         32323
_refine_ls_number_restraints     577
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0526
_refine_ls_R_factor_gt           0.0486
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0893P)^2^+25.0396P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1330
_refine_ls_wR_factor_ref         0.1368
_reflns_Friedel_coverage         0.846
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.965
_reflns_number_gt                29891
_reflns_number_total             32323
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9nr08321a2.cif
_cod_data_source_block           am004
_cod_original_formula_sum        'C154 H142 Ag10 N11 O9.50 P12'
_cod_database_code               1556090
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.654
_shelx_estimated_absorpt_t_min   0.293
_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. Shared sites
{O9A, N9}
{O9, N12}
3. Restrained distances
 C151-N10
 1.137 with sigma of 0.01
 C151-C152
 1.456 with sigma of 0.01
 C152-N10
 2.593 with sigma of 0.02
 C153-C154 = C1H-C1A
 1.456 with sigma of 0.01
 C149-N9
 1.137 with sigma of 0.01
 C149-C150
 1.456 with sigma of 0.01
 C150-N9
 2.593 with sigma of 0.02
 N8-O6 = N8-O5 = N8-O4
 1.24586 with sigma of 0.01
 O6-O5 = O5-O4 = O4-O6
 2.1579 with sigma of 0.02
 N7A-O1A = N7A-O3A = N7A-O2A
 1.24586 with sigma of 0.01
 O1A-O3A = O3A-O2A = O2A-O1A
 2.1579 with sigma of 0.02
 N7-O2 = N7-O3 = N7-O1
 1.24586 with sigma of 0.01
 O2-O3 = O3-O1 = O1-O2
 2.1579 with sigma of 0.02
 C155-N12
 1.137 with sigma of 0.01
 C155-C156
 1.456 with sigma of 0.01
 C156-N12
 2.593 with sigma of 0.02
 N8A-O4A = N8A-O6A = N8A-O5A
 1.24586 with sigma of 0.01
 O4A-O6A = O6A-O5A = O5A-O4A
 2.1579 with sigma of 0.02
 C153-N11 = C1H-N11
 1.137 with sigma of 0.01
 C154-N11 = C1A-N11
 2.593 with sigma of 0.02
 C146-C145 \\sim C147-C148
 with sigma of 0.02
 O10-C145 \\sim O10-C147
 with sigma of 0.02
 C146-O10 \\sim O10-C148
 with sigma of 0.04
 C131-C132 \\sim C132-C127 \\sim C127-C128 \\sim C128-C129 \\sim C129-C130
\\sim C130-C131
 with sigma of 0.02
 C131-C129 \\sim C131-C129 \\sim C128-C132 \\sim C128-C130 \\sim C130-C132
\\sim C129-C127
 with sigma of 0.04
 C1B-C1C \\sim C1C-C1D \\sim C1D-C1E \\sim C1E-C1F \\sim C1F-C1G \\sim C1G-C1B
 with sigma of 0.02
 C1B-C1F \\sim C1B-C1F \\sim C1E-C1C \\sim C1E-C1G \\sim C1G-C1C \\sim C1F-C1D
 with sigma of 0.04
 P11-C1F \\sim P11-C127
 with sigma of 0.02
4. Restrained planarity
 N8, O6, O5, O4
 with sigma of 0.1
 N7A, O1A, O3A, O2A
 with sigma of 0.1
 N7, O2, O3, O1
 with sigma of 0.1
 N8A, O4A, O6A, O5A
 with sigma of 0.1
 C131, C132, C127, C128, C129, C130
 with sigma of 0.1
 C1B, C1C, C1D, C1E, C1F, C1G
 with sigma of 0.1
5. Rigid bond restraints
 N8, O6, O5, O4, N8A, O4A, O6A, O5A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Uiso/Uaniso restraints and constraints
N10 \\sim C151 \\sim C152: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
O10 \\sim C146 \\sim C145 \\sim C147 \\sim C148: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08
N8 \\sim O6 \\sim O5 \\sim O4: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
N9 \\sim C149 \\sim C150: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
N7A \\sim O1A \\sim O3A \\sim O2A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
N7 \\sim O2 \\sim O3 \\sim O1: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
N12 \\sim C155 \\sim C156: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
N8A \\sim O4A \\sim O6A \\sim O5A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C131 \\sim C132 \\sim C127 \\sim C128 \\sim C129 \\sim C130: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C1B \\sim C1C \\sim C1D \\sim C1E \\sim C1F \\sim C1G: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
N11 \\sim C153 \\sim C154: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
N11 \\sim C1H \\sim C1A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
Uanis(N8A) \\sim Ueq, Uanis(O4A) \\sim Ueq, Uanis(O6A) \\sim Ueq, Uanis(O5A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O9A) = Uanis(N9)
Uanis(O9) = Uanis(N12)
7. Rigid body (RIGU) restrains
 N10, C151, C152
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O10, C146, C145, C147, C148
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N8, O6, O5, O4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N9, C149, C150
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N7A, O1A, O3A, O2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N7, O2, O3, O1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N12, C155, C156
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N8A, O4A, O6A, O5A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C131, C132, C127, C128, C129, C130
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1B, C1C, C1D, C1E, C1F, C1G
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N11, C153, C154
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N11, C1H, C1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
8. Others
 Sof(C1B)=Sof(H12A)=Sof(C1C)=Sof(H13A)=Sof(C1D)=Sof(H13B)=Sof(C1E)=Sof(H13C)=
 Sof(C1F)=Sof(C1G)=Sof(H12B)=1-FVAR(1)
 Sof(C131)=Sof(H131)=Sof(C132)=Sof(H132)=Sof(C127)=Sof(C128)=Sof(H128)=
 Sof(C129)=Sof(H129)=Sof(C130)=Sof(H130)=FVAR(1)
 Sof(C153)=Sof(C154)=1-FVAR(2)
 Sof(C1A)=Sof(C1H)=FVAR(2)
 Fixed Sof: N8(0.6) O6(0.6) O5(0.6) O4(0.6) N9(0.5) C149(0.5) C150(0.5)
 H15D(0.5) H15E(0.5) H15F(0.5) N7A(0.4) O1A(0.4) O3A(0.4) O2A(0.4) N7(0.6)
 O2(0.6) O3(0.6) O1(0.6) N12(0.5) C155(0.5) C156(0.5) H15G(0.5) H15H(0.5)
 H15I(0.5) N8A(0.4) O4A(0.4) O6A(0.4) O5A(0.4) O9(0.5) O8(0.5) O9A(0.5)
9.a Secondary CH2 refined with riding coordinates:
 C145(H14D,H14E), C147(H14F,H14G)
9.b Me refined with riding coordinates:
 C148(H14H,H14I,H14J), C150(H15D,H15E,H15F), C156(H15G,H15H,H15I)
9.c Aromatic/amide H refined with riding coordinates:
 N3(H3), N4(H4), N1(H1), C18(H18), N2(H2), N5(H5), N6(H6), C92(H92), C65(H65),
 C48(H48), C16(H16), C134(H134), C126(H126), C140(H140), C116(H116), C110(H110),
  C104(H104), C17(H17), C63(H63), C96(H96), C122(H122), C123(H123), C144(H144),
 C124(H124), C44(H44), C62(H62), C64(H64), C135(H135), C136(H136), C80(H80),
 C74(H74), C105(H105), C100(H100), C84(H84), C111(H111), C112(H112), C98(H98),
 C86(H86), C56(H56), C138(H138), C66(H66), C101(H101), C114(H114), C99(H99),
 C87(H87), C15(H15), C90(H90), C28(H28), C102(H102), C40(H40), C142(H142),
 C68(H68), C22(H22), C83(H83), C14(H14), C137(H137), C75(H75), C57(H57),
 C36(H36), C35(H35), C107(H107), C141(H141), C125(H125), C45(H45), C117(H117),
 C59(H59), C76(H76), C12(H12), C88(H88), C108(H108), C50(H50), C93(H93),
 C41(H41), C58(H58), C77(H77), C113(H113), C69(H69), C60(H60), C81(H81),
 C51(H51), C23(H23), C143(H143), C106(H106), C39(H39), C72(H72), C95(H95),
 C47(H47), C42(H42), C118(H118), C46(H46), C38(H38), C52(H52), C11(H11),
 C82(H82), C2(H2A), C78(H78), C6(H6A), C53(H53), C5(H5A), C32(H32), C54(H54),
 C9(H9), C120(H120), C119(H119), C71(H71), C24(H24), C8(H8), C89(H89), C10(H10),
  C4(H4A), C94(H94), C70(H70), C34(H34), C26(H26), C27(H27), C21(H21), C29(H29),
  C30(H30), C20(H20), C3(H3A), C33(H33), C131(H131), C132(H132), C128(H128),
 C129(H129), C130(H130), C1B(H12A), C1C(H13A), C1D(H13B), C1E(H13C), C1G(H12B)
9.d Idealised Me refined as rotating group:
 C152(H15A,H15B,H15C), C146(H14A,H14B,H14C)
;
_shelx_res_checksum              94176
_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
;