A new supramolecular bonding motif involving NH bonds of ammonium salts and macrocycles derived from platinum corners and butadiynediyl linkers
Collins, Brenna K.; Bhuvanesh, Nattamai; Gladysz, John A.; Dalton Transactions  (2022) –; doi:10.1039/D2DT02680E

data_7711522
_publ_section_title
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 A new supramolecular bonding motif involving NH bonds of ammonium salts
 and macrocycles derived from platinum corners and butadiynediyl linkers
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT02680E
_journal_year                    2022
_chemical_formula_moiety
'C132 H114 P8 Pt4, 1.012(I), 1.62(C H2 Cl2), C4 H12 N'
_chemical_formula_sum            'C137.62 H129.24 Cl3.24 I1.01 N P8 Pt4'
_chemical_formula_weight         3068.45
_space_group_crystal_system      trigonal
_space_group_IT_number           147
_space_group_name_Hall           '-P 3'
_space_group_name_H-M_alt        'P -3'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-09-24
_audit_creation_method
;
Olex2 1.5
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6396)
;
_audit_update_record
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2022-06-30 deposited with the CCDC.	2022-09-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   35.0101(8)
_cell_length_b                   35.0101(8)
_cell_length_c                   21.4586(5)
_cell_measurement_reflns_used    9830
_cell_measurement_temperature    110.0
_cell_measurement_theta_max      24.974
_cell_measurement_theta_min      2.227
_cell_volume                     22778.2(9)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      110.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker Quest (PHOTON III)'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0807
_diffrn_reflns_av_unetI/netI     0.0291
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       41
_diffrn_reflns_limit_h_min       -41
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            528742
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.019
_diffrn_reflns_theta_max         25.019
_diffrn_reflns_theta_min         1.777
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.061
_exptl_absorpt_correction_T_max  0.4286
_exptl_absorpt_correction_T_min  0.2722
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1137 before and 0.0654 after correction.
The Ratio of minimum to maximum transmission is 0.6351.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.342
_exptl_crystal_description       block
_exptl_crystal_F_000             9016
_exptl_crystal_size_max          0.049
_exptl_crystal_size_mid          0.034
_exptl_crystal_size_min          0.021
_refine_diff_density_max         2.107
_refine_diff_density_min         -1.103
_refine_diff_density_rms         0.151
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1445
_refine_ls_number_reflns         26831
_refine_ls_number_restraints     336
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0732
_refine_ls_R_factor_gt           0.0506
_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^)+(0.0679P)^2^+176.0349P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1286
_refine_ls_wR_factor_ref         0.1481
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20621
_reflns_number_total             26831
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02680e2.cif
_cod_data_source_block           bciii57a4
_cod_original_cell_volume        22778.1(12)
_cod_database_code               7711522
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.920
_shelx_estimated_absorpt_t_min   0.826
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl2-C1A = Cl3-C1A
 1.771 with sigma of 0.01
 Cl1-C1B = Cl4-C1B
 1.771 with sigma of 0.01
 Cl3-C1A = Cl2-C1A
 1.77 with sigma of 0.02
 Cl5-C1D = Cl6-C1D
 1.771 with sigma of 0.01
 Cl2-Cl3
 2.916 with sigma of 0.03
 Cl1-Cl4
 2.916 with sigma of 0.03
 Cl5-Cl6
 2.916 with sigma of 0.03
 C1E-C1F = C1G-C1H
 1.51 with sigma of 0.02
 C1F-N6 = C1G-N6
 1.49 with sigma of 0.02
 C1F-C1G = C1E-N6
 2.5 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Cl2 \\sim Cl3 \\sim C1A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Cl1 \\sim Cl4 \\sim C1B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Cl5 \\sim Cl6 \\sim C1D: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
N6 \\sim C1E \\sim C1F \\sim C1G \\sim C1H: within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01 within 2A
C52 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim C51: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C36 \\sim C41 \\sim C40 \\sim C38 \\sim C39 \\sim C37: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C29 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C1A) = Uanis(C1B)
4. Rigid body (RIGU) restrains
 Cl2, Cl3, C1A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl1, Cl4, C1B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl5, Cl6, C1D
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N6, C1E, C1F, C1G, C1H
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C52, C47, C48, C49, C50, C51
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C36, C41, C40, C38, C39, C37
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C29, C24, C25, C26, C27, C28
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 1*[Sof(I4)]+1*[Sof(I2)]+1*[Sof(I5)]+1*[Sof(I3)]=0.66667 with esd of 0.005
 Sof(Cl1)=Sof(Cl4)=Sof(C1B)=Sof(H1Ba)=Sof(H1Bb)=1-FVAR(1)
 Sof(Cl2)=Sof(Cl3)=Sof(C1A)=Sof(H1Aa)=Sof(H1Ab)=FVAR(1)
 Fixed Sof: Cl5(0.62) Cl6(0.62) C1D(0.62) H1Da(0.62) H1Db(0.62)
6.a Free rotating group:
 Cl1(Cl4,C1B), Cl5(Cl6,C1D)
6.b Secondary CH2 refined with riding coordinates:
 C13(H13a,H13b), C15(H15a,H15b), C42(H42a,H42b), C44(H44a,H44b), C71(H71a,
 H71b), C73(H73a,H73b), C100(H10a,H10b), C102(H10c,H10d), C1B(H1Ba,H1Bb),
 C1A(H1Aa,H1Ab), C1D(H1Da,H1Db), N6(H6a,H6b), C1F(H1Fa,H1Fb), C1G(H1Ga,H1Gb)
6.c Me refined with riding coordinates:
 C1E(H1Ea,H1Eb,H1Ec), C1H(H1Ha,H1Hb,H1Hc)
6.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12),
 C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C25(H25), C26(H26), C27(H27),
  C28(H28), C29(H29), C31(H31), C32(H32), C33(H33), C34(H34), C35(H35),
 C37(H37), C48(H48), C49(H49), C50(H50), C51(H51), C52(H52), C54(H54), C55(H55),
  C56(H56), C57(H57), C58(H58), C60(H60), C61(H61), C62(H62), C63(H63),
 C64(H64), C66(H66), C67(H67), C68(H68), C69(H69), C70(H70), C77(H77), C78(H78),
  C79(H79), C80(H80), C81(H81), C83(H83), C84(H84), C85(H85), C86(H86),
 C87(H87), C89(H89), C90(H90), C91(H91), C92(H92), C93(H93), C95(H95), C96(H96),
  C97(H97), C98(H98), C99(H99), C106(H106), C107(H107), C108(H108), C109(H109),
 C110(H110), C112(H112), C113(H113), C114(H114), C115(H115), C116(H116)
6.e Fitted hexagon refined as free rotating group:
 C36(C37,C38,C39,C40,C41)
6.f Idealised Me refined as rotating group:
 C16(H16a,H16b,H16c), C17(H17a,H17b,H17c), C45(H45a,H45b,H45c), C46(H46a,H46b,
 H46c), C74(H74a,H74b,H74c), C75(H75a,H75b,H75c), C103(H10e,H10f,H10g),
 C104(H10h,H10i,H10j)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 401 electrons were 
found in a volume of 4447\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
1.5[CH2Cl2], 0.5[H2O] per Asymmetric Unit 
which account for 408 electrons 
per unit cell.

Data were collected on several crystals from different
batches using both Cu and Mo sources (depending on the
quality and size of the crystals, we here report 
our best structure model collected using Mo source). All the structure
models indicate the presence of diethylammonium
ion occupying the void created by the Pt4 complex. 
However, we found clear presence of only one location
for I (viz., I1) occupying special position (1/3,2/3,0.199)
with an occupancy of 0.3333. Our elemental analysis clearly
confirmed the presence of full iodine. Thus we have distributed
I at some of the residual electron density peaks with a
restraint set to add-up the total occupancy of I to 1.
Our Fourier difference maps showed several additional residual 
electron density peaks near disorded iodine suggesting 
the presence of partially occupied and or disordered solvent.
At this point we had the following reliability factors 
R1 - 5.81 and wR2 19.07. We used Olex2 to mask the latter solvent
molecules which decreased the reliability factors significantly
R1 - 5.06 and wR2 14.81.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              33744
_shelx_hkl_checksum              87985
_shelx_fab_checksum              64700
_olex2_submission_special_instructions 'No special instructions were received'