Phosphorus guiding palladium: [4+4] metallomacrocyclic PdII complex and self-assembly of heterometallic PdII/ZnII grid-type complex
Clauss, Reike; Hey-Hawkins, Evamarie; Dalton Transactions  (2022) –; doi:10.1039/D2DT01176J

data_7710389
_publ_section_title
;
 Phosphorus guiding palladium: [4+4] metallomacrocyclic PdII complex and
 self-assembly of heterometallic PdII/ZnII grid-type complex
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT01176J
_journal_year                    2022
_chemical_formula_moiety
'5(C H2 Cl2), C124 H112 N28 P4 Pd2 Zn2, 8(C F3 O3 S), 5(C2 H3 N)'
_chemical_formula_sum            'C150 H142 Cl12 F24 N34 O24 P4 Pd2 S8 Zn2'
_chemical_formula_weight         4410.27
_chemical_name_systematic        '[Pd2Zn2(1)4](OTf)8'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-03-28
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-04-20 deposited with the CCDC.	2022-05-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.9460(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.2836(3)
_cell_length_b                   25.6217(3)
_cell_length_c                   39.2969(6)
_cell_measurement_reflns_used    78722
_cell_measurement_temperature    180
_cell_measurement_theta_max      70.99
_cell_measurement_theta_min      3.45
_cell_volume                     18273.8(5)
_computing_cell_refinement       'X-Area Recipe 1.36.0.0 (STOE, 2020)'
_computing_data_collection       'X-Area Pilatus3_SV 1.31.170.0 (STOE, 2020)'
_computing_data_reduction
;
X-Area Integrate 1.78.3.0 (STOE, 2020)
X-Area LANA 1.83.8.0 (STOE, 2020)
;
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      180
_diffrn_detector                 Pilatus300K
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            'DECTRIS PILATUS 300K'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
 2199 frames, detector distance = 60 mm
;
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '0.5 mm diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_polarisn_norm  270
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54186
_diffrn_reflns_av_R_equivalents  0.0564
_diffrn_reflns_av_unetI/netI     0.0456
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            139978
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.686
_diffrn_reflns_theta_max         68.000
_diffrn_reflns_theta_min         3.450
_diffrn_source                   'GeniX 3D HF Cu'
_diffrn_source_current           0.600
_diffrn_source_power             0.030
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    5.513
_exptl_absorpt_correction_T_max  0.7570
_exptl_absorpt_correction_T_min  0.0149
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE X-Red32, absorption correction by Gaussian integration, analogous to
P. Coppens, "The Evaluation of Absorption and Extinction in Single-Crystal
Structure Analysis", published in: F. R. Ahmed (Editor), "Crystallographic
Computing", Munksgaard, Copenhagen (1970), 255 - 270. Afterwards scaling of
reflection intensities was performed within STOE LANA. J. Koziskova, F. Hahn,
J. Richter, J. Kozisek, Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136-140.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.603
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             8928
_exptl_crystal_recrystallization_method
'Vapour diffusion of CH2Cl2 into CH3CN solution'
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.660
_refine_diff_density_min         -1.173
_refine_diff_density_rms         0.121
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2579
_refine_ls_number_reflns         33201
_refine_ls_number_restraints     523
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.1218
_refine_ls_R_factor_gt           0.0926
_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^)+(0.1828P)^2^+29.8465P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2468
_refine_ls_wR_factor_ref         0.2792
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23389
_reflns_number_total             33201
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01176j2.cif
_cod_data_source_block           Pd2Zn2
_cod_database_code               7710389
_shelx_shelxl_version_number     2018/3
_extra_info
;
To avoid confusion: apostrophe labeled atom are not symmetry related. They are just labeled in comparison
to NMR labels and for clarity. CIF labeling differs from presented labeling in figures.
;
_shelx_estimated_absorpt_t_max   0.770
_shelx_estimated_absorpt_t_min   0.339
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C74-S6 = C75-S6A
 1.82 with sigma of 0.02
 C76-F13 = C76-F14 = C76-F15
 1.32 with sigma of 0.02
 S6-O7 = S6-O8 = S6-O9
 1.44 with sigma of 0.02
 C77-S4A
 1.82 with sigma of 0.02
 C79-F1A = C79-F2A = C79-F6A
 1.33 with sigma of 0.02
 C79-S1A
 1.82 with sigma of 0.02
 C78-S1
 1.82 with sigma of 0.02
 C85-S8
 1.82 with sigma of 0.02
 F13-F14 \\sim F14-F15 \\sim F15-F13
 with sigma of 0.04
 C76-F13 \\sim C76-F14 \\sim C76-F15
 with sigma of 0.02
 S4-O10 \\sim S4-O14 \\sim S4-O15
 with sigma of 0.02
 C70-Cl7 \\sim C70-Cl8
 with sigma of 0.02
 C77-F13A \\sim C77-F14A \\sim C77-F15A
 with sigma of 0.02
 C77-O10A \\sim C77-O14A \\sim C77-O15A
 with sigma of 0.04
 S4A-F13A \\sim S4A-F14A \\sim S4A-F15A
 with sigma of 0.04
 F13A-F14A \\sim F14A-F15A \\sim F15A-F13A
 with sigma of 0.04
 S4A-O10A \\sim S4A-O14A \\sim S4A-O15A
 with sigma of 0.02
 O10A-O14A \\sim O14A-O15A \\sim O10A-O15A
 with sigma of 0.04
 F1A-F2A \\sim F2A-F6A \\sim F6A-F1A
 with sigma of 0.04
 S1A-O1A \\sim S1A-O2A \\sim S1A-O3A
 with sigma of 0.02
 O1A-O2A \\sim O2A-O3A \\sim O1A-O3A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C73 \\sim F7A \\sim F8A \\sim F9A \\sim O4A \\sim O5A \\sim O6A \\sim S2A:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C70 \\sim Cl7 \\sim Cl8: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C76 \\sim F13A \\sim F14A \\sim F15A \\sim O10A \\sim O14A \\sim O15A \\sim
S4A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C71 \\sim F10 \\sim F11 \\sim F12 \\sim O11 \\sim O12 \\sim O13 \\sim S3:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C79 \\sim F1A \\sim F2A \\sim F6A \\sim O1A \\sim O2A \\sim O3A \\sim S1A:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
F1 \\sim F1A \\sim F2 \\sim F2A \\sim F6 \\sim F6A \\sim F21: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C85 \\sim F19 \\sim F20 \\sim F21 \\sim O20 \\sim O21 \\sim O22 \\sim S8:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C75) = Uanis(C74)
Uanis(C79) = Uanis(C78)
Uanis(C82) = Uanis(C85)
Uanis(F19) = Uanis(F21)
4. Rigid body (RIGU) restrains
 C76, F13, F14, F15, O10, O14, O15, S4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C70, Cl7, Cl8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C77, F13A, F14A, F15A, O10A, O14A, O15A, S4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1, F1A, F2, F2A, F6, F6A, F21
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C79, F1A, F2A, F6A, O1A, O2A, O3A, S1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C78, F1, F2, F6, O1, O2, O3, S1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C79)=Sof(F1A)=Sof(F2A)=Sof(F6A)=Sof(O1A)=Sof(O2A)=Sof(O3A)=Sof(S1A)=1-
 FVAR(1)
 Sof(C78)=Sof(F1)=Sof(F2)=Sof(F6)=Sof(O1)=Sof(O2)=Sof(O3)=Sof(S1)=FVAR(1)
 Sof(C75)=Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(O7A)=Sof(O8A)=Sof(O9A)=Sof(S6A)=1-
 FVAR(2)
 Sof(C74)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(O7)=Sof(O8)=Sof(O9)=Sof(S6)=FVAR(2)
 Sof(C77)=Sof(F13A)=Sof(F14A)=Sof(F15A)=Sof(O10A)=Sof(O14A)=Sof(O15A)=Sof(S4A)=
 1-FVAR(3)
 Sof(C76)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(O10)=Sof(O14)=Sof(O15)=Sof(S4)=FVAR(3)
 Sof(C73)=Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(O4A)=Sof(O5A)=Sof(O6A)=Sof(S2A)=1-
 FVAR(4)
 Sof(C72)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(O4)=Sof(O5)=Sof(O6)=Sof(S2)=FVAR(4)
 Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=1-FVAR(5)
 Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=FVAR(5)
6.a Secondary CH2 refined with riding coordinates:
 C70(H70A,H70B), C83(H83A,H83B), C86(H86A,H86B), C87(H87A,H87B), C88(H88A,H88B)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C2'(H2'), C02D(H02D), C02N(H02N), C02P(H02P), C02R(H02R), C03E(H03E),
 C03F(H03F), C03G(H03G), C03Q(H03Q), C04B(H04B), C04E(H04E), C04M(H04M),
 C04N(H04N), C04U(H04U), C04Y(H04Y), C5(H5), C5'(H5'), C05F(H05F), C9(H9),
 C9'(H9'), C11(H11), C11'(H11'), C12(H12), C12'(H12'), C13(H13), C13'(H13'),
 C14(H14), C14'(H14'), C15(H15), C15'(H15'), C17(H17), C17'(H17'), C18(H18),
 C18'(H18'), C19(H19), C19'(H19'), C20(H20), C20'(H20'), C23(H23), C23'(H23'),
 C24(H24), C24'(H24'), C25(H25), C25'(H25'), C26(H26), C26'(H26'), C27(H27),
 C27'(H27'), C29(H29), C29'(H29'), C30(H30), C30'(H30'), C31(H31), C31'(H31'),
 C32(H32), C32'(H32'), C33(H33), C33'(H33'), C34(H34), C34'(H34'), C36(H36),
 C036(H036), C36'(H36'), C040(H040), C41(H41), C041(H041), C43(H43), C44(H44),
 C45(H45), C46(H46), C47(H47), C49(H49), C50(H50), C51(H51), C052(H052),
 C52(H52), C054(H054), C55(H55), C56(H56), C57(H57), C58(H58), C59(H59),
 C61(H61), C62(H62), C63(H63), C64(H64), C65(H65)
6.c Idealised Me refined as rotating group:
 C04K(H04A,H04C,H04D), C7(H7A,H7B,H7C), C7'(H7'A,H7'B,H7'C), C8(H8A,H8B,H8C),
 C8'(H8'A,H8'B,H8'C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,
 H40C), C045(H04F,H04G,H04H), C67(H67A,H67B,H67C), C69(H69A,H69B,H69C),
 C81(H81A,H81B,H81C), C90(H90A,H90B,H90C), C91(H91A,H91B,H91C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 296 electrons were 
found in a volume of 996\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
1[CH2Cl2], 1[C2H3N] per Formula Unit 
which account for 256 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              78569
_shelx_fab_checksum              1588
_olex2_submission_special_instructions 'No special instructions were received'