Putting Cocrystal Stoichiometry to Work: A Reactive Hydrogen-Bonded "Superassembly" Enables Nanoscale Enlargement of a Metal-Organic Rhomboid via a Solid-State Photocycloaddition.
Chu, Qianli; Duncan, Andrew J. E.; Papaefstathiou, Giannis S.; Hamilton, Tamara D.; Atkinson, Manza B. J.; Mariappan, S. V. Santhana; MacGillivray, Leonard R.; Journal of the American Chemical Society 140 (2018) 4940–4944; doi:10.1021/jacs.8b01775

data_4132130
_publ_section_title
;
 Putting Cocrystal Stoichiometry to Work: A Reactive Hydrogen-Bonded
 &quot;Superassembly&quot; Enables Nanoscale Enlargement of a
 Metal-Organic Rhomboid via a Solid-State Photocycloaddition.
;
_journal_issue                   14
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4940
_journal_page_last               4944
_journal_paper_doi               10.1021/jacs.8b01775
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C56 H32 Cu2 F24 N4 O8, 4(C H Cl3)'
_chemical_formula_sum            'C60 H36 Cl12 Cu2 F24 N4 O8'
_chemical_formula_weight         1949.41
_chemical_name_common
;
 [Cu4(2-pyr-4-ppyr-cb)2(hfacac)8].8CHCl3       
;
_chemical_name_systematic
;
 [Cu4(K2,K1-2-pyr-4-ppyr-cb)]2[hfacac]8.8CHCl3 
;
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2017-06-13
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                74.866(5)
_cell_angle_beta                 84.001(5)
_cell_angle_gamma                78.978(5)
_cell_formula_units_Z            2
_cell_length_a                   14.240(3)
_cell_length_b                   16.400(3)
_cell_length_c                   17.079(3)
_cell_measurement_reflns_used    12132
_cell_measurement_temperature    190(2)
_cell_measurement_theta_max      25.03
_cell_measurement_theta_min      1.00
_cell_volume                     3772.9(12)
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor, 1997)'
_computing_data_collection       'Collect (Nonius BV, 1997-2000)'
_computing_data_reduction
;
 HKL Denzo, Scalepack (Otwinowski & Minor, 1997)
;
_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      190.15
_diffrn_measured_fraction_theta_full 0.962
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device_type  'Nonius KappaCCD'
_diffrn_measurement_method       'CCD phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0299
_diffrn_reflns_av_unetI/netI     0.0528
_diffrn_reflns_Laue_measured_fraction_full 0.962
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            24698
_diffrn_reflns_point_group_measured_fraction_full 0.962
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        25.241
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.716
_exptl_absorpt_coefficient_mu    1.102
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'HKL Scalepack (Otwinowski & Minor, 1997)'
_exptl_crystal_colour            'clear pale blue'
_exptl_crystal_density_diffrn    1.716
_exptl_crystal_description       plate
_exptl_crystal_F_000             1932
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.12
_exptl_transmission_factor_max   0.9850
_exptl_transmission_factor_min   0.8850
_refine_diff_density_max         1.118
_refine_diff_density_min         -0.627
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1396
_refine_ls_number_reflns         13133
_refine_ls_number_restraints     1610
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0849
_refine_ls_R_factor_gt           0.0581
_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^)+(0.0610P)^2^+7.9360P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1403
_refine_ls_wR_factor_ref         0.1530
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9744
_reflns_number_total             13133
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b01775_si_002.cif
_cod_data_source_block           rhomboid
_cod_database_code               4132130
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.879
_shelx_estimated_absorpt_t_min   0.699
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 F1-F2 \\sim F1-F3 \\sim F2-F3
 with sigma of 0.02
 F4-F5 \\sim F4-F6 \\sim F5-F6
 with sigma of 0.02
 C39-C41 \\sim C39-C41' \\sim C39-C41"
 with sigma of 0.02
 C41-F4 \\sim C41-F5 \\sim C41-F6 \\sim C41'-F4' \\sim C41-F5' \\sim C41-F6'
\\sim C41"-F4" \\sim C41"-F5"
 \\sim C41"-F6"
 with sigma of 0.02
 C45-F7 \\sim C45-F8 \\sim C45-F9 \\sim C45'-F7' \\sim C45'-F8' \\sim C45'-F9'
 with sigma of 0.02
 C42-C45 \\sim C42-C45'
 with sigma of 0.02
 F7-F8 \\sim F7-F9 \\sim F8-F9
 with sigma of 0.02
 C44-C46 \\sim C44-C46'
 with sigma of 0.02
 C46-F10 \\sim C46-F11 \\sim C46-F12 \\sim C46'-F10' \\sim C46'-F11' \\sim
C46'-F12'
 with sigma of 0.02
 C49-C51 \\sim C49-C51'
 with sigma of 0.02
 F16-F17 \\sim F16-F18 \\sim F17-F18
 with sigma of 0.02
 C51-F16 \\sim C51-F17 \\sim C51-F18 \\sim C51'-F16' \\sim C51'-F17' \\sim
C51'-F18'
 with sigma of 0.02
 C52-C55 \\sim C52-C55'
 with sigma of 0.02
 F19-F20 \\sim F19-F21 \\sim F20-F21
 with sigma of 0.02
 C55-F19 \\sim C55-F20 \\sim C55-F21 \\sim C55'-F19' \\sim C55'-F20' \\sim
C55'-F21'
 with sigma of 0.02
 C54-C56 \\sim C54-C56' \\sim C54-C56"
 with sigma of 0.02
 F22-F23 \\sim F22-F24 \\sim F23-F24
 with sigma of 0.02
 C56-F22 \\sim C56-F23 \\sim C56-F24 \\sim C56'-F22' \\sim C56'-F23' \\sim
C56'-F24' \\sim C56"-F22" ~
 C56"-F23" \\sim C56"-F24"
 with sigma of 0.02
 Cl1-Cl2 \\sim Cl1-Cl3 \\sim Cl2-Cl3
 with sigma of 0.02
 C57-Cl1 \\sim C57-Cl2 \\sim C57-Cl3 \\sim C57'-Cl1' \\sim C57'-Cl2' \\sim
C57'-Cl3'
 with sigma of 0.02
 Cl10-Cl11 \\sim Cl10-Cl12 \\sim Cl11-Cl12 \\sim Cl13-Cl14 \\sim Cl13-Cl15
\\sim Cl14-Cl15 \\sim Cl16-
 Cl17 \\sim Cl16-Cl18 \\sim Cl17-Cl18
 with sigma of 0.02
 C60-Cl10 \\sim C60-Cl11 \\sim C60-Cl12 \\sim C60'-Cl13 \\sim C60'-Cl14 \\sim
C60'-Cl15 \\sim C60"-
 Cl16 \\sim C60"-Cl17 \\sim C60"-Cl18
 with sigma of 0.02
 C59-Cl7 \\sim C59-Cl8 \\sim C59-Cl9 \\sim C59'-Cl7' \\sim C59'-Cl9' \\sim
C59'-Cl9'
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C41) = Uanis(C41')
Uanis(C45) = Uanis(C45')
Uanis(C51) = Uanis(C51')
Uanis(C56) = Uanis(C56') = Uanis(C56")
Uanis(C60) = Uanis(C60') = Uanis(C60")
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C41, F4, F5, F6} sigma for 1-2: 0.02, 1-3: 0.04
as
{C41', F4', F5', F6'}
{C41, F4, F5, F6} sigma for 1-2: 0.02, 1-3: 0.04
as
{C41", F4", F5", F6"}
{C45, F7, F8, F9} sigma for 1-2: 0.02, 1-3: 0.04
as
{C45', F7', F8', F9'}
{C46, F10, F11, F12} sigma for 1-2: 0.02, 1-3: 0.04
as
{C46', F10', F11', F12'}
{C51, F16, F17, F18} sigma for 1-2: 0.02, 1-3: 0.04
as
{C51', F16', F17', F18'}
{C55, F19, F20, F21} sigma for 1-2: 0.02, 1-3: 0.04
as
{C55', F19', F20', F21'}
{C56, F22, F23, F24} sigma for 1-2: 0.02, 1-3: 0.04
as
{C56', F22', F23', F24'}
{C56, F22, F23, F24} sigma for 1-2: 0.02, 1-3: 0.04
as
{C56", F22", F23", F24"}
{C57, Cl1, Cl2, Cl3} sigma for 1-2: 0.02, 1-3: 0.04
as
{C57', Cl1', Cl2', Cl3'}
{C60, Cl10, Cl11, Cl12} sigma for 1-2: 0.02, 1-3: 0.04
as
{C60', Cl13, Cl14, Cl15}
{C60, Cl10, Cl11, Cl12} sigma for 1-2: 0.02, 1-3: 0.04
as
{C60", Cl16, Cl17, Cl18}
{C59, Cl7, Cl8, Cl9} sigma for 1-2: 0.02, 1-3: 0.04
as
{C59', Cl7', Cl8', Cl9'}
6. Others
 1*[Sof(C56)+Sof(F22)+Sof(F23)+Sof(F24)]+1*[Sof(C56')+Sof(F22')+Sof(F23')+
 Sof(F24')]+1*[Sof(C56")+Sof(F22")+Sof(F23")+Sof(F24")]=1 with esd of 0.001
 1*[Sof(C60)+Sof(H60)+Sof(Cl10)+Sof(Cl11)+Sof(Cl12)]+1*[Sof(C60')+Sof(H60')+
 Sof(Cl13)+Sof(Cl14)+Sof(Cl15)]+1*[Sof(C60")+Sof(H60")+Sof(Cl16)+Sof(Cl17)+
 Sof(Cl18)]=1 with esd of 0.001
 1*[Sof(C41)+Sof(F4)+Sof(F5)+Sof(F6)]+1*[Sof(C41')+Sof(F4')+Sof(F5')+Sof(F6')]+
 1*[Sof(C41")+Sof(F4")+Sof(F5")+Sof(F6")]=1 with esd of 0.001
 Sof(C57')=Sof(H57')=Sof(Cl1')=Sof(Cl2')=Sof(Cl3')=1-FVAR(1)
 Sof(C57)=Sof(H57)=Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=FVAR(1)
 Sof(C59')=Sof(H59')=Sof(Cl7')=Sof(Cl8')=Sof(Cl9')=1-FVAR(2)
 Sof(C59)=Sof(H59)=Sof(Cl7)=Sof(Cl8)=Sof(Cl9)=FVAR(2)
 Sof(C46')=Sof(F10')=Sof(F11')=Sof(F12')=1-FVAR(3)
 Sof(C46)=Sof(F10)=Sof(F11)=Sof(F12)=FVAR(3)
 Sof(C55')=Sof(F19')=Sof(F20')=Sof(F21')=1-FVAR(4)
 Sof(C55)=Sof(F19)=Sof(F20)=Sof(F21)=FVAR(4)
 Sof(C51')=Sof(F16')=Sof(F17')=Sof(F18')=1-FVAR(5)
 Sof(C51)=Sof(F16)=Sof(F17)=Sof(F18)=FVAR(5)
 Sof(C56)=Sof(F22)=Sof(F23)=Sof(F24)=FVAR(6)
 Sof(C56')=Sof(F22')=Sof(F23')=Sof(F24')=FVAR(7)
 Sof(C56")=Sof(F22")=Sof(F23")=Sof(F24")=FVAR(8)
 Sof(C45')=Sof(F7')=Sof(F8')=Sof(F9')=1-FVAR(9)
 Sof(C45)=Sof(F7)=Sof(F8)=Sof(F9)=FVAR(9)
 Sof(C60)=Sof(H60)=Sof(Cl10)=Sof(Cl11)=Sof(Cl12)=FVAR(10)
 Sof(C60')=Sof(H60')=Sof(Cl13)=Sof(Cl14)=Sof(Cl15)=FVAR(11)
 Sof(C60")=Sof(H60")=Sof(Cl16)=Sof(Cl17)=Sof(Cl18)=FVAR(12)
 Sof(C41)=Sof(F4)=Sof(F5)=Sof(F6)=FVAR(13)
 Sof(C41')=Sof(F4')=Sof(F5')=Sof(F6')=FVAR(14)
 Sof(C41")=Sof(F4")=Sof(F5")=Sof(F6")=FVAR(15)
7.a Ternary CH refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C57(H57), C57'(H57'), C58(H58),
 C60(H60), C60'(H60'), C60"(H60"), C59(H59), C59'(H59')
7.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C7(H7), C8(H8), C10(H10), C11(H11), C17(H17),
 C18(H18), C20(H20), C21(H21), C23(H23), C24(H24), C25(H25), C26(H26), C28(H28),
  C29(H29), C30(H30), C31(H31), C33(H33), C34(H34), C35(H35), C36(H36),
 C38(H38), C43(H43), C48(H48), C53(H53)
;
_shelx_res_checksum              18538
_shelx_hkl_checksum              15340
_olex2_submission_special_instructions 'No special instructions were received'