Tailored homo- and hetero- lanthanide porphyrin dimers: a synthetic strategy for integrating multiple spintronic functionalities into a single molecule.
Le Roy, Jennifer J.; Cremers, Jonathan; Thomlinson, Isabel A.; Slota, Michael; Myers, William K.; Horton, Peter H.; Coles, Simon J.; Anderson, Harry L.; Bogani, Lapo; Chemical science 9 (2018) 8474–8481; doi:10.1039/c8sc03762k

data_1550066
_publ_section_title
;
 Tailored homo- and hetero- lanthanide porphyrin dimers: a synthetic
 strategy for integrating multiple spintronic functionalities into a
 single molecule.
;
_journal_issue                   45
_journal_name_full               'Chemical science'
_journal_page_first              8474
_journal_page_last               8481
_journal_paper_doi               10.1039/c8sc03762k
_journal_volume                  9
_journal_year                    2018
_chemical_formula_moiety
'C156 H212 Co2 Gd1.86 N8 O18 P6 Si2, 0.14(Gd)'
_chemical_formula_sum            'C156 H212 Co2 Gd2 N8 O18 P6 Si2'
_chemical_formula_weight         3161.68
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-02-16
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2017.02.06 svn.r3384 for OlexSys, GUI svn.r5312)
;
_audit_update_record
;
2017-07-27 deposited with the CCDC.
2018-10-18 downloaded from the CCDC.
;
_cell_angle_alpha                75.075(2)
_cell_angle_beta                 86.248(2)
_cell_angle_gamma                70.983(2)
_cell_formula_units_Z            1
_cell_length_a                   10.3106(2)
_cell_length_b                   14.6582(3)
_cell_length_c                   27.9536(4)
_cell_measurement_reflns_used    41283
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.5750
_cell_measurement_theta_min      1.9330
_cell_volume                     3858.64(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.9g (Rigaku OD, 2015)'
_computing_data_collection
'CrystalClear-SM Expert 3.1 b27 (Rigaku, 2013)'
_computing_data_reduction        'CrysAlisPro 1.171.39.9g (Rigaku OD, 2015)'
_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(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku HG Saturn724+ (2x2 bin mode)'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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    -94.00  71.00   1.00   40.00    --  -19.00  18.00-150.00  165
  2  \w    -78.00  22.00   1.00   40.00    --  -19.00 -72.00 -60.00  100
  3  \w    -31.00  71.00   1.00   40.00    --  -19.00  72.00-120.00  102
  4  \w    -68.00  21.00   1.00   40.00    --  -19.00 -72.00 120.00   89
  5  \w    -31.00  -9.00   1.00   40.00    --  -19.00  54.00  90.00   22
  6  \w    -69.00  71.00   1.00   40.00    --  -19.00  18.00 -60.00  140
  7  \w    -94.00  20.00   1.00   40.00    --  -19.00 -54.00 120.00  114
  8  \w    -59.00  58.00   1.00   40.00    --  -19.00  36.00  30.00  117
  9  \w    -80.00  14.00   1.00   40.00    --  -19.00 -72.00  90.00   94
 10  \w    -68.00  22.00   1.00   40.00    --  -19.00 -72.00 -90.00   90
 11  \w    -30.00  -4.00   1.00   40.00    --  -19.00  72.00  30.00   26
 12  \w    -94.00  -3.00   1.00   40.00    --  -19.00  18.00-120.00   91
;
_diffrn_measurement_device       'four-circle \k goniometer'
_diffrn_measurement_device_type
'Rigaku FRE+ equipped with VHF Varimax confocal mirrors and an AFC12 goniometer and HG Saturn 724+ detector'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroLoop'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0058308000
_diffrn_orient_matrix_UB_12      -0.0206093000
_diffrn_orient_matrix_UB_13      0.0256361000
_diffrn_orient_matrix_UB_21      0.0265731000
_diffrn_orient_matrix_UB_22      -0.0486762000
_diffrn_orient_matrix_UB_23      -0.0037890000
_diffrn_orient_matrix_UB_31      0.0675038000
_diffrn_orient_matrix_UB_32      -0.0008847000
_diffrn_orient_matrix_UB_33      0.0042788000
_diffrn_radiation_collimation    0.2
_diffrn_radiation_monochromator  'Confocal mirrors, VHF Varimax'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0490
_diffrn_reflns_av_unetI/netI     0.0376
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            88673
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         2.167
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           55.0
_diffrn_source_power             2.475
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku FRE+'
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    1.202
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79929
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.9g (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.361
_exptl_crystal_description       plate
_exptl_crystal_F_000             1648
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.005
_refine_diff_density_max         3.623
_refine_diff_density_min         -1.068
_refine_diff_density_rms         0.125
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.153
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1015
_refine_ls_number_reflns         17691
_refine_ls_number_restraints     1386
_refine_ls_restrained_S_all      1.148
_refine_ls_R_factor_all          0.0738
_refine_ls_R_factor_gt           0.0645
_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^)+(0.0440P)^2^+22.0340P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1512
_refine_ls_wR_factor_ref         0.1555
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15807
_reflns_number_total             17691
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc03762k2.cif
_cod_data_source_block           P2Gd2
_cod_depositor_comments
'Adding full bibliography for 1550065--1550077.cif.'
_cod_original_cell_volume        3858.65(13)
_cod_database_code               1550066
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C156 H212 Co2 Gd2 N8 O18 P6 Si2'
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_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. Uiso/Uaniso restraints and constraints
Uanis(O104) = Uanis(C101) = Uanis(C102)
Uanis(O105) = Uanis(C103) = Uanis(C104)
Uanis(O106) = Uanis(C105) = Uanis(C106)
Uanis(O107) = Uanis(C107) = Uanis(C108)
Uanis(O108) = Uanis(C109) = Uanis(C110)
Uanis(O109) = Uanis(C111) = Uanis(C112)
Uanis(O204) = Uanis(C201) = Uanis(C202)
Uanis(O205) = Uanis(C203) = Uanis(C204)
Uanis(O206) = Uanis(C205) = Uanis(C206)
Uanis(O207) = Uanis(C207) = Uanis(C208)
Uanis(O208) = Uanis(C209) = Uanis(C210)
Uanis(O209) = Uanis(C211) = Uanis(C212)
Uanis(C121) = Uanis(C122) = Uanis(C123) = Uanis(C124) = Uanis(C125)
Uanis(C221) = Uanis(C222) = Uanis(C223) = Uanis(C224) = Uanis(C225)
3. 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
4. Same fragment restrains
{Co1, P101, P102, P103, O101, O102, O103, O104, O105, O106, O107, O108, O109,
C101, C102, C103, C104, C105, C106, C107, C108, C109, C110, C111, C112, C121,
C122, C123, C124, C125} sigma for 1-2: 0.02, 1-3: 0.04
as
{Co1B, P201, P202, P203, O201, O202, O203, O204, O205, O206, O207, O208, O209,
C201, C202, C203, C204, C205, C206, C207, C208, C209, C210, C211, C212, C221,
C222, C223, C224, C225}
5. Others
 Sof(C54A)=Sof(C55A)=Sof(H55D)=Sof(H55E)=Sof(H55F)=Sof(C56A)=Sof(H56D)=
 Sof(H56E)=Sof(H56F)=Sof(C57A)=Sof(H57D)=Sof(H57E)=Sof(H57F)=1-FVAR(1)
 Sof(C54)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=Sof(C56)=Sof(H56A)=Sof(H56B)=
 Sof(H56C)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=FVAR(1)
 Sof(Gd1B)=1-FVAR(2)
 Sof(Gd1)=FVAR(2)
 Sof(Co1B)=Sof(P201)=Sof(P202)=Sof(P203)=Sof(O201)=Sof(O202)=Sof(O203)=
 Sof(O204)=Sof(O205)=Sof(O206)=Sof(O207)=Sof(O208)=Sof(O209)=Sof(C201)=
 Sof(H20A)=Sof(H20B)=Sof(C202)=Sof(H20C)=Sof(H20D)=Sof(H20E)=Sof(C203)=
 Sof(H20F)=Sof(H20G)=Sof(C204)=Sof(H20H)=Sof(H20I)=Sof(H20J)=Sof(C205)=
 Sof(H20K)=Sof(H20L)=Sof(C206)=Sof(H20M)=Sof(H20N)=Sof(H20O)=Sof(C207)=
 Sof(H20P)=Sof(H20Q)=Sof(C208)=Sof(H20R)=Sof(H20S)=Sof(H20T)=Sof(C209)=
 Sof(H20U)=Sof(H20V)=Sof(C210)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C211)=
 Sof(H21D)=Sof(H21E)=Sof(C212)=Sof(H21F)=Sof(H21G)=Sof(H21H)=Sof(C221)=
 Sof(H221)=Sof(C222)=Sof(H222)=Sof(C223)=Sof(H223)=Sof(C224)=Sof(H224)=
 Sof(C225)=Sof(H225)=1-FVAR(3)
 Sof(Co1)=Sof(P101)=Sof(P102)=Sof(P103)=Sof(O101)=Sof(O102)=Sof(O103)=
 Sof(O104)=Sof(O105)=Sof(O106)=Sof(O107)=Sof(O108)=Sof(O109)=Sof(C101)=
 Sof(H10A)=Sof(H10B)=Sof(C102)=Sof(H10C)=Sof(H10D)=Sof(H10E)=Sof(C103)=
 Sof(H10F)=Sof(H10G)=Sof(C104)=Sof(H10H)=Sof(H10I)=Sof(H10J)=Sof(C105)=
 Sof(H10K)=Sof(H10L)=Sof(C106)=Sof(H10M)=Sof(H10N)=Sof(H10O)=Sof(C107)=
 Sof(H10P)=Sof(H10Q)=Sof(C108)=Sof(H10R)=Sof(H10S)=Sof(H10T)=Sof(C109)=
 Sof(H10U)=Sof(H10V)=Sof(C110)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C111)=
 Sof(H11D)=Sof(H11E)=Sof(C112)=Sof(H11F)=Sof(H11G)=Sof(H11H)=Sof(C121)=
 Sof(H121)=Sof(C122)=Sof(H122)=Sof(C123)=Sof(H123)=Sof(C124)=Sof(H124)=
 Sof(C125)=Sof(H125)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C25(H25), C28(H28), C31(H31), C221(H221)
6.b Secondary CH2 refined with riding coordinates:
 C101(H10A,H10B), C103(H10F,H10G), C105(H10K,H10L), C107(H10P,H10Q), C109(H10U,
 H10V), C111(H11D,H11E), C201(H20A,H20B), C203(H20F,H20G), C205(H20K,H20L),
 C207(H20P,H20Q), C209(H20U,H20V), C211(H21D,H21E)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C7(H7), C8(H8), C12(H12), C13(H13), C17(H17), C18(H18),
 C35(H35), C37(H37), C39(H39), C49(H49), C51(H51), C53(H53), C121(H121),
 C122(H122), C123(H123), C124(H124), C125(H125), C222(H222), C223(H223),
 C224(H224), C225(H225)
6.d Fitted pentagon refined as free rotating group:
 C121(C122,C123,C124,C125), C221(C222,C223,C224,C225)
6.e Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C41(H41A,H41B,H41C), C42(H42A,
 H42B,H42C), C43(H43A,H43B,H43C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C),
 C47(H47A,H47B,H47C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C61(H61A,H61B,
 H61C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C),
 C102(H10C,H10D,H10E), C104(H10H,H10I,H10J), C106(H10M,H10N,H10O), C108(H10R,
 H10S,H10T), C110(H11A,H11B,H11C), C112(H11F,H11G,H11H), C55A(H55D,H55E,H55F),
 C56A(H56D,H56E,H56F), C57A(H57D,H57E,H57F), C202(H20C,H20D,H20E), C204(H20H,
 H20I,H20J), C206(H20M,H20N,H20O), C208(H20R,H20S,H20T), C210(H21A,H21B,H21C),
 C212(H21F,H21G,H21H)
;
_shelx_res_checksum              95465
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.399
_oxdiff_exptl_absorpt_empirical_full_min 0.664