Organolanthanide η1- and η5-pyrrolyl half-sandwich compounds: synthesis, structures, and magnetic properties
She, Yeye; Lu, Yanhua; Jia, Chaohong; Li, Yahong; Zhang, Yi-Quan; Yao, Jin-lei; New Journal of Chemistry 47 (2023) 15650–15657; doi:10.1039/D3NJ02225K

data_7062611
_publ_section_title
;
 Organolanthanide \h1- and \h5-pyrrolyl half-sandwich compounds:
 synthesis, structures, and magnetic properties
;
_journal_issue                   33
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              15650
_journal_page_last               15657
_journal_paper_doi               10.1039/D3NJ02225K
_journal_volume                  47
_journal_year                    2023
_chemical_formula_moiety         'C48 H54 Er2 N12 O2, 4(C7 H8)'
_chemical_formula_sum            'C76 H86 Er2 N12 O2'
_chemical_formula_weight         1534.08
_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   mixed
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2fsp31
_audit_creation_date             2023-06-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-06-30 deposited with the CCDC.	2023-07-21 downloaded from the CCDC.
;
_cell_angle_alpha                76.931(14)
_cell_angle_beta                 72.258(13)
_cell_angle_gamma                73.416(13)
_cell_formula_units_Z            2
_cell_length_a                   11.818(4)
_cell_length_b                   17.795(7)
_cell_length_c                   18.503(7)
_cell_measurement_reflns_used    7831
_cell_measurement_temperature    120.00
_cell_measurement_theta_max      53.825
_cell_measurement_theta_min      3.637
_cell_volume                     3510(2)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Bruker SMART APEX II diffractrometer'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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      120.0
_diffrn_measured_fraction_theta_full 0.975
_diffrn_measured_fraction_theta_max 0.956
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34138
_diffrn_reflns_av_R_equivalents  0.0782
_diffrn_reflns_av_unetI/netI     0.0930
_diffrn_reflns_Laue_measured_fraction_full 0.975
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            31178
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         54.489
_diffrn_reflns_theta_min         4.607
_exptl_absorpt_coefficient_mu    8.025
_exptl_absorpt_correction_T_max  0.7506
_exptl_absorpt_correction_T_min  0.4902
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1681 before and 0.0977 after correction. The Ratio of minimum to maximum transmission is 0.6531. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.451
_exptl_crystal_description       block
_exptl_crystal_F_000             1556
_exptl_crystal_recrystallization_method
'The crystals were growth by means of evaporation of a mixture of n-hexane and toluene at RT.'
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.116
_refine_diff_density_min         -1.678
_refine_diff_density_rms         0.151
_refine_ls_extinction_coef       0.0041(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.123
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1070
_refine_ls_number_reflns         12582
_refine_ls_number_restraints     1910
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0870
_refine_ls_R_factor_gt           0.0713
_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^)+(0.1339P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1985
_refine_ls_wR_factor_ref         0.2150
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9676
_reflns_number_total             12582
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3nj02225k2.cif
_cod_data_source_block           b230223lyh2_0m_a
_cod_depositor_comments
'Adding full bibliography for 7062611--7062613.cif.'
_cod_original_cell_volume        3511(2)
_cod_database_code               7062611
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.446
_shelx_estimated_absorpt_t_min   0.360
_exptl_crystal_mounting_method
'Crystals were removed from the crystallisation vial and immediately coated with polybutenes oil (CAS: 9003-29-6) on a glass slide. A suitable single crystal coated with polybutenes oil was sealed in capillary tube filled with argon. The capillary tube with single crystal was mounted on copper pin with solid paraffin.'
_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. Restrained distances
 C62A-C56A = C62-C56 = C69A-C63A = C69-C63 = C55-C49 = C55A-C49A = C76A-C70A =
 C76-C70
 1.5 with sigma of 0.01
 C76A-C75A \\sim C76A-C71A
 with sigma of 0.02
 C76-C75 \\sim C76-C71
 with sigma of 0.02
 C55-C54 \\sim C55-C50
 with sigma of 0.02
 C69-C64 \\sim C69-C68
 with sigma of 0.02
 C62-C61 \\sim C62-C57
 with sigma of 0.02
 C62A-C57A \\sim C62A-C61A
 with sigma of 0.02
 C69A-C64A \\sim C69A-C68A
 with sigma of 0.02
 C55A-C50A \\sim C55A-C54A
 with sigma of 0.02
3. Restrained planarity
 C76A, C70A, C71A, C75A, C72A, C74A, C73A
 with sigma of 0.1
 C52A, C49A, C50A, C54A, C55A, C51A, C53A
 with sigma of 0.1
 C52, C49, C50, C54, C55, C51, C53
 with sigma of 0.1
 C68, C63, C64, C69, C65, C67, C66
 with sigma of 0.1
 C60A, C57A, C58A, C56A, C62A, C59A, C61A
 with sigma of 0.1
 C61, C58, C57, C59, C56, C62, C60
 with sigma of 0.1
 C75, C70, C71, C76, C72, C74, C73
 with sigma of 0.1
 C68A, C63A, C64A, C69A, C65A, C67A, C66A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
O1 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C41A \\sim C42A \\sim C43A
\\sim C44A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C70 \\sim C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75 \\sim C76 \\sim C70A
\\sim C71A \\sim C72A \\sim C73A \\sim C74A \\sim C75A \\sim C76A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
C58 \\sim C57 \\sim C56 \\sim C61 \\sim C60 \\sim C59 \\sim C62 \\sim C58A
\\sim C57A \\sim C56A \\sim C61A \\sim C60A \\sim C59A \\sim C62A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C63A
\\sim C64A \\sim C65A \\sim C66A \\sim C67A \\sim C68A \\sim C69A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C49A
\\sim C50A \\sim C51A \\sim C52A \\sim C53A \\sim C54A \\sim C55A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
O2 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C45A \\sim C46A \\sim C47A
\\sim C48A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C70) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C73)
\\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C76) \\sim Ueq,
Uanis(C70A) \\sim Ueq, Uanis(C71A) \\sim Ueq, Uanis(C72A) \\sim Ueq,
Uanis(C73A) \\sim Ueq, Uanis(C74A) \\sim Ueq, Uanis(C75A) \\sim Ueq,
Uanis(C76A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C56) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C59)
\\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C62) \\sim Ueq,
Uanis(C56A) \\sim Ueq, Uanis(C57A) \\sim Ueq, Uanis(C58A) \\sim Ueq,
Uanis(C59A) \\sim Ueq, Uanis(C60A) \\sim Ueq, Uanis(C61A) \\sim Ueq,
Uanis(C62A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C63) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C66)
\\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C69) \\sim Ueq,
Uanis(C63A) \\sim Ueq, Uanis(C64A) \\sim Ueq, Uanis(C65A) \\sim Ueq,
Uanis(C66A) \\sim Ueq, Uanis(C67A) \\sim Ueq, Uanis(C68A) \\sim Ueq,
Uanis(C69A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C48A) \\sim Ueq, Uanis(C48) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 O1, C41, C42, C43, C44, C41A, C42A, C43A, C44A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C70, C71, C72, C73, C74, C75, C76, C70A, C71A, C72A, C73A, C74A, C75A, C76A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 O2, C45, C46, C47, C48, C45A, C46A, C47A, C48A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C49, C50, C51, C52, C53, C54, C55, C49A, C51A, C52A, C53A, C54A, C55A, C50A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C58, C57, C56, C61, C60, C59, C62, C58A, C57A, C56A, C61A, C60A, C59A, C62A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C63, C64, C65, C66, C67, C68, C69, C63A, C64A, C65A, C66A, C67A, C68A, C69A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
6. Same fragment restrains
{O1, C41A, C42A, C43A, C44A} sigma for 1-2: 0.02, 1-3: 0.04
as
{O1, C41, C42, C43, C44}
{O2, C45A, C46A, C47A, C48A} sigma for 1-2: 0.02, 1-3: 0.04
as
{O2, C45, C46, C47, C48}
7. Others
 Sof(C56A)=Sof(C57A)=Sof(H57A)=Sof(C58A)=Sof(H58A)=Sof(C59A)=Sof(H59A)=
 Sof(C60A)=Sof(H60A)=Sof(C61A)=Sof(H61A)=Sof(C62A)=Sof(H62D)=Sof(H62E)=
 Sof(H62F)=1-FVAR(1)
 Sof(C56)=Sof(C57)=Sof(H57)=Sof(C58)=Sof(H58)=Sof(C59)=Sof(H59)=Sof(C60)=
 Sof(H60)=Sof(C61)=Sof(H61)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=FVAR(1)
 Sof(C63A)=Sof(C64A)=Sof(H64A)=Sof(C65A)=Sof(H65A)=Sof(C66A)=Sof(H66A)=
 Sof(C67A)=Sof(H67A)=Sof(C68A)=Sof(H68A)=Sof(C69A)=Sof(H69D)=Sof(H69E)=
 Sof(H69F)=1-FVAR(2)
 Sof(C63)=Sof(C64)=Sof(H64)=Sof(C65)=Sof(H65)=Sof(C66)=Sof(H66)=Sof(C67)=
 Sof(H67)=Sof(C68)=Sof(H68)=Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=FVAR(2)
 Sof(C70A)=Sof(C71A)=Sof(H71A)=Sof(C72A)=Sof(H72A)=Sof(C73A)=Sof(H73A)=
 Sof(C74A)=Sof(H74A)=Sof(C75A)=Sof(H75A)=Sof(C76A)=Sof(H76D)=Sof(H76E)=
 Sof(H76F)=1-FVAR(3)
 Sof(C70)=Sof(C71)=Sof(H71)=Sof(C72)=Sof(H72)=Sof(C73)=Sof(H73)=Sof(C74)=
 Sof(H74)=Sof(C75)=Sof(H75)=Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=FVAR(3)
 Sof(C49A)=Sof(C50A)=Sof(H50A)=Sof(C51A)=Sof(H51A)=Sof(C52A)=Sof(H52A)=
 Sof(C53A)=Sof(H53A)=Sof(C54A)=Sof(H54A)=Sof(C55A)=Sof(H55D)=Sof(H55E)=
 Sof(H55F)=1-FVAR(4)
 Sof(C49)=Sof(C50)=Sof(H50)=Sof(C51)=Sof(H51)=Sof(C52)=Sof(H52)=Sof(C53)=
 Sof(H53)=Sof(C54)=Sof(H54)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=FVAR(4)
 Sof(C45A)=Sof(H45C)=Sof(H45D)=Sof(C46A)=Sof(H46C)=Sof(H46D)=Sof(C47A)=
 Sof(H47C)=Sof(H47D)=Sof(C48A)=Sof(H48C)=Sof(H48D)=1-FVAR(5)
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(C47)=Sof(H47A)=
 Sof(H47B)=Sof(C48)=Sof(H48A)=Sof(H48B)=FVAR(5)
 Sof(C41A)=Sof(H41C)=Sof(H41D)=Sof(C42A)=Sof(H42C)=Sof(H42D)=Sof(C43A)=
 Sof(H43C)=Sof(H43D)=Sof(C44A)=Sof(H44C)=Sof(H44D)=1-FVAR(6)
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C43)=Sof(H43A)=
 Sof(H43B)=Sof(C44)=Sof(H44A)=Sof(H44B)=FVAR(6)
 Fixed X: C41(0.88374)
8.a Riding coordinates:
 C76A(H76D,H76E,H76F)
8.b Ternary CH refined with riding coordinates:
 C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23)
8.c Secondary CH2 refined with riding coordinates:
 C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B), C44(H44A,H44B), C45(H45A,
 H45B), C46(H46A,H46B), C47(H47A,H47B), C48(H48A,H48B), C5(H5A,H5B), C16(H16A,
 H16B), C25(H25A,H25B), C36(H36A,H36B), C41A(H41C,H41D), C42A(H42C,H42D),
 C43A(H43C,H43D), C44A(H44C,H44D), C45A(H45C,H45D), C46A(H46C,H46D), C47A(H47C,
 H47D), C48A(H48C,H48D)
8.d Aromatic/amide H refined with riding coordinates:
 N1(H1), N12(H12), C1(H1A), C2(H2), C3(H3), C6(H6), C8(H8), C9(H9), C10(H10),
 C11(H11), C12(H12A), C13(H13), C15(H15), C26(H26), C28(H28), C29(H29),
 C30(H30), C31(H31), C32(H32), C33(H33), C35(H35), C38(H38), C39(H39), C40(H40),
  C50(H50), C51(H51), C52(H52), C53(H53), C54(H54), C57(H57), C58(H58),
 C59(H59), C60(H60), C61(H61), C64(H64), C65(H65), C66(H66), C67(H67), C68(H68),
  C71(H71), C72(H72), C73(H73), C74(H74), C75(H75), C50A(H50A), C51A(H51A),
 C52A(H52A), C53A(H53A), C54A(H54A), C57A(H57A), C58A(H58A), C59A(H59A),
 C60A(H60A), C61A(H61A), C64A(H64A), C65A(H65A), C66A(H66A), C67A(H67A),
 C68A(H68A), C71A(H71A), C72A(H72A), C73A(H73A), C74A(H74A), C75A(H75A)
8.e Fitted hexagon refined as free rotating group:
 C49(C50,C51,C52,C53,C54), C56(C57,C58,C59,C60,C61), C63(C64,C65,C66,C67,C68),
 C70(C71,C72,C73,C74,C75), C49A(C50A,C51A,C52A,C53A,C54A), C56A(C57A,C58A,C59A,
 C60A,C61A), C63A(C64A,C65A,C66A,C67A,C68A), C70A(C71A,C72A,C73A,C74A,C75A)
8.f Idealised Me refined as rotating group:
 C55(H55A,H55B,H55C), C62(H62A,H62B,H62C), C69(H69A,H69B,H69C), C76(H76A,H76B,
 H76C), C55A(H55D,H55E,H55F), C62A(H62D,H62E,H62F), C69A(H69D,H69E,H69F)
;
_olex2_submission_special_instructions 'No special instructions were received'