Nonlinear Optical Chromophores with Two Ferrocenyl, Octamethylferrocenyl, or 4-(Diphenylamino)phenyl Groups Attached to Rhenium(I) or Zinc(II) Centers
Coe, Benjamin J.; Foxon, Simon P.; Pilkington, Rachel A.; Sánchez, Sergio; Whittaker, Daniel; Clays, Koen; Depotter, Griet; Brunschwig, Bruce S.; Organometallics 34 (2015) 1701–; doi:10.1021/acs.organomet.5b00193

data_4087501
_publ_section_title
;
 Nonlinear Optical Chromophores with Two Ferrocenyl, Octamethylferrocenyl,
 or 4-(Diphenylamino)phenyl Groups Attached to Rhenium(I) or Zinc(II)
 Centers
;
_journal_issue                   9
_journal_name_full               Organometallics
_journal_page_first              1701
_journal_paper_doi               10.1021/acs.organomet.5b00193
_journal_volume                  34
_journal_year                    2015
_chemical_formula_moiety
'C53.15 H60.15 Cl1.46 Fe2 N2 O3 Re, 0.35(C1 H1 Cl3)'
_chemical_formula_sum            'C53.5 H60.5 Cl2.5 Fe2 N2 O3 Re'
_chemical_formula_weight         1166.06
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-02-23
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 105.931(3)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   15.8819(6)
_cell_length_b                   14.5187(7)
_cell_length_c                   24.1193(8)
_cell_measurement_reflns_used    2589
_cell_measurement_temperature    200
_cell_measurement_theta_max      65.608
_cell_measurement_theta_min      3.59
_cell_volume                     5347.9(4)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      200
_diffrn_measured_fraction_theta_full 0.977
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1147
_diffrn_reflns_av_unetI/netI     0.1115
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            25805
_diffrn_reflns_theta_full        66.59
_diffrn_reflns_theta_max         66.59
_diffrn_reflns_theta_min         3.59
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    10.090
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.4490
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1209 before and 0.0715 after correction.
The Ratio of minimum to maximum transmission is 0.5964.
The \l/2 correction factor is 0.0000.
;
_exptl_crystal_colour            'clear green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.448
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             2356
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.687
_refine_diff_density_min         -1.228
_refine_diff_density_rms         0.160
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.972
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     648
_refine_ls_number_reflns         9241
_refine_ls_number_restraints     598
_refine_ls_restrained_S_all      0.957
_refine_ls_R_factor_all          0.1086
_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
'calc w=1/[\s^2^(Fo^2^)+(0.1233P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1821
_refine_ls_wR_factor_ref         0.2018
_reflns_number_gt                6071
_reflns_number_total             9241
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            om5b00193_si_003.cif
_cod_data_source_block           8.0.5CHCl3
_cod_original_formula_sum        'C53.50 H60.50 Cl2.50 Fe2 N2 O3 Re'
_cod_database_code               4087501
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C54-Cl2 = C54-Cl3 = C54-Cl4 = C54A-Cl2A = C54A-Cl3A = C54A-Cl4A
 1.69 with sigma of 0.02
 C48-C49 \\sim C49-C50
 with sigma of 0.02
 C54-Cl2 \\sim C54-Cl3 \\sim C54-Cl4
 with sigma of 0.02
 Cl2-Cl3 \\sim Cl3-Cl4 \\sim Cl4-Cl2 \\sim Cl2A-Cl3A \\sim Cl3A-Cl4A \\sim
Cl4A-Cl2A
 with sigma of 0.02
 C54A-Cl2A \\sim C54A-Cl3A \\sim C54A-Cl4A
 with sigma of 0.02
3. Rigid bond restraints
 C8, C9, C10, C11, C12, C13, C15, C16, C14, C19, C18, C20, C21, C17, C25, C22,
 C24, C23, C45, C44, C43, C42, C46, C47, C49, C48, C50
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Cl2, Cl3, Cl3, Cl4, Cl4, Cl2, Cl2A, Cl3A, Cl3A, Cl4A, Cl4A, Cl2A, C54, C54A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C15 \\sim C16 \\sim
C14 \\sim C19 \\sim C18 \\sim C20 \\sim C21 \\sim C17 \\sim C25 \\sim C22 \\sim
C24 \\sim C23 \\sim C45 \\sim C44 \\sim C43 \\sim C42 \\sim C46 \\sim C47 \\sim
C49 \\sim C48 \\sim C50: within 1.7A with sigma of 0.005 and sigma for terminal
atoms of 0.2
Cl2 \\sim Cl3 \\sim Cl3 \\sim Cl4 \\sim Cl4 \\sim Cl2 \\sim Cl2A \\sim Cl3A
\\sim Cl3A \\sim Cl4A \\sim Cl4A \\sim Cl2A \\sim C54 \\sim C54A: within 2A
with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C8) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C15) \\sim Ueq,
Uanis(C16) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C18)
\\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C17) \\sim Ueq,
Uanis(C25) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C23)
\\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C43) \\sim Ueq,
Uanis(C42) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C49)
\\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C50) \\sim Ueq: with sigma of 0.02 and
sigma for terminal atoms of 0.04
Uanis(Cl2) \\sim Ueq, Uanis(Cl3) \\sim Ueq, Uanis(Cl3) \\sim Ueq, Uanis(Cl4)
\\sim Ueq, Uanis(Cl4) \\sim Ueq, Uanis(Cl2) \\sim Ueq, Uanis(Cl2A) \\sim Ueq,
Uanis(Cl3A) \\sim Ueq, Uanis(Cl3A) \\sim Ueq, Uanis(Cl4A) \\sim Ueq,
Uanis(Cl4A) \\sim Ueq, Uanis(Cl2A) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C54A)
\\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
5. Others
 Sof(C54A)=Sof(H54A)=Sof(Cl4A)=Sof(Cl2A)=Sof(Cl3A)=0.5*(1-FVAR(2))
 Sof(Cl2)=Sof(Cl3)=Sof(Cl4)=Sof(C54)=Sof(H54)=0.5*FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C54(H54), C54A(H54A)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C6(H6), C7(H7), C21(H21), C26(H26), C27(H27),
 C29(H29), C31(H31), C32(H32), C42(H42)
6.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,
 H25B,H25C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C),
 C41(H41A,H41B,H41C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,
 H49C), C50(H50A,H50B,H50C)
;