1,4,7-Triazacyclononane Ligands Bearing Tertiary Alkyl Nitrogen Substituents
Arumugam Thangavel; Marika Wieliczko; John Bacsa; Christopher C. Scarborough; Inorganic Chemistry 52 (2013) 13282–13287; doi:10.1021/ic402626p

data_4336788
_publ_contact_author_address
; 
Department of Chemistry
Emory University
Atlanta, GA 30322, USA
;
_publ_contact_author_email       scarborough@emory.edu
_publ_contact_author_name        'Scarborough, Christopher C.'
_publ_section_title
;
 1,4,7-Triazacyclononane Ligands Bearing Tertiary Alkyl Nitrogen
 Substituents
;
_journal_name_full               'Inorganic Chemistry'
_journal_page_first              13282
_journal_page_last               13287
_journal_paper_doi               10.1021/ic402626p
_journal_volume                  52
_journal_year                    2013
_chemical_formula_moiety         'C21 H42 Cr F3 N4 O3 S, 1(C F3 O3 S)'
_chemical_formula_sum            'C22 H42 Cr F6 N4 O6 S2'
_chemical_formula_weight         688.71
_chemical_name_systematic
;
 ?
;
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2013-06-10
_audit_creation_method
;
  Olex2 1.2-beta
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_audit_update_record
;
2013-06-12 # Formatted by publCIF
;
_cell_angle_alpha                90
_cell_angle_beta                 122.7420(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.088(2)
_cell_length_b                   11.3123(15)
_cell_length_c                   19.060(2)
_cell_measurement_reflns_used    4919
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      29.933
_cell_measurement_theta_min      2.221
_cell_volume                     3099.0(6)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       'APEX2 v2011.2-4 (Bruker, 2011)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      173(2)
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type
'Bruker D8 diffractometer with APEX2 detector'
_diffrn_measurement_method       '\f and \w scans with a narrow frame width'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1297
_diffrn_reflns_av_unetI/netI     0.1839
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_k_max       0
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            45685
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.564
_diffrn_reflns_theta_min         1.417
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.582
_exptl_absorpt_correction_T_max  0.74607
_exptl_absorpt_correction_T_min  0.54189
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.0726 before and 0.0536 after correction.
 The Ratio of minimum to maximum transmission not present.
 The \l/2 correction factor is Not present
 
For component 2:
 wR2(int) was 0.0844 before and 0.0654 after correction.
 The Ratio of minimum to maximum transmission is 0.73.
 The \l/2 correction factor is Not present

Final HKLF 4 output contains 45653 reflections, Rint = 0.1297
 (6930 with I > 3sig(I), Rint = 0.0613)
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.476
_exptl_crystal_description       prism
_exptl_crystal_F_000             1440
_exptl_crystal_size_max          0.264
_exptl_crystal_size_mid          0.181
_exptl_crystal_size_min          0.077
_refine_diff_density_max         2.043
_refine_diff_density_min         -1.037
_refine_diff_density_rms         0.175
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.979
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     531
_refine_ls_number_reflns         20181
_refine_ls_number_restraints     563
_refine_ls_restrained_S_all      0.986
_refine_ls_R_factor_all          0.2519
_refine_ls_R_factor_gt           0.1001
_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^)+(0.1468P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2426
_refine_ls_wR_factor_ref         0.3273
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7269
_reflns_number_total             20181
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic402626p_si_002_07.cif
_cod_data_source_block           1212ThangavelttacnCrOTf2MeCN
_cod_database_code               4336788
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 S2A-C22A
 1.814 with sigma of 0.005
 S2C-C22C
 1.814 with sigma of 0.005
 F6B-C22B = F5B-C22B = F4B-C22B
 1.322 with sigma of 0.005
 S2B-O5B = S2B-O6B = S2B-O4B
 1.433 with sigma of 0.005
 S2C-O5C = S2C-O6C = S2C-O4C
 1.433 with sigma of 0.005
 S1A-C1A
 1.814 with sigma of 0.005
 C5B-C4B = C5A-C4A
 1.522 with sigma of 0.01
 C3B-C2B = C3A-C2A
 1.522 with sigma of 0.01
 F3B-C1B = F1B-C1B = F2B-C1B
 1.322 with sigma of 0.005
 F3A-C1A = F1A-C1A = F2A-C1A
 1.322 with sigma of 0.005
 C3A-C2B = C5B-C4B = C7A-C6B
 1.52 with sigma of 0.005
 C7B-C6B = C7A-C6A
 1.522 with sigma of 0.005
 F5A-C22A \\sim F6A-C22A \\sim F4A-C22A
 with sigma of 0.005
 S2A-O4A \\sim S2A-O6A \\sim S2A-O5A
 with sigma of 0.005
 S2C-O5C \\sim S2C-O4C \\sim S2C-O6C
 with sigma of 0.005
 F6C-C22C \\sim F4C-C22C \\sim F5C-C22C
 with sigma of 0.005
 C8B-C10B \\sim C8B-C11B \\sim C9B-C8B
 with sigma of 0.005
 C8A-C10A \\sim C9A-C8A \\sim C8A-C11A
 with sigma of 0.005
 N3-C8B \\sim N3-C8A
 with sigma of 0.005
 N3-C5A \\sim N3-C5B
 with sigma of 0.005
 N2-C4A \\sim N2-C4B
 with sigma of 0.005
 N2-C3B \\sim N2-C3A
 with sigma of 0.005
 N1-C2A \\sim N1-C2B
 with sigma of 0.005
 F1A-C1A \\sim F3A-C1A \\sim F2A-C1A
 with sigma of 0.005
 S1A-O2A \\sim S1B-O2B
 with sigma of 0.005
 N1-C7B \\sim N1-C7A
 with sigma of 0.005
 N3-C6A \\sim N3-C6B
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
O4B \\sim O4A \\sim O4C \\sim O6C \\sim O6A \\sim O6B \\sim O5C \\sim O5A 
\\sim O5B: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
F4A \\sim F5A \\sim F6A \\sim F5B \\sim F4B \\sim F6B \\sim F4C \\sim F5C 
\\sim F6C: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.02
F2A \\sim F2B \\sim F3A \\sim F3B \\sim F1B \\sim F1A: within 1.7A with sigma 
of 0.005 and sigma for terminal atoms of 0.01
Uanis(C2A) \\sim Ueq, Uanis(C2B) \\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(C3B) 
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C6A) \\sim Ueq, Uanis(C7A) \\sim Ueq: with sigma of 0.004 and sigma for 
terminal atoms of 0.005
Uanis(F5B) = Uanis(F5C)
Uanis(S2B) = Uanis(S2C)
Uanis(C22B) = Uanis(C22C)
Uanis(F4B) = Uanis(F4C)
Uanis(F6B) = Uanis(F6C)
Uanis(C22A) = Uanis(C22C)
Uanis(S2A) = Uanis(S2C)
Uanis(F4A) = Uanis(F4C)
Uanis(F5A) = Uanis(F5C)
Uanis(F6A) = Uanis(F6C)
Uanis(C22C) = Uanis(C22B) = Uanis(C22A)
Uanis(O3A) = Uanis(O3B)
Uanis(C1A) = Uanis(C1B)
Uanis(S1A) = Uanis(S1B)
Uanis(C8A) = Uanis(C8B)
Uanis(C9A) = Uanis(C9B)
Uanis(C10A) = Uanis(C10B)
Uanis(C11A) = Uanis(C11B)
Uanis(C5A) = Uanis(C5B)
Uanis(C4A) = Uanis(C4B)
Uanis(C3B) = Uanis(C3A)
Uanis(C2A) = Uanis(C2B)
Uanis(O2A) = Uanis(O2B)
Uanis(C7B) = Uanis(C7A)
Uanis(C6A) = Uanis(C6B)
Uanis(C7A) = Uanis(C6A)
4. Same fragment restrains
{S2A, O4A, O5A, O6A, C22A, F4A, F5A, F6A}
as
{S2B, O4B, O5B, O6B, C22B, F5B, F4B, F6B}
{S2A, O4A, O5A, O6A, C22A, F4A, F5A, F6A}
as
{S2C, O4C, O5C, O6C, C22C, F4C, F5C, F6C}
5. others
 Fixed Sof: C1A(0.5) C1B(0.5) C2A(0.5) H2AA(0.5) H2AB(0.5) C2B(0.5) H2BA(0.5)
 H2BB(0.5) C3A(0.5) H3AA(0.5) H3AB(0.5) C3B(0.5) H3BA(0.5) H3BB(0.5) C4B(0.5)
 H4BA(0.5) H4BB(0.5) C4A(0.5) H4AA(0.5) H4AB(0.5) C5B(0.5) H5BA(0.5) H5BB(0.5)
 C5A(0.5) H5AA(0.5) H5AB(0.5) C6A(0.5) H6AA(0.5) H6AB(0.5) C6B(0.5) H6BA(0.5)
 H6BB(0.5) C7A(0.5) H7AA(0.5) H7AB(0.5) C7B(0.5) H7BA(0.5) H7BB(0.5) C8A(0.5)
 C8B(0.5) C9B(0.5) H9BA(0.5) H9BB(0.5) H9BC(0.5) C9A(0.5) H9AA(0.5) H9AB(0.5)
 H9AC(0.5) C10B(0.5) H10A(0.5) H10B(0.5) H10C(0.5) C10A(0.5) H10D(0.5)
 H10E(0.5) H10F(0.5) C11B(0.5) H11A(0.5) H11B(0.5) H11C(0.5) C11A(0.5)
 H11D(0.5) H11E(0.5) H11F(0.5) O2A(0.5) O2B(0.5) O3A(0.5) O3B(0.5) F1A(0.5)
 F1B(0.5) F2A(0.5) F2B(0.5) F3A(0.5) F3B(0.5) S1A(0.5) S1B(0.5) S2A(0.33333)
 O4A(0.33333) O5A(0.33333) O6A(0.33333) C22A(0.33333) F4A(0.33333) F5A(0.33333)
 F6A(0.33333) S2B(0.33333) O4B(0.33333) O5B(0.33333) O6B(0.33333) C22B(0.33333)
 F5B(0.33333) F4B(0.33333) F6B(0.33333) S2C(0.33333) O4C(0.33333) O5C(0.33333)
 O6C(0.33333) C22C(0.33333) F4C(0.33333) F5C(0.33333) F6C(0.33333)
6.a Secondary CH2 refined with riding coordinates:
 C2A(H2AA,H2AB), C2B(H2BA,H2BB), C3A(H3AA,H3AB), C3B(H3BA,H3BB), C4B(H4BA,
 H4BB), C4A(H4AA,H4AB), C5B(H5BA,H5BB), C5A(H5AA,H5AB), C6A(H6AA,H6AB),
 C6B(H6BA,H6BB), C7A(H7AA,H7AB), C7B(H7BA,H7BB)
6.b Idealised Me refined as rotating group:
 C9B(H9BA,H9BB,H9BC), C9A(H9AA,H9AB,H9AC), C10B(H10A,H10B,H10C), C10A(H10D,
 H10E,H10F), C11B(H11A,H11B,H11C), C11A(H11D,H11E,H11F), C13(H13A,H13B,H13C),
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C)
;
_shelxl_version_number           2013-4