Importance of molecular symmetry for enantiomeric excess recognition by NMR.
Norvaiša, Karolis; O'Brien, John E; Osadchuk, Irina; Twamley, Brendan; Borovkov, Victor; Senge, Mathias O.; Chemical communications (Cambridge, England) 58 (2022) 5423–5426; doi:10.1039/d2cc01319c

data_7129981
_publ_section_title
;
 Importance of molecular symmetry for enantiomeric excess recognition by
 NMR.
;
_journal_issue                   35
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              5423
_journal_page_last               5426
_journal_paper_doi               10.1039/d2cc01319c
_journal_volume                  58
_journal_year                    2022
_chemical_formula_moiety
'C60 H72 N8, 1.099(H O4 S), 3.701(O4 S), H O1.3 S0.2, 3.45(H2 O)'
_chemical_formula_sum            'C60 H84.38 N8 O23.95 S5'
_chemical_formula_weight         1461.23
_chemical_name_systematic
'a,a,b,b-5,10,15,20-Tetrakis(2-aminiumphenyl)-2,3,7,8,12,13,17,18-octaethyl-porphyrin tetra-hydrosulphate, sulphate, and water solvate'
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2021-11-08
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-01-21 deposited with the CCDC.	2022-03-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.962(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.7594(9)
_cell_length_b                   16.0888(8)
_cell_length_c                   24.9988(12)
_cell_measurement_reflns_used    9513
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      69.686
_cell_measurement_theta_min      2.92
_cell_volume                     7544.0(6)
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2016)'
_computing_data_collection       'APEX 3 (Bruker, 2017) '
_computing_data_reduction        'SAINT V8.40B (Bruker, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CMOS area detector'
_diffrn_detector_area_resol_mean 5.12
_diffrn_detector_type            'Bruker PHOTON 50'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_collimation    '0.5 mm double-pinhole'
_diffrn_radiation_detector       'Bruker PHOTON 50'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0578
_diffrn_reflns_av_unetI/netI     0.0345
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            94031
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.163
_diffrn_reflns_theta_min         2.922
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           0.6
_diffrn_source_power             0.029796
_diffrn_source_type              'Siemens, KFF Mo 2K -90 C'
_diffrn_source_voltage           49.66
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.066
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.6219
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0823 before and 0.0708 after correction.
The Ratio of minimum to maximum transmission is 0.8256.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.287
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Shard
_exptl_crystal_F_000             3088
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.07
_refine_diff_density_max         1.734
_refine_diff_density_min         -0.988
_refine_diff_density_rms         0.167
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.104
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1354
_refine_ls_number_reflns         14243
_refine_ls_number_restraints     3313
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.1537
_refine_ls_R_factor_gt           0.1354
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.3345P)^2^+4.4432P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3912
_refine_ls_wR_factor_ref         0.4253
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10735
_reflns_number_total             14243
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc01319c2.cif
_cod_data_source_block           kn007_2
_cod_depositor_comments          'Adding full bibliography for 7129981.cif.'
_cod_database_code               7129981
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.869
_shelx_estimated_absorpt_t_min   0.747
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H57A,H57B,H57C} of N57, {H9BA,H9BB,H9BC} of N9B, {H10A,
  H10B,H10C} of N107, {H2BA,H2BB,H2BC} of C2B, {H20A,H20B,H20C} of N207, {H16A,
  H16B,H16C} of N16B, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All O(H) groups, {H15A,H15B,H15C} of N157, {H13D,H13E,H13F} of C132, {H12D,
  H12E,H12F} of C122, {H17C,H17D,H17E} of C172, {H22A,H22B,H22C} of C22, {H18C,
  H18D,H18E} of C182, {H32A,H32B,H32C} of C32, {H72A,H72B,H72C} of C72, {H82A,
  H82B,H82C} of C82, All O(H,H) groups
2. Shared sites
{C101, C3B}
3. Restrained distances
 C101-C3B
 0.5 with sigma of 0.01
 S6S-S13S
 0.0001 with sigma of 0.01
 C171-C172 \\sim C1B-C2B
 with sigma of 0.01
 C101-C10 \\sim C3B-C10
 with sigma of 0.01
 N107-C102 \\sim N107-C4B
 with sigma of 0.01
 N9B-C4B \\sim N107-C102
 with sigma of 0.01
 S3A-O9A \\sim S3A-O10A \\sim S3A-O11A \\sim S3A-O12A
 with sigma of 0.01
 C51-C5 \\sim C10B-C5
 with sigma of 0.02
 C171-C17 \\sim C1B-C17
 with sigma of 0.01
 N57-C52 \\sim N16B-C15B
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2.5A with sigma of 0.05 and sigma
for terminal atoms of 0.05 within 2.5A
O63S \\sim S59S \\sim O60S \\sim O62S \\sim O61S \\sim O26S \\sim S23S \\sim
O27S \\sim O25S \\sim O24S: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
C101 \\sim C4B \\sim C5B \\sim C6B \\sim C7B \\sim C8B \\sim N107 \\sim C106
\\sim C3B \\sim C102 \\sim C103 \\sim C104 \\sim C105 \\sim N9B: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O40S \\sim O29S: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
S54S \\sim O57S \\sim O55S \\sim O56S \\sim O58S \\sim S43S \\sim O47S \\sim
O46S \\sim O45S \\sim O44S \\sim S31S \\sim O34S \\sim O32S \\sim O30S \\sim
O33S: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
C10B \\sim C15B \\sim C14B \\sim C13B \\sim C12B \\sim C11B \\sim N16B \\sim
N57 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
O67S \\sim S64S \\sim O65S \\sim O68S \\sim O66S \\sim O20S \\sim S18S \\sim
O19S \\sim O21S \\sim O22S: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(S48S) \\sim Ueq, Uanis(O51S) \\sim Ueq, Uanis(O49S) \\sim Ueq,
Uanis(O50S) \\sim Ueq, Uanis(O52S) \\sim Ueq, Uanis(S35S) \\sim Ueq,
Uanis(O36S) \\sim Ueq, Uanis(O37S) \\sim Ueq, Uanis(O39S) \\sim Ueq,
Uanis(O38S) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.001
Uanis(S54S) \\sim Ueq, Uanis(O57S) \\sim Ueq, Uanis(O55S) \\sim Ueq,
Uanis(O56S) \\sim Ueq, Uanis(O58S) \\sim Ueq, Uanis(S43S) \\sim Ueq,
Uanis(O47S) \\sim Ueq, Uanis(O46S) \\sim Ueq, Uanis(O45S) \\sim Ueq,
Uanis(O44S) \\sim Ueq, Uanis(S31S) \\sim Ueq, Uanis(O34S) \\sim Ueq,
Uanis(O32S) \\sim Ueq, Uanis(O30S) \\sim Ueq, Uanis(O33S) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(O53S) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C101) = Uanis(C3B)
Uanis(S6S) = Uanis(S13S)
5. Others
 1*[Sof(S54S)+Sof(O57S)+Sof(O55S)+Sof(O56S)+Sof(O58S)]+1*[Sof(S31S)+Sof(O34S)+
 Sof(O32S)+Sof(O30S)+Sof(O33S)]+1*[Sof(S43S)+Sof(O47S)+Sof(H47S)+Sof(O46S)+
 Sof(O45S)+Sof(O44S)]=0.75 with esd of 0.001
 Sof(C2B)=Sof(H2BA)=Sof(H2BB)=Sof(H2BC)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=1-FVAR(1)
 Sof(C171)=Sof(H17A)=Sof(H17B)=Sof(C172)=Sof(H17C)=Sof(H17D)=Sof(H17E)=FVAR(1)
 Sof(S13S)=Sof(O16S)=Sof(O15S)=Sof(O17S)=Sof(O14S)=1-FVAR(2)
 Sof(S6S)=Sof(O8S)=Sof(O10S)=Sof(O9S)=Sof(O7S)=FVAR(2)
 Sof(C4B)=Sof(C5B)=Sof(H5B)=Sof(C6B)=Sof(H6B)=Sof(C7B)=Sof(H7B)=Sof(C8B)=
 Sof(H8B)=Sof(C3B)=Sof(N9B)=Sof(H9BA)=Sof(H9BB)=Sof(H9BC)=1-FVAR(3)
 Sof(C101)=Sof(N107)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C106)=Sof(H106)=
 Sof(C102)=Sof(C103)=Sof(H103)=Sof(C104)=Sof(H104)=Sof(C105)=Sof(H105)=FVAR(3)
 Sof(S54S)=Sof(O57S)=Sof(O55S)=Sof(O56S)=Sof(O58S)=FVAR(4)
 Sof(S43S)=Sof(O47S)=Sof(H47S)=Sof(O46S)=Sof(O45S)=Sof(O44S)=FVAR(5)
 Sof(S31S)=Sof(O34S)=Sof(O32S)=Sof(O30S)=Sof(O33S)=FVAR(6)
 Sof(S59S)=Sof(O60S)=Sof(O63S)=Sof(H63S)=Sof(O62S)=Sof(O61S)=0.5*(1-FVAR(8))
 Sof(S23S)=Sof(O27S)=Sof(O26S)=Sof(O25S)=Sof(O24S)=0.5*FVAR(8)
 Sof(S35S)=Sof(O36S)=Sof(O37S)=Sof(O39S)=Sof(O38S)=0.75*(1-FVAR(9))
 Sof(S48S)=Sof(O51S)=Sof(O49S)=Sof(O50S)=Sof(O52S)=0.75*FVAR(9)
 Sof(C10B)=Sof(C15B)=Sof(C14B)=Sof(H14B)=Sof(C13B)=Sof(H13B)=Sof(C12B)=
 Sof(H12B)=Sof(C11B)=Sof(H11B)=Sof(N16B)=Sof(H16A)=Sof(H16B)=Sof(H16C)=1-FVAR(9)
 Sof(N57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=Sof(C51)=Sof(C52)=Sof(C53)=Sof(H53)=
 Sof(C54)=Sof(H54)=Sof(C55)=Sof(H55)=Sof(C56)=Sof(H56)=FVAR(9)
 Fixed Sof: S3A(0.5) O9A(0.5) H9A(0.5) O11A(0.5) O10A(0.5) O12A(0.5) S18S(0.2)
 O20S(0.2) O19S(0.2) O21S(0.2) O22S(0.2) O40S(0.25) H40A(0.25) H40B(0.25)
 O29S(0.5) H29A(0.5) H29B(0.5) O12S(0.5) H12G(0.5) H12H(0.5) O41S(0.25)
 H41A(0.25) H41B(0.25) O28S(0.25) H28A(0.25) H28B(0.25) O53S(0.2) H53A(0.2)
 H53B(0.2) S64S(0.3) O67S(0.3) O65S(0.3) O68S(0.3) O66S(0.3)
6.a Riding coordinates:
 O11S(H11A,H11C), O40S(H40A,H40B), O29S(H29A,H29B), O12S(H12G,H12H), O41S(H41A,
 H41B), O28S(H28A,H28B), O53S(H53A,H53B)
6.b Free rotating group:
 S18S(O20S,O19S,O21S,O22S), S54S(O57S,O55S,O56S,O58S), S48S(O51S,O49S,O50S,
 O52S), S35S(O36S,O37S,O39S,O38S), S43S(O47S,O46S,O45S,O44S), O20(H20D,H20E),
 S31S(O34S,O32S,O30S,O33S), S23S(O27S,O26S,O25S,O24S), S64S(O67S,O65S,O68S,O66S)
6.c Secondary CH2 refined with riding coordinates:
 C181(H18A,H18B), C21(H21A,H21B), C31(H31A,H31B), C71(H71A,H71B), C81(H81A,
 H81B), C121(H12A,H12C), C131(H13A,H13C), C171(H17A,H17B), C1B(H1BA,H1BB)
6.d Aromatic/amide H refined with riding coordinates:
 N24(H24), N23(H23), N22(H22), N21(H21), C205(H205), C204(H204), C203(H203),
 C202(H202), C14B(H14B), C13B(H13B), C12B(H12B), C11B(H11B), C5B(H5B), C6B(H6B),
  C7B(H7B), C8B(H8B), C153(H153), C154(H154), C155(H155), C156(H156),
 C106(H106), C103(H103), C104(H104), C105(H105), C53(H53), C54(H54), C55(H55),
 C56(H56)
6.e Tetrahedral OH refined with riding coordinates:
 O63S(H63S), O47S(H47S)
6.f Idealised Me refined with riding coordinates:
 C2B(H2BA,H2BB,H2BC)
6.g Idealised Me refined as rotating group:
 C182(H18C,H18D,H18E), N207(H20A,H20B,H20C), C22(H22A,H22B,H22C), C32(H32A,
 H32B,H32C), N16B(H16A,H16B,H16C), C72(H72A,H72B,H72C), C82(H82A,H82B,H82C),
 N107(H10A,H10B,H10C), C122(H12D,H12E,H12F), C132(H13D,H13E,H13F), N157(H15A,
 H15B,H15C), C172(H17C,H17D,H17E), N9B(H9BA,H9BB,H9BC), N57(H57A,H57B,H57C)
6.h Idealised tetrahedral OH refined as rotating group:
 O9A(H9A)
;
_shelx_res_checksum              30203
_shelx_hkl_checksum              61037
_olex2_submission_special_instructions 'No special instructions were received'