# Electronic Supplementary Material (ESI) for Chemical Science.
# This journal is © The Royal Society of Chemistry 2021

# CIF-file generated for LauRa3_0m-P 21/n       R = 0.03
 
#==============================================================================
data_global
#==============================================================================
 
# 0. AUDIT DETAILS
 
_audit_creation_date                              'Monday, 13 August 2018  '
_audit_creation_method                            'PLATON <TABLE ACC> option'
_audit_update_record
;
April 26th 2021: CIF updated for publication by author C.J.
;
 
#===============================================================================
 
# 1. SUBMISSION DETAILS
 
# Name and address of author for X-ray correspondence

_publ_contact_author_name                    # Name of author for correspondence
;
Prof. Dr. Corinna R. Hess
;
_publ_contact_author_address              # address of author for correspondence
;
Assistant Professorship of Bioinorganic Chemistry
Fakultät für Chemie
Technische Universität München
Lichtenbergstr. 4
85747 Garching
Germany
;
 
_publ_contact_author_email                    corinna.hess@ch.tum.de
_publ_contact_author_phone                    '+49(0)89 289 13686'
 
_publ_requested_journal                       'Chem. Sci.'
# Publication choise FI, CI or EI for Inorganic
#                    FM, CM or EM for Metal-organic
#                    FO, CO or EO for Organic
_publ_requested_category                      ?
_publ_requested_coeditor_name                 ?
 
_publ_contact_letter                         # Include date of submission
;
Date of submission: May 2020
;
 
#===============================================================================
 
# 2. PROCESSING SUMMARY (JOURNAL OFFICE ONLY)
 
#===============================================================================
 
# 3. TITLE AND AUTHOR LIST
 
_publ_section_title
;
The central role of the metal ion for photoactivity: Zn- vs. Ni-Mabiq
;
_publ_section_title_footnote
;
;
 
# The loop structure below should contain the names and adresses of all
# authors, in the required order of publication. Repeat as necessary.
 
 
loop_
_publ_author_name
_publ_author_footnote
_publ_author_address
       'Lauenstein, R.'
;   # author related footnote
?
;
;
       Department of Chemistry and Catalysis Research Center,
       Technical University of Munich,
       Lichtenbergstr. 4,
       85747 Garching,
       Germany.
;
       'Mader, S. L.'
;   # author related footnote
?
;
;
       Department of Chemistry,
       Technical University of Munich,
       Lichtenbergstr. 4,
       85747 Garching,
       Germany.
;
       'Derondeau, H.'
;   # author related footnote
?
;
;
       Lehrstuhl für BioMolekulare Optik,
       Fakultät für Physik,
       Ludwig-Maximilians-Universität München,
       Oettingenstr. 67,
       80538 Munich,
       Germany.
;
       'Esezobor, O. R.'
;   # author related footnote
?
;
;
       Department of Chemistry and Catalysis Research Center,
       Technical University of Munich,
       Lichtenbergstr. 4,
       85747 Garching,
       Germany.
;
       'Block, M.'
;   # author related footnote
?
;
;
       Lehrstuhl für BioMolekulare Optik,
       Fakultät für Physik,
       Ludwig-Maximilians-Universität München,
       Oettingenstr. 67,
       80538 Munich,
       Germany.
;
       'Römer, A. J.'
;   # author related footnote
?
;
;
       Department of Chemistry,
       Technical University of Munich,
       Lichtenbergstr. 4,
       85747 Garching,
       Germany.
;
       'Jandl, C.'
;   # author related footnote
?
;
;
       Department of Chemistry and Catalysis Research Center,
       Technical University of Munich,
       Lichtenbergstr. 4,
       85747 Garching,
       Germany.
;
       'Riedle, E.'
;   # author related footnote
?
;
;
       Lehrstuhl für BioMolekulare Optik,
       Fakultät für Physik,
       Ludwig-Maximilians-Universität München,
       Oettingenstr. 67,
       80538 Munich,
       Germany.
;
       'Kaila, V. R. I.'
;   # author related footnote
present address:
Department of Biochemistry and Biophysics,
Stockholm University,
Stockholm,
Sweden
;
;
       Department of Chemistry,
       Technical University of Munich,
       Lichtenbergstr. 4,
       85747 Garching,
       Germany.
;
       'Hauer, J.'
;   # author related footnote
?
;
;
       Department of Chemistry and Catalysis Research Center,
       Technical University of Munich,
       Lichtenbergstr. 4,
       85747 Garching,
       Germany.
       Photonics Institute,
       TU Wien,
       1040 Vienna,
       Austria.
;
       'Thyrhaug, E.'
;   # author related footnote
?
;
;
       Department of Chemistry and Catalysis Research Center,
       Technical University of Munich,
       Lichtenbergstr. 4,
       85747 Garching,
       Germany.
;
       'Hess, C. R.'
;   # author related footnote
?
;
;
       Department of Chemistry and Catalysis Research Center,
       Technical University of Munich,
       Lichtenbergstr. 4,
       85747 Garching,
       Germany.
;
 
#===============================================================================
 
# 4. TEXT
 
_publ_section_synopsis
;
 ?
;
_publ_section_abstract
;
Photoredox catalysts are integral components of artificial photosystems, and 
have recently emerged as powerful tools for catalysing numerous organic
reactions. However, the development of inexpensive and efficient
earth-abundant photoredox catalysts remains a challenge. We here present
the photochemical and photophysical properties of a Ni-Mabiq catalyst
([NiII(Mabiq)]OTf (1); Mabiq = 2-4:6-8-bis(3,3,4,4-tetramethyldihydropyrrolo)-
10-15-(2,2-biquinazolino)-[15]-1,3,5,8,10,14-hexaene1,3,7,9,11,14-N6) --- and
of a Zn-containing analogue ([ZnII(Mabiq)OTf] (2)) --- using steady state and
time resolved optical spectroscopy, time-dependent density functional theory
(TDDFT) calculations, and reactivity studies. The Ni and Zn complexes exhibit
similar absorption spectra, but markedly different photochemical properties.
These differences arise because the excited states of 2 are ligand-localized,
whereas metal-centered states account for the photoactivity of 1. The distinct
properties of the Ni and Zn complexes are manifest in their behavior in the
photo-driven Aza-Henry reaction and oxidative coupling of methoxybenzylamine.
;
 
# Insert blank lines between paragraphs
 
_publ_section_comment
;
;
_publ_section_exptl_prep
;
 The crystal was fixed on the top of a kapton micro sampler with
 perfluorinated ether and transferred to the diffractometer.
;
_publ_section_exptl_refinement
;
 Solution and refinements with the program APEX (Bruker 2015) 
 and SHELXL2014 (Sheldrick, 2014)in conjunction with SHELXLE (Huebschle, 2011).
 Hydrogen atoms could not be located in the difference Fourier maps
 and were calculated in ideal positions (riding model).
;
 
# Insert blank lines between references
 
_publ_section_references
;
 Allen, F. H.(2004). ENCIFER. J. Applied Cryst. 37, 335-338. 

 Bruker (2015). APEX suite of crystallographic software.
 APEX 3 Version 2015.5-2. Bruker AXS Inc., Madison, Wisconsin, USA.

 Bruker (2014). SAINT, Version 8.34A and SADABS Version 2014/5.
 Bruker AXS Inc., Madison, Wisconsin, USA.

 Flack, H.D. (1983). Acta Cryst. A39, 876-881.
 
 Huebschle, C. B.; Sheldrick, G. M.; Dittrich, B. (2011). SHELXLE. 
 J. Appl. Cryst., 44, (2011) 1281 - 1284.   

 Sheldrick, G. M. (2015). Acta Cryst. A71, 3-8.
 
 Sheldrick, G. M. (2014). SHELXL2014. University of Göttingen, Germany.

 Spek, A. L. (2011). PLATON, A Multipurpose Crystallographic Tool, Utrecht
 University, Utrecht, The Netherlands.
  
 Spek, A.L. (2003). J. Appl. Cryst. 36, 7-13.
 
 Wilson, A.J.C. (1992). Ed. International Tables for Crystallography,
 Volume C, Kluwer Academic Publishers, Dordrecht, The Netherlands.
;

_publ_section_acknowledgements
;
;
_publ_section_figure_captions
; View of the title compound with the atom numbering scheme.
Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
;
 
#===============================================================================
 
data_compound_2
 
#===============================================================================

# start Validation Reply Form
_vrf_PUBL024_GLOBAL
;
PROBLEM: The number of authors is greater than 9.
         Please specify the role of each of the co-authors
         for your paper.
RESPONSE: 
R. L.: Synthesis and characterisation, manuscript preparation, SI preparation
S. L. M.: TDDFT calculations, SI preparation 
H. D.: Transient absorption spectroscopy, SI preparation
O. Z. E.: Catalytic studies
M. B.: Transient absorption spectroscopy, SI preparation
A. J. R.: TDDFT calculations
C. J.: X-ray crystallography, SI preparation
E. R.: Transient absorption spectroscopy
V. R. I. K.: TDDFT calculations
J. H.: Transient absorption spectroscopy
E. T.: Transient absorption spectroscopy, manuscript preparation
C. R. H.: Research Conception, manuscript preparation
;
# end Validation Reply Form


#===============================================================================
 
# 5. CHEMICAL DATA
 
_chemical_name_systematic
;
;
_chemical_name_common                             ?
_chemical_melting_point                           ?
_chemical_formula_moiety
'C34 H33 F3 N8 O3 S Zn, C H2 Cl2'
_chemical_formula_structural                      ?
_chemical_formula_sum
'C35 H35 Cl2 F3 N8 O3 S Zn'
_chemical_formula_iupac                           ?
_chemical_formula_weight                             841.06
_chemical_compound_source                        'see text'
 
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
 C   C    0.0033    0.0016
' International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 H   H    0.0000    0.0000
' International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl  Cl    0.1484    0.1585
' International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 F   F    0.0171    0.0103
' International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 N   N    0.0061    0.0033
' International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 O   O    0.0106    0.0060
' International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 S   S    0.1246    0.1234
' International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Zn  Zn    0.2839    1.4301
' International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 
#===============================================================================
 
# 6. CRYSTAL DATA
 
_symmetry_cell_setting                              monoclinic
_symmetry_space_group_name_Hall                   '-P 2yn'
_symmetry_space_group_name_H-M                    'P 21/n'
_symmetry_Int_Tables_number                              14
 
loop_
_space_group_symop_id
_space_group_symop_operation_xyz
   1 x,y,z
   2 1/2-x,1/2+y,1/2-z
   3 -x,-y,-z
   4 1/2+x,1/2-y,1/2+z
 
_cell_length_a                                       13.2525(9)
_cell_length_b                                      18.3533(12)
_cell_length_c                                       15.0527(9)
_cell_angle_alpha                                            90
_cell_angle_beta                                      96.635(2)
_cell_angle_gamma                                            90
_cell_volume                                          3636.7(4)
_cell_formula_units_Z                                 4
_cell_measurement_temperature                       100
_cell_measurement_reflns_used     9724    
_cell_measurement_theta_min       2.2346      
_cell_measurement_theta_max       26.4004   
_cell_special_details
;
;
 
_exptl_crystal_description        'fragment'
_exptl_crystal_colour             'orange'
 
_exptl_crystal_size_max                               0.346
_exptl_crystal_size_mid                               0.334
_exptl_crystal_size_min                               0.269
_exptl_crystal_size_rad                           ?
_exptl_crystal_density_meas                       ?
_exptl_crystal_density_diffrn                         1.536
_exptl_crystal_density_method                    'Not Measured'
_exptl_crystal_F_000                                   1728
_exptl_absorpt_coefficient_mu                         0.944
_exptl_crystal_density_meas_temp                  ?
 
_exptl_absorpt_correction_type 'multi-scan'
_exptl_absorpt_process_details 'SADABS 2014/5, Bruker, 2014'
_exptl_absorpt_correction_T_min                   0.6801    
_exptl_absorpt_correction_T_max                   0.7454
 
#===============================================================================
 
# 7. EXPERIMENTAL DATA
 
_exptl_special_details
;
Diffractometer operator             C. Jandl
scanspeed                           1-2 s per frame
dx                                  40 mm
1918 frames measured in 10 data sets
phi-scans with delta_phi         = 0.5
omega-scans with delta_omega     = 0.5
shutterless mode
;
_diffrn_ambient_temperature                         100
_diffrn_radiation_wavelength                        0.71073
_diffrn_radiation_probe                           'x-ray'
_diffrn_radiation_type                            'MoK\a'
_diffrn_radiation_source          'TXS rotating anode'
_diffrn_radiation_monochromator   'Helios optic'

_diffrn_measurement_device        ' κ-geometry diffractometer '
_diffrn_measurement_device_type   ' Bruker Photon CMOS '
_diffrn_measurement_method        ' phi- and omega-rotation '
_diffrn_detector                  ' CMOS plate '
_diffrn_detector_area_resol_mean  16
 
# number of measured reflections (redundant set)
_diffrn_reflns_number                            104552
_diffrn_reflns_av_R_equivalents                    0.0556
_diffrn_reflns_av_unetI/netI                       0.0194
_diffrn_reflns_limit_h_min                          -16
_diffrn_reflns_limit_h_max                           16
_diffrn_reflns_limit_k_min                          -22
_diffrn_reflns_limit_k_max                           22
_diffrn_reflns_limit_l_min                          -18
_diffrn_reflns_limit_l_max                           18
_diffrn_reflns_theta_min                           2.22
_diffrn_reflns_theta_max                          26.02
_diffrn_reflns_theta_full                         25.24
_diffrn_measured_fraction_theta_max               0.999
_diffrn_measured_fraction_theta_full              0.999
_diffrn_reflns_reduction_process
;
;
 
# number of unique reflections
_reflns_number_total                                 7163
# number of observed reflections (> n sig(I))
_reflns_number_gt                                    6196
_reflns_threshold_expression                      I>2σ(I)
 
_computing_data_collection       'APEX III Control Software (Bruker, 2015)'
_computing_cell_refinement       'SAINT (Bruker, 2014)'
_computing_data_reduction        'SAINT (Bruker, 2014)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_computing_structure_refinement  
'SHELXL2014 (Sheldrick, 2014), SHELXLE (Huebschle, 2011)'
_computing_molecular_graphics    'PLATON (Spek, 2011)'
_computing_publication_material  'PLATON (Spek, 2011), enCIFer (Allen, 2014)'
 
#===============================================================================
 
# 8. REFINEMENT DATA
 
_refine_special_details
;
 Refinement on F² for ALL reflections except those
 flagged by the user for potential systematic errors.
 Weighted R-factors wR and all goodnesses of fit S
 are based on F², conventional R-factors R are based
 on F, with F set to zero for negative F². The
 observed criterion of F² > 2sigma(F²) is used only
 for calculating -R-factor-obs etc. and is not
 relevant to the choice of reflections for refinement.
 R-factors based on F² are statistically about twice
 as large as those based on F, and R-factors based on
 ALL data will be even larger.
;
_refine_ls_structure_factor_coef                  Fsqd
_refine_ls_matrix_type                            full
_refine_ls_weighting_scheme                       'calc'
_refine_ls_weighting_details
'W=1/[Σ²(FO²)+(0.0294P)²+4.3229P] WHERE P=(FO²+2FC²)/3'
_atom_sites_solution_primary                     'iterative'
_atom_sites_solution_secondary                   'difmap'
_atom_sites_solution_hydrogens                   'geom'
 
 
_refine_ls_hydrogen_treatment                    'constr'
 
_refine_ls_extinction_method                      'none'
_refine_ls_abs_structure_details                  ?
_refine_ls_abs_structure_Flack                   .
_refine_ls_number_reflns                               7163
_refine_ls_number_parameters                            523
_refine_ls_number_restraints                            126
_refine_ls_number_constraints                     ?
_refine_ls_R_factor_all                              0.0397
_refine_ls_R_factor_gt                               0.0309
_refine_ls_wR_factor_ref                             0.0742
_refine_ls_wR_factor_gt                              0.0702
_refine_ls_goodness_of_fit_ref                        1.030
_refine_ls_restrained_S_all                           1.035
_refine_ls_shift/su_max                               0.002
_refine_ls_shift/su_mean                              0.000
_refine_diff_density_max                              0.815
_refine_diff_density_min                             -0.606
_refine_diff_density_rms                              0.061
 
#===============================================================================
 
# 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS
 
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_thermal_displace_type
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_U_iso_or_equiv
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Zn1 Zn Uani 0.52543(2) 0.33613(2) 0.33586(2) 1.000 0.0111(1) d . . .
S1 S Uani 0.55061(4) 0.16352(3) 0.34022(3) 1.000 0.0184(1) d . . .
Cl1 Cl Uani 0.57555(5) 0.33429(4) 0.82615(5) 1.000 0.0455(2) d . . .
Cl2 Cl Uani 0.49419(6) 0.48063(4) 0.81860(6) 1.000 0.0566(3) d . . .
F1 F Uani 0.3703(4) 0.1316(4) 0.3833(3) 0.618(13) 0.0437(13) d DUP A 1
F1A F Uani 0.3650(5) 0.1647(6) 0.3834(5) 0.382(13) 0.0387(16) d DUP A 2
F2 F Uani 0.4693(5) 0.0394(2) 0.3716(3) 0.618(13) 0.0436(13) d DUP A 1
F2A F Uani 0.4255(8) 0.0558(5) 0.3707(5) 0.382(13) 0.0467(18) d DUP A 2
F3 F Uani 0.4936(6) 0.1091(4) 0.4859(4) 0.618(13) 0.0477(17) d DUP A 1
F3A F Uani 0.4715(8) 0.1197(7) 0.4877(6) 0.382(13) 0.0299(16) d DUP A 2
O1 O Uani 0.55779(12) 0.23343(8) 0.38772(9) 1.000 0.0220(4) d . . .
O2 O Uani 0.50155(12) 0.16838(9) 0.25038(9) 1.000 0.0269(5) d . . .
O3 O Uani 0.64133(14) 0.12160(10) 0.35524(12) 1.000 0.0421(6) d . . .
N1 N Uani 0.38593(12) 0.40331(9) 0.55650(11) 1.000 0.0157(5) d . . .
N2 N Uani 0.41081(12) 0.36408(8) 0.40952(10) 1.000 0.0125(5) d . . .
N3 N Uani 0.27140(12) 0.32699(9) 0.30328(11) 1.000 0.0147(5) d . . .
N4 N Uani 0.42260(11) 0.33228(8) 0.22890(10) 1.000 0.0123(5) d . . .
N5 N Uani 0.63533(12) 0.35924(9) 0.26088(10) 1.000 0.0126(4) d . . .
N6 N Uani 0.76611(12) 0.39576(9) 0.37659(10) 1.000 0.0135(5) d . . .
N7 N Uani 0.60690(12) 0.39308(8) 0.43783(10) 1.000 0.0125(4) d . . .
N8 N Uani 0.58979(12) 0.43897(9) 0.58374(10) 1.000 0.0144(5) d . . .
C1 C Uani 0.44227(14) 0.39123(10) 0.49251(12) 1.000 0.0132(5) d . . .
C2 C Uani 0.28500(15) 0.38537(10) 0.53751(13) 1.000 0.0159(6) d . . .
C3 C Uani 0.22031(16) 0.39475(11) 0.60492(14) 1.000 0.0216(6) d . . .
C4 C Uani 0.11966(17) 0.37576(12) 0.58789(15) 1.000 0.0264(7) d . . .
C5 C Uani 0.07983(16) 0.34869(12) 0.50421(16) 1.000 0.0248(7) d . . .
C6 C Uani 0.13998(15) 0.34030(11) 0.43697(14) 1.000 0.0191(6) d . . .
C7 C Uani 0.24430(14) 0.35810(10) 0.45307(13) 1.000 0.0150(5) d . . .
C8 C Uani 0.31256(14) 0.34935(10) 0.38678(13) 1.000 0.0136(5) d . . .
C9 C Uani 0.32077(14) 0.32231(10) 0.23351(13) 1.000 0.0137(5) d . . .
C10 C Uani 0.26735(14) 0.30004(11) 0.14334(13) 1.000 0.0162(6) d . . .
C11 C Uani 0.34417(15) 0.32740(11) 0.07922(13) 1.000 0.0164(6) d . . .
C12 C Uani 0.44230(14) 0.33019(10) 0.14293(12) 1.000 0.0133(5) d . . .
C13 C Uani 0.53943(14) 0.33632(10) 0.11648(12) 1.000 0.0144(5) d . . .
C14 C Uani 0.62953(14) 0.35066(10) 0.17176(12) 1.000 0.0126(5) d . . .
C15 C Uani 0.73201(14) 0.36447(10) 0.13778(12) 1.000 0.0140(5) d . . .
C16 C Uani 0.80518(14) 0.35811(11) 0.22694(13) 1.000 0.0152(5) d . . .
C17 C Uani 0.73327(14) 0.37411(10) 0.29586(12) 1.000 0.0125(5) d . . .
C18 C Uani 0.70549(14) 0.40954(10) 0.44315(12) 1.000 0.0121(5) d . . .
C19 C Uani 0.75331(14) 0.44179(10) 0.52400(12) 1.000 0.0132(5) d . . .
C20 C Uani 0.85771(15) 0.45866(10) 0.53766(13) 1.000 0.0158(5) d . . .
C21 C Uani 0.89883(16) 0.48698(11) 0.61811(14) 1.000 0.0194(6) d . . .
C22 C Uani 0.83764(16) 0.50012(11) 0.68661(13) 1.000 0.0205(6) d . . .
C23 C Uani 0.73611(16) 0.48438(11) 0.67502(13) 1.000 0.0180(6) d . . .
C24 C Uani 0.69176(15) 0.45476(10) 0.59321(12) 1.000 0.0141(5) d . . .
C25 C Uani 0.55354(14) 0.40963(10) 0.50780(12) 1.000 0.0124(5) d . . .
C26 C Uani 0.26058(16) 0.21644(11) 0.14527(15) 1.000 0.0232(6) d . . .
C27 C Uani 0.15964(16) 0.33029(13) 0.12499(15) 1.000 0.0269(7) d . . .
C28 C Uani 0.32199(17) 0.40652(12) 0.04844(15) 1.000 0.0263(7) d . . .
C29 C Uani 0.34947(16) 0.28017(13) -0.00365(14) 1.000 0.0240(6) d . . .
C30 C Uani 0.75453(16) 0.31103(12) 0.06481(13) 1.000 0.0201(6) d . . .
C31 C Uani 0.72998(16) 0.44226(11) 0.09947(14) 1.000 0.0223(6) d . . .
C32 C Uani 0.89827(15) 0.40807(13) 0.23399(14) 1.000 0.0229(6) d . . .
C33 C Uani 0.84102(16) 0.27890(12) 0.24543(14) 1.000 0.0221(6) d . . .
C34 C Uani 0.4655(5) 0.1088(3) 0.3983(4) 0.618(13) 0.0318(11) d DUP A 1
C34A C Uani 0.4469(7) 0.1234(5) 0.3999(7) 0.382(13) 0.0323(16) d DUP A 2
C35 C Uani 0.48433(18) 0.39338(12) 0.77167(15) 1.000 0.0258(7) d . . .
H3 H Uiso 0.24620 0.41400 0.66160 1.000 0.0260 c RU . .
H4 H Uiso 0.07640 0.38110 0.63360 1.000 0.0320 c RU . .
H5 H Uiso 0.01000 0.33600 0.49400 1.000 0.0300 c RU . .
H6 H Uiso 0.11200 0.32270 0.38010 1.000 0.0230 c RU . .
H13 H Uiso 0.54500 0.33010 0.05460 1.000 0.0170 c RU . .
H20 H Uiso 0.89940 0.45050 0.49140 1.000 0.0190 c RU . .
H21 H Uiso 0.96940 0.49780 0.62760 1.000 0.0230 c RU . .
H22 H Uiso 0.86720 0.52020 0.74170 1.000 0.0250 c RU . .
H23 H Uiso 0.69560 0.49340 0.72190 1.000 0.0220 c RU . .
H26A H Uiso 0.22680 0.19890 0.08790 1.000 0.0350 c RU . .
H26B H Uiso 0.22140 0.20130 0.19350 1.000 0.0350 c RU . .
H26C H Uiso 0.32910 0.19580 0.15560 1.000 0.0350 c RU . .
H27A H Uiso 0.16160 0.38360 0.12930 1.000 0.0400 c RU . .
H27B H Uiso 0.11790 0.31080 0.16910 1.000 0.0400 c RU . .
H27C H Uiso 0.13020 0.31600 0.06480 1.000 0.0400 c RU . .
H28A H Uiso 0.37800 0.42460 0.01730 1.000 0.0390 c RU . .
H28B H Uiso 0.31530 0.43730 0.10070 1.000 0.0390 c RU . .
H28C H Uiso 0.25860 0.40800 0.00780 1.000 0.0390 c RU . .
H29A H Uiso 0.28290 0.27950 -0.03950 1.000 0.0360 c RU . .
H29B H Uiso 0.36890 0.23040 0.01470 1.000 0.0360 c RU . .
H29C H Uiso 0.40010 0.30030 -0.03940 1.000 0.0360 c RU . .
H30A H Uiso 0.71080 0.32210 0.00940 1.000 0.0300 c RU . .
H30B H Uiso 0.74130 0.26120 0.08380 1.000 0.0300 c RU . .
H30C H Uiso 0.82590 0.31550 0.05440 1.000 0.0300 c RU . .
H31A H Uiso 0.79520 0.45290 0.07750 1.000 0.0330 c RU . .
H31B H Uiso 0.71830 0.47720 0.14650 1.000 0.0330 c RU . .
H31C H Uiso 0.67520 0.44630 0.05010 1.000 0.0330 c RU . .
H32A H Uiso 0.93830 0.39760 0.18470 1.000 0.0340 c RU . .
H32B H Uiso 0.94000 0.39950 0.29110 1.000 0.0340 c RU . .
H32C H Uiso 0.87610 0.45900 0.23070 1.000 0.0340 c RU . .
H33A H Uiso 0.78190 0.24650 0.24160 1.000 0.0330 c RU . .
H33B H Uiso 0.87830 0.27580 0.30540 1.000 0.0330 c RU . .
H33C H Uiso 0.88560 0.26420 0.20100 1.000 0.0330 c RU . .
H35A H Uiso 0.49380 0.39630 0.70750 1.000 0.0310 c RU . .
H35B H Uiso 0.41560 0.37370 0.77630 1.000 0.0310 c RU . .
 
 
#===============================================================================
 
# 10. MOLECULAR GEOMETRY
 
_geom_special_details
;
 Bond distances, angles etc. have been calculated using the
 rounded fractional coordinates. All su's are estimated
 from the variances of the (full) variance-covariance matrix.
 The cell esds are taken into account in the estimation of
 distances, angles and torsion angles
;
 
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_1
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
 Zn1     O1       2.0661(15)                     .       .                   yes
 Zn1     N2       2.0467(16)                     .       .                   yes
 Zn1     N4       1.9868(15)                     .       .                   yes
 Zn1     N5       1.9887(16)                     .       .                   yes
 Zn1     N7       2.0570(15)                     .       .                   yes
 S1      O1       1.4666(15)                     .       .                   yes
 S1      O2       1.4340(15)                     .       .                   yes
 S1      O3       1.4233(19)                     .       .                   yes
 S1      C34        1.809(6)                     .       .                   yes
 S1      C34A      1.877(10)                     .       .                   yes
 Cl1     C35        1.755(2)                     .       .                   yes
 Cl2     C35        1.749(2)                     .       .                   yes
 F1      C34        1.324(9)                     .       .                   yes
 F1A     C34A      1.324(13)                     .       .                   yes
 F2      C34        1.338(7)                     .       .                   yes
 F2A     C34A      1.336(13)                     .       .                   yes
 F3      C34        1.328(9)                     .       .                   yes
 F3A     C34A      1.326(14)                     .       .                   yes
 N1      C2         1.375(3)                     .       .                   yes
 N1      C1         1.304(2)                     .       .                   yes
 N2      C8         1.335(2)                     .       .                   yes
 N2      C1         1.365(2)                     .       .                   yes
 N3      C9         1.303(3)                     .       .                   yes
 N3      C8         1.374(3)                     .       .                   yes
 N4      C9         1.372(2)                     .       .                   yes
 N4      C12        1.350(2)                     .       .                   yes
 N5      C17        1.371(2)                     .       .                   yes
 N5      C14        1.344(2)                     .       .                   yes
 N6      C18        1.378(2)                     .       .                   yes
 N6      C17        1.305(2)                     .       .                   yes
 N7      C25        1.369(2)                     .       .                   yes
 N7      C18        1.334(2)                     .       .                   yes
 N8      C24        1.373(3)                     .       .                   yes
 N8      C25        1.304(2)                     .       .                   yes
 C1      C25        1.504(3)                     .       .                   no
 C2      C7         1.414(3)                     .       .                   no
 C2      C3         1.413(3)                     .       .                   no
 C3      C4         1.374(3)                     .       .                   no
 C4      C5         1.399(3)                     .       .                   no
 C5      C6         1.368(3)                     .       .                   no
 C6      C7         1.414(3)                     .       .                   no
 C7      C8         1.431(3)                     .       .                   no
 C9      C10        1.513(3)                     .       .                   no
 C10     C26        1.537(3)                     .       .                   no
 C10     C11        1.564(3)                     .       .                   no
 C10     C27        1.527(3)                     .       .                   no
 C11     C28        1.542(3)                     .       .                   no
 C11     C29        1.527(3)                     .       .                   no
 C11     C12        1.525(3)                     .       .                   no
 C12     C13        1.395(3)                     .       .                   no
 C13     C14        1.399(3)                     .       .                   no
 C14     C15        1.527(3)                     .       .                   no
 C15     C31        1.539(3)                     .       .                   no
 C15     C30        1.528(3)                     .       .                   no
 C15     C16        1.567(3)                     .       .                   no
 C16     C32        1.531(3)                     .       .                   no
 C16     C17        1.516(3)                     .       .                   no
 C16     C33        1.545(3)                     .       .                   no
 C18     C19        1.434(3)                     .       .                   no
 C19     C20        1.410(3)                     .       .                   no
 C19     C24        1.416(3)                     .       .                   no
 C20     C21        1.372(3)                     .       .                   no
 C21     C22        1.404(3)                     .       .                   no
 C22     C23        1.368(3)                     .       .                   no
 C23     C24        1.411(3)                     .       .                   no
 C3      H3           0.9500                     .       .                   no
 C4      H4           0.9500                     .       .                   no
 C5      H5           0.9500                     .       .                   no
 C6      H6           0.9500                     .       .                   no
 C13     H13          0.9500                     .       .                   no
 C20     H20          0.9500                     .       .                   no
 C21     H21          0.9500                     .       .                   no
 C22     H22          0.9500                     .       .                   no
 C23     H23          0.9500                     .       .                   no
 C26     H26B         0.9800                     .       .                   no
 C26     H26A         0.9800                     .       .                   no
 C26     H26C         0.9800                     .       .                   no
 C27     H27B         0.9800                     .       .                   no
 C27     H27C         0.9800                     .       .                   no
 C27     H27A         0.9800                     .       .                   no
 C28     H28C         0.9800                     .       .                   no
 C28     H28A         0.9800                     .       .                   no
 C28     H28B         0.9800                     .       .                   no
 C29     H29C         0.9800                     .       .                   no
 C29     H29B         0.9800                     .       .                   no
 C29     H29A         0.9800                     .       .                   no
 C30     H30B         0.9800                     .       .                   no
 C30     H30A         0.9800                     .       .                   no
 C30     H30C         0.9800                     .       .                   no
 C31     H31B         0.9800                     .       .                   no
 C31     H31A         0.9800                     .       .                   no
 C31     H31C         0.9800                     .       .                   no
 C32     H32B         0.9800                     .       .                   no
 C32     H32C         0.9800                     .       .                   no
 C32     H32A         0.9800                     .       .                   no
 C33     H33C         0.9800                     .       .                   no
 C33     H33A         0.9800                     .       .                   no
 C33     H33B         0.9800                     .       .                   no
 C35     H35A         0.9900                     .       .                   no
 C35     H35B         0.9900                     .       .                   no
 
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_2
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
 O1      Zn1     N2         99.13(6)             .       .       .           yes
 O1      Zn1     N4        111.51(6)             .       .       .           yes
 O1      Zn1     N5        105.98(7)             .       .       .           yes
 O1      Zn1     N7         96.52(6)             .       .       .           yes
 N2      Zn1     N4         88.02(6)             .       .       .           yes
 N2      Zn1     N5        153.13(7)             .       .       .           yes
 N2      Zn1     N7         80.03(6)             .       .       .           yes
 N4      Zn1     N5         91.51(6)             .       .       .           yes
 N4      Zn1     N7        150.99(6)             .       .       .           yes
 N5      Zn1     N7         87.68(6)             .       .       .           yes
 O1      S1      O2        113.71(9)             .       .       .           yes
 O1      S1      O3       112.92(10)             .       .       .           yes
 O1      S1      C34      105.01(19)             .       .       .           yes
 O1      S1      C34A        96.9(3)             .       .       .           yes
 O2      S1      O3       117.78(10)             .       .       .           yes
 O2      S1      C34        104.5(2)             .       .       .           yes
 O2      S1      C34A       101.5(3)             .       .       .           yes
 O3      S1      C34        100.7(2)             .       .       .           yes
 O3      S1      C34A       111.3(3)             .       .       .           yes
 Zn1     O1      S1        127.95(8)             .       .       .           yes
 C1      N1      C2       115.59(16)             .       .       .           yes
 Zn1     N2      C1       114.84(12)             .       .       .           yes
 Zn1     N2      C8       124.97(13)             .       .       .           yes
 C1      N2      C8       119.63(16)             .       .       .           yes
 C8      N3      C9       125.03(17)             .       .       .           yes
 Zn1     N4      C9       123.40(12)             .       .       .           yes
 Zn1     N4      C12      125.97(12)             .       .       .           yes
 C9      N4      C12      110.19(15)             .       .       .           yes
 Zn1     N5      C14      125.47(13)             .       .       .           yes
 Zn1     N5      C17      123.20(12)             .       .       .           yes
 C14     N5      C17      110.44(15)             .       .       .           yes
 C17     N6      C18      124.99(16)             .       .       .           yes
 Zn1     N7      C18      125.85(12)             .       .       .           yes
 Zn1     N7      C25      114.43(12)             .       .       .           yes
 C18     N7      C25      119.53(16)             .       .       .           yes
 C24     N8      C25      115.88(16)             .       .       .           yes
 N1      C1      N2       126.71(17)             .       .       .           yes
 N1      C1      C25      118.92(16)             .       .       .           yes
 N2      C1      C25      114.36(16)             .       .       .           yes
 N1      C2      C3       118.56(18)             .       .       .           yes
 N1      C2      C7       122.18(17)             .       .       .           yes
 C3      C2      C7       119.26(18)             .       .       .           no
 C2      C3      C4       119.46(19)             .       .       .           no
 C3      C4      C5         121.0(2)             .       .       .           no
 C4      C5      C6         121.0(2)             .       .       .           no
 C5      C6      C7       119.28(19)             .       .       .           no
 C2      C7      C6       119.99(18)             .       .       .           no
 C2      C7      C8       117.41(17)             .       .       .           no
 C6      C7      C8       122.60(18)             .       .       .           no
 N2      C8      N3       124.57(17)             .       .       .           yes
 N2      C8      C7       118.34(17)             .       .       .           yes
 N3      C8      C7       117.08(17)             .       .       .           yes
 N3      C9      N4       128.37(18)             .       .       .           yes
 N3      C9      C10      120.97(17)             .       .       .           yes
 N4      C9      C10      110.60(16)             .       .       .           yes
 C9      C10     C11      101.33(15)             .       .       .           no
 C9      C10     C26      105.96(16)             .       .       .           no
 C9      C10     C27      113.26(17)             .       .       .           no
 C11     C10     C26      112.06(16)             .       .       .           no
 C11     C10     C27      115.67(17)             .       .       .           no
 C26     C10     C27      108.12(17)             .       .       .           no
 C10     C11     C12      101.03(15)             .       .       .           no
 C10     C11     C28      111.88(17)             .       .       .           no
 C10     C11     C29      114.61(17)             .       .       .           no
 C12     C11     C28      106.05(16)             .       .       .           no
 C12     C11     C29      114.60(17)             .       .       .           no
 C28     C11     C29      108.31(17)             .       .       .           no
 N4      C12     C11      111.01(16)             .       .       .           yes
 N4      C12     C13      123.94(17)             .       .       .           yes
 C11     C12     C13      124.83(16)             .       .       .           no
 C12     C13     C14      126.69(17)             .       .       .           no
 N5      C14     C13      124.20(17)             .       .       .           yes
 N5      C14     C15      111.37(16)             .       .       .           yes
 C13     C14     C15      124.27(16)             .       .       .           no
 C14     C15     C16      100.79(14)             .       .       .           no
 C14     C15     C30      112.93(16)             .       .       .           no
 C14     C15     C31      107.57(15)             .       .       .           no
 C16     C15     C30      114.53(16)             .       .       .           no
 C16     C15     C31      111.87(16)             .       .       .           no
 C30     C15     C31      108.82(16)             .       .       .           no
 C15     C16     C17      101.30(14)             .       .       .           no
 C15     C16     C32      115.39(16)             .       .       .           no
 C15     C16     C33      111.81(16)             .       .       .           no
 C17     C16     C32      113.69(16)             .       .       .           no
 C17     C16     C33      105.28(16)             .       .       .           no
 C32     C16     C33      108.82(16)             .       .       .           no
 N5      C17     N6       128.15(17)             .       .       .           yes
 N5      C17     C16      109.92(15)             .       .       .           yes
 N6      C17     C16      121.87(17)             .       .       .           yes
 N6      C18     N7       124.32(16)             .       .       .           yes
 N6      C18     C19      117.09(16)             .       .       .           yes
 N7      C18     C19      118.57(16)             .       .       .           yes
 C18     C19     C20      123.01(17)             .       .       .           no
 C18     C19     C24      117.29(17)             .       .       .           no
 C20     C19     C24      119.68(17)             .       .       .           no
 C19     C20     C21      119.69(18)             .       .       .           no
 C20     C21     C22      120.61(19)             .       .       .           no
 C21     C22     C23      120.88(19)             .       .       .           no
 C22     C23     C24      119.82(18)             .       .       .           no
 N8      C24     C19      122.14(16)             .       .       .           yes
 N8      C24     C23      118.53(17)             .       .       .           yes
 C19     C24     C23      119.33(18)             .       .       .           no
 N7      C25     N8       126.54(17)             .       .       .           yes
 N7      C25     C1       114.64(15)             .       .       .           yes
 N8      C25     C1       118.82(16)             .       .       .           yes
 S1      C34     F1         112.2(4)             .       .       .           yes
 S1      C34     F2         109.6(5)             .       .       .           yes
 S1      C34     F3         111.0(5)             .       .       .           yes
 F1      C34     F2         108.5(6)             .       .       .           yes
 F1      C34     F3         108.7(6)             .       .       .           yes
 F2      C34     F3         106.6(5)             .       .       .           yes
 S1      C34A    F1A        108.4(7)             .       .       .           yes
 S1      C34A    F2A        110.3(7)             .       .       .           yes
 S1      C34A    F3A        112.8(8)             .       .       .           yes
 F1A     C34A    F2A        109.4(9)             .       .       .           yes
 F1A     C34A    F3A        108.6(9)             .       .       .           yes
 F2A     C34A    F3A        107.4(9)             .       .       .           yes
 C2      C3      H3           120.00             .       .       .           no
 C4      C3      H3           120.00             .       .       .           no
 C3      C4      H4           120.00             .       .       .           no
 C5      C4      H4           119.00             .       .       .           no
 C4      C5      H5           119.00             .       .       .           no
 C6      C5      H5           120.00             .       .       .           no
 C5      C6      H6           120.00             .       .       .           no
 C7      C6      H6           120.00             .       .       .           no
 C12     C13     H13          117.00             .       .       .           no
 C14     C13     H13          117.00             .       .       .           no
 C19     C20     H20          120.00             .       .       .           no
 C21     C20     H20          120.00             .       .       .           no
 C20     C21     H21          120.00             .       .       .           no
 C22     C21     H21          120.00             .       .       .           no
 C21     C22     H22          120.00             .       .       .           no
 C23     C22     H22          120.00             .       .       .           no
 C22     C23     H23          120.00             .       .       .           no
 C24     C23     H23          120.00             .       .       .           no
 C10     C26     H26A         109.00             .       .       .           no
 C10     C26     H26B         110.00             .       .       .           no
 C10     C26     H26C         110.00             .       .       .           no
 H26A    C26     H26B         109.00             .       .       .           no
 H26A    C26     H26C         109.00             .       .       .           no
 H26B    C26     H26C         109.00             .       .       .           no
 C10     C27     H27A         109.00             .       .       .           no
 C10     C27     H27B         110.00             .       .       .           no
 C10     C27     H27C         110.00             .       .       .           no
 H27A    C27     H27B         109.00             .       .       .           no
 H27A    C27     H27C         109.00             .       .       .           no
 H27B    C27     H27C         109.00             .       .       .           no
 C11     C28     H28A         109.00             .       .       .           no
 C11     C28     H28B         109.00             .       .       .           no
 C11     C28     H28C         109.00             .       .       .           no
 H28A    C28     H28B         109.00             .       .       .           no
 H28A    C28     H28C         109.00             .       .       .           no
 H28B    C28     H28C         110.00             .       .       .           no
 C11     C29     H29A         109.00             .       .       .           no
 C11     C29     H29B         110.00             .       .       .           no
 C11     C29     H29C         109.00             .       .       .           no
 H29A    C29     H29B         110.00             .       .       .           no
 H29A    C29     H29C         109.00             .       .       .           no
 H29B    C29     H29C         109.00             .       .       .           no
 C15     C30     H30A         109.00             .       .       .           no
 C15     C30     H30B         109.00             .       .       .           no
 C15     C30     H30C         109.00             .       .       .           no
 H30A    C30     H30B         109.00             .       .       .           no
 H30A    C30     H30C         109.00             .       .       .           no
 H30B    C30     H30C         109.00             .       .       .           no
 C15     C31     H31A         109.00             .       .       .           no
 C15     C31     H31B         109.00             .       .       .           no
 C15     C31     H31C         109.00             .       .       .           no
 H31A    C31     H31B         109.00             .       .       .           no
 H31A    C31     H31C         110.00             .       .       .           no
 H31B    C31     H31C         109.00             .       .       .           no
 C16     C32     H32A         109.00             .       .       .           no
 C16     C32     H32B         109.00             .       .       .           no
 C16     C32     H32C         109.00             .       .       .           no
 H32A    C32     H32B         109.00             .       .       .           no
 H32A    C32     H32C         110.00             .       .       .           no
 H32B    C32     H32C         109.00             .       .       .           no
 C16     C33     H33A         109.00             .       .       .           no
 C16     C33     H33B         109.00             .       .       .           no
 C16     C33     H33C         109.00             .       .       .           no
 H33A    C33     H33B         109.00             .       .       .           no
 H33A    C33     H33C         109.00             .       .       .           no
 H33B    C33     H33C         109.00             .       .       .           no
 Cl1     C35     Cl2      111.20(13)             .       .       .           yes
 Cl1     C35     H35A         109.00             .       .       .           no
 Cl1     C35     H35B         109.00             .       .       .           no
 Cl2     C35     H35A         109.00             .       .       .           no
 Cl2     C35     H35B         109.00             .       .       .           no
 H35A    C35     H35B         108.00             .       .       .           no
 
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
 N2      Zn1     O1      S1       118.83(12)     .       .       .       .   no
 N4      Zn1     O1      S1        27.36(14)     .       .       .       .   no
 N5      Zn1     O1      S1       -70.83(13)     .       .       .       .   no
 N7      Zn1     O1      S1      -160.27(12)     .       .       .       .   no
 O1      Zn1     N2      C1        83.11(13)     .       .       .       .   no
 O1      Zn1     N2      C8       -88.22(15)     .       .       .       .   no
 N4      Zn1     N2      C1      -165.42(13)     .       .       .       .   no
 N4      Zn1     N2      C8        23.25(15)     .       .       .       .   no
 N5      Zn1     N2      C1       -75.98(19)     .       .       .       .   no
 N5      Zn1     N2      C8       112.69(18)     .       .       .       .   no
 N7      Zn1     N2      C1       -11.97(12)     .       .       .       .   no
 N7      Zn1     N2      C8       176.70(16)     .       .       .       .   no
 O1      Zn1     N4      C9        76.58(15)     .       .       .       .   no
 O1      Zn1     N4      C12      -95.04(15)     .       .       .       .   no
 N2      Zn1     N4      C9       -22.45(14)     .       .       .       .   no
 N2      Zn1     N4      C12      165.93(15)     .       .       .       .   no
 N5      Zn1     N4      C9      -175.57(14)     .       .       .       .   no
 N5      Zn1     N4      C12       12.81(15)     .       .       .       .   no
 N7      Zn1     N4      C9       -87.64(19)     .       .       .       .   no
 N7      Zn1     N4      C12      100.74(18)     .       .       .       .   no
 O1      Zn1     N5      C14       97.03(16)     .       .       .       .   no
 O1      Zn1     N5      C17      -71.12(16)     .       .       .       .   no
 N2      Zn1     N5      C14     -104.47(19)     .       .       .       .   no
 N2      Zn1     N5      C17         87.4(2)     .       .       .       .   no
 N4      Zn1     N5      C14      -15.87(16)     .       .       .       .   no
 N4      Zn1     N5      C17      175.98(15)     .       .       .       .   no
 N7      Zn1     N5      C14     -166.85(16)     .       .       .       .   no
 N7      Zn1     N5      C17       24.99(15)     .       .       .       .   no
 O1      Zn1     N7      C18       87.04(15)     .       .       .       .   no
 O1      Zn1     N7      C25      -87.97(13)     .       .       .       .   no
 N2      Zn1     N7      C18     -174.80(16)     .       .       .       .   no
 N2      Zn1     N7      C25       10.20(12)     .       .       .       .   no
 N4      Zn1     N7      C18     -107.72(18)     .       .       .       .   no
 N4      Zn1     N7      C25       77.28(18)     .       .       .       .   no
 N5      Zn1     N7      C18      -18.79(15)     .       .       .       .   no
 N5      Zn1     N7      C25      166.21(13)     .       .       .       .   no
 O2      S1      O1      Zn1       -9.48(16)     .       .       .       .   no
 O3      S1      O1      Zn1      128.12(12)     .       .       .       .   no
 C34     S1      O1      Zn1       -123.1(2)     .       .       .       .   no
 O1      S1      C34     F1          71.5(5)     .       .       .       .   no
 O1      S1      C34     F2        -167.9(4)     .       .       .       .   no
 O1      S1      C34     F3         -50.3(5)     .       .       .       .   no
 O2      S1      C34     F1         -48.5(5)     .       .       .       .   no
 O2      S1      C34     F2          72.2(5)     .       .       .       .   no
 O2      S1      C34     F3        -170.3(5)     .       .       .       .   no
 O3      S1      C34     F1        -171.1(4)     .       .       .       .   no
 O3      S1      C34     F2         -50.4(5)     .       .       .       .   no
 O3      S1      C34     F3          67.1(5)     .       .       .       .   no
 C2      N1      C1      N2           1.1(3)     .       .       .       .   no
 C2      N1      C1      C25      179.78(16)     .       .       .       .   no
 C1      N1      C2      C3       177.89(18)     .       .       .       .   no
 C1      N1      C2      C7          -2.2(3)     .       .       .       .   no
 Zn1     N2      C1      N1      -169.68(16)     .       .       .       .   no
 Zn1     N2      C1      C25       11.61(19)     .       .       .       .   no
 C8      N2      C1      N1           2.2(3)     .       .       .       .   no
 C8      N2      C1      C25     -176.56(16)     .       .       .       .   no
 Zn1     N2      C8      N3         -14.0(3)     .       .       .       .   no
 Zn1     N2      C8      C7       166.80(13)     .       .       .       .   no
 C1      N2      C8      N3       175.04(17)     .       .       .       .   no
 C1      N2      C8      C7          -4.2(3)     .       .       .       .   no
 C9      N3      C8      N2          -5.4(3)     .       .       .       .   no
 C9      N3      C8      C7       173.85(18)     .       .       .       .   no
 C8      N3      C9      N4           5.7(3)     .       .       .       .   no
 C8      N3      C9      C10     -177.41(17)     .       .       .       .   no
 Zn1     N4      C9      N3          13.7(3)     .       .       .       .   no
 Zn1     N4      C9      C10     -163.45(12)     .       .       .       .   no
 C12     N4      C9      N3      -173.56(19)     .       .       .       .   no
 C12     N4      C9      C10          9.3(2)     .       .       .       .   no
 Zn1     N4      C12     C11      179.90(12)     .       .       .       .   no
 Zn1     N4      C12     C13         -5.4(3)     .       .       .       .   no
 C9      N4      C12     C11          7.3(2)     .       .       .       .   no
 C9      N4      C12     C13     -177.90(17)     .       .       .       .   no
 Zn1     N5      C14     C13         11.8(3)     .       .       .       .   no
 Zn1     N5      C14     C15     -172.69(12)     .       .       .       .   no
 C17     N5      C14     C13     -178.77(18)     .       .       .       .   no
 C17     N5      C14     C15         -3.3(2)     .       .       .       .   no
 Zn1     N5      C17     N6         -20.9(3)     .       .       .       .   no
 Zn1     N5      C17     C16      156.21(13)     .       .       .       .   no
 C14     N5      C17     N6       169.34(19)     .       .       .       .   no
 C14     N5      C17     C16        -13.5(2)     .       .       .       .   no
 C18     N6      C17     N5          -1.5(3)     .       .       .       .   no
 C18     N6      C17     C16     -178.32(17)     .       .       .       .   no
 C17     N6      C18     N7           9.6(3)     .       .       .       .   no
 C17     N6      C18     C19     -172.23(18)     .       .       .       .   no
 Zn1     N7      C18     N6           5.7(3)     .       .       .       .   no
 Zn1     N7      C18     C19     -172.46(13)     .       .       .       .   no
 C25     N7      C18     N6      -179.58(17)     .       .       .       .   no
 C25     N7      C18     C19          2.3(3)     .       .       .       .   no
 Zn1     N7      C25     N8       173.04(15)     .       .       .       .   no
 Zn1     N7      C25     C1        -7.01(19)     .       .       .       .   no
 C18     N7      C25     N8          -2.3(3)     .       .       .       .   no
 C18     N7      C25     C1       177.64(16)     .       .       .       .   no
 C25     N8      C24     C19          1.6(3)     .       .       .       .   no
 C25     N8      C24     C23     -177.96(17)     .       .       .       .   no
 C24     N8      C25     N7           0.3(3)     .       .       .       .   no
 C24     N8      C25     C1      -179.67(16)     .       .       .       .   no
 N1      C1      C25     N7       178.20(17)     .       .       .       .   no
 N1      C1      C25     N8          -1.9(3)     .       .       .       .   no
 N2      C1      C25     N7          -3.0(2)     .       .       .       .   no
 N2      C1      C25     N8       176.97(16)     .       .       .       .   no
 N1      C2      C3      C4      -178.69(19)     .       .       .       .   no
 C7      C2      C3      C4           1.4(3)     .       .       .       .   no
 N1      C2      C7      C6       179.86(18)     .       .       .       .   no
 N1      C2      C7      C8           0.2(3)     .       .       .       .   no
 C3      C2      C7      C6          -0.2(3)     .       .       .       .   no
 C3      C2      C7      C8      -179.91(17)     .       .       .       .   no
 C2      C3      C4      C5          -1.3(3)     .       .       .       .   no
 C3      C4      C5      C6           0.1(3)     .       .       .       .   no
 C4      C5      C6      C7           1.1(3)     .       .       .       .   no
 C5      C6      C7      C2          -1.0(3)     .       .       .       .   no
 C5      C6      C7      C8       178.63(19)     .       .       .       .   no
 C2      C7      C8      N2           3.0(3)     .       .       .       .   no
 C2      C7      C8      N3      -176.21(17)     .       .       .       .   no
 C6      C7      C8      N2      -176.63(18)     .       .       .       .   no
 C6      C7      C8      N3           4.1(3)     .       .       .       .   no
 N3      C9      C10     C11      161.74(17)     .       .       .       .   no
 N3      C9      C10     C26        -81.2(2)     .       .       .       .   no
 N3      C9      C10     C27         37.2(3)     .       .       .       .   no
 N4      C9      C10     C11        -20.9(2)     .       .       .       .   no
 N4      C9      C10     C26       96.20(18)     .       .       .       .   no
 N4      C9      C10     C27     -145.44(17)     .       .       .       .   no
 C9      C10     C11     C12       22.74(18)     .       .       .       .   no
 C9      C10     C11     C28      -89.70(18)     .       .       .       .   no
 C9      C10     C11     C29      146.51(17)     .       .       .       .   no
 C26     C10     C11     C12      -89.82(18)     .       .       .       .   no
 C26     C10     C11     C28      157.74(17)     .       .       .       .   no
 C26     C10     C11     C29         33.9(2)     .       .       .       .   no
 C27     C10     C11     C12      145.64(17)     .       .       .       .   no
 C27     C10     C11     C28         33.2(2)     .       .       .       .   no
 C27     C10     C11     C29        -90.6(2)     .       .       .       .   no
 C10     C11     C12     N4         -19.7(2)     .       .       .       .   no
 C10     C11     C12     C13      165.59(18)     .       .       .       .   no
 C28     C11     C12     N4        97.10(18)     .       .       .       .   no
 C28     C11     C12     C13        -77.6(2)     .       .       .       .   no
 C29     C11     C12     N4      -143.47(17)     .       .       .       .   no
 C29     C11     C12     C13         41.8(3)     .       .       .       .   no
 N4      C12     C13     C14         -5.0(3)     .       .       .       .   no
 C11     C12     C13     C14      169.04(18)     .       .       .       .   no
 C12     C13     C14     N5           1.5(3)     .       .       .       .   no
 C12     C13     C14     C15     -173.44(18)     .       .       .       .   no
 N5      C14     C15     C16         17.4(2)     .       .       .       .   no
 N5      C14     C15     C30      140.06(17)     .       .       .       .   no
 N5      C14     C15     C31      -99.85(18)     .       .       .       .   no
 C13     C14     C15     C16     -167.08(18)     .       .       .       .   no
 C13     C14     C15     C30        -44.4(2)     .       .       .       .   no
 C13     C14     C15     C31         75.7(2)     .       .       .       .   no
 C14     C15     C16     C17      -22.88(17)     .       .       .       .   no
 C14     C15     C16     C32     -146.13(17)     .       .       .       .   no
 C14     C15     C16     C33       88.79(18)     .       .       .       .   no
 C30     C15     C16     C17     -144.41(16)     .       .       .       .   no
 C30     C15     C16     C32         92.3(2)     .       .       .       .   no
 C30     C15     C16     C33        -32.7(2)     .       .       .       .   no
 C31     C15     C16     C17       91.17(18)     .       .       .       .   no
 C31     C15     C16     C32        -32.1(2)     .       .       .       .   no
 C31     C15     C16     C33     -157.16(16)     .       .       .       .   no
 C15     C16     C17     N5        23.42(19)     .       .       .       .   no
 C15     C16     C17     N6      -159.23(17)     .       .       .       .   no
 C32     C16     C17     N5       147.83(17)     .       .       .       .   no
 C32     C16     C17     N6         -34.8(3)     .       .       .       .   no
 C33     C16     C17     N5       -93.15(18)     .       .       .       .   no
 C33     C16     C17     N6          84.2(2)     .       .       .       .   no
 N6      C18     C19     C20         -0.7(3)     .       .       .       .   no
 N6      C18     C19     C24     -178.82(16)     .       .       .       .   no
 N7      C18     C19     C20      177.53(17)     .       .       .       .   no
 N7      C18     C19     C24         -0.6(3)     .       .       .       .   no
 C18     C19     C20     C21     -177.59(18)     .       .       .       .   no
 C24     C19     C20     C21          0.5(3)     .       .       .       .   no
 C18     C19     C24     N8          -1.4(3)     .       .       .       .   no
 C18     C19     C24     C23      178.10(17)     .       .       .       .   no
 C20     C19     C24     N8      -179.62(17)     .       .       .       .   no
 C20     C19     C24     C23         -0.1(3)     .       .       .       .   no
 C19     C20     C21     C22         -0.8(3)     .       .       .       .   no
 C20     C21     C22     C23          0.6(3)     .       .       .       .   no
 C21     C22     C23     C24         -0.2(3)     .       .       .       .   no
 C22     C23     C24     N8       179.50(18)     .       .       .       .   no
 C22     C23     C24     C19         -0.1(3)     .       .       .       .   no
 
loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
#
#D   H   A   D - H  H...A   D...A    D - H...A  symm(A)
#
C4      H4      O2          0.9500     2.3000   3.158(3)     149.00   4_455 yes
C22     H22     F2          0.9500     2.5000   3.194(5)     130.00   4_555 yes
C22     H22     F2A         0.9500     2.4400   3.057(8)     122.00   4_555 yes
C26     H26C    O2          0.9800     2.6000   3.509(3)     154.00     .   yes
C27     H27C    F3          0.9800     2.4700   3.066(7)     119.00   4_454 yes
C35     H35A    N1          0.9900     2.5400   3.354(3)     139.00     .   yes
C35     H35A    N8          0.9900     2.5000   3.401(3)     151.00     .   yes
 
 
 
#===END
