# Electronic Supplementary Material (ESI) for CrystEngComm.
# This journal is © The Royal Society of Chemistry 2024

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_agi923a
_database_code_depnum_ccdc_archive 'CCDC 2299275'
loop_
_audit_author_name
_audit_author_address
'Dr. Richard Staples'
;Michigan State University
United States of America
;
_audit_update_record             
;
2023-10-04 deposited with the CCDC.	2024-02-14 downloaded from the CCDC.
;
_audit_creation_date             2023-09-09
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
loop_
_audit_author_email
?
staples@chemistry.msu.edu
_chemical_name_common            Caff-Py
_chemical_name_systematic        ?
_chemical_formula_moiety         '2(C8 H10 N4 O2), 3(C6 H6 O3), 2.5(H2 O)'
_chemical_formula_sum            'C34 H43 N8 O15.50'
_chemical_formula_weight         811.76
_chemical_melting_point          379.83
_chemical_oxdiff_formula         C25H20N4O6F2
_chemical_oxdiff_usercomment     'AGI   CAF-PYr--sc  A'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           56
_space_group_name_H-M_alt        'P c c n'
_space_group_name_Hall           '-P 2ab 2ac'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y+1/2, z'
'-x, y+1/2, -z+1/2'
'x+1/2, -y, -z+1/2'
'-x, -y, -z'
'x-1/2, y-1/2, -z'
'x, -y-1/2, z-1/2'
'-x-1/2, y, z-1/2'

_cell_length_a                   13.97060(16)
_cell_length_b                   26.3924(3)
_cell_length_c                   19.9773(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     7365.95(15)
_cell_formula_units_Z            8
_cell_measurement_reflns_used    14440
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.3230
_cell_measurement_theta_min      3.3440
_shelx_estimated_absorpt_T_max   0.979
_shelx_estimated_absorpt_T_min   0.875
_exptl_absorpt_coefficient_mu    0.997
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.912
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.42.99a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.464
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             3416
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
0 0 1 0.0110
0 0 -1 0.0096
0 -1 0 0.0395
1 1 0 0.0148
-2 1 0 0.0466

_exptl_crystal_preparation       ?
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: dichloromethane'
_exptl_crystal_size_max          0.137
_exptl_crystal_size_mid          0.085
_exptl_crystal_size_min          0.021
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
0.0001 0.0002 0.9991 0.0556 -0.0531 0.0045
-0.0001 -0.0002 -0.9991 -0.0556 0.0531 -0.0045
0.0003 -0.9993 0.0000 0.0382 0.0413 0.0156
0.9994 0.9990 0.0002 -0.0630 -0.0583 0.0905
-1.9997 1.0000 -0.0004 0.0116 -0.0072 -0.2277

_exptl_special_details           
;
Data was collected using a Rigaku Synergy S Diffractometer diffractometer equipped 
with an Oxford 800 low-temperature apparatus operating at  100 K.  A suitable 
crystal was chosen and mounted on a nylon loop using Paratone oil.  Data  were 
measured based on the Pre-Experiment plugin of CrysAlisPro software.  Cell 
parameters were retrieved using CrysAlisPro software and data reduction was 
performed using the intergration software inside the CrysAlisPro which 
corrects for Lp. Scaling and absorption corrections were applied using SADABS6 
multi-scan technique, supplied by George Sheldrick.  The structure was solved 
by the direct method using the SHELXT program and refined by least squares 
method on F2, SHELXL, incorporated in OLEX2. 
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0475
_diffrn_reflns_av_unetI/netI     0.0403
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            41596
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.452
_diffrn_reflns_theta_min         3.349
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω   -121.00 -35.00   0.50    1.00    --  -47.13 -21.00 -48.00  172
  2  ω    -39.00  28.00   0.50    1.00    --  -47.13  21.00 117.00  134
  3  ω   -162.00 -86.00   0.50    4.00    --  -91.75-104.00 176.00  152
  4  ω   -162.00 -74.00   0.50    4.00    --  -91.75-127.00  98.00  176
  5  ω     43.00 109.00   0.50    4.00    --  113.25-127.00  98.00  132
  6  ω    101.00 178.00   0.50    4.00    --  113.25  21.00 117.00  154
  7  ω     86.00 122.00   0.50    4.00    --  113.25-143.00 -71.00   72
  8  ω    -65.00 -39.00   0.50    1.00    --  -47.11 127.00 174.00   52
  9  ω    -26.00  24.00   0.50    1.00    --   47.11 -19.00-150.00  100
 10  ω     44.00  69.00   0.50    4.00    --  113.25 -61.00 -60.00   50
 11  ω     61.00  94.00   0.50    4.00    --  113.25 -77.00 150.00   66
 12  ω     42.00  68.00   0.50    4.00    --  113.25 -77.00-120.00   52
 13  ω    118.00 174.00   0.50    4.00    --  113.25  45.00-180.00  112
 14  ω     49.00  93.00   0.50    4.00    --  113.25 -77.00  60.00   88
 15  ω     47.00 104.00   0.50    4.00    --  113.25-125.00-180.00  114
 16  ω     43.00  69.00   0.50    4.00    --  113.25 -61.00 -30.00   52
 17  ω     43.00  68.00   0.50    4.00    --  113.25 -61.00 150.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0248992000
_diffrn_orient_matrix_UB_12      -0.0381868000
_diffrn_orient_matrix_UB_13      0.0557078000
_diffrn_orient_matrix_UB_21      -0.0170320000
_diffrn_orient_matrix_UB_22      -0.0412984000
_diffrn_orient_matrix_UB_23      -0.0531335000
_diffrn_orient_matrix_UB_31      0.1060899000
_diffrn_orient_matrix_UB_32      -0.0155579000
_diffrn_orient_matrix_UB_33      0.0044984000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           1
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_source_voltage           50
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                6403
_reflns_number_total             7897
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.99a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.99a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.99a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         0.504
_refine_diff_density_min         -0.262
_refine_diff_density_rms         0.051
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     581
_refine_ls_number_reflns         7897
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0553
_refine_ls_R_factor_gt           0.0433
_refine_ls_restrained_S_all      1.033
_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/[σ²(Fo²)+(0.0560P)²+3.7611P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1127
_refine_ls_wR_factor_ref         0.1203
_refine_special_details          
;
The structure was refined by Least Squares using version 2018/2 
of XL (Sheldrick, 2008) incorporated in Olex2 (Dolomanov et al., 2009). 
All non-hydrogen atoms were refined anisotropically. 
Hydrogen atom positions were calculated geometrically and refined using the 
riding model, except for the hydrogen atom on the non-carbon atom(s) which were found 
by difference Fourier methods and refined isotropically when data permits.
;
_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.a Aromatic/amide H refined with riding coordinates:
 C3D(H3D), C3E(H3E), C4A(H4A), C5A(H5A), C6A(H6A), C4B(H4B), C5B(H5B),
 C6B(H6B), C4C(H4C), C5C(H5C), C6C(H6C)
2.b Idealised Me refined as rotating group:
 C6D(H6DA,H6DB,H6DC), C7D(H7DA,H7DB,H7DC), C8D(H8DA,H8DB,H8DC), C6E(H6EA,H6EB,
 H6EC), C7E(H7EA,H7EB,H7EC), C8E(H8EA,H8EB,H8EC)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
O1D O 0.68777(8) 0.32384(5) 0.39734(6) 0.0296(3) Uani 1 1 d . . . . .
O2D O 0.36554(9) 0.32676(5) 0.44453(6) 0.0309(3) Uani 1 1 d . . . . .
N1D N 0.52776(10) 0.32517(5) 0.42119(7) 0.0244(3) Uani 1 1 d . . . . .
N2D N 0.58604(9) 0.32204(5) 0.30970(7) 0.0227(3) Uani 1 1 d . . . . .
N3D N 0.46173(10) 0.32281(5) 0.22360(7) 0.0260(3) Uani 1 1 d . . . . .
N4D N 0.33565(10) 0.32432(5) 0.29479(7) 0.0258(3) Uani 1 1 d . . . . .
C1D C 0.60472(12) 0.32353(6) 0.37707(8) 0.0236(3) Uani 1 1 d . . . . .
C2D C 0.49279(11) 0.32228(6) 0.28747(8) 0.0221(3) Uani 1 1 d . . . . .
C3D C 0.36541(12) 0.32434(7) 0.23024(9) 0.0270(3) Uani 1 1 d . . . . .
H3D H 0.322757 0.325326 0.193222 0.032 Uiso 1 1 calc R U . . .
C4D C 0.41855(11) 0.32301(6) 0.33257(8) 0.0225(3) Uani 1 1 d . . . . .
C5D C 0.43110(12) 0.32491(6) 0.40287(8) 0.0244(3) Uani 1 1 d . . . . .
C6D C 0.55119(14) 0.32723(7) 0.49289(9) 0.0303(4) Uani 1 1 d . . . . .
H6DA H 0.574084 0.293965 0.507685 0.045 Uiso 1 1 calc R U . . .
H6DB H 0.493858 0.336484 0.518375 0.045 Uiso 1 1 calc R U . . .
H6DC H 0.601248 0.352614 0.500402 0.045 Uiso 1 1 calc R U . . .
C7D C 0.66765(12) 0.32465(7) 0.26326(9) 0.0279(4) Uani 1 1 d . . . . .
H7DA H 0.702814 0.356286 0.270638 0.042 Uiso 1 1 calc R U . . .
H7DB H 0.644177 0.323606 0.217050 0.042 Uiso 1 1 calc R U . . .
H7DC H 0.710303 0.295781 0.271156 0.042 Uiso 1 1 calc R U . . .
C8D C 0.23707(12) 0.32454(7) 0.31830(9) 0.0314(4) Uani 1 1 d . . . . .
H8DA H 0.225702 0.294559 0.346131 0.047 Uiso 1 1 calc R U . . .
H8DB H 0.193592 0.324016 0.279810 0.047 Uiso 1 1 calc R U . . .
H8DC H 0.225530 0.355187 0.344791 0.047 Uiso 1 1 calc R U . . .
O1E O 0.68938(8) 0.44333(5) -0.05829(6) 0.0261(3) Uani 1 1 d . . . . .
O2E O 0.36784(8) 0.43075(5) -0.10426(6) 0.0276(3) Uani 1 1 d . . . . .
N1E N 0.52959(9) 0.43492(5) -0.08110(7) 0.0216(3) Uani 1 1 d . . . . .
N2E N 0.58899(9) 0.43893(5) 0.03014(7) 0.0199(3) Uani 1 1 d . . . . .
N3E N 0.46585(10) 0.43667(5) 0.11665(7) 0.0234(3) Uani 1 1 d . . . . .
N4E N 0.33908(9) 0.43131(5) 0.04729(7) 0.0234(3) Uani 1 1 d . . . . .
C1E C 0.60703(11) 0.43912(6) -0.03735(8) 0.0212(3) Uani 1 1 d . . . . .
C2E C 0.49579(11) 0.43661(6) 0.05239(8) 0.0195(3) Uani 1 1 d . . . . .
C3E C 0.37022(12) 0.43306(6) 0.11087(8) 0.0250(3) Uani 1 1 d . . . . .
H3E H 0.328441 0.431859 0.148359 0.030 Uiso 1 1 calc R U . . .
C4E C 0.42097(11) 0.43377(6) 0.00809(8) 0.0197(3) Uani 1 1 d . . . . .
C5E C 0.43307(11) 0.43278(6) -0.06247(8) 0.0211(3) Uani 1 1 d . . . . .
C6E C 0.55298(13) 0.43155(7) -0.15298(8) 0.0281(4) Uani 1 1 d . . . . .
H6EA H 0.569865 0.465249 -0.169855 0.042 Uiso 1 1 calc R U . . .
H6EB H 0.497391 0.418656 -0.177577 0.042 Uiso 1 1 calc R U . . .
H6EC H 0.607240 0.408495 -0.159255 0.042 Uiso 1 1 calc R U . . .
C7E C 0.67031(11) 0.43974(6) 0.07667(8) 0.0236(3) Uani 1 1 d . . . . .
H7EA H 0.695391 0.474331 0.080004 0.035 Uiso 1 1 calc R U . . .
H7EB H 0.720682 0.417134 0.060140 0.035 Uiso 1 1 calc R U . . .
H7EC H 0.649147 0.428315 0.120939 0.035 Uiso 1 1 calc R U . . .
C8E C 0.23935(12) 0.42979(7) 0.02605(9) 0.0286(4) Uani 1 1 d . . . . .
H8EA H 0.220535 0.463131 0.008926 0.043 Uiso 1 1 calc R U . . .
H8EB H 0.198743 0.420831 0.064261 0.043 Uiso 1 1 calc R U . . .
H8EC H 0.231680 0.404385 -0.009323 0.043 Uiso 1 1 calc R U . . .
O1A O 0.69967(8) 0.44703(5) 0.33098(6) 0.0259(3) Uani 1 1 d . . . . .
H1A H 0.7381(19) 0.4455(10) 0.3670(13) 0.049(7) Uiso 1 1 d . . . . .
O2A O 0.57314(8) 0.44489(5) 0.23369(6) 0.0246(2) Uani 1 1 d . . . . .
H2A H 0.527(2) 0.4423(11) 0.2029(15) 0.067(9) Uiso 1 1 d . . . . .
O3A O 0.38120(8) 0.45006(5) 0.25903(6) 0.0271(3) Uani 1 1 d . . . . .
H3A H 0.3216(17) 0.4581(9) 0.2707(12) 0.041(6) Uiso 1 1 d . . . . .
C1A C 0.60583(11) 0.44807(6) 0.34977(8) 0.0208(3) Uani 1 1 d . . . . .
C2A C 0.53907(11) 0.44685(6) 0.29797(8) 0.0198(3) Uani 1 1 d . . . . .
C3A C 0.44161(11) 0.44985(6) 0.31270(8) 0.0205(3) Uani 1 1 d . . . . .
C4A C 0.41099(11) 0.45255(6) 0.37890(8) 0.0222(3) Uani 1 1 d . . . . .
H4A H 0.344572 0.453881 0.388957 0.027 Uiso 1 1 calc R U . . .
C5A C 0.47796(12) 0.45329(6) 0.43005(8) 0.0239(3) Uani 1 1 d . . . . .
H5A H 0.457017 0.455223 0.475219 0.029 Uiso 1 1 calc R U . . .
C6A C 0.57520(11) 0.45125(6) 0.41619(8) 0.0229(3) Uani 1 1 d . . . . .
H6A H 0.620574 0.452008 0.451596 0.027 Uiso 1 1 calc R U . . .
O1B O 0.38983(9) 0.19301(5) 0.58254(6) 0.0303(3) Uani 1 1 d . . . . .
H1B H 0.323(2) 0.1937(11) 0.5704(15) 0.068(8) Uiso 1 1 d . . . . .
O2B O 0.57749(8) 0.17281(5) 0.60396(6) 0.0262(3) Uani 1 1 d . . . . .
H2B H 0.5313(18) 0.1739(9) 0.6349(13) 0.046(7) Uiso 1 1 d . . . . .
O3B O 0.70414(8) 0.17620(5) 0.50580(6) 0.0276(3) Uani 1 1 d . . . . .
H3B H 0.739(2) 0.1747(10) 0.4700(15) 0.056(8) Uiso 1 1 d . . . . .
C1B C 0.44829(12) 0.19268(6) 0.52808(8) 0.0234(3) Uani 1 1 d . . . . .
C2B C 0.54474(11) 0.18327(6) 0.54120(8) 0.0217(3) Uani 1 1 d . . . . .
C3B C 0.61000(11) 0.18406(6) 0.48867(8) 0.0226(3) Uani 1 1 d . . . . .
C4B C 0.57987(12) 0.19232(6) 0.42311(8) 0.0250(3) Uani 1 1 d . . . . .
H4B H 0.624801 0.192687 0.387417 0.030 Uiso 1 1 calc R U . . .
C5B C 0.48312(13) 0.20003(7) 0.41069(9) 0.0276(3) Uani 1 1 d . . . . .
H5B H 0.461781 0.204929 0.366008 0.033 Uiso 1 1 calc R U . . .
C6B C 0.41714(12) 0.20068(7) 0.46269(9) 0.0265(3) Uani 1 1 d . . . . .
H6B H 0.351283 0.206528 0.453725 0.032 Uiso 1 1 calc R U . . .
O1C O 0.59444(10) 0.22758(5) 0.17245(8) 0.0415(4) Uani 1 1 d . . . . .
H1C H 0.646(2) 0.2321(11) 0.1461(14) 0.061(8) Uiso 1 1 d . . . . .
O2C O 0.41044(9) 0.20759(5) 0.18734(7) 0.0328(3) Uani 1 1 d . . . . .
H2C H 0.446(2) 0.2345(13) 0.1888(15) 0.074(9) Uiso 1 1 d . . . . .
O3C O 0.34341(8) 0.11031(5) 0.18911(7) 0.0295(3) Uani 1 1 d . . . . .
H3C H 0.3379(19) 0.0806(11) 0.2098(14) 0.060(8) Uiso 1 1 d . . . . .
C1C C 0.57014(12) 0.17764(6) 0.16887(9) 0.0258(3) Uani 1 1 d . . . . .
C2C C 0.47342(12) 0.16799(6) 0.17846(8) 0.0234(3) Uani 1 1 d . . . . .
C3C C 0.43952(11) 0.11840(6) 0.17853(8) 0.0233(3) Uani 1 1 d . . . . .
C4C C 0.50347(13) 0.07912(7) 0.16705(10) 0.0304(4) Uani 1 1 d . . . . .
H4C H 0.481020 0.045150 0.165857 0.036 Uiso 1 1 calc R U . . .
C5C C 0.59961(13) 0.08906(7) 0.15733(10) 0.0327(4) Uani 1 1 d . . . . .
H5C H 0.642761 0.061786 0.150106 0.039 Uiso 1 1 calc R U . . .
C6C C 0.63385(12) 0.13840(7) 0.15800(9) 0.0288(4) Uani 1 1 d . . . . .
H6C H 0.699925 0.145105 0.151104 0.035 Uiso 1 1 calc R U . . .
O1W O 0.19328(8) 0.46810(5) 0.27648(6) 0.0257(2) Uani 1 1 d . . . . .
H1WA H 0.1673(18) 0.4564(10) 0.3149(14) 0.053(7) Uiso 1 1 d . . . . .
H1WB H 0.172(2) 0.4993(13) 0.2694(16) 0.075(9) Uiso 1 1 d . . . . .
O2W O 0.29506(10) 0.30808(6) 0.56827(8) 0.0403(3) Uani 1 1 d . . . . .
H2WA H 0.336(2) 0.2981(12) 0.6025(17) 0.072(9) Uiso 1 1 d . . . . .
H2WB H 0.328(2) 0.3110(11) 0.5292(17) 0.067(9) Uiso 1 1 d . . . . .
O3W O 0.750000 0.250000 0.59894(9) 0.0260(3) Uani 1 2 d S T P . .
H3W H 0.7665(19) 0.2757(10) 0.5703(14) 0.058(8) Uiso 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
O1D C1D 1.229(2) . ?
O2D C5D 1.239(2) . ?
N1D C1D 1.391(2) . ?
N1D C5D 1.399(2) . ?
N1D C6D 1.470(2) . ?
N2D C1D 1.372(2) . ?
N2D C2D 1.376(2) . ?
N2D C7D 1.472(2) . ?
N3D C2D 1.348(2) . ?
N3D C3D 1.353(2) . ?
N4D C3D 1.355(2) . ?
N4D C4D 1.383(2) . ?
N4D C8D 1.455(2) . ?
C2D C4D 1.374(2) . ?
C3D H3D 0.9500 . ?
C4D C5D 1.416(2) . ?
C6D H6DA 0.9800 . ?
C6D H6DB 0.9800 . ?
C6D H6DC 0.9800 . ?
C7D H7DA 0.9800 . ?
C7D H7DB 0.9800 . ?
C7D H7DC 0.9800 . ?
C8D H8DA 0.9800 . ?
C8D H8DB 0.9800 . ?
C8D H8DC 0.9800 . ?
O1E C1E 1.229(2) . ?
O2E C5E 1.237(2) . ?
N1E C1E 1.395(2) . ?
N1E C5E 1.400(2) . ?
N1E C6E 1.475(2) . ?
N2E C1E 1.372(2) . ?
N2E C2E 1.377(2) . ?
N2E C7E 1.468(2) . ?
N3E C2E 1.350(2) . ?
N3E C3E 1.344(2) . ?
N4E C3E 1.343(2) . ?
N4E C4E 1.388(2) . ?
N4E C8E 1.457(2) . ?
C2E C4E 1.372(2) . ?
C3E H3E 0.9500 . ?
C4E C5E 1.420(2) . ?
C6E H6EA 0.9800 . ?
C6E H6EB 0.9800 . ?
C6E H6EC 0.9800 . ?
C7E H7EA 0.9800 . ?
C7E H7EB 0.9800 . ?
C7E H7EC 0.9800 . ?
C8E H8EA 0.9800 . ?
C8E H8EB 0.9800 . ?
C8E H8EC 0.9800 . ?
O1A H1A 0.90(3) . ?
O1A C1A 1.3640(19) . ?
O2A H2A 0.90(3) . ?
O2A C2A 1.3705(18) . ?
O3A H3A 0.89(2) . ?
O3A C3A 1.3645(19) . ?
C1A C2A 1.393(2) . ?
C1A C6A 1.397(2) . ?
C2A C3A 1.395(2) . ?
C3A C4A 1.392(2) . ?
C4A H4A 0.9500 . ?
C4A C5A 1.386(2) . ?
C5A H5A 0.9500 . ?
C5A C6A 1.387(2) . ?
C6A H6A 0.9500 . ?
O1B H1B 0.96(3) . ?
O1B C1B 1.360(2) . ?
O2B H2B 0.89(3) . ?
O2B C2B 1.3629(19) . ?
O3B H3B 0.87(3) . ?
O3B C3B 1.375(2) . ?
C1B C2B 1.395(2) . ?
C1B C6B 1.393(2) . ?
C2B C3B 1.390(2) . ?
C3B C4B 1.393(2) . ?
C4B H4B 0.9500 . ?
C4B C5B 1.389(2) . ?
C5B H5B 0.9500 . ?
C5B C6B 1.389(2) . ?
C6B H6B 0.9500 . ?
O1C H1C 0.90(3) . ?
O1C C1C 1.363(2) . ?
O2C H2C 0.87(3) . ?
O2C C2C 1.378(2) . ?
O3C H3C 0.89(3) . ?
O3C C3C 1.376(2) . ?
C1C C2C 1.388(2) . ?
C1C C6C 1.383(2) . ?
C2C C3C 1.392(2) . ?
C3C C4C 1.388(2) . ?
C4C H4C 0.9500 . ?
C4C C5C 1.382(2) . ?
C5C H5C 0.9500 . ?
C5C C6C 1.387(3) . ?
C6C H6C 0.9500 . ?
O1W H1WA 0.90(3) . ?
O1W H1WB 0.88(3) . ?
O2W H2WA 0.93(3) . ?
O2W H2WB 0.91(3) . ?
O3W H3W 0.92(3) . ?

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_3
_geom_angle_publ_flag
C1D N1D C5D 125.46(14) . . ?
C1D N1D C6D 116.51(14) . . ?
C5D N1D C6D 118.03(14) . . ?
C1D N2D C2D 119.77(14) . . ?
C1D N2D C7D 118.03(13) . . ?
C2D N2D C7D 121.99(14) . . ?
C2D N3D C3D 103.16(14) . . ?
C3D N4D C4D 105.22(14) . . ?
C3D N4D C8D 126.70(15) . . ?
C4D N4D C8D 128.07(15) . . ?
O1D C1D N1D 121.39(15) . . ?
O1D C1D N2D 120.21(15) . . ?
N2D C1D N1D 118.40(14) . . ?
N3D C2D N2D 127.60(15) . . ?
N3D C2D C4D 112.19(14) . . ?
C4D C2D N2D 120.20(15) . . ?
N3D C3D N4D 113.48(15) . . ?
N3D C3D H3D 123.3 . . ?
N4D C3D H3D 123.3 . . ?
N4D C4D C5D 130.10(15) . . ?
C2D C4D N4D 105.94(14) . . ?
C2D C4D C5D 123.87(15) . . ?
O2D C5D N1D 122.53(15) . . ?
O2D C5D C4D 125.19(15) . . ?
N1D C5D C4D 112.28(14) . . ?
N1D C6D H6DA 109.5 . . ?
N1D C6D H6DB 109.5 . . ?
N1D C6D H6DC 109.5 . . ?
H6DA C6D H6DB 109.5 . . ?
H6DA C6D H6DC 109.5 . . ?
H6DB C6D H6DC 109.5 . . ?
N2D C7D H7DA 109.5 . . ?
N2D C7D H7DB 109.5 . . ?
N2D C7D H7DC 109.5 . . ?
H7DA C7D H7DB 109.5 . . ?
H7DA C7D H7DC 109.5 . . ?
H7DB C7D H7DC 109.5 . . ?
N4D C8D H8DA 109.5 . . ?
N4D C8D H8DB 109.5 . . ?
N4D C8D H8DC 109.5 . . ?
H8DA C8D H8DB 109.5 . . ?
H8DA C8D H8DC 109.5 . . ?
H8DB C8D H8DC 109.5 . . ?
C1E N1E C5E 125.70(13) . . ?
C1E N1E C6E 116.27(13) . . ?
C5E N1E C6E 118.02(13) . . ?
C1E N2E C2E 119.42(13) . . ?
C1E N2E C7E 118.69(13) . . ?
C2E N2E C7E 121.86(13) . . ?
C3E N3E C2E 103.07(13) . . ?
C3E N4E C4E 105.36(13) . . ?
C3E N4E C8E 125.87(14) . . ?
C4E N4E C8E 128.70(14) . . ?
O1E C1E N1E 121.32(14) . . ?
O1E C1E N2E 120.45(15) . . ?
N2E C1E N1E 118.22(14) . . ?
N3E C2E N2E 126.85(14) . . ?
N3E C2E C4E 112.18(14) . . ?
C4E C2E N2E 120.97(14) . . ?
N3E C3E H3E 123.0 . . ?
N4E C3E N3E 113.91(14) . . ?
N4E C3E H3E 123.0 . . ?
N4E C4E C5E 131.10(14) . . ?
C2E C4E N4E 105.47(13) . . ?
C2E C4E C5E 123.43(14) . . ?
O2E C5E N1E 122.12(14) . . ?
O2E C5E C4E 125.67(15) . . ?
N1E C5E C4E 112.20(13) . . ?
N1E C6E H6EA 109.5 . . ?
N1E C6E H6EB 109.5 . . ?
N1E C6E H6EC 109.5 . . ?
H6EA C6E H6EB 109.5 . . ?
H6EA C6E H6EC 109.5 . . ?
H6EB C6E H6EC 109.5 . . ?
N2E C7E H7EA 109.5 . . ?
N2E C7E H7EB 109.5 . . ?
N2E C7E H7EC 109.5 . . ?
H7EA C7E H7EB 109.5 . . ?
H7EA C7E H7EC 109.5 . . ?
H7EB C7E H7EC 109.5 . . ?
N4E C8E H8EA 109.5 . . ?
N4E C8E H8EB 109.5 . . ?
N4E C8E H8EC 109.5 . . ?
H8EA C8E H8EB 109.5 . . ?
H8EA C8E H8EC 109.5 . . ?
H8EB C8E H8EC 109.5 . . ?
C1A O1A H1A 110.8(16) . . ?
C2A O2A H2A 113.2(19) . . ?
C3A O3A H3A 112.0(15) . . ?
O1A C1A C2A 116.01(14) . . ?
O1A C1A C6A 123.86(14) . . ?
C2A C1A C6A 120.12(14) . . ?
O2A C2A C1A 117.66(14) . . ?
O2A C2A C3A 122.59(14) . . ?
C1A C2A C3A 119.68(14) . . ?
O3A C3A C2A 115.98(14) . . ?
O3A C3A C4A 123.80(14) . . ?
C4A C3A C2A 120.22(14) . . ?
C3A C4A H4A 120.2 . . ?
C5A C4A C3A 119.59(15) . . ?
C5A C4A H4A 120.2 . . ?
C4A C5A H5A 119.6 . . ?
C4A C5A C6A 120.90(15) . . ?
C6A C5A H5A 119.6 . . ?
C1A C6A H6A 120.3 . . ?
C5A C6A C1A 119.46(15) . . ?
C5A C6A H6A 120.3 . . ?
C1B O1B H1B 112.2(18) . . ?
C2B O2B H2B 112.8(16) . . ?
C3B O3B H3B 109.9(18) . . ?
O1B C1B C2B 115.52(15) . . ?
O1B C1B C6B 124.16(15) . . ?
C6B C1B C2B 120.32(15) . . ?
O2B C2B C1B 122.22(15) . . ?
O2B C2B C3B 118.50(14) . . ?
C3B C2B C1B 119.28(15) . . ?
O3B C3B C2B 115.93(15) . . ?
O3B C3B C4B 123.15(15) . . ?
C2B C3B C4B 120.92(15) . . ?
C3B C4B H4B 120.5 . . ?
C5B C4B C3B 119.00(15) . . ?
C5B C4B H4B 120.5 . . ?
C4B C5B H5B 119.5 . . ?
C6B C5B C4B 120.94(16) . . ?
C6B C5B H5B 119.5 . . ?
C1B C6B H6B 120.3 . . ?
C5B C6B C1B 119.49(15) . . ?
C5B C6B H6B 120.3 . . ?
C1C O1C H1C 107.3(18) . . ?
C2C O2C H2C 105(2) . . ?
C3C O3C H3C 107.0(18) . . ?
O1C C1C C2C 114.37(15) . . ?
O1C C1C C6C 124.91(15) . . ?
C6C C1C C2C 120.71(15) . . ?
O2C C2C C1C 120.01(15) . . ?
O2C C2C C3C 119.74(14) . . ?
C1C C2C C3C 120.25(15) . . ?
O3C C3C C2C 118.56(14) . . ?
O3C C3C C4C 122.53(15) . . ?
C4C C3C C2C 118.91(15) . . ?
C3C C4C H4C 119.8 . . ?
C5C C4C C3C 120.46(16) . . ?
C5C C4C H4C 119.8 . . ?
C4C C5C H5C 119.6 . . ?
C4C C5C C6C 120.80(16) . . ?
C6C C5C H5C 119.6 . . ?
C1C C6C C5C 118.86(15) . . ?
C1C C6C H6C 120.6 . . ?
C5C C6C H6C 120.6 . . ?
H1WA O1W H1WB 109(3) . . ?
H2WA O2W H2WB 110(3) . . ?

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
C3D H3D O1B 0.95 2.45 3.005(2) 117.2 7_565 yes
C3E H3E O3A 0.95 2.38 2.998(2) 122.4 . yes
O1A H1A O1E 0.90(3) 1.80(3) 2.7029(16) 177(2) 8_756 yes
O2A H2A N3E 0.90(3) 1.93(3) 2.7858(18) 160(3) . yes
O3A H3A O1W 0.89(2) 1.82(2) 2.6909(17) 167(2) . yes
O1B H1B O2W 0.96(3) 1.66(3) 2.5989(18) 167(3) 2 yes
O2B H2B N3D 0.89(3) 2.02(3) 2.8881(19) 163(2) 7_566 yes
O2B H2B O1B 0.89(3) 2.29(2) 2.7094(17) 108.3(19) . yes
O3B H3B O1D 0.87(3) 1.78(3) 2.6411(17) 176(3) 2_655 yes
O1C H1C O3W 0.90(3) 1.79(3) 2.6889(17) 172(3) 7_565 yes
O2C H2C O1C 0.87(3) 2.11(3) 2.6409(18) 119(3) . yes
O3C H3C O1W 0.89(3) 1.90(3) 2.7554(18) 160(3) 2 yes
O1W H1WA O2E 0.90(3) 1.82(3) 2.7159(17) 172(2) 8_656 yes
O1W H1WB O2A 0.88(3) 2.03(3) 2.8516(17) 155(3) 4_465 yes
O2W H2WA O2C 0.93(3) 1.99(3) 2.903(2) 165(3) 7_566 yes
O2W H2WB O2D 0.91(3) 1.82(3) 2.706(2) 164(3) . yes
O3W H3W O3B 0.92(3) 1.86(3) 2.7688(17) 175(3) 2_655 yes

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
N2D C2D C4D N4D 178.57(14) . . . . ?
N2D C2D C4D C5D 1.7(2) . . . . ?
N3D C2D C4D N4D -0.28(18) . . . . ?
N3D C2D C4D C5D -177.13(15) . . . . ?
N4D C4D C5D O2D 2.2(3) . . . . ?
N4D C4D C5D N1D -176.95(15) . . . . ?
C1D N1D C5D O2D -179.53(15) . . . . ?
C1D N1D C5D C4D -0.3(2) . . . . ?
C1D N2D C2D N3D 177.42(15) . . . . ?
C1D N2D C2D C4D -1.2(2) . . . . ?
C2D N2D C1D O1D -179.28(15) . . . . ?
C2D N2D C1D N1D 0.1(2) . . . . ?
C2D N3D C3D N4D -0.55(19) . . . . ?
C2D C4D C5D O2D 178.27(16) . . . . ?
C2D C4D C5D N1D -0.9(2) . . . . ?
C3D N3D C2D N2D -178.25(15) . . . . ?
C3D N3D C2D C4D 0.50(18) . . . . ?
C3D N4D C4D C2D -0.06(17) . . . . ?
C3D N4D C4D C5D 176.51(17) . . . . ?
C4D N4D C3D N3D 0.39(19) . . . . ?
C5D N1D C1D O1D -179.92(15) . . . . ?
C5D N1D C1D N2D 0.7(2) . . . . ?
C6D N1D C1D O1D -0.1(2) . . . . ?
C6D N1D C1D N2D -179.41(14) . . . . ?
C6D N1D C5D O2D 0.6(2) . . . . ?
C6D N1D C5D C4D 179.82(14) . . . . ?
C7D N2D C1D O1D -4.4(2) . . . . ?
C7D N2D C1D N1D 174.95(14) . . . . ?
C7D N2D C2D N3D 2.8(2) . . . . ?
C7D N2D C2D C4D -175.90(15) . . . . ?
C8D N4D C3D N3D -178.43(15) . . . . ?
C8D N4D C4D C2D 178.74(15) . . . . ?
C8D N4D C4D C5D -4.7(3) . . . . ?
N2E C2E C4E N4E 179.17(13) . . . . ?
N2E C2E C4E C5E 0.3(2) . . . . ?
N3E C2E C4E N4E -0.70(18) . . . . ?
N3E C2E C4E C5E -179.60(14) . . . . ?
N4E C4E C5E O2E 2.2(3) . . . . ?
N4E C4E C5E N1E -178.46(15) . . . . ?
C1E N1E C5E O2E 177.52(15) . . . . ?
C1E N1E C5E C4E -1.9(2) . . . . ?
C1E N2E C2E N3E -179.20(15) . . . . ?
C1E N2E C2E C4E 1.0(2) . . . . ?
C2E N2E C1E O1E 176.90(14) . . . . ?
C2E N2E C1E N1E -2.5(2) . . . . ?
C2E N3E C3E N4E -0.66(19) . . . . ?
C2E C4E C5E O2E -179.23(15) . . . . ?
C2E C4E C5E N1E 0.1(2) . . . . ?
C3E N3E C2E N2E -179.04(15) . . . . ?
C3E N3E C2E C4E 0.82(18) . . . . ?
C3E N4E C4E C2E 0.26(17) . . . . ?
C3E N4E C4E C5E 179.05(16) . . . . ?
C4E N4E C3E N3E 0.25(19) . . . . ?
C5E N1E C1E O1E -176.27(15) . . . . ?
C5E N1E C1E N2E 3.1(2) . . . . ?
C6E N1E C1E O1E 4.9(2) . . . . ?
C6E N1E C1E N2E -175.69(14) . . . . ?
C6E N1E C5E O2E -3.7(2) . . . . ?
C6E N1E C5E C4E 176.92(14) . . . . ?
C7E N2E C1E O1E -4.8(2) . . . . ?
C7E N2E C1E N1E 175.79(13) . . . . ?
C7E N2E C2E N3E 2.6(2) . . . . ?
C7E N2E C2E C4E -177.27(14) . . . . ?
C8E N4E C3E N3E -176.95(15) . . . . ?
C8E N4E C4E C2E 177.36(15) . . . . ?
C8E N4E C4E C5E -3.9(3) . . . . ?
O1A C1A C2A O2A -0.2(2) . . . . ?
O1A C1A C2A C3A -177.43(14) . . . . ?
O1A C1A C6A C5A 178.47(15) . . . . ?
O2A C2A C3A O3A 0.8(2) . . . . ?
O2A C2A C3A C4A -178.99(14) . . . . ?
O3A C3A C4A C5A -178.49(15) . . . . ?
C1A C2A C3A O3A 177.94(14) . . . . ?
C1A C2A C3A C4A -1.9(2) . . . . ?
C2A C1A C6A C5A -0.1(2) . . . . ?
C2A C3A C4A C5A 1.3(2) . . . . ?
C3A C4A C5A C6A -0.2(2) . . . . ?
C4A C5A C6A C1A -0.4(2) . . . . ?
C6A C1A C2A O2A 178.54(14) . . . . ?
C6A C1A C2A C3A 1.3(2) . . . . ?
O1B C1B C2B O2B 2.9(2) . . . . ?
O1B C1B C2B C3B -177.72(14) . . . . ?
O1B C1B C6B C5B 179.37(16) . . . . ?
O2B C2B C3B O3B -2.8(2) . . . . ?
O2B C2B C3B C4B 177.15(14) . . . . ?
O3B C3B C4B C5B -179.84(15) . . . . ?
C1B C2B C3B O3B 177.81(14) . . . . ?
C1B C2B C3B C4B -2.3(2) . . . . ?
C2B C1B C6B C5B -1.0(2) . . . . ?
C2B C3B C4B C5B 0.2(2) . . . . ?
C3B C4B C5B C6B 1.4(3) . . . . ?
C4B C5B C6B C1B -1.0(3) . . . . ?
C6B C1B C2B O2B -176.74(15) . . . . ?
C6B C1B C2B C3B 2.7(2) . . . . ?
O1C C1C C2C O2C 3.0(2) . . . . ?
O1C C1C C2C C3C -177.62(16) . . . . ?
O1C C1C C6C C5C 178.25(18) . . . . ?
O2C C2C C3C O3C -1.5(2) . . . . ?
O2C C2C C3C C4C 177.64(16) . . . . ?
O3C C3C C4C C5C -179.36(17) . . . . ?
C1C C2C C3C O3C 179.12(15) . . . . ?
C1C C2C C3C C4C -1.8(2) . . . . ?
C2C C1C C6C C5C -0.5(3) . . . . ?
C2C C3C C4C C5C 1.6(3) . . . . ?
C3C C4C C5C C6C -0.8(3) . . . . ?
C4C C5C C6C C1C 0.3(3) . . . . ?
C6C C1C C2C O2C -178.16(16) . . . . ?
C6C C1C C2C C3C 1.2(3) . . . . ?

_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method 
'The crystal was mounted on a nylon loop with paratone oil'
_olex2_submission_original_sample_id 'AGI   CAF-PYr--sc  A'
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.221
_oxdiff_exptl_absorpt_empirical_full_min 0.841
