Supplementary Material (ESI) for Dalton Transactions
This journal is (c) The Royal Society of Chemistry 2006

data_global
_journal_name_full               'Dalton Trans.'

_journal_coden_Cambridge         0222

_publ_contact_author_name        'Juan Mareque Rivas'
_publ_contact_author_address     
;
Department of Chemistry
University of Edinburgh
The Kings Buildings
West Mains Road
Edinburgh
EH9 3JJ
UNITED KINGDOM
;

_publ_contact_author_email       JUAN.MAREQUE@ED.AC.UK

_publ_section_title              
;
The strength of hydrogen bonding to metal-bound
ligands can contribute to changes in the redox behaviour of metal
centres
;
loop_
_publ_author_name
'Juan Mareque Rivas'
'Sarah Hinchley'
'Laurent Metteau'
'S. Parsons'

# Attachment 'CIF.cif'

data_jm0505
_database_code_depnum_ccdc_archive 'CCDC 289833'

_audit_creation_method           SHELXL-97
_audit_creation_date             05-10-19

_chemical_compound_source        ' L. Matteau reation LM123c '

_exptl_crystal_recrystallization_method 
;
Slow evaporation of MeCN soln.
;

_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C33 H45 Cl Cu N7 O3'
_chemical_formula_sum            'C33 H45 Cl Cu N7 O3'
_chemical_formula_weight         686.75

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'
N N 0.0061 0.0033 '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'
Cu Cu 0.3201 1.2651 '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'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   P212121
_symmetry_space_group_name_Hall  'P 2ac 2ab'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'

_cell_length_a                   10.1526(2)
_cell_length_b                   18.4259(3)
_cell_length_c                   18.6888(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     3496.13(11)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    6902
_cell_measurement_theta_min      2.5
_cell_measurement_theta_max      29.5

_exptl_crystal_description       block
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.34
_exptl_crystal_size_min          0.25
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.305
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1448
_exptl_absorpt_coefficient_mu    0.744
_exptl_absorpt_correction_type   Multiscan
_exptl_absorpt_correction_T_min  0.690
_exptl_absorpt_correction_T_max  0.840
_exptl_absorpt_process_details   Sadabs

_exptl_special_details           
;
Data collection optimised with COSMO.
Oxford Cryosystems LT device.
;

_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker Smart Apex CCD'
_diffrn_measurement_method       'Omega and phi'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            61509
_diffrn_reflns_av_R_equivalents  0.0579
_diffrn_reflns_av_sigmaI/netI    0.0460
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_theta_min         2.18
_diffrn_reflns_theta_max         30.51
_reflns_number_total             10656
_reflns_number_gt                9242
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       Smart
_computing_cell_refinement       Saint
_computing_data_reduction        Saint
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    XP
_computing_publication_material  'XCIF, PLATON'

_refine_special_details          
;

H-atoms attached to N were located in a diffference map and refined freely.

222_ALERT_3_A Large Non-Solvent H Ueq(max)/Ueq(min) ... 6.57 Ratio
213_ALERT_2_C Atom O8 has ADP max/min Ratio ............. 3.10 prolat
220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.83 Ratio

The tBu groups librate more than the other atoms in the structure,
though this is not unusual, and the libration far from extreme.
Diagonalisation of the Uij tensors yields a max value of 0.1005.
O8 has an elongated ellipsoid (Umax= 0.1823), presumably reflecting
a small amount of disorder or high librational motion. At this level
disorder modelling is unlikely to lead to better data fitting than the
model presented.

761_ALERT_1_A CIF Contains no X-H Bonds ...................... ?
762_ALERT_1_A CIF Contains no X-Y-H or H-Y-H Angles .......... ?

No action.

232_ALERT_2_B Hirshfeld Test Diff (M-X) Cu - N22 .. 54.51 su
232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu - Cl1 .. 5.59 su

N22 is very weakly coordinated, and the Hirshfeld test does not really apply.
Ton Spek says that effect is not uncommon anyway in metal complexes.

061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.89

Sadabs corrects for all systematic errors that lead to disparities in the
intensities of symmetry-equivalent data. These may include absorption by the
mount, crystal decay etc.

241_ALERT_2_C Check High Ueq as Compared to Neighbors for Cu

The elongation in the metal centre is unusal. One possible causes is
absorption, though mu is not high, and other Uijs in the system are not
similarly distorted. Another explanation is that the Cu is slightly
disordered. This seems plausible because it is rather weakly bound in the
directions along the principal axis of the ellipsoid (Cu-N = 2.4 and 2.6 Ang).
There is no question that this metal is anything but Cu.

242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C19
352_ALERT_3_C Short N-H Bond (0.87A) N7 - H7N ... 0.76 Ang.
352_ALERT_3_C Short N-H Bond (0.87A) N17 - H17N ... 0.76 Ang.
795_ALERT_4_C C-Atom in CIF Coordinate List out of Sequence .. C8

No action taken.

910_ALERT_3_C # Missing FCF Reflections Below TH(Min) ........ 1
912_ALERT_3_C # Missing FCF Reflections Above STH/L=0.6 ...... 12

No action; completeness is fine.

#===============================================================================
Resolution & Completeness Statistics (Cumulative)
#===============================================================================
Theta sin(th)/Lambda Complete Expected Measured Missing
#-------------------------------------------------------------------------------
20.82 0.500 1.000 2105 2104 1
23.01 0.550 1.000 2767 2766 1
25.24 0.600 1.000 3559 3558 1
#----------------------------------------------------------- ACTA Min. Res. ----
27.51 0.650 1.000 4488 4487 1
29.84 0.700 1.000 5568 5567 1
30.51 0.714 0.998 5907 5894 13

Final shelx res file:

#TITL jm0505 in P2(1)2(1)2(1)
#CELL 0.71073 10.1526 18.4259 18.6888 90.000 90.000 90.000
#ZERR 4.00 0.0002 0.0003 0.0003 0.000 0.000 0.000
#LATT -1
#SYMM 0.5-X, -Y, 0.5+Z
#SYMM -X, 0.5+Y, 0.5-Z
#SYMM 0.5+X, 0.5-Y, -Z
#SFAC C H N CL CU O
#UNIT 132 180 28 4 4 12
#TEMP -123
#TWIN
#L.S. 4
#ACTA
#RTAB D1 CU N12
#RTAB D2 CU N22
#RTAB D3 CL1 N7
#RTAB D4 CL1 N17
#RTAB D5 CL1 N27
#HTAB
#FMAP 2
#PLAN 20
#WGHT 0.050400 2.005200
#BASF 0.01514
#FVAR 0.45547
#CU 5 0.667468 0.414820 0.884808 11.00000 0.06755 0.02404 =
#0.04978 -0.01163 -0.03697 0.00724
#CL1 4 0.762375 0.481641 0.969474 11.00000 0.02634 0.02038 =
#0.02262 -0.00248 -0.00161 -0.00265
#N1 3 0.608512 0.336151 0.807311 11.00000 0.02430 0.02106 =
#0.01963 0.00083 -0.00017 0.00013
#C1 1 0.475227 0.358438 0.785952 11.00000 0.02731 0.02618 =
#0.02774 -0.00426 -0.00676 -0.00111
#AFIX 23
#H1A 2 0.411757 0.341737 0.822642 11.00000 -1.20000
#H1B 2 0.452374 0.334290 0.740289 11.00000 -1.20000
#AFIX 0
#N2 3 0.537595 0.481401 0.817989 11.00000 0.03528 0.02094 =
#0.02815 0.00081 -0.00788 0.00113
#C2 1 0.461165 0.439290 0.776798 11.00000 0.02886 0.02856 =
#0.02210 0.00218 -0.00342 0.00189
#C3 1 0.365291 0.466839 0.731753 11.00000 0.03488 0.03988 =
#0.03097 0.00235 -0.01092 0.00078
#AFIX 43
#H3A 2 0.314931 0.435482 0.702093 11.00000 -1.20000
#AFIX 0
#C4 1 0.344350 0.540862 0.730817 11.00000 0.03755 0.04285 =
#0.03457 0.01207 -0.00934 0.00586
#AFIX 43
#H4A 2 0.277922 0.561055 0.701061 11.00000 -1.20000
#AFIX 0
#C5 1 0.420402 0.585178 0.773299 11.00000 0.04233 0.02930 =
#0.03369 0.01058 -0.00166 0.00818
#AFIX 43
#H5A 2 0.406787 0.636186 0.773623 11.00000 -1.20000
#AFIX 0
#C6 1 0.517673 0.553896 0.815802 11.00000 0.03784 0.02407 =
#0.02710 0.00567 -0.00166 0.00384
#N7 3 0.598408 0.594293 0.861259 11.00000 0.04765 0.01852 =
#0.03713 0.00406 -0.01127 0.00297
#O8 6 0.565155 0.706765 0.816611 11.00000 0.14176 0.02407 =
#0.08276 0.01564 -0.06213 -0.00686
#C9 1 0.689851 0.699958 0.925484 11.00000 0.05295 0.01802 =
#0.03735 -0.00213 -0.00271 0.00270
#C10C 1 0.830317 0.671374 0.926163 11.00000 0.05036 0.02870 =
#0.05689 -0.00062 -0.00354 -0.00493
#AFIX 33
#H10A 2 0.829099 0.618528 0.932051 11.00000 -1.50000
#H10B 2 0.878757 0.693440 0.965962 11.00000 -1.50000
#H10C 2 0.873639 0.683727 0.880914 11.00000 -1.50000
#AFIX 0
#C10A 1 0.620270 0.679989 0.995313 11.00000 0.08169 0.04340 =
#0.04709 -0.01332 0.01908 -0.00168
#AFIX 33
#H10D 2 0.618348 0.627076 1.000516 11.00000 -1.50000
#H10E 2 0.529939 0.698716 0.994433 11.00000 -1.50000
#H10F 2 0.667921 0.701374 1.035749 11.00000 -1.50000
#AFIX 0
#C10B 1 0.693782 0.783114 0.916869 11.00000 0.07639 0.02100 =
#0.06801 -0.00653 -0.00944 0.00158
#AFIX 33
#H10G 2 0.743023 0.804490 0.956744 11.00000 -1.50000
#H10H 2 0.603703 0.802227 0.916752 11.00000 -1.50000
#H10I 2 0.737120 0.795504 0.871634 11.00000 -1.50000
#AFIX 0
#C11 1 0.698356 0.336286 0.744967 11.00000 0.03338 0.02846 =
#0.02046 -0.00274 0.00059 -0.00222
#AFIX 23
#H11A 2 0.690152 0.383070 0.719301 11.00000 -1.20000
#H11B 2 0.672512 0.297045 0.711617 11.00000 -1.20000
#AFIX 0
#C12 1 0.839440 0.325432 0.767510 11.00000 0.03201 0.02384 =
#0.02202 0.00123 0.00562 -0.00240
#N12 3 0.882307 0.370074 0.819094 11.00000 0.02755 0.02164 =
#0.02121 -0.00054 0.00237 0.00043
#C13 1 0.919352 0.273597 0.736215 11.00000 0.04092 0.03062 =
#0.03110 -0.01261 0.00802 -0.00299
#AFIX 43
#H13A 2 0.886570 0.242726 0.699604 11.00000 -1.20000
#AFIX 0
#C14 1 1.047786 0.267855 0.759485 11.00000 0.03717 0.03356 =
#0.05057 -0.01334 0.01594 0.00402
#AFIX 43
#H14A 2 1.104421 0.232589 0.738788 11.00000 -1.20000
#AFIX 0
#C15 1 1.094373 0.312715 0.812323 11.00000 0.02579 0.03431 =
#0.05261 -0.00882 0.00683 0.00176
#AFIX 43
#H15A 2 1.182515 0.308978 0.828985 11.00000 -1.20000
#AFIX 0
#C16 1 1.007319 0.364356 0.840947 11.00000 0.02915 0.02383 =
#0.02715 -0.00042 0.00433 -0.00041
#N17 3 1.042807 0.414695 0.892792 11.00000 0.02021 0.02994 =
#0.03354 -0.00506 -0.00157 0.00707
#O18 6 1.261150 0.391234 0.903722 11.00000 0.02799 0.07008 =
#0.07855 -0.03171 -0.00856 0.01402
#C18 1 1.167331 0.428454 0.919395 11.00000 0.02825 0.03871 =
#0.03180 -0.00372 -0.00508 0.00236
#C19 1 1.178395 0.493780 0.968901 11.00000 0.02484 0.04359 =
#0.03331 -0.00617 -0.00659 0.00045
#C20C 1 1.121138 0.560669 0.932423 11.00000 0.06417 0.03482 =
#0.05524 -0.01212 -0.02447 0.00232
#AFIX 33
#H20A 2 1.027585 0.552576 0.922266 11.00000 -1.50000
#H20B 2 1.168290 0.569658 0.887534 11.00000 -1.50000
#H20C 2 1.130712 0.602795 0.964009 11.00000 -1.50000
#AFIX 0
#C20B 1 1.324700 0.506986 0.984664 11.00000 0.03265 0.06952 =
#0.06991 -0.02287 -0.01807 0.00018
#AFIX 33
#H20D 2 1.371365 0.516860 0.939806 11.00000 -1.50000
#H20E 2 1.362436 0.463830 1.007448 11.00000 -1.50000
#H20F 2 1.333782 0.548706 1.016812 11.00000 -1.50000
#AFIX 0
#C20A 1 1.105137 0.478407 1.038645 11.00000 0.06303 0.08917 =
#0.03080 -0.01167 -0.00037 -0.01874
#AFIX 33
#H20G 2 1.011624 0.470290 1.028398 11.00000 -1.50000
#H20H 2 1.114470 0.520001 1.070930 11.00000 -1.50000
#H20I 2 1.142307 0.435066 1.061361 11.00000 -1.50000
#AFIX 0
#C21 1 0.603373 0.263050 0.839520 11.00000 0.02778 0.01676 =
#0.02355 -0.00369 0.00073 -0.00170
#AFIX 23
#H21A 2 0.694102 0.244439 0.845854 11.00000 -1.20000
#H21B 2 0.556178 0.229701 0.806844 11.00000 -1.20000
#AFIX 0
#N22 3 0.566181 0.319476 0.955294 11.00000 0.02004 0.02067 =
#0.02297 -0.00263 0.00064 -0.00324
#C22 1 0.534226 0.264422 0.911162 11.00000 0.01989 0.01745 =
#0.02716 -0.00070 -0.00197 0.00067
#C23 1 0.446078 0.210905 0.929063 11.00000 0.03391 0.02285 =
#0.03506 -0.00494 -0.00137 -0.00977
#AFIX 43
#H23A 2 0.424942 0.173409 0.896116 11.00000 -1.20000
#AFIX 0
#C24 1 0.388674 0.212855 0.996288 11.00000 0.03034 0.02892 =
#0.04495 0.00325 0.00692 -0.01210
#AFIX 43
#H24A 2 0.327914 0.176236 1.010108 11.00000 -1.20000
#AFIX 0
#C25 1 0.419829 0.267858 1.042895 11.00000 0.03052 0.02743 =
#0.03181 0.00252 0.00907 -0.00419
#AFIX 43
#H25A 2 0.380961 0.270198 1.089077 11.00000 -1.20000
#AFIX 0
#C26 1 0.510663 0.320492 1.020391 11.00000 0.02385 0.02129 =
#0.02639 -0.00011 0.00193 0.00147
#N27 3 0.556829 0.375838 1.064793 11.00000 0.02900 0.02404 =
#0.02287 -0.00447 0.00660 -0.00497
#O28 6 0.407193 0.370409 1.155423 11.00000 0.04529 0.03722 =
#0.03902 -0.00705 0.02156 -0.00389
#C28 1 0.508371 0.395720 1.131055 11.00000 0.03670 0.02330 =
#0.02369 -0.00159 0.00730 0.00677
#C29 1 0.588949 0.453547 1.171375 11.00000 0.03968 0.02621 =
#0.02180 -0.00360 0.00461 0.00434
#C30C 1 0.737133 0.438113 1.167606 11.00000 0.03902 0.04294 =
#0.02952 -0.01089 -0.00724 0.00541
#AFIX 33
#H30A 2 0.785101 0.475770 1.193916 11.00000 -1.50000
#H30B 2 0.765585 0.438087 1.117497 11.00000 -1.50000
#H30C 2 0.755461 0.390613 1.188993 11.00000 -1.50000
#AFIX 0
#C30B 1 0.546039 0.452744 1.250046 11.00000 0.06711 0.04018 =
#0.02017 -0.00536 0.00850 0.00770
#AFIX 33
#H30D 2 0.596268 0.489222 1.276724 11.00000 -1.50000
#H30E 2 0.562592 0.404612 1.270464 11.00000 -1.50000
#H30F 2 0.451835 0.463886 1.253223 11.00000 -1.50000
#AFIX 0
#C30A 1 0.557813 0.527287 1.138346 11.00000 0.05067 0.02490 =
#0.03353 -0.00582 -0.00575 0.00295
#AFIX 33
#H30G 2 0.607809 0.565097 1.163294 11.00000 -1.50000
#H30H 2 0.463342 0.537181 1.142903 11.00000 -1.50000
#H30I 2 0.582284 0.526956 1.087622 11.00000 -1.50000
#AFIX 0
#C8 1 0.612990 0.668377 0.862567 11.00000 0.05991 0.01889 =
#0.04932 0.00017 -0.00885 0.00359
#H27N 2 0.622467 0.402188 1.048862 11.00000 0.03229
#H17N 2 0.986186 0.436877 0.906987 11.00000 0.01431
#H7N 2 0.637416 0.571807 0.888235 11.00000 0.04047

#HKLF 4

#REM jm0505 in P2(1)2(1)2(1)
#REM R1 = 0.0555 for 9242 Fo > 4sig(Fo) and 0.0664 for all 10656 data
#REM 419 parameters refined using 0 restraints

END

WGHT 0.0480 2.1217
REM Highest difference peak 1.210, deepest hole -1.267, 1-sigma level 0.069
Q1 1 0.7231 0.4268 0.8598 11.00000 0.05 1.21
Q2 1 0.6875 0.4669 0.9675 11.00000 0.05 0.44
Q3 1 0.6484 0.3825 0.8536 11.00000 0.05 0.44
Q4 1 0.8431 0.4732 0.9681 11.00000 0.05 0.41
Q5 1 0.7965 0.5202 0.9889 11.00000 0.05 0.38
Q6 1 0.6677 0.4604 0.8626 11.00000 0.05 0.37
Q7 1 0.7786 0.4421 0.9468 11.00000 0.05 0.35
Q8 1 0.8150 0.4993 0.9966 11.00000 0.05 0.35
Q9 1 0.7738 0.4883 1.0141 11.00000 0.05 0.33
Q10 1 0.6733 0.4616 0.8990 11.00000 0.05 0.32
Q11 1 0.7973 0.4621 0.9336 11.00000 0.05 0.32
Q12 1 0.6223 0.3742 0.9333 11.00000 0.05 0.31
Q13 1 0.5841 0.3806 0.8870 11.00000 0.05 0.31
Q14 1 0.6659 0.4455 1.1623 11.00000 0.05 0.31
Q15 1 1.2384 0.4980 0.9803 11.00000 0.05 0.30
Q16 1 0.4650 0.2999 1.0394 11.00000 0.05 0.30
Q17 1 0.4796 0.3764 1.1631 11.00000 0.05 0.30
Q18 1 0.3818 0.4604 0.7708 11.00000 0.05 0.29
Q19 1 0.5261 0.4578 0.7876 11.00000 0.05 0.29
Q20 1 0.5603 0.4528 1.2087 11.00000 0.05 0.28

;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.0504P)^2^+2.0052P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom/difmap
_refine_ls_hydrogen_treatment    riding/refall
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.015(11)
_refine_ls_number_reflns         10656
_refine_ls_number_parameters     419
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0664
_refine_ls_R_factor_gt           0.0555
_refine_ls_wR_factor_ref         0.1230
_refine_ls_wR_factor_gt          0.1184
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_restrained_S_all      1.072
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000

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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu Cu 0.66747(5) 0.41482(2) 0.88481(2) 0.04712(13) Uani 1 1 d . . .
Cl1 Cl 0.76238(6) 0.48164(3) 0.96947(3) 0.02312(11) Uani 1 1 d . . .
N1 N 0.6085(2) 0.33615(11) 0.80731(10) 0.0217(4) Uani 1 1 d . . .
C1 C 0.4752(3) 0.35844(14) 0.78595(14) 0.0271(5) Uani 1 1 d . . .
H1A H 0.4118 0.3417 0.8226 0.032 Uiso 1 1 calc R . .
H1B H 0.4524 0.3343 0.7403 0.032 Uiso 1 1 calc R . .
N2 N 0.5376(2) 0.48140(12) 0.81799(11) 0.0281(4) Uani 1 1 d . . .
C2 C 0.4612(3) 0.43929(14) 0.77680(13) 0.0265(5) Uani 1 1 d . . .
C3 C 0.3653(3) 0.46684(17) 0.73175(15) 0.0352(6) Uani 1 1 d . . .
H3A H 0.3149 0.4355 0.7021 0.042 Uiso 1 1 calc R . .
C4 C 0.3443(3) 0.54086(17) 0.73082(16) 0.0383(6) Uani 1 1 d . . .
H4A H 0.2779 0.5611 0.7011 0.046 Uiso 1 1 calc R . .
C5 C 0.4204(3) 0.58518(16) 0.77330(15) 0.0351(6) Uani 1 1 d . . .
H5A H 0.4068 0.6362 0.7736 0.042 Uiso 1 1 calc R . .
C6 C 0.5177(3) 0.55390(14) 0.81580(14) 0.0297(5) Uani 1 1 d . . .
N7 N 0.5984(3) 0.59429(12) 0.86126(14) 0.0344(5) Uani 1 1 d . . .
O8 O 0.5652(4) 0.70677(13) 0.81661(17) 0.0829(12) Uani 1 1 d . . .
C9 C 0.6899(3) 0.69996(14) 0.92548(16) 0.0361(6) Uani 1 1 d . . .
C10C C 0.8303(4) 0.67137(16) 0.92616(19) 0.0453(7) Uani 1 1 d . . .
H10A H 0.8291 0.6185 0.9321 0.068 Uiso 1 1 calc R . .
H10B H 0.8788 0.6934 0.9660 0.068 Uiso 1 1 calc R . .
H10C H 0.8736 0.6837 0.8809 0.068 Uiso 1 1 calc R . .
C10A C 0.6203(5) 0.6800(2) 0.9953(2) 0.0574(10) Uani 1 1 d . . .
H10D H 0.6183 0.6271 1.0005 0.086 Uiso 1 1 calc R . .
H10E H 0.5299 0.6987 0.9944 0.086 Uiso 1 1 calc R . .
H10F H 0.6679 0.7014 1.0357 0.086 Uiso 1 1 calc R . .
C10B C 0.6938(4) 0.78311(16) 0.9169(2) 0.0551(10) Uani 1 1 d . . .
H10G H 0.7430 0.8045 0.9567 0.083 Uiso 1 1 calc R . .
H10H H 0.6037 0.8022 0.9168 0.083 Uiso 1 1 calc R . .
H10I H 0.7371 0.7955 0.8716 0.083 Uiso 1 1 calc R . .
C11 C 0.6984(3) 0.33629(14) 0.74497(13) 0.0274(5) Uani 1 1 d . . .
H11A H 0.6902 0.3831 0.7193 0.033 Uiso 1 1 calc R . .
H11B H 0.6725 0.2970 0.7116 0.033 Uiso 1 1 calc R . .
C12 C 0.8394(3) 0.32543(13) 0.76751(13) 0.0260(5) Uani 1 1 d . . .
N12 N 0.8823(2) 0.37007(11) 0.81909(11) 0.0235(4) Uani 1 1 d . . .
C13 C 0.9194(3) 0.27360(16) 0.73621(15) 0.0342(6) Uani 1 1 d . . .
H13A H 0.8866 0.2427 0.6996 0.041 Uiso 1 1 calc R . .
C14 C 1.0478(3) 0.26785(17) 0.75949(18) 0.0404(7) Uani 1 1 d . . .
H14A H 1.1044 0.2326 0.7388 0.049 Uiso 1 1 calc R . .
C15 C 1.0944(3) 0.31272(16) 0.81232(17) 0.0376(7) Uani 1 1 d . . .
H15A H 1.1825 0.3090 0.8290 0.045 Uiso 1 1 calc R . .
C16 C 1.0073(3) 0.36436(14) 0.84095(13) 0.0267(5) Uani 1 1 d . . .
N17 N 1.0428(2) 0.41469(13) 0.89279(12) 0.0279(4) Uani 1 1 d . . .
O18 O 1.2611(2) 0.39123(15) 0.90372(15) 0.0589(7) Uani 1 1 d . . .
C18 C 1.1673(3) 0.42845(16) 0.91940(14) 0.0329(6) Uani 1 1 d . . .
C19 C 1.1784(3) 0.49378(16) 0.96890(15) 0.0339(6) Uani 1 1 d . . .
C20C C 1.1211(4) 0.56067(18) 0.9324(2) 0.0514(9) Uani 1 1 d . . .
H20A H 1.0276 0.5526 0.9223 0.077 Uiso 1 1 calc R . .
H20B H 1.1683 0.5697 0.8875 0.077 Uiso 1 1 calc R . .
H20C H 1.1307 0.6028 0.9640 0.077 Uiso 1 1 calc R . .
C20B C 1.3247(3) 0.5070(2) 0.9847(2) 0.0574(10) Uani 1 1 d . . .
H20D H 1.3714 0.5169 0.9398 0.086 Uiso 1 1 calc R . .
H20E H 1.3624 0.4638 1.0074 0.086 Uiso 1 1 calc R . .
H20F H 1.3338 0.5487 1.0168 0.086 Uiso 1 1 calc R . .
C20A C 1.1051(4) 0.4784(3) 1.03864(18) 0.0610(11) Uani 1 1 d . . .
H20G H 1.0116 0.4703 1.0284 0.092 Uiso 1 1 calc R . .
H20H H 1.1145 0.5200 1.0709 0.092 Uiso 1 1 calc R . .
H20I H 1.1423 0.4351 1.0614 0.092 Uiso 1 1 calc R . .
C21 C 0.6034(3) 0.26305(12) 0.83952(13) 0.0227(5) Uani 1 1 d . . .
H21A H 0.6941 0.2444 0.8459 0.027 Uiso 1 1 calc R . .
H21B H 0.5562 0.2297 0.8068 0.027 Uiso 1 1 calc R . .
N22 N 0.56618(19) 0.31948(11) 0.95529(10) 0.0212(4) Uani 1 1 d . . .
C22 C 0.5342(2) 0.26442(12) 0.91116(13) 0.0215(4) Uani 1 1 d . . .
C23 C 0.4461(3) 0.21090(14) 0.92906(15) 0.0306(5) Uani 1 1 d . . .
H23A H 0.4249 0.1734 0.8961 0.037 Uiso 1 1 calc R . .
C24 C 0.3887(3) 0.21286(16) 0.99629(17) 0.0347(6) Uani 1 1 d . . .
H24A H 0.3279 0.1762 1.0101 0.042 Uiso 1 1 calc R . .
C25 C 0.4198(3) 0.26786(14) 1.04289(14) 0.0299(5) Uani 1 1 d . . .
H25A H 0.3810 0.2702 1.0891 0.036 Uiso 1 1 calc R . .
C26 C 0.5107(2) 0.32049(13) 1.02039(13) 0.0238(5) Uani 1 1 d . . .
N27 N 0.5568(2) 0.37584(12) 1.06479(11) 0.0253(4) Uani 1 1 d . . .
O28 O 0.4072(2) 0.37041(12) 1.15542(11) 0.0405(5) Uani 1 1 d . . .
C28 C 0.5084(3) 0.39572(13) 1.13106(13) 0.0279(5) Uani 1 1 d . . .
C29 C 0.5889(3) 0.45355(14) 1.17138(13) 0.0292(5) Uani 1 1 d . . .
C30C C 0.7371(3) 0.43811(17) 1.16761(15) 0.0372(6) Uani 1 1 d . . .
H30A H 0.7851 0.4758 1.1939 0.056 Uiso 1 1 calc R . .
H30B H 0.7656 0.4381 1.1175 0.056 Uiso 1 1 calc R . .
H30C H 0.7555 0.3906 1.1890 0.056 Uiso 1 1 calc R . .
C30B C 0.5460(4) 0.45274(18) 1.25005(14) 0.0425(8) Uani 1 1 d . . .
H30D H 0.5963 0.4892 1.2767 0.064 Uiso 1 1 calc R . .
H30E H 0.5626 0.4046 1.2705 0.064 Uiso 1 1 calc R . .
H30F H 0.4518 0.4639 1.2532 0.064 Uiso 1 1 calc R . .
C30A C 0.5578(3) 0.52729(15) 1.13835(15) 0.0364(6) Uani 1 1 d . . .
H30G H 0.6078 0.5651 1.1633 0.055 Uiso 1 1 calc R . .
H30H H 0.4633 0.5372 1.1429 0.055 Uiso 1 1 calc R . .
H30I H 0.5823 0.5270 1.0876 0.055 Uiso 1 1 calc R . .
C8 C 0.6130(4) 0.66838(15) 0.86257(18) 0.0427(7) Uani 1 1 d . . .
H27N H 0.622(3) 0.4022(18) 1.0489(17) 0.032(8) Uiso 1 1 d . . .
H17N H 0.986(3) 0.4369(15) 0.9070(14) 0.014(7) Uiso 1 1 d . . .
H7N H 0.637(4) 0.572(2) 0.8882(19) 0.040(10) Uiso 1 1 d . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Cu 0.0675(3) 0.02404(15) 0.0498(2) -0.01163(16) -0.0370(2) 0.00724(19)
Cl1 0.0263(3) 0.0204(2) 0.0226(2) -0.0025(2) -0.0016(2) -0.0026(2)
N1 0.0243(10) 0.0211(9) 0.0196(9) 0.0008(7) -0.0002(7) 0.0001(8)
C1 0.0273(12) 0.0262(12) 0.0277(12) -0.0043(10) -0.0068(9) -0.0011(10)
N2 0.0353(11) 0.0209(9) 0.0281(10) 0.0008(9) -0.0079(9) 0.0011(9)
C2 0.0289(12) 0.0286(12) 0.0221(10) 0.0022(9) -0.0034(9) 0.0019(10)
C3 0.0349(15) 0.0399(15) 0.0310(13) 0.0023(11) -0.0109(11) 0.0008(12)
C4 0.0375(15) 0.0429(15) 0.0346(14) 0.0121(12) -0.0093(12) 0.0059(14)
C5 0.0423(15) 0.0293(12) 0.0337(13) 0.0106(12) -0.0017(11) 0.0082(13)
C6 0.0378(14) 0.0241(12) 0.0271(12) 0.0057(10) -0.0017(10) 0.0038(11)
N7 0.0477(14) 0.0185(10) 0.0371(13) 0.0041(9) -0.0113(11) 0.0030(10)
O8 0.142(3) 0.0241(11) 0.083(2) 0.0156(12) -0.062(2) -0.0069(15)
C9 0.0530(18) 0.0180(11) 0.0373(14) -0.0021(10) -0.0027(13) 0.0027(12)
C10C 0.0504(19) 0.0287(13) 0.0569(19) -0.0006(13) -0.0035(16) -0.0049(15)
C10A 0.082(3) 0.0434(18) 0.0471(19) -0.0133(16) 0.0191(19) -0.0017(19)
C10B 0.076(3) 0.0210(12) 0.068(2) -0.0065(14) -0.009(2) 0.0016(15)
C11 0.0334(13) 0.0285(12) 0.0205(11) -0.0027(9) 0.0006(9) -0.0022(10)
C12 0.0320(12) 0.0238(10) 0.0220(10) 0.0012(9) 0.0056(10) -0.0024(11)
N12 0.0276(10) 0.0216(9) 0.0212(9) -0.0005(8) 0.0024(8) 0.0004(8)
C13 0.0409(15) 0.0306(13) 0.0311(13) -0.0126(11) 0.0080(11) -0.0030(12)
C14 0.0372(15) 0.0336(14) 0.0506(17) -0.0133(13) 0.0159(13) 0.0040(13)
C15 0.0258(13) 0.0343(14) 0.0526(18) -0.0088(13) 0.0068(12) 0.0018(12)
C16 0.0291(13) 0.0238(11) 0.0272(11) -0.0004(10) 0.0043(10) -0.0004(10)
N17 0.0202(10) 0.0299(10) 0.0335(11) -0.0051(10) -0.0016(8) 0.0071(9)
O18 0.0280(11) 0.0701(17) 0.0786(18) -0.0317(14) -0.0086(11) 0.0140(12)
C18 0.0282(13) 0.0387(14) 0.0318(13) -0.0037(11) -0.0051(10) 0.0024(12)
C19 0.0248(12) 0.0436(15) 0.0333(12) -0.0062(12) -0.0066(11) 0.0004(11)
C20C 0.064(2) 0.0348(15) 0.055(2) -0.0121(15) -0.0245(17) 0.0023(16)
C20B 0.0326(16) 0.070(2) 0.070(2) -0.0229(19) -0.0181(16) 0.0002(17)
C20A 0.063(2) 0.089(3) 0.0308(15) -0.0117(19) -0.0004(15) -0.019(2)
C21 0.0278(12) 0.0168(10) 0.0236(11) -0.0037(8) 0.0007(9) -0.0017(9)
N22 0.0200(9) 0.0207(9) 0.0230(9) -0.0026(7) 0.0006(7) -0.0032(8)
C22 0.0199(11) 0.0175(10) 0.0272(11) -0.0007(9) -0.0020(9) 0.0007(9)
C23 0.0339(14) 0.0228(11) 0.0351(13) -0.0049(10) -0.0014(11) -0.0098(11)
C24 0.0303(13) 0.0289(13) 0.0450(15) 0.0033(12) 0.0069(12) -0.0121(11)
C25 0.0305(12) 0.0274(12) 0.0318(13) 0.0025(10) 0.0091(10) -0.0042(11)
C26 0.0239(11) 0.0213(10) 0.0264(11) -0.0001(9) 0.0019(9) 0.0015(9)
N27 0.0290(11) 0.0240(10) 0.0229(10) -0.0045(8) 0.0066(8) -0.0050(9)
O28 0.0453(12) 0.0372(11) 0.0390(11) -0.0070(9) 0.0216(9) -0.0039(10)
C28 0.0367(14) 0.0233(11) 0.0237(11) -0.0016(9) 0.0073(10) 0.0068(10)
C29 0.0397(14) 0.0262(12) 0.0218(11) -0.0036(9) 0.0046(10) 0.0043(11)
C30C 0.0390(15) 0.0429(15) 0.0295(12) -0.0109(11) -0.0072(11) 0.0054(13)
C30B 0.067(2) 0.0402(16) 0.0202(12) -0.0054(11) 0.0085(13) 0.0077(16)
C30A 0.0507(17) 0.0249(12) 0.0335(14) -0.0058(11) -0.0058(12) 0.0029(12)
C8 0.060(2) 0.0189(11) 0.0493(18) 0.0002(12) -0.0089(15) 0.0036(13)

_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
Cu N1 2.135(2) . ?
Cu N2 2.192(2) . ?
Cu Cl1 2.2244(6) . ?
Cu N22 2.425(2) . ?
N1 C1 1.469(3) . ?
N1 C21 1.476(3) . ?
N1 C11 1.480(3) . ?
C1 C2 1.506(4) . ?
N2 C2 1.340(3) . ?
N2 C6 1.352(3) . ?
C2 C3 1.383(4) . ?
C3 C4 1.381(4) . ?
C4 C5 1.376(5) . ?
C5 C6 1.392(4) . ?
C6 N7 1.396(4) . ?
N7 C8 1.373(3) . ?
O8 C8 1.214(4) . ?
C9 C10C 1.520(5) . ?
C9 C8 1.526(4) . ?
C9 C10A 1.529(5) . ?
C9 C10B 1.541(4) . ?
C11 C12 1.506(4) . ?
C12 N12 1.340(3) . ?
C12 C13 1.383(4) . ?
N12 C16 1.337(3) . ?
C13 C14 1.379(5) . ?
C14 C15 1.372(4) . ?
C15 C16 1.405(4) . ?
C16 N17 1.389(3) . ?
N17 C18 1.382(3) . ?
O18 C18 1.210(4) . ?
C18 C19 1.522(4) . ?
C19 C20C 1.524(4) . ?
C19 C20A 1.527(5) . ?
C19 C20B 1.534(4) . ?
C21 C22 1.512(3) . ?
N22 C26 1.341(3) . ?
N22 C22 1.347(3) . ?
C22 C23 1.373(4) . ?
C23 C24 1.385(4) . ?
C24 C25 1.373(4) . ?
C25 C26 1.403(4) . ?
C26 N27 1.396(3) . ?
N27 C28 1.382(3) . ?
O28 C28 1.217(3) . ?
C28 C29 1.540(4) . ?
C29 C30A 1.525(4) . ?
C29 C30C 1.533(4) . ?
C29 C30B 1.534(4) . ?

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
N1 Cu N2 79.91(8) . . ?
N1 Cu Cl1 168.50(6) . . ?
N2 Cu Cl1 110.86(6) . . ?
N1 Cu N22 75.98(7) . . ?
N2 Cu N22 117.39(8) . . ?
Cl1 Cu N22 101.44(5) . . ?
C1 N1 C21 109.5(2) . . ?
C1 N1 C11 110.69(19) . . ?
C21 N1 C11 110.14(19) . . ?
C1 N1 Cu 104.64(15) . . ?
C21 N1 Cu 110.66(14) . . ?
C11 N1 Cu 111.11(15) . . ?
N1 C1 C2 113.2(2) . . ?
C2 N2 C6 117.9(2) . . ?
C2 N2 Cu 110.58(17) . . ?
C6 N2 Cu 131.34(18) . . ?
N2 C2 C3 123.0(2) . . ?
N2 C2 C1 116.9(2) . . ?
C3 C2 C1 119.9(2) . . ?
C4 C3 C2 118.6(3) . . ?
C5 C4 C3 119.5(3) . . ?
C4 C5 C6 118.8(3) . . ?
N2 C6 C5 122.2(3) . . ?
N2 C6 N7 114.9(2) . . ?
C5 C6 N7 122.9(3) . . ?
C8 N7 C6 127.2(3) . . ?
C10C C9 C8 110.7(3) . . ?
C10C C9 C10A 110.1(3) . . ?
C8 C9 C10A 109.2(3) . . ?
C10C C9 C10B 108.7(3) . . ?
C8 C9 C10B 108.2(3) . . ?
C10A C9 C10B 109.9(3) . . ?
N1 C11 C12 111.4(2) . . ?
N12 C12 C13 122.5(3) . . ?
N12 C12 C11 115.4(2) . . ?
C13 C12 C11 122.1(2) . . ?
C16 N12 C12 118.7(2) . . ?
C14 C13 C12 118.3(3) . . ?
C15 C14 C13 120.5(3) . . ?
C14 C15 C16 117.7(3) . . ?
N12 C16 N17 114.0(2) . . ?
N12 C16 C15 122.3(2) . . ?
N17 C16 C15 123.7(3) . . ?
C18 N17 C16 127.6(2) . . ?
O18 C18 N17 122.0(3) . . ?
O18 C18 C19 122.5(3) . . ?
N17 C18 C19 115.5(2) . . ?
C18 C19 C20C 109.8(2) . . ?
C18 C19 C20A 109.6(3) . . ?
C20C C19 C20A 110.2(3) . . ?
C18 C19 C20B 108.3(2) . . ?
C20C C19 C20B 109.1(3) . . ?
C20A C19 C20B 109.7(3) . . ?
N1 C21 C22 111.24(19) . . ?
C26 N22 C22 117.7(2) . . ?
C26 N22 Cu 131.38(16) . . ?
C22 N22 Cu 108.37(15) . . ?
N22 C22 C23 123.3(2) . . ?
N22 C22 C21 116.3(2) . . ?
C23 C22 C21 120.4(2) . . ?
C22 C23 C24 118.5(2) . . ?
C25 C24 C23 119.8(2) . . ?
C24 C25 C26 118.1(2) . . ?
N22 C26 N27 114.1(2) . . ?
N22 C26 C25 122.6(2) . . ?
N27 C26 C25 123.2(2) . . ?
C28 N27 C26 127.4(2) . . ?
O28 C28 N27 122.3(2) . . ?
O28 C28 C29 122.0(2) . . ?
N27 C28 C29 115.6(2) . . ?
C30A C29 C30C 110.5(3) . . ?
C30A C29 C30B 109.7(2) . . ?
C30C C29 C30B 108.7(2) . . ?
C30A C29 C28 107.9(2) . . ?
C30C C29 C28 111.7(2) . . ?
C30B C29 C28 108.1(2) . . ?
O8 C8 N7 121.6(3) . . ?
O8 C8 C9 121.8(3) . . ?
N7 C8 C9 116.6(3) . . ?

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        30.51
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         1.210
_refine_diff_density_min         -1.267
_refine_diff_density_rms         0.069