# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2005 data_global _audit_creation_method Xtal3.6 _audit_creation_date 02-05-13 _audit_update_record ? _journal_coden_Cambridge 182 loop_ _publ_author_name 'Andrew Ozarowski' 'Louis C. Brunel' 'Elena A. Buvaylo' 'Julia Jezierska' 'V. N. Kokozay' 'Brian W. Skelton' 'O. Y. Vassilyeva' _publ_contact_author_name 'Andrew Ozarowski' _publ_contact_author_address ; CIMAR National High Magnetic Field Laboratory 1800 E. Paul Dirac Drive Tallahassee Florida 32310 UNITED STATES OF AMERICA ; _publ_contact_author_email OZAROWSK@MAGNET.FSU.EDU _publ_requested_journal 'Chemical Communications' _publ_section_title ; A Cu-Zn-Cu-Zn heterometallomacrocycle shows significant antiferromagnetic coupling between paramagnetic centres mediated by diamagnetic metal ; _publ_section_references ; Sheldrick, G M. (1996). SADABS. Program for Empirical Absorption Correction of Area Detector Data. University of Gottingen, Germany. Siemens (1995). SMART and SAINT. Area-Detector Control and Integration Software. Siemens Analytical X-ray Systems Inc., Madison, Wisconsin, USA. Hall, S.R., King, G.S.D., and Stewart., J.M. (1995). The Xtal 3.5 User's Manual. University of Western Australia, Lamb: Perth. ; #======================================================================= # Data block for single structure (one for each study in the paper) #======================================================================= data_lv713 _database_code_depnum_ccdc_archive 'CCDC 278978' # 2. EXPERIMENTAL DATA #--------------------- _chemical_formula_sum 'C17 H50 Br4 Cu2 N6 O9 Zn2' _chemical_formula_moiety 'C16 H46 Br2 Cu2 N6 O8 Zn2, Br2, C H4 O' _chemical_formula_weight 1060.11 _chemical_melting_point ? _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M C_1_2/c_1 _symmetry_space_group_name_Hall -c_2yc loop_ _symmetry_equiv_pos_as_xyz +x,+y,+z -x,+y,1/2-z -x,-y,-z +x,-y,1/2+z 1/2+x,1/2+y,+z 1/2-x,1/2+y,1/2-z 1/2-x,1/2-y,-z 1/2+x,1/2-y,1/2+z _cell_length_a 20.959(4) _cell_length_b 9.625(2) _cell_length_c 18.365(3) _cell_angle_alpha 90.00000 _cell_angle_beta 101.415(4) _cell_angle_gamma 90.00000 _cell_volume 3631.5(12) _cell_formula_units_Z 4 _exptl_crystal_density_diffrn 1.939 _exptl_crystal_density_meas ? _exptl_crystal_density_method ? _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength .71073 _cell_measurement_reflns_used 5669 _cell_measurement_theta_min 2.5 _cell_measurement_theta_max 34.5 _cell_measurement_temperature 150 _exptl_absorpt_coefficient_mu 6.908 _exptl_crystal_description prism _exptl_crystal_size_max .16 _exptl_crystal_size_mid .13 _exptl_crystal_size_min .1 _exptl_crystal_size_rad ? _exptl_crystal_colour blue _diffrn_measurement_device_type ; Bruker SMART CCD diffractometer ; _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; SADABS; Sheldrick, 1996 ; _exptl_absorpt_correction_T_min .47 _exptl_absorpt_correction_T_max .77 _diffrn_reflns_number 38279 _reflns_number_total 9536 _reflns_Friedel_coverage 0 _reflns_number_gt 5187 _reflns_threshold_expression 'F > 4.00 sig(F )' _diffrn_reflns_theta_max 37.6 _diffrn_reflns_theta_full 37.6 _diffrn_measured_fraction_theta_max 1 _diffrn_measured_fraction_theta_full 1 _diffrn_reflns_av_R_equivalents .065 _diffrn_reflns_limit_h_min -35 _diffrn_reflns_limit_h_max 35 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -31 _diffrn_reflns_limit_l_max 31 _diffrn_standards_number 0 _diffrn_standards_decay_% 0 _refine_ls_structure_factor_coef F _refine_ls_R_factor_gt .035 _refine_ls_wR_factor_ref .032 _refine_ls_goodness_of_fit_ref 1.051 _refine_ls_number_reflns 5187 _refine_ls_number_parameters 273 _refine_ls_weighting_scheme calc _refine_ls_weighting_details ? _refine_ls_hydrogen_treatment mixed _refine_ls_shift/su_max .037 _refine_diff_density_min -.772 _refine_diff_density_max 1.137 _refine_ls_extinction_method none _refine_ls_extinction_coef ? # 3. Information for the "methods" section #----------------------------------------- _computing_data_collection 'Siemens SMART (Siemens, 1995)' _computing_cell_refinement 'Siemens SAINT (Siemens, 1995)' _computing_data_reduction 'xtal ADDREF SORTRF' _computing_structure_solution xtal _computing_structure_refinement 'xtal CRYLSQ' _computing_molecular_graphics xtal _computing_publication_material 'xtal BONDLA CIFIO' # 4. Supplementary data for validation and tables #------------------------------------------------ loop_ _atom_type_symbol _atom_type_description _atom_type_oxidation_number _atom_type_number_in_cell _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C ? 0 68 .002 .002 'Int Tables Vol IV Tables 2.2B and 2.3.1' H ? 0 200 0 0 'Int Tables Vol IV Tables 2.2B and 2.3.1' Br ? 0 16 -.374 2.456 'Int Tables Vol IV Tables 2.2B and 2.3.1' Cu ? 0 8 .263 1.266 'Int Tables Vol IV Tables 2.2B and 2.3.1' N ? 0 24 .004 .003 'Int Tables Vol IV Tables 2.2B and 2.3.1' O ? 0 36 .008 .006 'Int Tables Vol IV Tables 2.2B and 2.3.1' Zn ? 0 8 .222 1.431 'Int Tables Vol IV Tables 2.2B and 2.3.1' loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_calc_flag _atom_site_calc_attached_atom _atom_site_occupancy _atom_site_disorder_assembly _atom_site_disorder_group Zn -.041338(14) .34748(3) .038794(17) .01711(14) Uani ? ? 1.00000 ? ? Cu .121548(15) .42545(3) .091640(17) .01494(14) Uani ? ? 1.00000 ? ? Br1 -.084852(16) .13652(3) .074464(17) .02888(15) Uani ? ? 1.00000 ? ? Br2 -.196517(16) .57851(4) .167732(17) .03564(17) Uani ? ? 1.00000 ? ? N1 .14945(10) .2340(3) .13304(12) .0203(11) Uani ? ? 1.00000 ? ? C1 .10654(14) .1281(3) .08863(17) .0249(14) Uani ? ? 1.00000 ? ? C2 .07320(13) .1919(3) .01569(16) .0211(13) Uani ? ? 1.00000 ? ? O1 .05007(8) .3263(2) .02963(10) .0164(8) Uani ? ? 1.00000 ? ? C3 .15013(15) .2225(3) .21379(16) .0276(15) Uani ? ? 1.00000 ? ? C4 .08875(16) .2816(4) .23339(17) .0306(16) Uani ? ? 1.00000 ? ? O2 .07964(9) .4252(2) .21367(11) .0260(10) Uani ? ? 1.00000 ? ? N2 .20065(10) .5383(3) .14099(12) .0193(11) Uani ? ? 1.00000 ? ? C5 .18628(15) .6857(3) .12099(17) .0287(15) Uani ? ? 1.00000 ? ? C6 .11384(15) .7068(3) .11186(16) .0255(14) Uani ? ? 1.00000 ? ? O3 .08174(9) .6035(2) .06279(10) .0206(9) Uani ? ? 1.00000 ? ? C7 .26219(13) .4863(4) .12262(16) .0269(15) Uani ? ? 1.00000 ? ? C8 .25732(15) .4677(4) .04012(17) .0321(17) Uani ? ? 1.00000 ? ? O4 .20152(10) .3846(2) .01241(11) .0278(11) Uani ? ? 1.00000 ? ? N01 -.04415(11) .5071(3) .10871(13) .0207(11) Uani ? ? 1.00000 ? ? C02 .0093(16) .8700(18) .2720(15) .208(10) Uiso ? ? .50000 ? ? O02 -.0500(12) .875(3) .2263(19) .484(19) Uiso ? ? .50000 ? ? H1 .1854(13) .216(3) .1275(15) .021(8) Uiso ? ? 1.00000 ? ? H1a .0710(13) .096(3) .1206(14) .010(7) Uiso ? ? 1.00000 ? ? H1b .1286(14) .047(3) .0820(16) .026(8) Uiso ? ? 1.00000 ? ? H2a .0361(14) .141(3) -.0108(17) .028(9) Uiso ? ? 1.00000 ? ? H2b .1000(13) .208(3) -.0184(15) .018(7) Uiso ? ? 1.00000 ? ? H3a .1911(16) .280(4) .242(2) .047(10) Uiso ? ? 1.00000 ? ? H3b .1528(15) .123(3) .2310(18) .039(10) Uiso ? ? 1.00000 ? ? H4a .0903(15) .276(3) .2840(17) .037(10) Uiso ? ? 1.00000 ? ? H4b .0507(13) .231(3) .2077(15) .021(8) Uiso ? ? 1.00000 ? ? H2O .0966(14) .459(3) .2384(17) .031(9) Uiso ? ? 1.00000 ? ? H2 .2069(13) .532(3) .1860(15) .018(8) Uiso ? ? 1.00000 ? ? H5a .1943(13) .702(3) .0733(15) .018(7) Uiso ? ? 1.00000 ? ? H5b .2136(15) .753(3) .1605(17) .035(9) Uiso ? ? 1.00000 ? ? H6a .1004(14) .686(3) .1571(16) .027(8) Uiso ? ? 1.00000 ? ? H6b .1035(13) .796(3) .0944(15) .021(8) Uiso ? ? 1.00000 ? ? H7a .2736(14) .390(3) .1478(16) .023(8) Uiso ? ? 1.00000 ? ? H7b .2977(13) .552(3) .1422(16) .022(8) Uiso ? ? 1.00000 ? ? H8a .2927(15) .419(3) .0277(17) .033(9) Uiso ? ? 1.00000 ? ? H8b .2477(13) .552(3) .0166(15) .021(8) Uiso ? ? 1.00000 ? ? H4O .1956(15) .385(3) -.0257(17) .033(9) Uiso ? ? 1.00000 ? ? H01a -.0121(15) .498(4) .1444(17) .035(9) Uiso ? ? 1.00000 ? ? H01b -.0358(17) .577(4) .083(2) .046(11) Uiso ? ? 1.00000 ? ? H01c -.0787(15) .522(3) .1149(17) .033(9) Uiso ? ? 1.00000 ? ? loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_12 _atom_site_aniso_U_13 _atom_site_aniso_U_23 Zn .01384(14) .01817(17) .01924(15) -.00119(12) .00306(11) -.00143(13) Cu .01169(14) .01621(17) .01629(15) -.00075(13) .00130(11) .00001(14) Br1 .03534(17) .02382(16) .03124(16) -.01213(13) .01569(13) -.00520(14) Br2 .02895(16) .0595(2) .01919(14) .02122(16) .00663(12) .00895(16) N1 .0148(11) .0249(14) .0210(11) .0047(9) .0033(9) .0037(10) C1 .0265(15) .0172(15) .0312(16) .0022(12) .0065(12) .0009(13) C2 .0180(13) .0205(15) .0250(14) -.0005(11) .0047(11) -.0055(12) O1 .0122(8) .0155(10) .0210(9) .0003(7) .0018(7) -.0029(8) C3 .0317(17) .0288(18) .0211(14) .0037(13) .0024(12) .0091(13) C4 .0335(17) .038(2) .0221(15) -.0029(15) .0098(13) .0055(14) O2 .0221(10) .0335(13) .0219(10) -.0019(9) .0034(8) -.0060(9) N2 .0156(11) .0280(14) .0136(10) -.0036(9) .0011(8) -.0013(9) C5 .0293(16) .0274(17) .0262(16) -.0096(13) -.0020(12) .0002(13) C6 .0325(16) .0162(15) .0246(15) .0011(12) -.0023(12) -.0043(12) O3 .0191(10) .0174(10) .0218(10) -.0007(8) -.0042(8) -.0024(8) C7 .0167(14) .041(2) .0230(14) -.0055(13) .0033(11) -.0066(14) C8 .0230(15) .048(2) .0279(16) -.0098(14) .0123(13) -.0105(15) O4 .0224(10) .0442(14) .0179(10) -.0105(10) .0068(8) -.0069(9) N01 .0185(12) .0204(13) .0245(12) -.0006(10) .0075(9) -.0023(10) # 5. Molecular Geometry #---------------------- loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag #<< enter YES for value to be published Zn Br1 . . 2.3707(6) ? Zn O1 . . 1.9667(19) ? Zn N01 . . 2.010(2) ? Zn O3 . '3 565' 1.9481(18) ? Cu N1 . . 2.035(2) ? Cu O1 . . 1.9432(17) ? Cu O2 . . 2.564(2) ? Cu N2 . . 2.038(2) ? Cu O3 . . 1.933(2) ? Cu O4 . . 2.459(2) ? N1 C1 . . 1.491(4) ? N1 C3 . . 1.484(4) ? N1 H1 . . .80(3) ? C1 C2 . . 1.513(4) ? C1 H1a . . 1.08(3) ? C1 H1b . . .92(3) ? C2 O1 . . 1.423(4) ? C2 H2a . . .96(3) ? C2 H2b . . .93(3) ? C3 C4 . . 1.514(5) ? C3 H3a . . 1.07(3) ? C3 H3b . . 1.01(3) ? C4 O2 . . 1.432(4) ? C4 H4a . . .93(3) ? C4 H4b . . .97(3) ? O2 H2O . . .61(3) ? N2 C5 . . 1.482(4) ? N2 C7 . . 1.483(4) ? N2 H2 . . .81(3) ? C5 C6 . . 1.508(4) ? C5 H5a . . .94(3) ? C5 H5b . . 1.05(3) ? C6 O3 . . 1.419(3) ? C6 H6a . . .95(3) ? C6 H6b . . .93(3) ? C7 C8 . . 1.509(4) ? C7 H7a . . 1.04(3) ? C7 H7b . . .99(3) ? C8 O4 . . 1.425(4) ? C8 H8a . . .94(3) ? C8 H8b . . .92(3) ? O4 H4O . . .69(3) ? N01 H01a . . .85(3) ? N01 H01b . . .86(4) ? N01 H01c . . .77(3) ? C02 O02 . . 1.36(4) ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_2 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag #<< enter YES for value to be published Br1 Zn O1 . . . 111.69(6) ? Br1 Zn N01 . . . 114.61(7) ? Br1 Zn O3 . . '3 565' 110.73(6) ? O1 Zn N01 . . . 106.62(8) ? O1 Zn O3 . . '3 565' 100.91(8) ? N01 Zn O3 . . '3 565' 111.37(9) ? N1 Cu O1 . . . 84.58(8) ? N1 Cu O2 . . . 78.19(8) ? N1 Cu N2 . . . 99.68(9) ? N1 Cu O3 . . . 169.00(9) ? N1 Cu O4 . . . 84.09(9) ? O1 Cu O2 . . . 98.86(7) ? O1 Cu N2 . . . 170.76(9) ? O1 Cu O3 . . . 91.94(8) ? O1 Cu O4 . . . 96.40(8) ? O2 Cu N2 . . . 90.07(8) ? O2 Cu O3 . . . 92.09(8) ? O2 Cu O4 . . . 155.32(6) ? N2 Cu O3 . . . 85.32(9) ? N2 Cu O4 . . . 76.03(8) ? O3 Cu O4 . . . 106.70(8) ? Cu N1 C1 . . . 108.49(16) ? Cu N1 C3 . . . 112.71(19) ? Cu N1 H1 . . . 111(2) ? C1 N1 C3 . . . 112.4(2) ? C1 N1 H1 . . . 105(2) ? C3 N1 H1 . . . 107(2) ? N1 C1 C2 . . . 109.3(2) ? N1 C1 H1a . . . 107.9(13) ? N1 C1 H1b . . . 112.5(17) ? C2 C1 H1a . . . 110.5(13) ? C2 C1 H1b . . . 112.3(18) ? H1a C1 H1b . . . 104(2) ? C1 C2 O1 . . . 108.9(2) ? C1 C2 H2a . . . 115.3(18) ? C1 C2 H2b . . . 115.3(15) ? O1 C2 H2a . . . 106.3(18) ? O1 C2 H2b . . . 104.1(17) ? H2a C2 H2b . . . 106(3) ? Zn O1 Cu . . . 123.37(10) ? Zn O1 C2 . . . 118.81(16) ? Cu O1 C2 . . . 107.54(14) ? N1 C3 C4 . . . 111.7(2) ? N1 C3 H3a . . . 107(2) ? N1 C3 H3b . . . 112(2) ? C4 C3 H3a . . . 109(2) ? C4 C3 H3b . . . 106(2) ? H3a C3 H3b . . . 110(2) ? C3 C4 O2 . . . 112.3(3) ? C3 C4 H4a . . . 111(2) ? C3 C4 H4b . . . 110.5(18) ? O2 C4 H4a . . . 106(2) ? O2 C4 H4b . . . 107.8(17) ? H4a C4 H4b . . . 109(3) ? Cu O2 C4 . . . 99.82(17) ? Cu O2 H2O . . . 113(3) ? C4 O2 H2O . . . 107(3) ? Cu N2 C5 . . . 107.01(16) ? Cu N2 C7 . . . 112.74(18) ? Cu N2 H2 . . . 112(2) ? C5 N2 C7 . . . 114.2(2) ? C5 N2 H2 . . . 108(2) ? C7 N2 H2 . . . 104(2) ? N2 C5 C6 . . . 107.9(2) ? N2 C5 H5a . . . 109.2(18) ? N2 C5 H5b . . . 111.1(17) ? C6 C5 H5a . . . 103.7(16) ? C6 C5 H5b . . . 113.2(18) ? H5a C5 H5b . . . 111(2) ? C5 C6 O3 . . . 108.5(2) ? C5 C6 H6a . . . 109.9(17) ? C5 C6 H6b . . . 109.0(18) ? O3 C6 H6a . . . 102.8(18) ? O3 C6 H6b . . . 112.3(16) ? H6a C6 H6b . . . 114(3) ? Cu O3 C6 . . . 108.82(15) ? Cu O3 Zn . . '3 565' 124.01(10) ? C6 O3 Zn . . '3 565' 119.99(17) ? N2 C7 C8 . . . 112.3(2) ? N2 C7 H7a . . . 109.4(17) ? N2 C7 H7b . . . 109.3(18) ? C8 C7 H7a . . . 107.7(16) ? C8 C7 H7b . . . 109.8(18) ? H7a C7 H7b . . . 108(2) ? C7 C8 O4 . . . 108.2(3) ? C7 C8 H8a . . . 113.7(18) ? C7 C8 H8b . . . 109.2(18) ? O4 C8 H8a . . . 105.2(18) ? O4 C8 H8b . . . 103.8(16) ? H8a C8 H8b . . . 116(3) ? Cu O4 C8 . . . 107.84(18) ? Cu O4 H4O . . . 126(3) ? C8 O4 H4O . . . 109(3) ? Zn N01 H01a . . . 107(2) ? Zn N01 H01b . . . 102(2) ? Zn N01 H01c . . . 113(2) ? H01a N01 H01b . . . 107(3) ? H01a N01 H01c . . . 122(3) ? H01b N01 H01c . . . 104(3) ? _exptl_crystal_F_000 2096 loop_ _diffrn_standard_refln_index_h _diffrn_standard_refln_index_k _diffrn_standard_refln_index_l ? ? ? loop_ _diffrn_attenuator_code _diffrn_attenuator_scale ? ? _reflns_limit_h_min 0 _reflns_limit_h_max 35 _reflns_limit_k_min 0 _reflns_limit_k_max 16 _reflns_limit_l_min -31 _reflns_limit_l_max 30 _reflns_number_observed ? _reflns_d_resolution_high .582 _reflns_d_resolution_low 10.251 _diffrn_reflns_av_sigmaI/netI .176 _diffrn_reflns_theta_min 1.98 _diffrn_reflns_reduction_process ? _diffrn_ambient_temperature 150 _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_radiation_detector 'CCD area detector' _refine_ls_extinction_expression ? _refine_ls_matrix_type full _refine_ls_number_restraints 0 _refine_ls_number_constraints 0 _refine_ls_R_factor_all .096 _refine_ls_wR_factor_all .038 _refine_ls_goodness_of_fit_all .905 _refine_ls_shift/su_mean .001 #===END