# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Chuan-De Wu' _publ_contact_author_email CDWU@ZJU.EDU.CN _publ_section_title ; Heterogeneous catalyzed aryl-nitrogen bond formations with a valine derivate bridged metal-organic coordination polymer ; loop_ _publ_author_name 'Chuan-De Wu' 'Li Li' 'Lianxu Shi' # Attachment 'B823335G-CrystData.cif' data_B823335G _database_code_depnum_ccdc_archive 'CCDC 695224' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C20 H26 Cu N4 O4' _chemical_formula_weight 449.99 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' O O 0.0106 0.0060 '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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M C2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 15.833(3) _cell_length_b 9.330(2) _cell_length_c 15.152(3) _cell_angle_alpha 90.00 _cell_angle_beta 114.57(3) _cell_angle_gamma 90.00 _cell_volume 2035.4(7) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 5910 _cell_measurement_theta_min 3.13 _cell_measurement_theta_max 23.00 _exptl_crystal_description needle _exptl_crystal_colour purple _exptl_crystal_size_max 0.2 _exptl_crystal_size_mid 0.07 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.468 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 940 _exptl_absorpt_coefficient_mu 1.107 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.911 _exptl_absorpt_correction_T_max 0.957 _exptl_absorpt_process_details '(ABSCOR; Higashi, 1995)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 'Rigaku R-AXIS RAPID' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number none _diffrn_standards_interval_count none _diffrn_standards_interval_time none _diffrn_standards_decay_% none _diffrn_reflns_number 5910 _diffrn_reflns_av_R_equivalents 0.1518 _diffrn_reflns_av_sigmaI/netI 0.0957 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 3.13 _diffrn_reflns_theta_max 23.00 _reflns_number_total 1344 _reflns_number_gt 618 _reflns_threshold_expression >2\s(I) _computing_data_collection 'PROCESS-AUTO (Rigaku, 1998)' _computing_cell_refinement 'PROCESS-AUTO (Rigaku, 1998)' _computing_data_reduction 'CrystalStructure (Rigaku/MSC, 2004)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXL-97 (Sheldrick, 1997)' _computing_publication_material 'CrystalStructure and PLATON (Spek, 2003)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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 'calc w=1/[\s^2^(Fo^2^)+(0.0117P)^2^+11.7683P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1344 _refine_ls_number_parameters 138 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1898 _refine_ls_R_factor_gt 0.0907 _refine_ls_wR_factor_ref 0.1583 _refine_ls_wR_factor_gt 0.1294 _refine_ls_goodness_of_fit_ref 1.062 _refine_ls_restrained_S_all 1.062 _refine_ls_shift/su_max 0.000 _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 Cu1 Cu 0.0000 0.3314(4) 0.7500 0.0832(9) Uani 0.75 2 d SP . . Cu2 Cu 0.0000 0.2010(10) 0.7500 0.057(2) Uani 0.25 2 d SP . . O1 O 0.4935(5) 0.1331(12) 1.1198(5) 0.103(3) Uani 1 1 d . . . O2 O 0.5021(5) 0.3709(13) 1.1209(6) 0.105(3) Uani 1 1 d . . . N1 N 0.4270(4) 0.3573(12) 0.9156(5) 0.115(4) Uani 1 1 d . . . H1B H 0.4492 0.4315 0.8990 0.138 Uiso 1 1 calc R . . N2 N 0.1350(5) 0.3287(14) 0.8001(5) 0.103(3) Uani 1 1 d . . . C1 C 0.1810(7) 0.4364(15) 0.7838(7) 0.105(4) Uani 1 1 d . . . H1A H 0.1457 0.5090 0.7430 0.126 Uiso 1 1 calc R . . C2 C 0.2755(7) 0.4514(13) 0.8210(7) 0.098(4) Uani 1 1 d . . . H2A H 0.3025 0.5321 0.8074 0.118 Uiso 1 1 calc R . . C3 C 0.3303(7) 0.3412(17) 0.8804(7) 0.099(4) Uani 1 1 d . . . C4 C 0.2872(6) 0.2468(17) 0.8993(6) 0.108(4) Uani 1 1 d . . . H4A H 0.3197 0.1754 0.9431 0.129 Uiso 1 1 calc R . . C5 C 0.1875(6) 0.2430(16) 0.8558(7) 0.107(4) Uani 1 1 d . . . H5A H 0.1602 0.1655 0.8725 0.128 Uiso 1 1 calc R . . C6 C 0.4876(5) 0.2564(15) 0.9763(6) 0.091(3) Uani 1 1 d . . . H6A H 0.4634 0.1634 0.9464 0.109 Uiso 1 1 calc R . . C7 C 0.5842(5) 0.2700(16) 0.9743(6) 0.107(4) Uani 1 1 d . . . H7A H 0.6080 0.3660 0.9979 0.128 Uiso 1 1 calc R . . C8 C 0.4933(6) 0.246(3) 1.0826(8) 0.101(4) Uani 1 1 d . . . C9 C 0.6494(7) 0.1655(18) 1.0406(8) 0.152(6) Uani 1 1 d . . . H9A H 0.6516 0.1772 1.1045 0.228 Uiso 1 1 calc R . . H9B H 0.7102 0.1810 1.0428 0.228 Uiso 1 1 calc R . . H9C H 0.6291 0.0701 1.0178 0.228 Uiso 1 1 calc R . . C10 C 0.5754(6) 0.2574(18) 0.8705(6) 0.130(5) Uani 1 1 d . . . H10A H 0.6352 0.2717 0.8699 0.195 Uiso 1 1 calc R . . H10B H 0.5330 0.3288 0.8307 0.195 Uiso 1 1 calc R . . H10C H 0.5526 0.1638 0.8456 0.195 Uiso 1 1 calc R . . 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 Cu1 0.0549(14) 0.105(2) 0.0737(17) 0.000 0.0112(10) 0.000 Cu2 0.021(3) 0.131(7) 0.018(3) 0.000 0.0065(19) 0.000 O1 0.081(5) 0.146(9) 0.071(5) 0.027(5) 0.023(4) -0.029(5) O2 0.077(5) 0.163(9) 0.075(5) 0.029(6) 0.031(4) 0.007(5) N1 0.044(4) 0.227(11) 0.067(5) 0.031(6) 0.017(3) 0.012(6) N2 0.045(5) 0.182(10) 0.071(5) 0.011(7) 0.012(4) -0.006(6) C1 0.050(7) 0.162(12) 0.090(7) -0.022(9) 0.016(5) 0.000(7) C2 0.084(7) 0.141(11) 0.063(6) 0.008(8) 0.025(5) 0.005(7) C3 0.081(8) 0.160(12) 0.053(6) 0.012(8) 0.024(5) -0.008(8) C4 0.056(6) 0.177(12) 0.072(6) 0.031(9) 0.010(5) -0.022(7) C5 0.061(6) 0.177(12) 0.088(7) 0.030(9) 0.037(5) 0.023(8) C6 0.047(5) 0.149(9) 0.065(6) 0.008(8) 0.012(4) 0.005(6) C7 0.058(5) 0.192(13) 0.064(5) 0.018(8) 0.019(4) 0.014(8) C8 0.030(4) 0.171(14) 0.078(8) -0.005(13) 0.000(4) -0.011(9) C9 0.080(7) 0.261(18) 0.125(9) 0.025(12) 0.052(7) 0.017(10) C10 0.083(6) 0.241(15) 0.068(6) 0.014(10) 0.033(5) 0.015(9) _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 Cu1 Cu2 1.217(8) . ? Cu1 N2 1.948(7) 2_556 ? Cu1 N2 1.948(7) . ? Cu1 O1 1.961(7) 7_557 ? Cu1 O1 1.961(7) 8_455 ? Cu2 O2 2.081(8) 8_455 ? Cu2 O2 2.081(8) 7_557 ? Cu2 N2 2.283(10) 2_556 ? Cu2 N2 2.283(10) . ? Cu2 C8 2.543(12) 7_557 ? Cu2 C8 2.543(12) 8_455 ? O1 C8 1.197(18) . ? O1 Cu1 1.961(7) 7_557 ? O2 C8 1.281(17) . ? O2 Cu2 2.081(8) 7_557 ? N1 C6 1.385(12) . ? N1 C3 1.405(11) . ? N1 H1B 0.8600 . ? N2 C5 1.208(12) . ? N2 C1 1.324(13) . ? C1 C2 1.368(12) . ? C1 H1A 0.9300 . ? C2 C3 1.404(15) . ? C2 H2A 0.9300 . ? C3 C4 1.220(14) . ? C4 C5 1.436(11) . ? C4 H4A 0.9300 . ? C5 H5A 0.9300 . ? C6 C7 1.546(10) . ? C6 C8 1.578(14) . ? C6 H6A 0.9800 . ? C7 C9 1.471(15) . ? C7 C10 1.526(10) . ? C7 H7A 0.9800 . ? C8 Cu2 2.543(12) 7_557 ? C9 H9A 0.9600 . ? C9 H9B 0.9600 . ? C9 H9C 0.9600 . ? C10 H10A 0.9600 . ? C10 H10B 0.9600 . ? C10 H10C 0.9600 . ? 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 Cu2 Cu1 N2 89.3(4) . 2_556 ? Cu2 Cu1 N2 89.3(4) . . ? N2 Cu1 N2 178.5(8) 2_556 . ? Cu2 Cu1 O1 99.7(3) . 7_557 ? N2 Cu1 O1 89.1(3) 2_556 7_557 ? N2 Cu1 O1 91.1(3) . 7_557 ? Cu2 Cu1 O1 99.7(3) . 8_455 ? N2 Cu1 O1 91.1(3) 2_556 8_455 ? N2 Cu1 O1 89.1(3) . 8_455 ? O1 Cu1 O1 160.5(7) 7_557 8_455 ? Cu1 Cu2 O2 108.8(4) . 8_455 ? Cu1 Cu2 O2 108.8(4) . 7_557 ? O2 Cu2 O2 142.4(9) 8_455 7_557 ? Cu1 Cu2 N2 58.5(3) . 2_556 ? O2 Cu2 N2 103.5(3) 8_455 2_556 ? O2 Cu2 N2 95.9(3) 7_557 2_556 ? Cu1 Cu2 N2 58.5(3) . . ? O2 Cu2 N2 95.9(3) 8_455 . ? O2 Cu2 N2 103.5(4) 7_557 . ? N2 Cu2 N2 117.1(7) 2_556 . ? Cu1 Cu2 C8 78.9(6) . 7_557 ? O2 Cu2 C8 171.8(9) 8_455 7_557 ? O2 Cu2 C8 30.1(4) 7_557 7_557 ? N2 Cu2 C8 82.9(4) 2_556 7_557 ? N2 Cu2 C8 85.6(4) . 7_557 ? Cu1 Cu2 C8 78.9(6) . 8_455 ? O2 Cu2 C8 30.1(4) 8_455 8_455 ? O2 Cu2 C8 171.8(9) 7_557 8_455 ? N2 Cu2 C8 85.6(4) 2_556 8_455 ? N2 Cu2 C8 82.9(4) . 8_455 ? C8 Cu2 C8 157.7(12) 7_557 8_455 ? C8 O1 Cu1 108.3(9) . 7_557 ? C8 O2 Cu2 95.3(8) . 7_557 ? C6 N1 C3 121.6(10) . . ? C6 N1 H1B 119.2 . . ? C3 N1 H1B 119.2 . . ? C5 N2 C1 111.1(10) . . ? C5 N2 Cu1 127.3(10) . . ? C1 N2 Cu1 121.2(9) . . ? C5 N2 Cu2 99.5(10) . . ? C1 N2 Cu2 147.8(8) . . ? Cu1 N2 Cu2 32.2(2) . . ? N2 C1 C2 126.4(12) . . ? N2 C1 H1A 116.8 . . ? C2 C1 H1A 116.8 . . ? C1 C2 C3 117.9(11) . . ? C1 C2 H2A 121.1 . . ? C3 C2 H2A 121.1 . . ? C4 C3 C2 115.0(11) . . ? C4 C3 N1 128.1(12) . . ? C2 C3 N1 116.8(12) . . ? C3 C4 C5 121.7(13) . . ? C3 C4 H4A 119.1 . . ? C5 C4 H4A 119.1 . . ? N2 C5 C4 127.6(13) . . ? N2 C5 H5A 116.2 . . ? C4 C5 H5A 116.2 . . ? N1 C6 C7 110.4(9) . . ? N1 C6 C8 116.6(10) . . ? C7 C6 C8 112.8(6) . . ? N1 C6 H6A 105.3 . . ? C7 C6 H6A 105.3 . . ? C8 C6 H6A 105.3 . . ? C9 C7 C10 112.9(10) . . ? C9 C7 C6 110.6(9) . . ? C10 C7 C6 110.3(7) . . ? C9 C7 H7A 107.6 . . ? C10 C7 H7A 107.6 . . ? C6 C7 H7A 107.6 . . ? O1 C8 O2 127.5(12) . . ? O1 C8 C6 121.4(17) . . ? O2 C8 C6 111.0(17) . . ? O1 C8 Cu2 73.1(7) . 7_557 ? O2 C8 Cu2 54.6(6) . 7_557 ? C6 C8 Cu2 165.4(16) . 7_557 ? C7 C9 H9A 109.5 . . ? C7 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C7 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C7 C10 H10A 109.5 . . ? C7 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? C7 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? _diffrn_measured_fraction_theta_max 0.946 _diffrn_reflns_theta_full 23.00 _diffrn_measured_fraction_theta_full 0.946 _refine_diff_density_max 0.297 _refine_diff_density_min -0.254 _refine_diff_density_rms 0.059