# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2007 data_global _journal_name_full Chem.Commun. _journal_coden_cambridge 0182 _publ_section_title ;Photochemical [2+2] cycloaddition as a tool to study solid state structural transformation ; loop_ _publ_author_name J.Vittal M.Nagarathinam _publ_contact_author_name 'Jagadese Vittal' _publ_contact_author_email CHMJJV@NUS.EDU.SG # Attachment 'MAN12.cif' #CCDC 659646 data_man12 _database_code_depnum_ccdc_archive 'CCDC 659646' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C16 H18 Cd N2 O5' _chemical_formula_weight 430.72 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' Cd Cd -0.8075 1.2024 '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 13.2612(8) _cell_length_b 14.7065(9) _cell_length_c 8.6573(5) _cell_angle_alpha 90.00 _cell_angle_beta 92.7440(10) _cell_angle_gamma 90.00 _cell_volume 1686.46(17) _cell_formula_units_Z 4 _cell_measurement_temperature 223(2) _cell_measurement_reflns_used 3548 _cell_measurement_theta_min 2.77 _cell_measurement_theta_max 28.48 _exptl_crystal_description cubes _exptl_crystal_colour colorless _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.696 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 864 _exptl_absorpt_coefficient_mu 1.323 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.6011 _exptl_absorpt_correction_T_max 1.0000 _exptl_absorpt_process_details 'SADABS (Sheldrick, 2004)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 223(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 ? _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4833 _diffrn_reflns_av_R_equivalents 0.0257 _diffrn_reflns_av_sigmaI/netI 0.0264 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 2.07 _diffrn_reflns_theta_max 25.00 _reflns_number_total 1494 _reflns_number_gt 1368 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker AXS, SMART' _computing_cell_refinement 'Bruker AXS, SAINT' _computing_data_reduction 'Bruker AXS, SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker AXS, SHELXTL' _computing_publication_material 'Bruker AXS, SHELXTL' _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. Both Cd(II) and O of aqua ligand are sitting on twofold symmetry. One H atom of aqua ligand was located butDFIX option was used to constraint the position of this atom in the LS refinements. ; _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^)+(0.0260P)^2^+8.3671P] 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 mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0049(5) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 1494 _refine_ls_number_parameters 116 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0451 _refine_ls_R_factor_gt 0.0398 _refine_ls_wR_factor_ref 0.0933 _refine_ls_wR_factor_gt 0.0873 _refine_ls_goodness_of_fit_ref 1.179 _refine_ls_restrained_S_all 1.178 _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 Cd1 Cd 0.5000 0.61612(3) 0.7500 0.0450(2) Uani 1 2 d SD . . N1 N 0.3320(3) 0.5852(3) 0.6494(5) 0.0502(9) Uani 1 1 d . . . C1 C 0.2853(4) 0.6374(3) 0.5443(7) 0.0632(14) Uani 1 1 d . . . H1 H 0.3211 0.6866 0.5045 0.076 Uiso 1 1 calc R . . C2 C 0.1869(4) 0.6235(3) 0.4897(7) 0.0614(15) Uani 1 1 d . . . H2 H 0.1573 0.6638 0.4165 0.074 Uiso 1 1 calc R . . C3 C 0.1319(4) 0.5510(3) 0.5419(5) 0.0498(11) Uani 1 1 d . . . C4 C 0.1820(4) 0.4953(5) 0.6482(7) 0.0729(17) Uani 1 1 d . . . H4 H 0.1491 0.4439 0.6862 0.087 Uiso 1 1 calc R . . C5 C 0.2793(4) 0.5141(5) 0.6991(7) 0.0749(18) Uani 1 1 d . . . H5 H 0.3107 0.4750 0.7726 0.090 Uiso 1 1 calc R . . C6 C 0.0285(3) 0.5356(3) 0.4836(5) 0.0536(12) Uani 1 1 d . . . H6 H -0.0005 0.5799 0.4170 0.064 Uiso 1 1 calc R . . O1 O 0.4049(3) 0.7586(3) 0.8538(4) 0.0728(11) Uani 1 1 d . . . O2 O 0.4574(3) 0.6444(3) 0.9954(4) 0.0650(10) Uani 1 1 d . . . C7 C 0.4134(4) 0.7199(3) 0.9798(6) 0.0524(11) Uani 1 1 d . . . C8 C 0.3706(5) 0.7610(4) 1.1220(7) 0.0770(17) Uani 1 1 d . . . H8A H 0.3668 0.8265 1.1104 0.115 Uiso 1 1 calc R . . H8B H 0.4138 0.7460 1.2120 0.115 Uiso 1 1 calc R . . H8C H 0.3035 0.7368 1.1353 0.115 Uiso 1 1 calc R . . O3 O 0.5000 0.4571(3) 0.7500 0.0591(13) Uani 1 2 d SD . . H3 H 0.518(5) 0.42187(12) 0.831(3) 0.10(2) Uiso 1 1 d 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 Cd1 0.0416(3) 0.0529(3) 0.0399(3) 0.000 -0.0051(2) 0.000 N1 0.039(2) 0.059(2) 0.051(2) -0.0040(19) -0.0090(17) 0.0038(18) C1 0.062(3) 0.046(3) 0.079(4) 0.000(3) -0.025(3) -0.002(2) C2 0.062(3) 0.045(3) 0.075(4) -0.005(2) -0.029(3) 0.007(2) C3 0.045(2) 0.061(3) 0.043(2) -0.011(2) -0.0022(19) 0.009(2) C4 0.043(3) 0.105(5) 0.069(3) 0.033(3) -0.011(2) -0.012(3) C5 0.042(3) 0.109(5) 0.072(4) 0.041(3) -0.014(2) -0.010(3) C6 0.043(3) 0.070(3) 0.047(3) -0.009(2) -0.007(2) 0.014(2) O1 0.093(3) 0.065(2) 0.060(2) 0.0042(19) 0.006(2) 0.011(2) O2 0.077(3) 0.076(2) 0.0417(18) -0.0024(17) 0.0007(17) 0.028(2) C7 0.045(3) 0.055(3) 0.056(3) -0.010(2) -0.002(2) 0.003(2) C8 0.076(4) 0.087(4) 0.067(4) -0.021(3) 0.006(3) 0.021(3) O3 0.068(3) 0.046(3) 0.061(3) 0.000 -0.019(3) 0.000 _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 Cd1 O2 2.262(3) . ? Cd1 O2 2.262(3) 6_657 ? Cd1 O3 2.338(5) . ? Cd1 N1 2.397(4) . ? Cd1 N1 2.397(4) 6_657 ? Cd1 O1 2.626(4) 6_657 ? Cd1 O1 2.626(4) . ? N1 C1 1.321(6) . ? N1 C5 1.340(7) . ? C1 C2 1.381(7) . ? C2 C3 1.381(7) . ? C3 C4 1.379(7) . ? C3 C6 1.456(6) . ? C4 C5 1.371(7) . ? C6 C6 1.331(10) 5_566 ? O1 C7 1.231(6) . ? O2 C7 1.259(6) . ? C7 C8 1.507(7) . ? 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 O2 Cd1 O2 158.9(2) . 6_657 ? O2 Cd1 O3 100.57(10) . . ? O2 Cd1 O3 100.57(10) 6_657 . ? O2 Cd1 N1 96.10(14) . . ? O2 Cd1 N1 87.90(14) 6_657 . ? O3 Cd1 N1 79.06(10) . . ? O2 Cd1 N1 87.90(14) . 6_657 ? O2 Cd1 N1 96.10(14) 6_657 6_657 ? O3 Cd1 N1 79.06(10) . 6_657 ? N1 Cd1 N1 158.1(2) . 6_657 ? O2 Cd1 O1 108.69(14) . 6_657 ? O2 Cd1 O1 52.18(12) 6_657 6_657 ? O3 Cd1 O1 142.92(9) . 6_657 ? N1 Cd1 O1 118.72(14) . 6_657 ? N1 Cd1 O1 79.76(14) 6_657 6_657 ? O2 Cd1 O1 52.18(12) . . ? O2 Cd1 O1 108.69(14) 6_657 . ? O3 Cd1 O1 142.92(9) . . ? N1 Cd1 O1 79.76(14) . . ? N1 Cd1 O1 118.72(14) 6_657 . ? O1 Cd1 O1 74.16(18) 6_657 . ? C1 N1 C5 116.1(4) . . ? C1 N1 Cd1 122.5(4) . . ? C5 N1 Cd1 121.4(3) . . ? N1 C1 C2 123.6(5) . . ? C3 C2 C1 120.5(5) . . ? C4 C3 C2 115.6(5) . . ? C4 C3 C6 123.7(5) . . ? C2 C3 C6 120.7(4) . . ? C5 C4 C3 120.7(5) . . ? N1 C5 C4 123.4(5) . . ? C6 C6 C3 125.7(6) 5_566 . ? C7 O1 Cd1 84.8(3) . . ? C7 O2 Cd1 101.4(3) . . ? O1 C7 O2 121.7(5) . . ? O1 C7 C8 121.1(5) . . ? O2 C7 C8 117.2(5) . . ? 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 O2 Cd1 N1 C1 114.9(4) . . . . ? O2 Cd1 N1 C1 -44.3(4) 6_657 . . . ? O3 Cd1 N1 C1 -145.5(4) . . . . ? N1 Cd1 N1 C1 -145.5(4) 6_657 . . . ? O1 Cd1 N1 C1 -0.3(5) 6_657 . . . ? O1 Cd1 N1 C1 65.1(4) . . . . ? O2 Cd1 N1 C5 -64.1(5) . . . . ? O2 Cd1 N1 C5 136.7(5) 6_657 . . . ? O3 Cd1 N1 C5 35.5(4) . . . . ? N1 Cd1 N1 C5 35.5(4) 6_657 . . . ? O1 Cd1 N1 C5 -179.3(4) 6_657 . . . ? O1 Cd1 N1 C5 -113.8(5) . . . . ? C5 N1 C1 C2 2.2(8) . . . . ? Cd1 N1 C1 C2 -176.9(4) . . . . ? N1 C1 C2 C3 -1.4(9) . . . . ? C1 C2 C3 C4 -0.5(8) . . . . ? C1 C2 C3 C6 -179.4(5) . . . . ? C2 C3 C4 C5 1.6(9) . . . . ? C6 C3 C4 C5 -179.6(6) . . . . ? C1 N1 C5 C4 -1.0(9) . . . . ? Cd1 N1 C5 C4 178.0(5) . . . . ? C3 C4 C5 N1 -0.9(11) . . . . ? C4 C3 C6 C6 -4.4(9) . . . 5_566 ? C2 C3 C6 C6 174.3(6) . . . 5_566 ? O2 Cd1 O1 C7 -0.5(3) . . . . ? O2 Cd1 O1 C7 -170.2(3) 6_657 . . . ? O3 Cd1 O1 C7 49.5(4) . . . . ? N1 Cd1 O1 C7 105.5(3) . . . . ? N1 Cd1 O1 C7 -62.0(3) 6_657 . . . ? O1 Cd1 O1 C7 -130.5(4) 6_657 . . . ? O2 Cd1 O2 C7 28.6(3) 6_657 . . . ? O3 Cd1 O2 C7 -151.4(3) . . . . ? N1 Cd1 O2 C7 -71.4(3) . . . . ? N1 Cd1 O2 C7 130.1(3) 6_657 . . . ? O1 Cd1 O2 C7 51.7(3) 6_657 . . . ? O1 Cd1 O2 C7 0.5(3) . . . . ? Cd1 O1 C7 O2 0.9(5) . . . . ? Cd1 O1 C7 C8 -178.6(5) . . . . ? Cd1 O2 C7 O1 -1.1(6) . . . . ? Cd1 O2 C7 C8 178.4(4) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 2.080 _refine_diff_density_min -0.689 _refine_diff_density_rms 0.098