# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry # This journal is © The Royal Society of Chemistry 2012 data_global _journal_coden_Cambridge 1145 _journal_volume ? _journal_page_first ? _journal_year ? loop_ _publ_author_name 'Spencer, Elinor' 'Ross, Nancy' 'Angel, Ross' _publ_contact_author_name 'Dr Elinor Spencer' _publ_contact_author_email nross@vt.edu _publ_section_title ; The High Pressure Behaviour of the 3D Copper Carbonate Framework {[Cu(CO3)2](CH6N3)2}n ; # Attachment '- Spencer_CIF.txt' data_Cmpd_1_Ambient_Conditions _database_code_depnum_ccdc_archive 'CCDC 848834' #TrackingRef '- Spencer_CIF.txt' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C2 Cu O6, 2(C H6 N3)' _chemical_formula_sum 'C4 H12 Cu N6 O6' _chemical_formula_weight 303.74 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 Tetragonal _symmetry_space_group_name_H-M P-4n2 _symmetry_space_group_name_Hall 'P -4 -2n' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' 'y, -x, -z' '-y, x, -z' 'x+1/2, -y+1/2, z+1/2' '-x+1/2, y+1/2, z+1/2' 'y+1/2, x+1/2, -z+1/2' '-y+1/2, -x+1/2, -z+1/2' _cell_length_a 9.05820(10) _cell_length_b 9.05820(10) _cell_length_c 12.5660(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1031.05(2) _cell_formula_units_Z 4 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 6476 _cell_measurement_theta_min 3.168 _cell_measurement_theta_max 30.000 _exptl_crystal_description Fragment _exptl_crystal_colour Blue _exptl_crystal_size_max 0.3413 _exptl_crystal_size_mid 0.2827 _exptl_crystal_size_min 0.1093 _exptl_crystal_density_meas 'Not measured' _exptl_crystal_density_diffrn 1.957 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 620 _exptl_absorpt_coefficient_mu 2.152 _exptl_absorpt_correction_T_min 0.600 _exptl_absorpt_correction_T_max 0.817 _exptl_absorpt_correction_type analytical _exptl_absorpt_process_details ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.15 (release 10-01-2008 CrysAlis171 .NET) (compiled Jan 10 2008,16:37:18) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) ; _diffrn_ambient_temperature 298(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 ; \k-geometry diffractometer,Gemini, Oxford Diffraction Ltd., ; _diffrn_measurement_device_type 'Oxford Diffraction Sapphire 3 CCD' _diffrn_source_voltage 50 _diffrn_source_current 40 _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean 16.0355 _diffrn_standards_number 2 _diffrn_standards_interval_count 50 _diffrn_standards_interval_time ? _diffrn_standards_decay_% <2% _diffrn_reflns_number 9076 _diffrn_reflns_av_R_equivalents 0.0436 _diffrn_reflns_av_sigmaI/netI 0.0181 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 3.18 _diffrn_reflns_theta_max 24.99 _reflns_number_total 913 _reflns_number_gt 867 _reflns_threshold_expression >2sigma(I) _computing_data_collection ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.58 (release 29-01-2010 CrysAlis171 .NET) (compiled Jan 29 2010,16:49:25) ; _computing_cell_refinement ; CrysAlisPro, Agilent Technologies, Version 1.171.32.15 (release 10-01-2008 CrysAlis171 .NET) (compiled Jan 20 2011,15:58:25) ; _computing_data_reduction ; CrysAlisPro, Agilent Technologies, Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET) (compiled Jan 20 2011,15:58:25) ; _computing_structure_refinement ; shelxl-97 (G.M.Sheldrick, 2008, Acta Cryst., A64,112) WinGX (L.J Farrugia, 1999, J. Appl. Cryst., 32, 837) ; _computing_molecular_graphics ; CrystalMaker V.2.0.6, CrystalMaker Software Ltd.' ; _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^)+(0.0718P)^2^+0.0684P] 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 SHELXL _refine_ls_extinction_coef 0.038(4) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.99(5) _refine_ls_number_reflns 913 _refine_ls_number_parameters 79 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0342 _refine_ls_R_factor_gt 0.0330 _refine_ls_wR_factor_ref 0.0980 _refine_ls_wR_factor_gt 0.0973 _refine_ls_goodness_of_fit_ref 1.160 _refine_ls_restrained_S_all 1.160 _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 1.0000 0.5000 0.2500 0.0138(3) Uani 1 4 d S . . Cu2 Cu 0.5000 0.5000 0.0000 0.0151(3) Uani 1 4 d S . . C1 C 0.7576(4) 0.5417(3) 0.1202(4) 0.0183(7) Uani 1 1 d . . . O1 O 0.8856(2) 0.5980(3) 0.13789(17) 0.0253(6) Uani 1 1 d . . . O2 O 0.6851(2) 0.5968(2) 0.03874(17) 0.0237(5) Uani 1 1 d . . . O3 O 0.7032(3) 0.4404(3) 0.17585(18) 0.0310(6) Uani 1 1 d . . . C2 C 0.5054(3) 0.7489(7) 0.3796(5) 0.0256(8) Uani 1 1 d . . . N1 N 0.5822(4) 0.6750(4) 0.3080(3) 0.0453(9) Uani 1 1 d . . . H1A H 0.5379 0.6334 0.2554 0.054 Uiso 1 1 calc R . . H1B H 0.6765 0.6685 0.3139 0.054 Uiso 1 1 calc R . . N2 N 0.3623(3) 0.7583(4) 0.3699(2) 0.0426(9) Uani 1 1 d . . . H2A H 0.3126 0.8138 0.4124 0.051 Uiso 1 1 calc R . . H2B H 0.3176 0.7091 0.3211 0.051 Uiso 1 1 calc R . . N3 N 0.5748(3) 0.8239(4) 0.4541(3) 0.0400(9) Uani 1 1 d . . . H3A H 0.5258 0.8795 0.4968 0.048 Uiso 1 1 calc R . . H3B H 0.6691 0.8172 0.4600 0.048 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 0.0143(4) 0.0143(4) 0.0126(5) 0.000 0.000 0.0003(2) Cu2 0.0134(4) 0.0134(4) 0.0186(5) 0.000 0.000 0.000 C1 0.0193(17) 0.0153(14) 0.0202(16) -0.015(2) 0.0012(12) -0.0012(19) O1 0.0201(13) 0.0320(13) 0.0238(10) 0.0029(10) -0.0049(9) 0.0014(9) O2 0.0211(13) 0.0231(12) 0.0268(12) 0.0032(9) -0.0077(9) -0.0008(9) O3 0.0443(15) 0.0234(14) 0.0253(12) 0.0020(12) 0.0021(12) -0.0032(11) C2 0.0188(17) 0.032(2) 0.0264(19) -0.0026(16) 0.0017(13) 0.0001(11) N1 0.035(2) 0.049(2) 0.052(2) -0.0279(17) 0.0104(16) -0.0043(14) N2 0.0246(16) 0.066(2) 0.0376(17) -0.0140(17) -0.0032(16) 0.0041(14) N3 0.0229(16) 0.057(2) 0.0397(18) -0.0224(17) -0.0012(14) 0.0025(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 Cu1 O1 1.961(2) 2_765 ? Cu1 O1 1.961(2) . ? Cu1 O1 1.961(2) 8_665 ? Cu1 O1 1.961(2) 7_545 ? Cu2 O2 1.954(2) . ? Cu2 O2 1.954(2) 2_665 ? Cu2 O2 1.954(2) 4_655 ? Cu2 O2 1.954(2) 3_565 ? C1 O3 1.254(5) . ? C1 O1 1.286(4) . ? C1 O2 1.315(5) . ? C2 N2 1.305(4) . ? C2 N3 1.317(7) . ? C2 N1 1.319(7) . ? N1 H1A 0.8600 . ? N1 H1B 0.8600 . ? N2 H2A 0.8600 . ? N2 H2B 0.8600 . ? N3 H3A 0.8600 . ? N3 H3B 0.8600 . ? 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 O1 Cu1 O1 88.16(12) 2_765 . ? O1 Cu1 O1 173.87(14) 2_765 8_665 ? O1 Cu1 O1 92.17(13) . 8_665 ? O1 Cu1 O1 92.17(13) 2_765 7_545 ? O1 Cu1 O1 173.87(14) . 7_545 ? O1 Cu1 O1 88.16(12) 8_665 7_545 ? O2 Cu2 O2 151.14(13) . 2_665 ? O2 Cu2 O2 93.56(3) . 4_655 ? O2 Cu2 O2 93.56(3) 2_665 4_655 ? O2 Cu2 O2 93.56(3) . 3_565 ? O2 Cu2 O2 93.56(3) 2_665 3_565 ? O2 Cu2 O2 151.14(13) 4_655 3_565 ? O3 C1 O1 123.2(3) . . ? O3 C1 O2 121.0(3) . . ? O1 C1 O2 115.8(3) . . ? C1 O1 Cu1 114.9(2) . . ? C1 O2 Cu2 116.9(2) . . ? N2 C2 N3 120.4(5) . . ? N2 C2 N1 119.6(6) . . ? N3 C2 N1 119.6(3) . . ? C2 N1 H1A 120.0 . . ? C2 N1 H1B 120.0 . . ? H1A N1 H1B 120.0 . . ? C2 N2 H2A 120.0 . . ? C2 N2 H2B 120.0 . . ? H2A N2 H2B 120.0 . . ? C2 N3 H3A 120.0 . . ? C2 N3 H3B 120.0 . . ? H3A N3 H3B 120.0 . . ? 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 O3 C1 O1 Cu1 6.0(5) . . . . ? O2 C1 O1 Cu1 -173.8(2) . . . . ? O1 Cu1 O1 C1 101.9(2) 2_765 . . . ? O1 Cu1 O1 C1 -84.3(2) 8_665 . . . ? O1 Cu1 O1 C1 8.7(2) 7_545 . . . ? O3 C1 O2 Cu2 -6.2(5) . . . . ? O1 C1 O2 Cu2 173.6(2) . . . . ? O2 Cu2 O2 C1 39.5(2) 2_665 . . . ? O2 Cu2 O2 C1 143.5(3) 4_655 . . . ? O2 Cu2 O2 C1 -64.5(2) 3_565 . . . ? 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 N1 H1B O1 0.86 2.19 3.026(4) 165.5 8_665 N2 H2B O3 0.86 2.28 3.089(4) 156.7 2_665 N2 H2A O2 0.86 2.12 2.966(4) 166.2 5_465 N3 H3B O2 0.86 2.12 2.978(4) 174.3 8_665 N3 H3A O1 0.86 2.19 2.961(4) 149.2 5_465 _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 24.99 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.439 _refine_diff_density_min -0.381 _refine_diff_density_rms 0.069 data_Crystal_I_1.45GPa _database_code_depnum_ccdc_archive 'CCDC 848835' #TrackingRef '- Spencer_CIF.txt' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C2 Cu O6, 2(C H6 N3)' _chemical_formula_sum 'C4 H12 Cu N6 O6' _chemical_formula_weight 303.74 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 Tetragonal _symmetry_space_group_name_H-M P-4n2 _symmetry_space_group_name_Hall 'P -4 -2n' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' 'y, -x, -z' '-y, x, -z' 'x+1/2, -y+1/2, z+1/2' '-x+1/2, y+1/2, z+1/2' 'y+1/2, x+1/2, -z+1/2' '-y+1/2, -x+1/2, -z+1/2' _cell_length_a 8.9664(3) _cell_length_b 8.9664(3) _cell_length_c 12.3548(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 993.28(5) _cell_formula_units_Z 4 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 3981 _cell_measurement_theta_min 3.2944 _cell_measurement_theta_max 30.1543 _exptl_crystal_preparation ; Crystal mounted in a diamond-anvil cell Crystal held under 1.45GPa of pressure ; _exptl_crystal_description Fragment _exptl_crystal_colour Blue _exptl_crystal_size_max 0.34 _exptl_crystal_size_mid 0.28 _exptl_crystal_size_min 0.11 _exptl_crystal_density_diffrn 2.031 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 620 _exptl_absorpt_coefficient_mu 2.233 _exptl_absorpt_correction_mu 2.220 _exptl_absorpt_correction_T_min 0.238 _exptl_absorpt_correction_T_max 0.309 _exptl_absorpt_correction_type Gaussian _exptl_absorpt_process_details ; Gaussian integration over a grid of 16 x 8 x 16 points = 2048 total grid points Based upon method of Burnham (1966) Data corrected for diamond-anvil cell absorption Note that exptl_absorpt_correction_tmin and _tmax the total correction factors applied to the intensities The individual factors are: range of dac transmission factors (min-max) 0.314 0.394 range of gasket transmission (min-max) 0.973 1.000 range of P media transmission (min-max) 1.000 1.000 thickness of diamond anvil 1: 1.500 mm, mu = 0.2000 mm-1 thickness of platten 1: 3.300 mm, mu = 0.0500 mm-1 thickness of diamond anvil 2: 1.500 mm, mu = 0.2000 mm-1 thickness of platten 2: 3.300 mm, mu = 0.0500 mm-1 Gasket shadowing corrections were made based upon Gasket thickness = 145.0 microns, radius = 250.0 microns Gasket absorption coeff = 30.00 mm-1 REFLECTION WAS CONSIDERED TOTALLY OBSCURED IF FRACTION CRYSTAL ILLUMINATED WAS LESS THAN 0.20 Non-absorbing pressure medium ; _diffrn_ambient_temperature 298(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_radiation_probe X-ray _diffrn_detector 'Oxford Diffraction, Xcalibur1 CCD' _diffrn_measurement_device '\k-geometry diffractometer' _diffrn_measurement_device_type 'Oxford Diffraction Xcalibur1' _diffrn_measurement_method 'phi and omega scans' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_reduction_process ; Data averaged using Blessing (1987) criteria ; _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_h_min -3 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_number 7689 _diffrn_reflns_theta_full 30.00 _diffrn_reflns_theta_max 29.96 _diffrn_reflns_theta_min 4.00 _diffrn_measured_fraction_theta_max 0.648 _diffrn_measured_fraction_theta_full 0.647 _diffrn_reflns_av_R_equivalents 0.960 _diffrn_reflns_unetI/netI 0.003 _reflns_number_total 595 _reflns_number_gt 385 _reflns_threshold_expression 'Fsqd > 2.0u(Fsqd)' _computing_data_collection ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.58 (release 29-01-2010 CrysAlis171 .NET) (compiled Jan 29 2010,16:49:25) ; _computing_cell_refinement ; CrysAlisPro, Agilent Technologies, Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET) (compiled Jan 20 2011,15:58:25) ; _computing_data_reduction ; Average v2.2 (Angel, 2003) www.crystal.vt.edu/crystal Absorb Angel (2004) J. Appl. Cryst. 37:486-492 ; _computing_structure_refinement ; shelxl-97 (G.M.Sheldrick, 2008, Acta Cryst., A64,112) WinGX (L.J Farrugia, 1999, J. Appl. Cryst., 32, 837) ; _computing_molecular_graphics ; CrystalMaker V.2.0.6, CrystalMaker Software Ltd.' ; _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^)+(0.0737P)^2^+1.9991P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.27(12) _refine_ls_number_reflns 501 _refine_ls_number_parameters 32 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0714 _refine_ls_R_factor_gt 0.0569 _refine_ls_wR_factor_ref 0.1498 _refine_ls_wR_factor_gt 0.1386 _refine_ls_goodness_of_fit_ref 1.099 _refine_ls_restrained_S_all 1.098 _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 1.0000 0.5000 0.2500 0.0094(5) Uiso 1 4 d S . . Cu2 Cu 0.5000 0.5000 0.0000 0.0117(6) Uiso 1 4 d S . . C1 C 0.7605(12) 0.5442(10) 0.1190(8) 0.0092(15) Uiso 1 1 d . . . O1 O 0.8867(8) 0.6027(8) 0.1371(4) 0.0175(13) Uiso 1 1 d . . . O2 O 0.6853(8) 0.6004(8) 0.0369(5) 0.0173(14) Uiso 1 1 d . . . O3 O 0.7065(9) 0.4406(9) 0.1752(5) 0.0210(16) Uiso 1 1 d . . . C2 C 0.5062(13) 0.751(2) 0.3757(13) 0.0319(10) Uiso 1 1 d D . . N1 N 0.5806(14) 0.6730(12) 0.3049(6) 0.0319(10) Uiso 1 1 d D . . H1A H 0.6764 0.6695 0.3081 0.038 Uiso 1 1 calc R . . H1B H 0.5339 0.6250 0.2551 0.038 Uiso 1 1 calc R . . N2 N 0.3612(12) 0.7587(13) 0.3686(8) 0.0319(10) Uiso 1 1 d D . . H2A H 0.3118 0.8120 0.4140 0.038 Uiso 1 1 calc R . . H2B H 0.3151 0.7105 0.3186 0.038 Uiso 1 1 calc R . . N3 N 0.5750(13) 0.8237(12) 0.4511(7) 0.0319(10) Uiso 1 1 d D . . H3A H 0.6707 0.8209 0.4549 0.038 Uiso 1 1 calc R . . H3B H 0.5250 0.8748 0.4975 0.038 Uiso 1 1 calc R . . _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 O1 1.956(6) 8_665 ? Cu1 O1 1.956(6) 7_545 ? Cu1 O1 1.956(6) 2_765 ? Cu1 O1 1.956(6) . ? Cu2 O2 1.944(7) . ? Cu2 O2 1.944(7) 2_665 ? Cu2 O2 1.944(7) 3_565 ? Cu2 O2 1.944(7) 4_655 ? C1 O3 1.256(13) . ? C1 O1 1.267(12) . ? C1 O2 1.318(12) . ? C2 N3 1.29(2) . ? C2 N1 1.30(2) . ? C2 N2 1.305(15) . ? N1 H1A 0.8600 . ? N1 H1B 0.8600 . ? N2 H2A 0.8600 . ? N2 H2B 0.8600 . ? N3 H3A 0.8600 . ? N3 H3B 0.8600 . ? 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 O1 Cu1 O1 89.0(3) 8_665 7_545 ? O1 Cu1 O1 176.1(5) 8_665 2_765 ? O1 Cu1 O1 91.1(3) 7_545 2_765 ? O1 Cu1 O1 91.1(3) 8_665 . ? O1 Cu1 O1 176.1(5) 7_545 . ? O1 Cu1 O1 89.0(3) 2_765 . ? O2 Cu2 O2 152.9(3) . 2_665 ? O2 Cu2 O2 93.15(8) . 3_565 ? O2 Cu2 O2 93.15(8) 2_665 3_565 ? O2 Cu2 O2 93.15(8) . 4_655 ? O2 Cu2 O2 93.15(8) 2_665 4_655 ? O2 Cu2 O2 152.9(3) 3_565 4_655 ? O3 C1 O1 123.6(9) . . ? O3 C1 O2 120.7(9) . . ? O1 C1 O2 115.7(8) . . ? C1 O1 Cu1 113.2(6) . . ? C1 O2 Cu2 116.1(6) . . ? N3 C2 N1 120.7(11) . . ? N3 C2 N2 119.7(16) . . ? N1 C2 N2 119.6(16) . . ? C2 N1 H1A 120.0 . . ? C2 N1 H1B 120.0 . . ? H1A N1 H1B 120.0 . . ? C2 N2 H2A 120.0 . . ? C2 N2 H2B 120.0 . . ? H2A N2 H2B 120.0 . . ? C2 N3 H3A 120.0 . . ? C2 N3 H3B 120.0 . . ? H3A N3 H3B 120.0 . . ? 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 O3 C1 O1 Cu1 7.1(13) . . . . ? O2 C1 O1 Cu1 -174.0(6) . . . . ? O1 Cu1 O1 C1 -84.6(7) 8_665 . . . ? O1 Cu1 O1 C1 7.4(6) 7_545 . . . ? O1 Cu1 O1 C1 99.4(7) 2_765 . . . ? O3 C1 O2 Cu2 -6.4(12) . . . . ? O1 C1 O2 Cu2 174.6(6) . . . . ? O2 Cu2 O2 C1 40.2(6) 2_665 . . . ? O2 Cu2 O2 C1 -63.0(6) 3_565 . . . ? O2 Cu2 O2 C1 143.4(7) 4_655 . . . ? _refine_diff_density_max 0.445 _refine_diff_density_min -0.611 _refine_diff_density_rms 0.115 data_Crystal_I_3.21GPa _database_code_depnum_ccdc_archive 'CCDC 848836' #TrackingRef '- Spencer_CIF.txt' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C2 Cu O6, 2(C H6 N3)' _chemical_formula_sum 'C4 H12 Cu N6 O6' _chemical_formula_weight 303.74 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 Tetragonal _symmetry_space_group_name_H-M P-4n2 _symmetry_space_group_name_Hall 'P -4 -2n' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' 'y, -x, -z' '-y, x, -z' 'x+1/2, -y+1/2, z+1/2' '-x+1/2, y+1/2, z+1/2' 'y+1/2, x+1/2, -z+1/2' '-y+1/2, -x+1/2, -z+1/2' _cell_length_a 8.8645(3) _cell_length_b 8.8645(3) _cell_length_c 12.1191(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 952.31(5) _cell_formula_units_Z 4 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 3738 _cell_measurement_theta_min 3.3530 _cell_measurement_theta_max 30.0235 _exptl_crystal_preparation ; Crystal mounted in a diamond-anvil cell Crystal held under 3.21GPa of pressure ; _exptl_crystal_description Fragment _exptl_crystal_colour Blue _exptl_crystal_size_max 0.34 _exptl_crystal_size_mid 0.28 _exptl_crystal_size_min 0.11 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.118 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 620 _exptl_absorpt_coefficient_mu 2.330 _exptl_absorpt_correction_mu 2.322 _exptl_absorpt_correction_T_min 0.218 _exptl_absorpt_correction_T_max 0.306 _exptl_absorpt_correction_type Gaussian _exptl_absorpt_process_details ; Gaussian integration over a grid of 16 x 8 x 16 points = 2048 total grid points Based upon method of Burnham (1966) Data corrected for diamond-anvil cell absorption Note that exptl_absorpt_correction_tmin and _tmax the total correction factors applied to the intensities The individual factors are: range of dac transmission factors (min-max) 0.301 0.394 range of gasket transmission (min-max) 0.973 1.000 range of P media transmission (min-max) 1.000 1.000 thickness of diamond anvil 1: 1.500 mm, mu = 0.2000 mm-1 thickness of platten 1: 3.300 mm, mu = 0.0500 mm-1 thickness of diamond anvil 2: 1.500 mm, mu = 0.2000 mm-1 thickness of platten 2: 3.300 mm, mu = 0.0500 mm-1 Gasket shadowing corrections were made based upon Gasket thickness = 145.0 microns, radius = 250.0 microns Gasket absorption coeff = 30.00 mm-1 REFLECTION WAS CONSIDERED TOTALLY OBSCURED IF FRACTION CRYSTAL ILLUMINATED WAS LESS THAN 0.20 Non-absorbing pressure medium ; _diffrn_ambient_temperature 298(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_radiation_probe X-ray _diffrn_detector 'Oxford Diffraction, Xcalibur1 CCD' _diffrn_measurement_device '\k-geometry diffractometer' _diffrn_measurement_device_type 'Oxford Diffraction Xcalibur1' _diffrn_measurement_method 'phi and omega scans' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_reduction_process ; Data averaged using Blessing (1987) criteria ; _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_h_min -3 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_number 7336 _diffrn_reflns_theta_full 30.00 _diffrn_reflns_theta_max 30.01 _diffrn_reflns_theta_min 4.07 _diffrn_measured_fraction_theta_max 0.633 _diffrn_measured_fraction_theta_full 0.632 _diffrn_reflns_av_R_equivalents 0.935 _diffrn_reflns_unetI/netI 0.004 _reflns_number_total 563 _reflns_number_gt 367 _reflns_threshold_expression 'Fsqd > 2.0u(Fsqd)' _computing_data_collection ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.58 (release 29-01-2010 CrysAlis171 .NET) (compiled Jan 29 2010,16:49:25) ; _computing_cell_refinement ; CrysAlisPro, Agilent Technologies, Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET) (compiled Jan 20 2011,15:58:25) ; _computing_data_reduction ; Average v2.2 (Angel, 2003) www.crystal.vt.edu/crystal Absorb Angel (2004) J. Appl. Cryst. 37:486-492 ; _computing_structure_refinement ; shelxl-97 (G.M.Sheldrick, 2008, Acta Cryst., A64,112) WinGX (L.J Farrugia, 1999, J. Appl. Cryst., 32, 837) ; _computing_molecular_graphics ; CrystalMaker V.2.0.6, CrystalMaker Software Ltd.' ; _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^)+(0.1000P)^2^+0.0000P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.55(16) _refine_ls_number_reflns 472 _refine_ls_number_parameters 32 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0893 _refine_ls_R_factor_gt 0.0742 _refine_ls_wR_factor_ref 0.2061 _refine_ls_wR_factor_gt 0.1945 _refine_ls_goodness_of_fit_ref 1.385 _refine_ls_restrained_S_all 1.383 _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 1.0000 0.5000 0.2500 0.0099(7) Uiso 1 4 d S . . Cu2 Cu 0.5000 0.5000 0.0000 0.0124(7) Uiso 1 4 d S . . C1 C 0.7647(14) 0.5449(13) 0.1174(9) 0.010(2) Uiso 1 1 d . . . O1 O 0.8890(11) 0.6081(10) 0.1344(6) 0.0197(17) Uiso 1 1 d . . . O2 O 0.6843(10) 0.6023(10) 0.0338(6) 0.0189(17) Uiso 1 1 d . . . O3 O 0.7131(11) 0.4417(11) 0.1752(6) 0.0196(19) Uiso 1 1 d . . . C2 C 0.5076(19) 0.753(3) 0.3721(17) 0.0416(16) Uiso 1 1 d D . . N1 N 0.5786(18) 0.6782(17) 0.2980(9) 0.0416(16) Uiso 1 1 d D . . H1A H 0.6756 0.6764 0.2982 0.050 Uiso 1 1 calc R . . H1B H 0.5293 0.6298 0.2482 0.050 Uiso 1 1 calc R . . N2 N 0.3599(17) 0.7503(16) 0.3682(10) 0.0416(16) Uiso 1 1 d D . . H2A H 0.3147 0.6999 0.3174 0.050 Uiso 1 1 calc R . . H2B H 0.3082 0.7990 0.4165 0.050 Uiso 1 1 calc R . . N3 N 0.5739(17) 0.8277(18) 0.4491(8) 0.0416(16) Uiso 1 1 d D . . H3A H 0.6708 0.8292 0.4525 0.050 Uiso 1 1 calc R . . H3B H 0.5214 0.8762 0.4970 0.050 Uiso 1 1 calc R . . _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 O1 1.962(7) 8_665 ? Cu1 O1 1.962(7) . ? Cu1 O1 1.962(7) 2_765 ? Cu1 O1 1.962(7) 7_545 ? Cu2 O2 1.913(8) . ? Cu2 O2 1.913(8) 4_655 ? Cu2 O2 1.913(8) 2_665 ? Cu2 O2 1.913(8) 3_565 ? C1 O3 1.240(16) . ? C1 O1 1.253(15) . ? C1 O2 1.339(14) . ? C2 N1 1.28(3) . ? C2 N3 1.29(3) . ? C2 N2 1.31(2) . ? N1 H1A 0.8600 . ? N1 H1B 0.8600 . ? N2 H2A 0.8600 . ? N2 H2B 0.8600 . ? N3 H3A 0.8600 . ? N3 H3B 0.8600 . ? 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 O1 Cu1 O1 91.1(4) 8_665 . ? O1 Cu1 O1 178.9(6) 8_665 2_765 ? O1 Cu1 O1 88.9(4) . 2_765 ? O1 Cu1 O1 88.9(4) 8_665 7_545 ? O1 Cu1 O1 178.9(6) . 7_545 ? O1 Cu1 O1 91.1(4) 2_765 7_545 ? O2 Cu2 O2 92.63(9) . 4_655 ? O2 Cu2 O2 155.3(4) . 2_665 ? O2 Cu2 O2 92.63(9) 4_655 2_665 ? O2 Cu2 O2 92.63(9) . 3_565 ? O2 Cu2 O2 155.3(4) 4_655 3_565 ? O2 Cu2 O2 92.63(9) 2_665 3_565 ? O3 C1 O1 124.1(11) . . ? O3 C1 O2 120.8(11) . . ? O1 C1 O2 115.0(10) . . ? C1 O1 Cu1 109.9(7) . . ? C1 O2 Cu2 115.9(7) . . ? N1 C2 N3 123.3(15) . . ? N1 C2 N2 117(2) . . ? N3 C2 N2 119(2) . . ? C2 N1 H1A 120.0 . . ? C2 N1 H1B 120.0 . . ? H1A N1 H1B 120.0 . . ? C2 N2 H2A 120.0 . . ? C2 N2 H2B 120.0 . . ? H2A N2 H2B 120.0 . . ? C2 N3 H3A 120.0 . . ? C2 N3 H3B 120.0 . . ? H3A N3 H3B 120.0 . . ? 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 O3 C1 O1 Cu1 8.4(15) . . . . ? O2 C1 O1 Cu1 -175.0(8) . . . . ? O1 Cu1 O1 C1 -84.2(8) 8_665 . . . ? O1 Cu1 O1 C1 96.8(8) 2_765 . . . ? O1 Cu1 O1 C1 6.3(7) 7_545 . . . ? O3 C1 O2 Cu2 -7.1(15) . . . . ? O1 C1 O2 Cu2 176.2(7) . . . . ? O2 Cu2 O2 C1 143.1(8) 4_655 . . . ? O2 Cu2 O2 C1 41.0(7) 2_665 . . . ? O2 Cu2 O2 C1 -61.1(7) 3_565 . . . ? _refine_diff_density_max 0.654 _refine_diff_density_min -0.883 _refine_diff_density_rms 0.154 data_Crystal_I_3.95GPa _database_code_depnum_ccdc_archive 'CCDC 848837' #TrackingRef '- Spencer_CIF.txt' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C2 Cu O6, 2(C H6 N3)' _chemical_formula_sum 'C4 H12 Cu N6 O6' _chemical_formula_weight 303.74 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 Tetragonal _symmetry_space_group_name_H-M P-4n2 _symmetry_space_group_name_Hall 'P -4 -2n' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' 'y, -x, -z' '-y, x, -z' 'x+1/2, -y+1/2, z+1/2' '-x+1/2, y+1/2, z+1/2' 'y+1/2, x+1/2, -z+1/2' '-y+1/2, -x+1/2, -z+1/2' _cell_length_a 8.8048(2) _cell_length_b 8.8048(2) _cell_length_c 12.0310(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 932.70(3) _cell_formula_units_Z 4 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 3535 _cell_measurement_theta_min 3.3795 _cell_measurement_theta_max 30.0710 _exptl_crystal_preparation ; Crystal mounted in a diamond-anvil cell Crystal held under 3.95GPa of pressure ; _exptl_crystal_description Fragment _exptl_crystal_colour Blue _exptl_crystal_size_max 0.34 _exptl_crystal_size_mid 0.28 _exptl_crystal_size_min 0.11 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.163 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 620 _exptl_absorpt_coefficient_mu 2.379 _exptl_absorpt_correction_mu 2.379 _exptl_absorpt_correction_T_min 0.217 _exptl_absorpt_correction_T_max 0.304 _exptl_absorpt_correction_type Gaussian _exptl_absorpt_process_details ; Gaussian integration over a grid of 16 x 8 x 16 points = 2048 total grid points Based upon method of Burnham (1966) Data corrected for diamond-anvil cell absorption Note that exptl_absorpt_correction_tmin and _tmax the total correction factors applied to the intensities The individual factors are: range of dac transmission factors (min-max) 0.302 0.394 range of gasket transmission (min-max) 0.972 1.000 range of P media transmission (min-max) 1.000 1.000 thickness of diamond anvil 1: 1.500 mm, mu = 0.2000 mm-1 thickness of platten 1: 3.300 mm, mu = 0.0500 mm-1 thickness of diamond anvil 2: 1.500 mm, mu = 0.2000 mm-1 thickness of platten 2: 3.300 mm, mu = 0.0500 mm-1 Gasket shadowing corrections were made based upon Gasket thickness = 145.0 microns, radius = 250.0 microns Gasket absorption coeff = 30.00 mm-1 REFLECTION WAS CONSIDERED TOTALLY OBSCURED IF FRACTION CRYSTAL ILLUMINATED WAS LESS THAN 0.20 Non-absorbing pressure medium ; _diffrn_ambient_temperature 298(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_radiation_probe X-ray _diffrn_detector 'Oxford Diffraction, Xcalibur1 CCD' _diffrn_measurement_device '\k-geometry diffractometer' _diffrn_measurement_device_type 'Oxford Diffraction Xcalibur1' _diffrn_measurement_method 'phi and omega scans' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_reduction_process ; Data averaged using Blessing (1987) criteria ; _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_h_min -3 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_number 7095 _diffrn_reflns_theta_full 30.00 _diffrn_reflns_theta_max 30.00 _diffrn_reflns_theta_min 4.10 _diffrn_measured_fraction_theta_max 0.629 _diffrn_measured_fraction_theta_full 0.629 _diffrn_reflns_av_R_equivalents 0.948 _diffrn_reflns_unetI/netI 0.004 _reflns_number_total 544 _reflns_number_gt 349 _reflns_threshold_expression 'Fsqd > 2.0u(Fsqd)' _computing_data_collection ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.58 (release 29-01-2010 CrysAlis171 .NET) (compiled Jan 29 2010,16:49:25) ; _computing_cell_refinement ; CrysAlisPro, Agilent Technologies, Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET) (compiled Jan 20 2011,15:58:25) ; _computing_data_reduction ; Average v2.2 (Angel, 2003) www.crystal.vt.edu/crystal Absorb Angel (2004) J. Appl. Cryst. 37:486-492 ; _computing_structure_refinement ; shelxl-97 (G.M.Sheldrick, 2008, Acta Cryst., A64,112) WinGX (L.J Farrugia, 1999, J. Appl. Cryst., 32, 837) ; _computing_molecular_graphics ; CrystalMaker V.2.0.6, CrystalMaker Software Ltd.' ; _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^)+(0.1713P)^2^+1.1225P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.7(2) _refine_ls_number_reflns 456 _refine_ls_number_parameters 32 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.1045 _refine_ls_R_factor_gt 0.0884 _refine_ls_wR_factor_ref 0.2658 _refine_ls_wR_factor_gt 0.2416 _refine_ls_goodness_of_fit_ref 1.145 _refine_ls_restrained_S_all 1.145 _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 1.0000 0.5000 0.2500 0.0097(8) Uiso 1 4 d S . . Cu2 Cu 0.5000 0.5000 0.0000 0.0136(9) Uiso 1 4 d S . . C1 C 0.7655(15) 0.5452(14) 0.1159(10) 0.009(2) Uiso 1 1 d . . . O1 O 0.8905(13) 0.6135(13) 0.1338(7) 0.022(2) Uiso 1 1 d . . . O2 O 0.6850(12) 0.6060(12) 0.0324(7) 0.021(2) Uiso 1 1 d . . . O3 O 0.7145(13) 0.4414(13) 0.1742(7) 0.020(2) Uiso 1 1 d . . . C2 C 0.508(3) 0.754(3) 0.368(2) 0.054(2) Uiso 1 1 d D . . N1 N 0.579(2) 0.683(2) 0.2952(12) 0.054(2) Uiso 1 1 d D . . H1A H 0.6769 0.6863 0.2944 0.064 Uiso 1 1 calc R . . H1B H 0.5311 0.6320 0.2457 0.064 Uiso 1 1 calc R . . N2 N 0.358(2) 0.741(2) 0.3697(14) 0.054(2) Uiso 1 1 d D . . H2A H 0.3124 0.6858 0.3211 0.064 Uiso 1 1 calc R . . H2B H 0.3059 0.7887 0.4193 0.064 Uiso 1 1 calc R . . N3 N 0.572(2) 0.833(3) 0.4452(11) 0.054(2) Uiso 1 1 d D . . H3A H 0.6690 0.8397 0.4481 0.064 Uiso 1 1 calc R . . H3B H 0.5168 0.8795 0.4937 0.064 Uiso 1 1 calc R . . _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 O1 1.970(10) 7_545 ? Cu1 O1 1.970(10) 2_765 ? Cu1 O1 1.970(10) . ? Cu1 O1 1.970(10) 8_665 ? Cu2 O2 1.917(10) . ? Cu2 O2 1.917(10) 3_565 ? Cu2 O2 1.917(10) 2_665 ? Cu2 O2 1.917(10) 4_655 ? C1 O3 1.237(19) . ? C1 O1 1.273(17) . ? C1 O2 1.341(16) . ? C2 N1 1.24(4) . ? C2 N3 1.29(4) . ? C2 N2 1.32(3) . ? N1 H1A 0.8600 . ? N1 H1B 0.8600 . ? N2 H2A 0.8600 . ? N2 H2B 0.8600 . ? N3 H3A 0.8600 . ? N3 H3B 0.8600 . ? 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 O1 Cu1 O1 90.4(6) 7_545 2_765 ? O1 Cu1 O1 178.5(7) 7_545 . ? O1 Cu1 O1 89.6(6) 2_765 . ? O1 Cu1 O1 89.6(6) 7_545 8_665 ? O1 Cu1 O1 178.5(7) 2_765 8_665 ? O1 Cu1 O1 90.4(6) . 8_665 ? O2 Cu2 O2 92.37(11) . 3_565 ? O2 Cu2 O2 156.5(5) . 2_665 ? O2 Cu2 O2 92.37(11) 3_565 2_665 ? O2 Cu2 O2 92.37(11) . 4_655 ? O2 Cu2 O2 156.5(5) 3_565 4_655 ? O2 Cu2 O2 92.37(11) 2_665 4_655 ? O3 C1 O1 124.5(12) . . ? O3 C1 O2 121.9(12) . . ? O1 C1 O2 113.3(11) . . ? C1 O1 Cu1 107.7(8) . . ? C1 O2 Cu2 114.0(9) . . ? N1 C2 N3 124(2) . . ? N1 C2 N2 118(3) . . ? N3 C2 N2 118(3) . . ? C2 N1 H1A 120.0 . . ? C2 N1 H1B 120.0 . . ? H1A N1 H1B 120.0 . . ? C2 N2 H2A 120.0 . . ? C2 N2 H2B 120.0 . . ? H2A N2 H2B 120.0 . . ? C2 N3 H3A 120.0 . . ? C2 N3 H3B 120.0 . . ? H3A N3 H3B 120.0 . . ? 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 O3 C1 O1 Cu1 10.4(16) . . . . ? O2 C1 O1 Cu1 -175.6(9) . . . . ? O1 Cu1 O1 C1 -175.4(8) 7_545 . . . ? O1 Cu1 O1 C1 93.9(9) 2_765 . . . ? O1 Cu1 O1 C1 -84.6(9) 8_665 . . . ? O3 C1 O2 Cu2 -8.1(16) . . . . ? O1 C1 O2 Cu2 177.6(8) . . . . ? O2 Cu2 O2 C1 -59.6(7) 3_565 . . . ? O2 Cu2 O2 C1 41.9(8) 2_665 . . . ? O2 Cu2 O2 C1 143.4(10) 4_655 . . . ? _refine_diff_density_max 0.953 _refine_diff_density_min -1.135 _refine_diff_density_rms 0.200