#------------------------------------------------------------------------------ #$Date: 2020-05-20 07:19:51 +0300 (Wed, 20 May 2020) $ #$Revision: 252202 $ #$URL: file:///home/coder/svn-repositories/cod/cif/7/24/05/7240559.cif $ #------------------------------------------------------------------------------ # # This file is available in the Crystallography Open Database (COD), # http://www.crystallography.net/ # # All data on this site have been placed in the public domain by the # contributors. # data_7240559 loop_ _publ_author_name 'M\;aczka, Miros\/law' 'G\;agor, Anna' 'Pikul, Adam' 'Stefa\'nska, Dagmara' _publ_section_title ; Novel hypophosphite hybrid perovskites of [CH3NH2NH2][Mn(H2POO)3] and [CH3NH2NH2][Mn(H2POO)2.83(HCOO)0.17] exhibiting antiferromagnetic order and red photoluminescence ; _journal_issue 32 _journal_name_full 'RSC Advances' _journal_page_first 19020 _journal_paper_doi 10.1039/D0RA03397A _journal_volume 10 _journal_year 2020 _chemical_formula_sum 'C H13 Mn N2 O6 P3' _chemical_formula_weight 296.98 _space_group_crystal_system orthorhombic _space_group_IT_number 62 _space_group_name_Hall '-P 2ac 2n' _space_group_name_H-M_alt 'P n m a' _atom_sites_solution_hydrogens mixed _audit_creation_method SHELXL-2018/3 _audit_update_record ; 2020-03-09 deposited with the CCDC. 2020-05-13 downloaded from the CCDC. ; _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_formula_units_Z 4 _cell_length_a 9.4005(6) _cell_length_b 13.2990(8) _cell_length_c 8.6191(6) _cell_measurement_reflns_used 1413 _cell_measurement_temperature 295(2) _cell_measurement_theta_max 29.0770 _cell_measurement_theta_min 2.7890 _cell_volume 1077.54(12) _computing_structure_refinement 'SHELXL-2018/3 (Sheldrick, 2018)' _diffrn_ambient_temperature 295(2) _diffrn_detector 'CCD plate' _diffrn_detector_area_resol_mean 10.6249 _diffrn_detector_type Atlas _diffrn_measured_fraction_theta_full 0.999 _diffrn_measured_fraction_theta_max 0.999 _diffrn_measurement_device 'four-circle diffractometer' _diffrn_measurement_device_type 'Xcalibur, Atlas' _diffrn_radiation_monochromator graphite _diffrn_radiation_probe x-ray _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_reflns_av_R_equivalents 0.0223 _diffrn_reflns_av_unetI/netI 0.0253 _diffrn_reflns_Laue_measured_fraction_full 0.999 _diffrn_reflns_Laue_measured_fraction_max 0.999 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_l_max 6 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_number 3038 _diffrn_reflns_point_group_measured_fraction_full 0.999 _diffrn_reflns_point_group_measured_fraction_max 0.999 _diffrn_reflns_theta_full 25.242 _diffrn_reflns_theta_max 25.669 _diffrn_reflns_theta_min 2.816 _diffrn_source 'fine-focus sealed X-ray tube' _diffrn_source_type 'Enhance (Mo) X-ray Source' _exptl_absorpt_coefficient_mu 1.672 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_correction_T_min 0.83777 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_crystal_density_diffrn 1.831 _exptl_crystal_description prism _exptl_crystal_F_000 608 _exptl_crystal_size_max 0.22 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.09 _refine_diff_density_max 0.364 _refine_diff_density_min -0.564 _refine_diff_density_rms 0.084 _refine_ls_extinction_coef 0.0162(19) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_extinction_method 'SHELXL-2018/3 (Sheldrick 2018)' _refine_ls_goodness_of_fit_ref 1.054 _refine_ls_hydrogen_treatment constr _refine_ls_matrix_type full _refine_ls_number_parameters 69 _refine_ls_number_reflns 1067 _refine_ls_number_restraints 0 _refine_ls_restrained_S_all 1.054 _refine_ls_R_factor_all 0.0432 _refine_ls_R_factor_gt 0.0343 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 _refine_ls_structure_factor_coef Fsqd _refine_ls_weighting_details 'w=1/[\s^2^(Fo^2^)+(0.0520P)^2^+1.2782P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.0929 _refine_ls_wR_factor_ref 0.1002 _reflns_Friedel_coverage 0.000 _reflns_number_gt 873 _reflns_number_total 1067 _reflns_threshold_expression 'I > 2\s(I)' _cod_data_source_file d0ra03397a2.cif _cod_data_source_block rt _cod_database_code 7240559 _shelx_shelxl_version_number 2018/3 _shelx_space_group_comment ; The symmetry employed for this shelxl refinement is uniquely defined by the following loop, which should always be used as a source of symmetry information in preference to the above space-group names. They are only intended as comments. ; _oxdiff_exptl_absorpt_empirical_full_min 0.869 _oxdiff_exptl_absorpt_empirical_full_max 1.265 _oxdiff_exptl_absorpt_empirical_details ; Empirical correction (ABSPACK) includes: - Absorption correction using spherical harmonics - Frame scaling ; _shelx_res_file ; TITL mhyd_mn_po2_30m_a.res in Pnma rt.res created by SHELXL-2018/3 at 15:10:16 on 05-Feb-2020 REM Old TITL MHyd_Mn_PO2_30m in Pnma REM SHELXT solution in Pnma REM R1 0.121, Rweak 0.143, Alpha 0.033, Orientation as input CELL 0.71073 9.400544 13.298978 8.619116 90 90 90 ZERR 4 0.000586 0.00076 0.000608 0 0 0 LATT 1 SYMM 0.5-X,-Y,0.5+Z SYMM -X,0.5+Y,-Z SYMM 0.5+X,0.5-Y,0.5-Z SFAC H N O P Mn C UNIT 52 8 24 12 4 4 L.S. 10 0 0 PLAN 20 BOND $H list 4 fmap 2 53 shel 10 0.82 omit 0 4 0 ACTA bond $H htab EQIV $6 x, -y+1/2, z HTAB N2 O1_$6 EQIV $7 -x+1/2, y-1/2, z+1/2 HTAB N2 O3_$7 HTAB N2 O1 EQIV $1 -x+1/2, -y+1, z+1/2 HTAB N2 O3_$1 HTAB N1 O2_$6 WGHT 0.052000 1.278200 EXTI 0.016166 FVAR 5.72383 Mn1 5 0.500000 0.500000 0.500000 10.50000 0.02231 0.01569 = 0.02528 -0.00003 -0.00085 -0.00062 P1 4 0.490017 0.750000 0.647079 10.50000 0.04292 0.01851 = 0.02929 0.00000 -0.00446 0.00000 AFIX 23 H1A 1 0.588373 0.749999 0.681104 10.50000 -1.20000 H1B 1 0.431209 0.750000 0.739553 10.50000 -1.20000 AFIX 0 P2 4 0.181665 0.516295 0.670963 11.00000 0.05017 0.02494 = 0.04603 0.00373 0.02224 0.00233 AFIX 23 H2A 1 0.122681 0.555166 0.600751 11.00000 -1.20000 H2B 1 0.233171 0.563682 0.735488 11.00000 -1.20000 AFIX 0 O1 3 0.085871 0.456184 0.773451 11.00000 0.04307 0.03012 = 0.03310 -0.00355 0.01578 -0.00526 O2 3 0.286923 0.459821 0.576784 11.00000 0.03254 0.03350 = 0.04758 -0.00524 0.01393 -0.00801 O3 3 0.464015 0.655227 0.563916 11.00000 0.06081 0.02184 = 0.05988 -0.01000 -0.00262 0.00213 N2 2 0.177179 0.250000 0.762742 10.50000 0.02708 0.02501 = 0.03901 0.00000 0.00530 0.00000 AFIX 23 HB 1 0.130826 0.196081 0.797165 10.50000 -1.20000 HC 1 0.130826 0.303919 0.797165 10.50000 -1.20000 AFIX 0 N1 2 0.170735 0.250000 0.595611 10.50000 0.04988 0.03146 = 0.03348 0.00000 0.00440 0.00000 AFIX 7 HA 1 0.222836 0.201908 0.558817 11.00000 -1.20000 AFIX 0 C1 6 0.320137 0.250000 0.831855 10.50000 0.03362 0.04657 = 0.04527 0.00000 0.00001 0.00000 AFIX 133 HD 1 0.371350 0.191662 0.797459 10.50000 -1.50000 HE 1 0.312246 0.248816 0.942887 10.50000 -1.50000 HF 1 0.370174 0.309523 0.800353 10.50000 -1.50000 AFIX 0 HKLF 4 REM mhyd_mn_po2_30m_a.res in Pnma REM wR2 = 0.1002, GooF = S = 1.054, Restrained GooF = 1.054 for all data REM R1 = 0.0343 for 873 Fo > 4sig(Fo) and 0.0432 for all 1067 data REM 69 parameters refined using 0 restraints END WGHT 0.0501 1.3529 REM Instructions for potential hydrogen bonds HTAB N2 O1_$6 HTAB N2 O3_$7 HTAB N2 O1 HTAB N2 O3_$1 HTAB N1 O2_$6 REM Highest difference peak 0.364, deepest hole -0.564, 1-sigma level 0.084 Q1 1 0.6539 0.7500 0.7207 10.50000 0.05 0.36 Q2 1 0.0015 0.2500 0.8529 10.50000 0.05 0.33 Q3 1 0.4730 0.6641 0.5152 11.00000 0.05 0.30 Q4 1 0.3924 0.7500 0.8231 10.50000 0.05 0.28 Q5 1 0.5409 0.6542 0.5978 11.00000 0.05 0.28 Q6 1 0.3359 0.7625 0.7488 11.00000 0.05 0.27 Q7 1 0.3498 0.2500 0.7562 10.50000 0.05 0.25 Q8 1 0.4412 0.6797 0.6201 11.00000 0.05 0.24 Q9 1 0.2509 0.5805 0.7915 11.00000 0.05 0.23 Q10 1 0.4636 0.6606 0.6410 11.00000 0.05 0.23 Q11 1 0.1794 0.6177 0.6969 11.00000 0.05 0.20 Q12 1 0.0621 0.5006 0.7787 11.00000 0.05 0.20 Q13 1 0.0934 0.2500 0.9527 10.50000 0.05 0.20 Q14 1 0.1507 0.4416 0.7207 11.00000 0.05 0.19 Q15 1 0.5338 0.6099 0.5245 11.00000 0.05 0.19 Q16 1 0.2832 0.5202 0.5721 11.00000 0.05 0.19 Q17 1 0.1513 0.4829 0.6006 11.00000 0.05 0.19 Q18 1 0.0598 0.5552 0.5577 11.00000 0.05 0.19 Q19 1 0.1342 0.4360 0.8458 11.00000 0.05 0.18 Q20 1 0.5221 0.7202 0.4532 11.00000 0.05 0.18 ; _shelx_res_checksum 47212 loop_ _space_group_symop_operation_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z' 'x+1/2, -y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'x, -y-1/2, z' '-x-1/2, y-1/2, z-1/2' 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_site_symmetry_order _atom_site_calc_flag _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group Mn1 Mn 0.500000 0.500000 0.500000 0.0211(3) Uani 1 2 d S . P . . P1 P 0.49002(13) 0.750000 0.64708(14) 0.0302(3) Uani 1 2 d S T P . . H1A H 0.588373 0.749999 0.681104 0.036 Uiso 1 2 calc R U P . . H1B H 0.431209 0.750000 0.739553 0.036 Uiso 1 2 calc R U P . . P2 P 0.18166(11) 0.51629(7) 0.67096(12) 0.0404(3) Uani 1 1 d . . . . . H2A H 0.122681 0.555166 0.600751 0.048 Uiso 1 1 calc R U . . . H2B H 0.233171 0.563682 0.735488 0.048 Uiso 1 1 calc R U . . . O1 O 0.0859(2) 0.45618(16) 0.7735(3) 0.0354(6) Uani 1 1 d . . . . . O2 O 0.2869(2) 0.45982(17) 0.5768(3) 0.0379(6) Uani 1 1 d . . . . . O3 O 0.4640(3) 0.65523(18) 0.5639(3) 0.0475(7) Uani 1 1 d . . . . . N2 N 0.1772(4) 0.250000 0.7627(5) 0.0304(8) Uani 1 2 d S T P . . HB H 0.130826 0.196081 0.797165 0.036 Uiso 0.5 1 calc R U P . . HC H 0.130826 0.303919 0.797165 0.036 Uiso 0.5 1 calc R U P . . N1 N 0.1707(5) 0.250000 0.5956(4) 0.0383(10) Uani 1 2 d S T P . . HA H 0.222836 0.201908 0.558817 0.046 Uiso 1 1 d R U . . . C1 C 0.3201(5) 0.250000 0.8319(6) 0.0418(12) Uani 1 2 d S T P . . HD H 0.371350 0.191662 0.797459 0.063 Uiso 0.5 1 calc R U P . . HE H 0.312246 0.248816 0.942887 0.063 Uiso 0.5 2 calc R U P . . HF H 0.370174 0.309523 0.800353 0.063 Uiso 0.5 1 calc R U P . . 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 Mn1 0.0223(4) 0.0157(4) 0.0253(4) 0.0000(2) -0.0009(2) -0.0006(2) P1 0.0429(7) 0.0185(6) 0.0293(6) 0.000 -0.0045(5) 0.000 P2 0.0502(6) 0.0249(5) 0.0460(6) 0.0037(4) 0.0222(5) 0.0023(4) O1 0.0431(13) 0.0301(11) 0.0331(12) -0.0036(10) 0.0158(11) -0.0053(10) O2 0.0325(12) 0.0335(12) 0.0476(14) -0.0052(12) 0.0139(11) -0.0080(10) O3 0.0608(16) 0.0218(11) 0.0599(17) -0.0100(11) -0.0026(14) 0.0021(12) N2 0.0271(19) 0.0250(17) 0.039(2) 0.000 0.0053(17) 0.000 N1 0.050(3) 0.031(2) 0.033(2) 0.000 0.0044(19) 0.000 C1 0.034(3) 0.047(3) 0.045(3) 0.000 0.000(2) 0.000 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 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' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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 O3 Mn1 O3 180.00(15) 5_666 . ? O3 Mn1 O2 90.74(9) 5_666 5_666 ? O3 Mn1 O2 89.26(10) . 5_666 ? O3 Mn1 O2 89.26(10) 5_666 . ? O3 Mn1 O2 90.74(10) . . ? O2 Mn1 O2 180.0 5_666 . ? O3 Mn1 O1 85.16(10) 5_666 6_657 ? O3 Mn1 O1 94.84(10) . 6_657 ? O2 Mn1 O1 89.84(9) 5_666 6_657 ? O2 Mn1 O1 90.16(9) . 6_657 ? O3 Mn1 O1 94.84(10) 5_666 2_564 ? O3 Mn1 O1 85.16(10) . 2_564 ? O2 Mn1 O1 90.16(9) 5_666 2_564 ? O2 Mn1 O1 89.84(9) . 2_564 ? O1 Mn1 O1 180.0 6_657 2_564 ? O3 P1 O3 118.0(2) . 7_575 ? O3 P1 H1A 107.8 . . ? O3 P1 H1A 107.8 7_575 . ? O3 P1 H1B 107.8 . . ? O3 P1 H1B 107.8 7_575 . ? H1A P1 H1B 107.1 . . ? O2 P2 O1 117.05(13) . . ? O2 P2 H2A 108.0 . . ? O1 P2 H2A 108.0 . . ? O2 P2 H2B 108.0 . . ? O1 P2 H2B 108.0 . . ? H2A P2 H2B 107.3 . . ? P2 O1 Mn1 127.35(13) . 2_565 ? P2 O2 Mn1 130.98(14) . . ? P1 O3 Mn1 156.37(18) . . ? N1 N2 C1 116.3(4) . . ? N1 N2 HB 108.2 . . ? C1 N2 HB 108.2 . . ? N1 N2 HC 108.2 . . ? C1 N2 HC 108.2 . . ? HB N2 HC 107.4 . . ? N2 N1 HA 110.0 . . ? N2 N1 HA 110.0(8) . 7_565 ? HA N1 HA 95.2 . 7_565 ? N2 C1 HD 109.5 . . ? N2 C1 HE 109.5 . . ? HD C1 HE 109.5 . . ? N2 C1 HF 109.5 . . ? HD C1 HF 109.5 . . ? HE C1 HF 109.5 . . ? 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 Mn1 O3 2.163(2) 5_666 ? Mn1 O3 2.163(2) . ? Mn1 O2 2.176(2) 5_666 ? Mn1 O2 2.176(2) . ? Mn1 O1 2.192(2) 6_657 ? Mn1 O1 2.192(2) 2_564 ? P1 O3 1.470(2) . ? P1 O3 1.470(2) 7_575 ? P1 H1A 0.9700 . ? P1 H1B 0.9700 . ? P2 O2 1.484(2) . ? P2 O1 1.493(2) . ? P2 H2A 0.9700 . ? P2 H2B 0.9700 . ? N2 N1 1.442(5) . ? N2 C1 1.470(6) . ? N2 HB 0.8900 . ? N2 HC 0.8900 . ? N1 HA 0.8657 . ? C1 HD 0.9600 . ? C1 HE 0.9600 . ? C1 HF 0.9600 . ? 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 _geom_hbond_publ_flag N2 HB O1 0.89 2.08 2.875(2) 148.4 7_565 yes N2 HB O3 0.89 2.53 3.176(5) 130.5 8_656 yes N2 HC O1 0.89 2.08 2.875(2) 148.4 . yes N2 HC O3 0.89 2.53 3.176(5) 130.5 2_565 yes N1 HA O2 0.87 2.24 3.001(3) 146.8 7_565 yes