Supporting Information Heteroligand o-semiquinonato-formazanato cobalt complexes Natalia A. Protasenko, Andrey I. Poddel sky,*, Artem S. Bogomyakov, Georgy K. Fukin, Vladimir K. Cherkasov G.A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 Tropinina Street, 603137 Nizhny Novgorod, Russia International Tomography Center, Siberian Branch, Russian Academy of Sciences, Institutskaya Street 3a, 630090 Novosibirsk, Russia Contact author information: Andrey I. Poddel sky, email: aip@iomc.ras.ru
Contents Materials and methods 3 Synthesis of [Co(SQ)(Form)] (1) 3 Synthesis of [Co(SQ) 2 (Form)] (2): 3 Magnetic Measurements by SQUID 4 Single crystal X-ray diffraction 4 Table S1. Crystallographic data for complexes 1 and 2 5 Table S2. The selected bond lengths for 1 and 2 6 Figure S1. The temperature dependences of χ of [Co(SQ)(Form)] (1) (a) and [Co(SQ) 2 (Form)] (2) (b) 7 Figure S2. The temperature dependences of χt for [Co(SQ)(Form)] (1) ( ) and [Co(SQ) 2 (Form)] (2) ( ). 8 Figure S3. EPR spectrum of solid sample of complex 2 at room temperature. 9 References 10 2
Materials and methods All manipulations were carried out under vacuum using glass ampoules. 3,6-Di-tert-butyl-obenzoquinone 1 and 1,3,5-triphenylformazane 2 were prepared according to literature procedures. Solvents were purified following standard procedures 3. The IR spectra were recorded on a FSM-1201 spectrometer in a Nujol. The EPR spectra were obtained using a Bruker EMX spectrometer (9.75 GHz). The C, H, N elemental analysis was performed on an Elemental Analyzer Euro EA 3000 instrument; the Co content was accomplished by combustion analysis. The mass spectra of compounds were recorded on a mass spectrometer Polaris Q/Trace GC Ultra (Ion Trap analyzer), 70 ev, ion source temperature 250 C, the sample temperature 50 450 C. Optical absorption spectra were recorded in the 300 1100 nm range on Perkin Elmer Lambda 25 UV Vis spectrophotometer. Synthesis of [Co(SQ)(Form)] (1): The sample of 3,6-Q (0.185 g, 0.84 mmol) dissolved in 50 ml toluene was added to Co 2 (CO) 8 (0.145 g, 0.42 mmol) and 1,3,5-triphenylformazane (0.252 g, 0.84 mmol) under vacuum at ambient temperature. The mixture was stirred for about 1 h. After that time the solution was degassed and kept overnight at 0 C. The dark microcrystalline precipitate of 1 was filtered off and dried under vacuum. Additional quantities of 1 were produced by the same way from mother liquor. The total yield is 0.371 g (76%). Elem. anal. Calcd. for 1 (C 33 H 35 CoN 4 O 2 ): C, 68.50; H, 6.10; Co, 10.19; N, 9.68. Found: C, 68.23; H, 6.07; Co, 9.94; N, 9.78. IR (Nujol, KBr) cm -1 : 1587 (w), 1552 (m), 1480 (m), 1341 (w), 1278 (w), 1218 (m), 1201 (s), 1111 (w), 1081 (w), 1028 (m), 980 (m), 960 (w), 906 (w), 832 (w), 759 (s), 721 (w), 686 (s), 673 (m), 651 (w), 638 (w), 584 (w), 569 (w), 534 (w), 506 (w), 488 (w). EI-MS: m/z 578 [M + ]. The slow crystallization from toluene\hexane (1:1) gave rod-like dark blue crystals of 1 suitable for an X-ray analysis. Synthesis of [Co(SQ) 2 (Form)] (2): The sample of 3,6-Q (0.257 g, 1.17 mmol) dissolved in 80 ml toluene was added to Co 2 (CO) 8 (0.100 g, 0.29 mmol) and 1,3,5-triphenylformazane (0.180 g, 0.60 mmol) under vacuum at ambient temperature. The mixture was stirred for about 3 h. When reaction finished, the solution was degassed and its volume was reduced to a half. After storage of the reaction mixture at 0 C, the black powder of 2 was filtered off and dried under vacuum. Additional quantities of 2 were produced by the same way from mother liquor. The total yield is 0.384 g (83%). Elem. anal. Calcd. for 2 (C 47 H 55 CoN 4 O 4 ): C, 70.66; H, 6.94; Co, 7.38; N, 7.01. Found: C, 70.80; H, 7.05; Co, 7.24; N, 6.94. IR (Nujol, KBr) cm -1 : 1601 (m), 1593 (m), 1552 (m), 1498 (w), 1485 (m), 1426 (s), 1419 (s), 1357 (m), 1344 (m), 1331 (m), 1307 (s), 1280 (s), 1248 (w), 1198 (s), 1167 (w), 1154 (w), 1082 (w), 1072 (w), 1026 (m), 993 (m), 976 (m), 957 (m), 910 (m), 893 (w), 831 (m), 809 (w), 766 (m), 756 (s), 692 (s), 681 (m), 665 (m), 652 (m), 620 (w), 565 (w), 542 (m), 523 (w), 506 (w), 488 (m), 482 (m), 452 (m). EI-MS: m/z 798 [M + ]. X-ray suitable cuboid-like crystals of 2 were grown by the slow recrystallization of complex from CH 2 Cl 2 solution. 3
Magnetic Measurements by SQUID The magnetic susceptibility of the polycrystalline complexes 1 and 2 was measured with a QuantumDesign MPMSXL SQUID magnetometer in the temperature range of 2 300 K with magnetic field of up to 5 koe. None of complexes exhibited any field dependence of molar magnetization at low temperatures. Diamagnetic corrections were made using the Pascal constants. The effective magnetic moment was calculated as µ eff (T)=[(3k/N A µ 2 B )χt] 1/2 (8χT) 1/2. Single crystal X-ray diffraction The single crystals 1 and 2 suitable for X-ray diffraction were obtained by the slow recrystallization from toluene\hexane (1:1) and dichloromethane respectively. Intensity data for complexes were collected at 100 K on an Bruker D8 Quest for 1 and a Oxford Xcalibur Eos for 2 diffractometers (graphite monochromator, Mo-K α radiation). SADABS 4 for 1 and Scale3 Abspack 5 for 2 were used to perform area-detector scaling and absorption corrections. The intensity data were integrated by SAINT 6 and CrysAlis Pro 5 programs, respectively. The structures were solved by direct methods and were refined on F 2 using all reflections with SHELXTL package. 7 All non-hydrogen atoms were refined anisotropically. The hydrogen atoms were placed in calculated positions and refined in the riding-model. The crystallographic data are given in Table S1. The selected bond lengths and angles are given in Table S2. The structures were deposited in Cambridge Crystallographic Data Centre and received the following CCDC numbers: 1058915 for 1 and 1404515 for 2. This material is available free of charge via the Internet at http://pubs.acs.org. These data can also be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/ retrieving.html or from the Cambridge Crystallographic Data Centre, Union Road, Cambridge CB2 1EZ, U.K. [fax (+44) 1223-336- 033 or e-mail deposit@ccdc.cam.ac.uk]. 4
Table S1. Crystallographic data for complexes 1 and 2. Complex 1 Complex 2 Formula C 33 H 35 CoN 4 O 2 C 47 H 55 CoN 4 O 4 Molecular weight 578.58 798.88 System triclinic triclinic Space group P-1 P-1 a (Å) 9.6090(9) 11.13108(18) b (Å) 10.7936(11) 12.45679(20) c (Å) 14.8816(15) 16.1930(3) α ( ) 99.022(2) 81.2978(13) β ( ) 103.509(2) 80.6453(13) γ ( ) 103.094(2) 73.6151(14) Volume (Å 3 ) 1425.4(2) 2112.22(6) Z 2 2 ρ calcd (g cm -3 ) 1.348 1.256 Absorption coefficient (mm -1 ) 0.639 0.454 Crystal size (mm x mm x mm) 0.38 x 0.09 x 0.05 0.50 x 0.40 x 0.40 Theta range for data collection ( ) 2.572-29.999 3.042-25.997 Measured reflections, all/ independent/r Int 19004/8246/0.0236 30795/8292/0.0260 Absorption correction Semi-empirical from equivalents Semi-empirical from equivalents Data / restraints / parameters 8246 / 0 / 367 8292 / 0 / 517 Goodness-of-fit on F 2 1.066 1.035 R[F 2 >2σ(F 2 )] R 1 =0.0358 wr 2 =0.0881 R 1 =0.0310 wr 2 =0.0823 R[F 2 ] R 1 =0.0443 wr 2 =0.0912 R 1 =0.0362 wr 2 =0.0847 Largest diff. peak and hole (e Å -3 ) 0.897 and -0.417 0.355 and -0.401 5
Table S2. The selected bond lengths for 1 and 2. Complex 1 Complex 2 Co(1)-O(1) Co(1)-O(2) Co(1)-N(1) Co(1)-N(4) C(1)-O(1) C(2)-O(2) N(1)-N(2) C(16)-N(1) C(15)-N(2) N(3)-N(4) C(15)-N(3) C(28)-N(4) C(1)-C(2) C(1)-C(6) C(2)-C(3) C(3)-C(4) C(4)-C(5) C(5)-C(6) C(15)-C(22) O(1)-Co(1)-O(2) N(1)-Co(1)-N(4) N(1)-Co(1)-O(1) N(4)-Co(1)-O(2) N(1)-Co(1)-O(2) N(4)-Co(1)-O(1) Bond length ( ) 1.8742(7) 1.8651(8) 1.8118(9) 1.8085(8) 1.2971(13) 1.2960(12) 1.3118(12) 1.4341(12) 1.3403(13) 1.3093(12) 1.3401(13) 1.4353(12) 1.4421(13) 1.4263(13) 1.4263(15) 1.3719(14) 1.4240(14) 1.3717(15) 1.4812(15) Angle (º) 83.16(3) 90.22(4) 93.37(3) 92.56(4) 171.97(4) 173.37(4) Co(1)-O(1) Co(1)-O(2) Co(1)-O(4) Co(1)-O(3) Co(1)-N(1) Co(1)-N(4) C(1)-O(1) C(2)-O(2) C(15)-O(3) C(16)-O(4) N(1)-N(2) C(29)-N(1) C(35)-N(2) N(3)-N(4) C(35)-N(3) C(42)-N(4) C(1)-C(6) C(1)-C(2) C(2)-C(3) C(3)-C(4) C(4)-C(5) C(5)-C(6) C(15)-C(20) C(15)-C(16) C(16)-C(17) C(17)-C(18) C(18)-C(19) C(19)-C(20) C(35)-C(36) Bond length ( ) 1.8831(10) 1.9105(10) 1.8950(10) 1.9166(10) 1.8983(12) 1.9075(12) 1.3053(17) 1.2915(18) 1.2950(17) 1.3016(17) 1.2884(17) 1.4429(18) 1.3472(18) 1.2873(17) 1.3450(18) 1.4376(18) 1.427(2) 1.4529(19) 1.434(2) 1.367(2) 1.422(2) 1.370(2) 1.437(2) 1.453(2) 1.4350(19) 1.366(2) 1.423(2) 1.365(2) 1.4779(19) O(1)-Co(1)-O(2) O(3)-Co(1)-O(4) N(1)-Co(1)-N(4) N(1)-Co(1)-O(3) O(1)-Co(1)-O(4) O(2)-Co(1)-N(4) Angle (º) 85.40(4) 84.68(4) 85.80(5) 178.18(5) 172.54(4) 174.27(5) 6
Figure S1. The temperature dependences of χ of [Co(SQ)(Form)] (1) (a) and [Co(SQ) 2 (Form)] (2) (b). 7
Figure S2. The temperature dependences of χt for [Co(SQ)(Form)] (1) ( ) and [Co(SQ) 2 (Form)] (2) ( ). 8
Figure S3. EPR spectrum of solid sample of complex 2 at room temperature. 9
References (1) Garnov, V. A.; Nevodchikov, V. I.; Abakumova, L. G.; Abakumov, G. A.; Cherkasov, V. K.; Russ. Chem. Bull. 1987, 36, 1728-1730. (2) Ashley, J. N.; Davis, B. M.; Nineham, A. W.; Slack, R. J. Chem. Soc. 1953, 3881-3888. (3) Perrin, D. D.; Armarego, W. L. F.; Perrin, D. R. Purification of Laboratory Chemicals, Pergamon Press, Oxford, 1980. (4) Sheldrick G. M. (2012) SADABS v.2012/1, Bruker/Siemens Area Detector Absorption Correction Program, Bruker AXS, Madison, Wisconsin, USA. (5) CrysAlisPro - Software Package, Agilent Technologies (2012) (6) Bruker (2012) SAINT Data Reduction and Correction Program v. 8.27B, Bruker AXS, Madison, Wisconsin, USA. (7) Sheldrick G. M. (2003) SHELXTL v. 6.14, Structure Determination Software Suite, Bruker AXS, Madison, Wisconsin, USA. 10