[N (2 Amino­ethyl) N,N bis­(3 amino­propyl)­amine]­di­chlorocobalt(III) chloride, [Co(abap)Cl2]Cl

(1)metal-organic papers Acta Crystallographica Section E. Structure Reports Online. [N-(2-Aminoethyl)-N,N-bis(3-aminopropyl)amine]dichlorocobalt(III) chloride, [Co(abap)Cl2]Cl. ISSN 1600-5368. Rachel L. Fanshawe, Charles R. Clark² and Allan G. Blackman* Department of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand ² Additional correspondence author: clarkc@alkali.otago.ac.nz Correspondence e-mail: blackman@alkali.otago.ac.nz. Key indicators Single-crystal X-ray study T = 173 K Ê Mean (C±C) = 0.004 A R factor = 0.023 wR factor = 0.051 Data-to-parameter ratio = 19.7 For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.. # 2001 International Union of Crystallography Printed in Great Britain ± all rights reserved. Acta Cryst. (2001). E57, m17±m18. Structural analysis of the title compound, [Co(abap)Cl2]Cl, where abap is N-(2-aminoethyl)-N,N-bis(3-aminopropyl)amine (C8H22N4), con®rms that the asymmetric amine ligand is oriented such that the N atoms of the ®ve-membered chelate ring are in the same plane as the chloride ligands.. Received 22 November 2000 Accepted 4 December 2000 Online 14 December 2000. Comment The asymmetric tetraamine ligand abap [abap is N-(2aminoethyl)-N,N-bis(3-aminopropyl)amine] can coordinate to four mututally cis sites of a six-coordinate metal complex in two ways. Coordination such that the N atoms of a sixmembered chelate ring lie in the same plane as the remaining ligand(s) gives the `6' isomer, as found in the structurally characterized complex [Co(abap)O2NO](ClO4)2 (Fanshawe & Blackman, 1995), while the `5' isomer results on coordination of the ligand so that the ®ve-membered chelate ring lies in the same plane as the ancillary ligand(s). The structure of [Co(abap)Cl2]Cl, (I), described herein con®rms assignment of this complex as the `5' isomer.. The structure consists of a CoIII ion coordinated to four N atoms of the abap ligand, with coordination completed by two chloride ligands. A single chloride counter-ion balances the charge. CoÐN bond lengths are typical of CoIII complexes, with the bond to the tertiary N atom of the abap ligand being Ê ]. Similarly lengthened CoÐN the longest [2.030 (2) A (tertiary) bonds have been observed in [Co(abap)(NO2)2]X (X = Clÿ, ClO4ÿH2O, PF6ÿH2O, IÿH2O), all of which crystallize as the `5' isomer (Bernal et al., 1996). The six-membered chelate rings adopt chair conformations, while the conformation of the ®ve-membered ring is . The bond angles involving the primary N atoms of the six-membered chelate rings (C5Ð N12ÐCo1 and C8ÐN13ÐCo1) are 122.10 (16) and 121.92 (15) , respectively. The expansion of these angles, when compared to the corresponding angle in the ®ve-membered chelate ring [C1ÐN11ÐCo1 109.89 (15) ] presumably re¯ects the inherently greater strain present in a six-membered ring having one angle signi®cantly larger than 90 . DOI: 101107/S1600536800019656. Rachel L. Fanshawe et al.. . [CoCl2(C8H22N4)]Cl. m17.

(2) metal-organic papers Re®nement w = 1/[ 2(Fo2) + (0.0258P)2 + 0.2974P] where P = (Fo2 + 2Fc2)/3 (/)max = 0.001 Ê ÿ3 max = 0.25 e A Ê ÿ3 min = ÿ0.18 e A Absolute structure: Flack (1983); 1110 Friedel pairs Flack parameter = 0.004 (13). Re®nement on F 2 R[F 2 > 2(F 2)] = 0.023 wR(F 2) = 0.051 S = 1.05 2850 re¯ections 145 parameters H-atom parameters constrained. Table 1. Ê ,  ). Selected geometric parameters (A. Figure 1. Co1ÐN11 Co1ÐN13 Co1ÐN12 Co1ÐN14 Co1ÐCl2 Co1ÐCl1 N11ÐC1 N12ÐC5 N13ÐC8. 1.9528 (19) 1.9728 (19) 1.982 (2) 2.030 (2) 2.2510 (6) 2.2835 (8) 1.481 (3) 1.487 (3) 1.482 (3). N14ÐC2 N14ÐC3 N14ÐC6 C1ÐC2 C3ÐC4 C4ÐC5 C6ÐC7 C7ÐC8. 1.508 (3) 1.516 (3) 1.518 (3) 1.501 (3) 1.520 (3) 1.505 (4) 1.510 (3) 1.510 (3). N11ÐCo1ÐN13 N11ÐCo1ÐN12 N13ÐCo1ÐN12 N11ÐCo1ÐN14 N13ÐCo1ÐN14 N12ÐCo1ÐN14 N11ÐCo1ÐCl2 N13ÐCo1ÐCl2 N12ÐCo1ÐCl2. 88.88 (8) 92.78 (8) 169.68 (9) 86.23 (8) 96.15 (8) 94.13 (8) 178.09 (6) 89.32 (6) 89.11 (6). N14ÐCo1ÐCl2 N11ÐCo1ÐCl1 N13ÐCo1ÐCl1 N12ÐCo1ÐCl1 N14ÐCo1ÐCl1 Cl2ÐCo1ÐCl1 C1ÐN11ÐCo1 C5ÐN12ÐCo1 C8ÐN13ÐCo1. 93.33 (6) 87.85 (6) 85.17 (6) 84.71 (6) 173.90 (6) 92.64 (3) 109.89 (15) 122.10 (16) 121.92 (15). The cation of (I) with displacement ellipsoids at the 50% probability level.. Experimental [Co(abap)(O2NO)](ClO4)2 (1.0 g) was dissolved in water and loaded onto a Dowex 50 W  2 cation-exchange column. The column was washed with water and 1 M HCl before the complex was eluted with 2 M HCl. The purple eluate was collected and taken to dryness by rotary evaporation to give a blue solid which was crystallized from dilute HCl. X-ray quality crystals were obtained on slow evaporation of a concentrated solution of the product in 5 M HCl. Crystal data [CoCl2(C8H22N4)]Cl Mr = 339.58 Orthorhombic, P212121 Ê a = 8.405 (2) A Ê b = 10.2633 (14) A Ê c = 15.9652 (15) A Ê3 V = 1377.2 (5) A Z=4 Dx = 1.638 Mg mÿ3. Mo K radiation Cell parameters from 16 re¯ections  = 5±12.5  = 1.81 mmÿ1 T = 173 (2) K Block, blue 0.42  0.20  0.18 mm. Data collection Rint = 0.017 max = 27 h = ÿ10 ! 8 k = 0 ! 13 l = 0 ! 20 3 standard re¯ections every 997 re¯ections intensity decay: <2%. Siemens P4 diffractometer ! scans Absorption correction: scan (SHELXTL-Plus; Sheldrick, 1990) Tmin = 0.662, Tmax = 0.772 3058 measured re¯ections 2850 independent re¯ections 2717 re¯ections with I > 2(I). m18. Rachel L. Fanshawe et al.. . [CoCl2(C8H22N4)]Cl. Data collection: XSCANS (Siemens, 1991); cell re®nement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: WinGX (Farrugia, 1999); software used to prepare material for publication: WinGX.. We thank Professor W. T. Robinson (University of Canterbury) for the data collection. This work is supported by a University of Otago Division of Sciences Research Grant.. References Bernal, I. & Xubin, X. & Somoza, F. (1996). Fundamental Principles of Molecular Modeling, edited by W. Gans, A. Amann & J. C. A. Boeyens, pp. 223±244. New York: Plenum. Fanshawe, R. L. & Blackman, A. G. (1995). Inorg. Chem. 34, 421±423. Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837±838. Flack, H. D. (1983). Acta Cryst. A39, 876±881. Sheldrick, G. M. (1990). SHELXTL-Plus. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany. Siemens (1991). XSCANS User's Manual. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.. Acta Cryst. (2001). E57, m17±m18.

(3) supporting information. supporting information Acta Cryst. (2001). E57, m17–m18. [doi:10.1107/S1600536800019656]. [N-(2-Aminoethyl)-N,N-bis(3-aminopropyl)amine]dichlorocobalt(III) chloride, [Co(abap)Cl2]Cl Rachel L. Fanshawe, Charles R. Clark and Allan G. Blackman S1. Comment The asymmetric tetraamine ligand abap {abap is N-(2-aminoethyl)-N,N-bis(3-aminopropyl)amine} can coordinate to four mututally cis sites of a six-coordinate metal complex in two ways. Coordination such that the N atoms of a six-membered chelate ring lie in the same plane as the remaining ligand(s) gives the `6′ isomer, as found in the structurally characterized complex [Co(abap)O2NO](ClO4)2 (Fanshawe & Blackman, 1995), while the `5′ isomer results on coordination of the ligand so that the five-membered chelate ring lies in the same plane as the ancillary ligand(s). The structure of [Co(abap)Cl2]Cl described herein confirms assignment of this complex as the `5′ isomer. The structure consists of a CoIII ion coordinated to four N atoms of the abap ligand, with coordination completed by two chloride ligands. A single chloride counter-ion balances the charge. Co—N bond lengths are typical of CoIII complexes, with the bond to the tertiary N atom of the abap ligand being the longest [2.030 (2) Å]. Similarly lengthened Co—N (tertiary) bonds have been observed in [Co(abap)(NO2)2]X (X = Cl-, ClO4-·H2O, PF6-·H2O, I-·H2O), all of which crystallize as the `5′ isomer (Bernal et al., 1996). The six-membered chelate rings adopt chair conformations, while the conformation of the five-membered ring is λ. The bond angles involving the primary N atoms of the six-membered chelate rings (C5—N12—Co1 and C8—N13— Co1) are 122.10 (16) and 121.92 (15)°, respectively. The expansion of these angles, when compared to the corresponding angle in the five-membered chelate ring [C1—N11—Co1 109.89 (15)°] presumably reflects the inherently greater strain present in a six-membered ring having one angle significantly larger than 90°. S2. Experimental [Co(abap)(O2NO)](ClO4)2 (1.0 g) was dissolved in water and loaded onto a Dowex 50 W x 2 cation-exchange column. The column was washed with water and 1 M HCl before the complex was eluted with 2 M HCl. The purple eluate was collected and taken to dryness by rotary evaporation to give a blue solid which was crystallized from dilute HCl. X-ray quality crystals were obtained on slow evaporation of a concentrated solution of the product in 5 M HCl.. Acta Cryst. (2001). E57, m17–m18. sup-1.

(4) supporting information. Figure 1 The cation of (I) with displacement ellipsoids at the 50% probability level. [N-(2-Aminoethyl)-N,N-bis(3-aminopropyl)amine]dichlorocobalt(III) chloride Crystal data [CoCl2(C8H22N4)]Cl Mr = 339.58 Orthorhombic, P212121 a = 8.405 (2) Å b = 10.2633 (14) Å c = 15.9652 (15) Å V = 1377.2 (5) Å3 Z=4 F(000) = 704. Acta Cryst. (2001). E57, m17–m18. Dx = 1.638 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 16 reflections θ = 5–12.5° µ = 1.81 mm−1 T = 173 K Block, blue 0.42 × 0.20 × 0.18 mm. sup-2.

(5) supporting information Data collection Siemens P4 diffractometer Radiation source: fine-focus sealed tube Graphite monochromator ω scans Absorption correction: ψ scan (SHELXTL-Plus; Sheldrick, 1990) Tmin = 0.662, Tmax = 0.772 3058 measured reflections. 2850 independent reflections 2717 reflections with I > 2σ(I) Rint = 0.017 θmax = 27.0°, θmin = 2.4° h = −10→8 k = 0→13 l = 0→20 3 standard reflections every 997 reflections intensity decay: <2%. Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.023 wR(F2) = 0.051 S = 1.05 2850 reflections 145 parameters 0 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map. Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ2(Fo2) + (0.0258P)2 + 0.2974P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.001 Δρmax = 0.25 e Å−3 Δρmin = −0.18 e Å−3 Absolute structure: Flack (1983); 1110 Friedel pairs Absolute structure parameter: 0.004 (13). Special details Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2). Co1 Cl1 Cl2 Cl3 N11 H11A H11B N12 H12A H12B N13 H13A H13B N14. x. y. z. Uiso*/Ueq. 0.83241 (3) 1.07387 (7) 0.75209 (7) 1.18810 (7) 0.9031 (2) 0.8943 1.0083 0.7618 (2) 0.8282 0.7811 0.9374 (2) 0.9886 1.0153 0.6235 (2). 0.94312 (3) 1.00598 (6) 0.86582 (5) 0.81084 (6) 1.0042 (2) 1.0934 0.9825 1.11931 (19) 1.1453 1.1741 0.77486 (18) 0.7831 0.7648 0.89841 (18). 0.904417 (19) 0.95605 (4) 1.02940 (3) 0.72166 (4) 0.79472 (11) 0.7920 0.7869 0.93904 (12) 0.9817 0.8946 0.88178 (12) 0.8311 0.9217 0.84746 (12). 0.01263 (7) 0.02292 (13) 0.01936 (12) 0.02283 (13) 0.0174 (4) 0.021* 0.021* 0.0185 (4) 0.022* 0.022* 0.0152 (4) 0.018* 0.018* 0.0147 (4). Acta Cryst. (2001). E57, m17–m18. sup-3.

(6) supporting information C1 H1A H1B C2 H2A H2B C3 H3A H3B C4 H4A H4B C5 H5A H5B C6 H6A H6B C7 H7A H7B C8 H8A H8B. 0.8049 (3) 0.8399 0.8150 0.6358 (3) 0.5700 0.5937 0.4762 (3) 0.4558 0.3847 0.4800 (3) 0.5085 0.3723 0.5963 (3) 0.5838 0.5745 0.5835 (3) 0.5558 0.4868 0.7082 (3) 0.6595 0.7469 0.8472 (3) 0.8078 0.9191. 0.9440 (3) 0.8533 0.9940 0.9459 (3) 0.8898 1.0359 0.9593 (2) 0.9161 0.9397 1.1056 (2) 1.1498 1.1353 1.1457 (2) 1.2398 1.0966 0.7542 (2) 0.7308 0.7410 0.6590 (2) 0.5717 0.6865 0.6508 (2) 0.6296 0.5797. 0.72812 (14) 0.7177 0.6753 0.75831 (14) 0.7217 0.7547 0.88573 (15) 0.9401 0.8488 0.90051 (19) 0.8475 0.9167 0.96740 (17) 0.9795 1.0195 0.84920 (16) 0.9076 0.8149 0.81917 (16) 0.8132 0.7633 0.87878 (14) 0.9356 0.8608. 0.0215 (5) 0.026* 0.026* 0.0202 (5) 0.024* 0.024* 0.0198 (5) 0.024* 0.024* 0.0254 (5) 0.030* 0.030* 0.0237 (5) 0.028* 0.028* 0.0191 (5) 0.023* 0.023* 0.0214 (5) 0.026* 0.026* 0.0184 (5) 0.022* 0.022*. Atomic displacement parameters (Å2). Co1 Cl1 Cl2 Cl3 N11 N12 N13 N14 C1 C2 C3 C4 C5 C6 C7 C8. U11. U22. U33. U12. U13. U23. 0.01138 (14) 0.0152 (3) 0.0207 (3) 0.0222 (3) 0.0158 (10) 0.0176 (10) 0.0121 (10) 0.0134 (10) 0.0238 (13) 0.0197 (12) 0.0108 (11) 0.0167 (12) 0.0221 (13) 0.0155 (12) 0.0196 (13) 0.0183 (12). 0.01210 (13) 0.0213 (3) 0.0223 (3) 0.0175 (3) 0.0170 (9) 0.0156 (9) 0.0157 (9) 0.0146 (9) 0.0249 (11) 0.0248 (12) 0.0207 (13) 0.0221 (12) 0.0178 (11) 0.0153 (11) 0.0173 (11) 0.0130 (10). 0.01442 (13) 0.0322 (3) 0.0151 (2) 0.0288 (3) 0.0194 (10) 0.0222 (10) 0.0178 (10) 0.0162 (9) 0.0157 (10) 0.0160 (10) 0.0281 (13) 0.0374 (14) 0.0312 (13) 0.0265 (13) 0.0273 (13) 0.0238 (11). −0.00034 (13) −0.0019 (2) −0.0005 (2) −0.0001 (2) 0.0016 (9) −0.0009 (9) 0.0004 (8) 0.0011 (7) 0.0028 (11) 0.0032 (11) 0.0024 (10) 0.0068 (10) 0.0056 (10) −0.0042 (10) −0.0002 (10) 0.0008 (10). 0.00047 (12) −0.0044 (2) 0.0019 (2) 0.0054 (3) 0.0026 (8) 0.0009 (9) −0.0014 (8) 0.0005 (7) −0.0006 (9) −0.0044 (9) 0.0038 (9) 0.0017 (12) 0.0070 (11) −0.0031 (10) −0.0050 (10) −0.0017 (10). −0.00006 (12) −0.0048 (3) 0.0012 (2) −0.0045 (2) 0.0020 (8) −0.0027 (8) 0.0002 (7) 0.0013 (7) 0.0038 (11) 0.0041 (10) −0.0024 (10) −0.0036 (12) −0.0060 (11) −0.0012 (10) −0.0046 (10) 0.0010 (9). Acta Cryst. (2001). E57, m17–m18. sup-4.

(7) supporting information Geometric parameters (Å, º) Co1—N11 Co1—N13 Co1—N12 Co1—N14 Co1—Cl2 Co1—Cl1 N11—C1 N12—C5 N13—C8. 1.9528 (19) 1.9728 (19) 1.982 (2) 2.030 (2) 2.2510 (6) 2.2835 (8) 1.481 (3) 1.487 (3) 1.482 (3). N14—C2 N14—C3 N14—C6 C1—C2 C3—C4 C4—C5 C6—C7 C7—C8. 1.508 (3) 1.516 (3) 1.518 (3) 1.501 (3) 1.520 (3) 1.505 (4) 1.510 (3) 1.510 (3). N11—Co1—N13 N11—Co1—N12 N13—Co1—N12 N11—Co1—N14 N13—Co1—N14 N12—Co1—N14 N11—Co1—Cl2 N13—Co1—Cl2 N12—Co1—Cl2 N14—Co1—Cl2 N11—Co1—Cl1 N13—Co1—Cl1 N12—Co1—Cl1 N14—Co1—Cl1 Cl2—Co1—Cl1 C1—N11—Co1. 88.88 (8) 92.78 (8) 169.68 (9) 86.23 (8) 96.15 (8) 94.13 (8) 178.09 (6) 89.32 (6) 89.11 (6) 93.33 (6) 87.85 (6) 85.17 (6) 84.71 (6) 173.90 (6) 92.64 (3) 109.89 (15). C5—N12—Co1 C8—N13—Co1 C2—N14—C3 C2—N14—C6 C3—N14—C6 C2—N14—Co1 C3—N14—Co1 C6—N14—Co1 N11—C1—C2 C1—C2—N14 N14—C3—C4 C5—C4—C3 N12—C5—C4 C7—C6—N14 C8—C7—C6 N13—C8—C7. 122.10 (16) 121.92 (15) 107.63 (18) 110.35 (19) 102.35 (17) 106.89 (14) 115.65 (14) 113.81 (14) 106.97 (19) 111.31 (19) 116.9 (2) 113.2 (2) 110.0 (2) 118.1 (2) 111.9 (2) 111.61 (18). Acta Cryst. (2001). E57, m17–m18. sup-5.

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