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ISSN: 2056-9890
Volume 70| Part 10| October 2014| Pages 242-245

Crystal structure of nitrido[5,10,15,20-tetra­kis(4-methylphenyl)­porphyrinato]­manganese(V)

aDepartment of Chemistry, Geoscience, and Physics, 1000 Edgewood College Drive, Edgewood College, Madison, WI 53711, USA, and bDepartment of Chemistry, University of Wisconsin-Madison, 1101 University Ave, Madison, WI 53706, USA
*Correspondence e-mail: iguzei@chem.wisc.edu

Edited by M. Zeller, Youngstown State University, USA (Received 29 July 2014; accepted 13 September 2014; online 24 September 2014)

The title compound, [Mn(C48H36N4)(N)], is a manganese(V) complex with the transition metal in a square-pyramidal coordination geometry and a nitride as the axial ligand. The complex resides on a crystallographic inversion center and only one half of it is symmetry independent. The MnV atom and the nitride N atom are equally disordered across the inversion center. The Mn≡N distance is 1.516 (4) Å. The MnV atom is displaced from the plane defined by the four equatorial nitro­gen atoms toward the nitride ligand by 0.3162 (6) Å.

1. Chemical context

Tetra­pyrrole ligands have been used as a supporting ligand to stabilize high-valent, manganese compounds with manganese in 5-coordination and nitride ligands with short Mn≡N bond lengths. These complexes are characterized by Mn≡N distances of approximately 1.5 Å and the central metal displaced from the plane of the four equatorial N atoms toward the nitride ligand by up to 0.55 Å. In the course of our studies of Mn complexes we prepared and isolated the title complex, 5,10,15,20-tetra­kis-tetra­tolyl­porphyrinato­nitrido­manganese(V) (I)[link], and con­duc­ted its structural characterization to investigate how its geometry compares to that of its congeners.

[Scheme 1]

We have found five examples of five-coordinate nitride Mn complexes deposited with the Cambridge Structural Database (CSD; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]): (tetra­kis-tetra-4-meth­oxy­phen­yl)porphyrinato­nitrido­manganese(V) (II) (Hill & Hollander, 1982[Hill, C. L. & Hollander, F. J. (1982). J. Am. Chem. Soc. 104, 7318-7319.]), (5,15-dimethyl-2,3,7,8,12,13,17,18-octa­ethyl-5H,15H-porphinato)nitridomanganese(V) (III) (Buchler et al., 1983[Buchler, J. W., Dreher, C., Lay, K.-L., Lee, Y. J. A. & Scheidt, W. R. (1983). Inorg. Chem. 22, 888-891.]),(5,10,15-tris­(penta­fluoro­phen­yl)corrole)(mesityl­imido)manganese(V) toluene solvate (IV) (Eikey et al., 2002[Eikey, R. A., Khan, S. I. & Abu-Omar, M. M. (2002). Angew. Chem. Int. Ed. 41, 3592-3593.]), (2,3,7,8,12,13,17,18-octa­kis­(4-t-butyl­phen­yl)corrolazinato)-(mesitylimido)-manganese(V) di­chloro­methane solvate (V) (Lansky et al., 2006[Lansky, D. E., Kosack, J. R., Sarjeant, A. A. & Goldberg, D. P. (2006). Inorg. Chem. 45, 8477-8479.]), and nitrido-(6,11,17-tris­(4-nitro­phen­yl)-16,21,22,23,24-pentaaza­penta­cyclo­[16.2.1.12,5.17,10.112,15]tetra­cosa-1,3,5,7,9,11,13,15,17,19-deca­enato)manganese(V) di­chloro­methane solv­ate, (VI) (Singh et al., 2013[Singh, P., Dutta, G., Goldberg, I., Mahammed, A. & Gross, Z. (2013). Inorg. Chem. 52, 9349-9355.]). Herein we report the comparison of key structural parameters of (I)[link] to those of (II)–(VI).

2. Structural commentary

In the crystal structure of the title complex (I)[link] (Fig. 1[link]), the central MnV atom possesses a square-pyramidal geometry. The equatorial plane is formed by the four nitro­gen atoms of the porphyrin whereas the apical position is occupied by the nitride ligand. The complex resides on a crystallographic inversion center and only one half of it is symmetry independent. The Mn1 atom and nitride ligand atom N1 are equally disordered over two positions. This crystallographic behavior (disorder about an inversion center) was also observed in the case of (II). Whereas both complexes exhibit inversion symmetry, the Mn—N distances in them are not equal pairwise (as one would expect based on the fact that only one half of the complex is unique) because the MnV atom is displaced from the equatorial plane not perpendicularly to it but at a small angle. Thus, the Mn—N distances in (I)[link] range from 1.958 (2) to 2.070 (2) Å and between 1.983 (2) and 2.060 (2) Å in (II). The selected geometrical parameters for (I)–(VI) are presented in Table 1[link]. A somewhat counter-intuitive trend correlates the average Mn—N(eq) distance and the displacement of the Mn from the equatorial plane: the shorter the Mn—N(eq) distance, the larger the displacement. The correlation between the Mn—N(eq) distances and Mn≡N distance is not consistent, but in general the shorter the Mn—N(eq) distances, the longer the Mn≡N bond length, as might be expected. We have also conducted a CSD search for MnV complexes with manganese in six-coordination and with a nitride ligand and found seven relevant compounds, but none of them was a porphyrin or a porphyrin derivative. The intention was to determine whether the expected metal–ligand bond lengthening occurs as the metal coordination number increases. It was found that for the five-coordinate (I)–(VI) the average Mn≡N distance is 1.54 (5) Å, whereas for the seven six-coordinate complexes this distance is 1.527 (10) Å. Thus, the difference in the nature of the ligands (porphyrin vs tetra-aza­cyclo-tetra­deca­ne) accounts for the prediction `reversal'.

Table 1
Selected metric parameters for (I)–(VI) (Å)

Compound Mn≡N Mn—N(eq, av) Mn—N4 displacement
(I) 1.516 (4) 2.02 (5) 0.3162 (6)
(II) 1.512 (2) 2.02 (3) 0.388
(III) 1.512 2.006 (3) 0.426
(IV) 1.613 1.92 (2) 0.513
(V) 1.595 1.893 (10) 0.550
(VI) 1.512 1.99 (3) 0.460
[Figure 1]
Figure 1
A mol­ecular drawing of (I)[link] shown with displacement parameters at the 50% probability level. All H atoms and the disordered mates of atoms Mn1 and N1 are omitted. [Symmetry operator (1): −x + 1, −y + 1, −z.]

3. Supra­molecular features

Whereas there are possible weak non-classical inter­actions such as C—H⋯π and C—H⋯N(nitride) (Table 2[link]), no ππ stacking inter­actions are detected. The mol­ecules pack forming porphyrin/tolyl layers along the [100] direction with a 14.2619 (10) Å separation between identical layers (Fig. 2[link]). The dihedral angle between the adjacent porphyrin core planes within the same layer is 30.037 (4)°.

Table 2
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the N3/C13–C16 and C6–C11 rings, respectively.

D—H⋯A D—H H⋯A DA D—H⋯A
C10—H10⋯N1i 0.95 2.42 3.203 (5) 140
C11—H11⋯Cg1ii 0.95 2.77 3.332 (3) 119
C19—H19⋯Cg2iii 0.95 2.68 3.619 (3) 170
Symmetry codes: (i) [x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]; (ii) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iii) [-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}].
[Figure 2]
Figure 2
A packing diagram of (I) shown along the [001] direction. All H atoms are omitted.

4. Synthesis and crystallization

The title compound, 5,10,15,20-tetra­kis-tetra­tolyl­porphyrin­ato­nitridomanganese(V), was prepared according to the procedure developed by Buchler et al. (1982[Buchler, J. W., Dreher, C. & Lay, K. Z. Z. (1982). Z. Naturforsch. Teil B, 39, 1155-1162.]). (TTP)Mn(C2H3O2) where TTP is the dianion of meso-tetratolylporphyrin (2.08 g, 2.65 mmol) was dissolved in methanol and eluted down an alumina column with methanol. The methanol was removed and the product redissolved in 400 ml di­chloro­methane. This solution was treated with 12 ml of an ammonia solution made by diluting 2 ml of concentrated ammonia with 10 ml of water and allowed to stir for fifteen minutes. A 10% sodium hypochlorite solution (6 ml) was added and the reaction was stirred an additional 15 minutes, resulting in a red solution. The solution was then washed with two 100 ml portions of water to remove the excess ammonia and hypochlorite and the sodium chloride formed during the reaction. The filtrate was placed on a neutral alumina column and the product was eluted with di­chloro­methane. Unreacted manganese(III) porphyrin can be recovered by eluting with methanol. The product was dried under reduced pressure. UV–vis (λmax 535, 421 nm) are in excellent agreement with those obtained by Buchler et al. (1982[Buchler, J. W., Dreher, C. & Lay, K. Z. Z. (1982). Z. Naturforsch. Teil B, 39, 1155-1162.]) (536 and 421 nm). The NMR spectrum (Anasazi 60 MHz FT–NMR: 1H NMR (296 K, CDCl3, p.p.m.) 8.94 (s, 8H), 8.03 (d, 8H), 7.53 (d 8H), 2.68 (s, 12H)) matches the literature data as well. A yield of 1.82 g, 93% based on (TTP)Mn(C2H3O2) was obtained. (TTP)Mn≡N used to grow the crystal for the structural determination was purified by taking a di­chloro­methane solution and eluting through neutral alumina column with di­chloro­methane.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. All hydrogen atoms were included in the structure-factor calculation at idealized positions and were allowed to ride on the neighboring atoms with relative isotropic displacement coefficients.

Table 3
Experimental details

Crystal data
Chemical formula [Mn(C48H36N4)(N)]
Mr 737.76
Crystal system, space group Monoclinic, P21/c
Temperature (K) 100
a, b, c (Å) 14.2619 (10), 8.6200 (11), 15.4685 (18)
β (°) 94.188 (7)
V3) 1896.6 (4)
Z 2
Radiation type Cu Kα
μ (mm−1) 3.14
Crystal size (mm) 0.17 × 0.11 × 0.03
 
Data collection
Diffractometer Bruker SMART APEX2 area detector
Absorption correction Multi-scan (SADABS; Bruker, 2012[Bruker (2012). SADABS. Bruker-AXS, Madison, Wisconsin, USA.])
Tmin, Tmax 0.529, 0.662
No. of measured, independent and observed [I > 2σ(I)] reflections 30677, 3602, 3184
Rint 0.050
(sin θ/λ)max−1) 0.610
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.131, 1.03
No. of reflections 3602
No. of parameters 255
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.33, −0.38
Computer programs: APEX2 and SAINT-Plus (Bruker, 2014[Bruker (2014). APEX2 and SAINT-Plus, Bruker AXS, Madison, Wisconsin, USA.]), SHELXT and SHELXL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]), publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]) and GX (Guzei, 2013[Guzei, I. A. (2013). In-house Crystallographic Program GX. Molecular Structure Laboratory, University of Wisconsin-Madison, Madison, WI, USA.]).

Supporting information


Chemical context top

Tetra­pyrrole ligands have been used as a supporting ligand to stabilize high-valent, five-coordinate manganese nitride compounds with short MnN bond lengths. These complexes are characterized by MnN distances of approximately 1.5 Å and the central metal being displaced from the plane of the four equatorial N atoms toward the nitride ligand by up to 0.55 Å. In the course of our studies of Mn complexes we prepared and isolated the title complex, 5,10,15,20-tetra­kis-tetra­tolyl­porphyrinatonitridomanganese(V), (I), and conducted its structural characterization to investigate how its geometry compares to that of its congeners. We have found five examples of five-coordinate nitride Mn complexes reported to the Cambridge Structural Database (Allen, 2002): (tetra­kis-tetra-4-meth­oxy­phenyl)­porphyrinatonitridomanganese(V) (II) (Hill et al., 1982),

(5,15-di­methyl-2,3,7,8,12,13,17,18-o­cta­ethyl-5H,15H-porphinato)nitridomanganese(V) (III) (Buchler et al., 1983),

(5,10,15-tris­(penta­fluoro­phenyl)­corrole)(mesitylimido)manganese(V) toluene solvate (IV) (Eikey et al., 2002), (2,3,7,8,12,13,17,18-o­cta­kis(4-t-butyl­phenyl)­corrolazinato)-(mesitylimido)-manganese(v) di­chloro­methane solvate (V) (Lansky et al., 2006), and nitrido-(6,11,17-tris­(4-nitro­phenyl)-16,21,22,23,24-penta­aza­penta­cyclo­[16.2.1.12,5.17,10.112,15]tetra­cosa-1,3,5,7,9,11,13,15,17,19-decaenato)manganese di­chloro­methane solvate, (VI) (Singh et al., 2013). Herein we report the comparison of key structural parameters of (I) to those of (II)-(-VI).

Structural commentary top

In the crystal structure of the title five-coordinate complex (I) (Fig. 1), the central Mn atom possesses a square pyramidal geometry. The equatorial plane is formed by the four nitro­gen atoms of the porphyrin whereas the apical position is occupied by the nitride ligand. The complex resides on a crystallographic inversion center and only one half of it is symmetry independent. The Mn1 atom and nitride ligand atom N1 are equally disordered over two positions. This crystallographic behavior (disorder about an inversion center) was also observed in the case of (II). Whereas both complexes exhibit inversion symmetry, the Mn—N distances in them are not equal pairwise (as one would expect based on the fact that only one half of the complex is unique) because the Mn atom is displaced from the equatorial plane not perpendicularly to it but at a small angle. Thus, the Mn—N distances in (I) range from 1.958 (2) to 2.070 (2) Å and between 1.983 (2) and 2.060 (2) Å in (II). The selected geometrical parameters for (I)–(VI) are presented in Table 1. A somewhat counter-intuitive trend correlates the average Mn—N(eq) distance and the displacement of the Mn from the equatorial plane: the shorter the Mn—N(eq) distance, the larger the displacement. The correlation between the Mn—N(eq) distances and MnN distance is not consistent, but in general the shorter the Mn—N(eq) distances, the longer the MnN bond length, as might be expected. We have also conducted a CSD search for six-coordinate Mn complexes with a nitride ligand and found seven relevant compounds, but none of them was a porphyrin or a porphyrin derivative. The intention was to determine whether the expected metal–ligand bond lengthening occurs as the metal coordination number increases. It was found that for the five-coordinate (I)–(VI) the average MnN distance is 1.54 (5) Å, whereas for the seven six-coordinate complexes this distance is 1.527 (10) Å. Thus, the difference in the nature of the ligands (porphyrin vs tetra-aza­cyclo-tetra­decane) accounts for the prediction `reversal'.

Supra­molecular features top

Whereas there are possible weak non-classical inter­actions such as C—H···π and C—H···N(nitride), no ππ stacking inter­actions are detected. The molecules pack forming porphyrin/tolyl layers along the [100] direction with a 14.2619 (10) Å separation between identical layers (Fig. 2). The dihedral angle between the adjacent porphyrin core planes within the same layer is 30.037 (4)°.

Synthesis and crystallization top

The title compound, 5,10,15,20-tetra­kis-tetra­tolyl­porphyrinatonitridomanganese(V), was prepared according to the procedure developed by Buchler et al. (1982). (TTP)Mn—C2H3O2 (2.08 g, 2.65 mmol) was dissolved in methanol and eluted down an alumina column with methanol. The methanol was removed and the product redissolved in 400 ml di­chloro­methane. This solution was treated with 12 ml of an ammonia solution made by diluting 2 ml of concentrated ammonia with 10 ml of water and allowed to stir for fifteen minutes. A 10% sodium hypochlorite solution (6 ml) was added and the reaction was stirred an additional 15 minutes, resulting in a red solution. The solution was then washed with two 100 ml portions of water to remove the excess ammonia and hypochlorite and the sodium chloride formed during the reaction. The filtrate was placed on a neutral alumina column and the product was eluted with di­chloro­methane. Unreacted manganese(III) porphyrin can be recovered by eluting with methanol. The product was dried under reduced pressure. UV–vis (λmax 535, 421 nm) are in excellent agreement with those obtained by Buchler et al. (1982) (536 and 421 nm). The NMR spectrum (Anasazi 60 MHz FT–NMR: 1H NMR (296 K, CDCl3, p.p.m.) 8.94 (s, 8H), 8.03 (d, 8H), 7.53 (d 8H), 2.68 (s, 12H)) matches the literature data as well. A yield of 1.82 g, 93% based on (TTP)Mn- C2H3O2 was obtained. (TTP)MnN used to grow the crystal for the structural determination was purified by taking a di­chloro­methane solution and eluting through neutral alumina column with di­chloro­methane.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms were included in the structure factor calculation at idealized positions and were allowed to ride on the neighboring atoms with relative isotropic displacement coefficients.

Related literature top

For related literature, see: Allen (2002); Buchler et al. (1982, 1983); Dolomanov et al. (2009); Eikey et al. (2002); Hill & Hollander (1982); Lansky et al. (2006); Sheldrick (2008); Singh et al. (2013).

Structure description top

Tetra­pyrrole ligands have been used as a supporting ligand to stabilize high-valent, five-coordinate manganese nitride compounds with short MnN bond lengths. These complexes are characterized by MnN distances of approximately 1.5 Å and the central metal being displaced from the plane of the four equatorial N atoms toward the nitride ligand by up to 0.55 Å. In the course of our studies of Mn complexes we prepared and isolated the title complex, 5,10,15,20-tetra­kis-tetra­tolyl­porphyrinatonitridomanganese(V), (I), and conducted its structural characterization to investigate how its geometry compares to that of its congeners. We have found five examples of five-coordinate nitride Mn complexes reported to the Cambridge Structural Database (Allen, 2002): (tetra­kis-tetra-4-meth­oxy­phenyl)­porphyrinatonitridomanganese(V) (II) (Hill et al., 1982),

(5,15-di­methyl-2,3,7,8,12,13,17,18-o­cta­ethyl-5H,15H-porphinato)nitridomanganese(V) (III) (Buchler et al., 1983),

(5,10,15-tris­(penta­fluoro­phenyl)­corrole)(mesitylimido)manganese(V) toluene solvate (IV) (Eikey et al., 2002), (2,3,7,8,12,13,17,18-o­cta­kis(4-t-butyl­phenyl)­corrolazinato)-(mesitylimido)-manganese(v) di­chloro­methane solvate (V) (Lansky et al., 2006), and nitrido-(6,11,17-tris­(4-nitro­phenyl)-16,21,22,23,24-penta­aza­penta­cyclo­[16.2.1.12,5.17,10.112,15]tetra­cosa-1,3,5,7,9,11,13,15,17,19-decaenato)manganese di­chloro­methane solvate, (VI) (Singh et al., 2013). Herein we report the comparison of key structural parameters of (I) to those of (II)-(-VI).

In the crystal structure of the title five-coordinate complex (I) (Fig. 1), the central Mn atom possesses a square pyramidal geometry. The equatorial plane is formed by the four nitro­gen atoms of the porphyrin whereas the apical position is occupied by the nitride ligand. The complex resides on a crystallographic inversion center and only one half of it is symmetry independent. The Mn1 atom and nitride ligand atom N1 are equally disordered over two positions. This crystallographic behavior (disorder about an inversion center) was also observed in the case of (II). Whereas both complexes exhibit inversion symmetry, the Mn—N distances in them are not equal pairwise (as one would expect based on the fact that only one half of the complex is unique) because the Mn atom is displaced from the equatorial plane not perpendicularly to it but at a small angle. Thus, the Mn—N distances in (I) range from 1.958 (2) to 2.070 (2) Å and between 1.983 (2) and 2.060 (2) Å in (II). The selected geometrical parameters for (I)–(VI) are presented in Table 1. A somewhat counter-intuitive trend correlates the average Mn—N(eq) distance and the displacement of the Mn from the equatorial plane: the shorter the Mn—N(eq) distance, the larger the displacement. The correlation between the Mn—N(eq) distances and MnN distance is not consistent, but in general the shorter the Mn—N(eq) distances, the longer the MnN bond length, as might be expected. We have also conducted a CSD search for six-coordinate Mn complexes with a nitride ligand and found seven relevant compounds, but none of them was a porphyrin or a porphyrin derivative. The intention was to determine whether the expected metal–ligand bond lengthening occurs as the metal coordination number increases. It was found that for the five-coordinate (I)–(VI) the average MnN distance is 1.54 (5) Å, whereas for the seven six-coordinate complexes this distance is 1.527 (10) Å. Thus, the difference in the nature of the ligands (porphyrin vs tetra-aza­cyclo-tetra­decane) accounts for the prediction `reversal'.

Whereas there are possible weak non-classical inter­actions such as C—H···π and C—H···N(nitride), no ππ stacking inter­actions are detected. The molecules pack forming porphyrin/tolyl layers along the [100] direction with a 14.2619 (10) Å separation between identical layers (Fig. 2). The dihedral angle between the adjacent porphyrin core planes within the same layer is 30.037 (4)°.

For related literature, see: Allen (2002); Buchler et al. (1982, 1983); Dolomanov et al. (2009); Eikey et al. (2002); Hill & Hollander (1982); Lansky et al. (2006); Sheldrick (2008); Singh et al. (2013).

Synthesis and crystallization top

The title compound, 5,10,15,20-tetra­kis-tetra­tolyl­porphyrinatonitridomanganese(V), was prepared according to the procedure developed by Buchler et al. (1982). (TTP)Mn—C2H3O2 (2.08 g, 2.65 mmol) was dissolved in methanol and eluted down an alumina column with methanol. The methanol was removed and the product redissolved in 400 ml di­chloro­methane. This solution was treated with 12 ml of an ammonia solution made by diluting 2 ml of concentrated ammonia with 10 ml of water and allowed to stir for fifteen minutes. A 10% sodium hypochlorite solution (6 ml) was added and the reaction was stirred an additional 15 minutes, resulting in a red solution. The solution was then washed with two 100 ml portions of water to remove the excess ammonia and hypochlorite and the sodium chloride formed during the reaction. The filtrate was placed on a neutral alumina column and the product was eluted with di­chloro­methane. Unreacted manganese(III) porphyrin can be recovered by eluting with methanol. The product was dried under reduced pressure. UV–vis (λmax 535, 421 nm) are in excellent agreement with those obtained by Buchler et al. (1982) (536 and 421 nm). The NMR spectrum (Anasazi 60 MHz FT–NMR: 1H NMR (296 K, CDCl3, p.p.m.) 8.94 (s, 8H), 8.03 (d, 8H), 7.53 (d 8H), 2.68 (s, 12H)) matches the literature data as well. A yield of 1.82 g, 93% based on (TTP)Mn- C2H3O2 was obtained. (TTP)MnN used to grow the crystal for the structural determination was purified by taking a di­chloro­methane solution and eluting through neutral alumina column with di­chloro­methane.

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms were included in the structure factor calculation at idealized positions and were allowed to ride on the neighboring atoms with relative isotropic displacement coefficients.

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT-Plus (Bruker, 2014); data reduction: SAINT-Plus (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009), publCIF (Westrip, 2010), GX (Guzei, 2013).

Figures top
[Figure 1] Fig. 1. A molecular drawing of (I) shown with 50% probability ellipsoids. All H atoms and the disordered mates of atoms Mn1 and N1 are omitted. Symmetry operator (1): -x+1, -y+1, -z.
[Figure 2] Fig. 2. A packing diagram of (I) shown along the [001] direction. All H atoms are omitted.
Nitrido[5,10,15,20-tetrakis(4-methylphenyl)porphyrinato]manganese(V) top
Crystal data top
[Mn(C48H36N4)(N)]F(000) = 768
Mr = 737.76Dx = 1.292 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54178 Å
a = 14.2619 (10) ÅCell parameters from 6388 reflections
b = 8.6200 (11) Åθ = 3.1–70.1°
c = 15.4685 (18) ŵ = 3.14 mm1
β = 94.188 (7)°T = 100 K
V = 1896.6 (4) Å3Plate, red
Z = 20.17 × 0.11 × 0.03 mm
Data collection top
Bruker SMART APEX2 area detector
diffractometer
3602 independent reflections
Radiation source: sealed X-ray tube, Siemens, K FFCU 2K 903184 reflections with I > 2σ(I)
Equatorially mounted graphite monochromatorRint = 0.050
Detector resolution: 7.9 pixels mm-1θmax = 70.1°, θmin = 3.1°
0.60° ω and 0.6° φ scansh = 1717
Absorption correction: multi-scan
(SADABS; Bruker, 2012)
k = 1010
Tmin = 0.529, Tmax = 0.662l = 1817
30677 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051H-atom parameters constrained
wR(F2) = 0.131 w = 1/[σ2(Fo2) + (0.060P)2 + 2.340P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
3602 reflectionsΔρmax = 0.33 e Å3
255 parametersΔρmin = 0.38 e Å3
0 restraints
Crystal data top
[Mn(C48H36N4)(N)]V = 1896.6 (4) Å3
Mr = 737.76Z = 2
Monoclinic, P21/cCu Kα radiation
a = 14.2619 (10) ŵ = 3.14 mm1
b = 8.6200 (11) ÅT = 100 K
c = 15.4685 (18) Å0.17 × 0.11 × 0.03 mm
β = 94.188 (7)°
Data collection top
Bruker SMART APEX2 area detector
diffractometer
3602 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2012)
3184 reflections with I > 2σ(I)
Tmin = 0.529, Tmax = 0.662Rint = 0.050
30677 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0510 restraints
wR(F2) = 0.131H-atom parameters constrained
S = 1.03Δρmax = 0.33 e Å3
3602 reflectionsΔρmin = 0.38 e Å3
255 parameters
Special details top

Experimental. SADABS-2012/1 (Bruker, 2012) was used for absorption correction. wR2(int) was 0.0782 before and 0.0582 after correction. The Ratio of minimum to maximum transmission is 0.8001. The λ/2 correction factor is 0.0015.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Mn10.50071 (8)0.53650 (7)0.00428 (7)0.0127 (2)0.5
N10.5205 (3)0.7069 (5)0.0218 (3)0.0192 (8)0.5
N20.37815 (13)0.5252 (2)0.05324 (12)0.0169 (4)
N30.56288 (13)0.4454 (2)0.11560 (12)0.0163 (4)
C10.29422 (16)0.5754 (3)0.01319 (15)0.0181 (5)
C20.22512 (17)0.5934 (3)0.07588 (15)0.0215 (5)
H20.16240.62920.06490.026*
C30.26662 (17)0.5498 (3)0.15313 (15)0.0211 (5)
H30.23820.54780.20680.025*
C40.36146 (17)0.5071 (3)0.13943 (15)0.0180 (5)
C50.42756 (16)0.4624 (3)0.20622 (15)0.0171 (5)
C60.39372 (16)0.4411 (3)0.29439 (15)0.0174 (5)
C70.33021 (16)0.3227 (3)0.30958 (15)0.0204 (5)
H70.31090.25310.26410.024*
C80.29492 (18)0.3051 (3)0.39015 (16)0.0251 (5)
H80.25140.22420.39890.030*
C90.32215 (19)0.4042 (3)0.45822 (16)0.0274 (6)
C100.38655 (18)0.5215 (3)0.44361 (16)0.0234 (5)
H100.40640.59000.48950.028*
C110.42188 (17)0.5396 (3)0.36346 (15)0.0196 (5)
H110.46590.62000.35510.023*
C120.2833 (2)0.3839 (4)0.54568 (18)0.0408 (7)
H12A0.23600.30110.54230.061*
H12B0.25420.48110.56280.061*
H12C0.33440.35620.58870.061*
C130.52194 (16)0.4379 (3)0.19367 (14)0.0172 (5)
C140.59120 (16)0.3965 (3)0.26207 (15)0.0196 (5)
H140.58060.38210.32150.024*
C150.67421 (16)0.3820 (3)0.22588 (15)0.0193 (5)
H150.73330.35800.25520.023*
C160.65615 (16)0.4097 (2)0.13484 (15)0.0168 (5)
C170.72421 (16)0.3948 (2)0.07477 (15)0.0167 (5)
C180.82071 (16)0.3429 (3)0.10650 (14)0.0185 (5)
C190.83537 (17)0.1947 (3)0.14103 (15)0.0222 (5)
H190.78370.12600.14430.027*
C200.92477 (18)0.1470 (3)0.17059 (16)0.0277 (6)
H200.93320.04550.19380.033*
C211.00228 (17)0.2432 (3)0.16720 (16)0.0287 (6)
C220.98775 (17)0.3902 (3)0.13146 (16)0.0280 (6)
H221.03980.45790.12750.034*
C230.89872 (17)0.4393 (3)0.10163 (16)0.0240 (5)
H230.89070.54020.07750.029*
C241.09940 (19)0.1923 (4)0.20193 (19)0.0436 (8)
H24A1.10740.21360.26430.065*
H24B1.14690.24960.17210.065*
H24C1.10670.08090.19190.065*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0124 (3)0.0133 (6)0.0122 (4)0.0005 (5)0.0005 (2)0.0007 (5)
N10.0141 (18)0.021 (2)0.022 (2)0.0007 (15)0.0009 (14)0.0023 (16)
N20.0201 (10)0.0159 (9)0.0144 (9)0.0013 (7)0.0009 (7)0.0007 (7)
N30.0191 (10)0.0153 (9)0.0143 (9)0.0012 (7)0.0009 (7)0.0003 (7)
C10.0191 (11)0.0153 (10)0.0195 (12)0.0010 (9)0.0003 (9)0.0008 (9)
C20.0199 (11)0.0221 (12)0.0224 (12)0.0052 (9)0.0013 (9)0.0000 (10)
C30.0243 (12)0.0212 (12)0.0178 (12)0.0044 (9)0.0020 (9)0.0018 (9)
C40.0220 (12)0.0160 (11)0.0162 (11)0.0022 (9)0.0014 (9)0.0013 (9)
C50.0225 (12)0.0121 (10)0.0167 (11)0.0001 (8)0.0006 (9)0.0021 (9)
C60.0191 (11)0.0162 (11)0.0167 (11)0.0047 (9)0.0014 (8)0.0009 (9)
C70.0249 (12)0.0166 (11)0.0192 (12)0.0010 (9)0.0012 (9)0.0009 (9)
C80.0278 (13)0.0222 (12)0.0255 (13)0.0043 (10)0.0037 (10)0.0040 (10)
C90.0350 (14)0.0304 (14)0.0173 (12)0.0004 (11)0.0056 (10)0.0040 (10)
C100.0286 (13)0.0240 (12)0.0169 (12)0.0027 (10)0.0022 (9)0.0020 (10)
C110.0221 (12)0.0177 (11)0.0183 (11)0.0007 (9)0.0026 (9)0.0013 (9)
C120.058 (2)0.0450 (18)0.0214 (14)0.0083 (15)0.0135 (13)0.0014 (13)
C130.0230 (12)0.0140 (10)0.0144 (11)0.0014 (9)0.0001 (9)0.0001 (9)
C140.0244 (12)0.0207 (11)0.0134 (11)0.0037 (9)0.0006 (9)0.0004 (9)
C150.0223 (12)0.0181 (11)0.0171 (11)0.0026 (9)0.0019 (9)0.0021 (9)
C160.0185 (11)0.0124 (10)0.0191 (11)0.0002 (8)0.0024 (8)0.0005 (9)
C170.0188 (11)0.0129 (10)0.0181 (11)0.0016 (8)0.0003 (8)0.0008 (9)
C180.0179 (11)0.0235 (12)0.0140 (11)0.0003 (9)0.0003 (8)0.0000 (9)
C190.0209 (12)0.0253 (13)0.0205 (12)0.0010 (10)0.0009 (9)0.0035 (10)
C200.0259 (13)0.0354 (14)0.0218 (12)0.0081 (11)0.0021 (10)0.0091 (11)
C210.0177 (12)0.0503 (17)0.0182 (12)0.0049 (11)0.0014 (9)0.0042 (12)
C220.0180 (12)0.0424 (16)0.0235 (13)0.0060 (11)0.0014 (9)0.0021 (12)
C230.0230 (12)0.0273 (13)0.0217 (12)0.0025 (10)0.0012 (9)0.0028 (10)
C240.0215 (14)0.074 (2)0.0354 (16)0.0090 (14)0.0013 (11)0.0160 (16)
Geometric parameters (Å, º) top
Mn1—N11.516 (4)C10—H100.9500
Mn1—N2i2.070 (2)C10—C111.381 (3)
Mn1—N21.958 (2)C11—H110.9500
Mn1—N32.036 (2)C12—H12A0.9800
Mn1—N3i2.010 (2)C12—H12B0.9800
N1—Mn1i2.154 (4)C12—H12C0.9800
N2—Mn1i2.070 (2)C13—C141.439 (3)
N2—C11.377 (3)C14—H140.9500
N2—C41.380 (3)C14—C151.352 (3)
N3—Mn1i2.010 (2)C15—H150.9500
N3—C131.381 (3)C15—C161.433 (3)
N3—C161.377 (3)C16—C171.398 (3)
C1—C21.441 (3)C17—C1i1.391 (3)
C1—C17i1.391 (3)C17—C181.496 (3)
C2—H20.9500C18—C191.394 (3)
C2—C31.348 (3)C18—C231.395 (3)
C3—H30.9500C19—H190.9500
C3—C41.432 (3)C19—C201.385 (3)
C4—C51.401 (3)C20—H200.9500
C5—C61.491 (3)C20—C211.386 (4)
C5—C131.390 (3)C21—C221.392 (4)
C6—C71.396 (3)C21—C241.513 (3)
C6—C111.401 (3)C22—H220.9500
C7—H70.9500C22—C231.385 (4)
C7—C81.386 (3)C23—H230.9500
C8—H80.9500C24—H24A0.9800
C8—C91.389 (4)C24—H24B0.9800
C9—C101.396 (4)C24—H24C0.9800
C9—C121.509 (3)
N1—Mn1—N298.00 (16)C11—C10—H10119.5
N1—Mn1—N2i100.09 (16)C6—C11—H11119.6
N1—Mn1—N399.09 (16)C10—C11—C6120.9 (2)
N1—Mn1—N3i98.97 (16)C10—C11—H11119.6
N2—Mn1—N2i161.90 (4)C9—C12—H12A109.5
N2—Mn1—N3i90.30 (9)C9—C12—H12B109.5
N2—Mn1—N389.97 (9)C9—C12—H12C109.5
N3—Mn1—N2i86.50 (9)H12A—C12—H12B109.5
N3i—Mn1—N2i87.59 (9)H12A—C12—H12C109.5
N3i—Mn1—N3161.72 (4)H12B—C12—H12C109.5
C1—N2—Mn1i127.80 (16)N3—C13—C5126.2 (2)
C1—N2—Mn1125.57 (16)N3—C13—C14110.1 (2)
C1—N2—C4105.34 (19)C5—C13—C14123.7 (2)
C4—N2—Mn1i126.48 (16)C13—C14—H14126.5
C4—N2—Mn1126.96 (16)C15—C14—C13107.1 (2)
C13—N3—Mn1124.89 (15)C15—C14—H14126.5
C13—N3—Mn1i128.27 (16)C14—C15—H15126.5
C16—N3—Mn1128.56 (15)C14—C15—C16107.0 (2)
C16—N3—Mn1i125.49 (15)C16—C15—H15126.5
C16—N3—C13105.32 (18)N3—C16—C15110.56 (19)
N2—C1—C2110.2 (2)N3—C16—C17125.7 (2)
N2—C1—C17i126.5 (2)C17—C16—C15123.6 (2)
C17i—C1—C2123.3 (2)C1i—C17—C16122.9 (2)
C1—C2—H2126.6C1i—C17—C18118.7 (2)
C3—C2—C1106.8 (2)C16—C17—C18118.5 (2)
C3—C2—H2126.6C19—C18—C17120.6 (2)
C2—C3—H3126.3C19—C18—C23117.9 (2)
C2—C3—C4107.4 (2)C23—C18—C17121.5 (2)
C4—C3—H3126.3C18—C19—H19119.8
N2—C4—C3110.2 (2)C20—C19—C18120.5 (2)
N2—C4—C5126.1 (2)C20—C19—H19119.8
C5—C4—C3123.6 (2)C19—C20—H20119.1
C4—C5—C6117.6 (2)C19—C20—C21121.8 (2)
C13—C5—C4123.0 (2)C21—C20—H20119.1
C13—C5—C6119.4 (2)C20—C21—C22117.6 (2)
C7—C6—C5120.1 (2)C20—C21—C24121.7 (3)
C7—C6—C11117.9 (2)C22—C21—C24120.7 (3)
C11—C6—C5121.9 (2)C21—C22—H22119.4
C6—C7—H7119.5C23—C22—C21121.1 (2)
C8—C7—C6120.9 (2)C23—C22—H22119.4
C8—C7—H7119.5C18—C23—H23119.5
C7—C8—H8119.5C22—C23—C18121.0 (2)
C7—C8—C9121.0 (2)C22—C23—H23119.5
C9—C8—H8119.5C21—C24—H24A109.5
C8—C9—C10118.3 (2)C21—C24—H24B109.5
C8—C9—C12120.5 (2)C21—C24—H24C109.5
C10—C9—C12121.2 (2)H24A—C24—H24B109.5
C9—C10—H10119.5H24A—C24—H24C109.5
C11—C10—C9121.0 (2)H24B—C24—H24C109.5
Mn1i—N2—C1—C2175.04 (15)C5—C6—C7—C8177.2 (2)
Mn1—N2—C1—C2162.51 (16)C5—C6—C11—C10177.3 (2)
Mn1i—N2—C1—C17i4.7 (3)C5—C13—C14—C15179.8 (2)
Mn1—N2—C1—C17i17.7 (3)C6—C5—C13—N3176.6 (2)
Mn1i—N2—C4—C3174.60 (15)C6—C5—C13—C141.8 (3)
Mn1—N2—C4—C3162.78 (16)C6—C7—C8—C90.4 (4)
Mn1—N2—C4—C513.7 (3)C7—C6—C11—C101.1 (3)
Mn1i—N2—C4—C58.9 (3)C7—C8—C9—C100.4 (4)
Mn1i—N3—C13—C59.4 (3)C7—C8—C9—C12180.0 (3)
Mn1—N3—C13—C513.1 (3)C8—C9—C10—C110.4 (4)
Mn1i—N3—C13—C14169.23 (15)C9—C10—C11—C60.3 (4)
Mn1—N3—C13—C14168.34 (15)C11—C6—C7—C81.1 (3)
Mn1i—N3—C16—C15170.66 (15)C12—C9—C10—C11180.0 (3)
Mn1—N3—C16—C15166.71 (15)C13—N3—C16—C150.9 (2)
Mn1—N3—C16—C1716.1 (3)C13—N3—C16—C17176.3 (2)
Mn1i—N3—C16—C176.5 (3)C13—C5—C6—C7114.5 (2)
N2—C1—C2—C31.7 (3)C13—C5—C6—C1167.2 (3)
N2—C4—C5—C6176.6 (2)C13—C14—C15—C161.7 (3)
N2—C4—C5—C133.4 (4)C14—C15—C16—N31.7 (3)
N3—C13—C14—C151.2 (3)C14—C15—C16—C17175.6 (2)
N3—C16—C17—C1i4.2 (4)C15—C16—C17—C1i179.0 (2)
N3—C16—C17—C18175.2 (2)C15—C16—C17—C181.7 (3)
C1—N2—C4—C31.2 (2)C16—N3—C13—C5178.7 (2)
C1—N2—C4—C5177.7 (2)C16—N3—C13—C140.1 (2)
C1—C2—C3—C40.9 (3)C16—C17—C18—C1965.0 (3)
C1i—C17—C18—C19114.4 (2)C16—C17—C18—C23115.9 (3)
C1i—C17—C18—C2364.8 (3)C17i—C1—C2—C3178.0 (2)
C2—C3—C4—N20.2 (3)C17—C18—C19—C20179.8 (2)
C2—C3—C4—C5176.8 (2)C17—C18—C23—C22179.8 (2)
C3—C4—C5—C67.3 (3)C18—C19—C20—C210.1 (4)
C3—C4—C5—C13172.6 (2)C19—C18—C23—C221.0 (4)
C4—N2—C1—C21.8 (2)C19—C20—C21—C221.1 (4)
C4—N2—C1—C17i178.0 (2)C19—C20—C21—C24178.2 (2)
C4—C5—C6—C765.5 (3)C20—C21—C22—C231.0 (4)
C4—C5—C6—C11112.8 (3)C21—C22—C23—C180.0 (4)
C4—C5—C13—N33.5 (4)C23—C18—C19—C200.9 (3)
C4—C5—C13—C14178.1 (2)C24—C21—C22—C23178.2 (2)
Symmetry code: (i) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
Cg1 and Cg2 are the centroids of the N3/C13–C16 and C6–C11 rings, respectively.
D—H···AD—HH···AD···AD—H···A
C10—H10···N1ii0.952.423.203 (5)140
C11—H11···Cg1iii0.952.773.332 (3)119
C19—H19···Cg2iv0.952.683.619 (3)170
Symmetry codes: (ii) x, y+3/2, z+1/2; (iii) x+1, y+1/2, z+1/2; (iv) x+1, y1/2, z+1/2.
Selected metric parameters for (I)–(VI) (Å) top
CompoundMnNMn—N(av)Mn—N4 displacement
(I)1.516 (4)2.02 (5)0.3162 (6)
(II)1.512 (2)2.02 (3)0.388
(III)1.5122.006 (3)0.426
(IV)1.6131.92 (2)0.513
(V)1.5951.893 (10)0.550
(VI)1.5121.99 (3)0.460
Hydrogen-bond geometry (Å, º) top
Cg1 and Cg2 are the centroids of the N3/C13–C16 and C6–C11 rings, respectively.
D—H···AD—HH···AD···AD—H···A
C10—H10···N1i0.952.423.203 (5)140
C11—H11···Cg1ii0.952.773.332 (3)119
C19—H19···Cg2iii0.952.683.619 (3)170
Symmetry codes: (i) x, y+3/2, z+1/2; (ii) x+1, y+1/2, z+1/2; (iii) x+1, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Mn(C48H36N4)(N)]
Mr737.76
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)14.2619 (10), 8.6200 (11), 15.4685 (18)
β (°) 94.188 (7)
V3)1896.6 (4)
Z2
Radiation typeCu Kα
µ (mm1)3.14
Crystal size (mm)0.17 × 0.11 × 0.03
Data collection
DiffractometerBruker SMART APEX2 area detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2012)
Tmin, Tmax0.529, 0.662
No. of measured, independent and
observed [I > 2σ(I)] reflections
30677, 3602, 3184
Rint0.050
(sin θ/λ)max1)0.610
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.131, 1.03
No. of reflections3602
No. of parameters255
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.33, 0.38

Computer programs: APEX2 (Bruker, 2014), SAINT-Plus (Bruker, 2014), SHELXT (Sheldrick, 2008), SHELXL (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009), publCIF (Westrip, 2010), GX (Guzei, 2013).

 

Acknowledgements

The authors are grateful to University of Wisconsin-Madison for the support of this structural investigation.

References

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Volume 70| Part 10| October 2014| Pages 242-245
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