research communications
Synthesis, FT–IR characterization and κ4N)manganese(III) trifluoromethanesulfonate
of aqua(5,10,15,20-tetraphenylporphyrinato-aLaboratoire de Physico-chimie des Matériaux, Faculté des Sciences de Monastir, Avenue de l'Environnement, 5019 Monastir, University of Monastir, Tunisia, bFaculdade de Medicina, Veterinària, Universidade Tecnica de Lisboa, Avenida da Universidade Tecnica, 1300-477 Lisboa, Portugal, and cREQUIMTE/CQFB Departamento de Quimica, Faculdade de Ciencias e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
*Correspondence e-mail: wafashdoul@gmail.com
In the title salt, [Mn(C44H28N4)(H2O)](CF3SO3) or [MnIII(TPP)(H2O)](CF3SO3) (where TPP is the dianion of 5,10,15,20-tetraphenylporphyrin), the MnIII cation is chelated by the four pyrrole N atoms of the porphyrinate anion and additionally coordinated by an aqua ligand in an apical site, completing the distorted square-pyramidal coordination environment. The average Mn—N(pyrrole) bond length is 1.998 (9) Å and the Mn—O(aqua) bond length is 2.1057 (15) Å. The central MnIII ion is displaced by 0.1575 (5) Å from the N4C20 mean plane of the porphyrinate anion towards the apical aqua ligand. The porphyrinate macrocycle exhibits a moderate ruffling and strong saddle deformations. In the the [MnIII(TPP)(H2O)]+ cation and the trifluoromethanesulfonate counter-ions are arranged in alternating planes packed along [001]. The components are linked together through O—H⋯O hydrogen bonds and much weaker C—H⋯O and C—H⋯F interactions. The crystal packing is further stabilized by weak C—H⋯π interactions involving the pyrrole and phenyl rings of the porphyrin moieties.
CCDC reference: 1474973
1. Chemical context
While the role of manganese et al., 1972), synthetic manganese porphyrin complexes have been used extensively as models for monoxygenases enzymes (Meunier et al., 1988; Groves & Nemo, 1983) or as DNA cleavage agents (Rodriguez & Bard, 1992; Bernadou et al., 1989). The latter can also be considered as potential contrast enhancement agents for (Fawwaz et al., 1990).
in biological processes has not been unambiguously established (BoucherIn most MnIII–porphyrin complexes, the metal is five-coordinate and is in its high-spin state whereby polar solvents readily can displace the coordinating anionic ligand to yield solvated complexes (Godziela et al., 1986; Janson et al., 1973). In our case, the reaction of chlorido-(5,10,15,20-tetraphenylporphyrinato)manganese(III) with hygroscopic silver triflate let to the formation of an aqua-[5,10,15,20-tetraphenylporphyrinato)]manganese(III) salt, [Mn(C44H28N4)(H2O)](CF3SO3), (I) or [MnIII(TPP)(H2O)](CF3SO3) (where TPP is the dianion of 5,10,15,20-tetraphenylporphyrin). The coordination of a water molecule instead of the triflate ion to MnIII can be explained, as mentioned above, by the weak affinity of manganese(III) to an ionic ligand and in particular by the triflate anion which is known to be a weakly coordinating ligand.
In order to gain more insight into the structure of aqua–MnIII metalloporphyrins, we report herein the synthesis, and the spectroscopic data of compound (I).
2. Structural commentary
The central MnIII cation of the complex [MnIII(TPP)(H2O)] cation exhibits a distorted square-pyramidal coordination environment (Fig. 1). The equatorial plane is formed by four nitrogen atoms of the porphyrin ligand while the apical position is occupied by the aqua ligand. The of (I) is completed by one CF3SO3− counter-ion. The Mn—O(aqua) bond length of 2.1057 (15) Å is considerably shorter than those of other aqua–MnIII metalloporphyrins which range from 2.166 to 2.258 Å (Dawe et al., 2005; Turner, et al., 1996). The average equatorial manganese–N(pyrrole) distance is 1.998 (9) Å, which is close to related [MnIII(Porph)(X)]+ ion complexes (Porph and X are a porphyrinato and a monodentate neutral ligand, respectively), e.g. [MnIII(TClPP)(py)]+ (TClPP is 5,10,15,20-(tetra-4-chlorophenyl)porphyrinato) where the average Mn—N(pyrrole) bond length is 2.007 (2) Å (Rittenberg et al., 2000). In Fig. 2, the displacements of each atom in (I) from the mean plane of the 24-atom porphyrin macrocycle in units of 0.01 Å is illustrated. The MnIII ion is displaced by 0.158 (5) Å from the 24-atom porphyrin mean plane (PC) which is slightly higher than in the [MnIII(DBHPP)(H2O)]+ (DBHPP = 5,10,15,20-(3,5-di-t-butyl-4-hydroxyphenyl)porphyrinato) species (Mn—PC = 0.122 Å), but smaller than in the [MnIII(TPP)(py)]+ ion complex (Mn—PC = 0.199 Å; Dawe et al., 2005). As can be seen in Fig. 2, the porphyrin core presents (i) high saddle distortions as seen by the displacements of the pyrrole rings alternately above and below the mean porphyrin macrocycle and (ii) a moderate ruffling which is indicated by the high values of the displacements of the meso-C atoms above and below the porphyrin mean plane (Scheidt & Lee, 1987).
3. Supramolecular features
In the crystal packing of (I), the manganese porphyrin complex cations and the triflate anions are arranged in alternating planes packed along [001] (Fig. 3). The distance between the C20N4Mn mean planes (porphyrin cores) of two neighbouring [Mn(TPP)H2O)]+ cation complexes is 4.677 Å. The cationic and anionic entities are linked together through two O—H⋯O hydrogen bonds of medium strength between the aqua ligand and the O atoms of the triflate anion (Table 1, Fig. 3). The crystal packing of (I) is further consolidated by weak C—H⋯O and C—H⋯F hydrogen-bonding and C—H⋯π interactions involving the phenyl and pyrrole rings. The values of these interactions range between 3.449 (2) Å and 3.676 (3) Å (Table 1, Fig. 4).
4. Database survey
A search of the Cambridge Structural Database (CSD, Version 5.31; Groom et al., 2016) revealed (i) eight diaqua–MnIII metalloporphyrins, e.g. the [MnIII(TPP)(H2O)2]+ cation (Byrn et al., 1993) and (ii) two mono-aqua-=MnIII e.g. the [MnIII(TPP)(H2O)]+ cation (Diskin-Posner et al., 1999) and the [MnIII(DBHPP)(H2O)]+ cation [DBHPP = 5,10,15,20-(3,5-di-t-butyl-4-hydroxyphenyl)porphyrinato; Dawe et al., 2005].
5. Synthesis and crystallization
To a solution of [MnIII(TPP)Cl] (100 mg, 0.142 mmol) (Cheng & Scheidt, 1996) in chloroform (10 ml) was added an excess of one equivalent of silver triflate (100 mg, 0.389 mmol). The reaction mixture was stirred at room temperature for 12 h. Crystals of the title complex were obtained by diffusion of hexanes through the chloroform solution. We assume that water was delivered from the hygroscopic silver triflate salt.
Spectroscopic analysis: UV–vis spectrum in chloroform: λmax (nm) 386, 474, 570 and 604.
6. FT–IR spectroscopy
The FT–IR spectrum of (I) (Fig. 5) was recorded in the 4000–400 cm−1 range using a PerkinElmer Spectrum Two FTIR spectrometer. The spectrum presents characteristic vibrational bands of the TPP porphyrinato moiety. The C—H stretching frequencies of the porphyrin molecule are in the range 3060 to 2860 cm−1, the C=C and C=N stretching frequencies are assigned at 1728 cm−1 and 1654 cm−1, respectively. A strong band attributed to the bending vibration of the CCH moieties of the porphyrin core is centred around 1010 cm−1. The two absorption bands at 3456 cm−1 and 3242 cm−1 are attributed to the antisymmetric and symmetric OH stretching frequencies of the aqua ligand, while the bending vibration of the same ligand is at 1629 cm−1. The presence of the triflate counter-ion is confirmed by the following absorption bands: a medium–strong band at 1308 cm−1 attributed to the asymmetric stretching frequency of the SO3 group, a strong band at 1231 cm−1 corresponding to the symmetric stretching frequency of the CF3 moiety, a medium–strong band at 1162 cm−1 attributed to νas(CF3), a strong band at 1027 cm−1 corresponding to νs(SO3), a strong band at 633 cm−1 attributed to the bending vibration of the SO3 group and a weak and a medium–strong band at 576 cm−1 and 515 cm−1 corresponding to δas(CF3) and δas(SO3) vibrations, respectively.
7. details
Crystal data, data collection and structure . Carbon-bound hydrogen atoms were placed in calculated positions and refined as riding atoms with C—H = 0.93 Å with Uiso(H) = 1.2Ueq(C). The two hydrogen-atom positions of the aqua ligand were discernible from difference maps. However, for the final model these positions were calculated by using the CALC-OH program (Nardelli et al., 1999) and were modelled with fixed isotropic displacement parameters.
details are summarized in Table 2
|
Supporting information
CCDC reference: 1474973
10.1107/S2056989016006630/wm5285sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016006630/wm5285Isup2.hkl
While the role of manganese
in biological processes has not been unambiguously established (Boucher et al., 1972), synthetic manganese porphyrin complexes have been used extensively as models for monoxygenases enzymes (Meunier et al., 1988; Groves & Nemo, 1983) or as DNA cleavage agents (Rodriguez & Bard, 1992; Bernadou et al., 1989). The latter can also be considered as potential contrast enhancement agents for (Fawwaz et al., 1990).In most MnIII–porphyrin complexes, the metal is five-coordinate and is in its high-spin state whereby polar solvents readily can displace the coordinating anionic ligand to yield solvated complexes (Godziela et al., 1986; Janson et al., 1973). In our case, the reaction of chlorido-(5,10,15,20-tetraphenylporphyrinato)manganese(III) with hygroscopic silver triflate let to the formation of an aqua-[5,10,15,20-tetraphenylporphyrinato)]manganese(III) salt, [Mn(C44H28N4)(H2O)](CF3SO3), (I) or [MnIII(TPP)(H2O)](CF3SO3) (where TPP is the dianion of 5,10,15,20-tetraphenylporphyrin). The coordination of a water molecule instead of the triflate ion to MnIII can be explained, as mentioned above, by the weak affinity of manganese(III) to an ionic ligand and in particular by the triflate anion which is known to be a weakly coordinating ligand.
In order to gain more insight into the structure of aqua–MnIII metalloporphyrins, we report herein the synthesis,
and the spectroscopic data of compound (I).The central MnIII cation of the complex [MnIII(TPP)(H2O)] cation exhibits a distorted square-pyramidal coordination environment (Fig. 1). The equatorial plane is formed by four nitrogen atoms of the porphyrin ligand while the apical position is occupied by the aqua ligand. The
of (I) is completed by one SO3CF3- counter-ion. The Mn—O(aqua) bond length of 2.1057 (15) Å is considerably shorter than those of other aqua–MnIII metalloporphyrins which range from 2.166 to 2.258 Å (Dawe et al., 2005; Turner, et al., 1996). The average equatorial manganese–N(pyrrole) distance is 1.998 (9) Å, which is close to related [MnIII(Porph)(X)]+ ion complexes (Porph and X are a porphyrinato and a monodentate neutral ligand, respectively), e.g. [MnIII(TClPP)(py)]+ (TClPP is 5,10,15,20-(tetra-4-chlorophenyl)porphyrinato) where the average Mn—N(pyrrole) bond length is 2.007 (2) Å (Rittenberg et al., 2000). In Fig. 2, the displacements of each atom in (I) from the mean plane of the 24-atom porphyrin macrocycle in units of 0.01 Å is illustrated. The MnIII ion is displaced by 0.158 (5) Å from the 24-atom porphyrin mean plane (PC) which is slightly higher than in the [MnIII(DBHPP)(H2O)]+ (DBHPP = 5,10,15,20-(3,5-di-t-butyl-4-hydroxyphenyl)porphyrinato) species (Mn—PC = 0.122 Å), but smaller than in the [MnIII(TPP)(py)]+ ion complex (Mn—PC = 0.199 Å; Dawe et al., 2005). As can be seen in Fig. 2, the porphyrin core presents (i) high saddle distortions as seen by the displacements of the pyrrole rings alternately above and below the mean porphyrin macrocycle and (ii) a moderate ruffling which is indicated by the high values of the displacements of the meso-C atoms above and below the porphyrin mean plane (Scheidt & Lee, 1987).In the crystal packing of (I), the manganese porphyrin complex cations and the triflate anions are arranged in alternating planes packed along [001] (Fig. 3). The distance between the C20N4Mn mean planes (porphyrin cores) of two neighbouring [Mn(TPP)H2O)]+ cation complexes is 4.677 Å. The cationic and anionic entities are linked together through two O—H···O hydrogen bonds of medium strength between the aqua ligand and the O atoms of the triflate anion (Table 1, Fig. 3). The crystal packing of (I) is further consolidated by weak C—H···O and C—H···F hydrogen-bonding and C—H···π interactions involving the phenyl and pyrrole rings. The values of these interactions range between 3.449 (2) Å and 3.676 (3) Å (Table 1, Fig. 4).
A search of the Cambridge Structural Database (CSD, Version 5.31; Groom et al., 2016) revealed (i) eight diaqua–MnIII metalloporphyrins, e.g. the [MnIII(TPP)(H2O)2]+ cation (Byrn et al., 1993) and (ii) two mono-aqua-=MnIII
e.g. the [MnIII(TPP)(H2O)]+ cation (Diskin-Posner et al., 1999) and the [MnIII(DBHPP)(H2O)]+ cation [DBHPP = 5,10,15,20-(3,5-di-t-butyl-4-hydroxyphenyl)porphyrinato; Dawe et al., 2005].To a solution of [MnIII(TPP)Cl] (100 mg, 0.142 mmol) (Cheng & Scheidt, 1996) in chloroform (10 ml) was added an excess of one equivalent of silver triflate (100 mg, 0.389 mmol). The reaction mixture was stirred at room temperature for 12 h. Crystals of the title complex were obtained by diffusion of hexanes through the chloroform solution. We assume that water was delivered from the hygroscopic silver triflate salt.
Spectroscopic analysis: UV–vis spectrum in chloroform : λmax (nm) 386, 474, 570 and 604.
The FT–IR spectrum of (I) (Fig. 5) was recorded in the 4000–400 cm-1 range using a PerkinElmer Spectrum Two FTIR spectrometer. The spectrum presents characteristic vibrational bands of the TPP porphyrinato moiety. The C—H stretching frequencies of the porphyrin molecule are in the range 3060 to 2860 cm-1, the C═C and C═N stretching frequencies are assigned at 1728 cm-1 and 1654 cm-1, respectively. A strong band attributed to the bending vibration of the CCH moieties of the porphyrin core is centred around 1010 cm-1. The two absorption bands at 3456 cm-1 and 3242 cm-1 are attributed to the antisymmetric and symmetric OH stretching frequencies of the aqua ligand, while the bending vibration of the same ligand is at 1629 cm-1. The presence of the triflate counter-ion is confirmed by the following absorption bands: a medium–strong band at 1308 cm-1 attributed to the asymmetric stretching frequency of the SO3 group, a strong band at 1231 cm-1 corresponding to the symmetric stretching frequency of the CF3 moiety, a medium–strong band at 1162 cm-1 attributed to νas(CF3), a strong band at 1027 cm-1 corresponding to νs(SO3), a strong band at 633 cm-1 attributed to the bending vibration of the SO3 group and a weak and a medium–strong band at 576 cm-1 and 515 cm-1 corresponding to δas(CF3) and δas(SO3) vibrations, respectively.
Crystal data, data collection and structure
details are summarized in Table 2. Carbon-bound hydrogen atoms were placed in calculated positions and refined as riding atoms with C—H = 0.93 Å with Uiso(H) = 1.2Ueq(C). The two hydrogen-atom positions of the aqua ligand were discernible from difference maps. However, for the final model these positions were calculated by using the CALC-OH program (Nardelli et al., 1999) and were modelled with fixed isotropic displacement parameters.While the role of manganese
in biological processes has not been unambiguously established (Boucher et al., 1972), synthetic manganese porphyrin complexes have been used extensively as models for monoxygenases enzymes (Meunier et al., 1988; Groves & Nemo, 1983) or as DNA cleavage agents (Rodriguez & Bard, 1992; Bernadou et al., 1989). The latter can also be considered as potential contrast enhancement agents for (Fawwaz et al., 1990).In most MnIII–porphyrin complexes, the metal is five-coordinate and is in its high-spin state whereby polar solvents readily can displace the coordinating anionic ligand to yield solvated complexes (Godziela et al., 1986; Janson et al., 1973). In our case, the reaction of chlorido-(5,10,15,20-tetraphenylporphyrinato)manganese(III) with hygroscopic silver triflate let to the formation of an aqua-[5,10,15,20-tetraphenylporphyrinato)]manganese(III) salt, [Mn(C44H28N4)(H2O)](CF3SO3), (I) or [MnIII(TPP)(H2O)](CF3SO3) (where TPP is the dianion of 5,10,15,20-tetraphenylporphyrin). The coordination of a water molecule instead of the triflate ion to MnIII can be explained, as mentioned above, by the weak affinity of manganese(III) to an ionic ligand and in particular by the triflate anion which is known to be a weakly coordinating ligand.
In order to gain more insight into the structure of aqua–MnIII metalloporphyrins, we report herein the synthesis,
and the spectroscopic data of compound (I).The central MnIII cation of the complex [MnIII(TPP)(H2O)] cation exhibits a distorted square-pyramidal coordination environment (Fig. 1). The equatorial plane is formed by four nitrogen atoms of the porphyrin ligand while the apical position is occupied by the aqua ligand. The
of (I) is completed by one SO3CF3- counter-ion. The Mn—O(aqua) bond length of 2.1057 (15) Å is considerably shorter than those of other aqua–MnIII metalloporphyrins which range from 2.166 to 2.258 Å (Dawe et al., 2005; Turner, et al., 1996). The average equatorial manganese–N(pyrrole) distance is 1.998 (9) Å, which is close to related [MnIII(Porph)(X)]+ ion complexes (Porph and X are a porphyrinato and a monodentate neutral ligand, respectively), e.g. [MnIII(TClPP)(py)]+ (TClPP is 5,10,15,20-(tetra-4-chlorophenyl)porphyrinato) where the average Mn—N(pyrrole) bond length is 2.007 (2) Å (Rittenberg et al., 2000). In Fig. 2, the displacements of each atom in (I) from the mean plane of the 24-atom porphyrin macrocycle in units of 0.01 Å is illustrated. The MnIII ion is displaced by 0.158 (5) Å from the 24-atom porphyrin mean plane (PC) which is slightly higher than in the [MnIII(DBHPP)(H2O)]+ (DBHPP = 5,10,15,20-(3,5-di-t-butyl-4-hydroxyphenyl)porphyrinato) species (Mn—PC = 0.122 Å), but smaller than in the [MnIII(TPP)(py)]+ ion complex (Mn—PC = 0.199 Å; Dawe et al., 2005). As can be seen in Fig. 2, the porphyrin core presents (i) high saddle distortions as seen by the displacements of the pyrrole rings alternately above and below the mean porphyrin macrocycle and (ii) a moderate ruffling which is indicated by the high values of the displacements of the meso-C atoms above and below the porphyrin mean plane (Scheidt & Lee, 1987).In the crystal packing of (I), the manganese porphyrin complex cations and the triflate anions are arranged in alternating planes packed along [001] (Fig. 3). The distance between the C20N4Mn mean planes (porphyrin cores) of two neighbouring [Mn(TPP)H2O)]+ cation complexes is 4.677 Å. The cationic and anionic entities are linked together through two O—H···O hydrogen bonds of medium strength between the aqua ligand and the O atoms of the triflate anion (Table 1, Fig. 3). The crystal packing of (I) is further consolidated by weak C—H···O and C—H···F hydrogen-bonding and C—H···π interactions involving the phenyl and pyrrole rings. The values of these interactions range between 3.449 (2) Å and 3.676 (3) Å (Table 1, Fig. 4).
A search of the Cambridge Structural Database (CSD, Version 5.31; Groom et al., 2016) revealed (i) eight diaqua–MnIII metalloporphyrins, e.g. the [MnIII(TPP)(H2O)2]+ cation (Byrn et al., 1993) and (ii) two mono-aqua-=MnIII
e.g. the [MnIII(TPP)(H2O)]+ cation (Diskin-Posner et al., 1999) and the [MnIII(DBHPP)(H2O)]+ cation [DBHPP = 5,10,15,20-(3,5-di-t-butyl-4-hydroxyphenyl)porphyrinato; Dawe et al., 2005].The FT–IR spectrum of (I) (Fig. 5) was recorded in the 4000–400 cm-1 range using a PerkinElmer Spectrum Two FTIR spectrometer. The spectrum presents characteristic vibrational bands of the TPP porphyrinato moiety. The C—H stretching frequencies of the porphyrin molecule are in the range 3060 to 2860 cm-1, the C═C and C═N stretching frequencies are assigned at 1728 cm-1 and 1654 cm-1, respectively. A strong band attributed to the bending vibration of the CCH moieties of the porphyrin core is centred around 1010 cm-1. The two absorption bands at 3456 cm-1 and 3242 cm-1 are attributed to the antisymmetric and symmetric OH stretching frequencies of the aqua ligand, while the bending vibration of the same ligand is at 1629 cm-1. The presence of the triflate counter-ion is confirmed by the following absorption bands: a medium–strong band at 1308 cm-1 attributed to the asymmetric stretching frequency of the SO3 group, a strong band at 1231 cm-1 corresponding to the symmetric stretching frequency of the CF3 moiety, a medium–strong band at 1162 cm-1 attributed to νas(CF3), a strong band at 1027 cm-1 corresponding to νs(SO3), a strong band at 633 cm-1 attributed to the bending vibration of the SO3 group and a weak and a medium–strong band at 576 cm-1 and 515 cm-1 corresponding to δas(CF3) and δas(SO3) vibrations, respectively.
To a solution of [MnIII(TPP)Cl] (100 mg, 0.142 mmol) (Cheng & Scheidt, 1996) in chloroform (10 ml) was added an excess of one equivalent of silver triflate (100 mg, 0.389 mmol). The reaction mixture was stirred at room temperature for 12 h. Crystals of the title complex were obtained by diffusion of hexanes through the chloroform solution. We assume that water was delivered from the hygroscopic silver triflate salt.
Spectroscopic analysis: UV–vis spectrum in chloroform : λmax (nm) 386, 474, 570 and 604.
detailsCrystal data, data collection and structure
details are summarized in Table 2. Carbon-bound hydrogen atoms were placed in calculated positions and refined as riding atoms with C—H = 0.93 Å with Uiso(H) = 1.2Ueq(C). The two hydrogen-atom positions of the aqua ligand were discernible from difference maps. However, for the final model these positions were calculated by using the CALC-OH program (Nardelli et al., 1999) and were modelled with fixed isotropic displacement parameters.Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).Fig. 1. The structures of the molecular entities in compound (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms except those of the aqua ligand have been omitted for clarity. | |
Fig. 2. Formal diagram of the porphyrinate core illustrating the displacements of each atom from the 24-atoms core plane in units of 0.01 Å. | |
Fig. 3. The crystal structure of the title compound in a projection approximately along [100]. H atoms have been omitted. | |
Fig. 4. The crystal packing of (I), viewed down [100], showing the weak C—H···O and C—H···F hydrogen bonds and the C—H···π intermolecular interactions. | |
Fig. 5. The FT–IR spectrum of (I). |
[Mn(C44H28N4)(H2O)](CF3O3S) | Z = 2 |
Mr = 834.76 | F(000) = 856 |
Triclinic, P1 | Dx = 1.497 Mg m−3 |
a = 11.0909 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.9169 (1) Å | Cell parameters from 9884 reflections |
c = 13.7931 (1) Å | θ = 2.3–25.3° |
α = 78.333 (3)° | µ = 0.48 mm−1 |
β = 81.162 (4)° | T = 296 K |
γ = 74.179 (3)° | Plate, blue |
V = 1851.66 (5) Å3 | 0.48 × 0.38 × 0.16 mm |
Bruker APEXII CCD diffractometer | 5533 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.059 |
φ and ω scans | θmax = 25.3°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −13→13 |
Tmin = 0.835, Tmax = 0.862 | k = −15→15 |
44659 measured reflections | l = −16→16 |
6753 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.036 | Hydrogen site location: mixed |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0358P)2 + 1.4431P] where P = (Fo2 + 2Fc2)/3 |
6753 reflections | (Δ/σ)max = 0.001 |
523 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
[Mn(C44H28N4)(H2O)](CF3O3S) | γ = 74.179 (3)° |
Mr = 834.76 | V = 1851.66 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.0909 (1) Å | Mo Kα radiation |
b = 12.9169 (1) Å | µ = 0.48 mm−1 |
c = 13.7931 (1) Å | T = 296 K |
α = 78.333 (3)° | 0.48 × 0.38 × 0.16 mm |
β = 81.162 (4)° |
Bruker APEXII CCD diffractometer | 6753 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 5533 reflections with I > 2σ(I) |
Tmin = 0.835, Tmax = 0.862 | Rint = 0.059 |
44659 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.26 e Å−3 |
6753 reflections | Δρmin = −0.41 e Å−3 |
523 parameters |
Geometry. 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. |
x | y | z | Uiso*/Ueq | ||
Mn | 0.88152 (3) | 0.04367 (3) | 0.20851 (2) | 0.01081 (9) | |
S | 1.10820 (5) | 0.19791 (5) | 0.42751 (4) | 0.02139 (14) | |
F1 | 1.00980 (15) | 0.40991 (12) | 0.38570 (11) | 0.0370 (4) | |
F2 | 0.97858 (18) | 0.33973 (14) | 0.54012 (12) | 0.0517 (5) | |
F3 | 1.16153 (17) | 0.36360 (14) | 0.47867 (13) | 0.0528 (5) | |
N1 | 0.84244 (15) | −0.10052 (14) | 0.22339 (12) | 0.0122 (4) | |
N2 | 0.70036 (15) | 0.11097 (14) | 0.25129 (13) | 0.0127 (4) | |
N3 | 0.91427 (15) | 0.19154 (14) | 0.17965 (13) | 0.0126 (4) | |
N4 | 1.04477 (15) | −0.01412 (14) | 0.12917 (13) | 0.0126 (4) | |
O1 | 0.94653 (14) | 0.00719 (12) | 0.35015 (11) | 0.0191 (3) | |
H1O1 | 0.9612 | 0.0559 | 0.3758 | 0.029* | |
H2O1 | 0.9150 | −0.0320 | 0.3960 | 0.029* | |
O2 | 1.16554 (17) | 0.13077 (15) | 0.51405 (13) | 0.0330 (4) | |
O3 | 1.19208 (15) | 0.20862 (16) | 0.33828 (13) | 0.0368 (5) | |
O4 | 0.98825 (15) | 0.18025 (14) | 0.41556 (13) | 0.0263 (4) | |
C1 | 0.92919 (19) | −0.19910 (17) | 0.21380 (15) | 0.0130 (4) | |
C2 | 0.8723 (2) | −0.28720 (18) | 0.25639 (16) | 0.0160 (5) | |
H2 | 0.9116 | −0.3613 | 0.2617 | 0.019* | |
C3 | 0.7507 (2) | −0.24308 (18) | 0.28749 (16) | 0.0159 (5) | |
H3 | 0.6908 | −0.2813 | 0.3169 | 0.019* | |
C4 | 0.73116 (19) | −0.12714 (17) | 0.26691 (15) | 0.0129 (4) | |
C5 | 0.61668 (19) | −0.05325 (17) | 0.28771 (15) | 0.0135 (4) | |
C6 | 0.60387 (19) | 0.05814 (17) | 0.27983 (15) | 0.0139 (4) | |
C7 | 0.49042 (19) | 0.13390 (18) | 0.31028 (16) | 0.0169 (5) | |
H7 | 0.4117 | 0.1195 | 0.3294 | 0.020* | |
C8 | 0.51858 (19) | 0.23006 (18) | 0.30619 (16) | 0.0179 (5) | |
H8 | 0.4634 | 0.2934 | 0.3238 | 0.021* | |
C9 | 0.64944 (19) | 0.21664 (17) | 0.26963 (16) | 0.0147 (4) | |
C10 | 0.71524 (19) | 0.29641 (17) | 0.25885 (16) | 0.0149 (5) | |
C11 | 0.83947 (19) | 0.28350 (17) | 0.21575 (15) | 0.0136 (4) | |
C12 | 0.90644 (19) | 0.36721 (17) | 0.19642 (15) | 0.0152 (5) | |
H12 | 0.8766 | 0.4366 | 0.2131 | 0.018* | |
C13 | 1.0209 (2) | 0.32687 (17) | 0.14944 (16) | 0.0158 (5) | |
H13 | 1.0843 | 0.3634 | 0.1282 | 0.019* | |
C14 | 1.02682 (19) | 0.21810 (17) | 0.13828 (15) | 0.0131 (4) | |
C15 | 1.12767 (19) | 0.15067 (17) | 0.08940 (15) | 0.0133 (4) | |
C16 | 1.13167 (19) | 0.04401 (17) | 0.08165 (15) | 0.0141 (4) | |
C17 | 1.2333 (2) | −0.02581 (18) | 0.03017 (16) | 0.0177 (5) | |
H17 | 1.3016 | −0.0056 | −0.0097 | 0.021* | |
C18 | 1.2119 (2) | −0.12660 (18) | 0.05006 (16) | 0.0178 (5) | |
H18 | 1.2634 | −0.1885 | 0.0269 | 0.021* | |
C19 | 1.09597 (19) | −0.12092 (17) | 0.11317 (15) | 0.0127 (4) | |
C20 | 1.04806 (19) | −0.21024 (17) | 0.15937 (15) | 0.0133 (4) | |
C21 | 0.50146 (19) | −0.09467 (17) | 0.32576 (16) | 0.0136 (4) | |
C22 | 0.4326 (2) | −0.11748 (18) | 0.26001 (17) | 0.0175 (5) | |
H22 | 0.4625 | −0.1140 | 0.1929 | 0.021* | |
C23 | 0.3192 (2) | −0.14545 (19) | 0.29440 (18) | 0.0229 (5) | |
H23 | 0.2729 | −0.1597 | 0.2501 | 0.027* | |
C24 | 0.2747 (2) | −0.15223 (19) | 0.39465 (19) | 0.0252 (6) | |
H24 | 0.1983 | −0.1700 | 0.4173 | 0.030* | |
C25 | 0.3445 (2) | −0.13248 (19) | 0.46090 (18) | 0.0249 (5) | |
H25 | 0.3157 | −0.1381 | 0.5283 | 0.030* | |
C26 | 0.4576 (2) | −0.10425 (19) | 0.42650 (17) | 0.0220 (5) | |
H26 | 0.5045 | −0.0916 | 0.4712 | 0.026* | |
C27 | 0.65225 (19) | 0.39954 (17) | 0.29927 (16) | 0.0166 (5) | |
C28 | 0.5486 (2) | 0.47481 (17) | 0.25887 (18) | 0.0204 (5) | |
H28 | 0.5179 | 0.4627 | 0.2042 | 0.024* | |
C29 | 0.4914 (2) | 0.56791 (19) | 0.30047 (19) | 0.0262 (6) | |
H29 | 0.4219 | 0.6177 | 0.2737 | 0.031* | |
C30 | 0.5363 (2) | 0.58722 (19) | 0.38062 (19) | 0.0277 (6) | |
H30 | 0.4972 | 0.6498 | 0.4080 | 0.033* | |
C31 | 0.6399 (2) | 0.5135 (2) | 0.42083 (18) | 0.0267 (6) | |
H31 | 0.6708 | 0.5267 | 0.4749 | 0.032* | |
C32 | 0.6974 (2) | 0.41993 (19) | 0.38034 (17) | 0.0211 (5) | |
H32 | 0.7668 | 0.3704 | 0.4076 | 0.025* | |
C33 | 1.23923 (19) | 0.19472 (17) | 0.04546 (16) | 0.0143 (4) | |
C34 | 1.2315 (2) | 0.27465 (18) | −0.03917 (16) | 0.0186 (5) | |
H34 | 1.1560 | 0.3021 | −0.0677 | 0.022* | |
C35 | 1.3358 (2) | 0.31373 (19) | −0.08132 (16) | 0.0207 (5) | |
H35 | 1.3305 | 0.3661 | −0.1388 | 0.025* | |
C36 | 1.4477 (2) | 0.27500 (18) | −0.03809 (17) | 0.0201 (5) | |
H36 | 1.5176 | 0.3014 | −0.0663 | 0.024* | |
C37 | 1.4554 (2) | 0.19683 (19) | 0.04725 (18) | 0.0217 (5) | |
H37 | 1.5302 | 0.1715 | 0.0769 | 0.026* | |
C38 | 1.3521 (2) | 0.15609 (18) | 0.08875 (17) | 0.0193 (5) | |
H38 | 1.3581 | 0.1029 | 0.1456 | 0.023* | |
C39 | 1.12663 (19) | −0.32285 (17) | 0.15003 (16) | 0.0144 (5) | |
C40 | 1.1623 (2) | −0.35598 (18) | 0.05741 (17) | 0.0188 (5) | |
H40 | 1.1365 | −0.3076 | 0.0003 | 0.023* | |
C41 | 1.2358 (2) | −0.46031 (19) | 0.04959 (18) | 0.0240 (5) | |
H41 | 1.2608 | −0.4808 | −0.0128 | 0.029* | |
C42 | 1.2722 (2) | −0.53402 (19) | 0.13410 (19) | 0.0240 (5) | |
H42 | 1.3207 | −0.6042 | 0.1289 | 0.029* | |
C43 | 1.2360 (2) | −0.50259 (19) | 0.22619 (19) | 0.0251 (5) | |
H43 | 1.2595 | −0.5522 | 0.2832 | 0.030* | |
C44 | 1.1650 (2) | −0.39772 (18) | 0.23441 (17) | 0.0200 (5) | |
H44 | 1.1428 | −0.3771 | 0.2968 | 0.024* | |
C45 | 1.0622 (3) | 0.3343 (2) | 0.45958 (18) | 0.0303 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn | 0.00810 (16) | 0.01012 (17) | 0.01448 (17) | −0.00357 (12) | 0.00103 (12) | −0.00258 (12) |
S | 0.0188 (3) | 0.0274 (3) | 0.0197 (3) | −0.0098 (2) | −0.0019 (2) | −0.0023 (2) |
F1 | 0.0468 (9) | 0.0266 (8) | 0.0406 (9) | −0.0118 (7) | −0.0137 (7) | −0.0019 (7) |
F2 | 0.0748 (12) | 0.0514 (11) | 0.0325 (9) | −0.0204 (9) | 0.0149 (9) | −0.0241 (8) |
F3 | 0.0723 (12) | 0.0507 (11) | 0.0550 (11) | −0.0442 (10) | −0.0334 (9) | 0.0059 (9) |
N1 | 0.0103 (9) | 0.0125 (9) | 0.0144 (9) | −0.0038 (7) | 0.0003 (7) | −0.0032 (7) |
N2 | 0.0103 (9) | 0.0111 (9) | 0.0177 (9) | −0.0049 (7) | −0.0001 (7) | −0.0024 (7) |
N3 | 0.0108 (9) | 0.0115 (9) | 0.0159 (9) | −0.0034 (7) | 0.0002 (7) | −0.0032 (7) |
N4 | 0.0102 (8) | 0.0137 (9) | 0.0148 (9) | −0.0049 (7) | 0.0010 (7) | −0.0037 (7) |
O1 | 0.0246 (8) | 0.0204 (8) | 0.0165 (8) | −0.0124 (7) | −0.0038 (7) | −0.0019 (6) |
O2 | 0.0372 (10) | 0.0343 (11) | 0.0300 (10) | −0.0187 (9) | −0.0115 (8) | 0.0081 (8) |
O3 | 0.0204 (9) | 0.0542 (13) | 0.0262 (10) | −0.0013 (8) | 0.0057 (7) | −0.0016 (9) |
O4 | 0.0204 (8) | 0.0283 (10) | 0.0358 (10) | −0.0113 (7) | −0.0036 (7) | −0.0106 (8) |
C1 | 0.0138 (10) | 0.0115 (11) | 0.0148 (11) | −0.0031 (9) | −0.0032 (8) | −0.0037 (8) |
C2 | 0.0162 (11) | 0.0119 (11) | 0.0203 (12) | −0.0037 (9) | −0.0017 (9) | −0.0030 (9) |
C3 | 0.0144 (11) | 0.0168 (11) | 0.0186 (11) | −0.0088 (9) | −0.0001 (9) | −0.0024 (9) |
C4 | 0.0123 (10) | 0.0151 (11) | 0.0134 (10) | −0.0070 (9) | 0.0002 (8) | −0.0033 (8) |
C5 | 0.0127 (10) | 0.0170 (11) | 0.0124 (10) | −0.0060 (9) | −0.0004 (8) | −0.0033 (8) |
C6 | 0.0108 (10) | 0.0162 (11) | 0.0152 (11) | −0.0050 (9) | 0.0000 (8) | −0.0029 (9) |
C7 | 0.0089 (10) | 0.0189 (12) | 0.0226 (12) | −0.0044 (9) | −0.0001 (9) | −0.0030 (9) |
C8 | 0.0106 (10) | 0.0142 (11) | 0.0255 (12) | −0.0008 (9) | 0.0033 (9) | −0.0032 (9) |
C9 | 0.0114 (10) | 0.0127 (11) | 0.0190 (11) | −0.0022 (9) | 0.0001 (9) | −0.0030 (9) |
C10 | 0.0136 (11) | 0.0119 (11) | 0.0180 (11) | −0.0022 (9) | −0.0013 (9) | −0.0013 (9) |
C11 | 0.0141 (11) | 0.0124 (11) | 0.0142 (11) | −0.0034 (9) | −0.0013 (8) | −0.0020 (9) |
C12 | 0.0171 (11) | 0.0119 (11) | 0.0167 (11) | −0.0042 (9) | −0.0002 (9) | −0.0029 (9) |
C13 | 0.0144 (11) | 0.0150 (11) | 0.0192 (11) | −0.0078 (9) | 0.0001 (9) | −0.0015 (9) |
C14 | 0.0118 (10) | 0.0136 (11) | 0.0148 (11) | −0.0056 (8) | −0.0024 (8) | −0.0001 (9) |
C15 | 0.0118 (10) | 0.0162 (11) | 0.0124 (10) | −0.0056 (9) | −0.0006 (8) | −0.0010 (9) |
C16 | 0.0113 (10) | 0.0169 (11) | 0.0145 (11) | −0.0049 (9) | −0.0006 (8) | −0.0020 (9) |
C17 | 0.0121 (10) | 0.0207 (12) | 0.0206 (12) | −0.0069 (9) | 0.0045 (9) | −0.0050 (9) |
C18 | 0.0148 (11) | 0.0168 (12) | 0.0218 (12) | −0.0029 (9) | 0.0023 (9) | −0.0079 (9) |
C19 | 0.0116 (10) | 0.0143 (11) | 0.0128 (10) | −0.0026 (8) | −0.0019 (8) | −0.0037 (8) |
C20 | 0.0119 (10) | 0.0143 (11) | 0.0154 (11) | −0.0025 (9) | −0.0034 (8) | −0.0058 (9) |
C21 | 0.0099 (10) | 0.0099 (10) | 0.0205 (11) | −0.0018 (8) | 0.0002 (9) | −0.0035 (9) |
C22 | 0.0169 (11) | 0.0176 (12) | 0.0186 (11) | −0.0058 (9) | −0.0036 (9) | −0.0006 (9) |
C23 | 0.0166 (11) | 0.0220 (13) | 0.0329 (14) | −0.0087 (10) | −0.0104 (10) | 0.0000 (10) |
C24 | 0.0121 (11) | 0.0203 (13) | 0.0407 (15) | −0.0066 (10) | 0.0020 (10) | 0.0006 (11) |
C25 | 0.0239 (13) | 0.0257 (13) | 0.0245 (13) | −0.0118 (11) | 0.0111 (10) | −0.0054 (10) |
C26 | 0.0236 (12) | 0.0260 (13) | 0.0203 (12) | −0.0119 (10) | 0.0022 (10) | −0.0081 (10) |
C27 | 0.0134 (11) | 0.0126 (11) | 0.0238 (12) | −0.0075 (9) | 0.0083 (9) | −0.0049 (9) |
C28 | 0.0148 (11) | 0.0130 (11) | 0.0312 (13) | −0.0057 (9) | 0.0047 (10) | −0.0013 (10) |
C29 | 0.0170 (12) | 0.0147 (12) | 0.0416 (15) | −0.0040 (10) | 0.0086 (11) | −0.0015 (11) |
C30 | 0.0265 (13) | 0.0144 (12) | 0.0402 (15) | −0.0101 (10) | 0.0176 (11) | −0.0091 (11) |
C31 | 0.0323 (14) | 0.0251 (13) | 0.0270 (13) | −0.0175 (11) | 0.0115 (11) | −0.0108 (11) |
C32 | 0.0187 (12) | 0.0185 (12) | 0.0257 (13) | −0.0078 (10) | 0.0059 (10) | −0.0044 (10) |
C33 | 0.0151 (11) | 0.0119 (11) | 0.0170 (11) | −0.0052 (9) | 0.0035 (9) | −0.0064 (9) |
C34 | 0.0163 (11) | 0.0230 (12) | 0.0176 (11) | −0.0075 (9) | −0.0007 (9) | −0.0033 (9) |
C35 | 0.0241 (12) | 0.0224 (12) | 0.0162 (11) | −0.0113 (10) | 0.0026 (9) | −0.0004 (9) |
C36 | 0.0153 (11) | 0.0223 (13) | 0.0248 (12) | −0.0100 (10) | 0.0080 (9) | −0.0092 (10) |
C37 | 0.0103 (11) | 0.0241 (13) | 0.0307 (13) | −0.0046 (9) | 0.0001 (10) | −0.0062 (10) |
C38 | 0.0165 (11) | 0.0149 (11) | 0.0245 (12) | −0.0044 (9) | −0.0001 (9) | −0.0001 (9) |
C39 | 0.0086 (10) | 0.0136 (11) | 0.0228 (12) | −0.0063 (9) | 0.0002 (9) | −0.0040 (9) |
C40 | 0.0199 (12) | 0.0176 (12) | 0.0201 (12) | −0.0049 (9) | −0.0045 (9) | −0.0035 (9) |
C41 | 0.0223 (12) | 0.0229 (13) | 0.0301 (13) | −0.0052 (10) | 0.0000 (10) | −0.0145 (11) |
C42 | 0.0160 (11) | 0.0137 (12) | 0.0412 (15) | 0.0000 (9) | −0.0016 (10) | −0.0079 (11) |
C43 | 0.0180 (12) | 0.0193 (13) | 0.0320 (14) | −0.0008 (10) | −0.0023 (10) | 0.0038 (11) |
C44 | 0.0156 (11) | 0.0209 (12) | 0.0200 (12) | −0.0015 (9) | 0.0017 (9) | −0.0022 (10) |
C45 | 0.0404 (15) | 0.0339 (15) | 0.0239 (13) | −0.0219 (13) | −0.0076 (12) | −0.0013 (11) |
Mn—N1 | 1.9893 (17) | C17—H17 | 0.9300 |
Mn—N3 | 1.9912 (17) | C18—C19 | 1.431 (3) |
Mn—N4 | 2.0044 (17) | C18—H18 | 0.9300 |
Mn—N2 | 2.0079 (17) | C19—C20 | 1.397 (3) |
Mn—O1 | 2.1057 (15) | C20—C39 | 1.497 (3) |
S—O3 | 1.4313 (17) | C21—C22 | 1.392 (3) |
S—O2 | 1.4475 (18) | C21—C26 | 1.392 (3) |
S—O4 | 1.4482 (16) | C22—C23 | 1.390 (3) |
S—C45 | 1.820 (3) | C22—H22 | 0.9300 |
F1—C45 | 1.342 (3) | C23—C24 | 1.388 (3) |
F2—C45 | 1.333 (3) | C23—H23 | 0.9300 |
F3—C45 | 1.336 (3) | C24—C25 | 1.385 (3) |
N1—C4 | 1.386 (3) | C24—H24 | 0.9300 |
N1—C1 | 1.388 (3) | C25—C26 | 1.388 (3) |
N2—C9 | 1.386 (3) | C25—H25 | 0.9300 |
N2—C6 | 1.388 (3) | C26—H26 | 0.9300 |
N3—C11 | 1.386 (3) | C27—C32 | 1.391 (3) |
N3—C14 | 1.392 (3) | C27—C28 | 1.395 (3) |
N4—C16 | 1.387 (3) | C28—C29 | 1.389 (3) |
N4—C19 | 1.390 (3) | C28—H28 | 0.9300 |
O1—H1O1 | 0.8437 | C29—C30 | 1.371 (4) |
O1—H2O1 | 0.8225 | C29—H29 | 0.9300 |
C1—C20 | 1.399 (3) | C30—C31 | 1.386 (4) |
C1—C2 | 1.431 (3) | C30—H30 | 0.9300 |
C2—C3 | 1.352 (3) | C31—C32 | 1.386 (3) |
C2—H2 | 0.9300 | C31—H31 | 0.9300 |
C3—C4 | 1.428 (3) | C32—H32 | 0.9300 |
C3—H3 | 0.9300 | C33—C34 | 1.390 (3) |
C4—C5 | 1.394 (3) | C33—C38 | 1.393 (3) |
C5—C6 | 1.390 (3) | C34—C35 | 1.387 (3) |
C5—C21 | 1.499 (3) | C34—H34 | 0.9300 |
C6—C7 | 1.432 (3) | C35—C36 | 1.384 (3) |
C7—C8 | 1.349 (3) | C35—H35 | 0.9300 |
C7—H7 | 0.9300 | C36—C37 | 1.384 (3) |
C8—C9 | 1.437 (3) | C36—H36 | 0.9300 |
C8—H8 | 0.9300 | C37—C38 | 1.387 (3) |
C9—C10 | 1.390 (3) | C37—H37 | 0.9300 |
C10—C11 | 1.394 (3) | C38—H38 | 0.9300 |
C10—C27 | 1.499 (3) | C39—C44 | 1.394 (3) |
C11—C12 | 1.433 (3) | C39—C40 | 1.395 (3) |
C12—C13 | 1.351 (3) | C40—C41 | 1.388 (3) |
C12—H12 | 0.9300 | C40—H40 | 0.9300 |
C13—C14 | 1.427 (3) | C41—C42 | 1.384 (3) |
C13—H13 | 0.9300 | C41—H41 | 0.9300 |
C14—C15 | 1.392 (3) | C42—C43 | 1.379 (3) |
C15—C16 | 1.392 (3) | C42—H42 | 0.9300 |
C15—C33 | 1.495 (3) | C43—C44 | 1.386 (3) |
C16—C17 | 1.431 (3) | C43—H43 | 0.9300 |
C17—C18 | 1.353 (3) | C44—H44 | 0.9300 |
N1—Mn—N3 | 174.02 (7) | N4—C19—C20 | 125.14 (18) |
N1—Mn—N4 | 89.12 (7) | N4—C19—C18 | 109.24 (18) |
N3—Mn—N4 | 89.97 (7) | C20—C19—C18 | 125.35 (19) |
N1—Mn—N2 | 89.98 (7) | C19—C20—C1 | 122.82 (19) |
N3—Mn—N2 | 89.29 (7) | C19—C20—C39 | 118.81 (18) |
N4—Mn—N2 | 164.27 (7) | C1—C20—C39 | 118.38 (18) |
N1—Mn—O1 | 92.84 (6) | C22—C21—C26 | 119.10 (19) |
N3—Mn—O1 | 93.14 (7) | C22—C21—C5 | 120.39 (19) |
N4—Mn—O1 | 98.57 (6) | C26—C21—C5 | 120.38 (19) |
N2—Mn—O1 | 97.16 (7) | C23—C22—C21 | 120.1 (2) |
O3—S—O2 | 115.56 (11) | C23—C22—H22 | 119.9 |
O3—S—O4 | 115.55 (11) | C21—C22—H22 | 119.9 |
O2—S—O4 | 114.10 (10) | C24—C23—C22 | 120.3 (2) |
O3—S—C45 | 103.65 (12) | C24—C23—H23 | 119.8 |
O2—S—C45 | 103.18 (11) | C22—C23—H23 | 119.8 |
O4—S—C45 | 102.25 (11) | C25—C24—C23 | 119.8 (2) |
C4—N1—C1 | 105.76 (16) | C25—C24—H24 | 120.1 |
C4—N1—Mn | 126.66 (14) | C23—C24—H24 | 120.1 |
C1—N1—Mn | 126.07 (13) | C24—C25—C26 | 119.8 (2) |
C9—N2—C6 | 105.76 (16) | C24—C25—H25 | 120.1 |
C9—N2—Mn | 126.80 (13) | C26—C25—H25 | 120.1 |
C6—N2—Mn | 127.04 (14) | C25—C26—C21 | 120.7 (2) |
C11—N3—C14 | 105.63 (16) | C25—C26—H26 | 119.6 |
C11—N3—Mn | 126.19 (13) | C21—C26—H26 | 119.6 |
C14—N3—Mn | 126.89 (14) | C32—C27—C28 | 119.1 (2) |
C16—N4—C19 | 105.98 (16) | C32—C27—C10 | 119.0 (2) |
C16—N4—Mn | 126.78 (14) | C28—C27—C10 | 121.9 (2) |
C19—N4—Mn | 127.21 (13) | C29—C28—C27 | 119.8 (2) |
Mn—O1—H1O1 | 121.1 | C29—C28—H28 | 120.1 |
Mn—O1—H2O1 | 120.2 | C27—C28—H28 | 120.1 |
H1O1—O1—H2O1 | 106.1 | C30—C29—C28 | 120.7 (2) |
N1—C1—C20 | 125.04 (18) | C30—C29—H29 | 119.7 |
N1—C1—C2 | 109.52 (17) | C28—C29—H29 | 119.7 |
C20—C1—C2 | 124.94 (19) | C29—C30—C31 | 120.0 (2) |
C3—C2—C1 | 107.47 (19) | C29—C30—H30 | 120.0 |
C3—C2—H2 | 126.3 | C31—C30—H30 | 120.0 |
C1—C2—H2 | 126.3 | C30—C31—C32 | 119.9 (2) |
C2—C3—C4 | 107.52 (19) | C30—C31—H31 | 120.1 |
C2—C3—H3 | 126.2 | C32—C31—H31 | 120.1 |
C4—C3—H3 | 126.2 | C31—C32—C27 | 120.5 (2) |
N1—C4—C5 | 125.91 (19) | C31—C32—H32 | 119.7 |
N1—C4—C3 | 109.65 (18) | C27—C32—H32 | 119.7 |
C5—C4—C3 | 124.44 (19) | C34—C33—C38 | 119.23 (19) |
C6—C5—C4 | 123.34 (19) | C34—C33—C15 | 120.34 (19) |
C6—C5—C21 | 117.17 (18) | C38—C33—C15 | 120.43 (19) |
C4—C5—C21 | 119.42 (18) | C35—C34—C33 | 120.4 (2) |
N2—C6—C5 | 125.75 (19) | C35—C34—H34 | 119.8 |
N2—C6—C7 | 109.63 (18) | C33—C34—H34 | 119.8 |
C5—C6—C7 | 124.33 (19) | C36—C35—C34 | 120.2 (2) |
C8—C7—C6 | 107.52 (18) | C36—C35—H35 | 119.9 |
C8—C7—H7 | 126.2 | C34—C35—H35 | 119.9 |
C6—C7—H7 | 126.2 | C37—C36—C35 | 119.8 (2) |
C7—C8—C9 | 107.46 (19) | C37—C36—H36 | 120.1 |
C7—C8—H8 | 126.3 | C35—C36—H36 | 120.1 |
C9—C8—H8 | 126.3 | C36—C37—C38 | 120.3 (2) |
N2—C9—C10 | 125.64 (18) | C36—C37—H37 | 119.8 |
N2—C9—C8 | 109.51 (18) | C38—C37—H37 | 119.8 |
C10—C9—C8 | 124.8 (2) | C37—C38—C33 | 120.1 (2) |
C9—C10—C11 | 123.1 (2) | C37—C38—H38 | 119.9 |
C9—C10—C27 | 118.79 (18) | C33—C38—H38 | 119.9 |
C11—C10—C27 | 118.01 (18) | C44—C39—C40 | 118.3 (2) |
N3—C11—C10 | 125.85 (19) | C44—C39—C20 | 120.49 (19) |
N3—C11—C12 | 109.62 (17) | C40—C39—C20 | 121.18 (19) |
C10—C11—C12 | 124.42 (19) | C41—C40—C39 | 120.7 (2) |
C13—C12—C11 | 107.48 (19) | C41—C40—H40 | 119.7 |
C13—C12—H12 | 126.3 | C39—C40—H40 | 119.7 |
C11—C12—H12 | 126.3 | C42—C41—C40 | 120.3 (2) |
C12—C13—C14 | 107.60 (18) | C42—C41—H41 | 119.8 |
C12—C13—H13 | 126.2 | C40—C41—H41 | 119.8 |
C14—C13—H13 | 126.2 | C43—C42—C41 | 119.5 (2) |
N3—C14—C15 | 125.19 (19) | C43—C42—H42 | 120.3 |
N3—C14—C13 | 109.66 (18) | C41—C42—H42 | 120.3 |
C15—C14—C13 | 125.08 (19) | C42—C43—C44 | 120.5 (2) |
C16—C15—C14 | 123.68 (19) | C42—C43—H43 | 119.7 |
C16—C15—C33 | 118.41 (18) | C44—C43—H43 | 119.7 |
C14—C15—C33 | 117.88 (18) | C43—C44—C39 | 120.7 (2) |
N4—C16—C15 | 125.79 (19) | C43—C44—H44 | 119.7 |
N4—C16—C17 | 109.47 (18) | C39—C44—H44 | 119.7 |
C15—C16—C17 | 124.51 (19) | F2—C45—F3 | 107.6 (2) |
C18—C17—C16 | 107.46 (18) | F2—C45—F1 | 107.3 (2) |
C18—C17—H17 | 126.3 | F3—C45—F1 | 107.1 (2) |
C16—C17—H17 | 126.3 | F2—C45—S | 111.41 (17) |
C17—C18—C19 | 107.71 (19) | F3—C45—S | 111.2 (2) |
C17—C18—H18 | 126.1 | F1—C45—S | 112.04 (17) |
C19—C18—H18 | 126.1 | ||
C4—N1—C1—C20 | 169.3 (2) | Mn—N4—C19—C20 | −7.5 (3) |
Mn—N1—C1—C20 | −24.0 (3) | C16—N4—C19—C18 | −3.5 (2) |
C4—N1—C1—C2 | −2.9 (2) | Mn—N4—C19—C18 | 178.36 (14) |
Mn—N1—C1—C2 | 163.78 (14) | C17—C18—C19—N4 | 1.8 (2) |
N1—C1—C2—C3 | 2.7 (2) | C17—C18—C19—C20 | −172.4 (2) |
C20—C1—C2—C3 | −169.5 (2) | N4—C19—C20—C1 | 12.1 (3) |
C1—C2—C3—C4 | −1.4 (2) | C18—C19—C20—C1 | −174.7 (2) |
C1—N1—C4—C5 | −177.8 (2) | N4—C19—C20—C39 | −168.24 (19) |
Mn—N1—C4—C5 | 15.7 (3) | C18—C19—C20—C39 | 5.0 (3) |
C1—N1—C4—C3 | 2.1 (2) | N1—C1—C20—C19 | 4.3 (3) |
Mn—N1—C4—C3 | −164.52 (14) | C2—C1—C20—C19 | 175.3 (2) |
C2—C3—C4—N1 | −0.4 (2) | N1—C1—C20—C39 | −175.41 (19) |
C2—C3—C4—C5 | 179.4 (2) | C2—C1—C20—C39 | −4.4 (3) |
N1—C4—C5—C6 | −9.4 (3) | C6—C5—C21—C22 | 101.0 (2) |
C3—C4—C5—C6 | 170.8 (2) | C4—C5—C21—C22 | −82.1 (3) |
N1—C4—C5—C21 | 173.97 (19) | C6—C5—C21—C26 | −74.9 (3) |
C3—C4—C5—C21 | −5.8 (3) | C4—C5—C21—C26 | 101.9 (2) |
C9—N2—C6—C5 | −170.4 (2) | C26—C21—C22—C23 | 2.4 (3) |
Mn—N2—C6—C5 | 2.7 (3) | C5—C21—C22—C23 | −173.6 (2) |
C9—N2—C6—C7 | 3.6 (2) | C21—C22—C23—C24 | −0.8 (3) |
Mn—N2—C6—C7 | 176.68 (14) | C22—C23—C24—C25 | −0.9 (4) |
C4—C5—C6—N2 | −0.3 (3) | C23—C24—C25—C26 | 1.1 (4) |
C21—C5—C6—N2 | 176.46 (19) | C24—C25—C26—C21 | 0.5 (4) |
C4—C5—C6—C7 | −173.4 (2) | C22—C21—C26—C25 | −2.2 (3) |
C21—C5—C6—C7 | 3.3 (3) | C5—C21—C26—C25 | 173.8 (2) |
N2—C6—C7—C8 | −3.5 (3) | C9—C10—C27—C32 | 111.9 (2) |
C5—C6—C7—C8 | 170.5 (2) | C11—C10—C27—C32 | −65.5 (3) |
C6—C7—C8—C9 | 2.0 (2) | C9—C10—C27—C28 | −67.2 (3) |
C6—N2—C9—C10 | 175.0 (2) | C11—C10—C27—C28 | 115.4 (2) |
Mn—N2—C9—C10 | 1.9 (3) | C32—C27—C28—C29 | −0.7 (3) |
C6—N2—C9—C8 | −2.3 (2) | C10—C27—C28—C29 | 178.37 (19) |
Mn—N2—C9—C8 | −175.45 (14) | C27—C28—C29—C30 | 0.5 (3) |
C7—C8—C9—N2 | 0.2 (3) | C28—C29—C30—C31 | 0.1 (3) |
C7—C8—C9—C10 | −177.2 (2) | C29—C30—C31—C32 | −0.5 (3) |
N2—C9—C10—C11 | 8.3 (3) | C30—C31—C32—C27 | 0.2 (3) |
C8—C9—C10—C11 | −174.7 (2) | C28—C27—C32—C31 | 0.3 (3) |
N2—C9—C10—C27 | −168.9 (2) | C10—C27—C32—C31 | −178.76 (19) |
C8—C9—C10—C27 | 8.0 (3) | C16—C15—C33—C34 | 109.7 (2) |
C14—N3—C11—C10 | 176.3 (2) | C14—C15—C33—C34 | −72.0 (3) |
Mn—N3—C11—C10 | −16.0 (3) | C16—C15—C33—C38 | −70.2 (3) |
C14—N3—C11—C12 | 0.0 (2) | C14—C15—C33—C38 | 108.1 (2) |
Mn—N3—C11—C12 | 167.73 (14) | C38—C33—C34—C35 | 1.4 (3) |
C9—C10—C11—N3 | −1.0 (3) | C15—C33—C34—C35 | −178.5 (2) |
C27—C10—C11—N3 | 176.29 (19) | C33—C34—C35—C36 | −1.4 (3) |
C9—C10—C11—C12 | 174.8 (2) | C34—C35—C36—C37 | 0.2 (3) |
C27—C10—C11—C12 | −7.9 (3) | C35—C36—C37—C38 | 0.9 (3) |
N3—C11—C12—C13 | −0.2 (2) | C36—C37—C38—C33 | −0.8 (3) |
C10—C11—C12—C13 | −176.6 (2) | C34—C33—C38—C37 | −0.3 (3) |
C11—C12—C13—C14 | 0.3 (2) | C15—C33—C38—C37 | 179.6 (2) |
C11—N3—C14—C15 | −177.1 (2) | C19—C20—C39—C44 | 118.9 (2) |
Mn—N3—C14—C15 | 15.3 (3) | C1—C20—C39—C44 | −61.4 (3) |
C11—N3—C14—C13 | 0.2 (2) | C19—C20—C39—C40 | −61.7 (3) |
Mn—N3—C14—C13 | −167.42 (14) | C1—C20—C39—C40 | 118.0 (2) |
C12—C13—C14—N3 | −0.3 (2) | C44—C39—C40—C41 | −1.0 (3) |
C12—C13—C14—C15 | 177.0 (2) | C20—C39—C40—C41 | 179.56 (19) |
N3—C14—C15—C16 | −4.6 (3) | C39—C40—C41—C42 | 1.7 (3) |
C13—C14—C15—C16 | 178.6 (2) | C40—C41—C42—C43 | −0.8 (3) |
N3—C14—C15—C33 | 177.27 (18) | C41—C42—C43—C44 | −0.8 (3) |
C13—C14—C15—C33 | 0.4 (3) | C42—C43—C44—C39 | 1.4 (3) |
C19—N4—C16—C15 | −170.7 (2) | C40—C39—C44—C43 | −0.5 (3) |
Mn—N4—C16—C15 | 7.4 (3) | C20—C39—C44—C43 | 178.9 (2) |
C19—N4—C16—C17 | 4.0 (2) | O3—S—C45—F2 | 177.39 (18) |
Mn—N4—C16—C17 | −177.90 (14) | O2—S—C45—F2 | −61.8 (2) |
C14—C15—C16—N4 | −7.3 (3) | O4—S—C45—F2 | 56.9 (2) |
C33—C15—C16—N4 | 170.85 (19) | O3—S—C45—F3 | −62.62 (19) |
C14—C15—C16—C17 | 178.8 (2) | O2—S—C45—F3 | 58.23 (19) |
C33—C15—C16—C17 | −3.1 (3) | O4—S—C45—F3 | 176.92 (17) |
N4—C16—C17—C18 | −3.0 (2) | O3—S—C45—F1 | 57.18 (19) |
C15—C16—C17—C18 | 171.8 (2) | O2—S—C45—F1 | 178.03 (17) |
C16—C17—C18—C19 | 0.7 (2) | O4—S—C45—F1 | −63.28 (19) |
C16—N4—C19—C20 | 170.7 (2) |
Cg2, Cg3, Cg4, Cg7, Cg9 and Cg11 are the centroids of the N2/C6–C9, N3/C11–C14, N4/C16–C19, Mn/N2/C9–C11/N3, C21–C26 and C33–C38 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O1···O4 | 0.84 | 1.91 | 2.745 (2) | 171 |
O1—H2O1···O2i | 0.82 | 1.90 | 2.715 (2) | 171 |
C7—H7···O3ii | 0.93 | 2.39 | 3.170 (3) | 141 |
C44—H44···F2i | 0.93 | 2.50 | 3.397 (3) | 162 |
C23—H23···Cg4ii | 0.93 | 2.85 | 3.603 (3) | 139 |
C25—H25···Cg2iii | 0.93 | 2.89 | 3.650 (3) | 139 |
C30—H30···Cg9iv | 0.93 | 2.82 | 3.610 (3) | 144 |
C37—H37···Cg2v | 0.93 | 2.97 | 3.676 (3) | 133 |
C40—H40···Cg3vi | 0.93 | 2.62 | 3.449 (2) | 148 |
C42—H42···Cg11vii | 0.93 | 2.89 | 3.631 (3) | 137 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) x−1, y, z; (iii) −x+1, −y, −z+1; (iv) x, y+1, z; (v) x+1, y, z; (vi) −x+2, −y, −z; (vii) x, y−1, z. |
Cg2, Cg3, Cg4, Cg7, Cg9 and Cg11 are the centroids of the N2/C6–C9, N3/C11–C14, N4/C16–C19, Mn/N2/C9–C11/N3, C21–C26 and C33–C38 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O1···O4 | 0.84 | 1.91 | 2.745 (2) | 171 |
O1—H2O1···O2i | 0.82 | 1.90 | 2.715 (2) | 171 |
C7—H7···O3ii | 0.93 | 2.39 | 3.170 (3) | 141 |
C44—H44···F2i | 0.93 | 2.50 | 3.397 (3) | 162 |
C23—H23···Cg4ii | 0.93 | 2.85 | 3.603 (3) | 139 |
C25—H25···Cg2iii | 0.93 | 2.89 | 3.650 (3) | 139 |
C30—H30···Cg9iv | 0.93 | 2.82 | 3.610 (3) | 144 |
C37—H37···Cg2v | 0.93 | 2.97 | 3.676 (3) | 133 |
C40—H40···Cg3vi | 0.93 | 2.62 | 3.449 (2) | 148 |
C42—H42···Cg11vii | 0.93 | 2.89 | 3.631 (3) | 137 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) x−1, y, z; (iii) −x+1, −y, −z+1; (iv) x, y+1, z; (v) x+1, y, z; (vi) −x+2, −y, −z; (vii) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C44H28N4)(H2O)](CF3O3S) |
Mr | 834.76 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 11.0909 (1), 12.9169 (1), 13.7931 (1) |
α, β, γ (°) | 78.333 (3), 81.162 (4), 74.179 (3) |
V (Å3) | 1851.66 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.48 |
Crystal size (mm) | 0.48 × 0.38 × 0.16 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.835, 0.862 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 44659, 6753, 5533 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.086, 1.05 |
No. of reflections | 6753 |
No. of parameters | 523 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.41 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SIR2004 (Burla et al., 2005), SHELXL2014 (Sheldrick, 2015), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012).
Acknowledgements
The authors gratefully acknowledge financial support from the Ministry of Higher Education and Scientific Research of Tunisia.
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