research communications
II compound: catena-poly[guanidinium [[aquachloridomanganese(II)]-μ2-oxalato-κ4O1,O2:O1′,O2′] monohydrate]
and spectroscopic analysis of a new oxalate-bridged MnaLaboratoire de Matériaux et Cristallochimie, Faculté des Sciences de Tunis, Université de Tunis El Manar, 2092 Manar II Tunis, Tunisia, and bUniversité de Gabès, Faculté des Sciences de Gabès, Campus Universitaire, Cité Erriadh Zrig, Gabès, 6072, Tunisia
*Correspondence e-mail: faouzi.zid@fst.rnu.tn
As part of our studies on the synthesis and the characterization of oxalate-bridged compounds M–ox–M (ox = oxalate dianion and M = transition metal ion), we report the of a new oxalate-bridged MnII phase, {(CH6N3)[Mn(C2O4)Cl(H2O)]·H2O}n. In the compound, a succession of MnII ions (situated on inversion centers) adopting a distorted octahedral coordination and bridged by oxalate ligands forms parallel zigzag chains running along the c axis. These chains are interconnected through O—H⋯O hydrogen-bonding interactions to form anionic layers parallel to (010). Individual layers are held together via strong hydrogen bonds involving the guanidinium cations (N—H⋯O and N—H⋯Cl) and the disordered non-coordinating water molecule (O—H⋯O and O—H⋯Cl), as well as by guanidinium π–π stacking. The structural data were confirmed by IR and UV–Visible spectroscopic analysis.
Keywords: crystal structure; manganese; oxalate bridge; coordination polymer.
CCDC reference: 1474882
1. Chemical context
Much attention had been devoted to the coordination chemistry of oxalate (ox) anions due to the interesting structural features and physical properties they possess (Chérif et al., 2011; Dridi et al., 2013; Decurtins et al., 1997). Oxalate anions have been demonstrated to be one of the most versatile bridging ligands for the construction of coordination polymers when combined with transition metal cations. Manganese(II) is a promising cation with possibilities of forming one-dimensional oxalato-based coordination polymers, as evidenced by reports describing the structures of several topologically similar MnII–ox–MnII chains [see, for example, García-Couceiro et al. (2005) or Beznischenko et al. (2009)]. In those compounds, the oxalate-bridged manganese framework may be considered as a single-chain magnet based on the oxalate linker (e.g. Clemente-León et al., 2011). In this work, we report the synthesis and determination of a new oxalate-bridged coordination compound, {(CH6N3)[Mn(C2O4)Cl(H2O)]·H2O}n (I).
2. Structural commentary
The principal structural motifs of the title compound are the complex anion [MnCl(C2O4)(H2O)]−, the organic cation (CH6N3)+ and one disordered non-coordinating water molecule. A bond-valence-sum calculation, assuming Mn—O and Mn—Cl bonds, gives a BVS value (Brown & Altermatt, 1985) of 2.05 (7), confirming the +II of Mn and ensuring electrical neutrality of the formed unit. The coordination environment of the MnII ion involves two oxalate ligands exhibiting bis-chelating coordination modes, one chloride atom and one oxygen atom of the aqua ligand (Fig. 1) in a slightly distorted octahedral geometry. The small bite angles of the bis-chelating oxalate groups [73.99 (6)° for O3—Mn1—O4 and 75.35 (7)° for O1—Mn1—O2] and the extended Mn1—Cl1 bond [2.458 (2) Å] account for this distortion. The polyhedral distance and angle distortions, calculated from the Mn—O and Mn—Cl distances and O—Mn—O and O—Mn—Cl angles in the MnO5Cl unit, were found to be IDd = 0.03 (2) and IDa = 0.22 (4)%, respectively (Baur, 1974; Wildner, 1992).
The equatorial plane of the MnO5Cl octahedron is formed by atoms Mn1, OW1, O1, O2 and O3, with a calculated root-mean-square deviation of the fitted atoms of 0.1038 Å. The axial positions are occupied by the chloride atom [Mn1—Cl1 = 2.458 (2) Å] and one oxygen atom from the bridging oxalato group [Mn1—O4 = 2.248 (2) Å]. The two oxalato groups are almost perpendicular with a dihedral angle of 89.09 (6)°. The oxalate ion is located on an inversion center that also relates the two Mn atoms bonded to the oxalate ion with each other. The bridged metal ions are nearly coplanar with the oxalate plane with a mean deviation of 0.0147 (8) Å.
The MnII ion, as a d5 high-spin system with a spherical electron distribution, has a limited number of commonly observed coordination geometries that are based on minimization of ligand–ligand repulsion. Among the Mn—O distances, the shortest are those involving an oxygen atom from the oxalate ion trans to another oxygen atom from the second oxalate ion. The range of these distances is 2.180 (1) to 2.194 (1) Å, which is in accord with those observed in other oxalate-bridged compounds such as one of the polymorphs of catena-poly[[diaquamanganese(II)]-μ-oxalato-κ4O1,O2:O1′,O2′] (Soleimannejad et al., 2007). The Mn—O distances involving the oxygen atoms of the oxalate ion trans to the coordinating water molecule and trans to the chloride atom are slightly longer at 2.202 (2) and 2.248 (2) Å.
The view of the structure packing (Fig. 2) shows the layered structure based on anionic zigzag oxalate-bridged MnII chains running along the c axis. The intra-chain Mn⋯Mn distances through bridging oxalate are 5.695 (2) and 5.778 (2) Å, somewhat longer than the value of 5.652 Å previously observed for {[Mn(C2O4)(C8H7N3)]·1.5H2O}n (An & Zhu, 2009) involving a pyridyl-pyrazolide ligand instead of chloride and aqua ligands in the coordination environment of the MnII ion.
The geometric parameters for the guanidinium cations do not show any unusual features and are in agreement with those previously reported (Sakai et al. 2003; Vaidhyanathan et al., 2001). The bond lengths [1.318 (2)–1.329 (2) Å] and angles [119.27 (16)–120.57 (16)°] are in the typical ranges, confirming a highly resonance-stabilized electronic structure and a completely delocalized charge between the three sp2 nitrogen atoms. Conjugation of the nitrogen lone pairs with the empty p-orbital of the sp2 carbon atom creates a planar cation.
3. Supramolecular features
Neighbouring oxalate-bridged zigzag chains are connected with each other via O—H⋯O hydrogen bonds involving the coordinating water molecule. Its oxygen atom acts as a hydrogen-bond donor and establishes strong hydrogen bonds (Table 1) towards one of the oxalate oxygen atoms of a neighbouring chain (Fig. 3), OW1—HW2⋯O3v [symmetry code: (v) −x + 2, −y + 1, −z], leading to the formation of anionic layers parallel to (010). A disordered non-coordinating water molecule acts as acceptor (Fig. 3) for the other hydrogen atom involving the coordinating water molecule via the hydrogen bonds OW1—HW1⋯OW2i and OW1—HW1⋯OW2Bi [symmetry code: (i) x, y − 1, z]. Both disorder components of the non-coordinating water molecules act as hydrogen-bond donors towards oxygen atom O3 (Fig. 3) via the hydrogen bonds OW2—HW3⋯O3 and OW2B—HW5⋯O3, but they form different hydrogen bonds via their second H atom, to chlorine atoms in different lattice positions via hydrogen bonds OW2—HW4⋯Cl1vi and OW2B-–HW6⋯Cl1 [symmetry code: (vi) −x + 2, −y + 2, −z]. The combined water hydrogen bonds link the anionic layers into a 3D framework.
The three N atoms of the guanidinium cation act as donors of hydrogen bonds N1—H1A⋯O2i, N1—H1B⋯O4, N2—H2A⋯Cl1ii, N2—H2B⋯Cl1iii, N2—H2A⋯O4, N3—H3A⋯O1iv and N3—H3B⋯Cl1iii [Table 1; symmetry codes: (i) x, y − 1, z; (ii) x − 1, y, z; (iii) −x + 1, −y + 1, −z + 1; (iv) −x + 1, −y, −z + 1], consolidating the anionic layers and giving additional stability to the three-dimensional structure as illustrated in Fig. 4. The guanidinium cations are also paired via π–π stacking with an interplanar distance of 3.547 (3) Å between C3 and C3(−x, −y, −z + 1) (Di Tondo & Pritchard, 2012), as shown in Fig. 5.
4. IR and UV–Vis characterizations
The IR spectrum was recorded in the 4000–400 cm−1 region using a Perkin–Elmer spectrometer with the sample diluted in a pressed KBr pellet. The most intense IR absorption bands of (I) are given in Table 2. The spectrum (Fig. 6) displays broad and strong bands centered at 3390 and 3182 cm−1 assigned to [ν(O—H) + νas(NH2)] and νs(NH2), respectively (Sasikala et al., 2015). The broadness of these bands is indicative of the presence of both coordinating and non-coordinating water molecules, as well as –NH2 groups involved in an extensive hydrogen-bond framework, in agreement with the A weak band observed at 2352 cm−1 is attributed to an N—H⋯O stretching mode. The characteristic vibrations of the bridging oxalato ligand are observed at 1657 cm−1 [νas(COO)], 1312 and 1409 cm−1 [νs(COO)] and 793 cm−1 [δ(COO)] (Ma et al., 2007). All these bands are consistent with the literature for a bis-chelating coordination of the oxalato ligand. Additional bands observed at around 605 and 521 cm−1 can be attributed to ν(Mn—Cl) (Zgolli et al., 2011) and ν(Mn—O) (Biradar & Mruthyunjayaswamy, 2013), respectively.
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Some crystals, selected under the microscope, were dissolved in 10 cm3 of distilled water. The solution obtained was analyzed using a UV–Visible spectrometer. The spectrum of (I) (Table 3 and Fig. 7) shows significant transitions at 206 nm (with a shoulder at 240 nm) and 329 nm. The first band is due to the π→π* transition of the guanidinium π system (Hoffmann et al., 2009), the second witnesses the metal-to-ligand charge-transfer (Sun et al., 1996) and the last corresponds to the n→π* transition (Sasikala et al., 2015). An examination of the visible region of the spectrum does not reveal obvious d–d transitions (insert of Fig. 7) which may be too weak to be seen, as they are spin and Laporte forbidden, in accordance with the compound being almost colourless.
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5. Synthesis and crystallization
Aqueous solutions of ammonium oxalate and guanidine hydrochloride were added to Mn(SO4)·H2O dissolved in 10 cm3 of water in a 1:2:1 molar ratio. The resulting solution was left at room temperature and colourless crystals suitable for X-ray diffraction were obtained after two weeks of slow evaporation.
6. Refinement
Crystal data, data collection and structure .
details are summarized in Table 4
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Guanidinium hydrogen atoms were positioned geometrically as riding atoms (N—H = 0.86 Å) using adequate HFIX instructions and refined with AFIX instructions. Hydrogen atoms of the coordinating water molecule were found in Fourier difference maps. O—H distances were restrained to a value of 0.85 (1) Å and H⋯H distances were restrained to a value of 1.387 (1) Å.
The oxygen atom of the non-coordinating water molecule had unusually high displacement parameters, and was refined as disordered over two alternative mutually exclusive positions. The solvent molecule may be considered as being located vertically between negative-charged anionic layers formed by hydrogen-bonded polymeric chains and located horizontally between positive-charged pairs of guanidinium cations. This pseudo-channel affects its hydrogen-bonding interactions, see the discussion in the first paragraph of the Supramolecular features section and Fig. 3, which may explain the observed disorder.
The disordered oxygen atom was refined as disordered over two positions OW2 and OW2B which were restrained to have similar geometries. Their hydrogen atoms were located from the Fourier difference maps. The O—H bond lengths were restrained to a value of 0.85 (1) Å and the H⋯H distances were restrained to a value of 1.387 (1) Å. The interatomic distances between the two pairs OW2 and HW5 and OW2B and HW3 were restrained to be equal using a SADI instruction with an effective standard deviation of 0.02. The hydrogen-bonding distance of hydrogen atom HW6 to chlorine atom Cl1 was restrained to 2.80 (1) Å. Subject to these and the above conditions, the occupancy ratio of the disordered non-coordinating water molecule refined to 0.816 (13):0.184 (13).
Supporting information
CCDC reference: 1474882
10.1107/S2056989016006605/zl2659sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016006605/zl2659Isup2.hkl
Much attention had been devoted to the coordination chemistry of oxalate anions due to the interesting structural features and physical properties they possess (Chérif et al., 2011; Dridi et al., 2013; Decurtins et al., 1997). Oxalate anions have been demonstrated to be one of the most versatile bridging ligands for the construction of coordination polymers when combined with transition metal cations. Manganese(II) is a promising cation with possibilities of forming one-dimensional oxalato-based coordination polymers, as evidenced by reports describing the structures of several topologically similar MnII–ox–MnII chains [see, for example, García-Couceiro et al. (2005) or Beznischenko et al. (2009)]. In those compounds, the oxalate-bridged manganese framework may be considered as a single-chain magnet based on the oxalate linker (e.g. Clemente-León et al., 2011). In this work, we report the synthesis and
determination of a new oxalate-bridged coordination compound, {(CH6N3)[Mn(C2O4)Cl(H2O)]·H2O}n (I).\ The
of the title compound contains the complex anion [MnCl(C2O4)(H2O)]-, the organic cation (CH6N3)+ and one disordered non-coordinating water molecule. A bond-valence-sum calculation, assuming Mn—O and Mn—Cl bonds, gives a BVS value (Brown & Altermatt, 1985) of 2.05 (7), confirming the +II of Mn and ensuring electrical neutrality of the formed unit. The coordination environment of the Mn+II ion involves two oxalate ligands exhibiting bis-chelating coordination modes, one chloride atom and one oxygen atom of a coordinating water molecule (Fig. 1) in a slightly distorted octahedral geometry. The small bite angles of the bis-chelating oxalate groups [73.99 (6)° for O3—Mn1—O4 and 75.35 (7)° for O1—Mn1—O2] and the extended Mn1—Cl1 bond [2.458 (2) Å] account for this distortion. The polyhedral distance and angle distortions, calculated from the Mn—O and Mn—Cl distances and O—Mn—O and O—Mn—Cl angles in the MnO5Cl unit, were found to be IDd = 0.03 (2) and IDa = 0.22 (4)%, respectively (Baur, 1974; Wildner, 1992).The equatorial plane of the MnO5Cl octahedron is formed by atoms Mn1, OW1, O1, O2 and O3, with a calculated root-mean-square deviation of the fitted atoms of 0.1038 Å. The axial positions are occupied by the chloride atom [Mn1—Cl1 = 2.458 (2) Å] and one oxygen atom from the bridging oxalato group [Mn1—O4 = 2.248 (2) Å]. The two oxalato groups are almost perpendicular with a dihedral angle of 89.09 (6)°. The oxalate ion is located on an inversion center that also relates the two Mn atoms bonded to the oxalate ion with each other. The bridged metal ions are nearly coplanar with the oxalate plane with a mean deviation of 0.0147 (8) Å.
The Mn+II ion, as a d5 high-spin system with a spherical electron distribution, has a limited number of commonly observed coordination geometries that are based on minimization of ligand–ligand repulsion. Among the Mn—O distances, the shortest are those involving an oxygen atom from the oxalate ion trans to another oxygen atom from the second oxalate ion. The range of these distances is 2.180 (1) to 2.194 (1) Å, which is in accord with those observed in other oxalate-bridged compounds such as one of the polymorphs of catena-poly[[diaquamanganese(II)]-µ-oxalato-κ4O1,\ O2:O1',O2'] (Soleimannejad et al., 2007). The Mn—O distances involving the oxygen atoms of the oxalate ion trans to the coordinated water molecule and trans to the chloride atom are with 2.202 (2) and 2.248 (2) Å slightly longer.
The view of the structure packing (Fig. 2) shows the layered structure based on anionic zigzag oxalate-bridged Mn+II chains running along the c axis. The intra-chain Mn···Mn distances through bridging oxalate are 5.695 (su?) and 5.777 (su?) Å, somewhat longer than the value of 5.652 Å previously observed for {[Mn(C2O4)(C8H7N3)]·1.5H2O}n (An & Zhu, 2009) involving a pyridyl-pyrazolide ligand instead of chloride and water in the coordination environment of the Mn+II ion.
The geometric parameters for the guanidinium cations do not show any unusual features and are in agreement with those previously reported (Ken Sakai et al. 2003; Vaidhyanathan et al., 2001). The bond lengths [1.318 (2)–1.329 (2) Å] and angles [119.27 (16)–120.57 (16)°] are in the typical ranges, confirming a highly resonance-stabilized electronic structure and a completely delocalized charge between the three sp2 nitrogen atoms. Conjugation of the nitrogen lone pairs with the empty p-orbital of the sp2 carbon atom creates a planar cation.
Neighbouring oxalate-bridged zigzag chains are connected with each other via O—H···O hydrogen bonds involving the coordinating water molecule. Its oxygen atom acts as a hydrogen-bond donor and establishes strong hydrogen bonds (Table 1) towards one of the oxalate oxygen atoms of a neighbouring chain (Fig. 3), OW1—HW2···O3v [symmetry code: (v) -x + 2, -y + 1, -z], leading to formation of anionic layers parallel to (010). A disordered non-coordinating water molecule acts as acceptor (Fig. 3) for the other hydrogen atom involving the coordinating water molecule via the hydrogen bonds OW1—HW1···OW2i and OW1—HW1···OW2Bi [symmetry code: (i) x, y - 1, z]. Both disorder components of the non-ccordinating water molecules act as hydrogen-bond donors towards oxygen atom O3 (Fig. 3) via the hydrogen bonds OW2—HW3···O3 and OW2B—HW5···O3, but they form different hydrogen bonds via their second H atom, to chlorine atoms in different lattice positions via hydrogen bonds OW2—HW4···Cl1vi and OW2B-–HW6···Cl1 [symmetry code: (vi) -x + 2, -y + 2, -z]. The combined water hydrogen bonds link the anionic layers into a 3D framework.
The three N atoms of the guanidinium cation act as donors of strong hydrogen bonds N1—H1A···O2i, N1—H1B···O4, N2—H2A···Cl1ii, N2—H2B···Cl1iii, N2—H2A···O4, N3—H3A···O1iv and N3—H3B···Cl1iii [Table 1; symmetry codes: (i) x, y - 1, z; (ii) x - 1, y, z; (iii) -x + 1, -y + 1, -z + 1; (iv) -x + 1, -y, -z + 1], consolidating the anionic layers and giving additional stability to the three-dimensional structure as illustrated in Fig. 4. The guanidinium cations are also paired via π–π stacking with an interplanar distance of 3.547 (3) Å between C3 and C3(-x, -y, -z + 1) (Di Tondo & Pritchard, 2012), as shown in Fig. 5.
The IR spectrum was recorded in the 4000–400 cm-1 region using a Perkin–Elmer spectrometer with the sample diluted in a pressed KBr pellet. The most intense IR absorption bands of (I) are given in Table 2. The spectrum (Fig. 6) displays broad and strong bands centered at 3390 and 3182 cm-1 assigned to [ν(O—H) + νas(NH2)] and νs(NH2), respectively (Sasikala et al., 2015). The broadness of these bands is indicative of the presence of both coordinating and non-coordinating water molecules, as well as –NH2 groups involved in an extensive hydrogen-bond framework, in agreement with the A weak band observed at 2352 cm-1 is attributed to an N—H···O stretching mode. The characteristic vibrations of the bridging oxalato ligand are observed at 1657 cm-1 [νas(COO)], 1312 and 1409 cm-1 [νs(COO)] and 793 cm-1 [δ(COO)] (Ma et al., 2007). All these bands are consistent with the literature for a bis-chelating coordination of the oxalato ligand. Additional bands observed at around 605 and 521 cm-1 can be attributed to ν(Mn—Cl) (Zgolli et al., 2011) and ν(Mn—O) (Biradar et al., 2013), respectively.
Some crystals, selected under the microscope were dissolved in 10 cm3 of distilled water. The solution obtained was analyzed using a UV–Visible spectrometer. The spectrum of (I) (Table 3 and Fig. 7) shows significant transitions at 206 nm (with a shoulder at 240 nm) and 329 nm. The first band is due to the π→π* transition of the guanidinium π system (Hoffmann et al., 2009), the second witnesses the metal-to-ligand charge-transfer (Sun et al., 1996) and the last corresponds to the n→π* transition (Sasikala et al., 2015). An examination of the visible region of the spectrum does not reveal obvious d–d transitions (insert of Fig. 7) which may be too weak to be seen, as they are spin and Laporte forbidden, in accordance with the compound being almost colourless (Table 4).
Aqueous solutions of ammonium oxalate and guanidine hydrochloride were added to Mn(SO4)·H2O dissolved in 10 cm3 of water in a 1:2:1 molar ratio. The resulting solution was left at room temperature and colourless crystals suitable for X-ray diffraction were obtained after two weeks of slow evaporation.
Crystal data, data collection and structure
details are summarized in Table 4.Guanidinium hydrogen atoms were positioned geometrically as riding atoms (N—H = 0.86 Å) using adequate HFIX instructions and refined with AFIX instructions. Hydrogen atoms of the coordinating water molecule were found in Fourier difference maps. O—H distances were restrained to a value of 0.85 (1) Å and H···H distances were restrained to a value of 1.387 (1) Å.
The oxygen atom of the non-coordinating water molecule had unusually high displacement parameters, and was refined as disordered over two alternative mutually exclusive positions. The solvent molecule may be considered as being located vertically between negative-charged anionic layers formed by hydrogen-bonded polymeric chains and located horizontally between positive-charged pairs of guanidinium cations. This pseudo-channel affects its hydrogen-bonding interactions, see the discussion in the first paragraph of the Supramolecular features section and Fig. 3, which may explain the observed disorder.
The disordered oxygen atom was refined as disordered over two positions OW2 and OW2B which were restrained to have similar geometries. Their hydrogen atoms were located from the Fourier difference maps. The O—H bond lengths were restrained to a value of 0.85 (1) Å and the H···H distances were restrained to a value of 1.387 (1) Å. The interatomic distances between the two pairs OW2 and HW5 and OW2B and HW3 were restrained to be equal using a SADI instruction with an effective standard deviation of 0.02. The hydrogen-bonding distance of hydrogen atom HW6 to chlorine atom Cl1 was restrained to 2.80 (1) Å. Subject to these and the above conditions, the occupancy ratio of the disordered non-coordinating water molecule refined to 0.816 (13):0.184 (13).
Much attention had been devoted to the coordination chemistry of oxalate anions due to the interesting structural features and physical properties they possess (Chérif et al., 2011; Dridi et al., 2013; Decurtins et al., 1997). Oxalate anions have been demonstrated to be one of the most versatile bridging ligands for the construction of coordination polymers when combined with transition metal cations. Manganese(II) is a promising cation with possibilities of forming one-dimensional oxalato-based coordination polymers, as evidenced by reports describing the structures of several topologically similar MnII–ox–MnII chains [see, for example, García-Couceiro et al. (2005) or Beznischenko et al. (2009)]. In those compounds, the oxalate-bridged manganese framework may be considered as a single-chain magnet based on the oxalate linker (e.g. Clemente-León et al., 2011). In this work, we report the synthesis and
determination of a new oxalate-bridged coordination compound, {(CH6N3)[Mn(C2O4)Cl(H2O)]·H2O}n (I).\ The
of the title compound contains the complex anion [MnCl(C2O4)(H2O)]-, the organic cation (CH6N3)+ and one disordered non-coordinating water molecule. A bond-valence-sum calculation, assuming Mn—O and Mn—Cl bonds, gives a BVS value (Brown & Altermatt, 1985) of 2.05 (7), confirming the +II of Mn and ensuring electrical neutrality of the formed unit. The coordination environment of the Mn+II ion involves two oxalate ligands exhibiting bis-chelating coordination modes, one chloride atom and one oxygen atom of a coordinating water molecule (Fig. 1) in a slightly distorted octahedral geometry. The small bite angles of the bis-chelating oxalate groups [73.99 (6)° for O3—Mn1—O4 and 75.35 (7)° for O1—Mn1—O2] and the extended Mn1—Cl1 bond [2.458 (2) Å] account for this distortion. The polyhedral distance and angle distortions, calculated from the Mn—O and Mn—Cl distances and O—Mn—O and O—Mn—Cl angles in the MnO5Cl unit, were found to be IDd = 0.03 (2) and IDa = 0.22 (4)%, respectively (Baur, 1974; Wildner, 1992).The equatorial plane of the MnO5Cl octahedron is formed by atoms Mn1, OW1, O1, O2 and O3, with a calculated root-mean-square deviation of the fitted atoms of 0.1038 Å. The axial positions are occupied by the chloride atom [Mn1—Cl1 = 2.458 (2) Å] and one oxygen atom from the bridging oxalato group [Mn1—O4 = 2.248 (2) Å]. The two oxalato groups are almost perpendicular with a dihedral angle of 89.09 (6)°. The oxalate ion is located on an inversion center that also relates the two Mn atoms bonded to the oxalate ion with each other. The bridged metal ions are nearly coplanar with the oxalate plane with a mean deviation of 0.0147 (8) Å.
The Mn+II ion, as a d5 high-spin system with a spherical electron distribution, has a limited number of commonly observed coordination geometries that are based on minimization of ligand–ligand repulsion. Among the Mn—O distances, the shortest are those involving an oxygen atom from the oxalate ion trans to another oxygen atom from the second oxalate ion. The range of these distances is 2.180 (1) to 2.194 (1) Å, which is in accord with those observed in other oxalate-bridged compounds such as one of the polymorphs of catena-poly[[diaquamanganese(II)]-µ-oxalato-κ4O1,\ O2:O1',O2'] (Soleimannejad et al., 2007). The Mn—O distances involving the oxygen atoms of the oxalate ion trans to the coordinated water molecule and trans to the chloride atom are with 2.202 (2) and 2.248 (2) Å slightly longer.
The view of the structure packing (Fig. 2) shows the layered structure based on anionic zigzag oxalate-bridged Mn+II chains running along the c axis. The intra-chain Mn···Mn distances through bridging oxalate are 5.695 (su?) and 5.777 (su?) Å, somewhat longer than the value of 5.652 Å previously observed for {[Mn(C2O4)(C8H7N3)]·1.5H2O}n (An & Zhu, 2009) involving a pyridyl-pyrazolide ligand instead of chloride and water in the coordination environment of the Mn+II ion.
The geometric parameters for the guanidinium cations do not show any unusual features and are in agreement with those previously reported (Ken Sakai et al. 2003; Vaidhyanathan et al., 2001). The bond lengths [1.318 (2)–1.329 (2) Å] and angles [119.27 (16)–120.57 (16)°] are in the typical ranges, confirming a highly resonance-stabilized electronic structure and a completely delocalized charge between the three sp2 nitrogen atoms. Conjugation of the nitrogen lone pairs with the empty p-orbital of the sp2 carbon atom creates a planar cation.
Neighbouring oxalate-bridged zigzag chains are connected with each other via O—H···O hydrogen bonds involving the coordinating water molecule. Its oxygen atom acts as a hydrogen-bond donor and establishes strong hydrogen bonds (Table 1) towards one of the oxalate oxygen atoms of a neighbouring chain (Fig. 3), OW1—HW2···O3v [symmetry code: (v) -x + 2, -y + 1, -z], leading to formation of anionic layers parallel to (010). A disordered non-coordinating water molecule acts as acceptor (Fig. 3) for the other hydrogen atom involving the coordinating water molecule via the hydrogen bonds OW1—HW1···OW2i and OW1—HW1···OW2Bi [symmetry code: (i) x, y - 1, z]. Both disorder components of the non-ccordinating water molecules act as hydrogen-bond donors towards oxygen atom O3 (Fig. 3) via the hydrogen bonds OW2—HW3···O3 and OW2B—HW5···O3, but they form different hydrogen bonds via their second H atom, to chlorine atoms in different lattice positions via hydrogen bonds OW2—HW4···Cl1vi and OW2B-–HW6···Cl1 [symmetry code: (vi) -x + 2, -y + 2, -z]. The combined water hydrogen bonds link the anionic layers into a 3D framework.
The three N atoms of the guanidinium cation act as donors of strong hydrogen bonds N1—H1A···O2i, N1—H1B···O4, N2—H2A···Cl1ii, N2—H2B···Cl1iii, N2—H2A···O4, N3—H3A···O1iv and N3—H3B···Cl1iii [Table 1; symmetry codes: (i) x, y - 1, z; (ii) x - 1, y, z; (iii) -x + 1, -y + 1, -z + 1; (iv) -x + 1, -y, -z + 1], consolidating the anionic layers and giving additional stability to the three-dimensional structure as illustrated in Fig. 4. The guanidinium cations are also paired via π–π stacking with an interplanar distance of 3.547 (3) Å between C3 and C3(-x, -y, -z + 1) (Di Tondo & Pritchard, 2012), as shown in Fig. 5.
The IR spectrum was recorded in the 4000–400 cm-1 region using a Perkin–Elmer spectrometer with the sample diluted in a pressed KBr pellet. The most intense IR absorption bands of (I) are given in Table 2. The spectrum (Fig. 6) displays broad and strong bands centered at 3390 and 3182 cm-1 assigned to [ν(O—H) + νas(NH2)] and νs(NH2), respectively (Sasikala et al., 2015). The broadness of these bands is indicative of the presence of both coordinating and non-coordinating water molecules, as well as –NH2 groups involved in an extensive hydrogen-bond framework, in agreement with the A weak band observed at 2352 cm-1 is attributed to an N—H···O stretching mode. The characteristic vibrations of the bridging oxalato ligand are observed at 1657 cm-1 [νas(COO)], 1312 and 1409 cm-1 [νs(COO)] and 793 cm-1 [δ(COO)] (Ma et al., 2007). All these bands are consistent with the literature for a bis-chelating coordination of the oxalato ligand. Additional bands observed at around 605 and 521 cm-1 can be attributed to ν(Mn—Cl) (Zgolli et al., 2011) and ν(Mn—O) (Biradar et al., 2013), respectively.
Some crystals, selected under the microscope were dissolved in 10 cm3 of distilled water. The solution obtained was analyzed using a UV–Visible spectrometer. The spectrum of (I) (Table 3 and Fig. 7) shows significant transitions at 206 nm (with a shoulder at 240 nm) and 329 nm. The first band is due to the π→π* transition of the guanidinium π system (Hoffmann et al., 2009), the second witnesses the metal-to-ligand charge-transfer (Sun et al., 1996) and the last corresponds to the n→π* transition (Sasikala et al., 2015). An examination of the visible region of the spectrum does not reveal obvious d–d transitions (insert of Fig. 7) which may be too weak to be seen, as they are spin and Laporte forbidden, in accordance with the compound being almost colourless (Table 4).
Aqueous solutions of ammonium oxalate and guanidine hydrochloride were added to Mn(SO4)·H2O dissolved in 10 cm3 of water in a 1:2:1 molar ratio. The resulting solution was left at room temperature and colourless crystals suitable for X-ray diffraction were obtained after two weeks of slow evaporation.
detailsCrystal data, data collection and structure
details are summarized in Table 4.Guanidinium hydrogen atoms were positioned geometrically as riding atoms (N—H = 0.86 Å) using adequate HFIX instructions and refined with AFIX instructions. Hydrogen atoms of the coordinating water molecule were found in Fourier difference maps. O—H distances were restrained to a value of 0.85 (1) Å and H···H distances were restrained to a value of 1.387 (1) Å.
The oxygen atom of the non-coordinating water molecule had unusually high displacement parameters, and was refined as disordered over two alternative mutually exclusive positions. The solvent molecule may be considered as being located vertically between negative-charged anionic layers formed by hydrogen-bonded polymeric chains and located horizontally between positive-charged pairs of guanidinium cations. This pseudo-channel affects its hydrogen-bonding interactions, see the discussion in the first paragraph of the Supramolecular features section and Fig. 3, which may explain the observed disorder.
The disordered oxygen atom was refined as disordered over two positions OW2 and OW2B which were restrained to have similar geometries. Their hydrogen atoms were located from the Fourier difference maps. The O—H bond lengths were restrained to a value of 0.85 (1) Å and the H···H distances were restrained to a value of 1.387 (1) Å. The interatomic distances between the two pairs OW2 and HW5 and OW2B and HW3 were restrained to be equal using a SADI instruction with an effective standard deviation of 0.02. The hydrogen-bonding distance of hydrogen atom HW6 to chlorine atom Cl1 was restrained to 2.80 (1) Å. Subject to these and the above conditions, the occupancy ratio of the disordered non-coordinating water molecule refined to 0.816 (13):0.184 (13).
Data collection: CAD-4 EXPRESS (Duisenberg, 1992); cell
CAD-4 EXPRESS (Duisenberg, 1992); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).Fig. 1. The structural unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level for non-H atoms. [Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) -x + 1, -y + 1, -z.] | |
Fig. 2. View of the structure packing showing Mn–Ox–Mn chains (highlighted by a ball-and-stick model) and layers parallel to (010) (blue planes). | |
Fig. 3. View of the hydrogen bonds developed by both coordinating (blue dashed lines) and non-coordinating (green dashed lines) water molecules. [Symmetry codes: (i) x, y - 1, z; (v) -x + 2, -y + 1, -z; (vi) -x + 2, -y + 2, -z.] | |
Fig. 4. N—H···O and N—H···Cl hydrogen-bonding interactions developed by the guanidinium cations (dashed lines) in (I). Non-coordinating water molecules and hydrogen atoms of coordinating water molecules are omitted for clarity. [Symmetry codes: (i) x, y - 1, z; (ii) x - 1, y, z; (iii) -x + 1, -y + 1, -z + 1; (iv) -x + 1, -y, -z + 1.] | |
Fig. 5. π–π stacking interactions (orange dashed lines) between adjacent organic cations. [Symmetry code: (i) -x, -y, -z + 1.] | |
Fig. 6. The IR spectrum of (I) in KBr. | |
Fig. 7. The UV–Vis spectrum of (I) in water. The insert is an expansion of the visible region. |
(CH6N3)[Mn(C2O4)Cl(H2O)]·H2O | Z = 2 |
Mr = 274.53 | F(000) = 278 |
Triclinic, P1 | Dx = 1.884 Mg m−3 |
a = 6.740 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.514 (7) Å | Cell parameters from 25 reflections |
c = 9.810 (2) Å | θ = 10–15° |
α = 84.46 (3)° | µ = 1.65 mm−1 |
β = 78.15 (4)° | T = 298 K |
γ = 88.57 (6)° | Prism, colourless |
V = 484.0 (6) Å3 | 0.50 × 0.43 × 0.34 mm |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.016 |
Radiation source: fine-focus sealed tube | θmax = 27.0°, θmin = 2.1° |
ω/2θ scans | h = −8→8 |
Absorption correction: ψ scan (North et al., 1968) | k = −9→9 |
Tmin = 0.551, Tmax = 0.718 | l = −12→12 |
4226 measured reflections | 2 standard reflections every 120 reflections |
2114 independent reflections | intensity decay: 1.4% |
2018 reflections with I > 2σ(I) |
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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.065 | H-atom parameters not refined |
S = 1.10 | w = 1/[σ2(Fo2) + (0.034P)2 + 0.1929P] where P = (Fo2 + 2Fc2)/3 |
2114 reflections | (Δ/σ)max = 0.001 |
155 parameters | Δρmax = 0.39 e Å−3 |
11 restraints | Δρmin = −0.30 e Å−3 |
(CH6N3)[Mn(C2O4)Cl(H2O)]·H2O | γ = 88.57 (6)° |
Mr = 274.53 | V = 484.0 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.740 (5) Å | Mo Kα radiation |
b = 7.514 (7) Å | µ = 1.65 mm−1 |
c = 9.810 (2) Å | T = 298 K |
α = 84.46 (3)° | 0.50 × 0.43 × 0.34 mm |
β = 78.15 (4)° |
Enraf–Nonius CAD-4 diffractometer | 2018 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.016 |
Tmin = 0.551, Tmax = 0.718 | 2 standard reflections every 120 reflections |
4226 measured reflections | intensity decay: 1.4% |
2114 independent reflections |
R[F2 > 2σ(F2)] = 0.024 | 11 restraints |
wR(F2) = 0.065 | H-atom parameters not refined |
S = 1.10 | Δρmax = 0.39 e Å−3 |
2114 reflections | Δρmin = −0.30 e Å−3 |
155 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. |
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 > 2sigma(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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Mn1 | 0.72543 (3) | 0.49656 (3) | 0.22092 (2) | 0.02231 (9) | |
Cl1 | 1.03175 (7) | 0.65970 (6) | 0.23354 (5) | 0.03534 (12) | |
N2 | 0.1713 (2) | 0.28093 (18) | 0.43164 (16) | 0.0312 (3) | |
H2B | 0.1064 | 0.3297 | 0.5036 | 0.037* | |
H2A | 0.1950 | 0.3411 | 0.3509 | 0.037* | |
O4 | 0.47159 (18) | 0.36133 (16) | 0.15474 (12) | 0.0285 (2) | |
O2 | 0.50953 (17) | 0.66001 (14) | 0.35754 (11) | 0.0247 (2) | |
N1 | 0.3354 (3) | 0.03734 (19) | 0.33501 (16) | 0.0351 (3) | |
H1A | 0.3768 | −0.0715 | 0.3441 | 0.042* | |
H1B | 0.3592 | 0.0972 | 0.2542 | 0.042* | |
O3 | 0.69372 (19) | 0.63896 (16) | 0.02047 (12) | 0.0286 (2) | |
O1 | 0.66931 (18) | 0.34160 (15) | 0.42455 (11) | 0.0268 (2) | |
OW1 | 0.9107 (2) | 0.26878 (18) | 0.14629 (14) | 0.0367 (3) | |
HW1 | 0.854 (3) | 0.189 (3) | 0.112 (2) | 0.055* | |
HW2 | 1.027 (2) | 0.290 (3) | 0.100 (2) | 0.055* | |
C1 | 0.4541 (2) | 0.59228 (18) | 0.48007 (15) | 0.0198 (3) | |
N3 | 0.1977 (2) | 0.02218 (19) | 0.56968 (16) | 0.0326 (3) | |
H3A | 0.2386 | −0.0867 | 0.5796 | 0.039* | |
H3B | 0.1323 | 0.0721 | 0.6409 | 0.039* | |
C2 | 0.4359 (2) | 0.41972 (19) | 0.03918 (15) | 0.0221 (3) | |
C3 | 0.2351 (2) | 0.1125 (2) | 0.44522 (17) | 0.0253 (3) | |
OW2 | 0.7198 (6) | 1.0392 (5) | 0.0066 (7) | 0.0831 (13) | 0.816 (13) |
HW3 | 0.719 (8) | 0.9263 (18) | 0.025 (5) | 0.125* | 0.816 (13) |
HW4 | 0.793 (7) | 1.067 (6) | −0.074 (3) | 0.125* | 0.816 (13) |
OW2B | 0.712 (2) | 0.9962 (16) | 0.089 (2) | 0.061 (5) | 0.184 (13) |
HW5 | 0.637 (17) | 0.955 (12) | 0.039 (9) | 0.091* | 0.184 (13) |
HW6 | 0.79 (2) | 0.912 (12) | 0.115 (14) | 0.091* | 0.184 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.02388 (14) | 0.02454 (14) | 0.01771 (13) | −0.00049 (9) | −0.00325 (9) | 0.00002 (9) |
Cl1 | 0.0292 (2) | 0.0383 (2) | 0.0387 (2) | −0.00641 (17) | −0.00517 (17) | −0.00671 (17) |
N2 | 0.0365 (8) | 0.0223 (6) | 0.0341 (7) | 0.0016 (6) | −0.0084 (6) | 0.0032 (5) |
O4 | 0.0324 (6) | 0.0304 (6) | 0.0219 (5) | −0.0077 (5) | −0.0073 (5) | 0.0071 (4) |
O2 | 0.0291 (6) | 0.0231 (5) | 0.0197 (5) | 0.0029 (4) | −0.0024 (4) | 0.0026 (4) |
N1 | 0.0438 (9) | 0.0241 (7) | 0.0340 (8) | 0.0004 (6) | −0.0024 (7) | 0.0019 (6) |
O3 | 0.0299 (6) | 0.0319 (6) | 0.0242 (5) | −0.0109 (5) | −0.0080 (5) | 0.0039 (4) |
O1 | 0.0327 (6) | 0.0224 (5) | 0.0217 (5) | 0.0075 (4) | 0.0008 (4) | 0.0007 (4) |
OW1 | 0.0333 (7) | 0.0356 (7) | 0.0377 (7) | 0.0004 (5) | 0.0032 (6) | −0.0080 (5) |
C1 | 0.0211 (7) | 0.0174 (7) | 0.0208 (7) | −0.0008 (5) | −0.0048 (5) | 0.0000 (5) |
N3 | 0.0401 (8) | 0.0230 (7) | 0.0332 (7) | 0.0021 (6) | −0.0074 (6) | 0.0036 (6) |
C2 | 0.0231 (7) | 0.0222 (7) | 0.0194 (7) | −0.0006 (6) | −0.0015 (6) | 0.0000 (5) |
C3 | 0.0244 (7) | 0.0202 (7) | 0.0326 (8) | −0.0043 (6) | −0.0101 (6) | 0.0019 (6) |
OW2 | 0.123 (3) | 0.0459 (16) | 0.076 (3) | −0.0154 (15) | −0.002 (2) | −0.0180 (19) |
OW2B | 0.078 (8) | 0.031 (5) | 0.067 (11) | −0.012 (5) | 0.009 (6) | −0.020 (6) |
Mn1—O1 | 2.1798 (14) | O1—C1ii | 1.251 (2) |
Mn1—OW1 | 2.187 (2) | OW1—HW1 | 0.846 (9) |
Mn1—O3 | 2.1936 (13) | OW1—HW2 | 0.835 (9) |
Mn1—O2 | 2.2024 (18) | C1—O1ii | 1.251 (2) |
Mn1—O4 | 2.2476 (19) | C1—C1ii | 1.552 (3) |
Mn1—Cl1 | 2.4581 (19) | N3—C3 | 1.318 (2) |
N2—C3 | 1.329 (2) | N3—H3A | 0.8600 |
N2—H2B | 0.8600 | N3—H3B | 0.8600 |
N2—H2A | 0.8600 | C2—O3i | 1.257 (2) |
O4—C2 | 1.2434 (19) | C2—C2i | 1.547 (3) |
O2—C1 | 1.2451 (19) | OW2—HW3 | 0.850 (10) |
N1—C3 | 1.321 (2) | OW2—HW4 | 0.849 (10) |
N1—H1A | 0.8600 | OW2B—HW5 | 0.851 (10) |
N1—H1B | 0.8600 | OW2B—HW6 | 0.856 (10) |
O3—C2i | 1.257 (2) | ||
O1—Mn1—OW1 | 85.68 (7) | C3—N1—H1B | 120.0 |
O1—Mn1—O3 | 164.34 (5) | H1A—N1—H1B | 120.0 |
OW1—Mn1—O3 | 100.06 (7) | C2i—O3—Mn1 | 116.88 (11) |
O1—Mn1—O2 | 75.35 (7) | C1ii—O1—Mn1 | 116.15 (10) |
OW1—Mn1—O2 | 160.68 (5) | Mn1—OW1—HW1 | 117.6 (17) |
O3—Mn1—O2 | 97.39 (6) | Mn1—OW1—HW2 | 117.3 (17) |
O1—Mn1—O4 | 92.12 (7) | HW1—OW1—HW2 | 111.4 (15) |
OW1—Mn1—O4 | 85.45 (8) | O2—C1—O1ii | 126.35 (14) |
O3—Mn1—O4 | 73.99 (6) | O2—C1—C1ii | 117.50 (16) |
O2—Mn1—O4 | 91.49 (7) | O1ii—C1—C1ii | 116.15 (16) |
O1—Mn1—Cl1 | 100.46 (6) | C3—N3—H3A | 120.0 |
OW1—Mn1—Cl1 | 90.50 (7) | C3—N3—H3B | 120.0 |
O3—Mn1—Cl1 | 94.08 (6) | H3A—N3—H3B | 120.0 |
O2—Mn1—Cl1 | 96.47 (7) | O4—C2—O3i | 126.48 (15) |
O4—Mn1—Cl1 | 166.46 (3) | O4—C2—C2i | 116.80 (17) |
C3—N2—H2B | 120.0 | O3i—C2—C2i | 116.73 (16) |
C3—N2—H2A | 120.0 | N3—C3—N1 | 120.57 (16) |
H2B—N2—H2A | 120.0 | N3—C3—N2 | 119.27 (16) |
C2—O4—Mn1 | 115.50 (11) | N1—C3—N2 | 120.16 (16) |
C1—O2—Mn1 | 114.82 (10) | HW3—OW2—HW4 | 109.7 (17) |
C3—N1—H1A | 120.0 | HW5—OW2B—HW6 | 108.7 (18) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2iii | 0.86 | 2.19 | 3.047 (3) | 175 |
N1—H1B···O4 | 0.86 | 2.20 | 2.917 (3) | 140 |
N2—H2A···Cl1iv | 0.86 | 2.85 | 3.509 (3) | 135 |
N2—H2B···Cl1ii | 0.86 | 2.56 | 3.357 (2) | 154 |
N2—H2A···O4 | 0.86 | 2.38 | 3.054 (3) | 135 |
N3—H3A···O1v | 0.86 | 2.00 | 2.854 (3) | 172 |
N3—H3B···Cl1ii | 0.86 | 2.57 | 3.363 (3) | 154 |
OW1—HW1···OW2iii | 0.85 (1) | 1.96 (1) | 2.793 (4) | 170 (3) |
OW1—HW1···OW2Biii | 0.85 (1) | 1.82 (2) | 2.643 (11) | 165 (3) |
OW1—HW2···O3vi | 0.84 (1) | 2.06 (1) | 2.890 (3) | 176 (3) |
OW2—HW3···O3 | 0.85 (1) | 2.17 (2) | 3.005 (5) | 165 (5) |
OW2—HW4···Cl1vii | 0.85 (1) | 2.61 (3) | 3.319 (6) | 142 (4) |
OW2B—HW5···O3 | 0.85 (1) | 2.42 (11) | 2.840 (10) | 112 (9) |
OW2B—HW6···Cl1 | 0.86 (1) | 2.81 (1) | 3.656 (18) | 172 (11) |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z; (iv) x−1, y, z; (v) −x+1, −y, −z+1; (vi) −x+2, −y+1, −z; (vii) −x+2, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.86 | 2.19 | 3.047 (3) | 174.8 |
N1—H1B···O4 | 0.86 | 2.20 | 2.917 (3) | 140.1 |
N2—H2A···Cl1ii | 0.86 | 2.85 | 3.509 (3) | 134.7 |
N2—H2B···Cl1iii | 0.86 | 2.56 | 3.357 (2) | 153.8 |
N2—H2A···O4 | 0.86 | 2.38 | 3.054 (3) | 135.0 |
N3—H3A···O1iv | 0.86 | 2.00 | 2.854 (3) | 172.1 |
N3—H3B···Cl1iii | 0.86 | 2.57 | 3.363 (3) | 153.7 |
OW1—HW1···OW2i | 0.846 (9) | 1.958 (11) | 2.793 (4) | 170 (3) |
OW1—HW1···OW2Bi | 0.846 (9) | 1.818 (15) | 2.643 (11) | 165 (3) |
OW1—HW2···O3v | 0.835 (9) | 2.056 (10) | 2.890 (3) | 176 (3) |
OW2—HW3···O3 | 0.850 (10) | 2.175 (19) | 3.005 (5) | 165 (5) |
OW2—HW4···Cl1vi | 0.849 (10) | 2.61 (3) | 3.319 (6) | 142 (4) |
OW2B—HW5···O3 | 0.851 (10) | 2.42 (11) | 2.840 (10) | 112 (9) |
OW2B—HW6···Cl1 | 0.856 (10) | 2.807 (10) | 3.656 (18) | 172 (11) |
Symmetry codes: (i) x, y−1, z; (ii) x−1, y, z; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y, −z+1; (v) −x+2, −y+1, −z; (vi) −x+2, −y+2, −z. |
Wavenumber | Assignment |
521 | ν(Mn—Cl) |
605 | ν(Mn—O) |
793 | δ(COO) |
1312, 1409 | νs(COO) |
1657 | νas(COO) |
2352 | ν(N—H···O) |
3182 | νs(NH2) |
3390 | ν(OH)(H2O) / νas(NH2) |
Experimental details
Crystal data | |
Chemical formula | (CH6N3)[Mn(C2O4)Cl(H2O)]·H2O |
Mr | 274.53 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 6.740 (5), 7.514 (7), 9.810 (2) |
α, β, γ (°) | 84.46 (3), 78.15 (4), 88.57 (6) |
V (Å3) | 484.0 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.65 |
Crystal size (mm) | 0.50 × 0.43 × 0.34 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.551, 0.718 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4226, 2114, 2018 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.638 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.065, 1.10 |
No. of reflections | 2114 |
No. of parameters | 155 |
No. of restraints | 11 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.39, −0.30 |
Computer programs: CAD-4 EXPRESS (Duisenberg, 1992), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), DIAMOND (Brandenburg, 2006), WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).
Acknowledgements
Financial support from the Ministry of Higher Education and Scientific Research of Tunisia is gratefully acknowledged.
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