research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 72| Part 3| March 2016| Pages 331-333

Crystal structure of 2,6-di­amino­pyridinium chloride

CROSSMARK_Color_square_no_text.svg

aInstitute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9/163, A-1060 Vienna, Austria, and bInstitute for Chemical Technologies and Analytics, Division of Structural Chemistry, TU Wien, Getreidemarkt 9/164-SC, A-1060 Vienna, Austria
*Correspondence e-mail: Matthias.Weil@tuwien.ac.at

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 5 February 2016; accepted 8 February 2016; online 13 February 2016)

The asymmetric unit of the title salt, C5H8N3+·Cl, comprises one half of the 2,6-di­amino­pyridinium cation (the other half being completed by the application of mirror symmetry) and one Cl counter-anion, also located on the mirror plane. The amino N atom shows a significant pyramidalization, with a dihedral angle of 30.4 (14)° between the least-squares planes of the amino group and the non-H atoms of the 2,6-di­amino­pyridinium moiety. In the crystal, the cationic mol­ecules and Cl counter-anions are arranged in sheets parallel to (001) consisting of alternating polar and non-polar parts associated with the the Cl anions, pyridinium and amino moieties, and the pyridine rings, respectively. N—H⋯Cl inter­actions within the polar part, as well as slipped ππ inter­actions in the non-polar part, help to establish the three-dimensional network.

1. Chemical context

Pincer compounds are an important class of chelating ligands, and their metal complexes have attracted tremendous inter­est due to their high stability, activity, variability and applicability in organic synthesis and catalysis (Szabo & Wendt, 2014[Szabo, K. J. & Wendt, O. F. (2014). In Pincer and Pincer-Type Complexes: Applications in Organic Synthesis and Catalysis. Weinheim: Wiley-VCH.]). Whereas a plethora of (mostly) precious transition-metal pincer complexes has been reported, information on group 6 pincer complexes is rather scarce. During a project aimed at the preparation and characterization of group 6 PNP pincer compounds (Öztopcu et al., 2013[Öztopcu, Ö., Holzhacker, C., Puchberger, M., Weil, M., Mereiter, K., Veiros, L. F. & Kirchner, K. (2013). Organometallics, 32, 3042-3052.]; de Aguiar et al., 2014[Aguiar, S. R. M. M. de, Öztopcu, Ö., Stöger, B., Mereiter, K., Veiros, L. F., Pittenauer, E., Allmaier, G. & Kirchner, K. (2014). Dalton Trans. 43, 14669-14679.]; Mastalir et al., 2016[Mastalir, M., de Aguiar, S. R. M. M., Glatz, M., Stöger, B. & Kirchner, K. (2016). Organometallics, 35, 229-232.]), crystals of the title salt, C5H8N3+·Cl, were obtained accidentally through hydrolysis of the employed ligand N,N'-bis­(diiso­propyl­phosphino)-2,6-di­amino­pyridine in the presence of CrCl3·6H2O. Here we report on the crystal structure of this salt.

[Scheme 1]

2. Structural commentary

The cation of the title structure is protonated at the pyridine N atom (Fig. 1[link]). The asymmetric unit comprises half a mol­ecule of the 2,6-di­amino­pyridinium cation, with a mirror plane running through the pyridinium group (N1—H1N1) and the para-C—H group (C3—H1C3); the Cl anion is also located on the mirror plane. In agreement with other 2,6-di­amino­pyridinium cations, the C—N(H)+—C angle involving the pyridinium group is enlarged [C1—N1—C1i = 123.37 (8)°; symmetry code: (i) x, −y, z] whereas the angle between the pyridinium N atom and the C atom in the ortho position (bearing the amino group) and in the meta position is reduced [N1—C1—C2 = 118.83 (6)°]. This situation is reversed in 2,6-di­amino­pyridine due to the non-protonated ring N atom in this structure (Schwalbe et al., 1987[Schwalbe, C. H., Williams, G. J. B. & Koetzle, T. F. (1987). Acta Cryst. C43, 2191-2195.]). A common feature of the non-protonated 2,6-di­amino­pyridine mol­ecule and the 2,6-di­amino­pyridinium cation is a significant pyramidalization of the amino N atom. In the title structure, the bond angle sum at this atom (N2) deviates with 349.0° clearly from the expected 360° for an ideal trigonal–planar group. The pyramidalization is also reflected by the dihedral angle of 30.4 (14)° between the least-squares planes of the amino group and the non-H atoms of the 2,6-di­amino­pyridinium moiety.

[Figure 1]
Figure 1
The mol­ecular structure of the cation and the inorganic anion in the title structure. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) x, −y, z.]

3. Supra­molecular features

The pyridinium N1—H1N1 group is the donor of a nearly linear hydrogen bond to the Cl counter anion (Table 1[link]). The amino group also participates in the formation of N—H⋯Cl hydrogen bonds, albeit of explicit weaker nature. One hydrogen atom (H2N2) is clearly involved in hydrogen bonding with an H2N2⋯Cl1 distance of 2.63 Å and an N2—H2N2⋯Cl1 angle of 157°. Although the DA contact involving the second hydrogen atom, H2N2, is 0.04 Å shorter than that of the other hydrogen bond of this group, the comparatively long H1N2⋯Cl distance of 2.88 Å and the very small N2—H1N2⋯Cl1 angle of 117° give room for inter­pretation whether or not this is a real hydrogen bond.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1N1⋯Cl1 0.90 (2) 2.18 (2) 3.0790 (11) 175.6 (19)
N2—H2N2⋯Cl1i 0.833 (13) 2.628 (13) 3.4086 (8) 156.5 (12)
N2—H1N2⋯Cl1ii 0.875 (13) 2.877 (13) 3.3601 (8) 116.8 (2)
Symmetry codes: (i) [x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]; (ii) [-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z].

In the crystal (Figs. 2[link] and 3[link]), the cationic mol­ecules and anions are arranged into layers with alternating polar and non-polar parts extending parallel to (001). Adjacent polar parts, comprising the Cl anions and the pyridinium and amino moieties, are linked through N—H⋯Cl hydrogen bonds into sheets with a thickness of ≃ c/2. The non-polar parts, i.e. the pyridine rings, inter­act through slipped ππ stacking along [001] with a centroid-to-centroid distance of 3.5129 (6) Å; the corresponding plane-to-plane distance between the pyridine rings is 3.344 Å.

[Figure 2]
Figure 2
Crystal packing of the organic and inorganic components in the title structure in a projection along [001]. N—H⋯Cl hydrogen bonds involving the pyridinium group are shown as magenta dotted lines and those involving the amino group are shown as orange dotted lines.
[Figure 3]
Figure 3
Crystal packing of the organic and inorganic components in the title structure in a projection along [100]. The colour code of the inter­molecular inter­actions is as in Fig. 2[link].

4. Database survey

A search in the CSD (Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]; CSD Version 5.31) revealed 87 different salts containing the 2,6-di­amino­pyridinium cation, with the majority of cases in the form of organic anions (46 representatives), followed by complex metal anions (31 representatives). Two structures are reported that contain additional metal cations and inorganic anions, and eight representatives are compiled with inorganic anions only, including the SiF62− salt (CSD code FOSXER; Gelmboldt et al., 2009[Gelmboldt, V. O., Ganin, E. V., Fonari, M. S., Koroeva, L. V., Ivanov, Y. E. & Botoshansky, M. M. (2009). J. Fluor. Chem. 130, 428-433.]), the Br salt (GOLMIF; Turrell et al., 2010[Turrell, P. J., Wright, J. A. & Pickett, C. J. (2010). Private communication (refcode GOLMIF). CCDC, Cambridge, England.]), the BF4 salt (IFOQAW; Benito-Garagorri et al.; 2007[Benito-Garagorri, D., Kirchner, K. & Mereiter, K. (2007). Private communication (refcode IFOQAW). CCDC, Cambridge, England.]), the Br salt monohydrate (ILINEW; Haddad & Al-Far, 2003[Haddad, S. F. & Al-Far, R. H. (2003). Acta Cryst. E59, o1444-o1446.]), the hydrogensulfate sulfate salt (KORRAM; Said & Naili, 2014[Said, S. & Naili, H. (2014). Private communication (refcode KORRAM). CCDC, Cambridge, England.]), the ClO4 salt (MIGWOP; Jazdoń et al., 2007[Jazdoń, M., Radecka-Paryzek, W. & Kubicki, M. (2007). Acta Cryst. E63, o3337.]), the H2PO4 salt (QEDHUE; Yu, 2012[Yu, G. (2012). Acta Cryst. E68, o2751.]) and the NO3 salt (XAKVAG; Kristiansson, 2000[Kristiansson, O. (2000). Z. Kristallogr. New Cryst. Struct. 215, 138.]). It should be noted that the chemically most related anhydrous Br salt crystallizes in space group I[\overline{4}]2d and hence shows no isotypism with the title Cl salt.

5. Synthesis and crystallization

N,N'-bis­(diiso­propyl­phosphino)-2,6-di­amino­pyridine (0.2 g, 0.53 mmol) was dissolved in dry tetra­hydro­furan (5 ml) under argon atmosphere. CrCl3·6H2O (0.134 g, 0.51 mmol) was added and the resulting mixture stirred for 4 h at room temperature. The formed purple solid was filtered off, washed with dry diethyl ether and dried. The solid was redissolved in aceto­nitrile for crystallization initiated by solvent diffusion with diethyl ether. The title compound grew in the form of yellow crystals as the only solid product. We assume that the Lewis acid CrCl3 in combination with water is able to cleave the P—N bond of the pincer compound accompanied by an in situ formation of HCl which eventually yields the title compound.

6. Refinement

All H atoms were clearly discernible from difference Fourier maps and were refined freely. Crystal data, data collection and structure refinement details are summarized in Table 2[link].

Table 2
Experimental details

Crystal data
Chemical formula C5H8N3+·Cl
Mr 145.6
Crystal system, space group Monoclinic, C2/m
Temperature (K) 100
a, b, c (Å) 10.8046 (10), 9.0459 (9), 6.8108 (7)
β (°) 96.710 (2)
V3) 661.11 (11)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.48
Crystal size (mm) 0.52 × 0.38 × 0.23
 
Data collection
Diffractometer Bruker Kappa APEXII CCD
Absorption correction Multi-scan (SADABS; Bruker, 2014[Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.80, 0.90
No. of measured, independent and observed [I > 3σ(I)] reflections 9529, 1538, 1407
Rint 0.031
(sin θ/λ)max−1) 0.808
 
Refinement
R[F2 > 3σ(F)], wR(F), S 0.024, 0.038, 2.24
No. of reflections 1538
No. of parameters 64
H-atom treatment All H-atom parameters refined
Δρmax, Δρmin (e Å−3) 0.49, −0.18
Computer programs: APEX2 (Bruker, 2014[Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SAINT (Bruker, 2014[Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SUPERFLIP (Palatinus & Chapuis, 2007[Palatinus, L. & Chapuis, G. (2007). J. Appl. Cryst. 40, 786-790.]), JANA2006 (Petříček et al., 2014[Petříček, V., Dušek, M. & Palatinus, L. (2014). Z. Kristallogr. 229, 345-352.]), XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Chemical context top

Pincer compounds are an important class of chelating ligands, and their metal complexes have attracted tremendous inter­est due to their high stability, activity, variability and applicability in organic synthesis and catalysis (Szabo & Wendt, 2014). Whereas a plethora of (mostly) precious transition-metal pincer complexes has been reported, information on group 6 pincer complexes is rather scarce. During a project aimed at the preparation and characterization of group 6 PNP pincer compounds (Öztopcu et al., 2013; de Aguiar et al., 2014; Mastalir et al., 2016), crystals of the title salt, C5H8N3+·Cl, were obtained accidentally through hydrolysis of the employed ligand N,N'-bis­(diiso­propyl­phosphino)-2,6-di­amino­pyridine in the presence of CrCl3·6H2O. Here we report on the crystal structure of this salt.

Structural commentary top

The cation of the title structure is protonated at the pyridine N atom (Fig. 1). The asymmetric unit comprises half a molecule of the 2,6-di­amino­pyridinium cation, with a mirror plane running through the pyridinium group (N1—H1N1) and the para-C—H group (C3—H1C3); the Cl anion is also located on the mirror plane. In agreement with other 2,6-di­amino­pyridinium cations, the C—N(H)+—C angle involving the pyridinium group is enlarged [C1—N1—C1i = 123.37 (8)°; symmetry code: (i) x, −y, z] whereas the angle between the pyridinium N atom and the C atom in the ortho position (bearing the amino group) and in the meta position is reduced [N1—C1—C2 = 118.83 (6)°]. This situation is reversed in 2,6-di­amino­pyridine due to the non-protonated ring N atom in this structure (Schwalbe et al., 1987). A common feature of the non-protonated 2,6-di­amino­pyridine molecule and the 2,6-di­amino­pyridinium cation is a significant pyramidalization of the amino N atom. In the title structure, the bond angle sum at this atom (N2) deviates with 349.0° clearly from the expected 360° for an ideal trigonal–planar group. The pyramidalization is also reflected by the dihedral angle of 30.4 (14)° between the least-squares planes of the amino group and the non-H atoms of the 2,6-di­amino­pyridinium moiety.

Supra­molecular features top

The pyridinium N1—H1N1 group is the donor of a nearly linear hydrogen bond to the Cl counter anion (Table 1). The amino group also participates in the formation of N—H···Cl hydrogen bonds, albeit of explicit weaker nature. One hydrogen atom (H2N2) is clearly involved in hydrogen bonding with an H2N2···Cl1 distance of 2.63 Å and an N2—H2N2···Cl1 angle of 157°. Although the D···A contact involving the second hydrogen atom, H2N2, is 0.04 Å shorter than that of the other hydrogen bond of this group, the comparatively long H1N2···Cl distance of 2.88 Å and the very small N2—H1N2···Cl1 angle of 117° give room for inter­pretation whether or not this is a real hydrogen bond.

In the crystal (Figs. 2 and 3), the cationic molecules and anions are arranged into layers with alternating polar and non-polar parts extending parallel to (001). Adjacent polar parts, comprising the Cl anions and the pyridinium and amino moieties, are linked through N—H···Cl hydrogen bonds into sheets with a thickness of c/2. The non-polar parts, i.e. the pyridine rings, inter­act through slipped ππ stacking along [001] with a centroid-to-centroid distance of 3.5129 (6) Å; the corresponding plane-to-plane distance between the pyridine rings is 3.344 Å.

Database survey top

A search in the CSD (Groom & Allen, 2014; CSD Version 5.31) revealed 87 different salts containing the 2,6-di­amino­pyridinium cation, with the majority of cases in the form of organic anions (46 representatives), followed by complex metal anions (31 representatives). Two structures are reported that contain additional metal cations and inorganic anions, and eight representatives are compiled with inorganic anions only, including the SiF62− salt (CSD code FOSXER; Gelmboldt et al., 2009), the Br salt (GOLMIF; Turrell et al., 2010), the BF4 salt (IFOQAW; Benito-Garagorri et al.; 2007), the Br salt monohydrate (ILINEW; Haddad & Al-Far, 2003), the hydrogensulfate sulfate salt (KORRAM; Said & Naili, 2014), the ClO4 salt (MIGWOP; Jazdoń et al., 2007), the H2PO4 salt (QEDHUE; Yu, 2012) and the NO3 salt (XAKVAG; Kristiansson, 2000). It should be noted that the chemically most related anhydrous Br salt crystallizes in space group I42d and hence shows no isotypism with the title Cl salt.

Synthesis and crystallization top

N,N'-bis­(diiso­propyl­phosphino)-2,6-di­amino­pyridine (0.2 g, 0.53 mmol) was dissolved in dry tetra­hydro­furan (5 ml) under argon atmosphere. CrCl3·6H2O (0.134 g, 0.51 mmol) was added and the resulting mixture stirred for 4 h at room temperature. The formed purple solid was filtered off, washed with dry di­ethyl ether and dried. The solid was redissolved in aceto­nitrile for crystallization initiated by solvent diffusion with di­ethyl ether. The title compound grew in form of yellow crystals as the only solid product. We assume that the Lewis acid CrCl3 in combination with water is able to cleave the P—N bond of the pincer compound accompanied by an in situ formation of HCl which eventually yields the title compound.

Refinement top

All H atoms were clearly discernible from difference maps and were refined freely. Crystal data, data collection and structure refinement details are summarized in Table 2.

Structure description top

Pincer compounds are an important class of chelating ligands, and their metal complexes have attracted tremendous inter­est due to their high stability, activity, variability and applicability in organic synthesis and catalysis (Szabo & Wendt, 2014). Whereas a plethora of (mostly) precious transition-metal pincer complexes has been reported, information on group 6 pincer complexes is rather scarce. During a project aimed at the preparation and characterization of group 6 PNP pincer compounds (Öztopcu et al., 2013; de Aguiar et al., 2014; Mastalir et al., 2016), crystals of the title salt, C5H8N3+·Cl, were obtained accidentally through hydrolysis of the employed ligand N,N'-bis­(diiso­propyl­phosphino)-2,6-di­amino­pyridine in the presence of CrCl3·6H2O. Here we report on the crystal structure of this salt.

The cation of the title structure is protonated at the pyridine N atom (Fig. 1). The asymmetric unit comprises half a molecule of the 2,6-di­amino­pyridinium cation, with a mirror plane running through the pyridinium group (N1—H1N1) and the para-C—H group (C3—H1C3); the Cl anion is also located on the mirror plane. In agreement with other 2,6-di­amino­pyridinium cations, the C—N(H)+—C angle involving the pyridinium group is enlarged [C1—N1—C1i = 123.37 (8)°; symmetry code: (i) x, −y, z] whereas the angle between the pyridinium N atom and the C atom in the ortho position (bearing the amino group) and in the meta position is reduced [N1—C1—C2 = 118.83 (6)°]. This situation is reversed in 2,6-di­amino­pyridine due to the non-protonated ring N atom in this structure (Schwalbe et al., 1987). A common feature of the non-protonated 2,6-di­amino­pyridine molecule and the 2,6-di­amino­pyridinium cation is a significant pyramidalization of the amino N atom. In the title structure, the bond angle sum at this atom (N2) deviates with 349.0° clearly from the expected 360° for an ideal trigonal–planar group. The pyramidalization is also reflected by the dihedral angle of 30.4 (14)° between the least-squares planes of the amino group and the non-H atoms of the 2,6-di­amino­pyridinium moiety.

The pyridinium N1—H1N1 group is the donor of a nearly linear hydrogen bond to the Cl counter anion (Table 1). The amino group also participates in the formation of N—H···Cl hydrogen bonds, albeit of explicit weaker nature. One hydrogen atom (H2N2) is clearly involved in hydrogen bonding with an H2N2···Cl1 distance of 2.63 Å and an N2—H2N2···Cl1 angle of 157°. Although the D···A contact involving the second hydrogen atom, H2N2, is 0.04 Å shorter than that of the other hydrogen bond of this group, the comparatively long H1N2···Cl distance of 2.88 Å and the very small N2—H1N2···Cl1 angle of 117° give room for inter­pretation whether or not this is a real hydrogen bond.

In the crystal (Figs. 2 and 3), the cationic molecules and anions are arranged into layers with alternating polar and non-polar parts extending parallel to (001). Adjacent polar parts, comprising the Cl anions and the pyridinium and amino moieties, are linked through N—H···Cl hydrogen bonds into sheets with a thickness of c/2. The non-polar parts, i.e. the pyridine rings, inter­act through slipped ππ stacking along [001] with a centroid-to-centroid distance of 3.5129 (6) Å; the corresponding plane-to-plane distance between the pyridine rings is 3.344 Å.

A search in the CSD (Groom & Allen, 2014; CSD Version 5.31) revealed 87 different salts containing the 2,6-di­amino­pyridinium cation, with the majority of cases in the form of organic anions (46 representatives), followed by complex metal anions (31 representatives). Two structures are reported that contain additional metal cations and inorganic anions, and eight representatives are compiled with inorganic anions only, including the SiF62− salt (CSD code FOSXER; Gelmboldt et al., 2009), the Br salt (GOLMIF; Turrell et al., 2010), the BF4 salt (IFOQAW; Benito-Garagorri et al.; 2007), the Br salt monohydrate (ILINEW; Haddad & Al-Far, 2003), the hydrogensulfate sulfate salt (KORRAM; Said & Naili, 2014), the ClO4 salt (MIGWOP; Jazdoń et al., 2007), the H2PO4 salt (QEDHUE; Yu, 2012) and the NO3 salt (XAKVAG; Kristiansson, 2000). It should be noted that the chemically most related anhydrous Br salt crystallizes in space group I42d and hence shows no isotypism with the title Cl salt.

Synthesis and crystallization top

N,N'-bis­(diiso­propyl­phosphino)-2,6-di­amino­pyridine (0.2 g, 0.53 mmol) was dissolved in dry tetra­hydro­furan (5 ml) under argon atmosphere. CrCl3·6H2O (0.134 g, 0.51 mmol) was added and the resulting mixture stirred for 4 h at room temperature. The formed purple solid was filtered off, washed with dry di­ethyl ether and dried. The solid was redissolved in aceto­nitrile for crystallization initiated by solvent diffusion with di­ethyl ether. The title compound grew in form of yellow crystals as the only solid product. We assume that the Lewis acid CrCl3 in combination with water is able to cleave the P—N bond of the pincer compound accompanied by an in situ formation of HCl which eventually yields the title compound.

Refinement details top

All H atoms were clearly discernible from difference maps and were refined freely. Crystal data, data collection and structure refinement details are summarized in Table 2.

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: JANA2006 (Petříček et al., 2014); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of the cation and the inorganic anion in the title structure. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) x, −y, z.]
[Figure 2] Fig. 2. Crystal packing of the organic and inorganic components in the title structure in a projection along [001]. N—H···Cl hydrogen bonds involving the pyridinium group are shown as magenta dotted lines and those involving the amino group are shown as orange dotted lines.
[Figure 3] Fig. 3. Crystal packing of the organic and inorganic components in the title structure in a projection along [100]. The colour code of the intermolecular interactions is as in Fig. 2.
2,6-Diaminopyridin-1-ium chloride top
Crystal data top
C5H8N3+·ClF(000) = 304
Mr = 145.6Dx = 1.462 Mg m3
Monoclinic, C2/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yCell parameters from 6316 reflections
a = 10.8046 (10) Åθ = 2.9–35.5°
b = 9.0459 (9) ŵ = 0.48 mm1
c = 6.8108 (7) ÅT = 100 K
β = 96.710 (2)°Block, yellow
V = 661.11 (11) Å30.52 × 0.38 × 0.23 mm
Z = 4
Data collection top
Bruker Kappa APEXII CCD
diffractometer
1538 independent reflections
Radiation source: X-ray tube1407 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.031
ω– and φ–scansθmax = 35.0°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2014)
h = 1717
Tmin = 0.80, Tmax = 0.90k = 1414
9529 measured reflectionsl = 1010
Refinement top
Refinement on F0 constraints
R[F2 > 2σ(F2)] = 0.024All H-atom parameters refined
wR(F2) = 0.038Weighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2)
S = 2.24(Δ/σ)max = 0.030
1538 reflectionsΔρmax = 0.49 e Å3
64 parametersΔρmin = 0.18 e Å3
0 restraints
Crystal data top
C5H8N3+·ClV = 661.11 (11) Å3
Mr = 145.6Z = 4
Monoclinic, C2/mMo Kα radiation
a = 10.8046 (10) ŵ = 0.48 mm1
b = 9.0459 (9) ÅT = 100 K
c = 6.8108 (7) Å0.52 × 0.38 × 0.23 mm
β = 96.710 (2)°
Data collection top
Bruker Kappa APEXII CCD
diffractometer
1538 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2014)
1407 reflections with I > 3σ(I)
Tmin = 0.80, Tmax = 0.90Rint = 0.031
9529 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.038All H-atom parameters refined
S = 2.24Δρmax = 0.49 e Å3
1538 reflectionsΔρmin = 0.18 e Å3
64 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.17115 (2)00.12206 (3)0.01401 (7)
N10.45600 (9)00.22925 (12)0.0132 (2)
N20.44617 (7)0.25682 (8)0.22357 (10)0.01951 (18)
C10.51532 (7)0.13257 (7)0.25660 (9)0.01272 (16)
C20.64225 (7)0.13396 (7)0.32011 (10)0.01334 (17)
C30.70393 (10)00.35111 (14)0.0136 (2)
H1C20.6796 (9)0.2256 (14)0.3421 (16)0.019 (3)*
H1C30.7905 (16)00.392 (2)0.015 (3)*
H1N20.3742 (16)0.2574 (17)0.150 (2)0.046 (4)*
H2N20.4841 (12)0.3350 (15)0.2058 (19)0.032 (3)*
H1N10.3735 (19)00.191 (3)0.039 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.01121 (13)0.01270 (11)0.01763 (12)00.00037 (8)0
N10.0093 (4)0.0176 (4)0.0128 (3)00.0018 (3)0
N20.0192 (3)0.0187 (3)0.0214 (3)0.0075 (2)0.0056 (2)0.0065 (2)
C10.0137 (3)0.0143 (3)0.0107 (2)0.0025 (2)0.0039 (2)0.00180 (19)
C20.0136 (3)0.0118 (3)0.0149 (3)0.0012 (2)0.0026 (2)0.00027 (19)
C30.0108 (4)0.0154 (4)0.0145 (4)00.0011 (3)0
Geometric parameters (Å, º) top
N1—C11.3622 (8)C1—C21.3890 (10)
N1—C11.3622 (8)C2—C31.3872 (9)
N1—H1N10.90 (2)C2—H1C20.927 (12)
N2—C11.3538 (10)C3—H1C30.944 (17)
N2—H1N20.875 (16)C3—C21.3872 (9)
N2—H2N20.833 (13)
C1—N1—C1123.37 (8)N2—C1—C2123.35 (6)
C1—N1—H1N1118.32 (4)C1—C2—C3118.60 (7)
C1—N1—H1N1118.32 (4)C1—C2—H1C2117.0 (6)
C1—N2—H1N2122.5 (10)C3—C2—H1C2124.4 (6)
C1—N2—H2N2117.2 (9)C2—C3—C2121.75 (9)
H1N2—N2—H2N2109.3 (13)C2—C3—H1C3119.12 (5)
N1—C1—N2117.81 (7)C2—C3—H1C3119.12 (5)
N1—C1—C2118.83 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···Cl10.90 (2)2.18 (2)3.0790 (11)175.6 (19)
N2—H2N2···Cl1i0.833 (13)2.628 (13)3.4086 (8)156.5 (12)
N2—H1N2···Cl1ii0.875 (13)2.877 (13)3.3601 (8)116.8 (2)
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x+1/2, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···Cl10.90 (2)2.18 (2)3.0790 (11)175.6 (19)
N2—H2N2···Cl1i0.833 (13)2.628 (13)3.4086 (8)156.5 (12)
N2—H1N2···Cl1ii0.875 (13)2.877 (13)3.3601 (8)116.8 (2)
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC5H8N3+·Cl
Mr145.6
Crystal system, space groupMonoclinic, C2/m
Temperature (K)100
a, b, c (Å)10.8046 (10), 9.0459 (9), 6.8108 (7)
β (°) 96.710 (2)
V3)661.11 (11)
Z4
Radiation typeMo Kα
µ (mm1)0.48
Crystal size (mm)0.52 × 0.38 × 0.23
Data collection
DiffractometerBruker Kappa APEXII CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2014)
Tmin, Tmax0.80, 0.90
No. of measured, independent and
observed [I > 3σ(I)] reflections
9529, 1538, 1407
Rint0.031
(sin θ/λ)max1)0.808
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.038, 2.24
No. of reflections1538
No. of parameters64
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.49, 0.18

Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SUPERFLIP (Palatinus & Chapuis, 2007), JANA2006 (Petříček et al., 2014), XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), publCIF (Westrip, 2010).

 

Acknowledgements

The X-ray centre of TU Wien is acknowledged for providing access to the single-crystal diffractometer.

References

First citationAguiar, S. R. M. M. de, Öztopcu, Ö., Stöger, B., Mereiter, K., Veiros, L. F., Pittenauer, E., Allmaier, G. & Kirchner, K. (2014). Dalton Trans. 43, 14669–14679.  PubMed Google Scholar
First citationBenito-Garagorri, D., Kirchner, K. & Mereiter, K. (2007). Private communication (refcode IFOQAW). CCDC, Cambridge, England.  Google Scholar
First citationBruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationGelmboldt, V. O., Ganin, E. V., Fonari, M. S., Koroeva, L. V., Ivanov, Y. E. & Botoshansky, M. M. (2009). J. Fluor. Chem. 130, 428–433.  CSD CrossRef CAS Google Scholar
First citationGroom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671.  Web of Science CSD CrossRef CAS Google Scholar
First citationHaddad, S. F. & Al-Far, R. H. (2003). Acta Cryst. E59, o1444–o1446.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationJazdoń, M., Radecka-Paryzek, W. & Kubicki, M. (2007). Acta Cryst. E63, o3337.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationKristiansson, O. (2000). Z. Kristallogr. New Cryst. Struct. 215, 138.  Google Scholar
First citationMacrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationMastalir, M., de Aguiar, S. R. M. M., Glatz, M., Stöger, B. & Kirchner, K. (2016). Organometallics, 35, 229–232.  CrossRef CAS Google Scholar
First citationÖztopcu, Ö., Holzhacker, C., Puchberger, M., Weil, M., Mereiter, K., Veiros, L. F. & Kirchner, K. (2013). Organometallics, 32, 3042–3052.  PubMed Google Scholar
First citationPalatinus, L. & Chapuis, G. (2007). J. Appl. Cryst. 40, 786–790.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationPetříček, V., Dušek, M. & Palatinus, L. (2014). Z. Kristallogr. 229, 345–352.  Google Scholar
First citationSaid, S. & Naili, H. (2014). Private communication (refcode KORRAM). CCDC, Cambridge, England.  Google Scholar
First citationSchwalbe, C. H., Williams, G. J. B. & Koetzle, T. F. (1987). Acta Cryst. C43, 2191–2195.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSzabo, K. J. & Wendt, O. F. (2014). In Pincer and Pincer-Type Complexes: Applications in Organic Synthesis and Catalysis. Weinheim: Wiley-VCH.  Google Scholar
First citationTurrell, P. J., Wright, J. A. & Pickett, C. J. (2010). Private communication (refcode GOLMIF). CCDC, Cambridge, England.  Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationYu, G. (2012). Acta Cryst. E68, o2751.  CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 72| Part 3| March 2016| Pages 331-333
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds