Crystal structure of bis­[(5-amino-1H-1,2,4-triazol-3-yl-κN4)acetato-κO]di­aqua­nickel(II) dihydrate

Chernyshev, V.M.; Chernysheva, A.V.; Abagyan, R.S.; Rybakov, V.B.

doi:10.1107/S1600536814021436

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ISSN: 2056-9890

Volume 70| Part 11| November 2014| Pages 286-289

doi:10.1107/S1600536814021436

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Crystal structure of bis[(5-amino-1H-1,2,4-triazol-3-yl-κN⁴)acetato-κO]diaquanickel(II) dihydrate

Victor M. Chernyshev,^a ^* Anna V. Chernysheva,^a Raisa S. Abagyan ^a and Victor B. Rybakov ^b

^aSouth–Russia State Technical University Prosveschenya, 132, Novocherkassk, Rostov Region, 346428, Russian Federation, and ^bDepartment of Chemistry, Moscow State University, 119992 Moscow, Russian Federation
^*Correspondence e-mail: chern13@yandex.ru

Edited by M. Weil, Vienna University of Technology, Austria (Received 19 September 2014; accepted 26 September 2014; online 4 October 2014)

The title compound, [Ni(C₄H₅N₄O₂)₂(H₂O)₂]·2H₂O, represents the first transition metal complex of the novel chelating triazole ligand, 2-(5-amino-1H-1,2,4-triazol-3-yl)acetic acid (ATAA), to be structurally characterized. In the molecule of the title complex, the nickel(II) cation is located on an inversion centre and is coordinated by two water molecules in axial positions and two O and two N atoms from two trans-oriented chelating anions of the deprotonated ATAA ligand, forming a slightly distorted octahedron. The trans angles of the octahedron are all 180° due to the inversion symmetry of the molecule. The cis-angles are in the range 87.25 (8)–92.75 (8)°. The six-membered chelate ring adopts a slightly twisted boat conformation with puckering parameters Q = 0.542 (2) Å, Θ = 88.5 (2) and φ = 15.4 (3)°. The molecular conformation is stabilized by intramolecular N—H⋯O hydrogen bonds between the amino group and the chelating carboxylate O atom of two trans-oriented ligands. In the crystal, the complex molecules and lattice water molecules are linked into a three-dimensional framework by an extensive network of N—H⋯O, O—H⋯O and O—H⋯N hydrogen bonds.

Keywords: Crystal structure; triazole; 2-(5-amino-1H-1,2,4-triazol-3-yl)acetic acid; chelating ligand; nickel coordination compound; crystal structure.

CCDC reference: 1026535

1. Chemical context

C-amino-1,2,4-triazoles are employed as polydentate ligands for the synthesis of coordination compounds with various metals that demonstrate useful spectroscopic, magnetic, biological and catalytic properties (Aromí et al., 2011 ; Liu et al., 2011 ; Gao et al., 2013 ; Hernández-Gil et al., 2014 ). Generally, aminotriazoles coordinate metals by either pyridine-type endocyclic nitrogen atoms or by the amino group (Aromí et al., 2011; Liu et al., 2011). Furthermore, aminotriazoles containing substituents with favorably oriented atoms bearing unshared electron pairs (N, S, O etc.) can act as chelating polydentate ligands (Biagini-Cingi et al., 1994 ; Prins et al., 1996 ; Ferrer et al., 2004 , 2012 ). 5-Amino-1H-1,2,4-triazole-3-carboxylic acid (ATCA, Fig. 1) was found to be a promising chelating ligand for which complexes with various metal cations have been reported recently (Chen et al., 2011 ; Sun et al., 2011 ; Wang et al., 2011 ; Hernández-Gil et al., 2012 ; Tseng et al., 2014 ). In these complexes, metal cations are chelated by the anions of ATCA owing to the formation of coordination bonds with nitrogen atoms of the triazole ring and the oxygen atom of the deprotonated carboxylic group.

Figure 1
Structural formulas of 5-amino-1H-1,2,4-triazole-3-carboxylic acid (ATCA) and 2-(5-amino-1H-1,2,4-triazol-3-yl)acetic acid (ATAA).

In a continuation of our work on the synthesis and reactivity of aminotriazole carboxylic acids (Chernyshev et al., 2006 , 2009 , 2010 ), we have focused our attention on another chelating ligand, namely 2-(5-amino-1H-1,2,4-triazol-3-yl)acetic acid (ATAA, Fig. 1), which can be considered as a homologue of ATCA. To the best of our knowledge, ATAA or its derivatives have not been studied previously for the synthesis of coordination compounds. Herein, we report the synthesis and crystal structure of an Ni^II complex of ATAA, the title compound [Ni(C₄H₅N₄O₂)₂(H₂O)₂]·2H₂O (1).

2. Structural commentary

In the molecule of the title complex (1), the Ni^II cation is six-coordinated by two bidentate chelating ligands, anions of ATAA, and by two water molecules, forming a slightly distorted octahedron (Fig. 2). The trans-angles of the octahedron are all 180° due to the inversion symmetry of the complete molecule. The cis-angles are in the range 87.25 (8)–92.75 (8)°. The third water molecule is not involved in coordination. The anions of ATAA coordinate the Ni^II cation through the nitrogen atom N1 of the triazole ring and the oxygen atom O53 of the carboxylate group (Fig. 2), similarly to the complexes of ATCA with various metal cations (Chen et al., 2011; Sun et al., 2011; Wang et al., 2011; Hernández-Gil et al., 2012). The six-membered chelate ring adopts a slightly twisted boat conformation with puckering parameters of Q = 0.542 (2) Å, Θ = 88.5 (2), φ = 15.4 (3)°. The Ni—N1 bond length is 2.051 (2) Å, and the Ni—O1 and Ni—O53 bond lengths are 2.083 (2) and 2.059 (2) Å, respectively, within the normal ranges for other reported Ni^II complexes (Lenstra et al., 1989 ; Virovets et al., 2000 ; Bushuev et al., 2002 ; Drozdzewski et al., 2003 ; Fan et al., 2010 ; Zheng et al., 2011 ; Jin et al., 2011 ). The aminotriazole fragment N1/C2/N3/N4/C5/N21 is planar (maximum deviation = 0.021 (3) Å for C2), its bond lengths and angles being analogous to complexes of C-amino-1,2,4-triazoles with transition metals (Ferrer et al., 2004; Siddiqui et al., 2011 ; Tabatabaee et al., 2011 ). The bonds C2—N3 [1.330 (4) Å] and C5—N4 [1.304 (3) Å] are shorter than the bonds C2—N1 [1.342 (3) Å] and C5—N1 [1.365 (3) Å]. The molecular conformation is stabilized by intramolecular N21—H21B⋯O53 hydrogen bonds (Fig. 2, Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N21—H21A⋯O2ⁱ	0.83 (2)	2.04 (2)	2.876 (3)	176 (3)
N21—H21B⋯O53ⁱⁱ	0.83 (2)	2.19 (2)	2.941 (3)	151 (3)
N3—H3⋯O54ⁱⁱⁱ	0.83 (3)	2.10 (3)	2.885 (3)	156 (3)
O1—H1A⋯O2^iv	0.82 (2)	1.92 (2)	2.739 (3)	176 (3)
O1—H1B⋯O54^v	0.82 (2)	1.96 (2)	2.780 (3)	173 (4)
O2—H2A⋯N4^vi	0.83 (2)	2.09 (2)	2.903 (3)	164 (3)
O2—H2B⋯O53^vii	0.83 (2)	1.98 (2)	2.811 (3)	176 (3)
Symmetry codes: (i) x, y, z-1; (ii) -x, -y, -z; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (v) -x-1, -y, -z; (vi) x+1, y, z+1; (vii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. Intramolecular N—H⋯O hydrogen bonds are shown as dashed lines. Equivalent atoms are generated by symmetry code −x, −y, −z.

3. Supramolecular features

In the crystal, molecules of the complex and lattice water molecules are linked into a three–dimensional framework by extensive N—H⋯O, O—H⋯O and O—H⋯N hydrogen bonds (Table 1, Fig. 3).

Figure 3
The crystal packing of the title compound viewed along the a axis. Hydrogen bonds are shown as dashed lines.

4. Database survey

More than twenty structures of chelate complexes of 3-substituted 5-amino-1,2,4-triazoles, in which N, O or S atoms of the substituent in the position 3 of the triazole ring play the role of a donor atom, were found in the Cambridge Structural Database (Version 5.35, November 2013 with 2 updates; Thomas et al., 2010 ). The database reveals a total of seven structures of coordination compounds of 5-amino-1H-1,2,4-triazole-3-carboxylic acid (ATCA) with various metals (Chen et al., 2011; Sun et al., 2011; Wang et al., 2011; Hernández-Gil et al., 2012; Tseng et al., 2014; Siddiqui et al., 2011), six of which are chelate complexes. Coordination compounds of metals with the ATAA ligands or its derivatives were not found in the literature.

5. Synthesis and crystallization

All attempts to prepare crystals of complex (1) suitable for X-ray investigation by mixing solutions of ATAA or its sodium salt with solutions of Ni^II salts were unsuccessful and only microcrystalline precipitates of the sparingly soluble complex were obtained. Crystals of acceptable quality were prepared by slow hydrolysis of ethyl 2-(5-amino-1H-1,2,4-triazol-3-yl)acetate (2) in an aqueous solution of nickel nitrate (Fig. 4). A solution of 0.65 g (3.8 mmol) of compound (2) in water (10 ml) was added to a solution of 0.55 g, (1.9 mmol) of Ni(NO₃)₂·6H₂O in water (5 ml). After standing at room temperature for two weeks, the formed crystals were collected by filtration yielding the target compound (1).

Figure 4
Reaction scheme showing the synthesis of the title compound (1).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. C-bound H atoms were placed in calculated positions with C—H = 0.97 Å for the CH₂ group and refined as riding, with U_iso(H) = 1.2U_eq(C). The N,O-bound H atoms that are involved in hydrogen bonds were found from difference Fourier maps. Their distances to the parent atoms were refined to be equal, with a common U_iso(H) value for pairs of related H atoms.

Table 2
Experimental details

Crystal data
Chemical formula
M_r	412.99
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	7.6270 (17), 7.2603 (16), 13.580 (3)
β (°)	91.91 (2)
V (Å³)	751.6 (3)
Z	2
Radiation type	Ag Kα, λ = 0.56085 Å
μ (mm⁻¹)	0.72
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968 )
T_min, T_max	0.945, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	1706, 1640, 1215
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.077, 1.02
No. of reflections	1640
No. of parameters	140
No. of restraints	3
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.31
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994 ), XCAD4 (Harms & Wocadlo, 1995 ), SHELXS97 and SHELXL2013 (Sheldrick, 2008 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 1026535

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814021436/wm5066sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814021436/wm5066Isup2.hkl

checkCIF report

Chemical context top

C-amino-1,2,4-triazoles are employed as polydentate ligands for the synthesis of coordination compounds with various metals that demonstrate useful spectroscopic, magnetic, biological and catalytic properties (Aromí et al., 2011; Liu et al., 2011; Gao et al., 2013; Hernández-Gil et al., 2014). Generally, aminotriazoles coordinate metals by either pyridine-type endocyclic nitrogen atoms or by the amino group (Aromí et al., 2011; Liu et al., 2011). Furthermore, aminotriazoles containing substituents with favorably oriented atoms bearing unshared electron pairs (N, S, O etc.) can act as chelating polydentate ligands (Biagini-Cingi et al., 1994; Prins et al., 1996; Ferrer et al., 2004, 2012). 5-Amino-1H-1,2,4-triazole-3-carboxylic acid (ATCA, Fig. 1) was found to be a promising chelating ligand for which complexes with various metal cations have been reported recently (Chen et al., 2011; Sun et al., 2011; Wang et al., 2011; Hernández-Gil et al., 2012; Tseng et al., 2014). In these complexes, metal cations are chelated by the anions of ATCA owing to the formation of coordination bonds with nitrogen atoms of the triazole ring and the oxygen atom of the deprotonated carboxylic group.

In a continuation our work on the synthesis and reactivity of aminotriazole carboxylic acids (Chernyshev et al., 2006, 2009, 2010), we have focused our attention on another chelating ligand, namely 2-(5-amino-1H-1,2,4-triazol-3-yl)acetic acid (ATAA, Fig. 1), which can be considered as a homologue of ATCA. To the best of our knowledge, ATAA or its derivatives have not been studied previously for the synthesis of coordination compounds. Herein, we report the synthesis and crystal structure of an Ni^II complex of ATAA, the title compound [Ni(C₄H₅N₄O₂)₂(H₂O)₂]·2H₂O (1) (Fig. 2).

Structural commentary top

In the molecule of the title complex (1), the Ni^II cation is six-coordinated by two bidentate chelating ligands, anions of ATAA, and by two water molecules, forming a slightly distorted octahedron (Fig. 2). The trans-angles of the octahedron are all 180° due to the inversion symmetry of the complete molecule. The cis-angles are in the range 87.25 (8)–92.75 (8)°. The third water molecule is not involved in coordination. The anions of ATAA coordinate the Ni^II cation through the nitrogen atom N1 of the triazole ring and the oxygen atom O53 of the carboxylate group (Fig. 2), similarly to the complexes of ATCA with various metal cations (Chen et al., 2011; Sun et al., 2011; Wang et al., 2011; Hernández-Gil et al., 2012). The six-membered chelate ring adopts a slightly twisted boat conformation with puckering parameters of Q = 0.542 (2) Å, Θ = 88.5 (2), ϕ = 15.4 (3)°. The Ni—N1 bond length is 2.051 (2) Å, and the Ni—O1 and Ni—O53 bond lengths are 2.083 (2) and 2.059 (2) Å, respectively, within the normal ranges for other reported Ni^II complexes (Lenstra et al., 1989; Virovets et al., 2000; Bushuev et al., 2002; Drozdzewski et al., 2003; Fan et al., 2010; Zheng et al., 2011; Jin et al., 2011). The aminotriazole fragment N1/C2/N3/N4/C5/N21 is planar (maximum deviation = 0.021 (3) Å for C2), its bond lengths and angles being analogous to complexes of C-amino-1,2,4-triazoles with transition metals (Ferrer et al., 2004; Siddiqui et al., 2011; Tabatabaee et al., 2011). The bonds C2—N3 [1.330 (4) Å] and C5—N4 [1.304 (3) Å] are shorter than the bonds C2—N1 [1.342 (3) Å] and C5—N1 [1.365 (3) Å]. The molecular conformation is stabilized by intramolecular N21—H21B···O53 hydrogen bonds (Fig. 2, Table 1).

Supramolecular features top

In the crystal, molecules of the complex and lattice water molecules are linked into a three–dimensional framework by extensive N—H···O, O—H···O and O—H···N hydrogen bonds (Table 1, Fig. 3).

Database survey top

More than twenty structures of chelate complexes of 3-substituted 5-amino-1,2,4-triazoles, in which N, O or S atoms of the substituent in the position 3 of the triazole ring play the role of a donor atom, were found in the Cambridge Structural Database (Version 5.35, November 2013 with 2 updates; Thomas et al., 2010). The database reveals a total of seven structures of coordination compounds of 5-amino-1H-1,2,4-triazole-3-carboxylic acid (ATCA) with various metals (Chen et al., 2011; Sun et al., 2011; Wang et al., 2011; Hernández-Gil et al., 2012; Tseng et al., 2014; Siddiqui et al., 2011), six of which are chelate complexes. Coordination compounds of metals with the ATAA ligands or its derivatives were not found in the literature.

Synthesis and crystallization top

All attempts to prepare crystals of complex (1) suitable for X-ray investigation by mixing solutions of ATAA or its sodium salt with solutions of Ni^II salts were unsuccessful and only microcrystalline precipitates of the sparingly soluble complex were obtained. Crystals of acceptable quality were prepared by slow hydrolysis of ethyl 2-(5-amino-1H-1,2,4-triazol-3-yl)acetate (2) in an aqueous solution of nickel nitrate (Fig. 4). A solution of 0.65 g (3.8 mmol) of compound (2) in water (10 ml) was added to a solution of 0.55 g, (1.9 mmol) of Ni(NO₃)₂·6H₂O in water (5 ml). After standing at room temperature for two weeks the formed crystals were collected by filtration yielding the target compound (1).

Refinement top

Related literature top

For related literature, see: Aromí et al. (2011); Biagini–Cingi, Manotti–Lanfredi, Ugozzoli & Haasnoot (1994); Bushuev et al. (2002); Chen, –C, Xu, –J, Wang, –B & Wang (2011); Chernyshev et al. (2006, 2009, 2010); Drozdzewski et al. (2003); Fan, –Z, Li, –J, Song, –D, Miao, –L, Hu & –W (2010); Ferrer et al. (2004, 2012); Gao, –Y, Xiong, –H, Chen, –J, Xie, –P, Ran, –R, Yue & –T (2013); Hernández–Gil, Ferrer, Castiñeiras & Lloret (2012); Hernández–Gil, Ferrer, Castiñeiras, Liu–González, Lloret, Ribes, Čoga, Bernecker & Mareque–Rivas (2014); Jin, –H, Li, Hu & Hu (2011); Lenstra et al. (1989); Liu et al. (2011); Prins et al. (1996); Siddiqui et al. (2011); Sun, –G, Xiong, Guo, –Y, Ding, Wang, Gao, –J, Zhu, –C & Verpoort (2011); Tabatabaee et al. (2011); Thomas et al. (2010); Tseng, –W, Luo, –T, Lu & –H (2014); Virovets et al. (2000); Wang et al. (2011); Zheng et al. (2011).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

Structural formulas of 5-amino-1H-1,2,4-triazole-3-carboxylic acid (ATCA) and 2-(5-amino-1H-1,2,4-triazol-3-yl)acetic acid (ATAA).

The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. Intramolecular N—H···O hydrogen bonds are shown as dashed lines.

The crystal packing of the title compound viewed along the a axis. Hydrogen bonds are shown as dashed lines.

Reaction scheme showing the synthesis of the title compound (1).

Bis[(5-amino-1H-1,2,4-triazol-3-yl-κN⁴)acetato-κO]diaquanickel(II) dihydrate top

Crystal data top

	F(000) = 428
M_r = 412.99	D_x = 1.825 Mg m⁻³
Monoclinic, P2₁/n	Ag Kα radiation, λ = 0.56085 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 7.6270 (17) Å	θ = 10.8–12.9°
b = 7.2603 (16) Å	µ = 0.72 mm⁻¹
c = 13.580 (3) Å	T = 295 K
β = 91.91 (2)°	Prism, light green
V = 751.6 (3) Å³	0.20 × 0.20 × 0.20 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	1215 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.021
Graphite monochromator	θ_max = 21.0°, θ_min = 2.4°
non–profiled ω–scans	h = −9→9
Absorption correction: ψ scan (North et al., 1968)	k = 0→9
T_min = 0.945, T_max = 0.958	l = 0→17
1706 measured reflections	1 standard reflections every 60 min
1640 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	3 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F² > 2σ(F²)] = 0.035	Secondary atom site location: difference Fourier map
wR(F²) = 0.077	w = 1/[σ²(F_o²) + (0.0282P)² + 0.467P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
1640 reflections	Δρ_max = 0.34 e Å⁻³
140 parameters	Δρ_min = −0.31 e Å⁻³

Crystal data top

	V = 751.6 (3) Å³
M_r = 412.99	Z = 2
Monoclinic, P2₁/n	Ag Kα radiation, λ = 0.56085 Å
a = 7.6270 (17) Å	µ = 0.72 mm⁻¹
b = 7.2603 (16) Å	T = 295 K
c = 13.580 (3) Å	0.20 × 0.20 × 0.20 mm
β = 91.91 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1215 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.021
T_min = 0.945, T_max = 0.958	1 standard reflections every 60 min
1706 measured reflections	intensity decay: 1%
1640 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	140 parameters
wR(F²) = 0.077	3 restraints
S = 1.02	Δρ_max = 0.34 e Å⁻³
1640 reflections	Δρ_min = −0.31 e Å⁻³

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R–factor wR and goodness of fit S are based on F², conventional R–factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R–factors(gt) etc. and is not relevant to the choice of reflections for refinement. R–factors based on F² are statistically about twice as large as those based on F, and R–factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ni	0.0000	0.0000	0.0000	0.01840 (14)
N1	−0.0590 (3)	0.0113 (4)	−0.14834 (14)	0.0215 (5)
C2	0.0459 (3)	0.0087 (5)	−0.22579 (18)	0.0237 (5)
N21	0.2095 (3)	−0.0555 (4)	−0.22436 (19)	0.0380 (8)
H21A	0.278 (3)	−0.036 (5)	−0.2696 (17)	0.040 (7)*
H21B	0.248 (4)	−0.090 (5)	−0.1692 (15)	0.040 (7)*
N3	−0.0433 (3)	0.0713 (4)	−0.30469 (18)	0.0307 (6)
H3	−0.010 (4)	0.083 (4)	−0.362 (2)	0.029 (9)*
N4	−0.2124 (3)	0.1187 (4)	−0.28023 (17)	0.0289 (6)
C5	−0.2135 (4)	0.0798 (4)	−0.18651 (19)	0.0218 (6)
C51	−0.3727 (3)	0.1003 (4)	−0.12754 (19)	0.0242 (6)
H51A	−0.4200	−0.0215	−0.1160	0.029*
H51B	−0.4597	0.1678	−0.1668	0.029*
C52	−0.3496 (3)	0.1962 (4)	−0.02933 (19)	0.0206 (6)
O53	−0.2044 (2)	0.1806 (3)	0.01848 (14)	0.0248 (5)
O54	−0.4765 (3)	0.2802 (3)	0.00309 (17)	0.0335 (5)
O1	−0.1634 (3)	−0.2263 (3)	0.01911 (18)	0.0327 (5)
H1A	−0.129 (4)	−0.313 (3)	0.053 (2)	0.048 (8)*
H1B	−0.271 (2)	−0.238 (5)	0.017 (3)	0.048 (8)*
O2	0.4528 (3)	0.0268 (3)	0.62437 (15)	0.0320 (5)
H2A	0.556 (3)	0.054 (5)	0.641 (2)	0.039 (7)*
H2B	0.404 (4)	0.110 (4)	0.591 (2)	0.039 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni	0.0162 (2)	0.0239 (3)	0.0150 (2)	0.0020 (2)	−0.00011 (16)	0.0011 (3)
N1	0.0180 (10)	0.0313 (13)	0.0150 (9)	0.0003 (12)	−0.0003 (8)	0.0021 (12)
C2	0.0253 (13)	0.0265 (14)	0.0193 (12)	−0.0005 (14)	0.0020 (10)	0.0020 (15)
N21	0.0282 (14)	0.063 (2)	0.0236 (13)	0.0098 (13)	0.0102 (10)	0.0131 (13)
N3	0.0322 (14)	0.0449 (16)	0.0152 (12)	0.0033 (12)	0.0051 (10)	0.0053 (11)
N4	0.0275 (13)	0.0400 (16)	0.0190 (12)	0.0058 (12)	−0.0017 (9)	0.0048 (11)
C5	0.0225 (13)	0.0246 (14)	0.0181 (13)	−0.0026 (12)	−0.0009 (11)	0.0006 (11)
C51	0.0161 (13)	0.0340 (17)	0.0224 (14)	0.0006 (12)	−0.0015 (11)	0.0017 (13)
C52	0.0202 (13)	0.0221 (14)	0.0196 (13)	0.0002 (11)	0.0032 (10)	0.0040 (11)
O53	0.0208 (10)	0.0322 (11)	0.0210 (10)	0.0049 (9)	−0.0042 (8)	−0.0041 (9)
O54	0.0238 (11)	0.0486 (13)	0.0282 (10)	0.0106 (10)	0.0032 (9)	−0.0058 (12)
O1	0.0202 (10)	0.0327 (13)	0.0448 (14)	−0.0046 (10)	−0.0041 (10)	0.0108 (11)
O2	0.0309 (11)	0.0371 (14)	0.0280 (11)	−0.0022 (11)	0.0007 (9)	0.0026 (11)

Geometric parameters (Å, º) top

Ni—N1	2.051 (2)	N3—H3	0.83 (3)
Ni—N1ⁱ	2.051 (2)	N4—C5	1.304 (3)
Ni—O53	2.0590 (19)	C5—C51	1.484 (4)
Ni—O53ⁱ	2.0590 (19)	C51—C52	1.509 (4)
Ni—O1	2.083 (2)	C51—H51A	0.9700
Ni—O1ⁱ	2.084 (2)	C51—H51B	0.9700
N1—C2	1.342 (3)	C52—O54	1.238 (3)
N1—C5	1.365 (3)	C52—O53	1.270 (3)
C2—N3	1.330 (4)	O1—H1A	0.822 (19)
C2—N21	1.332 (4)	O1—H1B	0.822 (19)
N21—H21A	0.834 (19)	O2—H2A	0.83 (2)
N21—H21B	0.834 (19)	O2—H2B	0.83 (2)
N3—N4	1.386 (3)

N1—Ni—N1ⁱ	180.0	H21A—N21—H21B	120 (3)
N1—Ni—O53	87.25 (8)	C2—N3—N4	110.3 (2)
N1ⁱ—Ni—O53	92.75 (8)	C2—N3—H3	129 (2)
N1—Ni—O53ⁱ	92.75 (8)	N4—N3—H3	121 (2)
N1ⁱ—Ni—O53ⁱ	87.25 (8)	C5—N4—N3	102.5 (2)
O53—Ni—O53ⁱ	180.00 (13)	N4—C5—N1	114.6 (2)
N1—Ni—O1	92.36 (9)	N4—C5—C51	122.5 (2)
N1ⁱ—Ni—O1	87.63 (9)	N1—C5—C51	122.9 (2)
O53—Ni—O1	91.63 (9)	C5—C51—C52	116.7 (2)
O53ⁱ—Ni—O1	88.37 (9)	C5—C51—H51A	108.1
N1—Ni—O1ⁱ	87.63 (9)	C52—C51—H51A	108.1
N1ⁱ—Ni—O1ⁱ	92.37 (9)	C5—C51—H51B	108.1
O53—Ni—O1ⁱ	88.37 (9)	C52—C51—H51B	108.1
O53ⁱ—Ni—O1ⁱ	91.63 (9)	H51A—C51—H51B	107.3
O1—Ni—O1ⁱ	180.0	O54—C52—O53	122.8 (3)
C2—N1—C5	103.7 (2)	O54—C52—C51	118.2 (2)
C2—N1—Ni	130.69 (17)	O53—C52—C51	119.0 (2)
C5—N1—Ni	123.09 (17)	C52—O53—Ni	130.20 (18)
N3—C2—N21	125.8 (2)	Ni—O1—H1A	120 (2)
N3—C2—N1	108.9 (2)	Ni—O1—H1B	132 (3)
N21—C2—N1	125.2 (2)	H1A—O1—H1B	104 (3)
C2—N21—H21A	123 (2)	H2A—O2—H2B	112 (3)
C2—N21—H21B	115 (2)

C5—N1—C2—N3	−0.3 (3)	Ni—N1—C5—N4	163.8 (2)
Ni—N1—C2—N3	−162.2 (2)	C2—N1—C5—C51	177.4 (3)
C5—N1—C2—N21	−177.1 (3)	Ni—N1—C5—C51	−18.9 (4)
Ni—N1—C2—N21	21.0 (5)	N4—C5—C51—C52	−133.3 (3)
N21—C2—N3—N4	177.1 (3)	N1—C5—C51—C52	49.6 (4)
N1—C2—N3—N4	0.4 (4)	C5—C51—C52—O54	151.7 (3)
C2—N3—N4—C5	−0.2 (3)	C5—C51—C52—O53	−31.5 (4)
N3—N4—C5—N1	0.0 (3)	O54—C52—O53—Ni	162.5 (2)
N3—N4—C5—C51	−177.2 (3)	C51—C52—O53—Ni	−14.2 (4)
C2—N1—C5—N4	0.2 (4)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21A···O2ⁱⁱ	0.83 (2)	2.04 (2)	2.876 (3)	176 (3)
N21—H21B···O53ⁱ	0.83 (2)	2.19 (2)	2.941 (3)	151 (3)
N3—H3···O54ⁱⁱⁱ	0.83 (3)	2.10 (3)	2.885 (3)	156 (3)
O1—H1A···O2^iv	0.82 (2)	1.92 (2)	2.739 (3)	176 (3)
O1—H1B···O54^v	0.82 (2)	1.96 (2)	2.780 (3)	173 (4)
O2—H2A···N4^vi	0.83 (2)	2.09 (2)	2.903 (3)	164 (3)
O2—H2B···O53^vii	0.83 (2)	1.98 (2)	2.811 (3)	176 (3)

Symmetry codes: (i) −x, −y, −z; (ii) x, y, z−1; (iii) x+1/2, −y+1/2, z−1/2; (iv) x−1/2, −y−1/2, z−1/2; (v) −x−1, −y, −z; (vi) x+1, y, z+1; (vii) x+1/2, −y+1/2, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21A···O2ⁱ	0.834 (19)	2.04 (2)	2.876 (3)	176 (3)
N21—H21B···O53ⁱⁱ	0.834 (19)	2.19 (2)	2.941 (3)	151 (3)
N3—H3···O54ⁱⁱⁱ	0.83 (3)	2.10 (3)	2.885 (3)	156 (3)
O1—H1A···O2^iv	0.822 (19)	1.919 (19)	2.739 (3)	176 (3)
O1—H1B···O54^v	0.822 (19)	1.96 (2)	2.780 (3)	173 (4)
O2—H2A···N4^vi	0.83 (2)	2.09 (2)	2.903 (3)	164 (3)
O2—H2B···O53^vii	0.83 (2)	1.98 (2)	2.811 (3)	176 (3)

Symmetry codes: (i) x, y, z−1; (ii) −x, −y, −z; (iii) x+1/2, −y+1/2, z−1/2; (iv) x−1/2, −y−1/2, z−1/2; (v) −x−1, −y, −z; (vi) x+1, y, z+1; (vii) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula
M_r	412.99
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	7.6270 (17), 7.2603 (16), 13.580 (3)
β (°)	91.91 (2)
V (Å³)	751.6 (3)
Z	2
Radiation type	Ag Kα, λ = 0.56085 Å
µ (mm⁻¹)	0.72
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.945, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	1706, 1640, 1215
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.077, 1.02
No. of reflections	1640
No. of parameters	140
No. of restraints	3
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.31

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012).

Acknowledgements

This work was supported financially by the Ministry of Education and Science of the Russian Federation (project No. 2945 of State Order No. 2014/143).

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Volume 70| Part 11| November 2014| Pages 286-289

doi:10.1107/S1600536814021436

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