Crystal structure of trans-(1,8-dibutyl-1,3,6,8,10,13-hexa­aza­cyclo­tetra­decane-κ4N3,N6,N10,N13)bis­(5-methyltetra­zolato-κN)nickel(II) from synchrotron data

Kim, D.-W.; Shin, J.W.; Kim, J.H.; Moon, D.

doi:10.1107/S2056989015000651

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ISSN: 2056-9890

Volume 71| Part 2| February 2015| Pages 173-175

doi:10.1107/S2056989015000651

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Crystal structure of trans-(1,8-dibutyl-1,3,6,8,10,13-hexaazacyclotetradecane-κ⁴N³,N⁶,N¹⁰,N¹³)bis(5-methyltetrazolato-κN)nickel(II) from synchrotron data

Dae-Woong Kim,^a Jong Won Shin,^a Jin Hong Kim ^a and Dohyun Moon ^a ^*

^aBeamline Department, Pohang Accelerator Laboratory, 80 Jigokro-127-beongil, Nam-Gu Pohang, Gyeongbuk 790-784, Republic of Korea
^*Correspondence e-mail: dmoon@postech.ac.kr

Edited by H. Ishida, Okayama University, Japan (Received 8 January 2015; accepted 13 January 2015; online 17 January 2015)

The structure of the title compound, [Ni(C₂H₃N₄)₂(C₁₆H₃₈N₆)], has been characterized from synchrotron radiation. The asymmetric unit consists of one half of the Ni^II complex molecule, which is related to the other half-molecule by an inversion center. The Ni^II ion is coordinated by four secondary N atoms of the macrocyclic ligand in a square-planar fashion in the equatorial plane and by two N atoms of the 5-methyltetrazolate anions in axial positions, resulting in a tetragonally distorted octahedral geometry. The average equatorial Ni—N bond length [2.060 (8) Å] is shorter than the axial Ni—N bond length [2.2183 (11) Å]. An intramolecular N—H⋯N hydrogen bond between the secondary amine N atom of the macrocyclic ligand and the non-coordinating N atom of the 5-methyltetrazolate ion stabilizes the molecular structure. Moreover, an intermolecular N—H⋯N hydrogen bond between the macrocyclic ligand and 5-methyltetrazolate group gives rise to a supramolecular sheet structure parallel to the bc plane.

Keywords: crystal structure; azamacrocyclic ligand; Jahn–Teller distortion; tetrazole derivatives; synchrotron data.

CCDC reference: 1043241

1. Chemical context

Coordination compounds with macrocyclic ligands have been studied widely in chemistry, metalloenzymes and materials science (Lehn, 1995 ). In particular, Ni^II macrocyclic complexes having vacant sites in the axial positions are good building blocks for assembling supramolecular frameworks (Min & Suh, 2001 ), with potential applications in gas adsorption/desorption (Lee & Suh, 2004 ), carbon dioxide reduction (Froehlich & Kubiak, 2012 ) and chiral separation (Ryoo et al., 2010 ). For example, Ni^II complexes with tetra-azamacrocyclic ligands have been studied as catalysts for water oxidation at neutral pH (Zhang et al., 2014 ) and their magnetic properties have been investigated with various auxiliary anionic moieties such as azide, dicyanamide and ferricyanide (Yuan et al., 2011 ). Moreover, tetrazole derivatives are versatile anions which can easily bridge to transition metal ions, thus allowing the assembly of multi-dimensional compounds (Zhao et al., 2008 ).

Here, we report the synthesis and crystal structure of an Ni^II azamacrocyclic complex with two tetrazole derivatives, trans-(1,8-dibutyl-1,3,6,8,10,13-hexaazacyclotetradecane-κ⁴N³,N⁶,N¹⁰,N¹³)bis(5-methyltetrazolato-κN)nickel(II), (I).

2. Structural commentary

In the title compound, the coordination environment around the Ni^II ion, in which the Ni^II ion lies on an inversion center, has a tetragonally distorted octahedral geometry. The Ni^II ion is bonded to four secondary N atoms of the azamacrocyclic ligand in a square-planar fashion in the equatorial plane, and to two N atoms from the 5-methyltetrazolate anions at the axial positions, as shown in Fig. 1. The average Ni—N_eq bond length and the Ni—N_ax length are 2.060 (8) and 2.2183 (11) Å, respectively. The axial bond lengths are much longer than the equatorial bond lengths, which can be attributed to a rather large Jahn–Teller distortion of the Ni^II ion and/or ring contraction of the azamacrocyclic ligand (Halcrow, 2013 ). The six-membered chelate rings adopt chair conformations and the five-membered chelate rings assume gauche conformations (Min & Suh, 2001). The N—N bond lengths in the 5-methyltetrazolate ion range from 1.3182 (15) to 1.3543 (16) Å, indicating that the tetrazolate ring is fully delocalized. An intramolecular N—H⋯N hydrogen bond between the secondary amine group of the macrocyclic ligand and the N atom of the 5-methyltetrazolate ion stabilizes the molecular structure (Fig. 1 and Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N7	1.00	2.07	2.8508 (16)	133
N2—H2⋯N6ⁱ	1.00	2.35	3.1403 (16)	135
Symmetry code: (i) $[x, -y+1, z-{\script{1\over 2}}]$ .

Figure 1
View of the molecular structure of the title compound, showing the atom-labelling scheme, with displacement ellipsoids drawn at the 50% probability level. H atoms bonded to C atoms have been omitted for clarity. Intramolecular N—H⋯N hydrogen bonds are shown as green dashed lines. [Symmetry code: (i) −x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1.]

3. Supramolecular features

The packing in the structure involves an intermolecular N—H⋯N hydrogen bond between the secondary amine group of the macrocyclic ligand and the non-coordinating N atom of the 5-methyltetrazolate ion (Table 1), which forms a rigid supramolecular sheet structure parallel to the bc plane (Fig. 2).

Figure 2
View of the crystal packing of the title compound, with N—H⋯N hydrogen bonds drawn as green (intramolecular) and red (intermolecular) dashed lines.

4. Database survey

A search of the Cambridge Structural Database (Version 5.35, May 2014 with 3 updates; Groom & Allen, 2014 ) indicated that 71 Ni^II azamacrocyclic complexes with alkyl pendant groups have been reported. These complexes with various alkyl pendant groups were investigated as good building blocks for supramolecular chemistry and also studied for their magnetic properties and gas sorption abilities due to the anions such as cyanido groups and carboxylic acid derivatives (Hyun et al., 2013 ; Shen et al., 2012 ). No corresponding Ni^II azamacrocyclic complex with a butyl pendant group and tetrazole derivatives has been reported, and the title compound was newly synthesized for this research.

5. Synthesis and crystallization

The title compound (I) was prepared as follows. The starting complex, [Ni(C₁₆H₃₈N₆)(ClO₄)₂], was prepared by a slight modification of the reported method (Jung et al., 1989 ). To an MeCN (10 mL) solution of [Ni(C₁₆H₃₈N₆)(ClO₄)₂] (0.10 g, 0.17 mmol) was slowly added an MeCN solution (5 mL) containing 5-methyl-1H-tetrazole (0.029 g, 0.34 mmol) and excess triethylamine (0.04 g, 0.40 mmol) at room temperature. The color of the solution turned from yellow to pale pink and a pale-pink precipitate was formed, which was filtered off, washed with MeCN, and diethyl ether, and dried in air. Single crystals of the title compound were obtained by layering of the MeCN solution of 5-methyl-1H-tetrazole on the MeCN solution of [Ni(C₁₆H₃₈N₆)(ClO₄)₂] for several days. Yield: 0.057 g (62%). FT–IR (ATR, cm⁻¹): 3215, 2954, 1590, 1488, 1457, 1376, 1237, 1019, 933.

Safety note: Although we have experienced no problem with the compounds reported in this study, perchlorate salts of metal complexes are often explosive and should be handled with great caution.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.98–0.99 Å and N—H = 1.00 Å, and with U_iso(H) values of 1.2 or 1.5U_eq of the parent atoms.

Table 2
Experimental details

Crystal data
Chemical formula	[Ni(C₂H₃N₄)₂(C₁₆H₃₈N₆)]
M_r	539.40
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	24.040 (5), 12.923 (3), 8.7170 (17)
β (°)	98.94 (3)
V (Å³)	2675.1 (9)
Z	4
Radiation type	Synchrotron, λ = 0.62998 Å
μ (mm⁻¹)	0.55
Crystal size (mm)	0.05 × 0.04 × 0.04

Data collection
Diffractometer	ADSC Q210 CCD area detector
Absorption correction	Empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997 )
T_min, T_max	0.973, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	12808, 3761, 3150
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.696

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.090, 1.08
No. of reflections	3761
No. of parameters	162
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.79
Computer programs: PAL ADSC Quantum-210 ADX (Arvai & Nielsen, 1983 ), HKL3000sm (Otwinowski & Minor, 1997), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2014/7 (Sheldrick, 2008 , 2015b ), DIAMOND4 (Putz & Brandenburg, 2014 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1043241

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015000651/is5389sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015000651/is5389Isup2.hkl

checkCIF report

Chemical context top

Coordination compounds with macrocyclic ligands have been studied widely in chemistry, metalloenzymes and materials science (Lehn, 1995). In particular, Ni^II macrocyclic complexes having vacant sites in the axial positions are good building blocks for assembling supramolecular frameworks (Min & Suh, 2001), with potential applications in gas adsorption/desorption (Lee & Suh, 2004), carbon dioxide reduction (Froehlich & Kubiak, 2012) and chiral separation (Ryoo et al., 2010). For example, Ni^II complexes with tetra-azamacrocyclic ligands have been studied as catalysts for water oxidation at neutral pH (Zhang et al., 2014) and their magnetic properties have been investigated with various auxiliary anionic moieties such as azide, dicyanamide and ferricyanide (Yuan et al., 2011). Moreover, tetrazole derivatives are versatile anions which can easily bridge to transition metal ions, thus allowing the assembly of multi-dimensional compounds (Zhao et al., 2008). Here, we report the synthesis and crystal structure of an Ni^II azamacrocyclic complex with two tetrazole derivatives, trans-(1,8-dibutyl-1,3,6,8,10,13-hexaazacyclotetradecane-κ⁴N³,N⁶,N¹⁰,N¹³)bis(5- methyltetrazolato-κN)nickel(II) (I).

Structural commentary top

In the title compound, the coordination environment around the Ni^II ion, in which the Ni^II ion lies on an inversion center, has a tetragonally distorted octahedral geometry. The Ni^II ion is bonded to four secondary N atoms of the azamacrocyclic ligand in a square-planar fashion in the equatorial plane, and to two N atoms from the 5-methyltetrazolate anions at the axial positions, as shown in Fig. 1. The average Ni—N_eq bond length and the Ni—N_ax length are 2.060 (2) and 2.2183 (11) Å, respectively. The axial bond lengths are much longer than the equatorial bond lengths, which can be attributed to a rather large Jahn–Teller distortion of the Ni^II ion and/or ring contraction of the azamacrocyclic ligand (Halcrow, 2013). The six-membered chelate rings adopt chair conformations and the five-membered chelate rings assume gauche conformations (Min & Suh, 2001). The N—N bond lengths in the 5-methyltetrazolate ion range from 1.3182 (15) to 1.3543 (16) Å, indicating that the tetrazolate ring is fully delocalized. An intramolecular N—H···N hydrogen bond between the secondary amine group of the macrocyclic ligand and the N atom of the 5-methyltetrazolate ion stabilizes the molecular structure (Fig. 1 and Table 1).

Supramolecular features top

The packing in the structure involves an intermolecular N—H···N hydrogen bond between the secondary amine group of the macrocyclic ligand and the non-coordinating N atom of the 5-methyltetrazolate ion (Table 1), which forms a rigid supramolecular two-dimensional sheet structure parallel to the bc plane (Fig. 2).

Database survey top

A search of the Cambridge Structural Database (Version 5.35, May 2014 with 3 updates; Groom & Allen, 2014) indicated that 71 Ni^II azamacrocyclic complexes with alkyl pendant groups have been reported. These complexes with various alkyl pendant groups were investigated as good building blocks for supramolecular chemistry and also studied for their magnetic properties and gas sorption abilities due to the anions such as cyanido groups and carboxylic acid derivatives (Hyun et al., 2013; Shen et al., 2012). No corresponding Ni^II azamacrocyclic complex with a butyl pendant group and tetrazole derivatives has been reported, and the title compound was newly synthesized for this research.

Synthesis and crystallization top

The title compound (I) was prepared as follows. The starting complex, [Ni(C₁₆H₃₈N₆)(ClO₄)₂], was prepared by a slightly modification of the reported method (Jung et al., 1989). To an MeCN (10 ml) solution of [Ni(C₁₆H₃₈N₆)(ClO₄)₂] (0.10 g, 0.17 mmol) was slowly added an MeCN solution (5 ml) containing 5-methyl-1H-tetrazole (0.029 g, 0.34 mmol) and excess triethylamine (0.04 g, 0.40 mmol) at room temperature. The color of the solution turned from yellow to pale pink and a pale-pink precipitate was formed, which was filtered off, washed with MeCN, and diethyl ether, and dried in air. Single crystals of the title compound were obtained by layering of the MeCN solution of 5-methyl-1H-tetrazole on the MeCN solution of [Ni(C₁₆H₃₈N₆)(ClO₄)₂] for several days. Yield: 0.057 g (62%). FT–IR (ATR, cm^-1): 3215, 2954, 1590, 1488, 1457, 1376, 1237, 1019, 933.

Safety note: Although we have experienced no problem with the compounds reported in this study, perchlorate salts of metal complexes are often explosive and should be handled with great caution.

Refinement top

Related literature top

For related literature, see: Froehlich & Kubiak (2012); Groom & Allen (2014); Halcrow (2013); Hyun, –M, Kim, Kim, Moon & Moon (2013); Jung et al. (1989); Lee & Suh (2004); Lehn (1995); Min & Suh (2001); Ryoo et al. (2010); Shen et al. (2012); Steed & Atwood (2009); Yuan, –H, Qian, –Y, Liu, –Y, Zhou & Song (2011); Zhang et al. (2014); Zhao et al. (2008).

Computing details top

Data collection: PAL ADSC Quantum-210 ADX (Arvai & Nielsen, 1983); cell refinement: HKL3000sm (Otwinowski & Minor, 1997); data reduction: HKL3000sm (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2008, 2015b); molecular graphics: DIAMOND4 (Putz & Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. View of the molecular structure of the title compound, showing the atom-labelling scheme, with displacement ellipsoids drawn at the 50% probability level. H atoms bonded to C atoms have been omitted for clarity. Intramolecular N—H···N hydrogen bonds are shown as green dashed lines. [Symmetry code: (i) -x + 1/2, -y + 3/2, -z + 1.]
	Fig. 2. View of the crystal packing of the title compound, with N—H···N hydrogen bonds drawn as green (intramolecular) and red (intermolecular) dashed lines.

trans-(1,8-Dibutyl-1,3,6,8,10,13-hexaazacyclotetradecane-κ⁴N³,N⁶,N¹⁰,N¹³)bis(5-methyltetrazolato-κN²)nickel(II) top

Crystal data top

[Ni(C₂H₃N₄)₂(C₁₆H₃₈N₆)]	F(000) = 1160
M_r = 539.40	D_x = 1.339 Mg m⁻³
Monoclinic, C2/c	Synchrotron radiation, λ = 0.62998 Å
a = 24.040 (5) Å	Cell parameters from 25946 reflections
b = 12.923 (3) Å	θ = 0.4–33.6°
c = 8.7170 (17) Å	µ = 0.55 mm⁻¹
β = 98.94 (3)°	T = 100 K
V = 2675.1 (9) Å³	Block, pink
Z = 4	0.05 × 0.04 × 0.04 mm

Data collection top

ADSC Q210 CCD area-detector diffractometer	3150 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magent	R_int = 0.042
ω scan	θ_max = 26.0°, θ_min = 1.6°
Absorption correction: empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997)	h = −33→33
T_min = 0.973, T_max = 0.978	k = −17→17
12808 measured reflections	l = −12→12
3761 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.090	w = 1/[σ²(F_o²) + (0.0565P)² + 0.106P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
3761 reflections	Δρ_max = 0.32 e Å⁻³
162 parameters	Δρ_min = −0.79 e Å⁻³

Crystal data top

[Ni(C₂H₃N₄)₂(C₁₆H₃₈N₆)]	V = 2675.1 (9) Å³
M_r = 539.40	Z = 4
Monoclinic, C2/c	Synchrotron radiation, λ = 0.62998 Å
a = 24.040 (5) Å	µ = 0.55 mm⁻¹
b = 12.923 (3) Å	T = 100 K
c = 8.7170 (17) Å	0.05 × 0.04 × 0.04 mm
β = 98.94 (3)°

Data collection top

ADSC Q210 CCD area-detector diffractometer	3761 independent reflections
Absorption correction: empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997)	3150 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.978	R_int = 0.042
12808 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.08	Δρ_max = 0.32 e Å⁻³
3761 reflections	Δρ_min = −0.79 e Å⁻³
162 parameters

Special details top

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

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

	x	y	z	U_iso*/U_eq
Ni1	0.2500	0.7500	0.5000	0.00596 (8)
N1	0.31782 (5)	0.83411 (8)	0.60560 (11)	0.0073 (2)
H1	0.3488	0.7841	0.6424	0.009*
N2	0.28136 (5)	0.73476 (8)	0.29352 (12)	0.0076 (2)
H2	0.3095	0.6773	0.3067	0.009*
N3	0.35616 (5)	0.86428 (8)	0.36376 (12)	0.0095 (2)
C1	0.29951 (5)	0.88036 (9)	0.74420 (13)	0.0094 (2)
H1A	0.2752	0.9411	0.7137	0.011*
H1B	0.3327	0.9038	0.8177	0.011*
C2	0.34005 (6)	0.90993 (9)	0.50278 (14)	0.0097 (2)
H2A	0.3110	0.9634	0.4716	0.012*
H2B	0.3733	0.9448	0.5621	0.012*
C3	0.31026 (6)	0.82902 (9)	0.24815 (14)	0.0096 (2)
H3A	0.3251	0.8147	0.1505	0.011*
H3B	0.2823	0.8854	0.2270	0.011*
C4	0.23296 (6)	0.70064 (10)	0.17841 (14)	0.0095 (2)
H4A	0.2464	0.6706	0.0864	0.011*
H4B	0.2083	0.7603	0.1441	0.011*
C5	0.40350 (6)	0.79167 (10)	0.39114 (15)	0.0119 (2)
H5A	0.4070	0.7560	0.2926	0.014*
H5B	0.3955	0.7386	0.4666	0.014*
C6	0.45926 (6)	0.84385 (12)	0.45282 (18)	0.0188 (3)
H6A	0.4686	0.8939	0.3747	0.023*
H6B	0.4553	0.8829	0.5483	0.023*
C7	0.50699 (7)	0.76635 (13)	0.4891 (2)	0.0237 (3)
H7A	0.5101	0.7263	0.3940	0.028*
H7B	0.4977	0.7172	0.5685	0.028*
C8	0.56368 (7)	0.81669 (16)	0.5480 (2)	0.0334 (4)
H8A	0.5737	0.8641	0.4688	0.050*
H8B	0.5926	0.7630	0.5696	0.050*
H8C	0.5612	0.8554	0.6434	0.050*
N4	0.30074 (5)	0.61260 (8)	0.58628 (12)	0.0100 (2)
N5	0.29007 (5)	0.51298 (9)	0.56721 (14)	0.0156 (2)
N6	0.33266 (5)	0.45876 (9)	0.64836 (16)	0.0185 (3)
N7	0.35088 (5)	0.62585 (9)	0.67914 (13)	0.0146 (2)
C9	0.36869 (6)	0.52976 (10)	0.71493 (17)	0.0157 (3)
C10	0.42228 (7)	0.50538 (13)	0.8200 (2)	0.0298 (4)
H10A	0.4139	0.4869	0.9230	0.045*
H10B	0.4470	0.5661	0.8285	0.045*
H10C	0.4411	0.4472	0.7773	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.00867 (12)	0.00459 (12)	0.00474 (11)	−0.00101 (8)	0.00141 (8)	−0.00027 (7)
N1	0.0102 (5)	0.0052 (5)	0.0069 (4)	−0.0004 (4)	0.0021 (4)	−0.0002 (4)
N2	0.0092 (5)	0.0077 (5)	0.0061 (4)	−0.0007 (4)	0.0016 (4)	−0.0005 (4)
N3	0.0085 (5)	0.0105 (5)	0.0097 (5)	−0.0006 (4)	0.0024 (4)	0.0003 (4)
C1	0.0120 (6)	0.0083 (5)	0.0080 (5)	−0.0012 (4)	0.0016 (4)	−0.0031 (4)
C2	0.0114 (6)	0.0068 (5)	0.0115 (5)	−0.0016 (4)	0.0032 (4)	0.0001 (4)
C3	0.0112 (6)	0.0095 (6)	0.0084 (5)	−0.0012 (4)	0.0026 (4)	0.0022 (4)
C4	0.0112 (6)	0.0109 (6)	0.0062 (5)	0.0000 (5)	0.0012 (4)	−0.0009 (4)
C5	0.0099 (6)	0.0126 (6)	0.0136 (6)	0.0010 (5)	0.0029 (5)	0.0006 (5)
C6	0.0117 (7)	0.0189 (7)	0.0250 (7)	−0.0002 (5)	0.0008 (5)	−0.0032 (6)
C7	0.0128 (7)	0.0257 (8)	0.0316 (8)	0.0019 (6)	−0.0001 (6)	0.0016 (6)
C8	0.0139 (8)	0.0426 (10)	0.0409 (10)	0.0023 (7)	−0.0038 (7)	−0.0053 (8)
N4	0.0123 (5)	0.0071 (5)	0.0108 (5)	−0.0002 (4)	0.0024 (4)	0.0009 (4)
N5	0.0149 (6)	0.0081 (5)	0.0233 (6)	0.0003 (4)	0.0017 (5)	0.0026 (4)
N6	0.0129 (6)	0.0099 (5)	0.0323 (7)	0.0017 (4)	0.0025 (5)	0.0051 (5)
N7	0.0134 (6)	0.0110 (5)	0.0180 (5)	0.0013 (4)	−0.0016 (4)	0.0027 (4)
C9	0.0127 (6)	0.0113 (6)	0.0233 (7)	0.0019 (5)	0.0028 (5)	0.0060 (5)
C10	0.0194 (8)	0.0199 (7)	0.0460 (10)	0.0024 (6)	−0.0079 (7)	0.0092 (7)

Geometric parameters (Å, º) top

Ni1—N1	2.0543 (12)	C5—C6	1.522 (2)
Ni1—N2	2.0661 (11)	C5—H5A	0.9900
Ni1—N4	2.2183 (11)	C5—H5B	0.9900
N1—C1	1.4752 (15)	C6—C7	1.519 (2)
N1—C2	1.4826 (15)	C6—H6A	0.9900
N1—H1	1.0000	C6—H6B	0.9900
N2—C4	1.4807 (17)	C7—C8	1.525 (2)
N2—C3	1.4860 (16)	C7—H7A	0.9900
N2—H2	1.0000	C7—H7B	0.9900
N3—C3	1.4474 (17)	C8—H8A	0.9800
N3—C2	1.4535 (16)	C8—H8B	0.9800
N3—C5	1.4657 (17)	C8—H8C	0.9800
C1—C4ⁱ	1.5244 (17)	N4—N5	1.3182 (15)
C1—H1A	0.9900	N4—N7	1.3543 (16)
C1—H1B	0.9900	N5—N6	1.3469 (17)
C2—H2A	0.9900	N6—C9	1.3314 (19)
C2—H2B	0.9900	N7—C9	1.3347 (17)
C3—H3A	0.9900	C9—C10	1.494 (2)
C3—H3B	0.9900	C10—H10A	0.9800
C4—C1ⁱ	1.5244 (17)	C10—H10B	0.9800
C4—H4A	0.9900	C10—H10C	0.9800
C4—H4B	0.9900

N1ⁱ—Ni1—N1	180.0	H3A—C3—H3B	107.6
N1ⁱ—Ni1—N2	86.04 (4)	N2—C4—C1ⁱ	107.88 (10)
N1—Ni1—N2	93.96 (4)	N2—C4—H4A	110.1
N1ⁱ—Ni1—N2ⁱ	93.96 (4)	C1ⁱ—C4—H4A	110.1
N1—Ni1—N2ⁱ	86.04 (4)	N2—C4—H4B	110.1
N2—Ni1—N2ⁱ	180.0	C1ⁱ—C4—H4B	110.1
N1ⁱ—Ni1—N4ⁱ	85.15 (4)	H4A—C4—H4B	108.4
N1—Ni1—N4ⁱ	94.86 (4)	N3—C5—C6	113.12 (11)
N2—Ni1—N4ⁱ	92.11 (4)	N3—C5—H5A	109.0
N2ⁱ—Ni1—N4ⁱ	87.89 (4)	C6—C5—H5A	109.0
N1ⁱ—Ni1—N4	94.86 (4)	N3—C5—H5B	109.0
N1—Ni1—N4	85.14 (4)	C6—C5—H5B	109.0
N2—Ni1—N4	87.89 (4)	H5A—C5—H5B	107.8
N2ⁱ—Ni1—N4	92.11 (4)	C7—C6—C5	112.13 (12)
N4ⁱ—Ni1—N4	180.0	C7—C6—H6A	109.2
C1—N1—C2	114.13 (10)	C5—C6—H6A	109.2
C1—N1—Ni1	105.32 (8)	C7—C6—H6B	109.2
C2—N1—Ni1	114.48 (8)	C5—C6—H6B	109.2
C1—N1—H1	107.5	H6A—C6—H6B	107.9
C2—N1—H1	107.5	C6—C7—C8	113.29 (14)
Ni1—N1—H1	107.5	C6—C7—H7A	108.9
C4—N2—C3	114.49 (10)	C8—C7—H7A	108.9
C4—N2—Ni1	105.31 (8)	C6—C7—H7B	108.9
C3—N2—Ni1	113.75 (7)	C8—C7—H7B	108.9
C4—N2—H2	107.7	H7A—C7—H7B	107.7
C3—N2—H2	107.7	C7—C8—H8A	109.5
Ni1—N2—H2	107.7	C7—C8—H8B	109.5
C3—N3—C2	115.80 (10)	H8A—C8—H8B	109.5
C3—N3—C5	113.60 (10)	C7—C8—H8C	109.5
C2—N3—C5	115.15 (10)	H8A—C8—H8C	109.5
N1—C1—C4ⁱ	108.83 (10)	H8B—C8—H8C	109.5
N1—C1—H1A	109.9	N5—N4—N7	109.66 (11)
C4ⁱ—C1—H1A	109.9	N5—N4—Ni1	130.78 (9)
N1—C1—H1B	109.9	N7—N4—Ni1	119.52 (8)
C4ⁱ—C1—H1B	109.9	N4—N5—N6	108.96 (11)
H1A—C1—H1B	108.3	C9—N6—N5	105.08 (11)
N3—C2—N1	113.80 (10)	C9—N7—N4	104.21 (11)
N3—C2—H2A	108.8	N6—C9—N7	112.09 (13)
N1—C2—H2A	108.8	N6—C9—C10	124.23 (13)
N3—C2—H2B	108.8	N7—C9—C10	123.67 (13)
N1—C2—H2B	108.8	C9—C10—H10A	109.5
H2A—C2—H2B	107.7	C9—C10—H10B	109.5
N3—C3—N2	114.21 (10)	H10A—C10—H10B	109.5
N3—C3—H3A	108.7	C9—C10—H10C	109.5
N2—C3—H3A	108.7	H10A—C10—H10C	109.5
N3—C3—H3B	108.7	H10B—C10—H10C	109.5
N2—C3—H3B	108.7

C2—N1—C1—C4ⁱ	168.66 (10)	C2—N3—C5—C6	−68.36 (14)
Ni1—N1—C1—C4ⁱ	42.26 (11)	N3—C5—C6—C7	176.68 (12)
C3—N3—C2—N1	70.86 (14)	C5—C6—C7—C8	178.80 (14)
C5—N3—C2—N1	−65.05 (14)	N7—N4—N5—N6	0.63 (15)
C1—N1—C2—N3	−177.96 (10)	Ni1—N4—N5—N6	−177.06 (9)
Ni1—N1—C2—N3	−56.49 (12)	N4—N5—N6—C9	−0.27 (16)
C2—N3—C3—N2	−71.26 (14)	N5—N4—N7—C9	−0.72 (15)
C5—N3—C3—N2	65.32 (14)	Ni1—N4—N7—C9	177.28 (9)
C4—N2—C3—N3	177.73 (10)	N5—N6—C9—N7	−0.20 (17)
Ni1—N2—C3—N3	56.58 (12)	N5—N6—C9—C10	178.68 (15)
C3—N2—C4—C1ⁱ	−167.67 (10)	N4—N7—C9—N6	0.56 (16)
Ni1—N2—C4—C1ⁱ	−41.97 (10)	N4—N7—C9—C10	−178.32 (14)
C3—N3—C5—C6	154.78 (11)

Symmetry code: (i) −x+1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N7	1.00	2.07	2.8508 (16)	133
N2—H2···N6ⁱⁱ	1.00	2.35	3.1403 (16)	135

Symmetry code: (ii) x, −y+1, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N7	1.00	2.07	2.8508 (16)	133
N2—H2···N6ⁱ	1.00	2.35	3.1403 (16)	135

Symmetry code: (i) x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	[Ni(C₂H₃N₄)₂(C₁₆H₃₈N₆)]
M_r	539.40
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	24.040 (5), 12.923 (3), 8.7170 (17)
β (°)	98.94 (3)
V (Å³)	2675.1 (9)
Z	4
Radiation type	Synchrotron, λ = 0.62998 Å
µ (mm⁻¹)	0.55
Crystal size (mm)	0.05 × 0.04 × 0.04

Data collection
Diffractometer	ADSC Q210 CCD area-detector diffractometer
Absorption correction	Empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.973, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	12808, 3761, 3150
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.696

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.090, 1.08
No. of reflections	3761
No. of parameters	162
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.79

Computer programs: PAL ADSC Quantum-210 ADX (Arvai & Nielsen, 1983), HKL3000sm (Otwinowski & Minor, 1997), SHELXT2014/5 (Sheldrick, 2015a), SHELXL2014/7 (Sheldrick, 2008, 2015b), DIAMOND4 (Putz & Brandenburg, 2014), publCIF (Westrip, 2010).

Acknowledgements

This work was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (NRF-2014R1A1A2058815) and supported by the Institute for Basic Science (IBS, IBS-R007-D1-2014-a01). The X-ray crystallography 2D-SMC beamline and the FT–IR experiment at the PLS-II were supported in part by MSIP and POSTECH.

References

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Volume 71| Part 2| February 2015| Pages 173-175

doi:10.1107/S2056989015000651

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