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

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

doi:10.1107/S2056989016001031

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ISSN: 2056-9890

Volume 72| Part 2| February 2016| Pages 223-225

doi:10.1107/S2056989016001031

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

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

^aBeamline Department, Pohang Accelerator Laboratory 80, Jigokro-127-beongil, Nam-Gu Pohang, Gyeongbuk 37673, Republic of Korea
^*Correspondence e-mail: dmoon@postech.ac.kr

Edited by M. Weil, Vienna University of Technology, Austria (Received 11 January 2016; accepted 18 January 2016; online 23 January 2016)

The title compound, [Ni(C₆H₄NO₂)₂(C₁₆H₃₈N₆)], was prepared through self-assembly of a nickel(II) azamacrocyclic complex with isonicotinic acid. The Ni^II atom is located on an inversion center and exhibits a distorted octahedral N₄O₂ coordination environment, with the four secondary N atoms of the azamacrocyclic ligand in the equatorial plane [average Ni—N_eq = 2.064 (11) Å] and two O atoms of monodentate isonicotinate anions in axial positions [Ni—O_ax = 2.137 (1) Å]. Intramolecular N—H⋯O hydrogen bonds between one of the secondary amine N atoms of the azamacrocyclic ligand and the non-coordinating carboxylate O atom of the anion stabilize the molecular structure. Intermolecular N—H⋯N hydrogen bonds, as well as π–π interactions between neighbouring pyridine rings, give rise to the formations of supramolecular ribbons extending parallel to [001].

Keywords: crystal structure; azamacrocyclic ligand; isonicotinic acid; π–π interactions; synchrotron data.

CCDC reference: 1447865

1. Chemical context

The molecular design and synthesis of coordination polymers with macrocyclic ligands have attracted considerable attention because of their potential applications in chemistry, environmental chemistry, and materials science (Churchard et al., 2010 ; Lehn, 2015 ). To obtain specific molecular compounds through assembly of supramolecular building blocks with properties such as guest recognition or catalytic effects, macrocyclic complexes involving vacant sites in an axial position are good candidates. Moreover, these complexes can also be easily derivatized by carboxylic acid moieties, such as 1,3,5-BTC (1,3,5-benzenetricarboxylic acid), 2,7-NDC (2,7-naphthalenedicarboxylic acid) or 1,3,5-CTC (1,3,5-cyclohexanetricarboxylic acid), forming interesting coordination compounds with supramolecular structures ranging from chains to networks (Min & Suh, 2001 ; Shin et al., 2016b ). For example, [Ni(L^R,^R)]₃[BTC^3–]₂·12H₂O·CH₃CN (L^R,^R = 1,8-bis[(R)-α-methylbenzyl]-1,3,6,8,10,13-hexaazacyclotetradecane) displays a two-dimensional supramolecular network structure and exhibits a selective chiral recognition for racemic material (Ryoo et al., 2010 ). Isonicotinic acid as another building unit can easily bind or interact with transition metal ions through its possible bridging or coordination modes associated with the carboxylic group and pyridine moieties, respectively, thus allowing the assembly of compounds with supramolecular structures or the formation of heterometallic complexes (Xie et al., 2014 ).

Here, we report on the synthesis and crystal structure of an Ni^II azamacrocyclic complex including isonicotinate anions, [Ni(C₆H₄NO₂)₂(C₁₆H₃₈N₆)], (I).

2. Structural commentary

Compound (I) is isotypic with its copper(II) analogue (Shin et al., 2015 ). The nickel(II) atom is located on an inversion center. The coordination environment around the nickel(II) atom is distorted octahedral with the four secondary amine N atoms of the azamacrocyclic ligand in the equatorial plane and two O atoms of two monodentate isonicotinate anions in axial positions (Fig. 1). The average Ni—N_eq bond lengths is 2.064 (11) Å and the Ni—O_ax bond length is 2.137 (1) Å. The longer axial bonds can be attributed to a ring contraction of the azamacrocyclic ligand (Melson, 1979 ). The six-membered NiC₂N₃ ring (Ni1–N1–C2–N3–C3–N2) adopts the expected chair conformation, whereas the five-membered NiC₂N₂ ring (Ni1–N1–C1–C4–N2) has a gauche conformation (Min & Suh, 2001). Since the carboxylate group is fully delocalized, the two C—O bonds and the bond angle (O1—C9—O2) are 1.267 (2), 1.248 (2) Å and 126.9 (2)°, respectively. The bond angles around the nickel(II) atom are in the normal range for an octahedral complex. Intramolecular N—H⋯O hydrogen bonds between one of the secondary amine groups of the azamacrocyclic ligand and the non-coordinating carboxylate O atom of the isonicotinate anion form six-membered rings and stabilize the molecular structure (Fig. 1, Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	1.00	1.98	2.892 (2)	150
N2—H2⋯N4ⁱ	1.00	2.23	3.143 (2)	151
Symmetry code: (i) -x+1, -y+1, -z.

Figure 1
View of the molecular structure of the title compound, showing the atom-labelling scheme, with displacement ellipsoids drawn at the 30% probability level. H atoms bonded to C atoms have been omitted for clarity. Intramolecular N—H⋯O hydrogen bonds are shown as red dashed lines. [Symmetry code: (i) −x + 1, −y + 1, −z + 1.]

3. Supramolecular features

The N4 atom of the isonicotinate anion forms an intermolecular hydrogen bond with an adjacent secondary amine group of the azamacrocyclic ligand (Fig. 2, Table 1) (Steed & Atwood, 2009 ). In addition, parallel pyridine rings (Hunter & Sanders, 1990 ) of the isonicotinate anions participate in π–π interactions with a centroid-to-centroid distance of 3.741 (1) Å and an interplanar separation of 3.547 (1) Å. The interplay between hydrogen bonds and π–π interactions give rise to the formation of supramolecular ribbons extending parallel to [001].

Figure 2
View of the crystal packing of the title compound, showing hydrogen bonds and π–π interactions (red: intramolecular N—H⋯O hydrogen bonds, green: intermolecular N—H⋯N hydrogen bonds, black: π–π interactions).

4. Database survey

A search of the Cambridge Structural Database (Version 5.36, May 2014 with 3 updates; Groom & Allen, 2014 ) reveals two complexes with the same nickel(II) azamacrocyclic building block (Kim et al., 2015a ,b ) for which synthesis, FT–IR spectroscopic data and the crystal structure have been reported.

5. Synthesis and crystallization

The starting complex, [Ni(C₁₆H₃₈N₆)(ClO₄)₂], was prepared in a slightly modified procedure with respect to the reported method (Kim et al., 2015b). To an acetonitrile solution (14 mL) of [Ni(C₁₆H₃₈N₆)(ClO₄)₂] (0.298 g, 0.52 mmol) was slowly added an acetonitrile solution (8 mL) containing isonicotinic acid (0.128 g, 1.04 mmol) and excess triethylamine (0.12 g, 1.20 mmol) at room temperature. The purple precipitate was filtered off, washed with acetonitrile and diethyl ether, and dried in air. Single crystals of compound (l) were obtained by layering of the acetonitrile solution of isonicotinic acid on the acetonitrile solution of [Ni(C₁₆H₃₈N₆)(ClO₄)₂] for several days. Yield: 0.167 g (52%). FT–IR (ATR, cm⁻¹): 3145, 3075, 2951, 2920, 1571, 1457, 1351, 1272, 1014, 915.

Safety note: Although we have experienced no problems 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 distances of 0.95 (ring H atoms) or 0.98–0.99 Å (open-chain H atoms), and an N—H distance of 1.0 Å, 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(C₆H₄NO₂)₂(C₁₆H₃₈N₆)]
M_r	617.44
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	8.0630 (16), 8.5110 (17), 10.927 (2)
α, β, γ (°)	80.52 (3), 88.26 (3), 86.44 (3)
V (Å³)	738.0 (3)
Z	1
Radiation type	Synchrotron, λ = 0.62998 Å
μ (mm⁻¹)	0.51
Crystal size (mm)	0.01 × 0.004 × 0.004

Data collection
Diffractometer	ADSC Q210 CCD area detector
Absorption correction	Empirical (HKL-3000SM SCALEPACK; Otwinowski & Minor, 1997 )
T_min, T_max	0.995, 0.998
No. of measured, independent and observed [I > 2σ(I)] reflections	7634, 3879, 3326
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.696

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.110, 1.04
No. of reflections	3879
No. of parameters	188
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.12, −0.95
Computer programs: PAL BL2D-SMDC (Shin et al., 2016 a), HKL-3000SM (Otwinowski & Minor, 1997), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), DIAMOND (Putz & Brandenburg, 2014 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1447865

Crystal structure: contains datablock I. DOI: 10.1107/S2056989016001031/wm5263sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989016001031/wm5263Isup2.hkl

checkCIF report

Chemical context top

The molecular design and synthesis of coordination polymers with macrocyclic ligands have attracted considerable attention because of their potential applications in chemistry, environmental chemistry, and materials science (Churchard et al., 2010; Lehn, 2015). To obtain specific molecular compounds through assembly of supramolecular building blocks with properties such as guest recognition or catalytic effects, macrocyclic complexes involving vacant sites in an axial position are good candidates. Moreover, these complexes can also be easily derivatized by carboxylic acid moieties, such as 1,3,5-BTC (1,3,5-benzenetricarboxylic acid), 2,7-NDC (2,7-naphthalenedicarboxylic acid) or 1,3,5-CTC (1,3,5-cyclohexanetricarboxylic acid), forming interesting coordination compounds with supramolecular structures ranging from chains to networks (Min & Suh, 2001; Shin et al., 2016b). For example, [Ni(L^R,^R)]₃[BTC^3–]₂·12H₂O·CH₃CN (L^R,^R = 1,8-bis[(R)-α-methylbenzyl]-1,3,6,8,10,13-hexaazacyclotetradecane) displays a two-dimensional supramolecular network structure and exhibits a selective chiral recognition for racemic material (Ryoo et al., 2010). Isonicotinic acid as another building unit can easily bind or interact with transition metal ions through its possible bridging or coordination modes associated with the carboxylic group and pyridine moieties, respectively, thus allowing the assembly of compounds with supramolecular structures or the formation of heterometallic complexes (Xie et al., 2014).

Here, we report on the synthesis and crystal structure of an Ni^II azamacrocyclic complex including isonicotinate anions, [Ni(C₆H₄NO₂)₂(C₁₆H₃₈N₆)], (I).

Structural commentary top

Compound (I) is isotypic with its copper(II) analogue (Shin et al., 2015). The nickel(II) atom is located on an inversion centre. The coordination environment around the nickel(II) atom is distorted octahedral with the four secondary amine N atoms of the azamacrocyclic ligand in the equatorial plane and two O atoms of two monodentate isonicotinate anions in axial positions (Fig. 1). The average Ni—N_eq bond lengths is 2.064 (11) Å and the Ni—O_ax bond length is 2.137 (1) Å. The longer axial bonds can be attributed to a ring contraction of the azamacrocyclic ligand (Melson, 1979). The six-membered NiC₂N₃ ring (Ni1–N1–C2–N3–C3–N2) adopts the expected chair conformation, whereas the five-membered NiC₂N₂ ring (Ni1–N1–C1–C4–N2) has a gauche conformation (Min & Suh, 2001). Since the carboxylate group is fully delocalized, the two C—O bonds and the bond angle (O1—C9—O2) are 1.267 (2), 1.248 (2) Å and 126.9 (2)°, respectively. The bond angles around the nickel(II) atom are in the normal range for an octahedral complex. Intramolecular N—H···O hydrogen bonds between one of the secondary amine groups of the azamacrocyclic ligand and the non-coordinating carboxylate O atom of the isonicotinate anion form six-membered rings and stabilize the molecular structure (Fig. 1, Table 1).

Supramolecular features top

The N4 atom of the isonicotinate anion forms an intermolecular hydrogen bond with an adjacent secondary amine group of the azamacrocyclic ligand (Fig. 2, Table 1) (Steed & Atwood, 2009). In addition, parallel pyridine rings (Hunter & Sanders, 1990) of the isonicotinate anions participate in π–π interactions with a centroid-to-centroid distance of 3.741 (1) Å and an interplanar separation of 3.547 (1) Å. The interplay between hydrogen bonds and π—π interactions give rise to the formation of supramolecular ribbons extending parallel to [001].

Database survey top

A search of the Cambridge Structural Database (Version 5.36, May 2014 with 3 updates; Groom & Allen, 2014) reveals two complexes with the same nickel(II) azamacrocyclic building block (Kim et al., 2015a,b) for which synthesis, FT–IR spectroscopic data and the crystal structure have been reported.

Synthesis and crystallization top

The starting complex, [Ni(C₁₆H₃₈N₆)(ClO₄)₂], was prepared in a slightly modified procedure with respect to the reported method (Kim et al., 2015b). To an acetonitrile solution (14 ml) of [Ni(C₁₆H₃₈N₆)(ClO₄)₂] (0.298 g, 0.52 mmol) was slowly added an acetonitrile solution (8 ml) containing isonicotinic acid (0.128 g, 1.04 mmol) and excess triethylamine (0.12 g, 1.20 mmol) at room temperature. The purple precipitate was filtered off, washed with acetonitrile and diethyl ether, and dried in air. Single crystals of compound (I) were obtained by layering of the acetonitrile solution of isonicotinic acid on the acetonitrile solution of [Ni(C₁₆H₃₈N₆)(ClO₄)₂] for several days. Yield: 0.167 g (52%). FT–IR (ATR, cm⁻¹): 3145, 3075, 2951, 2920, 1571, 1457, 1351, 1272, 1014, 915.

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

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. A l l H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.95 (ring H atoms) or 0.98–0.99 Å (open-chain H atoms), and an N—H distance of 1.0 Å, with U_iso(H) values of 1.2 or 1.5U_eq of the parent atoms.

Structure description top

The molecular design and synthesis of coordination polymers with macrocyclic ligands have attracted considerable attention because of their potential applications in chemistry, environmental chemistry, and materials science (Churchard et al., 2010; Lehn, 2015). To obtain specific molecular compounds through assembly of supramolecular building blocks with properties such as guest recognition or catalytic effects, macrocyclic complexes involving vacant sites in an axial position are good candidates. Moreover, these complexes can also be easily derivatized by carboxylic acid moieties, such as 1,3,5-BTC (1,3,5-benzenetricarboxylic acid), 2,7-NDC (2,7-naphthalenedicarboxylic acid) or 1,3,5-CTC (1,3,5-cyclohexanetricarboxylic acid), forming interesting coordination compounds with supramolecular structures ranging from chains to networks (Min & Suh, 2001; Shin et al., 2016b). For example, [Ni(L^R,^R)]₃[BTC^3–]₂·12H₂O·CH₃CN (L^R,^R = 1,8-bis[(R)-α-methylbenzyl]-1,3,6,8,10,13-hexaazacyclotetradecane) displays a two-dimensional supramolecular network structure and exhibits a selective chiral recognition for racemic material (Ryoo et al., 2010). Isonicotinic acid as another building unit can easily bind or interact with transition metal ions through its possible bridging or coordination modes associated with the carboxylic group and pyridine moieties, respectively, thus allowing the assembly of compounds with supramolecular structures or the formation of heterometallic complexes (Xie et al., 2014).

Here, we report on the synthesis and crystal structure of an Ni^II azamacrocyclic complex including isonicotinate anions, [Ni(C₆H₄NO₂)₂(C₁₆H₃₈N₆)], (I).

The N4 atom of the isonicotinate anion forms an intermolecular hydrogen bond with an adjacent secondary amine group of the azamacrocyclic ligand (Fig. 2, Table 1) (Steed & Atwood, 2009). In addition, parallel pyridine rings (Hunter & Sanders, 1990) of the isonicotinate anions participate in π–π interactions with a centroid-to-centroid distance of 3.741 (1) Å and an interplanar separation of 3.547 (1) Å. The interplay between hydrogen bonds and π—π interactions give rise to the formation of supramolecular ribbons extending parallel to [001].

A search of the Cambridge Structural Database (Version 5.36, May 2014 with 3 updates; Groom & Allen, 2014) reveals two complexes with the same nickel(II) azamacrocyclic building block (Kim et al., 2015a,b) for which synthesis, FT–IR spectroscopic data and the crystal structure have been reported.

Synthesis and crystallization top

The starting complex, [Ni(C₁₆H₃₈N₆)(ClO₄)₂], was prepared in a slightly modified procedure with respect to the reported method (Kim et al., 2015b). To an acetonitrile solution (14 ml) of [Ni(C₁₆H₃₈N₆)(ClO₄)₂] (0.298 g, 0.52 mmol) was slowly added an acetonitrile solution (8 ml) containing isonicotinic acid (0.128 g, 1.04 mmol) and excess triethylamine (0.12 g, 1.20 mmol) at room temperature. The purple precipitate was filtered off, washed with acetonitrile and diethyl ether, and dried in air. Single crystals of compound (I) were obtained by layering of the acetonitrile solution of isonicotinic acid on the acetonitrile solution of [Ni(C₁₆H₃₈N₆)(ClO₄)₂] for several days. Yield: 0.167 g (52%). FT–IR (ATR, cm⁻¹): 3145, 3075, 2951, 2920, 1571, 1457, 1351, 1272, 1014, 915.

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

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 2. A l l H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.95 (ring H atoms) or 0.98–0.99 Å (open-chain H atoms), and an N—H distance of 1.0 Å, with U_iso(H) values of 1.2 or 1.5U_eq of the parent atoms.

Computing details top

Data collection: PAL BL2D-SMDC (Shin et al., 2016a); cell refinement: HKL-3000SM (Otwinowski & Minor, 1997); data reduction: HKL-3000SM (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (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 30% probability level. H atoms bonded to C atoms have been omitted for clarity. Intramolecular N—H···O hydrogen bonds are shown as red dashed lines. [Symmetry code: (i) −x + 1, −y + 1, −z + 1.]
	Fig. 2. View of the crystal packing of the title compound, showing hydrogen bonds and π–π interactions (red: intramolecular N—H···O hydrogen bonds, green: intermolecular N—H···N hydrogen bonds, black: π–π interactions).

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

Crystal data top

[Ni(C₆H₄NO₂)₂(C₁₆H₃₈N₆)]	Z = 1
M_r = 617.44	F(000) = 330
Triclinic, P1	D_x = 1.389 Mg m⁻³
a = 8.0630 (16) Å	Synchrotron radiation, λ = 0.62998 Å
b = 8.5110 (17) Å	Cell parameters from 20128 reflections
c = 10.927 (2) Å	θ = 0.4–33.6°
α = 80.52 (3)°	µ = 0.51 mm⁻¹
β = 88.26 (3)°	T = 100 K
γ = 86.44 (3)°	Needle, pale pink
V = 738.0 (3) Å³	0.01 × 0.004 × 0.004 mm

Data collection top

ADSC Q210 CCD area-detector diffractometer	3326 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	R_int = 0.023
ω scan	θ_max = 26.0°, θ_min = 2.5°
Absorption correction: empirical (using intensity measurements) (HKL-3000SM SCALEPACK; Otwinowski & Minor, 1997)	h = −11→11
T_min = 0.995, T_max = 0.998	k = −11→11
7634 measured reflections	l = −15→15
3879 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0649P)² + 0.1918P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3879 reflections	Δρ_max = 1.12 e Å⁻³
188 parameters	Δρ_min = −0.95 e Å⁻³

Crystal data top

[Ni(C₆H₄NO₂)₂(C₁₆H₃₈N₆)]	γ = 86.44 (3)°
M_r = 617.44	V = 738.0 (3) Å³
Triclinic, P1	Z = 1
a = 8.0630 (16) Å	Synchrotron radiation, λ = 0.62998 Å
b = 8.5110 (17) Å	µ = 0.51 mm⁻¹
c = 10.927 (2) Å	T = 100 K
α = 80.52 (3)°	0.01 × 0.004 × 0.004 mm
β = 88.26 (3)°

Data collection top

ADSC Q210 CCD area-detector diffractometer	3879 independent reflections
Absorption correction: empirical (using intensity measurements) (HKL-3000SM SCALEPACK; Otwinowski & Minor, 1997)	3326 reflections with I > 2σ(I)
T_min = 0.995, T_max = 0.998	R_int = 0.023
7634 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.04	Δρ_max = 1.12 e Å⁻³
3879 reflections	Δρ_min = −0.95 e Å⁻³
188 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	0.5000	0.5000	0.5000	0.02066 (10)
O1	0.43513 (15)	0.41029 (17)	0.33736 (11)	0.0257 (3)
O2	0.18613 (16)	0.52908 (19)	0.28022 (12)	0.0322 (3)
N1	0.27809 (18)	0.6311 (2)	0.50735 (13)	0.0244 (3)
H1	0.2171	0.6276	0.4296	0.029*
N2	0.61452 (18)	0.67953 (19)	0.38249 (13)	0.0241 (3)
H2	0.5798	0.6766	0.2959	0.029*
N3	0.3946 (2)	0.8835 (2)	0.41256 (14)	0.0304 (3)
N4	0.3686 (2)	0.2837 (2)	−0.09149 (14)	0.0335 (4)
C1	0.1835 (2)	0.5457 (3)	0.61221 (15)	0.0276 (4)
H1A	0.0642	0.5807	0.6057	0.033*
H1B	0.2242	0.5692	0.6915	0.033*
C2	0.3004 (2)	0.8006 (2)	0.51521 (16)	0.0296 (4)
H2A	0.1895	0.8566	0.5192	0.036*
H2B	0.3574	0.8058	0.5933	0.036*
C3	0.5703 (2)	0.8414 (2)	0.41070 (18)	0.0308 (4)
H3A	0.6153	0.8493	0.4926	0.037*
H3B	0.6249	0.9202	0.3480	0.037*
C4	0.7938 (2)	0.6330 (3)	0.39084 (16)	0.0280 (4)
H4A	0.8376	0.6572	0.4689	0.034*
H4B	0.8552	0.6932	0.3203	0.034*
C5	0.3160 (2)	0.9034 (2)	0.29077 (17)	0.0310 (4)
H5A	0.2983	0.7968	0.2700	0.037*
H5B	0.3922	0.9575	0.2269	0.037*
C6	0.1502 (3)	0.9999 (3)	0.28701 (18)	0.0341 (4)
H6A	0.0727	0.9447	0.3493	0.041*
H6B	0.1671	1.1058	0.3093	0.041*
C7	0.0730 (3)	1.0223 (3)	0.15954 (19)	0.0390 (5)
H7A	0.1527	1.0726	0.0966	0.047*
H7B	0.0507	0.9166	0.1390	0.047*
C8	−0.0882 (3)	1.1257 (4)	0.1543 (2)	0.0502 (6)
H8A	−0.1692	1.0739	0.2140	0.075*
H8B	−0.1328	1.1395	0.0705	0.075*
H8C	−0.0667	1.2302	0.1750	0.075*
C9	0.3163 (2)	0.4477 (2)	0.26295 (15)	0.0235 (3)
C10	0.4760 (2)	0.2978 (3)	0.10910 (16)	0.0294 (4)
H10	0.5631	0.2691	0.1666	0.035*
C11	0.3367 (2)	0.3884 (2)	0.13963 (14)	0.0234 (3)
C12	0.2134 (2)	0.4252 (3)	0.05120 (16)	0.0300 (4)
H12	0.1158	0.4874	0.0676	0.036*
C13	0.2347 (2)	0.3703 (3)	−0.06044 (17)	0.0339 (4)
H13	0.1486	0.3957	−0.1191	0.041*
C14	0.4868 (2)	0.2496 (3)	−0.00601 (17)	0.0340 (4)
H14	0.5838	0.1887	−0.0256	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01767 (15)	0.03464 (19)	0.00987 (14)	0.00142 (11)	−0.00201 (9)	−0.00504 (11)
O1	0.0246 (6)	0.0412 (7)	0.0122 (5)	0.0012 (5)	−0.0054 (4)	−0.0073 (5)
O2	0.0235 (6)	0.0543 (9)	0.0207 (6)	0.0047 (6)	−0.0043 (5)	−0.0139 (6)
N1	0.0225 (7)	0.0384 (8)	0.0122 (6)	0.0027 (6)	−0.0022 (5)	−0.0048 (6)
N2	0.0227 (7)	0.0355 (8)	0.0142 (6)	0.0007 (6)	−0.0016 (5)	−0.0049 (6)
N3	0.0338 (8)	0.0354 (9)	0.0209 (7)	0.0055 (7)	−0.0018 (6)	−0.0041 (7)
N4	0.0344 (8)	0.0525 (11)	0.0148 (6)	0.0002 (7)	−0.0027 (6)	−0.0091 (7)
C1	0.0186 (7)	0.0485 (11)	0.0149 (7)	0.0026 (7)	0.0012 (5)	−0.0052 (7)
C2	0.0331 (9)	0.0384 (10)	0.0169 (8)	0.0078 (8)	−0.0008 (6)	−0.0068 (7)
C3	0.0339 (9)	0.0350 (10)	0.0240 (8)	−0.0011 (7)	−0.0018 (7)	−0.0063 (8)
C4	0.0205 (8)	0.0460 (11)	0.0173 (7)	−0.0038 (7)	0.0002 (6)	−0.0043 (7)
C5	0.0376 (10)	0.0345 (10)	0.0188 (8)	0.0059 (8)	−0.0014 (7)	−0.0011 (7)
C6	0.0356 (10)	0.0414 (11)	0.0227 (9)	0.0064 (8)	−0.0008 (7)	−0.0009 (8)
C7	0.0394 (11)	0.0506 (13)	0.0243 (9)	0.0048 (9)	−0.0033 (7)	−0.0006 (9)
C8	0.0400 (12)	0.0733 (18)	0.0320 (11)	0.0119 (11)	−0.0033 (9)	0.0018 (11)
C9	0.0213 (7)	0.0366 (9)	0.0128 (7)	−0.0044 (6)	−0.0018 (5)	−0.0040 (6)
C10	0.0258 (8)	0.0468 (11)	0.0160 (7)	0.0028 (7)	−0.0044 (6)	−0.0071 (7)
C11	0.0222 (7)	0.0365 (9)	0.0119 (7)	−0.0038 (7)	−0.0016 (5)	−0.0047 (7)
C12	0.0257 (8)	0.0484 (11)	0.0158 (7)	0.0020 (8)	−0.0044 (6)	−0.0062 (8)
C13	0.0307 (9)	0.0562 (13)	0.0157 (8)	0.0009 (8)	−0.0073 (6)	−0.0085 (8)
C14	0.0306 (9)	0.0534 (12)	0.0186 (8)	0.0056 (8)	−0.0017 (7)	−0.0106 (8)

Geometric parameters (Å, º) top

Ni1—N1ⁱ	2.0559 (16)	C3—H3B	0.9900
Ni1—N1	2.0559 (16)	C4—C1ⁱ	1.526 (3)
Ni1—N2	2.0720 (17)	C4—H4A	0.9900
Ni1—N2ⁱ	2.0720 (17)	C4—H4B	0.9900
Ni1—O1ⁱ	2.1371 (13)	C5—C6	1.523 (3)
Ni1—O1	2.1372 (13)	C5—H5A	0.9900
O1—C9	1.2669 (19)	C5—H5B	0.9900
O2—C9	1.248 (2)	C6—C7	1.521 (3)
N1—C1	1.471 (2)	C6—H6A	0.9900
N1—C2	1.481 (3)	C6—H6B	0.9900
N1—H1	1.0000	C7—C8	1.521 (3)
N2—C4	1.477 (2)	C7—H7A	0.9900
N2—C3	1.481 (3)	C7—H7B	0.9900
N2—H2	1.0000	C8—H8A	0.9800
N3—C3	1.440 (3)	C8—H8B	0.9800
N3—C2	1.444 (2)	C8—H8C	0.9800
N3—C5	1.471 (2)	C9—C11	1.516 (2)
N4—C13	1.336 (3)	C10—C14	1.384 (3)
N4—C14	1.340 (2)	C10—C11	1.386 (3)
C1—C4ⁱ	1.526 (3)	C10—H10	0.9500
C1—H1A	0.9900	C11—C12	1.393 (2)
C1—H1B	0.9900	C12—C13	1.379 (3)
C2—H2A	0.9900	C12—H12	0.9500
C2—H2B	0.9900	C13—H13	0.9500
C3—H3A	0.9900	C14—H14	0.9500

N1ⁱ—Ni1—N1	180.0	H3A—C3—H3B	107.6
N1ⁱ—Ni1—N2	85.97 (6)	N2—C4—C1ⁱ	108.14 (15)
N1—Ni1—N2	94.03 (6)	N2—C4—H4A	110.1
N1ⁱ—Ni1—N2ⁱ	94.03 (6)	C1ⁱ—C4—H4A	110.1
N1—Ni1—N2ⁱ	85.97 (6)	N2—C4—H4B	110.1
N2—Ni1—N2ⁱ	180.0	C1ⁱ—C4—H4B	110.1
N1ⁱ—Ni1—O1ⁱ	93.29 (6)	H4A—C4—H4B	108.4
N1—Ni1—O1ⁱ	86.71 (6)	N3—C5—C6	112.79 (16)
N2—Ni1—O1ⁱ	92.90 (6)	N3—C5—H5A	109.0
N2ⁱ—Ni1—O1ⁱ	87.10 (6)	C6—C5—H5A	109.0
N1ⁱ—Ni1—O1	86.71 (6)	N3—C5—H5B	109.0
N1—Ni1—O1	93.29 (6)	C6—C5—H5B	109.0
N2—Ni1—O1	87.10 (6)	H5A—C5—H5B	107.8
N2ⁱ—Ni1—O1	92.90 (6)	C7—C6—C5	111.93 (17)
O1ⁱ—Ni1—O1	180.0	C7—C6—H6A	109.2
C9—O1—Ni1	131.99 (12)	C5—C6—H6A	109.2
C1—N1—C2	114.34 (14)	C7—C6—H6B	109.2
C1—N1—Ni1	105.52 (11)	C5—C6—H6B	109.2
C2—N1—Ni1	112.75 (11)	H6A—C6—H6B	107.9
C1—N1—H1	108.0	C8—C7—C6	111.81 (19)
C2—N1—H1	108.0	C8—C7—H7A	109.3
Ni1—N1—H1	108.0	C6—C7—H7A	109.3
C4—N2—C3	113.96 (15)	C8—C7—H7B	109.3
C4—N2—Ni1	104.76 (11)	C6—C7—H7B	109.3
C3—N2—Ni1	113.72 (11)	H7A—C7—H7B	107.9
C4—N2—H2	108.0	C7—C8—H8A	109.5
C3—N2—H2	108.0	C7—C8—H8B	109.5
Ni1—N2—H2	108.0	H8A—C8—H8B	109.5
C3—N3—C2	115.84 (15)	C7—C8—H8C	109.5
C3—N3—C5	114.58 (15)	H8A—C8—H8C	109.5
C2—N3—C5	115.55 (16)	H8B—C8—H8C	109.5
C13—N4—C14	116.05 (17)	O2—C9—O1	126.88 (16)
N1—C1—C4ⁱ	108.60 (14)	O2—C9—C11	117.12 (15)
N1—C1—H1A	110.0	O1—C9—C11	115.99 (16)
C4ⁱ—C1—H1A	110.0	C14—C10—C11	119.30 (17)
N1—C1—H1B	110.0	C14—C10—H10	120.4
C4ⁱ—C1—H1B	110.0	C11—C10—H10	120.4
H1A—C1—H1B	108.4	C10—C11—C12	117.25 (16)
N3—C2—N1	114.07 (15)	C10—C11—C9	122.61 (15)
N3—C2—H2A	108.7	C12—C11—C9	120.14 (16)
N1—C2—H2A	108.7	C13—C12—C11	119.15 (18)
N3—C2—H2B	108.7	C13—C12—H12	120.4
N1—C2—H2B	108.7	C11—C12—H12	120.4
H2A—C2—H2B	107.6	N4—C13—C12	124.30 (17)
N3—C3—N2	114.51 (16)	N4—C13—H13	117.8
N3—C3—H3A	108.6	C12—C13—H13	117.8
N2—C3—H3A	108.6	N4—C14—C10	123.94 (18)
N3—C3—H3B	108.6	N4—C14—H14	118.0
N2—C3—H3B	108.6	C10—C14—H14	118.0

C2—N1—C1—C4ⁱ	−166.23 (14)	C5—C6—C7—C8	−177.2 (2)
Ni1—N1—C1—C4ⁱ	−41.74 (15)	Ni1—O1—C9—O2	−15.1 (3)
C3—N3—C2—N1	−72.6 (2)	Ni1—O1—C9—C11	164.15 (12)
C5—N3—C2—N1	65.5 (2)	C14—C10—C11—C12	0.4 (3)
C1—N1—C2—N3	179.49 (14)	C14—C10—C11—C9	−179.18 (18)
Ni1—N1—C2—N3	58.94 (17)	O2—C9—C11—C10	179.64 (18)
C2—N3—C3—N2	70.3 (2)	O1—C9—C11—C10	0.3 (3)
C5—N3—C3—N2	−68.2 (2)	O2—C9—C11—C12	0.1 (3)
C4—N2—C3—N3	−175.30 (14)	O1—C9—C11—C12	−179.24 (17)
Ni1—N2—C3—N3	−55.32 (18)	C10—C11—C12—C13	0.3 (3)
C3—N2—C4—C1ⁱ	167.84 (13)	C9—C11—C12—C13	179.86 (18)
Ni1—N2—C4—C1ⁱ	42.93 (14)	C14—N4—C13—C12	0.4 (3)
C3—N3—C5—C6	−160.49 (18)	C11—C12—C13—N4	−0.7 (3)
C2—N3—C5—C6	60.9 (2)	C13—N4—C14—C10	0.4 (3)
N3—C5—C6—C7	178.71 (18)	C11—C10—C14—N4	−0.8 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	1.00	1.98	2.892 (2)	150
N2—H2···N4ⁱⁱ	1.00	2.23	3.143 (2)	151

Symmetry code: (ii) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	1.00	1.98	2.892 (2)	150.0
N2—H2···N4ⁱ	1.00	2.23	3.143 (2)	150.6

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Ni(C₆H₄NO₂)₂(C₁₆H₃₈N₆)]
M_r	617.44
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.0630 (16), 8.5110 (17), 10.927 (2)
α, β, γ (°)	80.52 (3), 88.26 (3), 86.44 (3)
V (Å³)	738.0 (3)
Z	1
Radiation type	Synchrotron, λ = 0.62998 Å
µ (mm⁻¹)	0.51
Crystal size (mm)	0.01 × 0.004 × 0.004

Data collection
Diffractometer	ADSC Q210 CCD area-detector
Absorption correction	Empirical (using intensity measurements) (HKL-3000SM SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.995, 0.998
No. of measured, independent and observed [I > 2σ(I)] reflections	7634, 3879, 3326
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.696

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.110, 1.04
No. of reflections	3879
No. of parameters	188
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.12, −0.95

Computer programs: PAL BL2D-SMDC (Shin et al., 2016a), HKL-3000SM (Otwinowski & Minor, 1997), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), DIAMOND (Putz & Brandenburg, 2014), publCIF (Westrip, 2010).

Acknowledgements

This work was supported by 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-R007-D1–2016–a01). The X-ray crystallography BL2D–SMC beamline and FT–IR experiment at the PLS-II are supported in part by MSIP and POSTECH.

References

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Volume 72| Part 2| February 2016| Pages 223-225

doi:10.1107/S2056989016001031

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