Crystal structures of (1,4,7,10-tetra­aza­cyclo­dodecane-κ4N)bis­(tri­cyano­methanido-κN)nickel and (1,4,7,10-tetra­aza­cyclo­dodecane-κ4N)(tri­cyano­methanido-κN)copper tri­cyano­methanide

Luo, J.; Zhang, X.-R.; Qiu, L.-J.; Yang, F.; Liu, B.-S.

doi:10.1107/S2056989015009524

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ISSN: 2056-9890

Volume 71| Part 6| June 2015| Pages 693-697

doi:10.1107/S2056989015009524

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Crystal structures of (1,4,7,10-tetraazacyclododecane-κ⁴N)bis(tricyanomethanido-κN)nickel and (1,4,7,10-tetraazacyclododecane-κ⁴N)(tricyanomethanido-κN)copper tricyanomethanide

Jun Luo,^a Xin-Rong Zhang,^a Li-Juan Qiu,^a Feng Yang ^a and Bao-Shu Liu ^a ^*

^aSchool of Pharmacy, Second Military Medical University, Shanghai 200433, People's Republic of China
^*Correspondence e-mail: liubaoshu@126.com

Edited by J. Simpson, University of Otago, New Zealand (Received 11 May 2015; accepted 19 May 2015; online 23 May 2015)

The structures of two mononuclear transition-metal complexes with tricyanomethanide (tcm⁻) and 1,4,7,10-tetraazacyclododecane (cyclen) ligands, [Ni(C₄N₃)₂(C₈H₂₀N₄)], (I), and [Cu(C₄N₃)(C₈H₂₀N₄)](C₄N₃), (II), are reported. In the neutral complex (I), the nickel cation is coordinated by one cyclen ligand and two monodentate N-bound tcm⁻ anions in a distorted octahedral geometry. The tcm⁻ ligands are mutually cis. The Cu^II atom in (II) displays a distorted tetragonal–pyramidal geometry, with the four N-donor atoms of the cyclen ligand in the equatorial plane, and one tcm⁻ anion bound through a single N atom in an axial site, forming a monocation. The second tcm⁻ molecule acts as a counter-ion not directly coordinating to the copper cation. In both (I) and (II), extensive series of N—H⋯N and C—H⋯N hydrogen bonds generate three-dimensional network structures.

Keywords: crystal structures; tricyanomethanide; 1,4,7,10-tetraazacyclododecane; nickel complex; copper complex.

CCDC references: 1401692; 1401691

1. Chemical context

Coordination polymers constructed by the tricyanomethanide anion (tcm⁻) have attracted considerable interest due to their fascinating structural characteristics (Hunt et al., 2015 ; Hodgson et al., 2014 ; Chainok et al., 2012 ; Vreshch et al., 2013 ) and interesting magnetic properties (Luo et al., 2014 ; Herchel et al., 2014 ; Váhovská et al., 2014 ). To date, with the exception of a doubly interpenetrated (6,3) sheet, observed in Ag(tcm)₂⁻ (Abrahams et al., 2003 ), most binary tcm⁻ complexes display a rutile-like structure (Manson et al., 2000 , 1998 ; Hoshino et al., 1999 ; Feyerherm et al., 2004 ). To gain an insight into the influence of co-ligands on the structural and magnetic properties of tcm⁻ complexes, various co-ligands, such as hexamethylenetetramine, 4,4-bipyridyl and 1,2-di(pyridin-4-yl)ethane have been introduced to the binary tcm complexes. Among the Cu^I or Cd^II tcm⁻ complexes with such co-ligands, numerous structural types ranging from doubly interpenetrated (4,4) sheets to three-dimensional rutile networks have been observed (Batten et al., 2000 , 1998 ). By contrast, modification of the Mn^II–tcm binary system with 4,4-bipyridyl as a co-ligand leads to the formation of a one-dimensional chain-like structure (Manson et al., 2004 ). In addition, the Julve group (Yuste et al., 2007 , 2008 ) recently reported the polymeric structures of copper tcm⁻ complexes with co-ligands such as bis(2-pyridyl)pyrazine, 2,2′-bipyrazine and 2,3,5,6-tetrakis(2-pyridyl)pyrazine and found them to have interesting magnetic properties. 1,4,7,10-Tetraazacyclododecane (cyclen) is a novel co-ligand with four potential nitrogen donor atoms. However, no tcm⁻ complexes incorporating cyclen as a co-ligand have been reported previously. As part of our systematic investigation of the effect of cyclen as a co-ligand on the structures and properties of tcm⁻ complexes, we have prepared two new tcm⁻ complexes and we report herein the syntheses and crystal structures of Ni(cyclen)(C₄N₃)₂ (I) and [Cu(cyclen)(C₄N₃)]⁺(C₄N₃)⁻ (II).

2. Structural commentary

In (I), the nickel cation binds to the four N atoms of the cyclen and two N atoms of two tcm⁻ anions, forming a distorted octahedral geometry with the tcm⁻ ligands mutually cis. The equatorial plane is therefore formed by two N atoms (N1, N3) of the cyclen unit and the N5 and N8 atoms of the coordinating tcm⁻ anions. The apical sites are occupied by N2 and N4 from the cyclen ligand, Fig. 1.

Figure 1
View of the molecule of (I)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

In (II), the copper cation is also bound to the four N atoms (N1, N2, N3, N4) of a cyclen ligand but in the basal plane with the N5 atom of the tcm⁻ ligand in an apical site, forming a five-coordinate cation with a distorted square-pyramidal coordination geometry. The second tcm⁻ anion does not enter the inner coordination sphere of the metal (Fig. 2), but acts as a counter-anion that is linked to the cation in the asymmetric unit through an N1—H1⋯N9 hydrogen bond (Fig. 2).

Figure 2
A view of the molecule of (II)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. The hydrogen bond between the cation and anion is shown as a dashed line.

The Ni—N(cyclen) distances in (I) [2.051 (3)–2.134 (3) Å] show some variation, but these values are similar to the corresponding distances in other polyamine-containing nickel complexes (Shirase et al., 2009 ; Patel et al., 2008 ). The Ni—N(tcm) distances, 2.062 (3) and 2.101 (3) Å, Table 1, of (I) are not unusual, and these data are comparable to the corresponding distances in other closely related nickel complexes with tcm⁻ ligands (Luo et al., 2014, 2006 ).

Table 1
Selected geometric parameters (Å, °) for (I)

Ni1—N1	2.051 (3)	Ni1—N5	2.101 (3)
Ni1—N8	2.062 (3)	Ni1—N2	2.125 (3)
Ni1—N3	2.080 (3)	Ni1—N4	2.134 (3)

N1—Ni1—N8	87.4 (1)	N3—Ni1—N2	81.6 (1)
N1—Ni1—N3	97.3 (1)	N5—Ni1—N2	95.4 (1)
N8—Ni1—N3	175.3 (1)	N1—Ni1—N4	82.8 (1)
N1—Ni1—N5	171.8 (1)	N8—Ni1—N4	98.1 (1)
N8—Ni1—N5	84.9 (1)	N3—Ni1—N4	82.0 (1)
N3—Ni1—N5	90.4 (1)	N5—Ni1—N4	101.2 (1)
N1—Ni1—N2	83.0 (1)	N2—Ni1—N4	156.7 (1)
N8—Ni1—N2	99.7 (1)

In (II), the Cu—N(cyclen) distances range from 2.014 (2) to 2.034 (2) Å, and are similar to distances found in other reported copper complexes with polyamine co-ligands (Qi et al., 2014 ; Belda et al., 2013 ). In (II), the Cu—N(tcm) distance [2.097 (2) Å, Table 2) is also similar to the distances found in previously reported copper tcm⁻ complexes (Yuste et al., 2007, 2008).

Table 2
Selected geometric parameters (Å, °) for (II)

Cu1—N2	2.014 (2)	Cu1—N1	2.034 (2)
Cu1—N3	2.022 (2)	Cu1—N5	2.097 (2)
Cu1—N4	2.029 (2)

N2—Cu1—N3	85.61 (9)	N4—Cu1—N1	85.79 (9)
N2—Cu1—N4	148.42 (9)	N2—Cu1—N5	107.9 (1)
N3—Cu1—N4	85.57 (9)	N3—Cu1—N5	101.87 (9)
N2—Cu1—N1	86.11 (9)	N4—Cu1—N5	103.57 (9)
N3—Cu1—N1	148.55 (9)	N1—Cu1—N5	109.54 (9)

In (I), the N—Ni—N angles, involving two cis-related basal N atoms and the N(apical)—Ni—N(basal) angle range from 84.9 (1) to 97.3 (1)° and 81.6 (1) to 101.2 (1)°, respectively. The corresponding values for (II) are 85.57 (9) to 86.11 (9)° and 101.87 (9) to 109.54 (9)°, respectively, again indicating that the distortion from the octahedral and square-pyramidal geometries in (I) and (II) is not particularly severe.

Each tcm⁻ ligand is almost planar, with the mean deviations from the planes through all atoms of the coordinating tcm⁻ anions being 0.0128 and 0.0322 Å, respectively in (I). For (II), the corresponding deviations from the planes of the coordinating tcm⁻ anion and the tcm⁻ counter-anion are 0.0211 and 0.0074 Å respectively. Bond lengths and angles within the anions are also in good agreement with those found in other tcm⁻ complexes (Batten et al., 1999 ; Yuste et al., 2008).

3. Supramolecular features

In the crystal structure of (I), each complex molecule is linked to five others by a series of N—H⋯N and C—H⋯N hydrogen bonds. N1—H1⋯N10 and N2—H2⋯N6 hydrogen bonds each form inversion dimers, joining the complex molecule to two neighbouring molecules and generating R₂²(16) ring motifs (Bernstein et al., 1995 ). N3—H3⋯N7 and N4—H4⋯N6 hydrogen bonds link two additional complex molecules. A C4—H4B⋯N9 contact involves the fifth complex. This array of contacts combines to generate an extensive three-dimensional network (Fig. 3, Table 3).

Table 3
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯N7ⁱ	0.99	2.74	3.665 (5)	156
N3—H3⋯N7ⁱ	0.95 (2)	2.45 (3)	3.330 (5)	154 (4)
N1—H1⋯N10ⁱⁱ	0.90 (2)	2.11 (3)	2.907 (5)	148 (4)
N2—H2⋯N6ⁱⁱⁱ	0.91 (2)	2.22 (3)	3.064 (4)	155 (4)
C4—H4B⋯N9^iv	0.99	2.57	3.467 (5)	151
N4—H4⋯N6^v	0.90 (2)	2.70 (4)	3.372 (4)	133 (4)
C7—H7B⋯N6^v	0.99	2.70	3.397 (5)	128
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y+1, -z+1; (iii) -x+1, -y+1, -z; (iv) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 3
The three-dimensional network of (I)

, formed by hydrogen-bonding interactions, viewed along the b axis. Hydrogen bonds are drawn as dashed lines.

In the crystal structure of (II), N1—H1⋯N6 and N3—H3⋯N7 hydrogen bonds each form inversion dimers, also linking the complex cation to two neighbouring cations and generating R₂²(16) ring motifs. Each complex molecule is also linked via N—H⋯N and C—H⋯N hydrogen bonds to two adjacent complex cations and three tcm⁻ anions, forming another extensive three-dimensional network (Fig. 4, Table 4).

Table 4
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N9	0.87 (2)	2.79 (3)	3.525 (4)	143 (3)
C1—H1B⋯N6ⁱ	0.99	2.54	3.273 (4)	131
N1—H1⋯N6ⁱ	0.87 (2)	2.60 (3)	3.206 (4)	127 (3)
N4—H4⋯N9ⁱⁱ	0.84 (3)	2.24 (4)	3.067 (3)	168 (3)
N3—H3⋯N7ⁱⁱⁱ	0.92 (2)	2.05 (2)	2.928 (3)	159 (4)
N2—H2⋯N8^iv	0.94 (2)	2.19 (2)	3.003 (3)	144 (3)
C3—H3B⋯N10^v	0.99	2.64	3.531 (4)	150
C8—H8B⋯N8^vi	0.99	2.56	3.538 (4)	171
C3—H3A⋯N10^vi	0.99	2.64	3.460 (4)	140
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x, -y+2, -z+1; (iii) -x+1, -y+2, -z; (iv) -x+1, -y+1, -z+1; (v) x+1, y, z-1; (vi) -x, -y+1, -z+1.

Figure 4
The three-dimensional network of (II)

, formed by hydrogen-bonding interactions, viewed along the a axis. Hydrogen bonds are drawn as dashed lines.

4. Database survey

Structures of transition-metal complexes with two or more tcm⁻ ligands are quite common with 47 unique compounds recorded in the Cambridge Crystallographic Database (Version 5.36, November 2014 with two updates; Groom & Allen, 2014 ). Of these the majority, 35, are polymeric or oligomeric systems. Five of these are Ni^II complexes but only two of them [tris(2-aminoethyl)amine]bis(tricyanomethanide)nickel(II) (Luo et al., 2014) and cis-bis(tricyanomethanide-κN)[tris(2-aminoethyl)amine-κ⁴N]nickel(II) (Potočňák et al., 2007 ) are mononuclear, each with a distorted octahedral coordination environment and with the tcm⁻ ligands mutually cis.

The number of transition-metal complexes with the cyclen ligand is huge, with 116 unique hits in the current Database. Among these, there are twenty Ni^II complexes and nine Cu^II complexes. Representative Ni complexes include [Ni(cyclen)]₂[Pt(CN)₄]₂·6H₂O and [Ni(cyclen)]₂[(Ni(CN)₄)]₂·6H₂O (Yeung et al., 2006 ), while examples of Cu complexes are [Cu(cyclen)(Au(CN)₂)]⁺·[Au(CN)₂]⁻ (Yeung et al., 2000 ) and [Cu(cyclen)(NO₃)]⁺·NO₃⁻ (Clay et al., 1979 ). However, no complexes containing a transition metal coordinated by both cyclen and tcm⁻ ligands were found.

5. Synthesis and crystallization

A 5 ml ethanol solution of 1,4,7,10-tetraazacyclododecane (0.10 mmol, 17.23 mg) and 2 ml of a green aqueous solution of nickel(II) nitrate (0.10 mmol, 29.08 mg) were mixed and stirred for 5 min; the resulting solution was purple. A 3 ml ethanol–water solution (EtOH:H₂O = 2:1, v:v) of potassium tricyanomethanide (0.20 mmol, 25.83 mg) was then added. After stirring for another 5 min, the purple solution was filtered and the filtrate slowly evaporated in air. After two weeks, purple block-like crystals of (I) were isolated in 31% yield. Analysis calculated for C₁₆H₂₀N₁₀Ni: C 46.75%, H 4.90%, N 34.07%. Found C 46.91%, H 5.03%, N 34.26%. Using copper(II) nitrate instead of nickel(II) nitrate, blue block-like crystals of (II) were prepared in a similar manner in 25% yield. Analysis calculated for C₁₆H₂₀N₁₀Cu: C 46.20%, H 4.85%, N 33.67%. Found C 46.42%, H 5.01%, N 33.85%.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. In (I), the H1, H2, H3 and H4 atoms bound to the amine N atoms were found in a difference Fourier map and refined freely with isotropic displacement parameters. The N—H distances ranged from 0.90 (2) to 0.95 (2) Å. H atoms bound to carbon were constrained to an ideal geometry with C—H distances of 0.99 Å, and with U_iso = 1.2U_eq(C) for CH₂. In (II), the amine H1, H2, H3 and H4 atoms and the H atoms linked to carbon were refined similarly. The N—H distances were in the range 0.84 (3) to 0.94 (2) Å.

Table 5
Experimental details

	(I)	(II)
Crystal data
Chemical formula	[Ni(C₄N₃)₂(C₈H₂₀N₄)]	[Cu(C₄N₃)(C₈H₂₀N₄)](C₄N₃)
M_r	411.13	415.96
Crystal system, space group	Monoclinic, P2₁/c	Triclinic, P $[\overline{1}]$
Temperature (K)	173	173
a, b, c (Å)	10.6300 (12), 11.0150 (12), 17.1771 (18)	7.4074 (15), 11.552 (2), 11.625 (2)
α, β, γ (°)	90, 104.828 (2), 90	89.187 (3), 88.236 (3), 78.579 (3)
V (Å³)	1944.3 (4)	974.6 (3)
Z	4	2
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	1.02	1.14
Crystal size (mm)	0.06 × 0.05 × 0.04	0.10 × 0.07 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996 )	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.670, 0.746	0.680, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	12264, 4611, 3460	6936, 4267, 3639
R_int	0.032	0.021
(sin θ/λ)_max (Å⁻¹)	0.659	0.644

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.136, 1.05	0.033, 0.110, 1.13
No. of reflections	4611	4267
No. of parameters	259	260
No. of restraints	12	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.05, −0.67	0.43, −0.30
Computer programs: APEX2 and SAINT (Bruker, 2010 ), SHELXS97 and SHELXTL (Sheldrick, 2008 ) and SHELXL2013 (Sheldrick, 2015 ).

Supporting information

CCDC references: 1401692; 1401691

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S2056989015009524/sj5461sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015009524/sj5461Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S2056989015009524/sj5461IIsup3.hkl

Supporting information file. DOI: 10.1107/S2056989015009524/sj5461sup4.pdf

Supporting information file. DOI: 10.1107/S2056989015009524/sj5461sup5.pdf

Supporting information file. DOI: 10.1107/S2056989015009524/sj5461sup6.pdf

checkCIF report

Chemical context top

Coordination polymers constructed by the tricyanomethanide anion (tcm^-) have attracted considerable interest due to their fascinating structural characteristics (Hunt et al., 2015; Hodgson et al., 2014; Chainok et al., 2012; Vreshch et al., 2013) and interesting magnetic properties (Luo et al., 2014; Herchel et al., 2014; Váhovská et al., 2014). To date, with the exception of a doubly interpenetrated (6,3) sheet, observed in Ag(tcm)₂^- (Abrahams et al., 2003), most binary tcm^- complexes display a rutile-like structure (Manson et al., 2000, 1998; Hoshino et al., 1999; Feyerherm et al., 2004). To gain an insight into the influence of co-ligands on the structural and magnetic properties of tcm^- complexes, various co-ligands, such as hexamethylenetetramine, 4,4-bipyridyl and 1,2-di(pyridin-4-yl)ethane have been introduced to the binary tcm complexes. Among the Cu^I or Cd^II tcm^- complexes with such co-ligands, numerous structural types ranging from doubly interpenetrated (4,4) sheets to three-dimensional rutile networks have been observed (Batten et al., 2000, 1998). By contrast, modification of the Mn^II–tcm binary system with 4,4-bipyridyl as a co-ligand leads to the formation of a one-dimensional chain-like structure (Manson et al., 2004). In addition, the Julve group (Yuste et al., 2007, 2008) recently reported the polymeric structures of copper tcm^- complexes with co-ligands such as bis(2-pyridyl)pyrazine, 2,2'-bipyrazine and 2,3,5,6-tetrakis(2-pyridyl)pyrazine and found them to have interesting magnetic properties. 1,4,7,10-Tetraazacyclododecane (cyclen) is a novel co-ligand with four potential nitrogen donor atoms. However, no tcm^- complexes incorporating cyclen as a co-ligand have been reported previously. As part of our systematic investigation of the effect of cyclen as a co-ligand on the structures and properties of tcm^- complexes, we have prepared two new tcm^- complexes and we report herein the syntheses and crystal structures of Ni(cyclen)(C₄N₃)₂ (I) and [Cu(cyclen)(C₄N₃)]⁺(C₄N₃)^- (II).

Structural commentary top

In (I), the nickel cation binds to the four N atoms of the cyclen and two N atoms of two tcm^- anions, forming a distorted octahedral geometry with the tcm^- ligands mutually cis. The equatorial plane is therefore formed by two N atoms (N1, N3) of the cyclen unit and the N5 and N8 atoms of the coordinating tcm^- anions. The apical sites are occupied by N2 and N4 from the cyclen ligand, Fig. 1.

In (II), the copper cation is also bound to the four N atoms (N1, N2, N3, N4) of a cyclen ligand but in the basal plane with the N5 atom of the tcm^- ligand in an apical site, forming a five-coordinate cation with a distorted square-pyramidal coordination geometry. The second tcm^- anion does not enter the inner coordination sphere of the metal (Fig. 2), but acts as a counter-anion that is linked to the cation in the asymmetric unit through an N1—H1···N9 hydrogen bond (Fig. 2).

The Ni—N(cyclen) distances in (I) [2.051 (3)–2.134 (3) Å] show some variation, but these values are similar to the corresponding distances in other polyamine-containing nickel complexes (Shirase et al., 2009; Patel et al., 2008). The Ni—N(tcm) distances, 2.062 (3) and 2.101 (3) Å, Table 1, of (I) are not unusual, and these data are comparable to the corresponding distances in other closely related nickel complexes with tcm^- ligands (Luo et al., 2014, 2006).

In (II), the Cu—N(cyclen) distances range from 2.014 (2) to 2.034 (2) Å, and are similar to distances found in other reported copper complexes with polyamine co-ligands (Qi et al., 2014; Belda et al., 2013). In (II), the Cu—N(tcm) distance [2.097 (2) Å, Table 2) is also similar to the distances found in previously reported copper tcm^- complexes (Yuste et al., 2007, 2008).

Each tcm^- ligand is almost planar, with the mean deviations from the planes through all atoms of the coordinated tcm^- anions being 0.0128 and 0.0322 Å, respectively in (I). For (II), the corresponding deviations from the planes of the coordinating tcm^- anion and the tcm^- counter-anion are 0.0211 and 0.0074 Å respectively. Bond lengths and angles within the anions are also in good agreement with those found in other tcm^- complexes (Batten et al., 1999; Yuste et al., 2008).

Supramolecular features top

In the crystal structure of (I), each complex molecule is linked to five others by a series of N—H···N and C—H···N hydrogen bonds. N1—H1···N10 and N2—H2···N6 hydrogen bonds each form inversion dimers, joining the complex molecule to two neighbouring molecules and generating R²₂(16) ring motifs (Bernstein et al., 1995). N3—H3···N7 and N4—H4···N6 hydrogen bonds link two additional complex molecules. A C4—H4B···N9 contact involves the fifth complex. This array of contacts combines to generate an extensive the three-dimensional network (Fig. 3, Table 3).

In the crystal structure of (II), N1—H1···N6 and N3—H3···N7 hydrogen bonds each form inversion dimers, also linking the complex cation to two neighbouring cations and generating R²₂(16) ring motifs. Each complex molecule is also linked via N—H···N and C—H···N hydrogen bonds to two adjacent complex cations and three tcm^- anions, forming another extensive three-dimensional network (Fig. 4, Table 4).

Database survey top

Structures of transition-metal complexes with two or more tcm^- ligands are quite common with 47 unique compounds recorded in the Cambridge Crystallographic Database (Version 5.36, November 2014 with two updates; Groom & Allen, 2014). Of these the majority, 35, are polymeric or oligomeric systems. Five of these are Ni^II complexes but only two of them [tris(2-aminoethyl)amine]bis(tricyanomethanide)nickel(II) (Luo et al., 2014) and cis-bis(tricyanomethanide-κN)[tris(2-aminoethyl)amine-κ⁴N]nickel(II) (Potocnak et al., 2007) are mononuclear, each with a distorted octahedral coordination environment and with the tcm^- ligands mutually cis.

The number of transition-metal complexes with the cyclen ligand is huge, with 116 unique hits in the current Database. Among these, there are twenty Ni^II complexes and nine Cu^II complexes. Representative Ni complexes include [Ni(cyclen)]₂[Pt(CN)₄]₂·6H₂O and [Ni(cyclen)]₂[(Ni(CN)₄)]₂·6H₂O (Yeung et al., 2006), while examples of Cu complexes are [Cu(cyclen)(Au(CN)₂)]⁺·[Au(CN)₂]^- (Yeung et al., 2000) and [Cu(cyclen)(NO₃)]⁺·NO₃^- (Clay et al., 1979). However, no complexes containing a transition metal coordinated by both cyclen and tcm^- ligands were found.

Synthesis and crystallization top

Refinement top

In (I), the H1, H2, H3 and H4 atoms bound to the amine N atoms were found in a difference Fourier map and refined freely with isotropic displacement parameters. The N—H distances ranged from 0.90 (2) to 0.95 (2) Å. H atoms bound to carbon were constrained to an ideal geometry with C—H distances of 0.99 Å, and with U_iso = 1.2U_eq(C) for CH₂. In (II), the amine H1, H2, H3 and H4 atoms and the H atoms linked to carbon were refined similarly. The N—H distances were in the range 0.84 (3) to 0.94 (2) Å.

Related literature top

For related literature, see: Abrahams et al. (2003); Batten et al. (1998, 1999, 2000); Belda et al. (2013); Bernstein et al. (1995); Chainok et al. (2012); Clay et al. (1979); Feyerherm et al. (2004); Groom & Allen (2014); Herchel et al. (2014); Hodgson et al. (2014); Hoshino et al. (1999); Hunt et al. (2015); Luo et al. (2006, 2014); Manson & Schlueter (2004); Manson et al. (1998, 2000); Patel et al. (2008); Potocnak et al. (2007); Qi et al. (2014); Shirase et al. (2009); Váhovská et al. (2014); Vreshch et al. (2013); Yeung et al. (2000, 2006); Yuste et al. (2007, 2008).

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view of the molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. The hydrogen bond between the cation and anion is shown as a dashed line.
	Fig. 3. The three-dimensional network of (I), formed by hydrogen-bonding interactions, viewed along the b axis. Hydrogen bonds are drawn as dashed lines.
	Fig. 4. The three-dimensional network of (II), formed by hydrogen-bonding interactions, viewed along the a axis. Hydrogen bonds are drawn as dashed lines.

(I) (1,4,7,10-Tetraazacyclododecane-κ⁴N)bis(tricyanomethanido-κN)nickel top

Crystal data top

[Ni(C₄N₃)₂(C₈H₂₀N₄)]	F(000) = 856
M_r = 411.13	D_x = 1.405 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.6300 (12) Å	Cell parameters from 3344 reflections
b = 11.0150 (12) Å	θ = 2.5–27.8°
c = 17.1771 (18) Å	µ = 1.02 mm⁻¹
β = 104.828 (2)°	T = 173 K
V = 1944.3 (4) Å³	Block, purple
Z = 4	0.06 × 0.05 × 0.04 mm

Data collection top

Bruker APEXII CCD diffractometer	3460 reflections with I > 2σ(I)
ϕ and ω scans	R_int = 0.032
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θ_max = 27.9°, θ_min = 2.0°
T_min = 0.670, T_max = 0.746	h = −10→13
12264 measured reflections	k = −14→14
4611 independent reflections	l = −20→22

Refinement top

Refinement on F²	12 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.136	w = 1/[σ²(F_o²) + (0.0532P)² + 3.2428P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.004
4611 reflections	Δρ_max = 1.05 e Å⁻³
259 parameters	Δρ_min = −0.67 e Å⁻³

Crystal data top

[Ni(C₄N₃)₂(C₈H₂₀N₄)]	V = 1944.3 (4) Å³
M_r = 411.13	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.6300 (12) Å	µ = 1.02 mm⁻¹
b = 11.0150 (12) Å	T = 173 K
c = 17.1771 (18) Å	0.06 × 0.05 × 0.04 mm
β = 104.828 (2)°

Data collection top

Bruker APEXII CCD diffractometer	4611 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3460 reflections with I > 2σ(I)
T_min = 0.670, T_max = 0.746	R_int = 0.032
12264 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	12 restraints
wR(F²) = 0.136	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 1.05 e Å⁻³
4611 reflections	Δρ_min = −0.67 e Å⁻³
259 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	0.31796 (4)	0.67335 (4)	0.21935 (2)	0.02888 (13)
N1	0.2130 (3)	0.6100 (3)	0.29576 (17)	0.0345 (6)
H1	0.279 (3)	0.589 (4)	0.337 (2)	0.064 (14)*
N2	0.2664 (3)	0.5030 (3)	0.16203 (18)	0.0443 (7)
H2	0.339 (3)	0.472 (4)	0.151 (2)	0.055 (13)*
N3	0.1611 (4)	0.7305 (3)	0.12737 (19)	0.0530 (9)
H3	0.091 (4)	0.711 (3)	0.150 (2)	0.079*
N4	0.2863 (3)	0.8444 (3)	0.26943 (19)	0.0394 (7)
H4	0.365 (3)	0.881 (4)	0.284 (3)	0.073 (15)*
C1	0.1384 (4)	0.5016 (4)	0.2615 (3)	0.0506 (10)
H1A	0.0566	0.5259	0.2224	0.061*
H1B	0.1159	0.4536	0.3048	0.061*
C2	0.2200 (4)	0.4269 (4)	0.2202 (3)	0.0553 (11)
H2A	0.2955	0.3931	0.2607	0.066*
H2B	0.1680	0.3582	0.1916	0.066*
C3	0.1642 (5)	0.5211 (5)	0.0857 (3)	0.0642 (13)
H3A	0.1869	0.4734	0.0424	0.077*
H3B	0.0802	0.4901	0.0925	0.077*
C4	0.1492 (5)	0.6485 (4)	0.0617 (3)	0.0611 (13)
H4A	0.2159	0.6691	0.0328	0.073*
H4B	0.0628	0.6597	0.0237	0.073*
C5	0.1683 (5)	0.8539 (4)	0.1225 (3)	0.0748 (17)
H5A	0.0853	0.8850	0.0880	0.090*
H5B	0.2384	0.8753	0.0965	0.090*
C6	0.1952 (4)	0.9164 (4)	0.2047 (3)	0.0549 (11)
H6A	0.2333	0.9975	0.2009	0.066*
H6B	0.1119	0.9281	0.2195	0.066*
C7	0.2311 (4)	0.8170 (4)	0.3387 (2)	0.0448 (9)
H7A	0.1834	0.8888	0.3508	0.054*
H7B	0.3027	0.7990	0.3869	0.054*
C8	0.1402 (3)	0.7099 (4)	0.3202 (2)	0.0419 (9)
H8A	0.1108	0.6868	0.3684	0.050*
H8B	0.0628	0.7303	0.2762	0.050*
N5	0.4473 (3)	0.7223 (3)	0.15041 (17)	0.0456 (8)
N6	0.5442 (3)	0.6048 (3)	−0.07283 (18)	0.0410 (7)
N7	0.8599 (3)	0.6841 (4)	0.1448 (2)	0.0676 (11)
C9	0.6177 (3)	0.6745 (3)	0.07428 (19)	0.0313 (6)
C10	0.5245 (3)	0.7011 (3)	0.11644 (19)	0.0341 (7)
C11	0.5768 (3)	0.6366 (3)	−0.0066 (2)	0.0322 (7)
C12	0.7506 (3)	0.6795 (4)	0.1130 (2)	0.0400 (8)
N8	0.4834 (3)	0.6233 (3)	0.30541 (16)	0.0351 (6)
N9	0.8889 (4)	0.7038 (4)	0.4340 (2)	0.0632 (11)
N10	0.6565 (5)	0.4491 (7)	0.5383 (3)	0.121 (3)
C13	0.6733 (3)	0.5974 (3)	0.42904 (19)	0.0324 (7)
C14	0.5682 (3)	0.6129 (3)	0.36206 (18)	0.0300 (7)
C15	0.7916 (4)	0.6567 (3)	0.4323 (2)	0.0387 (8)
C16	0.6636 (4)	0.5171 (5)	0.4895 (2)	0.0639 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0232 (2)	0.0426 (2)	0.02079 (19)	0.00588 (18)	0.00552 (14)	0.00459 (17)
N1	0.0218 (13)	0.0488 (17)	0.0330 (15)	−0.0004 (12)	0.0069 (11)	0.0090 (13)
N2	0.0386 (17)	0.0516 (19)	0.0366 (16)	0.0118 (15)	−0.0017 (13)	−0.0061 (14)
N3	0.054 (2)	0.062 (2)	0.0366 (17)	0.0311 (18)	0.0001 (15)	0.0008 (15)
N4	0.0309 (15)	0.0434 (17)	0.0468 (17)	0.0001 (13)	0.0152 (13)	0.0001 (14)
C1	0.0335 (18)	0.053 (2)	0.063 (2)	−0.0105 (18)	0.0080 (17)	0.011 (2)
C2	0.044 (2)	0.045 (2)	0.068 (3)	−0.0018 (19)	−0.001 (2)	0.002 (2)
C3	0.057 (3)	0.075 (3)	0.046 (2)	0.022 (2)	−0.013 (2)	−0.016 (2)
C4	0.062 (3)	0.064 (3)	0.040 (2)	−0.017 (2)	−0.0205 (19)	0.0129 (19)
C5	0.076 (3)	0.044 (2)	0.078 (3)	−0.003 (2)	−0.028 (3)	0.016 (2)
C6	0.062 (3)	0.049 (2)	0.065 (3)	0.022 (2)	0.036 (2)	0.020 (2)
C7	0.0416 (19)	0.061 (2)	0.0325 (18)	0.0042 (19)	0.0109 (15)	−0.0095 (17)
C8	0.0279 (16)	0.070 (3)	0.0313 (17)	0.0059 (17)	0.0147 (14)	0.0073 (17)
N5	0.0432 (17)	0.069 (2)	0.0291 (15)	0.0105 (16)	0.0171 (13)	0.0107 (14)
N6	0.0416 (17)	0.0470 (18)	0.0360 (16)	−0.0025 (14)	0.0126 (13)	−0.0032 (13)
N7	0.0364 (18)	0.105 (3)	0.055 (2)	0.000 (2)	0.0007 (16)	−0.005 (2)
C9	0.0294 (15)	0.0376 (17)	0.0285 (15)	−0.0012 (14)	0.0103 (12)	0.0040 (14)
C10	0.0337 (17)	0.0421 (19)	0.0264 (15)	0.0010 (14)	0.0075 (13)	0.0079 (13)
C11	0.0275 (16)	0.0355 (17)	0.0356 (18)	−0.0026 (13)	0.0119 (13)	0.0037 (14)
C12	0.0337 (18)	0.051 (2)	0.0357 (18)	0.0001 (17)	0.0089 (14)	−0.0001 (16)
N8	0.0265 (14)	0.0517 (17)	0.0266 (13)	−0.0004 (13)	0.0061 (11)	0.0061 (12)
N9	0.044 (2)	0.064 (2)	0.069 (3)	−0.0160 (18)	−0.0102 (18)	0.0013 (19)
N10	0.062 (3)	0.217 (7)	0.075 (3)	−0.003 (4)	0.002 (2)	0.095 (4)
C13	0.0279 (16)	0.0429 (18)	0.0251 (15)	0.0065 (14)	0.0043 (12)	−0.0006 (13)
C14	0.0276 (15)	0.0385 (17)	0.0253 (15)	0.0039 (13)	0.0093 (12)	0.0003 (13)
C15	0.0366 (19)	0.0402 (19)	0.0315 (17)	0.0023 (16)	−0.0056 (14)	−0.0071 (14)
C16	0.0330 (19)	0.120 (4)	0.035 (2)	0.007 (2)	0.0033 (16)	0.028 (2)

Geometric parameters (Å, º) top

Ni1—N1	2.051 (3)	C3—H3B	0.9900
Ni1—N8	2.062 (3)	C4—H4A	0.9900
Ni1—N3	2.080 (3)	C4—H4B	0.9900
Ni1—N5	2.101 (3)	C5—C6	1.529 (7)
Ni1—N2	2.125 (3)	C5—H5A	0.9900
Ni1—N4	2.134 (3)	C5—H5B	0.9900
N1—C8	1.467 (5)	C6—H6A	0.9900
N1—C1	1.470 (5)	C6—H6B	0.9900
N1—H1	0.90 (2)	C7—C8	1.506 (6)
N2—C2	1.482 (6)	C7—H7A	0.9900
N2—C3	1.486 (5)	C7—H7B	0.9900
N2—H2	0.91 (2)	C8—H8A	0.9900
N3—C5	1.366 (6)	C8—H8B	0.9900
N3—C4	1.425 (6)	N5—C10	1.146 (4)
N3—H3	0.95 (2)	N6—C11	1.155 (4)
N4—C7	1.487 (5)	N7—C12	1.152 (5)
N4—C6	1.501 (5)	C9—C12	1.399 (5)
N4—H4	0.90 (2)	C9—C10	1.400 (4)
C1—C2	1.499 (6)	C9—C11	1.409 (5)
C1—H1A	0.9900	N8—C14	1.151 (4)
C1—H1B	0.9900	N9—C15	1.150 (5)
C2—H2A	0.9900	N10—C16	1.140 (6)
C2—H2B	0.9900	C13—C16	1.388 (5)
C3—C4	1.460 (6)	C13—C14	1.394 (4)
C3—H3A	0.9900	C13—C15	1.406 (5)

N1—Ni1—N8	87.4 (1)	C4—C3—N2	112.3 (4)
N1—Ni1—N3	97.3 (1)	C4—C3—H3A	109.1
N8—Ni1—N3	175.3 (1)	N2—C3—H3A	109.1
N1—Ni1—N5	171.8 (1)	C4—C3—H3B	109.1
N8—Ni1—N5	84.9 (1)	N2—C3—H3B	109.1
N3—Ni1—N5	90.4 (1)	H3A—C3—H3B	107.9
N1—Ni1—N2	83.0 (1)	N3—C4—C3	113.9 (4)
N8—Ni1—N2	99.7 (1)	N3—C4—H4A	108.8
N3—Ni1—N2	81.6 (1)	C3—C4—H4A	108.8
N5—Ni1—N2	95.4 (1)	N3—C4—H4B	108.8
N1—Ni1—N4	82.8 (1)	C3—C4—H4B	108.8
N8—Ni1—N4	98.1 (1)	H4A—C4—H4B	107.7
N3—Ni1—N4	82.0 (1)	N3—C5—C6	113.1 (4)
N5—Ni1—N4	101.2 (1)	N3—C5—H5A	109.0
N2—Ni1—N4	156.7 (1)	C6—C5—H5A	109.0
C8—N1—C1	117.0 (3)	N3—C5—H5B	109.0
C8—N1—Ni1	109.9 (2)	C6—C5—H5B	109.0
C1—N1—Ni1	110.3 (2)	H5A—C5—H5B	107.8
C8—N1—H1	109 (3)	N4—C6—C5	112.3 (3)
C1—N1—H1	110 (3)	N4—C6—H6A	109.1
Ni1—N1—H1	99 (3)	C5—C6—H6A	109.1
C2—N2—C3	112.1 (4)	N4—C6—H6B	109.1
C2—N2—Ni1	106.1 (2)	C5—C6—H6B	109.1
C3—N2—Ni1	109.5 (3)	H6A—C6—H6B	107.9
C2—N2—H2	112 (3)	N4—C7—C8	110.7 (3)
C3—N2—H2	110 (3)	N4—C7—H7A	109.5
Ni1—N2—H2	107 (3)	C8—C7—H7A	109.5
C5—N3—C4	125.3 (4)	N4—C7—H7B	109.5
C5—N3—Ni1	107.5 (3)	C8—C7—H7B	109.5
C4—N3—Ni1	107.5 (3)	H7A—C7—H7B	108.1
C5—N3—H3	108 (2)	N1—C8—C7	106.9 (3)
C4—N3—H3	105 (2)	N1—C8—H8A	110.3
Ni1—N3—H3	101 (3)	C7—C8—H8A	110.3
C7—N4—C6	112.9 (3)	N1—C8—H8B	110.3
C7—N4—Ni1	106.2 (2)	C7—C8—H8B	110.3
C6—N4—Ni1	107.8 (2)	H8A—C8—H8B	108.6
C7—N4—H4	113 (3)	C10—N5—Ni1	153.1 (3)
C6—N4—H4	111 (3)	C12—C9—C10	120.5 (3)
Ni1—N4—H4	106 (3)	C12—C9—C11	120.0 (3)
N1—C1—C2	108.5 (3)	C10—C9—C11	119.4 (3)
N1—C1—H1A	110.0	N5—C10—C9	179.3 (4)
C2—C1—H1A	110.0	N6—C11—C9	179.3 (4)
N1—C1—H1B	110.0	N7—C12—C9	179.7 (5)
C2—C1—H1B	110.0	C14—N8—Ni1	166.7 (3)
H1A—C1—H1B	108.4	C16—C13—C14	119.9 (3)
N2—C2—C1	109.9 (3)	C16—C13—C15	120.2 (3)
N2—C2—H2A	109.7	C14—C13—C15	119.7 (3)
C1—C2—H2A	109.7	N8—C14—C13	177.8 (4)
N2—C2—H2B	109.7	N9—C15—C13	178.7 (4)
C1—C2—H2B	109.7	N10—C16—C13	178.5 (7)
H2A—C2—H2B	108.2

C8—N1—C1—C2	164.6 (3)	C4—N3—C5—C6	−173.8 (4)
Ni1—N1—C1—C2	38.0 (4)	Ni1—N3—C5—C6	−46.3 (5)
C3—N2—C2—C1	−79.0 (4)	C7—N4—C6—C5	−124.4 (4)
Ni1—N2—C2—C1	40.5 (4)	Ni1—N4—C6—C5	−7.4 (4)
N1—C1—C2—N2	−53.1 (4)	N3—C5—C6—N4	36.6 (6)
C2—N2—C3—C4	130.8 (4)	C6—N4—C7—C8	80.8 (4)
Ni1—N2—C3—C4	13.3 (5)	Ni1—N4—C7—C8	−37.2 (3)
C5—N3—C4—C3	170.8 (5)	C1—N1—C8—C7	−170.0 (3)
Ni1—N3—C4—C3	43.3 (5)	Ni1—N1—C8—C7	−43.2 (3)
N2—C3—C4—N3	−38.4 (6)	N4—C7—C8—N1	54.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···N7ⁱ	0.99	2.74	3.665 (5)	156
N3—H3···N7ⁱ	0.95 (2)	2.45 (3)	3.330 (5)	154 (4)
N1—H1···N10ⁱⁱ	0.90 (2)	2.11 (3)	2.907 (5)	148 (4)
N2—H2···N6ⁱⁱⁱ	0.91 (2)	2.22 (3)	3.064 (4)	155 (4)
C4—H4B···N9^iv	0.99	2.57	3.467 (5)	151
N4—H4···N6^v	0.90 (2)	2.70 (4)	3.372 (4)	133 (4)
C7—H7B···N6^v	0.99	2.70	3.397 (5)	128

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+1, −z; (iv) x−1, −y+3/2, z−1/2; (v) x, −y+3/2, z+1/2.

(II) (1,4,7,10-Tetraazacyclododecane-κ⁴N)(tricyanomethanido-κN)copper tricyanomethanide top

Crystal data top

[Cu(C₄N₃)(C₈H₂₀N₄)](C₄N₃)	Z = 2
M_r = 415.96	F(000) = 430
Triclinic, P1	D_x = 1.417 Mg m⁻³
a = 7.4074 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.552 (2) Å	Cell parameters from 3012 reflections
c = 11.625 (2) Å	θ = 2.5–27.2°
α = 89.187 (3)°	µ = 1.14 mm⁻¹
β = 88.236 (3)°	T = 173 K
γ = 78.579 (3)°	Block, blue
V = 974.6 (3) Å³	0.10 × 0.07 × 0.06 mm

Data collection top

Bruker APEXII CCD diffractometer	3639 reflections with I > 2σ(I)
ϕ and ω scans	R_int = 0.021
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θ_max = 27.2°, θ_min = 1.8°
T_min = 0.680, T_max = 0.746	h = −9→9
6936 measured reflections	k = −14→12
4267 independent reflections	l = −14→14

Refinement top

Refinement on F²	3 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0554P)² + 0.4093P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max = 0.001
4267 reflections	Δρ_max = 0.43 e Å⁻³
260 parameters	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Cu(C₄N₃)(C₈H₂₀N₄)](C₄N₃)	γ = 78.579 (3)°
M_r = 415.96	V = 974.6 (3) Å³
Triclinic, P1	Z = 2
a = 7.4074 (15) Å	Mo Kα radiation
b = 11.552 (2) Å	µ = 1.14 mm⁻¹
c = 11.625 (2) Å	T = 173 K
α = 89.187 (3)°	0.10 × 0.07 × 0.06 mm
β = 88.236 (3)°

Data collection top

Bruker APEXII CCD diffractometer	4267 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3639 reflections with I > 2σ(I)
T_min = 0.680, T_max = 0.746	R_int = 0.021
6936 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	3 restraints
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	Δρ_max = 0.43 e Å⁻³
4267 reflections	Δρ_min = −0.30 e Å⁻³
260 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
Cu1	0.19693 (4)	0.78312 (3)	0.28777 (2)	0.01966 (11)
N1	0.1556 (3)	0.70853 (19)	0.44341 (18)	0.0247 (5)
N2	0.3779 (3)	0.63230 (19)	0.25312 (19)	0.0255 (5)
H2	0.499 (3)	0.629 (3)	0.275 (3)	0.030 (8)*
N3	0.1539 (3)	0.7915 (2)	0.11666 (19)	0.0262 (5)
H3	0.244 (5)	0.823 (4)	0.078 (3)	0.069 (13)*
N4	−0.0693 (3)	0.8686 (2)	0.30501 (19)	0.0235 (5)
H4	−0.080 (5)	0.943 (3)	0.305 (3)	0.032 (9)*
C1	0.2693 (4)	0.5872 (2)	0.4435 (2)	0.0309 (6)
H1A	0.2057	0.5339	0.4899	0.037*
H1B	0.3893	0.5877	0.4784	0.037*
C2	0.2999 (4)	0.5431 (2)	0.3211 (2)	0.0284 (6)
H2A	0.3864	0.4659	0.3191	0.034*
H2B	0.1818	0.5331	0.2888	0.034*
C3	0.3874 (4)	0.6128 (3)	0.1270 (2)	0.0320 (6)
H3A	0.4172	0.5271	0.1109	0.038*
H3B	0.4854	0.6495	0.0911	0.038*
C4	0.2027 (4)	0.6673 (3)	0.0775 (2)	0.0309 (6)
H4A	0.2107	0.6645	−0.0076	0.037*
H4B	0.1076	0.6232	0.1047	0.037*
C5	−0.0403 (4)	0.8503 (3)	0.0989 (2)	0.0314 (6)
H5A	−0.0867	0.8182	0.0296	0.038*
H5B	−0.0483	0.9362	0.0871	0.038*
C6	−0.1553 (4)	0.8288 (2)	0.2029 (2)	0.0278 (6)
H6A	−0.2830	0.8737	0.1960	0.033*
H6B	−0.1588	0.7438	0.2102	0.033*
C7	−0.1439 (4)	0.8372 (3)	0.4181 (2)	0.0309 (6)
H7A	−0.2777	0.8392	0.4133	0.037*
H7B	−0.1257	0.8950	0.4766	0.037*
C8	−0.0455 (4)	0.7147 (3)	0.4526 (2)	0.0297 (6)
H8A	−0.0816	0.6971	0.5326	0.036*
H8B	−0.0804	0.6553	0.4015	0.036*
N5	0.3467 (3)	0.9172 (2)	0.3085 (2)	0.0302 (5)
N6	0.4994 (4)	1.2516 (2)	0.4130 (3)	0.0458 (7)
N7	0.6191 (5)	1.1120 (3)	0.0561 (3)	0.0557 (9)
C9	0.4066 (3)	1.0003 (2)	0.2868 (2)	0.0234 (5)
C10	0.4822 (4)	1.0987 (2)	0.2587 (2)	0.0284 (6)
C11	0.4908 (4)	1.1832 (2)	0.3437 (3)	0.0317 (6)
C12	0.5559 (4)	1.1083 (3)	0.1476 (3)	0.0370 (7)
N8	0.2233 (3)	0.4808 (2)	0.7239 (2)	0.0346 (6)
N9	0.0455 (4)	0.8693 (2)	0.7001 (2)	0.0401 (6)
N10	−0.2516 (5)	0.6493 (3)	0.9329 (3)	0.0533 (8)
C13	0.0029 (4)	0.6708 (2)	0.7860 (2)	0.0261 (5)
C14	0.1277 (4)	0.5668 (2)	0.7519 (2)	0.0250 (5)
C15	0.0259 (4)	0.7809 (2)	0.7396 (2)	0.0283 (6)
C16	−0.1390 (4)	0.6607 (3)	0.8655 (3)	0.0341 (6)
H1	0.182 (5)	0.754 (3)	0.497 (3)	0.050 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01993 (17)	0.01743 (17)	0.02207 (17)	−0.00544 (11)	0.00296 (11)	0.00163 (11)
N1	0.0346 (13)	0.0202 (11)	0.0210 (10)	−0.0094 (9)	−0.0035 (9)	0.0010 (8)
N2	0.0224 (11)	0.0236 (11)	0.0300 (12)	−0.0038 (9)	0.0000 (9)	−0.0002 (9)
N3	0.0267 (12)	0.0276 (12)	0.0233 (11)	−0.0044 (9)	0.0063 (9)	0.0034 (9)
N4	0.0241 (11)	0.0175 (11)	0.0287 (11)	−0.0041 (8)	0.0034 (9)	−0.0007 (9)
C1	0.0408 (17)	0.0241 (13)	0.0281 (14)	−0.0071 (12)	−0.0062 (12)	0.0073 (11)
C2	0.0348 (15)	0.0184 (12)	0.0327 (14)	−0.0066 (11)	−0.0027 (11)	0.0021 (10)
C3	0.0290 (15)	0.0337 (15)	0.0299 (14)	0.0005 (11)	0.0095 (11)	−0.0043 (11)
C4	0.0348 (16)	0.0322 (15)	0.0239 (13)	−0.0030 (12)	0.0045 (11)	−0.0043 (11)
C5	0.0316 (15)	0.0304 (15)	0.0292 (14)	0.0006 (11)	−0.0039 (11)	0.0057 (11)
C6	0.0213 (13)	0.0256 (13)	0.0354 (15)	−0.0022 (10)	−0.0009 (11)	0.0000 (11)
C7	0.0306 (15)	0.0320 (15)	0.0296 (14)	−0.0062 (11)	0.0095 (11)	−0.0032 (11)
C8	0.0376 (16)	0.0313 (15)	0.0235 (13)	−0.0160 (12)	0.0068 (11)	0.0013 (11)
N5	0.0313 (13)	0.0243 (12)	0.0369 (13)	−0.0107 (10)	0.0020 (10)	0.0006 (10)
N6	0.0563 (19)	0.0349 (15)	0.0511 (17)	−0.0208 (13)	0.0016 (14)	−0.0070 (13)
N7	0.066 (2)	0.0471 (18)	0.0529 (18)	−0.0133 (15)	0.0308 (16)	0.0102 (14)
C9	0.0169 (12)	0.0253 (13)	0.0276 (13)	−0.0041 (10)	0.0028 (10)	−0.0001 (10)
C10	0.0309 (15)	0.0214 (13)	0.0344 (14)	−0.0099 (11)	0.0051 (11)	0.0008 (11)
C11	0.0303 (15)	0.0237 (14)	0.0432 (16)	−0.0110 (11)	0.0021 (12)	0.0051 (12)
C12	0.0390 (17)	0.0228 (14)	0.0495 (18)	−0.0085 (12)	0.0086 (14)	0.0048 (12)
N8	0.0275 (13)	0.0274 (13)	0.0476 (15)	−0.0024 (10)	−0.0018 (11)	−0.0020 (11)
N9	0.0374 (15)	0.0264 (13)	0.0558 (17)	−0.0061 (11)	0.0052 (12)	0.0008 (11)
N10	0.0554 (19)	0.0436 (17)	0.0609 (19)	−0.0139 (14)	0.0266 (16)	−0.0067 (14)
C13	0.0276 (14)	0.0237 (13)	0.0275 (13)	−0.0063 (10)	0.0004 (11)	−0.0015 (10)
C14	0.0237 (13)	0.0263 (14)	0.0265 (13)	−0.0079 (11)	−0.0039 (10)	0.0013 (10)
C15	0.0233 (13)	0.0270 (14)	0.0345 (14)	−0.0044 (11)	0.0022 (11)	−0.0066 (11)
C16	0.0372 (17)	0.0253 (14)	0.0406 (16)	−0.0084 (12)	0.0040 (13)	−0.0056 (12)

Geometric parameters (Å, º) top

Cu1—N2	2.014 (2)	C4—H4A	0.9900
Cu1—N3	2.022 (2)	C4—H4B	0.9900
Cu1—N4	2.029 (2)	C5—C6	1.504 (4)
Cu1—N1	2.034 (2)	C5—H5A	0.9900
Cu1—N5	2.097 (2)	C5—H5B	0.9900
N1—C8	1.477 (4)	C6—H6A	0.9900
N1—C1	1.486 (4)	C6—H6B	0.9900
N1—H1	0.87 (2)	C7—C8	1.513 (4)
N2—C3	1.484 (3)	C7—H7A	0.9900
N2—C2	1.485 (3)	C7—H7B	0.9900
N2—H2	0.94 (2)	C8—H8A	0.9900
N3—C4	1.483 (4)	C8—H8B	0.9900
N3—C5	1.483 (4)	N5—C9	1.157 (3)
N3—H3	0.92 (2)	N6—C11	1.148 (4)
N4—C7	1.478 (3)	N7—C12	1.152 (4)
N4—C6	1.484 (4)	C9—C10	1.393 (4)
N4—H4	0.84 (3)	C10—C12	1.399 (4)
C1—C2	1.514 (4)	C10—C11	1.411 (4)
C1—H1A	0.9900	N8—C14	1.145 (4)
C1—H1B	0.9900	N9—C15	1.147 (4)
C2—H2A	0.9900	N10—C16	1.152 (4)
C2—H2B	0.9900	C13—C16	1.399 (4)
C3—C4	1.515 (4)	C13—C15	1.413 (4)
C3—H3A	0.9900	C13—C14	1.416 (4)
C3—H3B	0.9900

N2—Cu1—N3	85.61 (9)	C4—C3—H3A	109.9
N2—Cu1—N4	148.42 (9)	N2—C3—H3B	109.9
N3—Cu1—N4	85.57 (9)	C4—C3—H3B	109.9
N2—Cu1—N1	86.11 (9)	H3A—C3—H3B	108.3
N3—Cu1—N1	148.55 (9)	N3—C4—C3	107.7 (2)
N4—Cu1—N1	85.79 (9)	N3—C4—H4A	110.2
N2—Cu1—N5	107.9 (1)	C3—C4—H4A	110.2
N3—Cu1—N5	101.87 (9)	N3—C4—H4B	110.2
N4—Cu1—N5	103.57 (9)	C3—C4—H4B	110.2
N1—Cu1—N5	109.54 (9)	H4A—C4—H4B	108.5
C8—N1—C1	115.0 (2)	N3—C5—C6	109.0 (2)
C8—N1—Cu1	104.5 (2)	N3—C5—H5A	109.9
C1—N1—Cu1	107.4 (2)	C6—C5—H5A	109.9
C8—N1—H1	106 (3)	N3—C5—H5B	109.9
C1—N1—H1	114 (3)	C6—C5—H5B	109.9
Cu1—N1—H1	109 (3)	H5A—C5—H5B	108.3
C3—N2—C2	114.3 (2)	N4—C6—C5	107.4 (2)
C3—N2—Cu1	109.0 (2)	N4—C6—H6A	110.2
C2—N2—Cu1	102.7 (2)	C5—C6—H6A	110.2
C3—N2—H2	106 (2)	N4—C6—H6B	110.2
C2—N2—H2	109 (2)	C5—C6—H6B	110.2
Cu1—N2—H2	116 (2)	H6A—C6—H6B	108.5
C4—N3—C5	114.9 (2)	N4—C7—C8	109.2 (2)
C4—N3—Cu1	104.9 (2)	N4—C7—H7A	109.8
C5—N3—Cu1	108.2 (2)	C8—C7—H7A	109.8
C4—N3—H3	100 (3)	N4—C7—H7B	109.8
C5—N3—H3	117 (3)	C8—C7—H7B	109.8
Cu1—N3—H3	111 (3)	H7A—C7—H7B	108.3
C7—N4—C6	115.8 (2)	N1—C8—C7	109.2 (2)
C7—N4—Cu1	108.7 (2)	N1—C8—H8A	109.8
C6—N4—Cu1	102.8 (2)	C7—C8—H8A	109.8
C7—N4—H4	106 (2)	N1—C8—H8B	109.8
C6—N4—H4	111 (2)	C7—C8—H8B	109.8
Cu1—N4—H4	112 (2)	H8A—C8—H8B	108.3
N1—C1—C2	109.4 (2)	C9—N5—Cu1	158.7 (2)
N1—C1—H1A	109.8	N5—C9—C10	178.4 (3)
C2—C1—H1A	109.8	C9—C10—C12	118.8 (3)
N1—C1—H1B	109.8	C9—C10—C11	119.6 (2)
C2—C1—H1B	109.8	C12—C10—C11	121.4 (2)
H1A—C1—H1B	108.2	N6—C11—C10	179.4 (4)
N2—C2—C1	107.4 (2)	N7—C12—C10	177.6 (3)
N2—C2—H2A	110.2	C16—C13—C15	122.2 (3)
C1—C2—H2A	110.2	C16—C13—C14	118.5 (2)
N2—C2—H2B	110.2	C15—C13—C14	119.3 (2)
C1—C2—H2B	110.2	N8—C14—C13	177.6 (3)
H2A—C2—H2B	108.5	N9—C15—C13	178.8 (3)
N2—C3—C4	108.8 (2)	N10—C16—C13	177.6 (4)
N2—C3—H3A	109.9

C8—N1—C1—C2	89.8 (3)	C4—N3—C5—C6	89.1 (3)
Cu1—N1—C1—C2	−26.1 (3)	Cu1—N3—C5—C6	−27.7 (3)
C3—N2—C2—C1	−170.3 (2)	C7—N4—C6—C5	−170.4 (2)
Cu1—N2—C2—C1	−52.5 (2)	Cu1—N4—C6—C5	−52.0 (2)
N1—C1—C2—N2	53.8 (3)	N3—C5—C6—N4	54.4 (3)
C2—N2—C3—C4	84.5 (3)	C6—N4—C7—C8	86.1 (3)
Cu1—N2—C3—C4	−29.6 (3)	Cu1—N4—C7—C8	−29.0 (3)
C5—N3—C4—C3	−166.7 (2)	C1—N1—C8—C7	−164.2 (2)
Cu1—N3—C4—C3	−48.1 (2)	Cu1—N1—C8—C7	−46.6 (2)
N2—C3—C4—N3	52.5 (3)	N4—C7—C8—N1	51.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N9	0.87 (2)	2.79 (3)	3.525 (4)	143 (3)
C1—H1B···N6ⁱ	0.99	2.54	3.273 (4)	131
N1—H1···N6ⁱ	0.87 (2)	2.60 (3)	3.206 (4)	127 (3)
N4—H4···N9ⁱⁱ	0.84 (3)	2.24 (4)	3.067 (3)	168 (3)
N3—H3···N7ⁱⁱⁱ	0.92 (2)	2.05 (2)	2.928 (3)	159 (4)
N2—H2···N8^iv	0.94 (2)	2.19 (2)	3.003 (3)	144 (3)
C3—H3B···N10^v	0.99	2.64	3.531 (4)	150
C8—H8B···N8^vi	0.99	2.56	3.538 (4)	171
C3—H3A···N10^vi	0.99	2.64	3.460 (4)	140

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

Selected geometric parameters (Å, º) for (I) top

Ni1—N1	2.051 (3)	Ni1—N5	2.101 (3)
Ni1—N8	2.062 (3)	Ni1—N2	2.125 (3)
Ni1—N3	2.080 (3)	Ni1—N4	2.134 (3)

N1—Ni1—N8	87.4 (1)	N3—Ni1—N2	81.6 (1)
N1—Ni1—N3	97.3 (1)	N5—Ni1—N2	95.4 (1)
N8—Ni1—N3	175.3 (1)	N1—Ni1—N4	82.8 (1)
N1—Ni1—N5	171.8 (1)	N8—Ni1—N4	98.1 (1)
N8—Ni1—N5	84.9 (1)	N3—Ni1—N4	82.0 (1)
N3—Ni1—N5	90.4 (1)	N5—Ni1—N4	101.2 (1)
N1—Ni1—N2	83.0 (1)	N2—Ni1—N4	156.7 (1)
N8—Ni1—N2	99.7 (1)

Selected geometric parameters (Å, º) for (II) top

Cu1—N2	2.014 (2)	Cu1—N1	2.034 (2)
Cu1—N3	2.022 (2)	Cu1—N5	2.097 (2)
Cu1—N4	2.029 (2)

N2—Cu1—N3	85.61 (9)	N4—Cu1—N1	85.79 (9)
N2—Cu1—N4	148.42 (9)	N2—Cu1—N5	107.9 (1)
N3—Cu1—N4	85.57 (9)	N3—Cu1—N5	101.87 (9)
N2—Cu1—N1	86.11 (9)	N4—Cu1—N5	103.57 (9)
N3—Cu1—N1	148.55 (9)	N1—Cu1—N5	109.54 (9)

Hydrogen-bond geometry (Å, º) for (I) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···N7ⁱ	0.99	2.74	3.665 (5)	155.7
N3—H3···N7ⁱ	0.95 (2)	2.45 (3)	3.330 (5)	154 (4)
N1—H1···N10ⁱⁱ	0.90 (2)	2.11 (3)	2.907 (5)	148 (4)
N2—H2···N6ⁱⁱⁱ	0.91 (2)	2.22 (3)	3.064 (4)	155 (4)
C4—H4B···N9^iv	0.99	2.57	3.467 (5)	150.9
N4—H4···N6^v	0.90 (2)	2.70 (4)	3.372 (4)	133 (4)
C7—H7B···N6^v	0.99	2.70	3.397 (5)	127.7

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+1, −z; (iv) x−1, −y+3/2, z−1/2; (v) x, −y+3/2, z+1/2.

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N9	0.87 (2)	2.79 (3)	3.525 (4)	143 (3)
C1—H1B···N6ⁱ	0.99	2.54	3.273 (4)	130.7
N1—H1···N6ⁱ	0.87 (2)	2.60 (3)	3.206 (4)	127 (3)
N4—H4···N9ⁱⁱ	0.84 (3)	2.24 (4)	3.067 (3)	168 (3)
N3—H3···N7ⁱⁱⁱ	0.92 (2)	2.05 (2)	2.928 (3)	159 (4)
N2—H2···N8^iv	0.94 (2)	2.19 (2)	3.003 (3)	144 (3)
C3—H3B···N10^v	0.99	2.64	3.531 (4)	150.3
C8—H8B···N8^vi	0.99	2.56	3.538 (4)	170.9
C3—H3A···N10^vi	0.99	2.64	3.460 (4)	140.2

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

Experimental details

	(I)	(II)
Crystal data
Chemical formula	[Ni(C₄N₃)₂(C₈H₂₀N₄)]	[Cu(C₄N₃)(C₈H₂₀N₄)](C₄N₃)
M_r	411.13	415.96
Crystal system, space group	Monoclinic, P2₁/c	Triclinic, P1
Temperature (K)	173	173
a, b, c (Å)	10.6300 (12), 11.0150 (12), 17.1771 (18)	7.4074 (15), 11.552 (2), 11.625 (2)
α, β, γ (°)	90, 104.828 (2), 90	89.187 (3), 88.236 (3), 78.579 (3)
V (Å³)	1944.3 (4)	974.6 (3)
Z	4	2
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	1.02	1.14
Crystal size (mm)	0.06 × 0.05 × 0.04	0.10 × 0.07 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.670, 0.746	0.680, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	12264, 4611, 3460	6936, 4267, 3639
R_int	0.032	0.021
(sin θ/λ)_max (Å⁻¹)	0.659	0.644

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.136, 1.05	0.033, 0.110, 1.13
No. of reflections	4611	4267
No. of parameters	259	260
No. of restraints	12	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.05, −0.67	0.43, −0.30

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2015), SHELXTL (Sheldrick, 2008).

Acknowledgements

This project was supported by the Shanghai Municipal Natural Science Foundation (No. 13ZR1448600).

References

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Volume 71| Part 6| June 2015| Pages 693-697

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