Crystal structure of poly[(2,2′-bi­pyridine-κ2N,N′)tetra­kis­(μ-cyanido-κ2N:C)dinickel(II)]

Zuo, M.; Wang, H.; Xu, J.; Zhu, L.; Cui, S.

doi:10.1107/S2056989015009706

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Volume 71| Part 6| June 2015| Pages 709-711

doi:10.1107/S2056989015009706

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Crystal structure of poly[(2,2′-bipyridine-κ²N,N′)tetrakis(μ-cyanido-κ²N:C)dinickel(II)]

Minghui Zuo,^a Haiyu Wang,^a Jie Xu,^a Lingling Zhu ^a and Shuxin Cui ^a ^*

^aCollege of Chemistry and Chemical Engineering, Mu Danjiang Normal University, Mu Danjiang 157012, People's Republic of China
^*Correspondence e-mail: cuisx981@163.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 11 May 2015; accepted 20 May 2015; online 28 May 2015)

The polymeric title complex, [Ni₂(CN)₄(C₁₀H₈N₂)]_n, was obtained serendipitously under hydrothermal conditions. The asymmetric unit consists of one half of an [Ni(CN)₄]²⁻ anion with the Ni²⁺ cation situated on an inversion centre, and one half of an [Ni(2,2′-bpy)]²⁺ cation (2,2′-bpy is 2,2′-bipyridine), with the second Ni²⁺ cation situated on a twofold rotation axis. The two Ni²⁺ cations exhibit different coordination spheres. Whereas the coordination of the metal in the anion is that of a slightly distorted square defined by four C-bound cyanide ligands, the coordination in the cation is that of a distorted octahedron defined by four N-bound cyanide ligands and two N atoms from the chelating 2,2′-bpy ligand. The two different Ni²⁺ cations are alternately bridged by the cyanide ligands, resulting in a two-dimensional structure extending parallel to (010). Within the sheets, π–π interactions between pyridine rings of neighbouring 2,2′-bpy ligands, with a centroid-to-centroid distance of 3.687 (3) Å, are present. The crystal packing is dominated by van der Waals forces. A weak C—H⋯N interaction between adjacent sheets is also observed.

Keywords: crystal structure; cyanide ligands; nickel; 2,2′-bipyridine; coordination polymer.

CCDC reference: 1058383

1. Chemical context

Coordination metal complexes have been the subject of intensive investigation not only due to their potential application to material science as catalytic, conductive, luminescent, magnetic, porous, chiral or non-linear optical materials (Janiak et al., 2003 ), but also because of their intriguing structural diversity (Kong et al., 2008 ). The assembly of functional molecular building blocks into crystalline polymeric materials through coordination bonds or other weak interactions has many advantages over traditional stepwise syntheses and was demonstrated to be an effective approach to fabricating new materials (Kopotkov et al., 2014 ). Using this approach, numerous materials with interesting structures and properties have been prepared through the reactions of cyanidometallate building blocks (Cui et al., 2011 ; Zhang & Lachgar, 2015 ). These compounds show novel functionalities due to strong interactions mediated by the linear cyanide bridges. The probably oldest and most interesting example is the Prussian blue framework, Fe₄[Fe(CN)₆]₃·14H₂O, and its analogues derived from the assembly of hexacyanidometalate anions [M(CN)₆]_n and transition-metal ions (Li et al., 2008 ). For instance, cyanide-bridged bimetallic assemblies were obtained from K₃[Fe(CN)₆] as a source of cyanidometalate anions, metal cations, and aromatic nitrogen-containing ligands. These compounds show interesting magnetic and other properties that can be affected through the careful choice of the building-block components (Shen et al., 2014 ).

Our own efforts are focused to assemble metallic complexes and the achievement of tuning their properties by crystal engineering of the terminal/bridging ligands. However, the hydrothermal reaction of Ni(acetate)₂, 2,2′-bipyridine and K₃[Fe(CN)₆] did not yield the expected bimetallic system analogous to coordinated iron ions which were reported in literature (Colacio et al., 2003 ), but to the serendipitous formation of the polymeric complex (I), [Ni₂(CN)₄(C₁₀H₈N₂)]_n, the crystal structure of which is reported here.

2. Structural commentary

The asymmetric unit of the structure of (I) contains formally one half of an [Ni(CN)₄]²⁻ (Ni1) anion, and one half of an [Ni(2,2′-bpy)]²⁺ (Ni2) cation (2,2′-bpy is 2,2′-bipyridine). The anion is completed by inversion symmetry, whereas the cation is completed by a twofold rotation axis (Fig. 1). The Ni1 atom shows a slightly distorted square-planar geometry through coordination by four C atoms (C6 and C6ⁱ, C7 and C7ⁱ) [symmetry code: (i)x + 2, −y, −z + 1] from four cyanide groups, bridging Ni1 to four adjacent Ni2 atoms. The latter exhibits an overall distorted octahedral environment, being defined by four N atoms (N3, N3ⁱⁱ, N2ⁱⁱ, N2ⁱⁱⁱ) [symmetry codes: (ii) −x + 1, y, −z + $[{3\over 2}]$ ; (iii) x − 1, y, z] from four [Ni(CN)₄]²⁻ groups, and two N atoms (N1 and N1ⁱⁱ) of one 2,2′-bpy ligand. The corresponding N1—Ni2—N1 bite angle is 77.32 (13)°. Relevant bond lengths involving the two metal cations are compiled in Table 1. As depicted in Fig. 2, the cyanide groups bridge nickel cations, forming undulating sheets of composition [Ni₂(CN)₄(2,2′-bpy)₂] parallel to (010), constituted by alternation of Ni1 and Ni2 ions.

Table 1
Selected bond lengths (Å)

Ni1—C6	1.863 (3)	Ni2—N1	2.102 (2)
Ni1—C7	1.871 (3)	Ni2—N2ⁱ	2.116 (2)
Ni2—N3	2.071 (2)
Symmetry code: (i) x-1, y, z.

Figure 1
The principal building units of complex (I)

, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. For symmetry codes, see text.

Figure 2
A view of the polymeric sheet of complex (I)

. Ni atoms are represented by hatched green spheres, C atoms are grey, N atoms blue and H atoms green.

3. Supramolecular features

Within a sheet, π–π interactions between pyridine rings with a centroid-to-centroid distance of 3.687 (3) Å are present. The adhesion of the sheets in the crystal packing is dominated by van der Waals forces. However, a weak non-classical C—H⋯N interaction (Table 2) between neighbouring sheets may participate in the stabilization of the crystal packing.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N3	0.96 (3)	2.54 (3)	3.129 (3)	120 (2)

4. Synthesis and crystallization

Ni(acetate)₂ (0.159 g, 0.64 mmol), 2,2′-bipyridine (0.047 g, 0.3 mmol) and K₃[Fe(CN)₆] (0.21 g, 0.64 mmol) dissolved in aqueous solution of 1M NaCl (8 ml) were added to a 15 ml Teflon-lined autoclave and heated at 433 K for 3 d. The autoclave was then cooled to room temperature. Green block-shaped crystals of (I) deposited on the wall of the container and were collected and air-dried.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. Hydrogen atoms bound to carbon were found in a difference map and were refined with U_iso(H) = 1.2U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	[Ni₂(CN)₄(C₁₀H₈N₂)]
M_r	377.68
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	6.519 (5), 16.698 (5), 12.019 (5)
β (°)	90.852 (5)
V (Å³)	1308.2 (12)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.88
Crystal size (mm)	0.40 × 0.10 × 0.06

Data collection
Diffractometer	Siemens SMART CCD
No. of measured, independent and observed [I > 2σ(I)] reflections	3858, 1156, 1039
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.074, 1.10
No. of reflections	1156
No. of parameters	118
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.40
Computer programs: SMART and SAINT (Bruker, 2007 ), SHELXS97, SHELXL97and XP in SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 1058383

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2056989015009706/wm5162sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015009706/wm5162Isup2.hkl

checkCIF report

Chemical context top

Coordination metal complexes have been the subject of intensive investigation not only due to their potential application to material science as catalytic, conductive, luminescent, magnetic, porous, chiral or non-linear optical materials (Janiak et al., 2003), but also because of their intriguing structural diversity (Kong et al., 2008). The assembly of functional molecular building blocks into crystalline polymeric materials through coordination bonds or other weak interactions has many advantages over traditional stepwise syntheses and was demonstrated to be an effective approach to fabricating new materials (Kopotkov et al., 2014). Using this approach, numerous materials with interesting structures and properties have been prepared through the reactions of cyanidometallate building blocks (Cui et al., 2011; Zhang & Lachgar, 2015). These compounds show novel functionalities due to strong interactions mediated by the linear cyanide bridges. The probably oldest and most interesting example is the Prussian blue framework, Fe₄[Fe(CN)₆]₃·14H₂O, and its analogues derived from the assembly of hexacyanidometalate anions [M(CN)₆]_n and transition-metal ions (Li et al., 2008). For instance, cyanide-bridged bimetallic assemblies were obtained from K₃[Fe(CN)₆] as a source of cyanidometalate anions, metal cations, and aromatic nitrogen-containing ligands. These compounds show interesting magnetic and other properties that can be affected through the careful choice of the building-block components (Shen et al., 2014).

Our own efforts are focused to assemble metallic complexes and the achievement of tuning their properties by crystal engineering of the terminal/bridging ligands. However, the hydrothermal reaction of Ni(acetate)₂, 2,2'-bipyridine and K₃[Fe(CN)₆] did not yield the expected bimetallic system analogous to coordinated iron ions which were reported in literature (Colacio et al., 2003), but to the serendipitous formation of the polymeric complex (I), [Ni₂(CN)₄(C₁₀H₈N₂)]_n, the crystal structure of which is reported here.

Structural commentary top

The asymmetric unit of the structure of (I) contains formally one half of an [Ni(CN)₄]^2- (Ni1) anion, and one half of an [Ni(2,2'-bpy)]²⁺ (Ni2) cation (2,2'-bpy is 2,2'-bipyridine). The anion is completed by inversion symmetry, whereas the cation is completed by a twofold rotation axis (Fig. 1). The Ni1 atom shows a slightly distorted square-planar geometry through coordination by four C atoms (C6 and C6ⁱ, C7 and C7ⁱ) [symmetry code: (i)x + 2, -y, -z + 1] from four cyanide groups, bridging Ni1 to four adjacent Ni2 atoms. The latter exhibits an overall distorted octahedral environment, being defined by four N atoms (N3, N3ⁱⁱ, N2ⁱⁱ, N2ⁱⁱⁱ) [symmetry codes: (ii) -x + 1, y, -z + 3/2; (iii) x - 1, y, z] from four [Ni(CN)₄]^2- groups, and two N atoms (N1 and N1ⁱⁱ) of one 2,2'-bpy ligand. The corresponding N1—Ni2—N1 bite angle is 77.32 (13)°. Relevant bond lengths involving the two metal cations are compiled in Table 1. As depicted in Fig. 2, the cyanide groups bridge nickel cations, forming undulating sheets of composition [Ni₄(CN)₄(bpy)₂] parallel to (010), constituted by alternation of Ni1 and Ni2 ions.

Supramolecular features top

Within a sheet, π–π interactions between pyridine rings with a centroid-to-centroid distance of 3.687 (3) Å are present. The adhesion of the sheets in the crystal packing is dominated by van der Waals forces. However, a weak non-classical C—H···N interaction (Table 2) between neighbouring sheets may participate in the stabilization of the crystal packing.

Synthesis and crystallization top

Ni(acetate)₂ (0.159 g, 0.64 mmol), 2,2'-bipyridine (0.047 g, 0.3 mmol) and K₃[Fe(CN)₆] (0.21 g, 0.64 mmol) dissolved in aqueous solution of 1M NaCl (8 ml) were added to a 15 ml Teflon-lined autoclave and heated at 433 K for 3 d. The autoclave was then cooled to room temperature. Green block-shaped crystals of (I) deposited on the wall of the container and were collected and air-dried.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 3. Hydrogen atoms bound to carbon were found in a difference map and were refined with U_iso(H) = 1.2U_eq(C).

Related literature top

For related literature, see: Colacio et al. (2003); Cui et al. (2011); Janiak (2003); Kong et al. (2008); Kopotkov et al. (2014); Li et al. (2008); Shen et al. (2014); Zhang & Lachgar (2015).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The principal building units of complex (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. For symmetry codes, see text.
	Fig. 2. A view of the polymeric sheet of complex (I). Ni atoms are represented by hatched green spheres, C atoms are grey, N atoms blue and H atoms green.

Poly[(2,2'-bipyridine-κ²N,N')tetrakis(µ-cyanido-κ²N:C)dinickel(II)] top

Crystal data top

[Ni₂(CN)₄(C₁₀H₈N₂)]	F(000) = 760
M_r = 377.68	D_x = 1.918 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 3858 reflections
a = 6.519 (5) Å	θ = 1.0–25.0°
b = 16.698 (5) Å	µ = 2.88 mm⁻¹
c = 12.019 (5) Å	T = 293 K
β = 90.852 (5)°	Block, green
V = 1308.2 (12) Å³	0.40 × 0.10 × 0.06 mm
Z = 4

Data collection top

Siemens SMART CCD diffractometer	1039 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.032
Graphite monochromator	θ_max = 25.0°, θ_min = 3.4°
Detector resolution: 9 pixels mm^-1	h = −7→7
ω scans	k = −19→16
3858 measured reflections	l = −14→10
1156 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0374P)² + 0.9543P] where P = (F_o² + 2F_c²)/3
1156 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.71 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

[Ni₂(CN)₄(C₁₀H₈N₂)]	V = 1308.2 (12) Å³
M_r = 377.68	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 6.519 (5) Å	µ = 2.88 mm⁻¹
b = 16.698 (5) Å	T = 293 K
c = 12.019 (5) Å	0.40 × 0.10 × 0.06 mm
β = 90.852 (5)°

Data collection top

Siemens SMART CCD diffractometer	1039 reflections with I > 2σ(I)
3858 measured reflections	R_int = 0.032
1156 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.71 e Å⁻³
1156 reflections	Δρ_min = −0.40 e Å⁻³
118 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.

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

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

	x	y	z	U_iso*/U_eq
Ni1	1.0000	0.0000	0.5000	0.01983 (19)
Ni2	0.5000	0.12867 (3)	0.7500	0.01682 (18)
C6	0.8027 (4)	0.02639 (16)	0.6043 (2)	0.0207 (6)
C1	0.8426 (4)	0.22353 (19)	0.6347 (3)	0.0275 (7)
N3	0.6828 (3)	0.04836 (14)	0.6654 (2)	0.0242 (5)
N1	0.6675 (3)	0.22697 (13)	0.6906 (2)	0.0198 (5)
C5	0.5950 (4)	0.29952 (16)	0.7170 (2)	0.0207 (6)
C7	1.1817 (4)	0.07283 (17)	0.5669 (2)	0.0220 (6)
C4	0.6937 (5)	0.36889 (18)	0.6855 (3)	0.0305 (7)
N2	1.2931 (3)	0.11329 (14)	0.6143 (2)	0.0240 (5)
C3	0.8723 (5)	0.3640 (2)	0.6262 (3)	0.0343 (8)
C2	0.9471 (5)	0.29004 (19)	0.6008 (3)	0.0317 (7)
H2	1.062 (5)	0.284 (2)	0.562 (3)	0.043 (10)*
H4	0.636 (4)	0.4223 (19)	0.711 (3)	0.031 (8)*
H1	0.892 (5)	0.171 (2)	0.616 (3)	0.033 (9)*
H3	0.940 (5)	0.409 (2)	0.608 (3)	0.038 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0146 (3)	0.0249 (3)	0.0202 (3)	−0.00164 (17)	0.0062 (2)	−0.0069 (2)
Ni2	0.0146 (3)	0.0183 (3)	0.0177 (3)	0.000	0.0058 (2)	0.000
C6	0.0184 (13)	0.0189 (14)	0.0248 (16)	−0.0028 (11)	0.0033 (12)	−0.0031 (12)
C1	0.0244 (15)	0.0288 (17)	0.0297 (18)	−0.0016 (12)	0.0091 (13)	−0.0005 (13)
N3	0.0212 (12)	0.0240 (13)	0.0275 (15)	0.0002 (9)	0.0066 (11)	−0.0042 (11)
N1	0.0186 (11)	0.0217 (12)	0.0192 (13)	−0.0020 (9)	0.0026 (9)	0.0021 (10)
C5	0.0217 (14)	0.0197 (15)	0.0208 (16)	−0.0016 (10)	−0.0013 (12)	0.0022 (11)
C7	0.0176 (13)	0.0254 (15)	0.0233 (16)	0.0018 (11)	0.0084 (12)	−0.0024 (12)
C4	0.0314 (17)	0.0264 (17)	0.034 (2)	−0.0035 (12)	0.0005 (14)	0.0030 (13)
N2	0.0187 (12)	0.0289 (13)	0.0245 (15)	−0.0021 (10)	0.0054 (10)	−0.0033 (11)
C3	0.0331 (18)	0.0323 (19)	0.037 (2)	−0.0125 (14)	0.0004 (15)	0.0098 (15)
C2	0.0241 (16)	0.0390 (19)	0.0323 (19)	−0.0083 (13)	0.0084 (14)	0.0054 (15)

Geometric parameters (Å, º) top

Ni1—C6ⁱ	1.863 (3)	C1—C2	1.368 (4)
Ni1—C6	1.863 (3)	C1—H1	0.95 (3)
Ni1—C7ⁱ	1.871 (3)	N1—C5	1.340 (3)
Ni1—C7	1.871 (3)	C5—C4	1.381 (4)
Ni2—N3ⁱⁱ	2.071 (2)	C5—C5ⁱⁱ	1.480 (5)
Ni2—N3	2.071 (2)	C7—N2	1.139 (4)
Ni2—N1	2.102 (2)	C4—C3	1.377 (5)
Ni2—N1ⁱⁱ	2.102 (2)	C4—H4	1.02 (3)
Ni2—N2ⁱⁱⁱ	2.116 (2)	N2—Ni2^v	2.116 (2)
Ni2—N2^iv	2.116 (2)	C3—C2	1.364 (5)
C6—N3	1.140 (4)	C3—H3	0.90 (4)
C1—N1	1.335 (4)	C2—H2	0.89 (4)

C6ⁱ—Ni1—C6	180.0	N1—C1—C2	123.3 (3)
C6ⁱ—Ni1—C7ⁱ	89.76 (12)	N1—C1—H1	117 (2)
C6—Ni1—C7ⁱ	90.24 (12)	C2—C1—H1	120 (2)
C6ⁱ—Ni1—C7	90.24 (12)	C6—N3—Ni2	158.3 (2)
C6—Ni1—C7	89.76 (12)	C1—N1—C5	117.7 (2)
C7ⁱ—Ni1—C7	180.00 (13)	C1—N1—Ni2	126.15 (19)
N3ⁱⁱ—Ni2—N3	99.29 (14)	C5—N1—Ni2	116.02 (18)
N3ⁱⁱ—Ni2—N1	167.94 (10)	N1—C5—C4	121.7 (3)
N3—Ni2—N1	91.91 (10)	N1—C5—C5ⁱⁱ	115.32 (15)
N3ⁱⁱ—Ni2—N1ⁱⁱ	91.91 (10)	C4—C5—C5ⁱⁱ	122.95 (18)
N3—Ni2—N1ⁱⁱ	167.94 (10)	N2—C7—Ni1	174.8 (3)
N1—Ni2—N1ⁱⁱ	77.32 (13)	C3—C4—C5	119.6 (3)
N3ⁱⁱ—Ni2—N2ⁱⁱⁱ	86.28 (10)	C3—C4—H4	122.1 (18)
N3—Ni2—N2ⁱⁱⁱ	84.71 (10)	C5—C4—H4	118.2 (18)
N1—Ni2—N2ⁱⁱⁱ	99.29 (9)	C7—N2—Ni2^v	148.4 (2)
N1ⁱⁱ—Ni2—N2ⁱⁱⁱ	91.61 (9)	C2—C3—C4	118.5 (3)
N3ⁱⁱ—Ni2—N2^iv	84.71 (10)	C2—C3—H3	122 (2)
N3—Ni2—N2^iv	86.28 (10)	C4—C3—H3	120 (2)
N1—Ni2—N2^iv	91.61 (9)	C3—C2—C1	119.1 (3)
N1ⁱⁱ—Ni2—N2^iv	99.29 (9)	C3—C2—H2	122 (2)
N2ⁱⁱⁱ—Ni2—N2^iv	166.06 (13)	C1—C2—H2	119 (2)
N3—C6—Ni1	174.8 (2)

N3ⁱⁱ—Ni2—N3—C6	173.2 (7)	N3—Ni2—N1—C5	174.8 (2)
N1—Ni2—N3—C6	−11.3 (6)	N1ⁱⁱ—Ni2—N1—C5	0.33 (14)
N1ⁱⁱ—Ni2—N3—C6	15.2 (9)	N2ⁱⁱⁱ—Ni2—N1—C5	89.9 (2)
N2ⁱⁱⁱ—Ni2—N3—C6	87.8 (6)	N2^iv—Ni2—N1—C5	−98.8 (2)
N2^iv—Ni2—N3—C6	−102.8 (6)	C1—N1—C5—C4	1.7 (4)
C2—C1—N1—C5	−1.9 (5)	Ni2—N1—C5—C4	178.3 (2)
C2—C1—N1—Ni2	−178.2 (2)	C1—N1—C5—C5ⁱⁱ	−177.6 (3)
N3ⁱⁱ—Ni2—N1—C1	149.5 (4)	Ni2—N1—C5—C5ⁱⁱ	−0.9 (4)
N3—Ni2—N1—C1	−8.8 (2)	N1—C5—C4—C3	−0.6 (5)
N1ⁱⁱ—Ni2—N1—C1	176.7 (3)	C5ⁱⁱ—C5—C4—C3	178.6 (3)
N2ⁱⁱⁱ—Ni2—N1—C1	−93.7 (2)	C5—C4—C3—C2	−0.3 (5)
N2^iv—Ni2—N1—C1	77.5 (2)	C4—C3—C2—C1	0.1 (5)
N3ⁱⁱ—Ni2—N1—C5	−26.9 (5)	N1—C1—C2—C3	1.0 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N3	0.96 (3)	2.54 (3)	3.129 (3)	120 (2)

Selected bond lengths (Å) top

Ni1—C6	1.863 (3)	Ni2—N1	2.102 (2)
Ni1—C7	1.871 (3)	Ni2—N2ⁱ	2.116 (2)
Ni2—N3	2.071 (2)

Symmetry code: (i) x−1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N3	0.96 (3)	2.54 (3)	3.129 (3)	120 (2)

Experimental details

Crystal data
Chemical formula	[Ni₂(CN)₄(C₁₀H₈N₂)]
M_r	377.68
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	6.519 (5), 16.698 (5), 12.019 (5)
β (°)	90.852 (5)
V (Å³)	1308.2 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.88
Crystal size (mm)	0.40 × 0.10 × 0.06

Data collection
Diffractometer	Siemens SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3858, 1156, 1039
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.074, 1.10
No. of reflections	1156
No. of parameters	118
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.40

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Acknowledgements

This research was supported by the Natural Science Foundation of Heilongjiang Province (QC2014C009).

References

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Volume 71| Part 6| June 2015| Pages 709-711

doi:10.1107/S2056989015009706

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