catena-Poly[[(2,2′:6′,2′′-terpyridine-κ3N,N′,N′′)(tricyano­methanido-κN)nickel(II)]-μ-tricyano­methanido]

Luo, J.; Zhang, X.-R.; Dai, W.-Q.; Cui, L.-L.; Liu, B.-S.

doi:10.1107/S1600536808030377

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Pages m1322-m1323

doi:10.1107/S1600536808030377

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catena-Poly[[(2,2′:6′,2′′-terpyridine-κ³N,N′,N′′)(tricyanomethanido-κN)nickel(II)]-μ-tricyanomethanido]

Jun Luo,^a ^* Xin-Rong Zhang,^a Wei-Quan Dai,^a Li-Li Cui ^a and Bao-Shu Liu ^a

^aSchool of Pharmacy, Second Military Medical University, Shanghai 200433, People's Republic of China
^*Correspondence e-mail: junluo30@263.net

(Received 6 September 2008; accepted 22 September 2008; online 27 September 2008)

In the title complex, [Ni(C₄N₃)₂(C₁₅H₁₁N₃)]_n, each of the two different Ni^II atoms is coordinated by one 2,2′:6′2′′-terpyridine (terpy) and three tricyanomethanide ligands in a distorted octahedral geometry. The Ni^II atoms are linked to each other, forming an infinite chain parallel to ( $[\overline{1}]$ 10). π–π Stacking interactions of terpy molecules between adjacent chains (centroid–centroid distance = 3.785 Å), along with weak intermolecular C—H⋯N hydrogen bonds involving the uncoordinated terminal N atoms of the tricyanomethanide ions and the terpyridine H atoms, result in the formation of a three-dimensional network structure.

Related literature

For general background, see: Abrahams et al. (2003 ); Batten & Murray (2003 ); Batten et al. (1998 , 2000 ); Feyerherm et al. (2003 , 2004 ); Manson & Schlueter (2004 ); Manson et al. (1998 , 2000 ); Miller & Manson (2001 ); Yuste et al. (2008 ). For related structures, see: Baker et al. (1995 ); Batten et al. (1999 ); Hoshino et al. (1999 ); Indumathy et al. (2007 ); Luo et al. (2005 ); Potočňák et al. (2007 ).

Experimental

Crystal data

[Ni(C₄N₃)₂(C₁₅H₁₁N₃)]
M_r = 944.24
Triclinic, $[P \overline 1]$
a = 8.410 (3) Å
b = 15.581 (5) Å
c = 16.816 (5) Å
α = 93.762 (4)°
β = 90.110 (4)°
γ = 97.572 (5)°
V = 2179.4 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.92 mm⁻¹
T = 293 (2) K
0.20 × 0.15 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.837, T_max = 0.874
10952 measured reflections
9204 independent reflections
6799 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.136
S = 1.03
9204 reflections
595 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N8ⁱ	0.93	2.61	3.213 (6)	123
C4—H4⋯N6ⁱⁱ	0.93	2.59	3.459 (7)	156
C7—H7⋯N6ⁱⁱ	0.93	2.55	3.434 (6)	158
C9—H9⋯N17ⁱⁱⁱ	0.93	2.60	3.517 (6)	167
C30—H30⋯N18^iv	0.93	2.60	3.386 (6)	143
C34—H34⋯N11^v	0.93	2.57	3.467 (6)	162
C40—H40⋯N8^vi	0.93	2.61	3.292 (7)	130
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y+1, -z; (iii) -x, -y+2, -z; (iv) -x+2, -y+2, -z; (v) -x+2, -y+2, -z+1; (vi) x, y+1, z.

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808030377/dn2372sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808030377/dn2372Isup2.hkl

checkCIF report

Comment top

Recently, coordination polymers assembled by tricyanomethanide (tcm) have attracted considerable interest bacause of their novel structure characteristics and fascinating magnetic properties (Batten et al., 2003; Miller et al., 2001; Feyerherm et al., 2003). To our knowledge, most binary tcm complexes display a rutile-like structure (Manson et al., 2000, 1998; Hoshino et al., 1999; Feyerherm et al., 2004), except that a doubly interpenetrated (6,3) sheet was observed in Ag(tcm)₂ (Abrahams et al., 2003). To clarify the structure-properties relationship of tcm complexes, diverse co-ligands such as hexamethylenetetramine, 4,4-bipyridyl, 1,2-bi(4-pyridyl)ethane were introduced and the structures as well as magnetic properties of the adjusted complexes have been systematically investigated. Among the Cu(I) or Cd(II) tcm complexes with these co-ligands, numerous structure types range from doubly interpenetrated (4,4) sheet to three-dimensional rutile networks were observed (Batten et al., 2000, 1998). By contrast, modification of the Mn(II)-tcm binary system with 4,4-bipyridyl as co-ligands leads to the formation of a one dimensional chain-like structure (Manson et al., 2004). On the other hand, 2,2':6'2''-terpyridine (terpy) is a novel co-ligand and has three potential nitrogen donor atoms. However, only few tcm complexes with terpy as a co-ligand have ever been reported (Yuste et al., 2008). In order to further study the effect of the nature of co-ligands on the structures and properties of tricyanomethanide complexes, we herein report the synthesis and crystal structure of the new tricyanomethanide complex [Ni(terpy)(C₄N₃)₂]₂ (I).

In (I) the asymmetric unit is built up from two nickel ions: Ni1 and Ni2. Both Ni atoms display a slightly distorted octahedral coordination with the three N atoms of the terpyridine molecule and one terminal tcm N atom forming the equatorial plane, whereas two bridging tcm N atoms are located in axial position .

The distances and angles within the two octahedrons are roughly similar within experimental error. The only significant difference appear in the bending at the N atom of terminal tcm ligand located in the equatorial plane. Indeed, the Ni2-N16-C44 angle, 167.5 (3)°, whereas the corresponding Ni1-N7-C20 angle is 177.6 (5)°. The Ni1 and Ni2 atoms are linked trough a tcm bridge and each dinuclear units are further linked trough symetry related tcm bridges to form an infinite chain structure parallel to the (-1 1 0) plane (Fig. 1).

Intermolecular C-H···N hydrogen bonding between the uncoordinated terminal N atoms of the tcm ions and the H atoms of terpyridine groups (Table 1) and π-π stacking interactions involving terpyridine rings between adjacent chains along with (Table 2), result in the formation of a three-dimensional network structure (Fig. 2).

The Ni—N(terpy) distances (1.985 (3) to 2.110 (3) Å) are almost equal to Ni—N(tcm) distances (2.014 (3) to 2.101 (3) Å), and are respectively comparable to the corresponding distances found in nickel-terpyridine (Baker et al., 1995) and nickel-tcm complexes (Luo et al., 2005; Potocnák et al., 2007).

The bond distances and angles within the terpyridine rings are in the normal ranges observed for terpyridine-containing complexes (Indumathy et al., 2007). Each tricyanomethanide moiety is almost planar and the bond distances and angles are in good agreement with those found in other tricyanomethanide complexes (Hoshino et al., 1999; Batten et al., 1999).

Related literature top

For related literature, see: Abrahams et al. (2003); Baker et al. (1995); Batten & Murray (2003); Batten et al. (1998, 1999, 2000); Feyerherm et al. (2003, 2004); Hoshino et al. (1999); Indumathy et al. (2007); Luo et al. (2005); Manson & Schlueter (2004); Manson et al. (1998, 2000); Miller & Manson (2001); Potočňák et al. (2007); Yuste et al. (2008). It would be much more useful to readers if the "Related literature" section had some kind of simple sub-division, so that, instead of just "For related literature, see···" it said, for example, "For general background, see···. For related structures, see···.? etc. Please revise this section as indicated.

Experimental top

A 5 ml ethanol solution of terpyridine (0.10 mmol, 23.33 mg) and a 2 ml aqueous pale-green solution of nickel nitrate (0.10 mmol, 29.08 mg) were mixed and stirred for 5 min, the mixed solution became yellow. To the mixture was added a 3 ml ethanol-water solution (EtOH:H₂O = 2:1, V:V) of potassium tricyanomethanide (0.20 mmol, 25.83 mg). After stirring for another 5 min, the yellow solution was filtered and the filtrate was slowly evaporated in air. After two weeks, pale-purple block crystals of (I) were isolated in 23% yield. Anal: Calculated for C46H22N18Ni2: C 58.52%, H 2.35%, N 26.70%. Found C 58.68%, H 2.43%, N 26.84%.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the one-dimensional chain in (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity [symmetry code: (i) x + 1, y + 1, z].
	Fig. 2. The three-dimensional network structure of (I) formed via terpy π-π interactions and hydrogen bonding interactions, viewed along the a axis.

catena-Poly[[(2,2':6',2''- terpyridine-κ³N,N',N'')(tricyanomethanido- κN)nickel(II)]-µ-tricyanomethanido] top

Crystal data top

[Ni(C₄N₃)₂(C₁₅H₁₁N₃)]	Z = 2
M_r = 944.24	F(000) = 960
Triclinic, P1	D_x = 1.439 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.410 (3) Å	Cell parameters from 944 reflections
b = 15.581 (5) Å	θ = 2.6–24.5°
c = 16.816 (5) Å	µ = 0.92 mm⁻¹
α = 93.762 (4)°	T = 293 K
β = 90.110 (4)°	Block, pale-purple
γ = 97.572 (5)°	0.20 × 0.15 × 0.15 mm
V = 2179.4 (11) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	9204 independent reflections
Radiation source: fine-focus sealed tube	6799 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 27.0°, θ_min = 1.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→8
T_min = 0.837, T_max = 0.874	k = −19→19
10952 measured reflections	l = −21→21

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0597P)² + 0.2733P] where P = (F_o² + 2F_c²)/3
9204 reflections	(Δ/σ)_max = 0.002
595 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[Ni(C₄N₃)₂(C₁₅H₁₁N₃)]	γ = 97.572 (5)°
M_r = 944.24	V = 2179.4 (11) Å³
Triclinic, P1	Z = 2
a = 8.410 (3) Å	Mo Kα radiation
b = 15.581 (5) Å	µ = 0.92 mm⁻¹
c = 16.816 (5) Å	T = 293 K
α = 93.762 (4)°	0.20 × 0.15 × 0.15 mm
β = 90.110 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	9204 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	6799 reflections with I > 2σ(I)
T_min = 0.837, T_max = 0.874	R_int = 0.031
10952 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 1.03	Δρ_max = 0.51 e Å⁻³
9204 reflections	Δρ_min = −0.32 e Å⁻³
595 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.22374 (5)	0.63410 (2)	0.27013 (2)	0.02854 (12)
Ni2	0.70217 (5)	1.13422 (3)	0.23620 (2)	0.03109 (12)
N1	0.4308 (3)	0.58137 (18)	0.23108 (17)	0.0379 (6)
N2	0.2387 (3)	0.66731 (17)	0.15730 (15)	0.0319 (6)
N3	0.0177 (3)	0.69351 (17)	0.25830 (16)	0.0341 (6)
N4	0.0978 (4)	0.51428 (19)	0.22881 (18)	0.0425 (7)
N5	−0.1568 (4)	0.24281 (18)	0.19521 (17)	0.0426 (7)
N6	0.2572 (6)	0.3427 (3)	0.0496 (3)	0.125 (2)
N7	0.2082 (4)	0.59875 (18)	0.38324 (17)	0.0418 (7)
N8	0.3241 (7)	0.4149 (3)	0.5555 (2)	0.0949 (15)
N9	0.0357 (5)	0.6229 (2)	0.6311 (2)	0.0722 (11)
N10	0.3504 (3)	0.75359 (18)	0.31275 (16)	0.0384 (7)
N11	0.6264 (5)	0.9131 (3)	0.5073 (2)	0.0762 (12)
N12	0.5724 (4)	1.02474 (18)	0.28128 (17)	0.0432 (7)
N13	0.9001 (3)	1.06682 (18)	0.22472 (16)	0.0369 (6)
N14	0.7987 (3)	1.15562 (17)	0.34463 (16)	0.0347 (6)
N15	0.5437 (4)	1.21064 (18)	0.29291 (17)	0.0414 (7)
N16	0.5894 (4)	1.11062 (19)	0.12874 (17)	0.0424 (7)
N17	0.1207 (5)	1.1214 (3)	0.0126 (2)	0.0764 (12)
N18	0.5484 (5)	1.1226 (3)	−0.1334 (2)	0.0696 (11)
C1	0.5173 (5)	0.5330 (3)	0.2712 (2)	0.0541 (10)
H1	0.4905	0.5231	0.3238	0.065*
C2	0.6450 (6)	0.4966 (4)	0.2383 (3)	0.0775 (15)
H2	0.7041	0.4636	0.2682	0.093*
C3	0.6826 (6)	0.5102 (4)	0.1607 (3)	0.0785 (15)
H3	0.7675	0.4861	0.1367	0.094*
C4	0.5941 (5)	0.5597 (3)	0.1187 (3)	0.0621 (12)
H4	0.6191	0.5700	0.0660	0.075*
C5	0.4680 (4)	0.5940 (2)	0.1547 (2)	0.0407 (8)
C6	0.3607 (4)	0.6445 (2)	0.11328 (19)	0.0367 (8)
C7	0.3729 (5)	0.6668 (3)	0.0341 (2)	0.0502 (10)
H7	0.4571	0.6521	0.0024	0.060*
C8	0.2584 (5)	0.7108 (3)	0.0042 (2)	0.0543 (10)
H8	0.2651	0.7259	−0.0484	0.065*
C9	0.1326 (4)	0.7333 (2)	0.0506 (2)	0.0459 (9)
H9	0.0552	0.7637	0.0303	0.055*
C10	0.1261 (4)	0.7091 (2)	0.1281 (2)	0.0375 (8)
C11	−0.0013 (4)	0.7247 (2)	0.1860 (2)	0.0351 (7)
C12	−0.1317 (5)	0.7642 (3)	0.1692 (2)	0.0526 (10)
H12	−0.1433	0.7854	0.1194	0.063*
C13	−0.2460 (5)	0.7723 (3)	0.2268 (3)	0.0673 (13)
H13	−0.3348	0.7997	0.2163	0.081*
C14	−0.2284 (5)	0.7398 (3)	0.2996 (3)	0.0619 (12)
H14	−0.3050	0.7441	0.3389	0.074*
C15	−0.0952 (5)	0.7010 (2)	0.3127 (2)	0.0472 (9)
H15	−0.0828	0.6788	0.3620	0.057*
C16	0.0740 (4)	0.4459 (2)	0.1991 (2)	0.0350 (7)
C17	0.0544 (4)	0.3643 (2)	0.1586 (2)	0.0409 (8)
C18	−0.0617 (4)	0.2975 (2)	0.17997 (19)	0.0353 (7)
C19	0.1645 (6)	0.3509 (3)	0.0985 (3)	0.0687 (14)
C20	0.2002 (4)	0.5758 (2)	0.4466 (2)	0.0382 (8)
C21	0.1934 (5)	0.5477 (2)	0.5238 (2)	0.0428 (9)
C22	0.2664 (6)	0.4744 (3)	0.5412 (2)	0.0597 (11)
C23	0.1061 (5)	0.5892 (2)	0.5829 (2)	0.0485 (9)
C24	0.4178 (4)	0.8188 (2)	0.33652 (19)	0.0332 (7)
C25	0.5722 (5)	0.9050 (2)	0.4446 (2)	0.0463 (9)
C26	0.5053 (4)	0.8968 (2)	0.3671 (2)	0.0378 (8)
C27	0.5407 (4)	0.9663 (2)	0.3185 (2)	0.0350 (7)
C28	0.9457 (5)	1.0230 (2)	0.1600 (2)	0.0485 (9)
H28	0.8846	1.0212	0.1136	0.058*
C29	1.0777 (5)	0.9805 (3)	0.1583 (3)	0.0605 (11)
H29	1.1036	0.9491	0.1123	0.073*
C30	1.1719 (5)	0.9848 (3)	0.2259 (3)	0.0731 (14)
H30	1.2636	0.9573	0.2260	0.088*
C31	1.1276 (5)	1.0309 (3)	0.2938 (3)	0.0671 (13)
H31	1.1894	1.0351	0.3401	0.081*
C32	0.9911 (4)	1.0703 (2)	0.2916 (2)	0.0442 (9)
C33	0.9294 (4)	1.1198 (2)	0.3613 (2)	0.0430 (8)
C34	0.9940 (5)	1.1274 (3)	0.4385 (2)	0.0647 (12)
H34	1.0863	1.1035	0.4501	0.078*
C35	0.9155 (6)	1.1716 (3)	0.4966 (2)	0.0680 (13)
H35	0.9547	1.1773	0.5487	0.082*
C36	0.7803 (6)	1.2073 (3)	0.4785 (2)	0.0565 (11)
H36	0.7277	1.2367	0.5182	0.068*
C37	0.7217 (4)	1.1993 (2)	0.4000 (2)	0.0386 (8)
C38	0.5795 (4)	1.2319 (2)	0.3709 (2)	0.0406 (8)
C39	0.4833 (5)	1.2792 (3)	0.4179 (3)	0.0574 (11)
H39	0.5097	1.2950	0.4710	0.069*
C40	0.3456 (6)	1.3029 (3)	0.3838 (3)	0.0734 (14)
H40	0.2778	1.3335	0.4148	0.088*
C41	0.3101 (6)	1.2817 (3)	0.3061 (3)	0.0743 (14)
H41	0.2189	1.2976	0.2828	0.089*
C42	0.4132 (5)	1.2357 (3)	0.2622 (3)	0.0587 (11)
H42	0.3900	1.2216	0.2084	0.070*
C43	0.5134 (4)	1.1105 (2)	0.0723 (2)	0.0392 (8)
C44	0.4195 (5)	1.1110 (2)	0.0033 (2)	0.0454 (9)
C45	0.2561 (5)	1.1160 (3)	0.0093 (2)	0.0504 (10)
C46	0.4922 (5)	1.1164 (2)	−0.0719 (2)	0.0499 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0306 (2)	0.0289 (2)	0.0255 (2)	0.00083 (17)	0.00230 (16)	0.00317 (16)
Ni2	0.0340 (2)	0.0308 (2)	0.0267 (2)	−0.00316 (17)	−0.00293 (17)	0.00346 (16)
N1	0.0352 (15)	0.0441 (17)	0.0344 (15)	0.0066 (13)	−0.0017 (12)	0.0014 (13)
N2	0.0316 (14)	0.0360 (15)	0.0277 (14)	0.0014 (12)	−0.0003 (11)	0.0058 (11)
N3	0.0313 (14)	0.0343 (15)	0.0368 (15)	0.0042 (12)	0.0032 (12)	0.0033 (12)
N4	0.0445 (17)	0.0367 (17)	0.0432 (17)	−0.0051 (13)	0.0066 (13)	0.0017 (13)
N5	0.0514 (18)	0.0373 (16)	0.0354 (16)	−0.0084 (14)	0.0021 (14)	0.0037 (13)
N6	0.121 (4)	0.106 (4)	0.132 (5)	−0.025 (3)	0.088 (4)	−0.033 (3)
N7	0.0541 (19)	0.0410 (16)	0.0310 (16)	0.0059 (14)	0.0054 (13)	0.0086 (13)
N8	0.155 (5)	0.093 (3)	0.049 (2)	0.056 (3)	0.000 (3)	0.016 (2)
N9	0.098 (3)	0.065 (2)	0.052 (2)	0.004 (2)	0.029 (2)	0.0060 (18)
N10	0.0433 (17)	0.0352 (16)	0.0343 (15)	−0.0040 (13)	−0.0001 (13)	0.0020 (12)
N11	0.088 (3)	0.073 (3)	0.064 (3)	−0.008 (2)	−0.028 (2)	0.014 (2)
N12	0.0507 (18)	0.0376 (16)	0.0369 (16)	−0.0125 (14)	−0.0061 (14)	0.0060 (13)
N13	0.0350 (15)	0.0400 (16)	0.0345 (15)	0.0005 (12)	−0.0042 (12)	0.0028 (12)
N14	0.0371 (15)	0.0346 (15)	0.0295 (14)	−0.0047 (12)	−0.0033 (12)	−0.0003 (11)
N15	0.0477 (18)	0.0407 (16)	0.0359 (16)	0.0052 (14)	0.0040 (13)	0.0050 (13)
N16	0.0453 (17)	0.0475 (17)	0.0330 (16)	−0.0010 (14)	−0.0077 (13)	0.0064 (13)
N17	0.064 (3)	0.098 (3)	0.070 (3)	0.009 (2)	−0.010 (2)	0.023 (2)
N18	0.087 (3)	0.080 (3)	0.040 (2)	0.010 (2)	0.0002 (19)	−0.0033 (18)
C1	0.054 (2)	0.067 (3)	0.044 (2)	0.020 (2)	−0.0013 (19)	0.0052 (19)
C2	0.069 (3)	0.110 (4)	0.063 (3)	0.051 (3)	−0.004 (2)	0.008 (3)
C3	0.060 (3)	0.116 (4)	0.068 (3)	0.045 (3)	0.012 (2)	−0.003 (3)
C4	0.045 (2)	0.097 (3)	0.047 (2)	0.023 (2)	0.0106 (19)	0.002 (2)
C5	0.0359 (18)	0.049 (2)	0.0357 (19)	0.0016 (16)	0.0041 (15)	−0.0015 (16)
C6	0.0363 (18)	0.0403 (19)	0.0322 (17)	0.0000 (15)	0.0046 (14)	0.0036 (14)
C7	0.050 (2)	0.065 (3)	0.0334 (19)	−0.002 (2)	0.0145 (17)	0.0046 (18)
C8	0.066 (3)	0.065 (3)	0.0304 (19)	−0.004 (2)	0.0008 (18)	0.0132 (18)
C9	0.044 (2)	0.057 (2)	0.039 (2)	0.0057 (18)	−0.0077 (16)	0.0151 (17)
C10	0.0379 (18)	0.0385 (18)	0.0343 (18)	−0.0035 (15)	−0.0001 (15)	0.0057 (14)
C11	0.0352 (18)	0.0332 (17)	0.0367 (18)	0.0029 (14)	−0.0039 (14)	0.0033 (14)
C12	0.049 (2)	0.058 (2)	0.055 (2)	0.0158 (19)	−0.0030 (19)	0.0154 (19)
C13	0.047 (2)	0.089 (3)	0.075 (3)	0.036 (2)	0.002 (2)	0.017 (3)
C14	0.043 (2)	0.087 (3)	0.062 (3)	0.031 (2)	0.014 (2)	0.010 (2)
C15	0.048 (2)	0.054 (2)	0.041 (2)	0.0088 (18)	0.0094 (17)	0.0064 (17)
C16	0.0310 (17)	0.0373 (19)	0.0356 (18)	−0.0018 (14)	0.0028 (14)	0.0081 (15)
C17	0.045 (2)	0.0344 (18)	0.0397 (19)	−0.0055 (15)	0.0071 (16)	−0.0012 (15)
C18	0.0408 (19)	0.0327 (17)	0.0304 (17)	−0.0012 (15)	−0.0020 (14)	−0.0004 (14)
C19	0.073 (3)	0.053 (3)	0.072 (3)	−0.014 (2)	0.031 (3)	−0.012 (2)
C20	0.0369 (18)	0.0367 (18)	0.039 (2)	−0.0009 (15)	−0.0004 (15)	0.0003 (15)
C21	0.055 (2)	0.044 (2)	0.0279 (17)	−0.0007 (17)	0.0034 (16)	0.0066 (15)
C22	0.086 (3)	0.066 (3)	0.028 (2)	0.010 (3)	0.003 (2)	0.0058 (19)
C23	0.058 (2)	0.047 (2)	0.037 (2)	−0.0065 (19)	0.0036 (18)	0.0083 (17)
C24	0.0309 (17)	0.0364 (18)	0.0330 (17)	0.0052 (14)	0.0061 (14)	0.0071 (14)
C25	0.047 (2)	0.040 (2)	0.050 (2)	−0.0037 (17)	−0.0137 (18)	0.0090 (17)
C26	0.0402 (19)	0.0316 (17)	0.0391 (19)	−0.0042 (15)	−0.0014 (15)	0.0028 (14)
C27	0.0303 (17)	0.0349 (18)	0.0369 (18)	−0.0029 (14)	−0.0043 (14)	−0.0050 (15)
C28	0.049 (2)	0.052 (2)	0.043 (2)	0.0051 (18)	−0.0011 (17)	−0.0005 (18)
C29	0.054 (3)	0.059 (3)	0.068 (3)	0.011 (2)	0.005 (2)	−0.009 (2)
C30	0.049 (3)	0.089 (4)	0.084 (4)	0.028 (2)	−0.006 (2)	−0.012 (3)
C31	0.045 (2)	0.085 (3)	0.073 (3)	0.020 (2)	−0.018 (2)	−0.007 (3)
C32	0.0366 (19)	0.049 (2)	0.045 (2)	0.0007 (17)	−0.0050 (16)	0.0018 (17)
C33	0.042 (2)	0.046 (2)	0.039 (2)	0.0000 (17)	−0.0084 (16)	0.0027 (16)
C34	0.063 (3)	0.084 (3)	0.048 (2)	0.013 (2)	−0.026 (2)	0.000 (2)
C35	0.080 (3)	0.083 (3)	0.037 (2)	0.004 (3)	−0.022 (2)	−0.008 (2)
C36	0.078 (3)	0.053 (2)	0.033 (2)	−0.007 (2)	0.003 (2)	−0.0044 (17)
C37	0.046 (2)	0.0333 (18)	0.0327 (18)	−0.0082 (15)	0.0027 (15)	0.0003 (14)
C38	0.047 (2)	0.0339 (18)	0.0391 (19)	−0.0024 (16)	0.0062 (16)	0.0027 (15)
C39	0.066 (3)	0.052 (2)	0.052 (2)	0.007 (2)	0.011 (2)	−0.0078 (19)
C40	0.072 (3)	0.070 (3)	0.082 (4)	0.026 (3)	0.019 (3)	−0.006 (3)
C41	0.071 (3)	0.086 (4)	0.073 (3)	0.037 (3)	−0.006 (3)	−0.003 (3)
C42	0.063 (3)	0.064 (3)	0.053 (2)	0.023 (2)	−0.005 (2)	0.002 (2)
C43	0.049 (2)	0.0325 (18)	0.0352 (19)	0.0032 (16)	−0.0038 (16)	0.0017 (15)
C44	0.055 (2)	0.047 (2)	0.0343 (19)	0.0079 (18)	−0.0129 (17)	0.0031 (16)
C45	0.058 (3)	0.054 (2)	0.039 (2)	0.006 (2)	−0.0147 (19)	0.0098 (17)
C46	0.062 (3)	0.049 (2)	0.039 (2)	0.0087 (19)	−0.0144 (19)	−0.0011 (17)

Geometric parameters (Å, º) top

Ni1—N2	1.999 (3)	C8—H8	0.9300
Ni1—N7	2.014 (3)	C9—C10	1.380 (5)
Ni1—N3	2.085 (3)	C9—H9	0.9300
Ni1—N4	2.097 (3)	C10—C11	1.482 (5)
Ni1—N10	2.101 (3)	C11—C12	1.364 (5)
Ni1—N1	2.110 (3)	C12—C13	1.378 (6)
Ni2—N14	1.984 (3)	C12—H12	0.9300
Ni2—N16	2.028 (3)	C13—C14	1.369 (6)
Ni2—N13	2.085 (3)	C13—H13	0.9300
Ni2—N12	2.088 (3)	C14—C15	1.365 (5)
Ni2—N5ⁱ	2.091 (3)	C14—H14	0.9300
Ni2—N15	2.092 (3)	C15—H15	0.9300
N1—C1	1.327 (5)	C16—C17	1.392 (5)
N1—C5	1.344 (4)	C17—C18	1.395 (5)
N2—C10	1.328 (4)	C17—C19	1.397 (5)
N2—C6	1.338 (4)	C20—C21	1.395 (5)
N3—C15	1.331 (4)	C21—C23	1.409 (5)
N3—C11	1.355 (4)	C21—C22	1.413 (6)
N4—C16	1.140 (4)	C24—C26	1.401 (4)
N5—C18	1.132 (4)	C25—C26	1.411 (5)
N5—Ni2ⁱⁱ	2.091 (3)	C26—C27	1.400 (5)
N6—C19	1.146 (5)	C28—C29	1.365 (5)
N7—C20	1.146 (4)	C28—H28	0.9300
N8—C22	1.140 (6)	C29—C30	1.377 (6)
N9—C23	1.145 (5)	C29—H29	0.9300
N10—C24	1.143 (4)	C30—C31	1.387 (6)
N11—C25	1.139 (5)	C30—H30	0.9300
N12—C27	1.141 (4)	C31—C32	1.373 (5)
N13—C28	1.332 (4)	C31—H31	0.9300
N13—C32	1.353 (4)	C32—C33	1.491 (5)
N14—C33	1.335 (5)	C33—C34	1.397 (5)
N14—C37	1.335 (4)	C34—C35	1.378 (6)
N15—C42	1.328 (5)	C34—H34	0.9300
N15—C38	1.355 (4)	C35—C36	1.372 (6)
N16—C43	1.143 (4)	C35—H35	0.9300
N17—C45	1.154 (5)	C36—C37	1.400 (5)
N18—C46	1.142 (5)	C36—H36	0.9300
C1—C2	1.379 (6)	C37—C38	1.456 (5)
C1—H1	0.9300	C38—C39	1.380 (5)
C2—C3	1.368 (6)	C39—C40	1.393 (6)
C2—H2	0.9300	C39—H39	0.9300
C3—C4	1.366 (6)	C40—C41	1.350 (7)
C3—H3	0.9300	C40—H40	0.9300
C4—C5	1.374 (5)	C41—C42	1.381 (6)
C4—H4	0.9300	C41—H41	0.9300
C5—C6	1.474 (5)	C42—H42	0.9300
C6—C7	1.400 (5)	C43—C44	1.403 (5)
C7—C8	1.366 (6)	C44—C45	1.391 (6)
C7—H7	0.9300	C44—C46	1.408 (5)
C8—C9	1.385 (5)

N2—Ni1—N7	179.14 (11)	N3—C11—C12	121.2 (3)
N2—Ni1—N3	78.14 (11)	N3—C11—C10	114.6 (3)
N7—Ni1—N3	102.22 (12)	C12—C11—C10	124.3 (3)
N2—Ni1—N4	88.50 (11)	C11—C12—C13	119.2 (4)
N7—Ni1—N4	90.72 (12)	C11—C12—H12	120.4
N3—Ni1—N4	90.48 (12)	C13—C12—H12	120.4
N2—Ni1—N10	92.11 (11)	C14—C13—C12	119.8 (4)
N7—Ni1—N10	88.67 (11)	C14—C13—H13	120.1
N3—Ni1—N10	89.83 (11)	C12—C13—H13	120.1
N4—Ni1—N10	179.36 (12)	C15—C14—C13	118.1 (4)
N2—Ni1—N1	78.21 (11)	C15—C14—H14	120.9
N7—Ni1—N1	101.39 (12)	C13—C14—H14	120.9
N3—Ni1—N1	156.10 (11)	N3—C15—C14	123.1 (4)
N4—Ni1—N1	85.56 (11)	N3—C15—H15	118.5
N10—Ni1—N1	94.38 (11)	C14—C15—H15	118.5
N14—Ni2—N16	176.27 (12)	N4—C16—C17	175.5 (4)
N14—Ni2—N13	78.68 (11)	C16—C17—C18	122.2 (3)
N16—Ni2—N13	103.93 (12)	C16—C17—C19	116.2 (3)
N14—Ni2—N12	85.18 (11)	C18—C17—C19	121.5 (3)
N16—Ni2—N12	92.16 (11)	N5—C18—C17	178.2 (4)
N13—Ni2—N12	88.96 (12)	N6—C19—C17	177.7 (5)
N14—Ni2—N5ⁱ	92.12 (11)	N7—C20—C21	179.0 (4)
N16—Ni2—N5ⁱ	90.61 (11)	C20—C21—C23	120.1 (4)
N13—Ni2—N5ⁱ	88.68 (12)	C20—C21—C22	119.6 (3)
N12—Ni2—N5ⁱ	176.72 (12)	C23—C21—C22	120.2 (3)
N14—Ni2—N15	78.53 (12)	N8—C22—C21	179.4 (6)
N16—Ni2—N15	98.84 (12)	N9—C23—C21	179.7 (5)
N13—Ni2—N15	157.21 (11)	N10—C24—C26	177.6 (4)
N12—Ni2—N15	89.09 (12)	N11—C25—C26	178.8 (4)
N5ⁱ—Ni2—N15	92.20 (12)	C27—C26—C24	120.4 (3)
C1—N1—C5	118.4 (3)	C27—C26—C25	118.1 (3)
C1—N1—Ni1	127.3 (3)	C24—C26—C25	121.2 (3)
C5—N1—Ni1	114.1 (2)	N12—C27—C26	177.5 (3)
C10—N2—C6	122.4 (3)	N13—C28—C29	123.2 (4)
C10—N2—Ni1	119.2 (2)	N13—C28—H28	118.4
C6—N2—Ni1	118.3 (2)	C29—C28—H28	118.4
C15—N3—C11	118.6 (3)	C28—C29—C30	119.0 (4)
C15—N3—Ni1	126.8 (3)	C28—C29—H29	120.5
C11—N3—Ni1	114.6 (2)	C30—C29—H29	120.5
C16—N4—Ni1	159.6 (3)	C29—C30—C31	118.8 (4)
C18—N5—Ni2ⁱⁱ	169.1 (3)	C29—C30—H30	120.6
C20—N7—Ni1	177.6 (3)	C31—C30—H30	120.6
C24—N10—Ni1	179.2 (3)	C32—C31—C30	119.0 (4)
C27—N12—Ni2	160.4 (3)	C32—C31—H31	120.5
C28—N13—C32	118.1 (3)	C30—C31—H31	120.5
C28—N13—Ni2	127.5 (2)	N13—C32—C31	121.9 (4)
C32—N13—Ni2	114.5 (2)	N13—C32—C33	114.2 (3)
C33—N14—C37	122.5 (3)	C31—C32—C33	123.9 (4)
C33—N14—Ni2	119.0 (2)	N14—C33—C34	121.0 (4)
C37—N14—Ni2	118.3 (2)	N14—C33—C32	113.6 (3)
C42—N15—C38	118.8 (3)	C34—C33—C32	125.4 (4)
C42—N15—Ni2	127.5 (3)	C35—C34—C33	117.4 (4)
C38—N15—Ni2	113.6 (2)	C35—C34—H34	121.3
C43—N16—Ni2	167.5 (3)	C33—C34—H34	121.3
N1—C1—C2	122.9 (4)	C36—C35—C34	120.8 (4)
N1—C1—H1	118.6	C36—C35—H35	119.6
C2—C1—H1	118.6	C34—C35—H35	119.6
C3—C2—C1	118.4 (4)	C35—C36—C37	119.7 (4)
C3—C2—H2	120.8	C35—C36—H36	120.2
C1—C2—H2	120.8	C37—C36—H36	120.2
C4—C3—C2	119.2 (4)	N14—C37—C36	118.7 (4)
C4—C3—H3	120.4	N14—C37—C38	114.5 (3)
C2—C3—H3	120.4	C36—C37—C38	126.8 (3)
C3—C4—C5	119.6 (4)	N15—C38—C39	121.0 (4)
C3—C4—H4	120.2	N15—C38—C37	114.9 (3)
C5—C4—H4	120.2	C39—C38—C37	124.1 (4)
N1—C5—C4	121.5 (4)	C38—C39—C40	118.5 (4)
N1—C5—C6	114.9 (3)	C38—C39—H39	120.7
C4—C5—C6	123.6 (3)	C40—C39—H39	120.7
N2—C6—C7	119.2 (3)	C41—C40—C39	120.4 (4)
N2—C6—C5	114.4 (3)	C41—C40—H40	119.8
C7—C6—C5	126.3 (3)	C39—C40—H40	119.8
C8—C7—C6	118.5 (4)	C40—C41—C42	118.1 (5)
C8—C7—H7	120.7	C40—C41—H41	121.0
C6—C7—H7	120.7	C42—C41—H41	121.0
C7—C8—C9	121.3 (3)	N15—C42—C41	123.2 (4)
C7—C8—H8	119.3	N15—C42—H42	118.4
C9—C8—H8	119.3	C41—C42—H42	118.4
C10—C9—C8	117.6 (4)	N16—C43—C44	179.5 (4)
C10—C9—H9	121.2	C45—C44—C43	120.2 (3)
C8—C9—H9	121.2	C45—C44—C46	119.0 (3)
N2—C10—C9	120.9 (3)	C43—C44—C46	120.4 (4)
N2—C10—C11	113.5 (3)	N17—C45—C44	178.3 (5)
C9—C10—C11	125.6 (3)	N18—C46—C44	178.0 (5)

Symmetry codes: (i) x+1, y+1, z; (ii) x−1, y−1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N8ⁱⁱⁱ	0.93	2.61	3.213 (6)	123
C4—H4···N6^iv	0.93	2.59	3.459 (7)	156
C7—H7···N6^iv	0.93	2.55	3.434 (6)	158
C9—H9···N17^v	0.93	2.60	3.517 (6)	167
C30—H30···N18^vi	0.93	2.60	3.386 (6)	143
C34—H34···N11^vii	0.93	2.57	3.467 (6)	162
C40—H40···N8^viii	0.93	2.61	3.292 (7)	130

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

Experimental details

Crystal data
Chemical formula	[Ni(C₄N₃)₂(C₁₅H₁₁N₃)]
M_r	944.24
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.410 (3), 15.581 (5), 16.816 (5)
α, β, γ (°)	93.762 (4), 90.110 (4), 97.572 (5)
V (Å³)	2179.4 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.92
Crystal size (mm)	0.20 × 0.15 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.837, 0.874
No. of measured, independent and observed [I > 2σ(I)] reflections	10952, 9204, 6799
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.136, 1.03
No. of reflections	9204
No. of parameters	595
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.32

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N8ⁱ	0.93	2.61	3.213 (6)	122.9
C4—H4···N6ⁱⁱ	0.93	2.59	3.459 (7)	156.2
C7—H7···N6ⁱⁱ	0.93	2.55	3.434 (6)	158.4
C9—H9···N17ⁱⁱⁱ	0.93	2.60	3.517 (6)	167.2
C30—H30···N18^iv	0.93	2.60	3.386 (6)	142.8
C34—H34···N11^v	0.93	2.57	3.467 (6)	162.3
C40—H40···N8^vi	0.93	2.61	3.292 (7)	130.3

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

π–π Interaction between some of the terpyridine rings top

(Symmetry code: (i) 1+x, y, z)



Ring 1	Ring 2ⁱ	Cg1 to Cg2 (Å)	Plane to plane (Å)	Offset (°)
N1 C1···C5	N3 C11···C15	3.785	3.67	13.9

Acknowledgements

This project was supported by the National Natural Science Foundation of China (grant No. 20571086).

References

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