Tris(2,2′-bi-1H-imidazole-κ2N3,N3′)­nickel(II) dinitrate N,N-dimethyl­formamide monosolvate

Qiu, Q.-M.; Yang, W.; Li, Z.-F.; Jin, Q.-H.; Zhang, C.-L.

doi:10.1107/S1600536811043030

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Pages m1589-m1590

doi:10.1107/S1600536811043030

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Tris(2,2′-bi-1H-imidazole-κ²N³,N^3′)nickel(II) dinitrate N,N-dimethylformamide monosolvate

Qi-Ming Qiu,^a Wei Yang,^a Zhong-Feng Li,^a Qiong-Hua Jin ^a ^* and Cun-Lin Zhang ^b

^aDepartment of Chemistry, Capital Normal University, Beijing 100048, People's Republic of China, and ^bKey Laboratory of Terahertz Optoelectronics, Ministry of Education, Department of Physics, Capital Normal University, Beijing 100048, People's Republic of China
^*Correspondence e-mail: jinqh204@163.com

(Received 5 October 2011; accepted 17 October 2011; online 22 October 2011)

The reaction of nickel salts and 4,4′-bipyridine with 2,2′-biimidazole (H₂biim) yielded the title complex, [Ni(C₆H₆N₄)₃](NO₃)₂·C₃H₇NO. The Ni^II atom is chelated by three H₂biim ligands in a distorted octahedral coordination geometry. The two nitrate anions and one dimethylformamide (DMF) molecule are not coordinated. The compound has a three-dimensional structure, formed by extensive hydrogen bonding between [Ni(H₂biim)₃]²⁺ cations and nitrate anions, each nitrate anion forming hydrogen bonds with an R₁²(4) motif. The DMF molecule is disordered over three sets of sites, with occupancy ratios of 0.341 (16):0.350 (17):0.309 (19).

Related literature

For related literature on the 2,2′-biimidazole ligand, see: Ding et al. (2005 ); Gruia et al. (2007 ); Martinez Lorente et al. (1995 ). For related structures, see: Dai et al. (2010 ); Jin et al. (2010 ); Yang et al. (2005 ).

Experimental

Crystal data

[Ni(C₆H₆N₄)₃](NO₃)₂·C₃H₇NO
M_r = 658.27
Monoclinic, C c
a = 12.2150 (11) Å
b = 20.864 (2) Å
c = 12.1080 (12) Å
β = 90.528 (1)°
V = 3085.6 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 298 K
0.36 × 0.19 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.788, T_max = 0.921
7496 measured reflections
4289 independent reflections
1969 reflections with I > 2σ(I)
R_int = 0.131

Refinement

R[F² > 2σ(F²)] = 0.109
wR(F²) = 0.276
S = 1.06
4289 reflections
437 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.61 e Å⁻³
Absolute structure: Flack (1983 ), 2702 Friedel pairs
Flack parameter: 0.00 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O5ⁱ	0.86	2.19	2.93 (2)	144
N2—H2⋯O4ⁱ	0.86	2.30	2.98 (2)	136
N4—H4⋯O1ⁱⁱ	0.86	1.91	2.77 (2)	176
N4—H4⋯O3ⁱⁱ	0.86	2.45	3.04 (3)	127
N6—H6⋯O6	0.86	2.05	2.90 (3)	171
N6—H6⋯O4	0.86	2.43	3.09 (2)	133
N8—H8⋯O2ⁱⁱⁱ	0.86	2.09	2.82 (3)	141
N8—H8⋯O3ⁱⁱⁱ	0.86	2.36	2.98 (2)	130
N10—H10⋯O5^iv	0.86	2.17	2.98 (3)	156
N10—H10⋯O6^iv	0.86	2.45	3.16 (2)	140
N12—H12⋯O2^v	0.86	2.29	2.97 (2)	136
Symmetry codes: (i) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x, -y+1, z+{\script{1\over 2}}]$ ; (iv) x+1, y, z; (v) $[x+1, -y+1, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811043030/zk2032sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811043030/zk2032Isup2.hkl

checkCIF report

Comment top

2,2'-Biimidazole is an excellent candidate for building a supramolecular structure involving directed hydrogen bonding interactions (Dai et al., 2010; Ding et al., 2005; Gruia et al., 2007; Jin et al., 2010; Yang et al., 2005). This versatile molecule can act as a non-deprotonated, mono-deprotonated or bis-deprotonated ligand (Martinez Lorente et al., 1995). Furthermore, the uncoordinated N—H groups in H₂biim can participate in various patterns of hydrogen bonds with other acceptors. This may provides useful information to understand the complicated process in biological systems (Gruia et al., 2007; Ding et al., 2005). Herein we report the compound [Ni(H₂biim)₃(NO₃)₂].C₃H₇NO.

The asymmetry unit of the title compound consists of one [Ni(H₂biim)₃]²⁺ cation,two nitrate anions and one free N,N-dimethyl formamide molecule(Fig.1). The complex is monoclinic in Cc space group. In the title complex, the metal center allows the formation of a distorted octahedral geometry with six nitrogen atoms of three chelating H₂biim ligands. The compound contains three bidentate H₂biim ligands which provide six external N—H groups, which form hyfrogen bonds with the O atoms of NO₃^- anions to generate an extended hydrogen-bonded three-dimensional structure (Fig.2).

In [Ni(H₂biim)₃(NO₃)₂].C₃H₇NO, the Ni—N bond lengths are in the range 2.005 (2)–2.106 (2) Å, which agree with those in the compound [Ni(C₆H₆N₄)₃](C₈H₄O₄) (C₈H₄O₄ = phthalate dianions)(Yang et al., 2005). The distorted N—Ni—N bite angles of H₂biim ligands [N3—Ni1—N1 = 81.1 (7)°, N5—Ni1—N7 = 81.6 (8)°, N9—Ni1—N11 = 80.2 (8)°] agree with the corresponding angles for [Ni(H₂biim)₃]²⁺ complexes (Yang et al., 2005). The hydrogen bonds are formed between the N—H donors of H₂biim and the oxygen atoms from NO₃^- (O4 and O5), with d(N2···O4) = 2.979 Å, d(N2···O5) = 2.930 Å, N2—H2···O4 =136.28° and N2—H2···O5 = 144.29°.

It is interesting that the solvated DMF did not come from the starting materials. This phenomena also appeared in other similar reactions of H₂biim with metal salts in the solvent CH₃OH and H₂O.

Related literature top

For related literature on the 2,2'-biimidazole ligand, see: Ding et al. (2005); Gruia et al. (2007); Martinez Lorente et al. (1995). For related structures, see: Dai et al. (2010); Jin et al. (2010); Yang et al. (2005).

Experimental top

The title complex has been prepared by adding 4,4'-bipyridine (0.2 mmol) and H₂biim (0.4 mmol) into a stirred CH₃OH (5 mL) and H₂O (5 mL) containing Ni(NO₃)₂.6H₂O (0.2 mmol). The mixture was refluxed for 30 min and then allowed to cool to ambient temperature. The filtrate was evaporated slowly at room temperature for several weeks to yield purple crystalline products.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); 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. .1. The molecular entities of the title compound, showing the atom-numbering scheme and with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The three-dimensional structure of the title complex formed through intermolecular N—H···O hydrogen bonds.

Tris(2,2'-bi-1H-imidazole-κ²N³,N^3')nickel(II) dinitrate N,N-dimethylformamide monosolvate top

Crystal data top

[Ni(C₆H₆N₄)₃](NO₃)₂·C₃H₇NO	F(000) = 1360
M_r = 658.27	D_x = 1.417 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 12.2150 (11) Å	Cell parameters from 1160 reflections
b = 20.864 (2) Å	θ = 2.5–17.3°
c = 12.1080 (12) Å	µ = 0.69 mm⁻¹
β = 90.528 (1)°	T = 298 K
V = 3085.6 (5) Å³	Block, purple
Z = 4	0.36 × 0.19 × 0.12 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	4289 independent reflections
Radiation source: fine-focus sealed tube	1969 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.131
phi and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −14→14
T_min = 0.788, T_max = 0.921	k = −23→24
7496 measured reflections	l = −14→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.109	H-atom parameters constrained
wR(F²) = 0.276	w = 1/[σ²(F_o²) + (0.117P)²] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
4289 reflections	Δρ_max = 0.54 e Å⁻³
437 parameters	Δρ_min = −0.61 e Å⁻³
3 restraints	Absolute structure: Flack (1983), 1549 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (6)

Crystal data top

[Ni(C₆H₆N₄)₃](NO₃)₂·C₃H₇NO	V = 3085.6 (5) Å³
M_r = 658.27	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 12.2150 (11) Å	µ = 0.69 mm⁻¹
b = 20.864 (2) Å	T = 298 K
c = 12.1080 (12) Å	0.36 × 0.19 × 0.12 mm
β = 90.528 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4289 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1969 reflections with I > 2σ(I)
T_min = 0.788, T_max = 0.921	R_int = 0.131
7496 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.109	H-atom parameters constrained
wR(F²) = 0.276	Δρ_max = 0.54 e Å⁻³
S = 1.06	Δρ_min = −0.61 e Å⁻³
4289 reflections	Absolute structure: Flack (1983), 1549 Friedel pairs
437 parameters	Absolute structure parameter: 0.00 (6)
3 restraints

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	Occ. (<1)
Ni1	0.6556 (2)	0.33319 (8)	0.3945 (2)	0.0423 (5)
N1	0.7111 (15)	0.2490 (8)	0.3170 (16)	0.065 (5)
N2	0.6946 (14)	0.1433 (8)	0.3119 (16)	0.075 (5)
H2	0.6816	0.1045	0.3317	0.090*
N3	0.6035 (15)	0.2688 (8)	0.5051 (14)	0.062 (5)
N4	0.5823 (19)	0.1662 (7)	0.5541 (19)	0.072 (6)
H4	0.5800	0.1251	0.5481	0.086*
N5	0.5220 (19)	0.3337 (7)	0.2926 (18)	0.068 (6)
N6	0.3559 (17)	0.3726 (9)	0.2553 (18)	0.085 (6)
H6	0.2946	0.3922	0.2640	0.102*
N7	0.5692 (17)	0.4055 (8)	0.4700 (15)	0.067 (5)
N8	0.4052 (15)	0.4534 (8)	0.4806 (16)	0.079 (6)
H8	0.3384	0.4638	0.4666	0.095*
N9	0.7373 (16)	0.3892 (8)	0.2801 (16)	0.065 (5)
N10	0.8848 (15)	0.4446 (7)	0.2328 (16)	0.067 (5)
H10	0.9503	0.4596	0.2342	0.081*
N11	0.7983 (16)	0.3544 (8)	0.4856 (16)	0.064 (5)
N12	0.9522 (14)	0.4110 (8)	0.4904 (17)	0.076 (5)
H12	1.0047	0.4360	0.4712	0.091*
N13	0.161 (2)	0.4854 (9)	0.0305 (15)	0.072 (5)
N14	0.154 (2)	0.4795 (11)	0.2929 (17)	0.081 (6)
N15	0.102 (8)	0.110 (4)	0.383 (5)	0.103 (14)	0.341 (16)
N16	0.103 (6)	0.237 (4)	0.409 (5)	0.103 (14)	0.350 (17)
N17	0.266 (9)	0.186 (4)	0.395 (7)	0.103 (14)	0.309 (19)
O1	0.0657 (16)	0.4662 (7)	0.0412 (16)	0.102 (5)
O2	0.1804 (15)	0.5453 (8)	0.0304 (14)	0.093 (5)
O3	0.2365 (15)	0.4472 (8)	0.0272 (12)	0.098 (5)
O4	0.2461 (15)	0.5046 (7)	0.2861 (11)	0.081 (4)
O5	0.0835 (15)	0.5192 (7)	0.2951 (14)	0.091 (5)
O6	0.1376 (15)	0.4256 (8)	0.2796 (14)	0.097 (5)
O7	0.266 (6)	0.077 (3)	0.364 (4)	0.104 (11)	0.341 (16)
O8	−0.002 (5)	0.155 (3)	0.400 (4)	0.104 (11)	0.350 (17)
O9	0.358 (5)	0.104 (3)	0.352 (5)	0.104 (11)	0.309 (19)
C1	0.6771 (18)	0.1972 (8)	0.3734 (19)	0.066 (6)
C2	0.737 (3)	0.1628 (11)	0.212 (3)	0.089 (9)
H2B	0.7517	0.1368	0.1521	0.107*
C3	0.7530 (18)	0.2277 (10)	0.219 (2)	0.071 (6)
H3	0.7867	0.2530	0.1663	0.086*
C4	0.6245 (18)	0.2077 (10)	0.4790 (18)	0.068 (6)
C5	0.5439 (16)	0.2016 (10)	0.6411 (19)	0.074 (6)
H5	0.5196	0.1846	0.7075	0.089*
C6	0.5468 (17)	0.2652 (10)	0.6160 (18)	0.074 (6)
H6A	0.5199	0.2991	0.6577	0.089*
C7	0.446 (2)	0.3781 (10)	0.321 (2)	0.075 (7)
C8	0.380 (2)	0.3300 (10)	0.173 (2)	0.088 (7)
H8A	0.3379	0.3212	0.1104	0.106*
C9	0.479 (2)	0.3029 (11)	0.2000 (19)	0.083 (7)
H9	0.5120	0.2692	0.1626	0.099*
C10	0.469 (2)	0.4126 (10)	0.422 (2)	0.073 (7)
C11	0.469 (2)	0.4745 (10)	0.567 (2)	0.080 (7)
H11	0.4484	0.5041	0.6199	0.096*
C12	0.5682 (19)	0.4447 (9)	0.5607 (19)	0.071 (6)
H12A	0.6259	0.4501	0.6105	0.085*
C13	0.833 (2)	0.4131 (9)	0.317 (2)	0.064 (6)
C14	0.8125 (19)	0.4477 (10)	0.147 (2)	0.082 (6)
H14	0.8234	0.4689	0.0801	0.099*
C15	0.7209 (19)	0.4138 (9)	0.1757 (19)	0.073 (6)
H15	0.6584	0.4085	0.1324	0.088*
C16	0.8647 (18)	0.3931 (10)	0.427 (2)	0.062 (6)
C17	0.9403 (19)	0.3817 (11)	0.591 (2)	0.077 (7)
H17	0.9886	0.3849	0.6504	0.092*
C18	0.8452 (18)	0.3468 (9)	0.5885 (19)	0.071 (6)
H18	0.8174	0.3224	0.6461	0.086*
C19	0.176 (8)	0.065 (3)	0.405 (7)	0.097 (15)	0.341 (16)
H19	0.1619	0.0286	0.4466	0.117*	0.341 (16)
C20	0.126 (11)	0.178 (6)	0.403 (10)	0.10 (2)	0.341 (16)
H20A	0.1347	0.1849	0.4811	0.143*	0.341 (16)
H20B	0.0657	0.2034	0.3760	0.143*	0.341 (16)
H20C	0.1914	0.1899	0.3657	0.143*	0.341 (16)
C21	−0.015 (7)	0.094 (4)	0.373 (6)	0.100 (14)	0.341 (16)
H21A	−0.0309	0.0804	0.2988	0.150*	0.341 (16)
H21B	−0.0573	0.1315	0.3897	0.150*	0.341 (16)
H21C	−0.0325	0.0604	0.4236	0.150*	0.341 (16)
C22	0.001 (7)	0.214 (4)	0.413 (6)	0.097 (15)	0.350 (17)
H22	−0.0604	0.2396	0.4246	0.117*	0.350 (17)
C23	0.195 (11)	0.192 (7)	0.390 (9)	0.10 (2)	0.350 (17)
H23A	0.1675	0.1534	0.3550	0.143*	0.350 (17)
H23B	0.2286	0.1809	0.4591	0.143*	0.350 (17)
H23C	0.2477	0.2116	0.3427	0.143*	0.350 (17)
C24	0.135 (6)	0.296 (3)	0.467 (6)	0.100 (14)	0.350 (17)
H24A	0.0830	0.3288	0.4518	0.150*	0.350 (17)
H24B	0.2063	0.3088	0.4425	0.150*	0.350 (17)
H24C	0.1380	0.2875	0.5452	0.150*	0.350 (17)
C25	0.364 (9)	0.159 (5)	0.392 (7)	0.097 (15)	0.309 (19)
H25	0.4286	0.1781	0.4163	0.117*	0.309 (19)
C26	0.166 (12)	0.147 (6)	0.386 (12)	0.10 (2)	0.309 (19)
H26A	0.1795	0.1111	0.3375	0.143*	0.309 (19)
H26B	0.1077	0.1725	0.3559	0.143*	0.309 (19)
H26C	0.1463	0.1313	0.4574	0.143*	0.309 (19)
C27	0.251 (8)	0.256 (4)	0.397 (6)	0.100 (14)	0.309 (19)
H27A	0.2538	0.2709	0.4717	0.150*	0.309 (19)
H27B	0.1813	0.2663	0.3645	0.150*	0.309 (19)
H27C	0.3081	0.2760	0.3552	0.150*	0.309 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0549 (11)	0.0431 (10)	0.0289 (10)	0.0010 (13)	−0.0019 (7)	−0.0009 (13)
N1	0.083 (13)	0.054 (10)	0.059 (13)	−0.001 (9)	0.002 (9)	−0.003 (10)
N2	0.113 (15)	0.051 (9)	0.061 (12)	0.011 (8)	0.017 (10)	−0.010 (9)
N3	0.084 (12)	0.052 (10)	0.051 (12)	−0.004 (8)	0.005 (9)	−0.002 (8)
N4	0.108 (18)	0.052 (11)	0.055 (14)	−0.008 (10)	0.012 (12)	0.015 (10)
N5	0.084 (13)	0.059 (10)	0.061 (13)	0.010 (10)	−0.014 (10)	−0.009 (9)
N6	0.096 (15)	0.088 (14)	0.072 (15)	0.023 (12)	−0.014 (13)	−0.004 (11)
N7	0.084 (15)	0.058 (10)	0.058 (13)	0.007 (9)	0.001 (10)	−0.002 (9)
N8	0.094 (14)	0.077 (11)	0.067 (14)	0.039 (10)	0.001 (11)	−0.012 (10)
N9	0.073 (13)	0.056 (10)	0.066 (14)	−0.003 (8)	−0.001 (10)	0.004 (9)
N10	0.069 (13)	0.062 (10)	0.071 (14)	−0.014 (9)	0.005 (10)	0.006 (10)
N11	0.076 (14)	0.053 (9)	0.061 (13)	−0.004 (9)	−0.014 (11)	0.000 (9)
N12	0.070 (12)	0.075 (12)	0.084 (15)	−0.018 (9)	−0.011 (10)	−0.008 (11)
N13	0.096 (17)	0.057 (12)	0.064 (13)	−0.004 (12)	0.018 (11)	0.023 (9)
N14	0.101 (18)	0.073 (15)	0.071 (15)	−0.011 (15)	−0.015 (12)	−0.006 (12)
N15	0.14 (4)	0.11 (3)	0.05 (2)	0.01 (3)	−0.01 (3)	0.03 (2)
N16	0.14 (4)	0.11 (3)	0.05 (2)	0.01 (3)	−0.01 (3)	0.03 (2)
N17	0.14 (4)	0.11 (3)	0.05 (2)	0.01 (3)	−0.01 (3)	0.03 (2)
O1	0.114 (15)	0.084 (11)	0.107 (15)	0.007 (10)	0.011 (11)	0.028 (10)
O2	0.121 (14)	0.074 (10)	0.085 (12)	−0.001 (9)	−0.003 (10)	0.013 (9)
O3	0.131 (14)	0.097 (11)	0.065 (11)	0.043 (11)	−0.005 (9)	0.027 (8)
O4	0.107 (13)	0.083 (10)	0.054 (10)	0.006 (10)	−0.009 (9)	0.011 (8)
O5	0.111 (13)	0.066 (9)	0.094 (14)	0.036 (9)	0.010 (10)	−0.012 (8)
O6	0.124 (14)	0.088 (11)	0.080 (13)	−0.002 (11)	−0.006 (10)	0.015 (10)
O7	0.14 (4)	0.11 (3)	0.056 (18)	0.00 (2)	−0.01 (2)	0.032 (18)
O8	0.14 (4)	0.11 (3)	0.056 (18)	0.00 (2)	−0.01 (2)	0.032 (18)
O9	0.14 (4)	0.11 (3)	0.056 (18)	0.00 (2)	−0.01 (2)	0.032 (18)
C1	0.092 (19)	0.050 (10)	0.057 (18)	0.008 (11)	0.004 (13)	−0.002 (11)
C2	0.12 (3)	0.072 (18)	0.07 (2)	0.011 (13)	0.013 (17)	−0.006 (14)
C3	0.100 (17)	0.058 (14)	0.056 (16)	0.010 (11)	0.008 (12)	−0.006 (11)
C4	0.089 (16)	0.061 (14)	0.054 (16)	−0.002 (11)	0.002 (12)	0.004 (12)
C5	0.101 (17)	0.061 (13)	0.060 (15)	0.004 (11)	0.030 (12)	0.008 (11)
C6	0.101 (17)	0.063 (13)	0.058 (15)	0.001 (11)	0.019 (12)	0.000 (10)
C7	0.084 (19)	0.069 (14)	0.071 (18)	0.011 (13)	−0.008 (14)	−0.014 (12)
C8	0.101 (19)	0.083 (15)	0.081 (17)	0.022 (15)	−0.014 (14)	−0.007 (15)
C9	0.096 (18)	0.078 (15)	0.074 (18)	0.017 (13)	−0.009 (14)	−0.005 (13)
C10	0.086 (18)	0.067 (13)	0.066 (17)	0.026 (12)	0.008 (13)	−0.006 (12)
C11	0.10 (2)	0.072 (14)	0.066 (17)	0.024 (13)	0.008 (14)	−0.010 (12)
C12	0.098 (17)	0.056 (12)	0.059 (15)	0.027 (12)	0.004 (12)	−0.010 (11)
C13	0.073 (16)	0.053 (11)	0.066 (17)	−0.004 (11)	0.004 (13)	−0.004 (11)
C14	0.088 (17)	0.082 (15)	0.077 (18)	−0.022 (13)	0.007 (14)	0.004 (13)
C15	0.090 (16)	0.064 (13)	0.066 (16)	−0.015 (11)	0.001 (12)	0.000 (11)
C16	0.067 (15)	0.056 (13)	0.064 (16)	−0.012 (10)	−0.002 (12)	−0.006 (11)
C17	0.073 (16)	0.075 (14)	0.083 (19)	−0.012 (12)	−0.018 (13)	−0.011 (14)
C18	0.078 (16)	0.063 (12)	0.073 (16)	0.001 (11)	−0.017 (12)	−0.002 (11)
C19	0.14 (5)	0.10 (3)	0.05 (3)	0.01 (3)	−0.01 (3)	0.03 (3)
C20	0.14 (7)	0.11 (6)	0.04 (3)	0.01 (5)	−0.02 (4)	0.04 (4)
C21	0.14 (4)	0.11 (3)	0.05 (3)	0.01 (3)	−0.01 (2)	0.03 (3)
C22	0.14 (5)	0.10 (3)	0.05 (3)	0.01 (3)	−0.01 (3)	0.03 (3)
C23	0.14 (7)	0.11 (6)	0.04 (3)	0.01 (5)	−0.02 (4)	0.04 (4)
C24	0.14 (4)	0.11 (3)	0.05 (3)	0.01 (3)	−0.01 (2)	0.03 (3)
C25	0.14 (5)	0.10 (3)	0.05 (3)	0.01 (3)	−0.01 (3)	0.03 (3)
C26	0.14 (7)	0.11 (6)	0.04 (3)	0.01 (5)	−0.02 (4)	0.04 (4)
C27	0.14 (4)	0.11 (3)	0.05 (3)	0.01 (3)	−0.01 (2)	0.03 (3)

Geometric parameters (Å, º) top

Ni1—N3	2.005 (18)	N17—C25	1.32 (11)
Ni1—N5	2.04 (2)	N17—C27	1.47 (11)
Ni1—N7	2.060 (19)	N17—C26	1.48 (16)
Ni1—N9	2.075 (19)	O7—C19	1.24 (10)
Ni1—N11	2.101 (18)	O8—C22	1.25 (8)
Ni1—N1	2.106 (18)	O9—C25	1.24 (9)
N1—C1	1.35 (2)	C1—C4	1.45 (3)
N1—C3	1.37 (3)	C2—C3	1.37 (3)
N2—C1	1.37 (2)	C2—H2B	0.9300
N2—C2	1.38 (4)	C3—H3	0.9300
N2—H2	0.8600	C5—C6	1.36 (3)
N3—C4	1.34 (2)	C5—H5	0.9300
N3—C6	1.52 (3)	C6—H6A	0.9300
N4—C4	1.36 (3)	C7—C10	1.44 (3)
N4—C5	1.37 (3)	C8—C9	1.37 (3)
N4—H4	0.8600	C8—H8A	0.9300
N5—C7	1.35 (3)	C9—H9	0.9300
N5—C9	1.39 (3)	C11—C12	1.36 (3)
N6—C7	1.36 (3)	C11—H11	0.9300
N6—C8	1.37 (3)	C12—H12A	0.9300
N6—H6	0.8600	C13—C16	1.45 (3)
N7—C10	1.36 (3)	C14—C15	1.37 (3)
N7—C12	1.37 (3)	C14—H14	0.9300
N8—C10	1.36 (3)	C15—H15	0.9300
N8—C11	1.37 (3)	C17—C18	1.37 (3)
N8—H8	0.8600	C17—H17	0.9300
N9—C13	1.35 (3)	C18—H18	0.9300
N9—C15	1.38 (3)	C19—H19	0.9300
N10—C14	1.36 (3)	C20—H20A	0.9600
N10—C13	1.37 (3)	C20—H20B	0.9600
N10—H10	0.8600	C20—H20C	0.9600
N11—C16	1.35 (3)	C21—H21A	0.9600
N11—C18	1.38 (3)	C21—H21B	0.9600
N12—C16	1.36 (2)	C21—H21C	0.9600
N12—C17	1.37 (3)	C22—H22	0.9300
N12—H12	0.8600	C23—H23A	0.9600
N13—O3	1.22 (2)	C23—H23B	0.9600
N13—O1	1.23 (2)	C23—H23C	0.9600
N13—O2	1.27 (2)	C24—H24A	0.9600
N14—O6	1.15 (2)	C24—H24B	0.9600
N14—O5	1.20 (2)	C24—H24C	0.9600
N14—O4	1.24 (3)	C25—H25	0.9300
N15—C19	1.32 (8)	C26—H26A	0.9600
N15—C21	1.47 (11)	C26—H26B	0.9600
N15—C20	1.48 (12)	C26—H26C	0.9600
N16—C22	1.33 (9)	C27—H27A	0.9600
N16—C24	1.47 (9)	C27—H27B	0.9600
N16—C23	1.48 (13)	C27—H27C	0.9600

N3—Ni1—N5	98.6 (8)	N2—C2—H2B	126.5
N3—Ni1—N7	91.5 (8)	N1—C3—C2	109 (3)
N5—Ni1—N7	81.6 (8)	N1—C3—H3	125.7
N3—Ni1—N9	168.8 (8)	C2—C3—H3	125.7
N5—Ni1—N9	88.9 (8)	N3—C4—N4	112 (2)
N7—Ni1—N9	97.8 (6)	N3—C4—C1	116.0 (19)
N3—Ni1—N11	93.3 (7)	N4—C4—C1	132 (2)
N5—Ni1—N11	166.6 (7)	C6—C5—N4	110 (2)
N7—Ni1—N11	92.2 (8)	C6—C5—H5	125.0
N9—Ni1—N11	80.2 (8)	N4—C5—H5	125.0
N3—Ni1—N1	81.1 (7)	C5—C6—N3	105.0 (18)
N5—Ni1—N1	89.7 (7)	C5—C6—H6A	127.5
N7—Ni1—N1	167.6 (8)	N3—C6—H6A	127.5
N9—Ni1—N1	90.8 (7)	N5—C7—N6	110 (2)
N11—Ni1—N1	98.1 (7)	N5—C7—C10	115 (2)
C1—N1—C3	107.2 (17)	N6—C7—C10	133 (3)
C1—N1—Ni1	110.0 (15)	C9—C8—N6	107 (2)
C3—N1—Ni1	141.4 (15)	C9—C8—H8A	126.6
C1—N2—C2	107.2 (17)	N6—C8—H8A	126.6
C1—N2—H2	126.4	C8—C9—N5	109 (2)
C2—N2—H2	126.4	C8—C9—H9	125.4
C4—N3—C6	104.5 (18)	N5—C9—H9	125.4
C4—N3—Ni1	114.7 (15)	N7—C10—N8	111 (2)
C6—N3—Ni1	140.7 (13)	N7—C10—C7	118 (2)
C4—N4—C5	107.7 (16)	N8—C10—C7	130 (2)
C4—N4—H4	126.1	C12—C11—N8	108 (2)
C5—N4—H4	126.1	C12—C11—H11	125.8
C7—N5—C9	105 (2)	N8—C11—H11	125.8
C7—N5—Ni1	113.4 (16)	C11—C12—N7	109 (2)
C9—N5—Ni1	141.2 (17)	C11—C12—H12A	125.4
C7—N6—C8	107 (2)	N7—C12—H12A	125.4
C7—N6—H6	126.3	N9—C13—N10	110 (2)
C8—N6—H6	126.3	N9—C13—C16	115 (2)
C10—N7—C12	105.4 (19)	N10—C13—C16	135 (2)
C10—N7—Ni1	110.6 (15)	N10—C14—C15	108 (2)
C12—N7—Ni1	143.3 (16)	N10—C14—H14	126.2
C10—N8—C11	106 (2)	C15—C14—H14	126.2
C10—N8—H8	127.1	C14—C15—N9	108 (2)
C11—N8—H8	127.1	C14—C15—H15	125.8
C13—N9—C15	106.4 (19)	N9—C15—H15	125.8
C13—N9—Ni1	114.3 (16)	N11—C16—N12	110 (2)
C15—N9—Ni1	139.1 (16)	N11—C16—C13	120 (2)
C14—N10—C13	107.1 (19)	N12—C16—C13	130 (2)
C14—N10—H10	126.5	N12—C17—C18	108 (2)
C13—N10—H10	126.5	N12—C17—H17	125.8
C16—N11—C18	107.3 (19)	C18—C17—H17	125.8
C16—N11—Ni1	110.4 (15)	C17—C18—N11	108 (2)
C18—N11—Ni1	142.0 (17)	C17—C18—H18	126.2
C16—N12—C17	107 (2)	N11—C18—H18	126.2
C16—N12—H12	126.6	O7—C19—N15	113 (8)
C17—N12—H12	126.6	O7—C19—H19	123.6
O3—N13—O1	120.2 (19)	N15—C19—H19	123.6
O3—N13—O2	120 (2)	O8—C22—N16	112 (8)
O1—N13—O2	120 (2)	O8—C22—H22	124.0
O6—N14—O5	124 (3)	N16—C22—H22	124.0
O6—N14—O4	124 (3)	N16—C23—H23A	109.5
O5—N14—O4	111 (2)	N16—C23—H23B	109.5
C19—N15—C21	122 (8)	H23A—C23—H23B	109.5
C19—N15—C20	121 (9)	N16—C23—H23C	109.5
C21—N15—C20	114 (8)	H23A—C23—H23C	109.5
C22—N16—C24	122 (8)	H23B—C23—H23C	109.5
C22—N16—C23	120 (9)	N16—C24—H24A	109.5
C24—N16—C23	114 (8)	N16—C24—H24B	109.5
C25—N17—C27	123 (10)	H24A—C24—H24B	109.5
C25—N17—C26	120 (10)	N16—C24—H24C	109.5
C27—N17—C26	116 (10)	H24A—C24—H24C	109.5
N1—C1—N2	109.6 (18)	H24B—C24—H24C	109.5
N1—C1—C4	117.7 (18)	O9—C25—N17	111 (10)
N2—C1—C4	132.5 (18)	O9—C25—H25	124.5
C3—C2—N2	107 (3)	N17—C25—H25	124.5
C3—C2—H2B	126.5

N3—Ni1—N1—C1	4.9 (14)	N2—C2—C3—N1	−6 (3)
N5—Ni1—N1—C1	−93.9 (15)	C6—N3—C4—N4	4 (2)
N7—Ni1—N1—C1	−49 (4)	Ni1—N3—C4—N4	−176.8 (15)
N9—Ni1—N1—C1	177.2 (14)	C6—N3—C4—C1	178.6 (17)
N11—Ni1—N1—C1	97.0 (14)	Ni1—N3—C4—C1	−3 (2)
N3—Ni1—N1—C3	169 (2)	C5—N4—C4—N3	−8 (3)
N5—Ni1—N1—C3	70 (2)	C5—N4—C4—C1	179 (2)
N7—Ni1—N1—C3	115 (4)	N1—C1—C4—N3	7 (3)
N9—Ni1—N1—C3	−19 (2)	N2—C1—C4—N3	−168 (2)
N11—Ni1—N1—C3	−99 (2)	N1—C1—C4—N4	−180 (2)
N5—Ni1—N3—C4	87.1 (16)	N2—C1—C4—N4	5 (4)
N7—Ni1—N3—C4	168.8 (15)	C4—N4—C5—C6	9 (3)
N9—Ni1—N3—C4	−45 (5)	N4—C5—C6—N3	−6 (2)
N11—Ni1—N3—C4	−98.9 (15)	C4—N3—C6—C5	1 (2)
N1—Ni1—N3—C4	−1.2 (15)	Ni1—N3—C6—C5	−177.4 (17)
N5—Ni1—N3—C6	−95 (2)	C9—N5—C7—N6	5 (3)
N7—Ni1—N3—C6	−13 (2)	Ni1—N5—C7—N6	−175.1 (16)
N9—Ni1—N3—C6	134 (4)	C9—N5—C7—C10	175 (2)
N11—Ni1—N3—C6	79 (2)	Ni1—N5—C7—C10	−5 (3)
N1—Ni1—N3—C6	177 (2)	C8—N6—C7—N5	−9 (3)
N3—Ni1—N5—C7	90.6 (18)	C8—N6—C7—C10	−176 (3)
N7—Ni1—N5—C7	0.3 (18)	C7—N6—C8—C9	9 (3)
N9—Ni1—N5—C7	−97.8 (18)	N6—C8—C9—N5	−7 (3)
N11—Ni1—N5—C7	−63 (6)	C7—N5—C9—C8	1 (3)
N1—Ni1—N5—C7	171.5 (19)	Ni1—N5—C9—C8	−179 (2)
N3—Ni1—N5—C9	−89 (3)	C12—N7—C10—N8	−2 (2)
N7—Ni1—N5—C9	−179 (3)	Ni1—N7—C10—N8	171.0 (15)
N9—Ni1—N5—C9	83 (3)	C12—N7—C10—C7	178 (2)
N11—Ni1—N5—C9	118 (4)	Ni1—N7—C10—C7	−9 (3)
N1—Ni1—N5—C9	−8 (3)	C11—N8—C10—N7	2 (3)
N3—Ni1—N7—C10	−93.7 (15)	C11—N8—C10—C7	−177 (2)
N5—Ni1—N7—C10	4.8 (15)	N5—C7—C10—N7	10 (3)
N9—Ni1—N7—C10	92.5 (16)	N6—C7—C10—N7	177 (2)
N11—Ni1—N7—C10	172.9 (16)	N5—C7—C10—N8	−170 (2)
N1—Ni1—N7—C10	−41 (4)	N6—C7—C10—N8	−3 (5)
N3—Ni1—N7—C12	74 (3)	C10—N8—C11—C12	−2 (3)
N5—Ni1—N7—C12	173 (3)	N8—C11—C12—N7	1 (3)
N9—Ni1—N7—C12	−100 (2)	C10—N7—C12—C11	0 (2)
N11—Ni1—N7—C12	−19 (3)	Ni1—N7—C12—C11	−168 (2)
N1—Ni1—N7—C12	127 (4)	C15—N9—C13—N10	−8 (2)
N3—Ni1—N9—C13	−58 (4)	Ni1—N9—C13—N10	175.0 (13)
N5—Ni1—N9—C13	169.8 (15)	C15—N9—C13—C16	179.3 (18)
N7—Ni1—N9—C13	88.5 (16)	Ni1—N9—C13—C16	3 (2)
N11—Ni1—N9—C13	−2.4 (14)	C14—N10—C13—N9	8 (2)
N1—Ni1—N9—C13	−100.5 (14)	C14—N10—C13—C16	178 (2)
N3—Ni1—N9—C15	127 (4)	C13—N10—C14—C15	−4 (2)
N5—Ni1—N9—C15	−5 (2)	N10—C14—C15—N9	−1 (2)
N7—Ni1—N9—C15	−87 (2)	C13—N9—C15—C14	6 (2)
N11—Ni1—N9—C15	−177 (2)	Ni1—N9—C15—C14	−179.2 (16)
N1—Ni1—N9—C15	84 (2)	C18—N11—C16—N12	−1 (2)
N3—Ni1—N11—C16	172.5 (15)	Ni1—N11—C16—N12	174.7 (13)
N5—Ni1—N11—C16	−34 (6)	C18—N11—C16—C13	−176.3 (19)
N7—Ni1—N11—C16	−95.9 (15)	Ni1—N11—C16—C13	−1 (2)
N9—Ni1—N11—C16	1.7 (14)	C17—N12—C16—N11	1 (2)
N1—Ni1—N11—C16	91.0 (15)	C17—N12—C16—C13	176 (2)
N3—Ni1—N11—C18	−15 (2)	N9—C13—C16—N11	−1 (3)
N5—Ni1—N11—C18	139 (4)	N10—C13—C16—N11	−171 (2)
N7—Ni1—N11—C18	77 (2)	N9—C13—C16—N12	−176 (2)
N9—Ni1—N11—C18	175 (2)	N10—C13—C16—N12	15 (4)
N1—Ni1—N11—C18	−96 (2)	C16—N12—C17—C18	−1 (2)
C3—N1—C1—N2	−1 (2)	N12—C17—C18—N11	0 (3)
Ni1—N1—C1—N2	168.2 (14)	C16—N11—C18—C17	0 (2)
C3—N1—C1—C4	−177.3 (19)	Ni1—N11—C18—C17	−172.9 (18)
Ni1—N1—C1—C4	−8 (2)	C21—N15—C19—O7	150 (7)
C2—N2—C1—N1	−2 (3)	C20—N15—C19—O7	−51 (11)
C2—N2—C1—C4	173 (3)	C24—N16—C22—O8	−153 (6)
C1—N2—C2—C3	5 (3)	C23—N16—C22—O8	0 (10)
C1—N1—C3—C2	5 (3)	C27—N17—C25—O9	−156 (8)
Ni1—N1—C3—C2	−160 (2)	C26—N17—C25—O9	18 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O5ⁱ	0.86	2.19	2.93 (2)	144
N2—H2···O4ⁱ	0.86	2.30	2.98 (2)	136
N4—H4···O1ⁱⁱ	0.86	1.91	2.77 (2)	176
N4—H4···O3ⁱⁱ	0.86	2.45	3.04 (3)	127
N6—H6···O6	0.86	2.05	2.90 (3)	171
N6—H6···O4	0.86	2.43	3.09 (2)	133
N8—H8···O2ⁱⁱⁱ	0.86	2.09	2.82 (3)	141
N8—H8···O3ⁱⁱⁱ	0.86	2.36	2.98 (2)	130
N10—H10···O5^iv	0.86	2.17	2.98 (3)	156
N10—H10···O6^iv	0.86	2.45	3.16 (2)	140
N12—H12···O2^v	0.86	2.29	2.97 (2)	136

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

Experimental details

Crystal data
Chemical formula	[Ni(C₆H₆N₄)₃](NO₃)₂·C₃H₇NO
M_r	658.27
Crystal system, space group	Monoclinic, Cc
Temperature (K)	298
a, b, c (Å)	12.2150 (11), 20.864 (2), 12.1080 (12)
β (°)	90.528 (1)
V (Å³)	3085.6 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.69
Crystal size (mm)	0.36 × 0.19 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.788, 0.921
No. of measured, independent and observed [I > 2σ(I)] reflections	7496, 4289, 1969
R_int	0.131
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.109, 0.276, 1.06
No. of reflections	4289
No. of parameters	437
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.61
Absolute structure	Flack (1983), 1549 Friedel pairs
Absolute structure parameter	0.00 (6)

Computer programs: SMART (Bruker, 2007), SAINT-Plus (Bruker, 2007), 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
N2—H2···O5ⁱ	0.86	2.19	2.93 (2)	144.3
N2—H2···O4ⁱ	0.86	2.30	2.98 (2)	136.3
N4—H4···O1ⁱⁱ	0.86	1.91	2.77 (2)	175.8
N4—H4···O3ⁱⁱ	0.86	2.45	3.04 (3)	126.7
N6—H6···O6	0.86	2.05	2.90 (3)	171.2
N6—H6···O4	0.86	2.43	3.09 (2)	133.2
N8—H8···O2ⁱⁱⁱ	0.86	2.09	2.82 (3)	141.3
N8—H8···O3ⁱⁱⁱ	0.86	2.36	2.98 (2)	129.9
N10—H10···O5^iv	0.86	2.17	2.98 (3)	155.5
N10—H10···O6^iv	0.86	2.45	3.16 (2)	140.0
N12—H12···O2^v	0.86	2.29	2.97 (2)	135.9

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

Acknowledgements

This work has been supported by the National Natural Science Foundation of China (grant No. 21171119), the National Keystone Basic Research Program (973 Program) under grant Nos. 2007CB310408 and 2006CB302901, and the Funding Project for Academic Human Resources Development in Institutions of Higher Learning Under the Jurisdiction of the Beijing Municipality Program for Excellent Talents of Beijing City (grant No. 2010D005016000002).

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