Bis[μ2-N′-acetyl-2-hydroxy-6-oxido­benzohydrazidato(3−)]octa­pyridine­trinickel(II)

Yang, Y.; Li, D.; Shi, X.

doi:10.1107/S1600536809020534

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page m746

doi:10.1107/S1600536809020534

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Bis[μ₂-N′-acetyl-2-hydroxy-6-oxidobenzohydrazidato(3−)]octapyridinetrinickel(II)

Yan Yang,^a Dacheng Li ^a ^* and Xuefeng Shi ^a

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: lidacheng62@lcu.edu.cn

(Received 19 May 2009; accepted 29 May 2009; online 6 June 2009)

The title trinuclear complex, [Ni₃(C₉H₇N₂O₄)₂(C₅H₅N)₈], possesses a crystallographically imposed center of symmetry occupied by one Ni^II ion. Each of the three Ni^II ions is coordinated by two O and four N atoms, respectively, in a distorted octahedral geometry. In the crystal, weak intermolecular C—H⋯π interactions link the molecules into ribbons propagating in the [100] direction.

Related literature

For applications of N-acetylsalicylhydrazide complexes, see: John et al. (2004 ); Lin et al. (2002 ).

Experimental

Crystal data

[Ni₃(C₉H₇N₂O₄)₂(C₅H₅N)₈]
M_r = 1223.26
Monoclinic, P 2₁ /n
a = 9.9349 (18) Å
b = 18.230 (3) Å
c = 16.262 (2) Å
β = 96.663 (2)°
V = 2925.3 (8) Å³
Z = 2
Mo Kα radiation
μ = 1.02 mm⁻¹
T = 298 K
0.53 × 0.45 × 0.44 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.614, T_max = 0.663
14103 measured reflections
5138 independent reflections
3047 reflections with I > 2σ(I)
R_int = 0.146

Refinement

R[F² > 2σ(F²)] = 0.075
wR(F²) = 0.210
S = 0.97
5138 reflections
368 parameters
1098 restraints
H-atom parameters constrained
Δρ_max = 1.32 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C27—H27⋯Cgⁱ	0.93	2.52	3.428 (4)	166
Symmetry code: (i) x+1, y, z. Cg is the centroid of the C2–C7 ring.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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 I, global. DOI: 10.1107/S1600536809020534/cv2565sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809020534/cv2565Isup2.hkl

checkCIF report

Comment top

In recent years, a large number of N-acetylsalicylhydrazide complexes have been prepared and studied due to their potential applications in chemically modified (Lin et al., 2002) and anion-selective separation agents (John et al., 2004). However, structures of nickel(II) complexes with N-acetyl-6-hydroxysalicylhydrzaide were not reported. So we have synthesized the title compound, which has been characterized by X-ray diffraction and elemental analysis.

The title complex (Fig. 1) contains three nickel(II) centers having distorted octahedral coordination environment, two ligand molecules and eight pyridine molecules. The triple-deprotonated N-acetyl-6-hydroxysalicylhydrzaide ligands bridge metal ions via hydrazide N—N group forming trinuclear nickel complex. In the crystal, the complex molecules are linked into ribbons via intermolecular C—H···π weak interactions (Table 1, Fig. 2).

Related literature top

For applications of N-acetylsalicylhydrazide complexes, see: John et al. (2004); Lin et al. (2002).

Experimental top

A solution of Ni(OAc)_2.4H₂O (0.4 mmol, 0.0996 g) in dimethylformamide (10 ml) was add to N-acetyl-(6-hydroxysalicylhydrzaide) (0.2 mmol, 0.042 g) in pyridine (10 ml). A reddish solution was obtained after refluxing for 3 h. After the solution had been stanging for two weeks, red block crystals suitable for X-ray diffraction appear.(m.p. >400 K). Elemental analysis calculated for C₅₈H₅₄N₁₂O₈Ni₃: C 56.95, H 4.45, N 13.74%; found: C 56.92, H 4.44, N 13.76%.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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. The molecular structure of the title complex, showing 40% probability displacement ellipsoids and the atomic numbering [symmetry code: (A) -x, -y, 2-z]. H atoms have been omitted for clarity.
	Fig. 2. A portion of the crystal packing showing one-dimensional ribbons. Intermolecular C—H···π interactions are shown as dashed lines. Most of H atoms are omitted.

Bis[µ₂-N'-acetyl-2-hydroxy-6- oxidobenzohydrazidato(3-)]octapyridinetrinickel(II) top

Crystal data top

[Ni₃(C₉H₇N₂O₄)₂(C₅H₅N)₈]	F(000) = 1268
M_r = 1223.26	D_x = 1.389 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.9349 (18) Å	Cell parameters from 4241 reflections
b = 18.230 (3) Å	θ = 2.2–26.2°
c = 16.262 (2) Å	µ = 1.02 mm⁻¹
β = 96.663 (2)°	T = 298 K
V = 2925.3 (8) Å³	Block, red
Z = 2	0.53 × 0.45 × 0.44 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	5138 independent reflections
Radiation source: fine-focus sealed tube	3047 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.146
phi and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.614, T_max = 0.663	k = −16→21
14103 measured reflections	l = −19→19

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)] = 0.075	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.210	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0999P)²] where P = (F_o² + 2F_c²)/3
5138 reflections	(Δ/σ)_max < 0.001
368 parameters	Δρ_max = 1.32 e Å⁻³
1098 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

[Ni₃(C₉H₇N₂O₄)₂(C₅H₅N)₈]	V = 2925.3 (8) Å³
M_r = 1223.26	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.9349 (18) Å	µ = 1.02 mm⁻¹
b = 18.230 (3) Å	T = 298 K
c = 16.262 (2) Å	0.53 × 0.45 × 0.44 mm
β = 96.663 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	5138 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3047 reflections with I > 2σ(I)
T_min = 0.614, T_max = 0.663	R_int = 0.146
14103 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.075	1098 restraints
wR(F²) = 0.210	H-atom parameters constrained
S = 0.97	Δρ_max = 1.32 e Å⁻³
5138 reflections	Δρ_min = −0.58 e Å⁻³
368 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	0.0000	0.0000	1.0000	0.0357 (3)
Ni2	−0.07930 (7)	0.24578 (3)	0.88362 (4)	0.0416 (3)
N1	−0.0186 (4)	0.1420 (2)	0.9063 (2)	0.0332 (9)
N2	−0.0473 (4)	0.11377 (19)	0.9860 (2)	0.0338 (9)
N3	0.2129 (4)	0.0283 (2)	1.0484 (3)	0.0434 (10)
N4	0.1185 (5)	0.2968 (2)	0.9214 (3)	0.0502 (11)
N5	−0.1604 (5)	0.3551 (2)	0.8698 (3)	0.0525 (11)
N6	−0.2903 (4)	0.2099 (2)	0.8443 (3)	0.0506 (11)
O1	0.0447 (3)	0.02165 (18)	0.88104 (19)	0.0391 (8)
O2	−0.0350 (4)	0.23782 (18)	0.7661 (2)	0.0441 (8)
O3	0.1899 (5)	−0.0024 (2)	0.7669 (3)	0.0712 (14)
H3	0.1430	−0.0122	0.8037	0.107*
O4	−0.1147 (3)	0.23505 (17)	1.0063 (2)	0.0395 (8)
C1	0.0280 (5)	0.0917 (3)	0.8579 (3)	0.0338 (11)
C2	0.0716 (5)	0.1143 (3)	0.7758 (3)	0.0398 (11)
C3	0.0407 (5)	0.1859 (3)	0.7368 (3)	0.0411 (11)
C4	0.0967 (5)	0.2028 (3)	0.6618 (3)	0.0473 (13)
H4	0.0820	0.2490	0.6381	0.057*
C5	0.1731 (6)	0.1513 (3)	0.6234 (3)	0.0544 (15)
H5	0.2057	0.1631	0.5737	0.065*
C6	0.2008 (6)	0.0828 (3)	0.6585 (3)	0.0566 (15)
H6	0.2515	0.0490	0.6323	0.068*
C7	0.1524 (6)	0.0643 (3)	0.7334 (3)	0.0472 (13)
C8	−0.0932 (5)	0.1671 (3)	1.0307 (3)	0.0398 (11)
C9	−0.1235 (7)	0.1487 (3)	1.1180 (4)	0.0637 (18)
H9A	−0.1324	0.1933	1.1484	0.096*
H9B	−0.0508	0.1199	1.1454	0.096*
H9C	−0.2065	0.1213	1.1153	0.096*
C10	0.2673 (8)	0.0927 (4)	1.0400 (5)	0.0862 (19)
H10	0.2164	0.1269	1.0074	0.103*
C11	0.3967 (9)	0.1145 (4)	1.0763 (6)	0.107 (3)
H11	0.4251	0.1627	1.0710	0.129*
C12	0.4777 (7)	0.0663 (4)	1.1179 (5)	0.088 (2)
H12	0.5658	0.0786	1.1390	0.105*
C13	0.4269 (8)	−0.0020 (5)	1.1287 (6)	0.107 (3)
H13	0.4792	−0.0373	1.1589	0.129*
C14	0.2941 (8)	−0.0185 (4)	1.0936 (5)	0.090 (2)
H14	0.2607	−0.0651	1.1025	0.108*
C15	0.1824 (6)	0.2935 (3)	0.9993 (4)	0.0557 (14)
H15	0.1414	0.2668	1.0382	0.067*
C16	0.3044 (7)	0.3272 (3)	1.0250 (4)	0.0666 (16)
H16	0.3460	0.3219	1.0789	0.080*
C17	0.3628 (7)	0.3692 (4)	0.9674 (5)	0.0728 (18)
H17	0.4438	0.3938	0.9829	0.087*
C18	0.3011 (7)	0.3746 (3)	0.8871 (5)	0.0688 (17)
H18	0.3398	0.4023	0.8480	0.083*
C19	0.1795 (7)	0.3376 (3)	0.8662 (4)	0.0604 (15)
H19	0.1379	0.3409	0.8120	0.073*
C20	−0.1519 (7)	0.4020 (3)	0.9337 (4)	0.0663 (16)
H20	−0.1007	0.3891	0.9831	0.080*
C21	−0.2174 (9)	0.4691 (4)	0.9283 (5)	0.091 (2)
H21	−0.2080	0.5009	0.9733	0.109*
C22	−0.2966 (9)	0.4892 (4)	0.8563 (5)	0.088 (2)
H22	−0.3422	0.5338	0.8527	0.106*
C23	−0.3065 (8)	0.4426 (4)	0.7915 (5)	0.088 (2)
H23	−0.3595	0.4543	0.7423	0.105*
C24	−0.2355 (7)	0.3765 (3)	0.7999 (4)	0.0719 (17)
H24	−0.2404	0.3454	0.7543	0.086*
C25	−0.3903 (6)	0.2194 (3)	0.8929 (4)	0.0618 (15)
H25	−0.3665	0.2354	0.9470	0.074*
C26	−0.5244 (7)	0.2068 (4)	0.8675 (5)	0.0719 (18)
H26	−0.5888	0.2123	0.9042	0.086*
C27	−0.5625 (7)	0.1861 (4)	0.7873 (5)	0.0825 (19)
H27	−0.6535	0.1789	0.7683	0.099*
C28	−0.4647 (7)	0.1759 (4)	0.7351 (5)	0.086 (2)
H28	−0.4876	0.1617	0.6803	0.103*
C29	−0.3281 (7)	0.1878 (4)	0.7675 (4)	0.0682 (16)
H29	−0.2612	0.1797	0.7330	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0354 (5)	0.0393 (5)	0.0350 (5)	−0.0006 (4)	0.0142 (4)	0.0001 (4)
Ni2	0.0364 (4)	0.0471 (4)	0.0422 (4)	0.0048 (3)	0.0081 (3)	0.0048 (3)
N1	0.026 (2)	0.0410 (19)	0.033 (2)	0.0001 (16)	0.0076 (17)	0.0064 (17)
N2	0.035 (2)	0.0358 (19)	0.032 (2)	0.0048 (17)	0.0112 (17)	0.0031 (16)
N3	0.039 (2)	0.047 (2)	0.046 (2)	−0.004 (2)	0.012 (2)	0.0028 (19)
N4	0.048 (3)	0.048 (2)	0.055 (3)	−0.002 (2)	0.008 (2)	0.005 (2)
N5	0.055 (3)	0.050 (2)	0.053 (3)	0.015 (2)	0.009 (2)	0.010 (2)
N6	0.036 (2)	0.058 (2)	0.058 (3)	0.001 (2)	0.009 (2)	−0.003 (2)
O1	0.040 (2)	0.0467 (18)	0.0337 (18)	−0.0003 (16)	0.0150 (16)	0.0000 (14)
O2	0.0369 (19)	0.0571 (19)	0.0390 (19)	0.0092 (16)	0.0071 (16)	0.0088 (15)
O3	0.101 (4)	0.057 (2)	0.066 (3)	0.011 (2)	0.052 (3)	0.003 (2)
O4	0.0376 (19)	0.0430 (17)	0.040 (2)	0.0016 (15)	0.0137 (16)	−0.0014 (15)
C1	0.025 (2)	0.043 (2)	0.035 (2)	−0.0048 (19)	0.008 (2)	−0.001 (2)
C2	0.036 (3)	0.050 (3)	0.036 (3)	−0.007 (2)	0.011 (2)	0.005 (2)
C3	0.032 (3)	0.053 (3)	0.040 (3)	−0.006 (2)	0.009 (2)	0.005 (2)
C4	0.043 (3)	0.058 (3)	0.041 (3)	0.000 (3)	0.006 (3)	0.009 (2)
C5	0.049 (3)	0.073 (3)	0.044 (3)	−0.007 (3)	0.016 (3)	0.011 (3)
C6	0.061 (4)	0.063 (3)	0.050 (3)	0.003 (3)	0.026 (3)	−0.004 (3)
C7	0.056 (3)	0.044 (3)	0.046 (3)	−0.010 (2)	0.018 (3)	0.001 (2)
C8	0.034 (3)	0.046 (3)	0.040 (3)	−0.004 (2)	0.009 (2)	0.000 (2)
C9	0.085 (5)	0.053 (3)	0.061 (4)	0.013 (3)	0.040 (4)	0.009 (3)
C10	0.065 (4)	0.075 (4)	0.110 (4)	−0.018 (3)	−0.025 (4)	0.030 (3)
C11	0.079 (5)	0.086 (5)	0.145 (6)	−0.032 (4)	−0.038 (5)	0.029 (4)
C12	0.053 (4)	0.085 (4)	0.120 (6)	−0.017 (4)	−0.014 (4)	0.018 (4)
C13	0.070 (5)	0.095 (5)	0.147 (7)	0.007 (4)	−0.027 (5)	0.022 (4)
C14	0.071 (4)	0.066 (4)	0.125 (5)	−0.008 (4)	−0.022 (4)	0.009 (4)
C15	0.050 (3)	0.060 (3)	0.057 (3)	−0.003 (3)	0.005 (3)	−0.001 (3)
C16	0.057 (4)	0.074 (4)	0.067 (4)	0.003 (3)	−0.001 (3)	−0.002 (3)
C17	0.055 (4)	0.071 (4)	0.093 (5)	−0.005 (3)	0.010 (4)	−0.010 (3)
C18	0.058 (4)	0.057 (3)	0.092 (5)	−0.007 (3)	0.016 (4)	0.011 (3)
C19	0.058 (3)	0.056 (3)	0.069 (4)	0.001 (3)	0.011 (3)	0.010 (3)
C20	0.075 (4)	0.066 (3)	0.060 (3)	0.013 (3)	0.018 (3)	0.005 (3)
C21	0.114 (5)	0.082 (4)	0.076 (5)	0.032 (4)	0.006 (4)	−0.004 (4)
C22	0.101 (5)	0.072 (4)	0.093 (5)	0.036 (4)	0.014 (4)	0.013 (4)
C23	0.096 (5)	0.090 (5)	0.074 (4)	0.032 (4)	−0.007 (4)	0.025 (4)
C24	0.080 (4)	0.066 (3)	0.068 (4)	0.006 (3)	0.003 (3)	0.002 (3)
C25	0.046 (3)	0.073 (3)	0.068 (4)	0.006 (3)	0.012 (3)	−0.007 (3)
C26	0.043 (3)	0.089 (4)	0.086 (5)	0.003 (3)	0.013 (3)	−0.007 (4)
C27	0.047 (4)	0.099 (5)	0.101 (5)	0.001 (4)	0.004 (4)	0.002 (4)
C28	0.055 (4)	0.122 (5)	0.078 (5)	−0.013 (4)	0.003 (4)	−0.002 (4)
C29	0.050 (3)	0.095 (4)	0.060 (3)	−0.007 (3)	0.006 (3)	−0.006 (3)

Geometric parameters (Å, º) top

Ni1—O1ⁱ	2.072 (3)	C9—H9A	0.9600
Ni1—O1	2.072 (3)	C9—H9B	0.9600
Ni1—N2	2.133 (4)	C9—H9C	0.9600
Ni1—N2ⁱ	2.133 (4)	C10—C11	1.408 (10)
Ni1—N3ⁱ	2.230 (4)	C10—H10	0.9300
Ni1—N3	2.230 (4)	C11—C12	1.323 (10)
Ni2—N1	2.007 (4)	C11—H11	0.9300
Ni2—O2	2.016 (3)	C12—C13	1.363 (10)
Ni2—O4	2.074 (3)	C12—H12	0.9300
Ni2—N5	2.152 (4)	C13—C14	1.407 (10)
Ni2—N4	2.196 (5)	C13—H13	0.9300
Ni2—N6	2.218 (5)	C14—H14	0.9300
N1—C1	1.326 (6)	C15—C16	1.379 (8)
N1—N2	1.453 (5)	C15—H15	0.9300
N2—C8	1.326 (6)	C16—C17	1.388 (8)
N3—C10	1.305 (7)	C16—H16	0.9300
N3—C14	1.335 (8)	C17—C18	1.380 (9)
N4—C15	1.351 (7)	C17—H17	0.9300
N4—C19	1.362 (7)	C18—C19	1.391 (9)
N5—C20	1.342 (7)	C18—H18	0.9300
N5—C24	1.343 (8)	C19—H19	0.9300
N6—C29	1.324 (7)	C20—C21	1.383 (9)
N6—C25	1.351 (6)	C20—H20	0.9300
O1—C1	1.336 (6)	C21—C22	1.382 (10)
O2—C3	1.331 (6)	C21—H21	0.9300
O3—C7	1.367 (6)	C22—C23	1.348 (10)
O3—H3	0.8200	C22—H22	0.9300
O4—C8	1.310 (6)	C23—C24	1.396 (9)
C1—C2	1.509 (6)	C23—H23	0.9300
C2—C7	1.442 (7)	C24—H24	0.9300
C2—C3	1.467 (7)	C25—C26	1.368 (9)
C3—C4	1.432 (7)	C25—H25	0.9300
C4—C5	1.399 (7)	C26—C27	1.369 (9)
C4—H4	0.9300	C26—H26	0.9300
C5—C6	1.387 (8)	C27—C28	1.375 (9)
C5—H5	0.9300	C27—H27	0.9300
C6—C7	1.401 (7)	C28—C29	1.414 (9)
C6—H6	0.9300	C28—H28	0.9300
C8—C9	1.523 (7)	C29—H29	0.9300

O1ⁱ—Ni1—O1	180.000 (1)	O3—C7—C2	120.9 (4)
O1ⁱ—Ni1—N2	102.49 (13)	C6—C7—C2	122.0 (5)
O1—Ni1—N2	77.51 (13)	O4—C8—N2	125.6 (4)
O1ⁱ—Ni1—N2ⁱ	77.51 (13)	O4—C8—C9	116.6 (4)
O1—Ni1—N2ⁱ	102.49 (13)	N2—C8—C9	117.8 (4)
N2—Ni1—N2ⁱ	180.000 (1)	C8—C9—H9A	109.5
O1ⁱ—Ni1—N3ⁱ	89.33 (14)	C8—C9—H9B	109.5
O1—Ni1—N3ⁱ	90.67 (14)	H9A—C9—H9B	109.5
N2—Ni1—N3ⁱ	89.97 (15)	C8—C9—H9C	109.5
N2ⁱ—Ni1—N3ⁱ	90.03 (16)	H9A—C9—H9C	109.5
O1ⁱ—Ni1—N3	90.67 (14)	H9B—C9—H9C	109.5
O1—Ni1—N3	89.33 (14)	N3—C10—C11	125.4 (7)
N2—Ni1—N3	90.03 (16)	N3—C10—H10	117.3
N2ⁱ—Ni1—N3	89.97 (15)	C11—C10—H10	117.3
N3ⁱ—Ni1—N3	180.0	C12—C11—C10	119.9 (7)
N1—Ni2—O2	90.71 (14)	C12—C11—H11	120.1
N1—Ni2—O4	79.35 (14)	C10—C11—H11	120.1
O2—Ni2—O4	170.05 (13)	C11—C12—C13	117.4 (7)
N1—Ni2—N5	173.36 (15)	C11—C12—H12	121.3
O2—Ni2—N5	95.04 (15)	C13—C12—H12	121.3
O4—Ni2—N5	94.86 (15)	C12—C13—C14	119.1 (8)
N1—Ni2—N4	96.18 (16)	C12—C13—H13	120.5
O2—Ni2—N4	90.50 (16)	C14—C13—H13	120.5
O4—Ni2—N4	90.97 (15)	N3—C14—C13	124.4 (7)
N5—Ni2—N4	87.10 (18)	N3—C14—H14	117.8
N1—Ni2—N6	91.67 (16)	C13—C14—H14	117.8
O2—Ni2—N6	90.48 (16)	N4—C15—C16	124.5 (6)
O4—Ni2—N6	89.41 (15)	N4—C15—H15	117.8
N5—Ni2—N6	84.98 (18)	C16—C15—H15	117.8
N4—Ni2—N6	172.08 (16)	C15—C16—C17	117.6 (7)
C1—N1—N2	113.7 (4)	C15—C16—H16	121.2
C1—N1—Ni2	131.4 (3)	C17—C16—H16	121.2
N2—N1—Ni2	114.3 (3)	C18—C17—C16	120.2 (7)
C8—N2—N1	110.1 (4)	C18—C17—H17	119.9
C8—N2—Ni1	137.8 (3)	C16—C17—H17	119.9
N1—N2—Ni1	112.1 (2)	C17—C18—C19	118.4 (6)
C10—N3—C14	113.6 (6)	C17—C18—H18	120.8
C10—N3—Ni1	124.0 (4)	C19—C18—H18	120.8
C14—N3—Ni1	122.3 (4)	N4—C19—C18	123.0 (6)
C15—N4—C19	116.4 (5)	N4—C19—H19	118.5
C15—N4—Ni2	123.5 (4)	C18—C19—H19	118.5
C19—N4—Ni2	120.0 (4)	N5—C20—C21	121.8 (6)
C20—N5—C24	116.8 (5)	N5—C20—H20	119.1
C20—N5—Ni2	121.3 (4)	C21—C20—H20	119.1
C24—N5—Ni2	121.5 (4)	C22—C21—C20	120.4 (7)
C29—N6—C25	116.4 (5)	C22—C21—H21	119.8
C29—N6—Ni2	121.1 (4)	C20—C21—H21	119.8
C25—N6—Ni2	121.9 (4)	C23—C22—C21	118.6 (7)
C1—O1—Ni1	114.3 (3)	C23—C22—H22	120.7
C3—O2—Ni2	125.8 (3)	C21—C22—H22	120.7
C7—O3—H3	109.5	C22—C23—C24	118.5 (7)
C8—O4—Ni2	109.9 (3)	C22—C23—H23	120.8
N1—C1—O1	122.3 (4)	C24—C23—H23	120.8
N1—C1—C2	119.5 (4)	N5—C24—C23	123.9 (6)
O1—C1—C2	118.1 (4)	N5—C24—H24	118.0
C7—C2—C3	117.1 (4)	C23—C24—H24	118.0
C7—C2—C1	118.9 (4)	N6—C25—C26	123.9 (6)
C3—C2—C1	123.9 (4)	N6—C25—H25	118.1
O2—C3—C4	116.3 (4)	C26—C25—H25	118.1
O2—C3—C2	125.2 (4)	C25—C26—C27	119.1 (7)
C4—C3—C2	118.5 (4)	C25—C26—H26	120.4
C5—C4—C3	121.3 (5)	C27—C26—H26	120.4
C5—C4—H4	119.3	C26—C27—C28	119.2 (7)
C3—C4—H4	119.3	C26—C27—H27	120.4
C6—C5—C4	120.8 (5)	C28—C27—H27	120.4
C6—C5—H5	119.6	C27—C28—C29	117.8 (7)
C4—C5—H5	119.6	C27—C28—H28	121.1
C5—C6—C7	120.1 (5)	C29—C28—H28	121.1
C5—C6—H6	119.9	N6—C29—C28	123.5 (6)
C7—C6—H6	119.9	N6—C29—H29	118.2
O3—C7—C6	117.1 (5)	C28—C29—H29	118.2

O2—Ni2—N1—C1	−1.3 (4)	N4—Ni2—O2—C3	80.9 (4)
O4—Ni2—N1—C1	178.3 (4)	N6—Ni2—O2—C3	−106.9 (4)
N5—Ni2—N1—C1	148.8 (14)	N1—Ni2—O4—C8	−6.2 (3)
N4—Ni2—N1—C1	−91.9 (4)	O2—Ni2—O4—C8	−3.8 (10)
N6—Ni2—N1—C1	89.2 (4)	N5—Ni2—O4—C8	170.5 (3)
O2—Ni2—N1—N2	−172.0 (3)	N4—Ni2—O4—C8	−102.3 (3)
O4—Ni2—N1—N2	7.6 (3)	N6—Ni2—O4—C8	85.6 (3)
N5—Ni2—N1—N2	−21.9 (17)	N2—N1—C1—O1	0.9 (6)
N4—Ni2—N1—N2	97.4 (3)	Ni2—N1—C1—O1	−169.9 (3)
N6—Ni2—N1—N2	−81.5 (3)	N2—N1—C1—C2	−175.6 (4)
C1—N1—N2—C8	180.0 (4)	Ni2—N1—C1—C2	13.7 (7)
Ni2—N1—N2—C8	−7.7 (5)	Ni1—O1—C1—N1	−2.7 (6)
C1—N1—N2—Ni1	1.3 (5)	Ni1—O1—C1—C2	173.8 (3)
Ni2—N1—N2—Ni1	173.68 (17)	N1—C1—C2—C7	164.7 (5)
O1ⁱ—Ni1—N2—C8	−0.1 (5)	O1—C1—C2—C7	−11.9 (7)
O1—Ni1—N2—C8	179.9 (5)	N1—C1—C2—C3	−13.2 (7)
N2ⁱ—Ni1—N2—C8	−18 (100)	O1—C1—C2—C3	170.2 (4)
N3ⁱ—Ni1—N2—C8	89.2 (5)	Ni2—O2—C3—C4	−159.8 (4)
N3—Ni1—N2—C8	−90.8 (5)	Ni2—O2—C3—C2	19.3 (7)
O1ⁱ—Ni1—N2—N1	178.0 (3)	C7—C2—C3—O2	178.3 (5)
O1—Ni1—N2—N1	−2.0 (3)	C1—C2—C3—O2	−3.8 (8)
N2ⁱ—Ni1—N2—N1	160 (100)	C7—C2—C3—C4	−2.6 (7)
N3ⁱ—Ni1—N2—N1	−92.7 (3)	C1—C2—C3—C4	175.3 (5)
N3—Ni1—N2—N1	87.3 (3)	O2—C3—C4—C5	−177.3 (5)
O1ⁱ—Ni1—N3—C10	−118.7 (5)	C2—C3—C4—C5	3.5 (8)
O1—Ni1—N3—C10	61.3 (5)	C3—C4—C5—C6	−2.2 (9)
N2—Ni1—N3—C10	−16.2 (5)	C4—C5—C6—C7	−0.1 (9)
N2ⁱ—Ni1—N3—C10	163.8 (5)	C5—C6—C7—O3	−176.4 (6)
N3ⁱ—Ni1—N3—C10	148 (100)	C5—C6—C7—C2	0.9 (9)
O1ⁱ—Ni1—N3—C14	57.0 (5)	C3—C2—C7—O3	177.7 (5)
O1—Ni1—N3—C14	−123.0 (5)	C1—C2—C7—O3	−0.4 (8)
N2—Ni1—N3—C14	159.5 (5)	C3—C2—C7—C6	0.5 (8)
N2ⁱ—Ni1—N3—C14	−20.5 (5)	C1—C2—C7—C6	−177.6 (5)
N3ⁱ—Ni1—N3—C14	−36 (100)	Ni2—O4—C8—N2	4.1 (6)
N1—Ni2—N4—C15	−63.4 (4)	Ni2—O4—C8—C9	−176.2 (4)
O2—Ni2—N4—C15	−154.1 (4)	N1—N2—C8—O4	2.2 (7)
O4—Ni2—N4—C15	16.0 (4)	Ni1—N2—C8—O4	−179.7 (4)
N5—Ni2—N4—C15	110.8 (4)	N1—N2—C8—C9	−177.5 (4)
N6—Ni2—N4—C15	108.7 (12)	Ni1—N2—C8—C9	0.6 (8)
N1—Ni2—N4—C19	120.4 (4)	C14—N3—C10—C11	−2.3 (11)
O2—Ni2—N4—C19	29.6 (4)	Ni1—N3—C10—C11	173.7 (7)
O4—Ni2—N4—C19	−160.2 (4)	N3—C10—C11—C12	5.3 (15)
N5—Ni2—N4—C19	−65.4 (4)	C10—C11—C12—C13	−4.6 (14)
N6—Ni2—N4—C19	−67.5 (14)	C11—C12—C13—C14	1.7 (14)
N1—Ni2—N5—C20	60.4 (17)	C10—N3—C14—C13	−0.8 (11)
O2—Ni2—N5—C20	−149.7 (5)	Ni1—N3—C14—C13	−176.9 (7)
O4—Ni2—N5—C20	31.3 (5)	C12—C13—C14—N3	1.1 (14)
N4—Ni2—N5—C20	−59.4 (5)	C19—N4—C15—C16	−1.4 (8)
N6—Ni2—N5—C20	120.3 (5)	Ni2—N4—C15—C16	−177.7 (4)
N1—Ni2—N5—C24	−111.6 (15)	N4—C15—C16—C17	2.3 (9)
O2—Ni2—N5—C24	38.3 (5)	C15—C16—C17—C18	−1.8 (9)
O4—Ni2—N5—C24	−140.7 (5)	C16—C17—C18—C19	0.6 (10)
N4—Ni2—N5—C24	128.6 (5)	C15—N4—C19—C18	0.0 (8)
N6—Ni2—N5—C24	−51.7 (5)	Ni2—N4—C19—C18	176.5 (4)
N1—Ni2—N6—C29	−84.5 (5)	C17—C18—C19—N4	0.4 (9)
O2—Ni2—N6—C29	6.3 (5)	C24—N5—C20—C21	0.2 (10)
O4—Ni2—N6—C29	−163.8 (5)	Ni2—N5—C20—C21	−172.2 (5)
N5—Ni2—N6—C29	101.3 (5)	N5—C20—C21—C22	1.4 (12)
N4—Ni2—N6—C29	103.4 (12)	C20—C21—C22—C23	−1.2 (13)
N1—Ni2—N6—C25	105.2 (4)	C21—C22—C23—C24	−0.4 (13)
O2—Ni2—N6—C25	−164.1 (4)	C20—N5—C24—C23	−1.9 (10)
O4—Ni2—N6—C25	25.8 (4)	Ni2—N5—C24—C23	170.5 (5)
N5—Ni2—N6—C25	−69.1 (4)	C22—C23—C24—N5	2.0 (12)
N4—Ni2—N6—C25	−67.0 (14)	C29—N6—C25—C26	0.6 (9)
O1ⁱ—Ni1—O1—C1	−157 (100)	Ni2—N6—C25—C26	171.4 (5)
N2—Ni1—O1—C1	2.4 (3)	N6—C25—C26—C27	−2.6 (11)
N2ⁱ—Ni1—O1—C1	−177.6 (3)	C25—C26—C27—C28	2.3 (11)
N3ⁱ—Ni1—O1—C1	92.3 (3)	C26—C27—C28—C29	−0.2 (12)
N3—Ni1—O1—C1	−87.7 (3)	C25—N6—C29—C28	1.6 (10)
N1—Ni2—O2—C3	−15.3 (4)	Ni2—N6—C29—C28	−169.3 (6)
O4—Ni2—O2—C3	−17.6 (10)	C27—C28—C29—N6	−1.8 (12)
N5—Ni2—O2—C3	168.1 (4)

Symmetry code: (i) −x, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C27—H27···Cgⁱⁱ	0.93	2.52	3.428 (4)	166

Symmetry code: (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	[Ni₃(C₉H₇N₂O₄)₂(C₅H₅N)₈]
M_r	1223.26
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	9.9349 (18), 18.230 (3), 16.262 (2)
β (°)	96.663 (2)
V (Å³)	2925.3 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.02
Crystal size (mm)	0.53 × 0.45 × 0.44

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.614, 0.663
No. of measured, independent and observed [I > 2σ(I)] reflections	14103, 5138, 3047
R_int	0.146
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.075, 0.210, 0.97
No. of reflections	5138
No. of parameters	368
No. of restraints	1098
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.32, −0.58

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), 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
C27—H27···Cgⁱ	0.93	2.52	3.428 (4)	165.97

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

Acknowledgements

We acknowledge financial support from the National Natural Science Foundation of China (grant No. 20671048).

References

John, R. P., Lee, K. J. & Lah, M. S. (2004). Chem. Commun. pp. 2660–2661. Web of Science CSD CrossRef Google Scholar
Lin, S., Liu, S. X. & Lin, B. Z. (2002). Inorg. Chim. Acta, 328, 69–73. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar

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