Bis(2,2′-bipyridine)bis­{μ3-cis-N-(2-carboxyl­atophen­yl)-N′-[3-(dimethyl­amino)prop­yl]oxamidato(3−)}­bis(per­chlorato)­tetra­nickel(II) methanol disolvate

Tian, C.; Gao, Z.

doi:10.1107/S160053680905017X

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page m1691

doi:10.1107/S160053680905017X

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Bis(2,2′-bipyridine)bis{μ₃-cis-N-(2-carboxylatophenyl)-N′-[3-(dimethylamino)propyl]oxamidato(3−)}bis(perchlorato)tetranickel(II) methanol disolvate

Chunliang Tian ^a and Zhongjun Gao ^a ^*

^aDeapartment of Chemistry, Jining University, Shandong 273155, People's Republic of China
^*Correspondence e-mail: zhongjungao@yahoo.cn

(Received 9 November 2009; accepted 22 November 2009; online 28 November 2009)

In the title methanol disolvate complex, [Ni₄(C₁₄H₁₆N₃O₄)₂(ClO₄)₂(C₁₀H₈N₂)₂]·2CH₃OH, the neutral tetranickel(II) system lies on a centre of inversion. The polyhedron around each Ni(II) atom is a square pyramid. The separations of the Ni atoms bridged by the oxamide and carboxyl groups are 5.227 (9) and 5.268 (6) Å, respectively. In the crystal structure, a two-dimensional supramolecular network structure involving O—H⋯O and C—H⋯O hydrogen bonding is observed.

Related literature

For a related structure, see: Tao et al. (2003 ).

Experimental

Crystal data

[Ni₄(C₁₄H₁₆N₃O₄)₂(ClO₄)₂(C₁₀H₈N₂)₂]
M_r = 1390.79
Triclinic, $[P \overline 1]$
a = 10.854 (4) Å
b = 11.309 (4) Å
c = 12.728 (5) Å
α = 67.724 (4)°
β = 73.357 (4)°
γ = 75.411 (4)°
V = 1367.0 (9) Å³
Z = 1
Mo Kα radiation
μ = 1.54 mm⁻¹
T = 298 K
0.21 × 0.16 × 0.14 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.738, T_max = 0.814
7296 measured reflections
4850 independent reflections
3963 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.087
S = 1.04
4850 reflections
383 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9⋯O1ⁱ	0.82	2.73	3.190 (4)	118
O9—H9⋯O2ⁱ	0.82	2.06	2.870 (4)	170
C4—H4⋯O9ⁱⁱ	0.93	2.52	3.387 (5)	155
C13—H13C⋯O9ⁱⁱⁱ	0.96	2.58	3.451 (5)	151
C3—H3⋯O2	0.93	2.41	2.744 (4)	101
C6—H6⋯O3	0.93	2.22	2.812 (3)	121
C10—H10B⋯O4	0.97	2.43	2.775 (4)	100
C13—H13A⋯O1	0.96	2.39	2.899 (4)	113
C13—H13B⋯O5	0.96	2.47	3.186 (4)	131
C14—H14C⋯O1	0.96	2.58	3.074 (5)	112
C24—H24⋯O4	0.93	2.59	3.065 (4)	112
Symmetry codes: (i) x, y+1, z; (ii) -x+2, -y, -z+1; (iii) -x+2, -y, -z+2.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); 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: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680905017X/pv2236sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680905017X/pv2236Isup2.hkl

checkCIF report

Comment top

The title compound (Fig. 1), is a tetranuclear nickel(II) complex. Its asymmetric unit is composed of a cis-oxamido bridged dinuclear nickel complex and a molecule of methanol solvate. Through carboxyl bridges, two dinuclear units are assembled to form a circular tetranuclear system lying about an inversion center. The cis-oxamido group coordinates to Ni1 and Ni2 in a usual mode with the bite angles of 83.53 (6) and 85.14 (11) °, respectively. Both Ni1 and Ni2 atoms are in square-pyramidal coordination geometries. The maximum displacement from the least-square plane defined by N1, N2, N3 and O1, is 0.0400 (11) Å for N1 and the Ni1 atom lies 0.1168 (12) Å out of this plane. The apical position of Ni1 is occupied by O5 with the Ni1—O5 bond length of 2.636 (8) Å. Ni2 atom coordinates to the exo-cis oxygen atoms of oxamido ligand (O3 and O4). The two oxygen atoms and the nitrogen atoms (N4 and N5) of bipyridine ligand complete the basal plane, from which the maximum deviations is 0.1311 (6) Å. The apical site is occupied by a carboxyl oxygen atom (O2ⁱ) with Ni2—O2ⁱ length of 2.276 (2) Å. The Ni—N bond lenghts in (I) (Table 1), lie in the range 1.945 (2)-2.067 (2)Å and are close to the corresponding bond lenghts reported in a nickel complex (Tao et al., 2003).

In the crystal, neutral tetranuclear complexes and methanol molecules are connected by classcial O—H···O and non-classical C—H···O hydrogen bonds into a two-dimensional network (Table 1).

Related literature top

For a related structure, see: Tao et al. (2003).

Experimental top

A methanol solution (5 ml) of Ni(ClO₄)₂^.6H₂O (0.732 g, 2 mmol) was added slowly into a methanol solution (5 ml) containing N-benzyl-N'-(3-amino-3-dimethylpropyl)oxamide (1 mmol, 0.293 g) and sodium ethoxide (0.204 g, 3 mmol). The mixture was stirred quickly for 1 h, then an aqueous solution (5 ml) of 2,2'-bipyridine (0.156 g, 1 mmol) was added dropwise into the mixture. The reaction solution was heated at 343 K with stirring for 8h. The resulting solution was filtered and the filtrate was kept at room temperature. Green crystals suitable for X-ray analysis were obtained from the filtrate by slow evaporation for about one week.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of (I) with 30% displacement ellipsoids (H atoms omitted for clarity).

Bis(2,2'-bipyridine)bis{µ₃-cis-N-(2-carboxylatophenyl)- N'-[3-(dimethylamino)propyl]oxamidato(3-)}bis(perchlorato)tetranickel(II) methanol disolvate top

Crystal data top

[Ni₄(C₁₄H₁₆N₃O₄)₂(ClO₄)₂(C₁₀H₈N₂)₂]	Z = 1
M_r = 1390.79	F(000) = 716
Triclinic, P1	D_x = 1.689 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.854 (4) Å	Cell parameters from 3928 reflections
b = 11.309 (4) Å	θ = 2.2–28.1°
c = 12.728 (5) Å	µ = 1.54 mm⁻¹
α = 67.724 (4)°	T = 298 K
β = 73.357 (4)°	Block, green
γ = 75.411 (4)°	0.21 × 0.16 × 0.14 mm
V = 1367.0 (9) Å³

Data collection top

Bruker SMART CCD diffractometer	4850 independent reflections
Radiation source: fine-focus sealed tube	3963 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ϕ and ω scans	θ_max = 25.2°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→13
T_min = 0.738, T_max = 0.814	k = −13→9
7296 measured reflections	l = −15→12

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0445P)² + 0.6427P] where P = (F_o² + 2F_c²)/3
4850 reflections	(Δ/σ)_max = 0.001
383 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

[Ni₄(C₁₄H₁₆N₃O₄)₂(ClO₄)₂(C₁₀H₈N₂)₂]	γ = 75.411 (4)°
M_r = 1390.79	V = 1367.0 (9) Å³
Triclinic, P1	Z = 1
a = 10.854 (4) Å	Mo Kα radiation
b = 11.309 (4) Å	µ = 1.54 mm⁻¹
c = 12.728 (5) Å	T = 298 K
α = 67.724 (4)°	0.21 × 0.16 × 0.14 mm
β = 73.357 (4)°

Data collection top

Bruker SMART CCD diffractometer	4850 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3963 reflections with I > 2σ(I)
T_min = 0.738, T_max = 0.814	R_int = 0.015
7296 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.04	Δρ_max = 0.33 e Å⁻³
4850 reflections	Δρ_min = −0.56 e Å⁻³
383 parameters

Special details top

Experimental. Yield, 61%, analysis, calculated for C₅₀H₅₆Cl₂N₁₀O₁₈Ni₄: C 43.18, H, 4.06; N 10.07%; found: C 43.22, H 4.15, N, 10.09%.

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 > 2sigma(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	0.84712 (3)	−0.11565 (3)	0.73827 (3)	0.03336 (11)
Ni2	0.72954 (3)	0.35869 (3)	0.46787 (3)	0.03195 (11)
O1	0.9263 (2)	−0.2738 (2)	0.70987 (18)	0.0586 (6)
O2	1.06150 (19)	−0.39494 (18)	0.61253 (18)	0.0456 (5)
O3	0.7747 (2)	0.18517 (17)	0.45514 (16)	0.0400 (5)
O4	0.73515 (19)	0.26666 (17)	0.63062 (16)	0.0380 (4)
N1	0.8309 (2)	−0.0280 (2)	0.57245 (18)	0.0318 (5)
N2	0.7889 (2)	0.0574 (2)	0.74936 (19)	0.0388 (5)
N3	0.8932 (2)	−0.2005 (2)	0.9003 (2)	0.0437 (6)
N4	0.6571 (2)	0.4495 (2)	0.32480 (19)	0.0367 (5)
N5	0.6681 (2)	0.5300 (2)	0.4873 (2)	0.0363 (5)
C1	0.9762 (3)	−0.2980 (3)	0.6150 (3)	0.0384 (6)
C2	0.9259 (3)	−0.2161 (3)	0.5073 (2)	0.0338 (6)
C3	0.9484 (3)	−0.2750 (3)	0.4233 (3)	0.0420 (7)
H3	0.9979	−0.3573	0.4349	0.050*
C4	0.8995 (3)	−0.2150 (3)	0.3240 (3)	0.0480 (7)
H4	0.9160	−0.2555	0.2689	0.058*
C5	0.8253 (3)	−0.0928 (3)	0.3077 (3)	0.0458 (7)
H5	0.7905	−0.0514	0.2416	0.055*
C6	0.8026 (3)	−0.0321 (3)	0.3886 (2)	0.0407 (7)
H6	0.7522	0.0498	0.3761	0.049*
C7	0.8531 (3)	−0.0904 (2)	0.4887 (2)	0.0324 (6)
C8	0.7944 (2)	0.0971 (2)	0.5502 (2)	0.0309 (6)
C9	0.7718 (3)	0.1443 (2)	0.6517 (2)	0.0330 (6)
C10	0.7595 (4)	0.0988 (3)	0.8514 (3)	0.0522 (8)
H10A	0.6682	0.0971	0.8886	0.063*
H10B	0.7746	0.1873	0.8263	0.063*
C11	0.8409 (4)	0.0144 (3)	0.9376 (3)	0.0613 (10)
H11A	0.8175	0.0462	1.0028	0.074*
H11B	0.9316	0.0221	0.9016	0.074*
C12	0.8276 (4)	−0.1261 (3)	0.9829 (3)	0.0593 (9)
H12A	0.7355	−0.1321	1.0053	0.071*
H12B	0.8628	−0.1677	1.0525	0.071*
C13	0.8543 (4)	−0.3307 (3)	0.9596 (3)	0.0563 (9)
H13A	0.9003	−0.3859	0.9142	0.084*
H13B	0.7622	−0.3233	0.9678	0.084*
H13C	0.8754	−0.3673	1.0350	0.084*
C14	1.0355 (3)	−0.2162 (4)	0.8801 (3)	0.0675 (10)
H14A	1.0617	−0.2516	0.9533	0.101*
H14B	1.0630	−0.1335	0.8377	0.101*
H14C	1.0750	−0.2738	0.8359	0.101*
C15	0.6502 (3)	0.3972 (3)	0.2487 (2)	0.0437 (7)
H15	0.6840	0.3101	0.2603	0.052*
C16	0.5948 (3)	0.4677 (3)	0.1537 (3)	0.0520 (8)
H16	0.5908	0.4289	0.1023	0.062*
C17	0.5453 (3)	0.5971 (3)	0.1365 (3)	0.0534 (8)
H17	0.5081	0.6469	0.0728	0.064*
C18	0.5513 (3)	0.6523 (3)	0.2147 (3)	0.0462 (7)
H18	0.5187	0.7393	0.2042	0.055*
C19	0.6065 (3)	0.5760 (3)	0.3084 (2)	0.0356 (6)
C20	0.6125 (3)	0.6218 (3)	0.4019 (2)	0.0351 (6)
C21	0.5636 (3)	0.7460 (3)	0.4056 (3)	0.0445 (7)
H21	0.5251	0.8083	0.3467	0.053*
C22	0.5732 (3)	0.7761 (3)	0.4990 (3)	0.0488 (8)
H22	0.5405	0.8588	0.5033	0.059*
C23	0.6312 (3)	0.6828 (3)	0.5847 (3)	0.0455 (7)
H23	0.6387	0.7015	0.6476	0.055*
C24	0.6781 (3)	0.5609 (3)	0.5758 (3)	0.0426 (7)
H24	0.7182	0.4980	0.6334	0.051*
Cl1	0.49509 (8)	−0.11510 (8)	0.81502 (7)	0.0508 (2)
O5	0.6183 (3)	−0.1925 (3)	0.8306 (3)	0.0928 (10)
O6	0.4947 (4)	−0.0733 (3)	0.6956 (3)	0.1125 (13)
O7	0.4736 (3)	−0.0026 (3)	0.8472 (3)	0.0911 (9)
O8	0.3950 (3)	−0.1885 (3)	0.8805 (4)	0.1155 (13)
O9	0.9657 (4)	0.4193 (3)	0.8309 (3)	0.1074 (12)
H9	0.9999	0.4646	0.7666	0.129*
C25	0.8308 (6)	0.4297 (5)	0.8360 (5)	0.123 (2)
H25A	0.7916	0.3737	0.9099	0.185*
H25B	0.8209	0.4049	0.7750	0.185*
H25C	0.7889	0.5176	0.8267	0.185*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0426 (2)	0.02493 (19)	0.02760 (19)	0.00177 (15)	−0.00980 (15)	−0.00623 (14)
Ni2	0.0383 (2)	0.02207 (18)	0.03246 (19)	0.00241 (14)	−0.01060 (15)	−0.00812 (14)
O1	0.0859 (17)	0.0354 (11)	0.0383 (12)	0.0159 (11)	−0.0141 (11)	−0.0103 (10)
O2	0.0396 (11)	0.0332 (11)	0.0550 (13)	0.0053 (9)	−0.0080 (9)	−0.0134 (9)
O3	0.0553 (13)	0.0289 (10)	0.0339 (10)	−0.0008 (9)	−0.0151 (9)	−0.0080 (8)
O4	0.0462 (12)	0.0275 (10)	0.0374 (10)	0.0018 (8)	−0.0103 (9)	−0.0114 (8)
N1	0.0363 (12)	0.0278 (11)	0.0302 (11)	−0.0024 (10)	−0.0077 (9)	−0.0098 (9)
N2	0.0522 (15)	0.0323 (12)	0.0298 (12)	−0.0015 (11)	−0.0115 (11)	−0.0094 (10)
N3	0.0489 (15)	0.0396 (14)	0.0371 (13)	−0.0032 (11)	−0.0124 (11)	−0.0068 (11)
N4	0.0383 (13)	0.0326 (12)	0.0367 (12)	−0.0034 (10)	−0.0083 (10)	−0.0101 (10)
N5	0.0352 (13)	0.0308 (12)	0.0393 (13)	−0.0027 (10)	−0.0064 (10)	−0.0105 (10)
C1	0.0363 (16)	0.0316 (15)	0.0440 (17)	−0.0056 (13)	−0.0044 (13)	−0.0120 (13)
C2	0.0291 (14)	0.0335 (14)	0.0389 (15)	−0.0065 (11)	−0.0028 (11)	−0.0144 (12)
C3	0.0401 (16)	0.0387 (16)	0.0489 (18)	−0.0033 (13)	−0.0038 (13)	−0.0225 (14)
C4	0.0510 (19)	0.0539 (19)	0.0478 (18)	−0.0093 (15)	−0.0067 (15)	−0.0286 (15)
C5	0.0536 (19)	0.0483 (18)	0.0398 (16)	−0.0132 (15)	−0.0133 (14)	−0.0136 (14)
C6	0.0465 (17)	0.0340 (15)	0.0421 (16)	−0.0040 (13)	−0.0137 (13)	−0.0116 (13)
C7	0.0313 (14)	0.0316 (14)	0.0332 (14)	−0.0073 (11)	−0.0028 (11)	−0.0111 (11)
C8	0.0307 (14)	0.0284 (13)	0.0306 (14)	−0.0015 (11)	−0.0075 (11)	−0.0079 (11)
C9	0.0320 (14)	0.0290 (14)	0.0363 (15)	−0.0030 (11)	−0.0072 (11)	−0.0103 (12)
C10	0.078 (2)	0.0426 (17)	0.0389 (17)	0.0012 (16)	−0.0177 (16)	−0.0195 (14)
C11	0.087 (3)	0.058 (2)	0.0435 (19)	0.0010 (19)	−0.0245 (18)	−0.0219 (16)
C12	0.081 (3)	0.055 (2)	0.0368 (17)	−0.0009 (18)	−0.0176 (17)	−0.0119 (15)
C13	0.068 (2)	0.0456 (19)	0.0420 (18)	−0.0086 (17)	−0.0132 (16)	0.0011 (14)
C14	0.049 (2)	0.077 (3)	0.066 (2)	−0.0087 (19)	−0.0188 (18)	−0.008 (2)
C15	0.0498 (18)	0.0396 (16)	0.0407 (16)	−0.0056 (14)	−0.0082 (14)	−0.0143 (13)
C16	0.062 (2)	0.055 (2)	0.0385 (17)	−0.0106 (17)	−0.0110 (15)	−0.0139 (15)
C17	0.054 (2)	0.059 (2)	0.0398 (17)	−0.0039 (16)	−0.0160 (15)	−0.0065 (15)
C18	0.0439 (18)	0.0388 (16)	0.0423 (17)	0.0022 (13)	−0.0104 (14)	−0.0034 (13)
C19	0.0296 (14)	0.0309 (14)	0.0390 (15)	−0.0020 (11)	−0.0046 (12)	−0.0073 (12)
C20	0.0302 (14)	0.0286 (14)	0.0414 (15)	−0.0033 (11)	−0.0060 (12)	−0.0079 (12)
C21	0.0414 (17)	0.0295 (15)	0.0558 (19)	−0.0017 (13)	−0.0088 (14)	−0.0105 (14)
C22	0.0462 (18)	0.0321 (16)	0.065 (2)	−0.0060 (14)	−0.0026 (15)	−0.0196 (15)
C23	0.0443 (17)	0.0427 (17)	0.0530 (19)	−0.0094 (14)	−0.0046 (14)	−0.0223 (15)
C24	0.0446 (17)	0.0414 (16)	0.0444 (17)	−0.0040 (13)	−0.0116 (14)	−0.0175 (14)
Cl1	0.0531 (5)	0.0441 (4)	0.0561 (5)	−0.0004 (4)	−0.0177 (4)	−0.0178 (4)
O5	0.0651 (18)	0.0728 (19)	0.117 (2)	0.0084 (15)	−0.0425 (17)	−0.0015 (17)
O6	0.156 (3)	0.104 (2)	0.074 (2)	0.046 (2)	−0.059 (2)	−0.0422 (19)
O7	0.122 (3)	0.0686 (18)	0.098 (2)	−0.0174 (17)	−0.0168 (19)	−0.0475 (17)
O8	0.081 (2)	0.076 (2)	0.181 (4)	−0.0366 (18)	0.016 (2)	−0.050 (2)
O9	0.180 (4)	0.0602 (19)	0.067 (2)	0.002 (2)	−0.036 (2)	−0.0106 (15)
C25	0.185 (6)	0.079 (3)	0.143 (5)	−0.048 (4)	−0.117 (5)	0.000 (3)

Geometric parameters (Å, º) top

Ni1—O1	1.899 (2)	C10—H10B	0.9700
Ni1—N2	1.945 (2)	C11—C12	1.500 (5)
Ni1—N1	2.002 (2)	C11—H11A	0.9700
Ni1—N3	2.067 (2)	C11—H11B	0.9700
Ni2—O4	1.9452 (19)	C12—H12A	0.9700
Ni2—O3	1.957 (2)	C12—H12B	0.9700
Ni2—N5	1.969 (2)	C13—H13A	0.9600
Ni2—N4	1.996 (2)	C13—H13B	0.9600
Ni2—O2ⁱ	2.276 (2)	C13—H13C	0.9600
O1—C1	1.276 (3)	C14—H14A	0.9600
O2—C1	1.248 (3)	C14—H14B	0.9600
O2—Ni2ⁱ	2.276 (2)	C14—H14C	0.9600
O3—C8	1.276 (3)	C15—C16	1.380 (4)
O4—C9	1.284 (3)	C15—H15	0.9300
N1—C8	1.310 (3)	C16—C17	1.381 (5)
N1—C7	1.426 (3)	C16—H16	0.9300
N2—C9	1.288 (3)	C17—C18	1.384 (4)
N2—C10	1.469 (4)	C17—H17	0.9300
N3—C14	1.468 (4)	C18—C19	1.376 (4)
N3—C13	1.484 (4)	C18—H18	0.9300
N3—C12	1.504 (4)	C19—C20	1.488 (4)
N4—C15	1.338 (4)	C20—C21	1.385 (4)
N4—C19	1.355 (3)	C21—C22	1.390 (4)
N5—C24	1.339 (4)	C21—H21	0.9300
N5—C20	1.351 (3)	C22—C23	1.373 (4)
C1—C2	1.498 (4)	C22—H22	0.9300
C2—C3	1.400 (4)	C23—C24	1.380 (4)
C2—C7	1.409 (4)	C23—H23	0.9300
C3—C4	1.375 (4)	C24—H24	0.9300
C3—H3	0.9300	Cl1—O8	1.405 (3)
C4—C5	1.386 (4)	Cl1—O6	1.411 (3)
C4—H4	0.9300	Cl1—O5	1.422 (3)
C5—C6	1.376 (4)	Cl1—O7	1.426 (3)
C5—H5	0.9300	O9—C25	1.424 (6)
C6—C7	1.393 (4)	O9—H9	0.8200
C6—H6	0.9300	C25—H25A	0.9600
C8—C9	1.513 (4)	C25—H25B	0.9600
C10—C11	1.494 (4)	C25—H25C	0.9600
C10—H10A	0.9700

O1—Ni1—N2	171.10 (10)	C11—C10—H10B	109.2
O1—Ni1—N1	91.11 (9)	H10A—C10—H10B	107.9
N2—Ni1—N1	84.53 (9)	C10—C11—C12	114.6 (3)
O1—Ni1—N3	87.70 (10)	C10—C11—H11A	108.6
N2—Ni1—N3	95.41 (10)	C12—C11—H11A	108.6
N1—Ni1—N3	171.13 (10)	C10—C11—H11B	108.6
O4—Ni2—O3	84.13 (8)	C12—C11—H11B	108.6
O4—Ni2—N5	94.63 (9)	H11A—C11—H11B	107.6
O3—Ni2—N5	174.87 (9)	C11—C12—N3	115.9 (3)
O4—Ni2—N4	159.66 (9)	C11—C12—H12A	108.3
O3—Ni2—N4	97.63 (9)	N3—C12—H12A	108.3
N5—Ni2—N4	81.80 (9)	C11—C12—H12B	108.3
O4—Ni2—O2ⁱ	102.30 (8)	N3—C12—H12B	108.3
O3—Ni2—O2ⁱ	91.41 (8)	H12A—C12—H12B	107.4
N5—Ni2—O2ⁱ	93.72 (8)	N3—C13—H13A	109.5
N4—Ni2—O2ⁱ	97.92 (9)	N3—C13—H13B	109.5
C1—O1—Ni1	131.07 (19)	H13A—C13—H13B	109.5
C1—O2—Ni2ⁱ	116.82 (18)	N3—C13—H13C	109.5
C8—O3—Ni2	112.51 (16)	H13A—C13—H13C	109.5
C9—O4—Ni2	112.20 (17)	H13B—C13—H13C	109.5
C8—N1—C7	123.5 (2)	N3—C14—H14A	109.5
C8—N1—Ni1	110.62 (17)	N3—C14—H14B	109.5
C7—N1—Ni1	125.87 (17)	H14A—C14—H14B	109.5
C9—N2—C10	118.0 (2)	N3—C14—H14C	109.5
C9—N2—Ni1	112.66 (18)	H14A—C14—H14C	109.5
C10—N2—Ni1	129.33 (18)	H14B—C14—H14C	109.5
C14—N3—C13	108.2 (3)	N4—C15—C16	122.5 (3)
C14—N3—C12	111.1 (3)	N4—C15—H15	118.8
C13—N3—C12	105.6 (3)	C16—C15—H15	118.8
C14—N3—Ni1	106.2 (2)	C17—C16—C15	118.5 (3)
C13—N3—Ni1	111.19 (19)	C17—C16—H16	120.7
C12—N3—Ni1	114.47 (19)	C15—C16—H16	120.7
C15—N4—C19	118.7 (2)	C16—C17—C18	119.6 (3)
C15—N4—Ni2	126.8 (2)	C16—C17—H17	120.2
C19—N4—Ni2	114.46 (19)	C18—C17—H17	120.2
C24—N5—C20	119.1 (2)	C19—C18—C17	118.9 (3)
C24—N5—Ni2	125.47 (19)	C19—C18—H18	120.6
C20—N5—Ni2	115.39 (19)	C17—C18—H18	120.6
O2—C1—O1	120.4 (3)	N4—C19—C18	121.8 (3)
O2—C1—C2	119.2 (3)	N4—C19—C20	114.1 (2)
O1—C1—C2	120.3 (2)	C18—C19—C20	124.1 (3)
C3—C2—C7	119.0 (3)	N5—C20—C21	121.3 (3)
C3—C2—C1	115.6 (2)	N5—C20—C19	114.3 (2)
C7—C2—C1	125.3 (2)	C21—C20—C19	124.4 (3)
C4—C3—C2	121.9 (3)	C20—C21—C22	118.9 (3)
C4—C3—H3	119.0	C20—C21—H21	120.6
C2—C3—H3	119.0	C22—C21—H21	120.6
C3—C4—C5	118.7 (3)	C23—C22—C21	119.6 (3)
C3—C4—H4	120.7	C23—C22—H22	120.2
C5—C4—H4	120.7	C21—C22—H22	120.2
C6—C5—C4	120.6 (3)	C22—C23—C24	118.7 (3)
C6—C5—H5	119.7	C22—C23—H23	120.7
C4—C5—H5	119.7	C24—C23—H23	120.7
C5—C6—C7	121.6 (3)	N5—C24—C23	122.4 (3)
C5—C6—H6	119.2	N5—C24—H24	118.8
C7—C6—H6	119.2	C23—C24—H24	118.8
C6—C7—C2	118.2 (2)	O8—Cl1—O6	110.1 (3)
C6—C7—N1	122.0 (2)	O8—Cl1—O5	110.0 (2)
C2—C7—N1	119.8 (2)	O6—Cl1—O5	107.5 (2)
O3—C8—N1	129.3 (2)	O8—Cl1—O7	109.6 (2)
O3—C8—C9	115.1 (2)	O6—Cl1—O7	107.6 (2)
N1—C8—C9	115.5 (2)	O5—Cl1—O7	112.0 (2)
O4—C9—N2	127.6 (2)	C25—O9—H9	109.5
O4—C9—C8	115.8 (2)	O9—C25—H25A	109.5
N2—C9—C8	116.6 (2)	O9—C25—H25B	109.5
N2—C10—C11	112.3 (3)	H25A—C25—H25B	109.5
N2—C10—H10A	109.2	O9—C25—H25C	109.5
C11—C10—H10A	109.2	H25A—C25—H25C	109.5
N2—C10—H10B	109.2	H25B—C25—H25C	109.5

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9···O1ⁱⁱ	0.82	2.73	3.190 (4)	118
O9—H9···O2ⁱⁱ	0.82	2.06	2.870 (4)	170
C4—H4···O9ⁱ	0.93	2.52	3.387 (5)	155
C13—H13C···O9ⁱⁱⁱ	0.96	2.58	3.451 (5)	151
C3—H3···O2	0.93	2.41	2.744 (4)	101
C6—H6···O3	0.93	2.22	2.812 (3)	121
C10—H10B···O4	0.97	2.43	2.775 (4)	100
C13—H13A···O1	0.96	2.39	2.899 (4)	113
C13—H13B···O5	0.96	2.47	3.186 (4)	131
C14—H14C···O1	0.96	2.58	3.074 (5)	112
C24—H24···O4	0.93	2.59	3.065 (4)	112

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

Experimental details

Crystal data
Chemical formula	[Ni₄(C₁₄H₁₆N₃O₄)₂(ClO₄)₂(C₁₀H₈N₂)₂]
M_r	1390.79
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	10.854 (4), 11.309 (4), 12.728 (5)
α, β, γ (°)	67.724 (4), 73.357 (4), 75.411 (4)
V (Å³)	1367.0 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.54
Crystal size (mm)	0.21 × 0.16 × 0.14

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.738, 0.814
No. of measured, independent and observed [I > 2σ(I)] reflections	7296, 4850, 3963
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.087, 1.04
No. of reflections	4850
No. of parameters	383
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.56

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9···O1ⁱ	0.82	2.73	3.190 (4)	117.6
O9—H9···O2ⁱ	0.82	2.06	2.870 (4)	169.7
C4—H4···O9ⁱⁱ	0.93	2.52	3.387 (5)	155.3
C13—H13C···O9ⁱⁱⁱ	0.96	2.58	3.451 (5)	151.1
C3—H3···O2	0.93	2.41	2.744 (4)	101.3
C6—H6···O3	0.93	2.22	2.812 (3)	121.1
C10—H10B···O4	0.97	2.43	2.775 (4)	100.3
C13—H13A···O1	0.96	2.39	2.899 (4)	112.7
C13—H13B···O5	0.96	2.47	3.186 (4)	130.9
C14—H14C···O1	0.96	2.58	3.074 (5)	112.1
C24—H24···O4	0.93	2.59	3.065 (4)	112.3

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

Acknowledgements

The financial support of the Science Foundation of Shandong is greatfully acknowledged.

References

Bruker, (1998). SMART and SAINT. Bruker AXS, Madison, Wisconsin, USA. 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
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tao, R. J., Zang, S. Q., Cheng, Y. X., Wang, Q. L., Hu, N. H., Niu, J. Y. & Liao, D. Z. (2003). Polyhedron 22, 2911–2916. Web of Science CSD CrossRef CAS Google Scholar

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