Di-μ2-acetato-di-μ2-azido-di-μ3-methanol-tetra­kis­{μ-2-[(2-methyl-1-oxidopropan-2-yl)imino­meth­yl]-6-meth­oxy­phenolato}tetra­nickel(II) methanol disolvate

Tan, S.-Y.; Chang, F.; Gao, Y.-P.

doi:10.1107/S1600536811055164

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Pages m150-m151

doi:10.1107/S1600536811055164

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Di-μ₂-acetato-di-μ₂-azido-di-μ₃-methanol-tetrakis{μ-2-[(2-methyl-1-oxidopropan-2-yl)iminomethyl]-6-methoxyphenolato}tetranickel(II) methanol disolvate

Shan-Yong Tan,^a Fei Chang ^a ^* and Yan-Peng Gao ^b

^aSchool of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, People's Republic of China, and ^bDepartment of Chemistry and Chemical Engineering, Ordos College of Inner Mongolia University, Erdos 017000, People's Republic of China
^*Correspondence e-mail: ndchfei@imu.edu.cn

(Received 13 November 2011; accepted 22 December 2011; online 14 January 2012)

In the centrosymmetric tetranuclear title complex, [Ni₄(C₁₂H₁₅NO₃)₂(CH₃COO)₂(N₃)₂(CH₃OH)₂]·2CH₃OH, the asymmetric unit comprises half of a complex molecule and a methanol solvent molecule. The Ni^II ions display two different coordination environments: (i) two O atoms from the Schiff base ligand, two O atoms from symmetry-related methanol molecules and an O atom from an acetate group, one N atom from the azide group, and (ii) two O atoms and one N atom from the Schiff base, one O atom from methanol, one O atom from the acetate anion, and one N atom from the azide group. Four coplanar Ni^II ions are connected by two μ₂-bridging O atoms from the two deprotonated Schiff bases, two μ₃-O atoms from methanol molecules, two μ_1,1-N atoms from two azide ions, and four O atoms from acetate groups. The shortest Ni⋯Ni distance in the tetranuclear unit is 2.962 (2) Å. O—H⋯O hydrogen bonds between the methanol solvent molecule and an acetate O atom feature in the crystal packing.

Related literature

For applications of transition metal complexes with luminescent and magnetic properties, see: Pasatoiu, Sutter et al. (2011 ); Pasatoiu, Tiseanu et al. (2011 ); Sasmal, Hazra et al. (2011 ); Sasmal, Sarkar et al. (2011 ). For the preparation of the 2-[[(2-hydroxy-1,1-dimethylethyl)imino]methyl]-6-methoxy-phenol ligand, see: Rao et al. (1998 ). For related structures, see: Oshio et al. (2005 ); Nihei et al. (2007 ).

Experimental

Crystal data

[Ni₄(C₁₂H₁₅NO₃)₂(C₂H₃O₂)₂(N₃)₂(CH₄O)₂]·2(CH₄O)
M_r = 1007.56
Monoclinic, P 2₁ /c
a = 9.5635 (14) Å
b = 11.8971 (16) Å
c = 18.845 (3) Å
β = 94.581 (2)°
V = 2137.3 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.81 mm⁻¹
T = 296 K
0.2 × 0.2 × 0.2 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.697, T_max = 0.704
15395 measured reflections
5277 independent reflections
4584 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.110
S = 0.84
5277 reflections
269 parameters
H-atom parameters constrained
Δρ_max = 1.47 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—O2	2.0052 (16)
Ni1—O3	2.0103 (18)
Ni1—O6ⁱ	2.0312 (17)
Ni1—N2	2.0720 (19)
Ni1—O6	2.0743 (16)
Ni1—O1	2.2897 (18)
Ni2—O2	1.9699 (16)
Ni2—N1	2.018 (2)
Ni2—O6	2.0282 (16)
Ni2—O5	2.0608 (18)
Ni2—O4	2.1709 (19)
Ni2—N2ⁱ	2.209 (2)
Symmetry code: (i) -x, -y+1, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯O4ⁱⁱ	0.82	1.88	2.698 (3)	175
Symmetry code: (ii) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); 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/S1600536811055164/kp2370sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811055164/kp2370Isup2.hkl

checkCIF report

Comment top

Multidentate Schiff base ligands play an important role in assembly of metal coordination complexes. There is increasing interest in transition metal complexes with multidentate Schiff base ligands because of their potential applications in in luminescent and magnetic properties (Pasatoiu et al., 2011; Sasmal, et al., 2011). Herein, we report the synthesis and crystal structure of a tetranuclearnickel(II) complex (Fig. 1, Table 1) with a tridentate Schiff base ligand 2-[(3-methoxysalicylidene)amino]-2-methyl-1-propanol with the azide coligand. The tetranuclear complex is centrosymmetric and a half of the molecule comprises an asymmetric unit which reveals two different coordiantion environments; Ni1 is coordinated by two O atoms (O1 and O2) of the ligand, one O atom from acetato group (O3), two O atoms from methanol (O6 and O6ⁱ) and N from azido group (N2), whereas Ni2 is coordinated by the two O and one N atoms from the ligand (O2, O5,N1), one O atom from acetato group (O4), one O from methanol (O6), and N from azido group (N2)(Figs.1 and 2, Table 1). The solvent methanol molecule acts as a proton donor to acetato group (O4) (Table 2, Fig. 2).

Related literature top

For applications of transition metal complexes with luminescent and magnetic properties, see: Pasatoiu, Sutter et al. (2011); Pasatoiu, Tiseanu et al. (20115); Sasmal, Hazra et al. (2011); Sasmal, Sarkar et al. (2011). For the preparation of the 2-[[(2-hydroxy-1,1-dimethylethyl)imino]methyl]-6-methoxy-phenol ligand, see: Rao et al. (1998). For related structures, see: Oshio et al. (2005); Nihei et al. (2007).

Experimental top

2-[(3-Methoxysalicylidene)amino]-2-methyl-1-propanol (0.1 mmol) in 15 mL of methyl alcohol is stirred for 30 m at room temperature. Then triethylamine(0.2 mmol) was added and stirred. After 10 m nickel(II) acetate tetrahydrate (0.15 mmol), sodium azide (0.1 mmol) were added and stirred for another 10 m. The resulting solution was filtered and left to evaporate slowly at room temperature for 4 days, giving green block crystals of the title complex for X-ray structure analysis.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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 asymmetric unit of the title compound with atom labels and 30% probability displacement ellipsoids. H ydrogen atoms are omitted for clarity.
	Fig. 2. The structural unit is a tetranuclear complex which is generated from the asymmetric unit by an inversion symmetry operation -x, -y+1, -z. Hydrogen bonds are shown as dashed lines.

Di-µ₂-acetato-di-µ₂-azido-di-µ₃-methanol-tetrakis{µ-2-[(2-methyl-1- oxidopropan-2-yl)iminomethyl]-6-methoxyphenolato}tetranickel(II) methanol disolvate top

Crystal data top

[Ni₄(C₁₂H₁₅NO₃)₂(C₂H₃O₂)₂(N₃)₂(CH₄O)₂]·2(CH₄O)	F(000) = 1044.0
M_r = 1007.56	D_x = 1.563 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8404 reflections
a = 9.5635 (14) Å	θ = 2.7–28.2°
b = 11.8971 (16) Å	µ = 1.81 mm⁻¹
c = 18.845 (3) Å	T = 296 K
β = 94.581 (2)°	Block, green
V = 2137.3 (5) Å³	0.2 × 0.2 × 0.2 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	5277 independent reflections
Radiation source: sealed tube	4584 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −12→12
T_min = 0.697, T_max = 0.704	k = −13→15
15395 measured reflections	l = −25→23

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 0.84	w = 1/[σ²(F_o²) + (0.0832P)² + 2.6493P] where P = (F_o² + 2F_c²)/3
5277 reflections	(Δ/σ)_max = 0.001
269 parameters	Δρ_max = 1.47 e Å⁻³
0 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

[Ni₄(C₁₂H₁₅NO₃)₂(C₂H₃O₂)₂(N₃)₂(CH₄O)₂]·2(CH₄O)	V = 2137.3 (5) Å³
M_r = 1007.56	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.5635 (14) Å	µ = 1.81 mm⁻¹
b = 11.8971 (16) Å	T = 296 K
c = 18.845 (3) Å	0.2 × 0.2 × 0.2 mm
β = 94.581 (2)°

Data collection top

Bruker APEXII CCD diffractometer	5277 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	4584 reflections with I > 2σ(I)
T_min = 0.697, T_max = 0.704	R_int = 0.017
15395 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 0.84	Δρ_max = 1.47 e Å⁻³
5277 reflections	Δρ_min = −0.55 e Å⁻³
269 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	0.15407 (3)	0.47649 (2)	0.012265 (15)	0.02862 (10)
Ni2	−0.03379 (3)	0.29667 (2)	0.057375 (15)	0.02882 (10)
C6	0.3281 (2)	0.4368 (2)	0.15200 (13)	0.0337 (5)
C5	0.2010 (2)	0.37608 (19)	0.15074 (12)	0.0299 (4)
C7	0.0623 (3)	0.2180 (2)	0.20063 (14)	0.0388 (5)
H7	0.0544	0.1718	0.2399	0.047*
C8	−0.1572 (3)	0.1358 (2)	0.15586 (15)	0.0447 (6)
C3	0.2992 (3)	0.2680 (2)	0.25272 (14)	0.0436 (6)
H3	0.2901	0.2130	0.2871	0.052*
C4	0.1870 (3)	0.2889 (2)	0.20048 (13)	0.0337 (5)
C1	0.4383 (3)	0.4150 (2)	0.20212 (15)	0.0428 (6)
H1	0.5213	0.4559	0.2026	0.051*
C2	0.4218 (3)	0.3292 (3)	0.25254 (16)	0.0494 (7)
H2	0.4952	0.3135	0.2864	0.059*
O2	0.10001 (16)	0.40585 (14)	0.10273 (8)	0.0309 (3)
O1	0.32663 (18)	0.51793 (15)	0.09962 (10)	0.0396 (4)
N1	−0.0370 (2)	0.21444 (17)	0.15087 (11)	0.0352 (4)
C11	−0.2605 (4)	0.1602 (3)	0.08853 (18)	0.0558 (8)
H11A	−0.3239	0.0971	0.0801	0.067*
H11B	−0.3161	0.2263	0.0970	0.067*
C9	−0.1127 (5)	0.0167 (3)	0.1622 (4)	0.1006 (19)
H9A	−0.0507	−0.0003	0.1261	0.151*
H9B	−0.1937	−0.0311	0.1564	0.151*
H9C	−0.0650	0.0042	0.2083	0.151*
C10	−0.2433 (4)	0.1707 (5)	0.2188 (2)	0.0819 (13)
H10A	−0.3341	0.1360	0.2133	0.123*
H10B	−0.2538	0.2510	0.2191	0.123*
H10C	−0.1951	0.1468	0.2628	0.123*
C12	0.2533 (3)	0.2440 (2)	0.00123 (15)	0.0405 (5)
C13	0.3687 (4)	0.1640 (3)	−0.0181 (3)	0.0784 (13)
H13A	0.3638	0.1544	−0.0688	0.118*
H13B	0.3565	0.0925	0.0042	0.118*
H13C	0.4585	0.1946	−0.0019	0.118*
O4	0.14558 (19)	0.20252 (15)	0.02585 (11)	0.0402 (4)
O3	0.27595 (19)	0.34597 (15)	−0.01089 (11)	0.0412 (4)
C14	0.4556 (3)	0.5730 (4)	0.0879 (2)	0.0688 (11)
H14A	0.4880	0.6143	0.1298	0.103*
H14B	0.4409	0.6237	0.0484	0.103*
H14C	0.5246	0.5179	0.0777	0.103*
O5	−0.1839 (2)	0.17807 (17)	0.02701 (10)	0.0444 (4)
O6	−0.02391 (17)	0.39361 (13)	−0.03062 (8)	0.0297 (3)
C15	−0.0307 (3)	0.3404 (2)	−0.09846 (13)	0.0413 (6)
H15A	0.0460	0.2886	−0.1001	0.062*
H15B	−0.0248	0.3962	−0.1349	0.062*
H15C	−0.1178	0.3005	−0.1062	0.062*
N2	0.1997 (2)	0.57829 (17)	−0.07205 (10)	0.0321 (4)
N3	0.2050 (2)	0.54193 (18)	−0.13116 (12)	0.0358 (4)
N6	0.2121 (3)	0.5107 (3)	−0.18836 (15)	0.0584 (7)
O7	0.8278 (3)	0.0154 (2)	0.93586 (16)	0.0720 (7)
H7A	0.8392	−0.0513	0.9455	0.108*
C16	0.7350 (7)	0.0260 (4)	0.8735 (3)	0.0965 (16)
H16A	0.6900	0.0982	0.8733	0.145*
H16B	0.6653	−0.0321	0.8729	0.145*
H16C	0.7870	0.0192	0.8322	0.145*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.02667 (16)	0.02808 (16)	0.03090 (16)	−0.00306 (10)	0.00100 (11)	0.00428 (10)
Ni2	0.03015 (16)	0.02786 (16)	0.02811 (16)	−0.00462 (10)	0.00031 (11)	0.00272 (10)
C6	0.0309 (11)	0.0338 (11)	0.0360 (11)	−0.0005 (9)	−0.0006 (9)	0.0017 (9)
C5	0.0304 (10)	0.0299 (10)	0.0287 (10)	−0.0007 (8)	−0.0018 (8)	0.0006 (8)
C7	0.0458 (14)	0.0361 (12)	0.0340 (12)	−0.0069 (10)	0.0000 (10)	0.0060 (9)
C8	0.0467 (14)	0.0461 (14)	0.0408 (13)	−0.0186 (12)	0.0000 (11)	0.0120 (11)
C3	0.0437 (14)	0.0452 (14)	0.0402 (13)	0.0021 (11)	−0.0079 (11)	0.0083 (11)
C4	0.0359 (12)	0.0344 (11)	0.0298 (11)	−0.0017 (9)	−0.0033 (9)	0.0044 (9)
C1	0.0321 (12)	0.0489 (15)	0.0458 (14)	−0.0027 (10)	−0.0066 (10)	0.0009 (11)
C2	0.0413 (14)	0.0584 (17)	0.0457 (15)	−0.0002 (13)	−0.0132 (11)	0.0060 (13)
O2	0.0292 (7)	0.0322 (8)	0.0302 (7)	−0.0057 (6)	−0.0039 (6)	0.0051 (6)
O1	0.0320 (8)	0.0405 (9)	0.0453 (10)	−0.0107 (7)	−0.0027 (7)	0.0085 (7)
N1	0.0394 (11)	0.0333 (10)	0.0328 (10)	−0.0077 (8)	0.0027 (8)	0.0050 (8)
C11	0.0539 (17)	0.0601 (19)	0.0527 (17)	−0.0169 (15)	−0.0008 (13)	0.0054 (14)
C9	0.068 (3)	0.0384 (18)	0.192 (6)	−0.0131 (17)	−0.010 (3)	0.030 (3)
C10	0.061 (2)	0.117 (4)	0.070 (2)	−0.028 (2)	0.0204 (19)	0.000 (2)
C12	0.0384 (12)	0.0334 (12)	0.0500 (14)	−0.0006 (10)	0.0048 (10)	−0.0017 (10)
C13	0.056 (2)	0.0417 (17)	0.143 (4)	0.0086 (15)	0.040 (2)	−0.002 (2)
O4	0.0397 (10)	0.0308 (9)	0.0506 (11)	−0.0015 (7)	0.0063 (8)	0.0009 (7)
O3	0.0385 (9)	0.0331 (9)	0.0533 (11)	0.0002 (7)	0.0114 (8)	0.0040 (8)
C14	0.0458 (17)	0.081 (3)	0.078 (2)	−0.0329 (17)	−0.0057 (15)	0.028 (2)
O5	0.0511 (11)	0.0456 (10)	0.0362 (9)	−0.0194 (9)	0.0015 (8)	−0.0011 (8)
O6	0.0330 (8)	0.0305 (8)	0.0254 (7)	−0.0029 (6)	0.0002 (6)	0.0011 (6)
C15	0.0497 (14)	0.0438 (14)	0.0304 (11)	−0.0052 (11)	0.0024 (10)	−0.0068 (10)
N2	0.0319 (9)	0.0334 (10)	0.0315 (9)	−0.0026 (7)	0.0047 (7)	0.0037 (8)
N3	0.0319 (10)	0.0362 (10)	0.0397 (11)	−0.0032 (8)	0.0051 (8)	0.0011 (8)
N6	0.0670 (18)	0.0652 (17)	0.0447 (14)	−0.0091 (14)	0.0151 (12)	−0.0128 (12)
O7	0.103 (2)	0.0377 (12)	0.0759 (17)	0.0026 (13)	0.0132 (15)	−0.0054 (11)
C16	0.136 (5)	0.079 (3)	0.071 (3)	0.019 (3)	−0.007 (3)	−0.006 (2)

Geometric parameters (Å, º) top

Ni1—O2	2.0052 (16)	C11—O5	1.436 (4)
Ni1—O3	2.0103 (18)	C11—H11A	0.9700
Ni1—O6ⁱ	2.0312 (17)	C11—H11B	0.9700
Ni1—N2	2.0720 (19)	C9—H9A	0.9600
Ni1—O6	2.0743 (16)	C9—H9B	0.9600
Ni1—O1	2.2897 (18)	C9—H9C	0.9600
Ni1—Ni1ⁱ	2.9988 (7)	C10—H10A	0.9600
Ni2—O2	1.9699 (16)	C10—H10B	0.9600
Ni2—N1	2.018 (2)	C10—H10C	0.9600
Ni2—O6	2.0282 (16)	C12—O3	1.256 (3)
Ni2—O5	2.0608 (18)	C12—O4	1.263 (3)
Ni2—O4	2.1709 (19)	C12—C13	1.524 (4)
Ni2—N2ⁱ	2.209 (2)	C13—H13A	0.9600
C6—O1	1.380 (3)	C13—H13B	0.9600
C6—C1	1.382 (3)	C13—H13C	0.9600
C6—C5	1.413 (3)	C14—H14A	0.9600
C5—O2	1.318 (3)	C14—H14B	0.9600
C5—C4	1.411 (3)	C14—H14C	0.9600
C7—N1	1.281 (3)	O6—C15	1.424 (3)
C7—C4	1.461 (3)	O6—Ni1ⁱ	2.0313 (17)
C7—H7	0.9300	C15—H15A	0.9600
C8—C9	1.481 (5)	C15—H15B	0.9600
C8—N1	1.491 (3)	C15—H15C	0.9600
C8—C10	1.553 (5)	N2—N3	1.200 (3)
C8—C11	1.572 (4)	N2—Ni2ⁱ	2.209 (2)
C3—C2	1.380 (4)	N3—N6	1.147 (3)
C3—C4	1.419 (3)	O7—C16	1.421 (6)
C3—H3	0.9300	O7—H7A	0.8200
C1—C2	1.412 (4)	C16—H16A	0.9600
C1—H1	0.9300	C16—H16B	0.9600
C2—H2	0.9300	C16—H16C	0.9600
O1—C14	1.429 (3)

O2—Ni1—O3	93.10 (7)	C6—O1—C14	118.1 (2)
O2—Ni1—O6ⁱ	88.34 (7)	C6—O1—Ni1	109.24 (13)
O3—Ni1—O6ⁱ	176.78 (7)	C14—O1—Ni1	124.70 (19)
O2—Ni1—N2	168.94 (7)	C7—N1—C8	120.3 (2)
O3—Ni1—N2	97.11 (8)	C7—N1—Ni2	124.16 (17)
O6ⁱ—Ni1—N2	81.68 (7)	C8—N1—Ni2	115.14 (16)
O2—Ni1—O6	82.69 (6)	O5—C11—C8	110.5 (3)
O3—Ni1—O6	91.16 (7)	O5—C11—H11A	109.5
O6ⁱ—Ni1—O6	86.16 (7)	C8—C11—H11A	109.5
N2—Ni1—O6	101.29 (7)	O5—C11—H11B	109.5
O2—Ni1—O1	72.48 (6)	C8—C11—H11B	109.5
O3—Ni1—O1	85.71 (8)	H11A—C11—H11B	108.1
O6ⁱ—Ni1—O1	97.47 (7)	C8—C9—H9A	109.5
N2—Ni1—O1	103.98 (7)	C8—C9—H9B	109.5
O6—Ni1—O1	154.73 (6)	H9A—C9—H9B	109.5
O2—Ni1—Ni1ⁱ	83.82 (5)	C8—C9—H9C	109.5
O3—Ni1—Ni1ⁱ	133.65 (6)	H9A—C9—H9C	109.5
O6ⁱ—Ni1—Ni1ⁱ	43.64 (4)	H9B—C9—H9C	109.5
N2—Ni1—Ni1ⁱ	92.14 (6)	C8—C10—H10A	109.5
O6—Ni1—Ni1ⁱ	42.52 (5)	C8—C10—H10B	109.5
O1—Ni1—Ni1ⁱ	135.53 (5)	H10A—C10—H10B	109.5
O2—Ni2—N1	89.73 (7)	C8—C10—H10C	109.5
O2—Ni2—O6	84.76 (6)	H10A—C10—H10C	109.5
N1—Ni2—O6	174.03 (7)	H10B—C10—H10C	109.5
O2—Ni2—O5	170.33 (7)	O3—C12—O4	127.0 (2)
N1—Ni2—O5	81.47 (8)	O3—C12—C13	114.9 (2)
O6—Ni2—O5	103.84 (7)	O4—C12—C13	118.1 (3)
O2—Ni2—O4	87.64 (7)	C12—C13—H13A	109.5
N1—Ni2—O4	93.21 (8)	C12—C13—H13B	109.5
O6—Ni2—O4	88.87 (7)	H13A—C13—H13B	109.5
O5—Ni2—O4	96.82 (8)	C12—C13—H13C	109.5
O2—Ni2—N2ⁱ	87.13 (7)	H13A—C13—H13C	109.5
N1—Ni2—N2ⁱ	98.98 (8)	H13B—C13—H13C	109.5
O6—Ni2—N2ⁱ	78.48 (7)	C12—O4—Ni2	125.71 (17)
O5—Ni2—N2ⁱ	90.26 (8)	C12—O3—Ni1	126.49 (17)
O4—Ni2—N2ⁱ	166.70 (7)	O1—C14—H14A	109.5
O1—C6—C1	125.7 (2)	O1—C14—H14B	109.5
O1—C6—C5	112.69 (19)	H14A—C14—H14B	109.5
C1—C6—C5	121.6 (2)	O1—C14—H14C	109.5
O2—C5—C4	123.4 (2)	H14A—C14—H14C	109.5
O2—C5—C6	117.2 (2)	H14B—C14—H14C	109.5
C4—C5—C6	119.4 (2)	C11—O5—Ni2	105.45 (16)
N1—C7—C4	125.1 (2)	C15—O6—Ni2	118.66 (15)
N1—C7—H7	117.5	C15—O6—Ni1ⁱ	120.45 (15)
C4—C7—H7	117.5	Ni2—O6—Ni1ⁱ	102.96 (7)
C9—C8—N1	112.8 (3)	C15—O6—Ni1	122.57 (15)
C9—C8—C10	111.1 (4)	Ni2—O6—Ni1	92.42 (6)
N1—C8—C10	109.8 (3)	Ni1ⁱ—O6—Ni1	93.84 (7)
C9—C8—C11	113.6 (3)	O6—C15—H15A	109.5
N1—C8—C11	105.7 (2)	O6—C15—H15B	109.5
C10—C8—C11	103.3 (3)	H15A—C15—H15B	109.5
C2—C3—C4	120.1 (3)	O6—C15—H15C	109.5
C2—C3—H3	120.0	H15A—C15—H15C	109.5
C4—C3—H3	120.0	H15B—C15—H15C	109.5
C5—C4—C3	118.9 (2)	N3—N2—Ni1	121.89 (17)
C5—C4—C7	123.1 (2)	N3—N2—Ni2ⁱ	116.32 (16)
C3—C4—C7	118.0 (2)	Ni1—N2—Ni2ⁱ	95.75 (8)
C6—C1—C2	118.4 (2)	N6—N3—N2	177.6 (3)
C6—C1—H1	120.8	C16—O7—H7A	109.5
C2—C1—H1	120.8	O7—C16—H16A	109.5
C3—C2—C1	121.6 (2)	O7—C16—H16B	109.5
C3—C2—H2	119.2	H16A—C16—H16B	109.5
C1—C2—H2	119.2	O7—C16—H16C	109.5
C5—O2—Ni2	122.38 (14)	H16A—C16—H16C	109.5
C5—O2—Ni1	118.15 (14)	H16B—C16—H16C	109.5
Ni2—O2—Ni1	96.32 (7)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O4ⁱⁱ	0.82	1.88	2.698 (3)	175

Symmetry code: (ii) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Ni₄(C₁₂H₁₅NO₃)₂(C₂H₃O₂)₂(N₃)₂(CH₄O)₂]·2(CH₄O)
M_r	1007.56
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	9.5635 (14), 11.8971 (16), 18.845 (3)
β (°)	94.581 (2)
V (Å³)	2137.3 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.81
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.697, 0.704
No. of measured, independent and observed [I > 2σ(I)] reflections	15395, 5277, 4584
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.110, 0.84
No. of reflections	5277
No. of parameters	269
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.47, −0.55

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Ni1—O2	2.0052 (16)	Ni2—O2	1.9699 (16)
Ni1—O3	2.0103 (18)	Ni2—N1	2.018 (2)
Ni1—O6ⁱ	2.0312 (17)	Ni2—O6	2.0282 (16)
Ni1—N2	2.0720 (19)	Ni2—O5	2.0608 (18)
Ni1—O6	2.0743 (16)	Ni2—O4	2.1709 (19)
Ni1—O1	2.2897 (18)	Ni2—N2ⁱ	2.209 (2)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O4ⁱⁱ	0.82	1.88	2.698 (3)	174.9

Symmetry code: (ii) −x+1, −y, −z+1.

Acknowledgements

This work was supported by the 211 Project of the postgraduate student programme of Inner Mongolia University, and the Inner Mongolia Natural Science Foundation of China (No. 200408020202).

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