Di-μ(2)-acetato-di-μ(2)-azido-di-μ(3)-methanol-tetra-kis-{μ-2-[(2-methyl-1-oxidopropan-2-yl)imino-meth-yl]-6-meth-oxy-phenolato}tetra-nickel(II) methanol disolvate.

In the centrosymmetric tetra-nuclear title complex, [Ni(4)(C(12)H(15)NO(3))(2)(CH(3)COO)(2)(N(3))(2)(CH(3)OH)(2)]·2CH(3)OH, the asymmetric unit comprises half of a complex mol-ecule and a methanol solvent mol-ecule. 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 mol-ecules 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 μ(2)-bridging O atoms from the two deprotonated Schiff bases, two μ(3)-O atoms from methanol mol-ecules, two μ(1,1)-N atoms from two azide ions, and four O atoms from acetate groups. The shortest Ni⋯Ni distance in the tetra-nuclear unit is 2.962 (2) Å. O-H⋯O hydrogen bonds between the methanol solvent mol-ecule 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 = 1007.56

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.110

S = 0.84

5277 reflections

269 parameters

H-atom parameters constrained

Δρmax = 1.47 e Å−3

Δρmin = −0.55 e Å−3

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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811055164/kp2370sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ni4(C12H15NO3)2(C2H3O2)2(N3)2(CH4O)2]·2(CH4O)	F(000) = 1044.0
Mr = 1007.56	Dx = 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

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

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(Fo2) + (0.0832P)2 + 2.6493P] where P = (Fo2 + 2Fc2)/3
5277 reflections	(Δ/σ)max = 0.001
269 parameters	Δρmax = 1.47 e Å−3
0 restraints	Δρmin = −0.55 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

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) .

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) .