Tetra-μ(3)-methano-lato-tetra-kis-[(2-formyl-6-meth-oxy-phenolato)methano-lnickel(II)].

The molecule of the title compound, [Ni(4)(CH(3)O)(4)(C(8)H(7)O(3))(4)(CH(3)OH)(4)], has S(4) symmetry. Each of the four Ni(II) atoms occupies every other corner of a cube, with the alternate corners occupied by μ(3)-methano-late bridging groups linking to three Ni(II) atoms. Each Ni(II) atom is in an O(6) octa-hedral coordination environment formed by three O atoms from three μ(3)-methano-late groups, one from methanol, and two others from a bidentate 2-formyl-6-meth-oxy-phenolate ligand. The Ni-O bond distances range from 2.0020 (14) to 2.0938 (14) Å, the cis bond angles range from 81.74 (6) to 97.63°, and the trans bond angles range from 168.76 (5) to 175.22 (6)°. There are bifurcated hydrogen-bonding inter-actions between the coordinated methanol OH groups and both the phenolic and meth-oxy O atoms of an adjoining 2-formyl-6-meth-oxy-phenolate moiety. In addition, there are weak inter-molecular C-H⋯O inter-actions involving the meth-oxy O atoms.

Related literature

For literature related to Ni4 cubane-type clusters, see; Andrew & Blake (1969 ▶); Barnes & Hatfield (1971 ▶); Bertrand et al. (1971 ▶, 1978 ▶); Brezina et al. (1998 ▶); Cromie et al. (2001 ▶); El Fallah et al. (1996 ▶); Gladfelter et al. (1981 ▶); Luo et al. (2007 ▶); Moragues-Canovas et al. (2004 ▶); Mukherjee et al. (2003 ▶); Ran et al. (2008 ▶); Yang et al. (2006 ▶).

Experimental

Crystal data

[Ni4(CH3O)4(C8H7O3)4(CH4O)4]

M = 1091.69

Tetragonal,

a = 22.2670 (9) Å

c = 9.70106 (10) Å

V = 4810.0 (3) Å3

Z = 4

Mo Kα radiation

μ = 1.62 mm−1

T = 110 K

0.47 × 0.28 × 0.24 mm

Data collection

Oxford Xcalibur diffractometer with a Ruby (Gemini Mo) detector

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007 ▶) T min = 0.463, T max = 1.000

12226 measured reflections

2962 independent reflections

2131 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.081

S = 0.99

2962 reflections

149 parameters

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.26 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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 datablocks I, global. DOI: 10.1107/S1600536810043497/bt5390sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810043497/bt5390Isup2.hkl

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

[Ni4(CH3O)4(C8H7O3)4(CH4O)4]	Dx = 1.508 Mg m−3
Mr = 1091.69	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/a	Cell parameters from 4573 reflections
Hall symbol: -I 4ad	θ = 5.0–29.3°
a = 22.2670 (9) Å	µ = 1.62 mm−1
c = 9.70106 (10) Å	T = 110 K
V = 4810.0 (3) Å3	Prism, green
Z = 4	0.47 × 0.28 × 0.24 mm
F(000) = 2272

Oxford Xcalibur diffractometer with a Ruby (Gemini Mo) detector	2962 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2131 reflections with I > 2σ(I)
graphite	Rint = 0.035
Detector resolution: 10.5081 pixels mm-1	θmax = 29.4°, θmin = 4.9°
ω scans	h = −21→30
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	k = −30→22
Tmin = 0.463, Tmax = 1.000	l = −13→12
12226 measured reflections

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) = 0.081	H-atom parameters constrained
S = 0.99	w = 1/[σ2(Fo2) + (0.0454P)2] where P = (Fo2 + 2Fc2)/3
2962 reflections	(Δ/σ)max = 0.001
149 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.26 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
Ni	0.478914 (11)	0.183990 (11)	0.26340 (2)	0.02258 (10)
O1	0.39721 (6)	0.14647 (6)	0.26250 (13)	0.0269 (3)
O2	0.48379 (6)	0.17818 (7)	0.05257 (15)	0.0344 (4)
O3	0.28657 (6)	0.11763 (6)	0.31043 (15)	0.0336 (3)
O1S	0.48109 (6)	0.19293 (6)	0.47507 (13)	0.0232 (3)
O2S	0.52889 (7)	0.10453 (6)	0.27601 (15)	0.0351 (4)
H2S	0.5524	0.1035	0.3436	0.042*
C1	0.36431 (9)	0.13635 (8)	0.1537 (2)	0.0264 (4)
C2	0.38418 (10)	0.14135 (10)	0.0123 (2)	0.0326 (5)
C3	0.34410 (11)	0.12800 (11)	−0.0989 (2)	0.0439 (6)
H3A	0.3580	0.1314	−0.1911	0.053*
C4	0.28728 (11)	0.11077 (11)	−0.0753 (2)	0.0471 (6)
H4A	0.2614	0.1016	−0.1502	0.057*
C5	0.26610 (10)	0.10643 (10)	0.0628 (3)	0.0390 (6)
H5A	0.2258	0.0944	0.0795	0.047*
C6	0.30315 (9)	0.11932 (9)	0.1725 (2)	0.0294 (5)
C7	0.44257 (10)	0.16174 (11)	−0.0244 (2)	0.0386 (6)
H7A	0.4510	0.1629	−0.1203	0.046*
C8	0.22877 (10)	0.09432 (13)	0.3404 (3)	0.0530 (7)
H8A	0.1984	0.1170	0.2889	0.080*
H8B	0.2209	0.0980	0.4394	0.080*
H8C	0.2271	0.0519	0.3136	0.080*
C1S	0.46424 (10)	0.14354 (9)	0.5602 (2)	0.0316 (5)
H1SA	0.4799	0.1497	0.6535	0.047*
H1SB	0.4809	0.1064	0.5220	0.047*
H1SC	0.4204	0.1406	0.5635	0.047*
C2S	0.51222 (14)	0.04601 (11)	0.2403 (3)	0.0646 (9)
H2SA	0.5060	0.0223	0.3242	0.097*
H2SB	0.5441	0.0276	0.1848	0.097*
H2SC	0.4749	0.0471	0.1869	0.097*

	U11	U22	U33	U12	U13	U23
Ni	0.02257 (15)	0.02712 (16)	0.01804 (14)	−0.00098 (11)	0.00057 (10)	−0.00374 (10)
O1	0.0258 (7)	0.0310 (8)	0.0241 (7)	−0.0014 (6)	−0.0011 (6)	−0.0027 (6)
O2	0.0285 (8)	0.0531 (10)	0.0218 (7)	−0.0090 (7)	0.0017 (6)	−0.0082 (7)
O3	0.0251 (7)	0.0362 (8)	0.0394 (8)	−0.0014 (6)	0.0064 (7)	0.0024 (7)
O1S	0.0285 (7)	0.0219 (7)	0.0193 (7)	−0.0004 (6)	0.0021 (5)	0.0019 (5)
O2S	0.0365 (8)	0.0299 (8)	0.0388 (9)	0.0023 (7)	−0.0096 (7)	−0.0111 (7)
C1	0.0269 (10)	0.0214 (10)	0.0309 (11)	−0.0003 (8)	−0.0010 (9)	−0.0038 (8)
C2	0.0297 (11)	0.0402 (12)	0.0281 (11)	−0.0042 (10)	0.0004 (9)	−0.0072 (9)
C3	0.0423 (14)	0.0598 (16)	0.0296 (12)	−0.0085 (12)	−0.0021 (10)	−0.0117 (11)
C4	0.0391 (14)	0.0616 (17)	0.0407 (14)	−0.0098 (12)	−0.0123 (11)	−0.0104 (12)
C5	0.0239 (11)	0.0391 (13)	0.0541 (15)	−0.0040 (9)	−0.0052 (10)	−0.0025 (12)
C6	0.0278 (11)	0.0254 (10)	0.0349 (12)	0.0017 (9)	0.0020 (9)	−0.0007 (9)
C7	0.0370 (13)	0.0560 (15)	0.0228 (11)	−0.0058 (12)	0.0034 (9)	−0.0085 (10)
C8	0.0245 (12)	0.0724 (18)	0.0621 (17)	−0.0014 (12)	0.0080 (12)	0.0126 (14)
C1S	0.0412 (12)	0.0259 (11)	0.0276 (11)	−0.0004 (10)	0.0049 (10)	0.0053 (9)
C2S	0.0657 (19)	0.0344 (15)	0.094 (2)	−0.0018 (13)	−0.0241 (16)	−0.0189 (15)

Ni—O1	2.0020 (14)	C2—C3	1.431 (3)
Ni—O1Si	2.0350 (13)	C3—C4	1.342 (3)
Ni—O2	2.0522 (15)	C3—H3A	0.9500
Ni—O1Sii	2.0568 (13)	C4—C5	1.424 (3)
Ni—O1S	2.0636 (13)	C4—H4A	0.9500
Ni—O2S	2.0938 (14)	C5—C6	1.377 (3)
O1—C1	1.305 (2)	C5—H5A	0.9500
O2—C7	1.239 (3)	C7—H7A	0.9500
O3—C6	1.389 (2)	C8—H8A	0.9800
O3—C8	1.418 (3)	C8—H8B	0.9800
O1S—C1S	1.425 (2)	C8—H8C	0.9800
O1S—Niii	2.0350 (13)	C1S—H1SA	0.9800
O1S—Nii	2.0568 (13)	C1S—H1SB	0.9800
O2S—C2S	1.398 (3)	C1S—H1SC	0.9800
O2S—H2S	0.8400	C2S—H2SA	0.9800
C1—C6	1.425 (3)	C2S—H2SB	0.9800
C1—C2	1.445 (3)	C2S—H2SC	0.9800
C2—C7	1.423 (3)
O1—Ni—O1Si	172.97 (5)	C4—C3—C2	121.3 (2)
O1—Ni—O2	91.00 (5)	C4—C3—H3A	119.4
O1Si—Ni—O2	92.41 (5)	C2—C3—H3A	119.4
O1—Ni—O1Sii	91.71 (5)	C3—C4—C5	119.5 (2)
O1Si—Ni—O1Sii	81.74 (6)	C3—C4—H4A	120.3
O2—Ni—O1Sii	97.63 (6)	C5—C4—H4A	120.3
O1—Ni—O1S	93.78 (5)	C6—C5—C4	120.98 (19)
O1Si—Ni—O1S	82.85 (5)	C6—C5—H5A	119.5
O2—Ni—O1S	175.22 (6)	C4—C5—H5A	119.5
O1Sii—Ni—O1S	82.32 (5)	C5—C6—O3	125.44 (18)
O1—Ni—O2S	97.51 (6)	C5—C6—C1	121.94 (19)
O1Si—Ni—O2S	88.72 (5)	O3—C6—C1	112.62 (17)
O2—Ni—O2S	88.67 (6)	O2—C7—C2	128.4 (2)
O1Sii—Ni—O2S	168.76 (5)	O2—C7—H7A	115.8
O1S—Ni—O2S	90.63 (5)	C2—C7—H7A	115.8
C1—O1—Ni	125.87 (12)	O3—C8—H8A	109.5
C7—O2—Ni	125.47 (14)	O3—C8—H8B	109.5
C6—O3—C8	116.67 (18)	H8A—C8—H8B	109.5
C1S—O1S—Niii	119.50 (11)	O3—C8—H8C	109.5
C1S—O1S—Nii	120.73 (12)	H8A—C8—H8C	109.5
Niii—O1S—Nii	97.91 (6)	H8B—C8—H8C	109.5
C1S—O1S—Ni	119.72 (12)	O1S—C1S—H1SA	109.5
Niii—O1S—Ni	97.19 (5)	O1S—C1S—H1SB	109.5
Nii—O1S—Ni	96.50 (5)	H1SA—C1S—H1SB	109.5
C2S—O2S—Ni	129.19 (15)	O1S—C1S—H1SC	109.5
C2S—O2S—H2S	109.5	H1SA—C1S—H1SC	109.5
Ni—O2S—H2S	113.6	H1SB—C1S—H1SC	109.5
O1—C1—C6	118.61 (18)	O2S—C2S—H2SA	109.5
O1—C1—C2	125.64 (18)	O2S—C2S—H2SB	109.5
C6—C1—C2	115.75 (18)	H2SA—C2S—H2SB	109.5
C7—C2—C3	116.59 (19)	O2S—C2S—H2SC	109.5
C7—C2—C1	122.81 (19)	H2SA—C2S—H2SC	109.5
C3—C2—C1	120.55 (19)	H2SB—C2S—H2SC	109.5
O1Si—Ni—O1—C1	109.0 (4)	O1Si—Ni—O2S—C2S	−161.5 (2)
O2—Ni—O1—C1	−10.03 (15)	O2—Ni—O2S—C2S	−69.1 (2)
O1Sii—Ni—O1—C1	87.64 (15)	O1Sii—Ni—O2S—C2S	166.6 (3)
O1S—Ni—O1—C1	170.05 (15)	O1S—Ni—O2S—C2S	115.7 (2)
O2S—Ni—O1—C1	−98.82 (15)	Ni—O1—C1—C6	−168.91 (13)
O1—Ni—O2—C7	6.22 (19)	Ni—O1—C1—C2	10.5 (3)
O1Si—Ni—O2—C7	−167.63 (19)	O1—C1—C2—C7	−3.7 (3)
O1Sii—Ni—O2—C7	−85.64 (19)	C6—C1—C2—C7	175.7 (2)
O1S—Ni—O2—C7	−174.7 (6)	O1—C1—C2—C3	178.9 (2)
O2S—Ni—O2—C7	103.71 (19)	C6—C1—C2—C3	−1.7 (3)
O1—Ni—O1S—C1S	46.98 (14)	C7—C2—C3—C4	−177.3 (2)
O1Si—Ni—O1S—C1S	−139.22 (15)	C1—C2—C3—C4	0.2 (4)
O2—Ni—O1S—C1S	−132.1 (7)	C2—C3—C4—C5	0.8 (4)
O1Sii—Ni—O1S—C1S	138.20 (15)	C3—C4—C5—C6	−0.3 (3)
O2S—Ni—O1S—C1S	−50.59 (14)	C4—C5—C6—O3	178.63 (19)
O1—Ni—O1S—Niii	−83.07 (6)	C4—C5—C6—C1	−1.3 (3)
O1Si—Ni—O1S—Niii	90.730 (9)	C8—O3—C6—C5	7.4 (3)
O2—Ni—O1S—Niii	97.9 (7)	C8—O3—C6—C1	−172.74 (18)
O1Sii—Ni—O1S—Niii	8.15 (6)	O1—C1—C6—C5	−178.32 (19)
O2S—Ni—O1S—Niii	179.37 (6)	C2—C1—C6—C5	2.2 (3)
O1—Ni—O1S—Nii	178.07 (5)	O1—C1—C6—O3	1.8 (2)
O1Si—Ni—O1S—Nii	−8.13 (6)	C2—C1—C6—O3	−177.69 (17)
O2—Ni—O1S—Nii	−1.0 (7)	Ni—O2—C7—C2	−2.4 (4)
O1Sii—Ni—O1S—Nii	−90.708 (8)	C3—C2—C7—O2	176.9 (2)
O2S—Ni—O1S—Nii	80.51 (6)	C1—C2—C7—O2	−0.6 (4)
O1—Ni—O2S—C2S	21.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O2S—H2S···O1i	0.84	2.05	2.8062 (19)	150
O2S—H2S···O3i	0.84	2.50	3.181 (2)	139
C5—H5A···O3iii	0.95	2.45	3.360 (3)	159
C1S—H1SC···O2Sii	0.98	2.47	3.106 (3)	122

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2S—H2S⋯O1i	0.84	2.05	2.8062 (19)	150
O2S—H2S⋯O3i	0.84	2.50	3.181 (2)	139
C5—H5A⋯O3ii	0.95	2.45	3.360 (3)	159
C1S—H1SC⋯O2Siii	0.98	2.47	3.106 (3)	122

Symmetry codes: (i) ; (ii) ; (iii) .