Tetra-μ3-methano­lato-tetra­kis­[(2-formyl-6-meth­oxy­phenolato)methano­lnickel(II)]

Ayikoe, K.; Butcher, R.J.; Gultneh, Y.

doi:10.1107/S1600536810043497

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Pages m1487-m1488

https://doi.org/10.1107/S1600536810043497

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Tetra-μ₃-methanolato-tetrakis[(2-formyl-6-methoxyphenolato)methanolnickel(II)]

Kouassi Ayikoe,^a Ray J. Butcher ^a ^* and Yilma Gultneh ^a

^aDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
^*Correspondence e-mail: rbutcher99@yahoo.com

(Received 22 October 2010; accepted 25 October 2010; online 31 October 2010)

The molecule of the title compound, [Ni₄(CH₃O)₄(C₈H₇O₃)₄(CH₃OH)₄], has S₄ symmetry. Each of the four Ni^II atoms occupies every other corner of a cube, with the alternate corners occupied by μ₃-methanolate bridging groups linking to three Ni^II atoms. Each Ni^II atom is in an O₆ octahedral coordination environment formed by three O atoms from three μ₃-methanolate groups, one from methanol, and two others from a bidentate 2-formyl-6-methoxyphenolate 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 interactions between the coordinated methanol OH groups and both the phenolic and methoxy O atoms of an adjoining 2-formyl-6-methoxyphenolate moiety. In addition, there are weak intermolecular C—H⋯O interactions involving the methoxy 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_r = 1091.69
Tetragonal, I 4₁ /a
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 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ) 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[F² > 2σ(F²)] = 0.032
wR(F²) = 0.081
S = 0.99
2962 reflections
149 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.26 e Å⁻³

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) $[-y+{\script{3\over 4}}, x-{\script{1\over 4}}, -z+{\script{3\over 4}}]$ ; (ii) $[-y+{\script{1\over 4}}, x-{\script{1\over 4}}, z-{\script{1\over 4}}]$ ; (iii) $[y+{\script{1\over 4}}, -x+{\script{3\over 4}}, -z+{\script{3\over 4}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810043497/bt5390sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810043497/bt5390Isup2.hkl

checkCIF report

Comment top

Polynuclear nickel(II) complexes have become a focused research area due to their single-molecule magnet properties, biomimetic activity and their flexibility to engender cluster construction. (Yang et al., 2006). The structural and magnetic properties of symmetric Ni₄O₄ cores have been correlated to the Ni—O—Ni angle. It has been shown that the Ni₄O₄ core exhibits ferromagnetic interactions when the Ni—O—Ni angle is less than 98° and antiferromagnetic interactions when the angle is greater than 109° (Andrew & Blake, 1969; Barnes & Hatfield, 1971; Bertrand et al., 1971, 1978; Gladfelter et al., 1981; Mukherjee et al., 2003). Moragues-Canovas et al. (2004) have synthesized and studied the low-temperature magnetism of the Ni₄O₄ cubane core complex with four pendant acetonitrile ions and four nitrate ions. Brezina et al. (1998), El Fallah et al. (1996), Luo et al. (2007), Cromie et al. (2001), and Ran et al. (2008) have synthesized, crystallized and studied their magnetism at low and/or various temperatures and confirmed the ferromagnetism/antiferromagnetism of such cubane Ni₄O₄ core complexes.

In Fig.(1), we report a structure of {Ni-(µ₃-OCH₃)[o-OC₆H₃(CH₃O)CHO](CH₃OH)}₄ which has a Ni₄O₄ cubane-type core centre formed from four µ₃-methanolate O atoms and four nickels. Each Ni^II is in an octahedral O₆ coordination environment completed with three µ₃-methanolate O atoms, a bidentate 2-formyl-6-methoxyphenolate ligand, and a coordinated methanol molecule. The Ni—O(cubane) 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)°. The three Ni—O µ₃-methanolate bond distances are 2.0350 (13), 2.0568 (13), and 2.0636 (13) Å. All Ni—O distances are within the normal ranges observed in other Ni complexes containing similar ligands. The o-vanillin, the methanol, and methanoate cause less distortion about the Ni's due to rigidity and stability established by the cubane Ni₄O₄. As a result, this coordination environment of the Ni is closer to perfect octahedral with the following bond angles: O(1S)#1-Ni—O(1S)#2 81.74 (6)°, O(1S)#2-Ni—O(1S) 82.32 (5)°, O(1S)#1-Ni—O(1S) 82.85 (5)°, Ni#1-O(1S)—Ni 96.50 (5)°, Ni#2-O(1S)—Ni 97.19 (5)°, Ni#2-O(1S)—Ni#1 97.91 (6)°. All the bond angles on the cubane (Ni—O—Ni and O—Ni—O) are close to but less than 98°. There are bifurcated hydrogen-bonding interactions between the coordinated methanol OH and both the phenolic and methoxy O of an adjoining 2-formyl-6-methoxyphenolate moiety. In addition there are weak intermolecular C—H···O interactions involving the methoxy O.

Related literature top

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 top

The complex was synthesized by reacting 0.53 g (1.45 mmol) of nickel perchlorate [Ni^II(ClO₄)₂.6H₂O] in methanol [MeOH] (20 ml) with a mixture of 0.23 g o-vanillin (1.46 mmol) and 0.26 g of 2-benzylaminopyridine (2-BAP) (1.46 mmol). The secondary amine and the aldehyde were initially mixed in 30 ml of methanol and refluxed with stirring overnight between 50 C and 60 C. The nickel salt solution and the ligands were then mixed and stirred overnight at room temperature (23°-25°), followed by reduced pressure (vacuum) evaporated to obtain a green oily (semi-solid). A portion of the washed product (about 0.025 g) was dissolved in 50/50 MeOH/Propanol. This solution obtained was filtered and layered with diethyl ether. Greenish X-ray quality crystals were obtained after five days of slow diffusion of the diethyl ether into the MeOH/Propanol solvent.

Structure description top

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).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis PRO (Oxford Diffraction, 2007); 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. Diagram showing the pseudo-cubic {Ni-(µ₃-OCH₃)[o-OC₆H₃(CH₃O)CHO](CH₃OH)}₄ cluster with unique part labelled. The bifurcated intramolecular hydrogen bonds are shown by dashed lines.
	Fig. 2. The molecular packing for {Ni-(µ₃-OCH₃)[o-OC₆H₃(CH₃O)CHO](CH₃OH)}₄ viewed down the c axis. Intra- and intermolecular interactions are shown by dashed lines.

Tetra-µ₃-methanolato-tetrakis[(2-formyl-6- methoxyphenolato)methanolnickel(II)] top

Crystal data top

[Ni₄(CH₃O)₄(C₈H₇O₃)₄(CH₄O)₄]	D_x = 1.508 Mg m⁻³
M_r = 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

Data collection top

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 monochromator	R_int = 0.035
Detector resolution: 10.5081 pixels mm^-1	θ_max = 29.4°, θ_min = 4.9°
ω scans	h = −21→30
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	k = −30→22
T_min = 0.463, T_max = 1.000	l = −13→12
12226 measured reflections

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) = 0.081	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0454P)²] where P = (F_o² + 2F_c²)/3
2962 reflections	(Δ/σ)_max = 0.001
149 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

[Ni₄(CH₃O)₄(C₈H₇O₃)₄(CH₄O)₄]	Z = 4
M_r = 1091.69	Mo Kα radiation
Tetragonal, I4₁/a	µ = 1.62 mm⁻¹
a = 22.2670 (9) Å	T = 110 K
c = 9.70106 (10) Å	0.47 × 0.28 × 0.24 mm
V = 4810.0 (3) Å³

Data collection top

Oxford Xcalibur diffractometer with a Ruby (Gemini Mo) detector	2962 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	2131 reflections with I > 2σ(I)
T_min = 0.463, T_max = 1.000	R_int = 0.035
12226 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.081	H-atom parameters constrained
S = 0.99	Δρ_max = 0.32 e Å⁻³
2962 reflections	Δρ_min = −0.26 e Å⁻³
149 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
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry codes: (i) −y+3/4, x−1/4, −z+3/4; (ii) y+1/4, −x+3/4, −z+3/4.

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) −y+3/4, x−1/4, −z+3/4; (ii) y+1/4, −x+3/4, −z+3/4; (iii) −y+1/4, x−1/4, z−1/4.

Experimental details

Crystal data
Chemical formula	[Ni₄(CH₃O)₄(C₈H₇O₃)₄(CH₄O)₄]
M_r	1091.69
Crystal system, space group	Tetragonal, I4₁/a
Temperature (K)	110
a, c (Å)	22.2670 (9), 9.70106 (10)
V (Å³)	4810.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.62
Crystal size (mm)	0.47 × 0.28 × 0.24

Data collection
Diffractometer	Oxford Xcalibur diffractometer with a Ruby (Gemini Mo) detector
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)
T_min, T_max	0.463, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12226, 2962, 2131
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.692

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.081, 0.99
No. of reflections	2962
No. of parameters	149
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.26

Computer programs: CrysAlis PRO (Oxford Diffraction, 2007), 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
O2S—H2S···O1ⁱ	0.84	2.05	2.8062 (19)	150.0
O2S—H2S···O3ⁱ	0.84	2.50	3.181 (2)	138.7
C5—H5A···O3ⁱⁱ	0.95	2.45	3.360 (3)	159.3
C1S—H1SC···O2Sⁱⁱⁱ	0.98	2.47	3.106 (3)	122.1

Symmetry codes: (i) −y+3/4, x−1/4, −z+3/4; (ii) −y+1/4, x−1/4, z−1/4; (iii) y+1/4, −x+3/4, −z+3/4.

Acknowledgements

RJB acknowledges the NSF-MRI programme (grant No. CHE-0619278) for funds to purchase the diffractometer.

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