A tetra­nuclear copper(II) complex constructed from the salen ligand with alkoxo groups

Zhang, M.-S.; Jin, J.-Y.; Wu, X.; Shao, K.-Z.; Su, Z.-M.

doi:10.1107/S1600536807050891

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A tetranuclear copper(II) complex constructed from the salen ligand with alkoxo groups

M.-S. Zhang, J.-Y. Jin, X. Wu, K.-Z. Shao and Z.-M. Su

In the title compound, tetrakis[μ₃-2-(5-hydroxy-2-oxidobenzylideneamino)-2-methylpropanolato]tetracopper(II) methanol tetrasolvate, [Cu₄(C₁₁H₁₃NO₃)₄]·4CH₃OH, two Cu₂ cores are linked by two μ₃-bridging alkoxo O atoms to form a centrosymmetric dimer of dicopper(II) units. Two Cu atoms coordinate to the NO₂ (a phenolic O atom, an alcoholic O atom and an imine N atom) chelator unit of one ligand and an alcohol O atom of the other ligand, forming a distorted planar coordination configure. The remaining Cu atoms coordinate in a pyramidal geometry. The distorted basal plane is also formed by the N₂O unit and the alcohol O atom from the second ligand, while an alcohol O atom from a third ligand occupies the axial position.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807050891/av3116sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807050891/av3116Isup2.hkl Contains datablock I

CCDC reference: 660426

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.004 Å
R factor = 0.036
wR factor = 0.094
Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT147_ALERT_1_C su on Symmetry Constrained Cell Angle(s) .......          ?
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          4
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   O2      ..       5.55 su
PLAT320_ALERT_2_C Check Hybridisation of  C6     in Main Residue .          ?
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C5     -   C6     ...       1.36 Ang.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          1
            O2  -CU2 -O3  -C9   -108.70  1.80   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          6
            O2  -CU2 -O3  -CU1    20.50  1.80   1.555   1.555   1.555   3.556
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         10
            O3  -CU2 -O2  -C3     98.10  1.80   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         15
            O5  -CU1 -O6  -C20   -80.00  4.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         19
            O5  -CU1 -O6  -CU2    50.00  4.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         23
            O5  -CU1 -O6  -CU2   150.00  4.00   1.555   1.555   1.555   3.556
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         43
            O6  -CU1 -O5  -C12    75.00  4.00   1.555   1.555   1.555   1.555
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C H4 O

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.20
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu2         (2)       2.22

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  16 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
  10 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

Comment top

There has been continuous interest in high-nuclearity transition-metal complexes in order to elucidate the fundamentals of magnetic interactions (Kahn O., 1993; Kahn O., 1995; Gatteschi D., 1994). Especially, polynuclear metal complexes including O-bridges arising from O-alkoxo moieties have attracted intense interest (Paap et al., 1981; Atkins et al., 1993). Generally, the flexibility of the coordination sphere around Cu^II with varied distortions due to a pseudo-Jahn-Teller effect leads to its tremendous structral diversity. It has been exemplied that contruction of the polynuclear Cu^II complexes from the polydentate Schiff-based ligands represents a promising route, because the ligands can function in both bridging and chelating modes (Liu et al., 2005; Xie et al., 2007). Here we report a new tetranuclear Cu^II complex constructed from the salen ligand with alkoxo moieties, N-(2,5-dihyroxyphenylmethylene)-1-amino-1-methylpropanol.

As shown in Fig. 1, X-ray single-crystal analysis reveals the existance of a tetranulear Cu^II molecular skeleton in compound. In an ansymmetry unit, there are two Cu^II atoms, two ligands and two solvent methanol molecules. The tetranuclear complex contains two kinds of Cu^II center. Two Cu1 atoms each coordinate to the NO2 (a phenolic oxygen atom, an alcoholic oxygen atom and an imine N atom) chelator unit in one ligand and an alcohol oxygen atom from the other ligand, forming a distorted planar coordination sphere. While two Cu2 each coordinate in a pyramidal geometry. Its distorted basal plane is also formed by the N2O unit and the alcohol oxygen atom from the second ligand, and an alcohol oxygen atom from the third ligand occupies the axial position with the Cu—O distance as 2.34 Å. Two of the four alcohol oxygen atoms O3 in the ligands act as one µ₂ bridged atom and the other two O6 act as µ₃ bridge to link to Cu atoms together, resulting in the tetranuclear structure. Such structure can be described as two Cu—Cu cores (separated in 3.05 Å) linked by two µ₃ bridged alcohol oxygen O6 and O6A atoms to form a centrosymmetric dimer of dicopper(II) moieties.

Related literature top

For related literature, see: Atkins et al. (1993); Gatteschi (1994); Kahn (1993, 1995); Liu et al. (2005); Xie et al. (2007); Paap et al. (1985).

Experimental top

1-Amino-1-methylpropanol (0.285 g, 3.20 mmol) was added to the solution of ethyl acetate containing 4-hydroxybenzaldehyde (0.345 g, 2.50 mmol). After keeping stirred at room temperature for 1 h, the precipitated yellow solid was then filtrated. Recrystallization from the mixture solvents (methanol:ethtyl acetate = 1:4) provided a yellow needle as the salen compound. Yield: 85%. ¹H NMR (300 MHz, CDCl₃) δ: 8.20 (s, 1H), 7.13 (d, J = 7.9 Hz, 1H), 6.12 (d, J = 7.9 Hz, 1H), 6.05 (s, 1H), 4.45 (s, 1H), 3.53 (s, 2H), 3.32 (s, 1H), 1.40 (s, 6H). ¹³C NMR (75 MHz, CDCl₃) δ: 177.27, 166.35, 135.76, 110.06, 106.62, 68.86, 58.14, 22.52. IR (KBr, cm^-1): 3061, 2972, 2900, 1636, 1229, 1072. Analysis found: C 63.41, H 7.50, N 6.72%; C₁₁H₁₅NO₃ requires: C 63.14, H 7.23, N 6.69%.

The salen ligand (0.230 g, 1.1 mmol) was dissolved in 10 ml me thanol. The other 10 ml of methanol solution containing 0.20 g copper acetate (1.0 mmol) was then slowly added when keeping stirred at room temperature. After two hours, the resulting green solid was filtrated and washed by methanol for 4–6 times. Drying in vacuum provied the tetranuclear Cu^II complex. Crystals suitable for single-crystal X-ray diffraction were selected directly from the sample as prepared. Analysis found: C 47.56, H 5.52, N 4.17%; C₄₈H₆₈N₄O₁₆Cu₄ requires: C 47.60, H 5.66, N 4.63%.

Computing details top

Data collection: SMART; cell refinement: SMART; data reduction: SMART; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top

Fig. 1. ORTEP drawing of the tetranuclear Cu^II complex, showing the non-hydrogen atoms as 50% probability thermal ellipsoids. The hydrogen atoms and solvent molecules are omitted for clarity. (Symmetry code (A): -x, -y, 1 - z).

tetrakis[µ₃-2-(5-hydroxy-2-oxidobenzylideneamino)-2- methylpropanolato]tetracopper(II) methanol tetrasolvate top

Crystal data top

[Cu₄(C₁₁H₁₃NO₃)₄]·4CH₄O	F(000) = 1252
M_r = 1211.27	D_x = 1.496 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71069 Å
a = 13.260 (1) Å	Cell parameters from 198 reflections
b = 15.3170 (11) Å	θ = 2.8–23.6°
c = 13.266 (1) Å	µ = 1.63 mm⁻¹
β = 94.936 (1)°	T = 293 K
V = 2684.4 (3) Å³	Block, green
Z = 2	0.27 × 0.21 × 0.19 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	5500 independent reflections
Radiation source: fine-focus sealed tube	4143 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω scans	θ_max = 26.4°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −16→16
T_min = 0.667, T_max = 0.747	k = −16→19
15163 measured reflections	l = −14→16

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) = 0.089	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0467P)² + 0.7871P] where P = (F_o² + 2F_c²)/3
5500 reflections	(Δ/σ)_max = 0.001
335 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

[Cu₄(C₁₁H₁₃NO₃)₄]·4CH₄O	V = 2684.4 (3) Å³
M_r = 1211.27	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.260 (1) Å	µ = 1.63 mm⁻¹
b = 15.3170 (11) Å	T = 293 K
c = 13.266 (1) Å	0.27 × 0.21 × 0.19 mm
β = 94.936 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	5500 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	4143 reflections with I > 2σ(I)
T_min = 0.667, T_max = 0.747	R_int = 0.032
15163 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.01	Δρ_max = 0.46 e Å⁻³
5500 reflections	Δρ_min = −0.31 e Å⁻³
335 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
Cu1	−0.03362 (3)	0.14760 (2)	0.40100 (2)	0.03335 (10)
Cu2	0.10141 (2)	−0.02196 (2)	0.43998 (3)	0.03326 (11)
N1	0.23637 (17)	−0.06909 (14)	0.43062 (18)	0.0355 (5)
N2	−0.06058 (17)	0.13685 (14)	0.25524 (17)	0.0343 (5)
O1	0.35289 (19)	0.33567 (14)	0.3623 (2)	0.0738 (8)
H1	0.3034	0.3627	0.3786	0.111*
O2	0.14247 (14)	0.09726 (11)	0.42952 (15)	0.0395 (5)
O3	0.06112 (14)	−0.14255 (11)	0.45695 (14)	0.0336 (4)
O4	−0.1033 (2)	0.55741 (12)	0.27462 (17)	0.0581 (6)
H4	−0.0864	0.5698	0.3338	0.087*
O5	−0.02680 (16)	0.27247 (12)	0.39976 (14)	0.0412 (5)
O6	−0.03814 (13)	0.01988 (11)	0.40057 (14)	0.0329 (4)
O7	−0.08781 (19)	0.65603 (14)	0.44334 (18)	0.0563 (6)
H7A	−0.0479	0.6758	0.4883	0.084*
O8	0.1988 (2)	0.43416 (18)	0.4108 (3)	0.0982 (11)
H8	0.1642	0.4167	0.4550	0.147*
C1	0.3369 (2)	0.2493 (2)	0.3721 (3)	0.0483 (8)
C2	0.2451 (2)	0.21476 (18)	0.3931 (2)	0.0404 (7)
H2	0.1907	0.2523	0.3986	0.048*
C3	0.2311 (2)	0.12554 (17)	0.4062 (2)	0.0342 (6)
C4	0.3151 (2)	0.06916 (18)	0.3953 (2)	0.0368 (6)
C5	0.4071 (2)	0.1072 (2)	0.3714 (3)	0.0511 (8)
H5	0.4618	0.0708	0.3629	0.061*
C6	0.4190 (3)	0.1945 (2)	0.3605 (3)	0.0571 (9)
H6	0.4808	0.2174	0.3454	0.068*
C7	0.3133 (2)	−0.02352 (18)	0.4083 (2)	0.0397 (7)
H7	0.3728	−0.0537	0.3999	0.048*
C8	0.2431 (2)	−0.16499 (17)	0.4481 (2)	0.0411 (7)
C9	0.1356 (2)	−0.19766 (18)	0.4189 (2)	0.0407 (7)
H9A	0.1242	−0.2005	0.3457	0.049*
H9B	0.1285	−0.2562	0.4452	0.049*
C10	0.2748 (3)	−0.1798 (2)	0.5603 (3)	0.0549 (9)
H10A	0.3433	−0.1604	0.5754	0.082*
H10B	0.2702	−0.2408	0.5756	0.082*
H10C	0.2309	−0.1474	0.6003	0.082*
C11	0.3168 (3)	−0.2113 (2)	0.3827 (3)	0.0659 (11)
H11A	0.3052	−0.1916	0.3140	0.099*
H11B	0.3063	−0.2732	0.3854	0.099*
H11C	0.3851	−0.1980	0.4079	0.099*
C12	−0.0571 (2)	0.32373 (17)	0.3224 (2)	0.0341 (6)
C13	−0.0653 (2)	0.41317 (17)	0.3394 (2)	0.0386 (7)
H13	−0.0501	0.4351	0.4043	0.046*
C14	−0.0956 (2)	0.46972 (18)	0.2615 (2)	0.0406 (7)
C15	−0.1183 (3)	0.43913 (19)	0.1646 (2)	0.0475 (8)
H15	−0.1381	0.4776	0.1124	0.057*
C16	−0.1115 (2)	0.35204 (19)	0.1458 (2)	0.0454 (7)
H16	−0.1270	0.3318	0.0802	0.055*
C17	−0.0816 (2)	0.29170 (17)	0.2229 (2)	0.0354 (6)
C18	−0.0791 (2)	0.20114 (18)	0.1946 (2)	0.0373 (6)
H18	−0.0921	0.1881	0.1262	0.045*
C19	−0.0595 (2)	0.04485 (17)	0.2171 (2)	0.0406 (7)
C20	−0.0882 (2)	−0.01003 (18)	0.3081 (2)	0.0422 (7)
H20A	−0.1608	−0.0070	0.3121	0.051*
H20B	−0.0704	−0.0706	0.2977	0.051*
C21	0.0475 (3)	0.0259 (2)	0.1897 (3)	0.0572 (9)
H21A	0.0620	0.0613	0.1330	0.086*
H21B	0.0530	−0.0346	0.1724	0.086*
H21C	0.0949	0.0392	0.2464	0.086*
C22	−0.1361 (3)	0.0277 (2)	0.1279 (3)	0.0657 (10)
H22A	−0.2011	0.0495	0.1427	0.098*
H22B	−0.1407	−0.0340	0.1154	0.098*
H22C	−0.1152	0.0567	0.0690	0.098*
C23	−0.1332 (3)	0.7280 (2)	0.3820 (3)	0.0661 (10)
H23A	−0.1480	0.7756	0.4254	0.099*
H23B	−0.1945	0.7083	0.3454	0.099*
H23C	−0.0866	0.7472	0.3351	0.099*
C24	0.1820 (3)	0.5212 (3)	0.3951 (4)	0.0832 (13)
H24A	0.2104	0.5535	0.4528	0.125*
H24B	0.1105	0.5319	0.3854	0.125*
H24C	0.2134	0.5395	0.3360	0.125*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0420 (2)	0.02276 (17)	0.0347 (2)	0.00045 (14)	−0.00022 (15)	0.00095 (14)
Cu2	0.03172 (18)	0.02416 (18)	0.0440 (2)	0.00098 (13)	0.00402 (15)	0.00292 (14)
N1	0.0353 (13)	0.0261 (12)	0.0450 (14)	0.0032 (10)	0.0037 (11)	−0.0022 (10)
N2	0.0388 (13)	0.0281 (12)	0.0351 (13)	0.0046 (10)	−0.0017 (10)	−0.0032 (10)
O1	0.0655 (17)	0.0387 (14)	0.121 (2)	−0.0166 (11)	0.0278 (17)	0.0148 (14)
O2	0.0327 (10)	0.0263 (10)	0.0598 (13)	−0.0008 (8)	0.0068 (9)	0.0032 (9)
O3	0.0392 (10)	0.0250 (9)	0.0367 (11)	0.0015 (8)	0.0044 (8)	−0.0006 (8)
O4	0.0942 (19)	0.0263 (11)	0.0519 (15)	0.0109 (11)	−0.0045 (14)	0.0002 (9)
O5	0.0641 (13)	0.0240 (10)	0.0337 (11)	−0.0001 (9)	−0.0068 (10)	0.0023 (8)
O6	0.0331 (10)	0.0240 (9)	0.0408 (11)	0.0002 (8)	−0.0017 (8)	0.0014 (8)
O7	0.0670 (16)	0.0447 (13)	0.0548 (15)	−0.0046 (11)	−0.0084 (12)	−0.0100 (11)
O8	0.089 (2)	0.0605 (19)	0.151 (3)	−0.0021 (16)	0.043 (2)	0.0052 (18)
C1	0.0504 (19)	0.0382 (17)	0.058 (2)	−0.0107 (15)	0.0113 (16)	0.0073 (15)
C2	0.0427 (17)	0.0323 (16)	0.0465 (18)	−0.0005 (12)	0.0065 (14)	0.0049 (13)
C3	0.0345 (15)	0.0329 (15)	0.0349 (16)	−0.0060 (12)	0.0014 (12)	0.0000 (12)
C4	0.0350 (15)	0.0362 (16)	0.0400 (16)	−0.0024 (12)	0.0070 (13)	0.0013 (12)
C5	0.0402 (18)	0.052 (2)	0.063 (2)	−0.0013 (15)	0.0153 (16)	0.0037 (16)
C6	0.049 (2)	0.052 (2)	0.073 (3)	−0.0119 (16)	0.0196 (18)	0.0070 (17)
C7	0.0341 (15)	0.0399 (17)	0.0455 (18)	0.0033 (13)	0.0060 (13)	−0.0051 (13)
C8	0.0414 (17)	0.0262 (15)	0.056 (2)	0.0068 (12)	0.0070 (14)	−0.0037 (13)
C9	0.0479 (17)	0.0268 (15)	0.0480 (18)	0.0004 (13)	0.0081 (14)	−0.0084 (13)
C10	0.052 (2)	0.0418 (18)	0.068 (2)	0.0065 (15)	−0.0090 (17)	0.0088 (16)
C11	0.058 (2)	0.0398 (19)	0.103 (3)	0.0079 (16)	0.025 (2)	−0.0133 (19)
C12	0.0356 (15)	0.0281 (14)	0.0388 (16)	0.0028 (11)	0.0044 (12)	0.0043 (12)
C13	0.0509 (18)	0.0282 (15)	0.0360 (16)	0.0023 (13)	0.0010 (13)	−0.0017 (12)
C14	0.0476 (18)	0.0290 (15)	0.0454 (18)	0.0059 (13)	0.0052 (14)	0.0027 (13)
C15	0.069 (2)	0.0336 (17)	0.0382 (18)	0.0074 (15)	−0.0038 (16)	0.0078 (13)
C16	0.061 (2)	0.0393 (17)	0.0344 (17)	0.0060 (15)	−0.0024 (15)	0.0018 (13)
C17	0.0431 (16)	0.0282 (15)	0.0349 (16)	0.0041 (12)	0.0025 (13)	0.0014 (12)
C18	0.0421 (16)	0.0369 (16)	0.0328 (16)	0.0031 (13)	0.0020 (13)	−0.0020 (12)
C19	0.0521 (18)	0.0269 (15)	0.0420 (17)	0.0067 (13)	−0.0013 (14)	−0.0084 (12)
C20	0.0442 (17)	0.0297 (15)	0.0508 (19)	−0.0040 (13)	−0.0064 (14)	−0.0055 (13)
C21	0.071 (2)	0.0448 (19)	0.058 (2)	0.0162 (17)	0.0179 (18)	−0.0056 (16)
C22	0.090 (3)	0.046 (2)	0.056 (2)	0.0023 (19)	−0.023 (2)	−0.0132 (16)
C23	0.076 (3)	0.054 (2)	0.065 (3)	0.0069 (19)	−0.008 (2)	−0.0059 (18)
C24	0.075 (3)	0.069 (3)	0.107 (4)	0.002 (2)	0.018 (3)	0.018 (2)

Geometric parameters (Å, º) top

Cu1—O5	1.9150 (18)	C8—C10	1.528 (4)
Cu1—N2	1.943 (2)	C8—C9	1.530 (4)
Cu1—O3ⁱ	1.9515 (18)	C8—C11	1.535 (4)
Cu1—O6	1.9572 (17)	C9—H9A	0.9700
Cu1—Cu2ⁱ	3.0477 (5)	C9—H9B	0.9700
Cu2—O2	1.9139 (18)	C10—H10A	0.9600
Cu2—O3	1.9414 (17)	C10—H10B	0.9600
Cu2—N1	1.944 (2)	C10—H10C	0.9600
Cu2—O6	1.9853 (17)	C11—H11A	0.9600
Cu2—O6ⁱ	2.3419 (18)	C11—H11B	0.9600
Cu2—Cu1ⁱ	3.0477 (5)	C11—H11C	0.9600
N1—C7	1.291 (3)	C12—C13	1.394 (4)
N2—C18	1.282 (3)	C13—H13	0.9300
N2—C19	1.498 (3)	C14—C15	1.377 (4)
O1—C1	1.348 (3)	C14—C13	1.382 (4)
O1—H1	0.8200	C15—H15	0.9300
O2—C3	1.314 (3)	C16—C15	1.361 (4)
O3—C9	1.424 (3)	C16—H16	0.9300
O3—Cu1ⁱ	1.9515 (18)	C17—C16	1.410 (4)
O4—C14	1.359 (3)	C17—C12	1.420 (4)
O4—H4	0.8200	C17—C18	1.438 (4)
O5—C12	1.327 (3)	C18—H18	0.9300
O6—C20	1.420 (3)	C19—C22	1.515 (4)
O6—Cu2ⁱ	2.3419 (18)	C19—C20	1.546 (4)
O7—C23	1.468 (4)	C20—H20A	0.9700
O7—H7A	0.8200	C20—H20B	0.9700
O8—C24	1.365 (4)	C21—C19	1.522 (4)
O8—H8	0.8200	C21—H21A	0.9600
C1—C2	1.378 (4)	C21—H21B	0.9600
C1—C6	1.393 (5)	C21—H21C	0.9600
C2—H2	0.9300	C22—H22A	0.9600
C3—C2	1.392 (4)	C22—H22B	0.9600
C3—C4	1.427 (4)	C22—H22C	0.9600
C4—C5	1.411 (4)	C23—H23A	0.9600
C5—H5	0.9300	C23—H23B	0.9600
C6—C5	1.356 (4)	C23—H23C	0.9600
C6—H6	0.9300	C24—H24A	0.9600
C7—C4	1.430 (4)	C24—H24B	0.9600
C7—H7	0.9300	C24—H24C	0.9600
C8—N1	1.488 (3)

O5—Cu1—N2	94.64 (8)	C7—N1—C8	122.1 (2)
O5—Cu1—O3ⁱ	93.48 (8)	C7—N1—Cu2	124.30 (19)
N2—Cu1—O3ⁱ	157.52 (9)	C8—N1—Cu2	113.59 (17)
O5—Cu1—O6	178.80 (8)	O5—C12—C13	118.6 (2)
N2—Cu1—O6	84.80 (8)	O5—C12—C17	123.0 (2)
O3ⁱ—Cu1—O6	87.42 (7)	C13—C12—C17	118.4 (2)
O5—Cu1—Cu2ⁱ	130.81 (6)	C8—C10—H10A	109.5
N2—Cu1—Cu2ⁱ	126.54 (7)	C8—C10—H10B	109.5
O3ⁱ—Cu1—Cu2ⁱ	38.36 (5)	H10A—C10—H10B	109.5
O6—Cu1—Cu2ⁱ	50.21 (5)	C8—C10—H10C	109.5
O2—Cu2—O3	177.49 (8)	H10A—C10—H10C	109.5
O2—Cu2—N1	94.62 (8)	H10B—C10—H10C	109.5
O3—Cu2—N1	85.30 (8)	O1—C1—C2	123.1 (3)
O2—Cu2—O6	86.42 (8)	O1—C1—C6	116.8 (3)
O3—Cu2—O6	94.48 (7)	C2—C1—C6	120.2 (3)
N1—Cu2—O6	161.01 (9)	N2—C19—C22	113.7 (2)
O2—Cu2—O6ⁱ	100.30 (7)	N2—C19—C21	107.2 (2)
O3—Cu2—O6ⁱ	77.56 (7)	C22—C19—C21	110.9 (3)
N1—Cu2—O6ⁱ	117.78 (8)	N2—C19—C20	103.7 (2)
O6—Cu2—O6ⁱ	80.52 (7)	C22—C19—C20	108.8 (3)
O2—Cu2—Cu1ⁱ	139.05 (6)	C21—C19—C20	112.3 (3)
O3—Cu2—Cu1ⁱ	38.59 (5)	C5—C6—C1	118.9 (3)
N1—Cu2—Cu1ⁱ	97.91 (7)	C5—C6—H6	120.5
O6—Cu2—Cu1ⁱ	93.57 (5)	C1—C6—H6	120.5
O6ⁱ—Cu2—Cu1ⁱ	39.95 (4)	C16—C15—C14	119.5 (3)
C9—O3—Cu2	108.47 (16)	C16—C15—H15	120.3
C9—O3—Cu1ⁱ	120.79 (17)	C14—C15—H15	120.3
Cu2—O3—Cu1ⁱ	103.05 (8)	C14—C13—C12	121.1 (3)
C14—O4—H4	109.5	C14—C13—H13	119.4
C3—O2—Cu2	126.69 (17)	C12—C13—H13	119.4
C20—O6—Cu1	109.69 (15)	O6—C20—C19	111.8 (2)
C20—O6—Cu2	118.65 (16)	O6—C20—H20A	109.3
Cu1—O6—Cu2	107.11 (8)	C19—C20—H20A	109.3
C20—O6—Cu2ⁱ	127.42 (16)	O6—C20—H20B	109.3
Cu1—O6—Cu2ⁱ	89.83 (7)	C19—C20—H20B	109.3
Cu2—O6—Cu2ⁱ	99.48 (7)	H20A—C20—H20B	107.9
C1—O1—H1	109.5	N1—C7—C4	125.9 (3)
C12—O5—Cu1	125.90 (17)	N1—C7—H7	117.0
C18—N2—C19	121.1 (2)	C4—C7—H7	117.0
C18—N2—Cu1	124.65 (19)	C5—C4—C3	118.1 (3)
C19—N2—Cu1	114.20 (17)	C5—C4—C7	117.4 (3)
C16—C17—C12	118.4 (2)	C3—C4—C7	124.5 (2)
C16—C17—C18	117.0 (3)	C1—C2—C3	122.2 (3)
C12—C17—C18	124.6 (2)	C1—C2—H2	118.9
O2—C3—C2	119.0 (2)	C3—C2—H2	118.9
O2—C3—C4	123.1 (2)	C6—C5—C4	122.8 (3)
C2—C3—C4	117.9 (2)	C6—C5—H5	118.6
O4—C14—C15	116.3 (3)	C4—C5—H5	118.6
O4—C14—C13	122.9 (3)	C19—C22—H22A	109.5
C15—C14—C13	120.7 (3)	C19—C22—H22B	109.5
N1—C8—C10	107.8 (2)	H22A—C22—H22B	109.5
N1—C8—C9	104.0 (2)	C19—C22—H22C	109.5
C10—C8—C9	111.7 (3)	H22A—C22—H22C	109.5
N1—C8—C11	113.6 (3)	H22B—C22—H22C	109.5
C10—C8—C11	110.3 (3)	C8—C11—H11A	109.5
C9—C8—C11	109.3 (3)	C8—C11—H11B	109.5
C19—C21—H21A	109.5	H11A—C11—H11B	109.5
C19—C21—H21B	109.5	C8—C11—H11C	109.5
H21A—C21—H21B	109.5	H11A—C11—H11C	109.5
C19—C21—H21C	109.5	H11B—C11—H11C	109.5
H21A—C21—H21C	109.5	C23—O7—H7A	109.5
H21B—C21—H21C	109.5	C24—O8—H8	109.5
N2—C18—C17	125.8 (3)	O7—C23—H23A	109.5
N2—C18—H18	117.1	O7—C23—H23B	109.5
C17—C18—H18	117.1	H23A—C23—H23B	109.5
O3—C9—C8	112.1 (2)	O7—C23—H23C	109.5
O3—C9—H9A	109.2	H23A—C23—H23C	109.5
C8—C9—H9A	109.2	H23B—C23—H23C	109.5
O3—C9—H9B	109.2	O8—C24—H24A	109.5
C8—C9—H9B	109.2	O8—C24—H24B	109.5
H9A—C9—H9B	107.9	H24A—C24—H24B	109.5
C15—C16—C17	121.9 (3)	O8—C24—H24C	109.5
C15—C16—H16	119.1	H24A—C24—H24C	109.5
C17—C16—H16	119.1	H24B—C24—H24C	109.5

O2—Cu2—O3—C9	−108.5 (17)	C11—C8—C9—O3	−164.9 (3)
N1—Cu2—O3—C9	−20.22 (18)	C12—C17—C16—C15	−0.7 (5)
O6—Cu2—O3—C9	140.72 (17)	C18—C17—C16—C15	178.8 (3)
O6ⁱ—Cu2—O3—C9	−140.02 (18)	C10—C8—N1—C7	88.9 (3)
Cu1ⁱ—Cu2—O3—C9	−129.2 (2)	C9—C8—N1—C7	−152.4 (3)
O2—Cu2—O3—Cu1ⁱ	20.7 (18)	C11—C8—N1—C7	−33.6 (4)
N1—Cu2—O3—Cu1ⁱ	108.93 (10)	C10—C8—N1—Cu2	−93.2 (2)
O6—Cu2—O3—Cu1ⁱ	−90.12 (9)	C9—C8—N1—Cu2	25.5 (3)
O6ⁱ—Cu2—O3—Cu1ⁱ	−10.87 (7)	C11—C8—N1—Cu2	144.3 (2)
O3—Cu2—O2—C3	97.8 (17)	O2—Cu2—N1—C7	−9.0 (2)
N1—Cu2—O2—C3	9.8 (2)	O3—Cu2—N1—C7	173.5 (2)
O6—Cu2—O2—C3	−151.2 (2)	O6—Cu2—N1—C7	83.4 (3)
O6ⁱ—Cu2—O2—C3	129.1 (2)	O6ⁱ—Cu2—N1—C7	−113.2 (2)
Cu1ⁱ—Cu2—O2—C3	117.5 (2)	Cu1ⁱ—Cu2—N1—C7	−150.0 (2)
O5—Cu1—O6—C20	−81 (4)	O2—Cu2—N1—C8	173.09 (19)
N2—Cu1—O6—C20	−18.51 (17)	O3—Cu2—N1—C8	−4.39 (19)
O3ⁱ—Cu1—O6—C20	140.38 (17)	O6—Cu2—N1—C8	−94.5 (3)
Cu2ⁱ—Cu1—O6—C20	130.12 (18)	O6ⁱ—Cu2—N1—C8	68.9 (2)
O5—Cu1—O6—Cu2	49 (4)	Cu1ⁱ—Cu2—N1—C8	32.17 (19)
N2—Cu1—O6—Cu2	111.50 (10)	Cu1—O5—C12—C13	167.74 (19)
O3ⁱ—Cu1—O6—Cu2	−89.61 (9)	Cu1—O5—C12—C17	−12.3 (4)
Cu2ⁱ—Cu1—O6—Cu2	−99.87 (9)	C16—C17—C12—O5	−179.0 (3)
O5—Cu1—O6—Cu2ⁱ	149 (4)	C18—C17—C12—O5	1.6 (4)
N2—Cu1—O6—Cu2ⁱ	−148.62 (8)	C16—C17—C12—C13	1.0 (4)
O3ⁱ—Cu1—O6—Cu2ⁱ	10.26 (7)	C18—C17—C12—C13	−178.4 (3)
O2—Cu2—O6—C20	116.44 (18)	C18—N2—C19—C22	−34.7 (4)
O3—Cu2—O6—C20	−65.91 (18)	Cu1—N2—C19—C22	144.6 (2)
N1—Cu2—O6—C20	22.7 (3)	C18—N2—C19—C21	88.3 (3)
O6ⁱ—Cu2—O6—C20	−142.5 (2)	Cu1—N2—C19—C21	−92.4 (2)
Cu1ⁱ—Cu2—O6—C20	−104.59 (17)	C18—N2—C19—C20	−152.7 (3)
O2—Cu2—O6—Cu1	−8.30 (9)	Cu1—N2—C19—C20	26.6 (3)
O3—Cu2—O6—Cu1	169.35 (9)	O1—C1—C6—C5	178.9 (3)
N1—Cu2—O6—Cu1	−102.1 (2)	C2—C1—C6—C5	−0.9 (5)
O6ⁱ—Cu2—O6—Cu1	92.77 (9)	C17—C16—C15—C14	−0.1 (5)
Cu1ⁱ—Cu2—O6—Cu1	130.67 (7)	O4—C14—C15—C16	179.6 (3)
O2—Cu2—O6—Cu2ⁱ	−101.07 (8)	C13—C14—C15—C16	0.5 (5)
O3—Cu2—O6—Cu2ⁱ	76.58 (7)	O4—C14—C13—C12	−179.2 (3)
N1—Cu2—O6—Cu2ⁱ	165.1 (2)	C15—C14—C13—C12	−0.2 (5)
O6ⁱ—Cu2—O6—Cu2ⁱ	0.0	O5—C12—C13—C14	179.4 (3)
Cu1ⁱ—Cu2—O6—Cu2ⁱ	37.90 (5)	C17—C12—C13—C14	−0.5 (4)
N2—Cu1—O5—C12	13.6 (2)	Cu1—O6—C20—C19	39.3 (3)
O3ⁱ—Cu1—O5—C12	−145.4 (2)	Cu2—O6—C20—C19	−84.1 (2)
O6—Cu1—O5—C12	76 (4)	Cu2ⁱ—O6—C20—C19	145.01 (18)
Cu2ⁱ—Cu1—O5—C12	−135.60 (19)	N2—C19—C20—O6	−42.4 (3)
O5—Cu1—N2—C18	−8.0 (2)	C22—C19—C20—O6	−163.7 (2)
O3ⁱ—Cu1—N2—C18	102.8 (3)	C21—C19—C20—O6	73.1 (3)
O6—Cu1—N2—C18	173.0 (2)	C8—N1—C7—C4	−176.7 (3)
Cu2ⁱ—Cu1—N2—C18	143.2 (2)	Cu2—N1—C7—C4	5.7 (4)
O5—Cu1—N2—C19	172.70 (19)	O2—C3—C4—C5	−179.2 (3)
O3ⁱ—Cu1—N2—C19	−76.5 (3)	C2—C3—C4—C5	−0.3 (4)
O6—Cu1—N2—C19	−6.23 (18)	O2—C3—C4—C7	−0.1 (4)
Cu2ⁱ—Cu1—N2—C19	−36.1 (2)	C2—C3—C4—C7	178.8 (3)
Cu2—O2—C3—C2	174.26 (19)	N1—C7—C4—C5	179.7 (3)
Cu2—O2—C3—C4	−6.9 (4)	N1—C7—C4—C3	0.6 (5)
C19—N2—C18—C17	−179.7 (3)	O1—C1—C2—C3	−177.9 (3)
Cu1—N2—C18—C17	1.1 (4)	C6—C1—C2—C3	1.9 (5)
C16—C17—C18—N2	−175.0 (3)	O2—C3—C2—C1	177.7 (3)
C12—C17—C18—N2	4.4 (5)	C4—C3—C2—C1	−1.3 (4)
Cu2—O3—C9—C8	41.2 (3)	C1—C6—C5—C4	−0.7 (5)
Cu1ⁱ—O3—C9—C8	−77.2 (3)	C3—C4—C5—C6	1.2 (5)
N1—C8—C9—O3	−43.3 (3)	C7—C4—C5—C6	−177.9 (3)
C10—C8—C9—O3	72.7 (3)

Symmetry code: (i) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu₄(C₁₁H₁₃NO₃)₄]·4CH₄O
M_r	1211.27
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	13.260 (1), 15.3170 (11), 13.266 (1)
β (°)	94.936 (1)
V (Å³)	2684.4 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.63
Crystal size (mm)	0.27 × 0.21 × 0.19

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.667, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	15163, 5500, 4143
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.089, 1.01
No. of reflections	5500
No. of parameters	335
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.31

Computer programs: SMART, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.

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