[mu]₂-Acetato-[kappa]²O:O'-tris­([mu]₂-ferrocene­carboxyl­ato-[kappa]²O:O')bis­[(N,N-dimethyl­formamide-[kappa]O)copper(II)]

The title compound, [Cu₂Fe₃(C₅H₅)₃(C₂H₃O₂)(C₆H₄O₂)₃(C₃H₇NO)₂], belongs to the classic dimeric paddle-wheel structure type. It is an unusual example in that it contains two different carboxyl­ate groups, viz. ferrocenecarboxyl­ate and acetate. With three ferrocenecarboxyl­ate groups and only one acetate group bridging the two Cu centres, a noncentrosymmetric mol­ecular arrangement results.

S1. Comment

The dimeric copper(II) carboxylates and their adducts, [Cu₂(O₂CR)₂L₂], have played a major role in copper(II) carboxylate chemistry (Agterberg et al., 1997; Moulton et al., 2003). The related complexes have received much attention because of their potential use as anti-inflammatory drugs (Demertzi et al., 2004; Weder et al., 2004). In addition, such complexes are good models for the investigation of the exchange interaction between paramagnetic centres in discrete molecules (Costa et al., 1998). The polarizability of the R group on the carboxylate has a vital relationship with the magnitude of the magnetic interaction (Porter & Doedens, 1984; Schlam et al., 2000). While the ferrocenyl unit itself always affects electron interactions in compounds, in this case it may help to probe the influence of the substituent R on the magnetic behaviour. Moreover, compounds containing ferrocenyl units always show some unusual properties and have potential applications in the field of materials science, such as molecular sensors (Beer, 1992), molecular magnets (Miller & Epstein, 1994) and nonlinear optical materials (Long, 1995). Dinuclear copper(II) complexes with two different kinds of carboxylate groups still remain rare, especially ones with bulky carboxylate groups like ferrocenecarboxylate (Churchill et al., 1985), which may be due to the existence of evident steric hindrance. We report here the synthesis and crystal structure of the title dimeric copper(II) carboxylate, (I), with ferrocenecarboxylate and acetate groups.

Only one noncentrosymmetric dimeric copper(II) carboxylate, Cu₂{µ-[(CO)₉Co₃(µ₃-CCO₂)]}₃[µ-(CH₃CO₂)][OC₄H₈]₂ (Banares et al., 1985), has been reported to date, according to the Cambridge Structural Database (CONQUEST, Version 1.3, updated May 2007; Bruno et al., 2002). Thus, complex (I) represents the second example.

In complex (I), the asymmetric unit contains two crystallographically independent Cu^II ions, three ferrocenecarboxylate groups, one acetate group and two dimethylformamide (DMF) molecules. The two Cu^II centres are separated by 2.618 (28) Å, and each Cu^II centre has a square-pyramidal coordination environment, with four O atoms from three ferrocenecarboxylate groups and one acetate group in the basal plane, and an O atom from a DMF molecule in the apical position. As expected, the apical Cu—O_DMF distances are notably longer than the basal ones between Cu and the O atoms from the carboxylate groups.

The novel character of (I) lies in its noncentrosymmetric structure type, which is still very rare in this classical kind of complex. In (I), there are three ferrocenecarboxylate groups and only one acetate group. The ferrocene substituents on the carboxylate ligands that are trans to each other are oriented to the same side of the Cu···Cu line, and the less bulky methyl substituent of the acetate ligand is located in the space between the two ferrocene units (Fig. 1). The arrangement of the ferrocenecarboxylate groups is therefore different from that in the centrosymmetric compound tetrakis(ferrocenecarboxylato)bis(tetrahydrofuran)copper(II) reported by Churchill et al. (1985), in which the four ferrocene units are arranged in a clockwise mode.

There is also a noticeable difference between the conformations of the coordination of the Cu^II and carboxylate O atoms of (I) and the Churchill complex. In the previously reported complex, the two Cu^II centres and the coordinated O atoms belonging to the same carboxylate group are nearly located in the same plane, with O—Cu—Cu—O torsion angles between them of -1.89 (30) and 0.83 (30)° for the two independent carboxylate groups. By contrast, in (I) the four corresponding torsion angles are distinctly larger: 15.01 (21), 14.43 (21), 14.04 (21) and 15.01 (19)°. The obvious variance may due to the different steric hindrance in the complexes. Perhaps as a result of the smaller steric hindrance, the O—Cu—Cu—O torsion angles of the other noncentrosymmetric dimeric copper(II) carboxylate (Banares et al., 1985) are also distinctly smaller than complex (I), with values ranging from -3.97 (29) to 4.57 (29)°.

Related literature

For related literature, see: Agterberg et al. (1997); Banares et al. (1985); Beer (1992); Bruno et al. (2002); Churchill et al. (1985); Costa et al. (1998); Demertzi et al. (2004); Long (1995); Miller & Epstein (1994); Moulton et al. (2003); Porter & Doedens (1984); Schlam et al. (2000); Sheldrick (1997); Weder et al. (2004).

S2. Experimental

For the preparation of (I), ferrocenecarboxylic acid (0.046 g, 0.02 mmol) and NaHCO₃ (0.017 g, 0.02 mmol) were dissolved in a mixture of CH₃OH (10 ml) and dimethylformamide (DMF; 2 ml). The solution was stirred for 1 h at room temperature. Cu(OAc)₂·H₂O (0.020 g, 0.01 mmol) was then added and the resulting solution was stirred for 3 h. All the volatiles were removed under vacuum and the residue was dissolved in a mixture of CH₂Cl₂ and DMF (v/v = 5:2). The resulting solution was allowed to stand at room temperature for about 7 d, after which rhombic crystals of (I) were collected for X-ray analysis.

S3. Refinement

H atoms bonded to C atoms were refined in idealized positions using the riding-model approximation, with C—H = 0.93 (Cp) and 0.96 Å (methyl), and with U_iso(H) = 1.2U_eq(C). Atoms C29, C30, C31, C32 and C33 of one Cp group were refined with the same anisotropic displacement parameters using the EADP instruction in SHELXL97 (Sheldrick, 1997). The same operation was also carried out on the methyl C atoms of the DMF molecules (C37, C38, C40 and C41).

Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: RAPID-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1993); software used to prepare material for publication: SHELXL97/2 (Sheldrick, 1997).

Figures

Fig. 1. The structure of (I), showing the atom-labelling scheme and 30% probability displacement ellipsoids. H atoms have been omitted for clarity.

µ₂-Acetato-κ²O:O'-tris(µ₂-ferrocenecarboxylato-κ²O:O')bis[(N,N-dimethylformamide-κO)copper(II)]

Crystal data

[Cu2Fe3(C5H5)3(C2H3O2)(C6H4O2)3(C3H7NO)2]	Z = 2
Mr = 1019.41	F(000) = 1040
Triclinic, P1	Dx = 1.666 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.948 (2) Å	Cell parameters from 14862 reflections
b = 13.548 (3) Å	θ = 3.1–27.5°
c = 15.828 (3) Å	µ = 2.14 mm^−1
α = 108.96 (3)°	T = 298 K
β = 94.57 (3)°	Rhombic, green
γ = 110.33 (3)°	0.30 × 0.26 × 0.26 mm
V = 2032.3 (10) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	9106 independent reflections
Radiation source: rotating anode	6613 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
oscillation scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −14→13
Tmin = 0.567, Tmax = 0.607	k = −17→17
19821 measured reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.184	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0962P)^2 + 3.4415P] where P = (Fo^2 + 2Fc^2)/3
9106 reflections	(Δ/σ)max < 0.001
486 parameters	Δρmax = 0.76 e Å^−3
0 restraints	Δρmin = −1.39 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.61220 (6)	0.29677 (5)	0.14850 (4)	0.02853 (16)
Cu2	0.87075 (6)	0.35953 (5)	0.16691 (4)	0.02790 (16)
Fe2	0.73811 (9)	0.15331 (7)	−0.19309 (5)	0.0366 (2)
Fe1	0.76655 (8)	0.22841 (7)	0.46343 (5)	0.0373 (2)
Fe3	0.74862 (10)	0.73109 (8)	0.36609 (7)	0.0506 (2)
O3	0.8335 (4)	0.3589 (3)	0.0433 (2)	0.0351 (8)
O7	0.8240 (4)	0.1930 (3)	0.1141 (3)	0.0381 (8)
O6	0.6555 (4)	0.4598 (3)	0.1752 (3)	0.0359 (8)
O4	0.6113 (4)	0.2705 (3)	0.0184 (2)	0.0380 (8)
O5	0.8760 (4)	0.5149 (3)	0.2192 (3)	0.0388 (9)
O2	0.6557 (4)	0.3314 (4)	0.2820 (2)	0.0420 (9)
O1	0.8682 (4)	0.3497 (4)	0.2867 (2)	0.0402 (9)
O8	0.6111 (4)	0.1451 (3)	0.1259 (3)	0.0398 (9)
O10	0.3985 (4)	0.2433 (4)	0.1349 (3)	0.0463 (10)
O9	1.0815 (4)	0.4089 (4)	0.1694 (3)	0.0442 (9)
N1	1.2437 (6)	0.4268 (6)	0.0902 (5)	0.0675 (18)
N2	0.2132 (7)	0.2176 (6)	0.1945 (6)	0.0697 (19)
C1	0.7695 (6)	0.3445 (4)	0.3222 (3)	0.0343 (11)
C2	0.7867 (6)	0.3563 (5)	0.4188 (4)	0.0395 (12)
C3	0.9086 (7)	0.3769 (5)	0.4743 (4)	0.0460 (14)
H3	0.9886	0.3847	0.4555	0.055*
C4	0.8882 (8)	0.3834 (5)	0.5624 (4)	0.0548 (17)
H4	0.9523	0.3977	0.6119	0.066*
C5	0.7540 (9)	0.3645 (6)	0.5617 (4)	0.0573 (18)
H5	0.7132	0.3626	0.6109	0.069*
C6	0.6905 (8)	0.3487 (6)	0.4738 (4)	0.0521 (16)
H6	0.6015	0.3357	0.4555	0.063*
C7	0.6141 (8)	0.0739 (7)	0.4289 (6)	0.068 (2)
H7	0.5252	0.0607	0.4304	0.082*
C8	0.7128 (10)	0.0913 (6)	0.5000 (5)	0.069 (2)
H8	0.7004	0.0921	0.5577	0.083*
C9	0.8316 (9)	0.1072 (6)	0.4718 (6)	0.069 (2)
H9	0.9123	0.1196	0.5060	0.083*
C10	0.8074 (9)	0.1012 (6)	0.3804 (6)	0.068 (2)
H10	0.8704	0.1100	0.3443	0.082*
C11	0.6745 (8)	0.0800 (6)	0.3539 (5)	0.0597 (18)
H11	0.6323	0.0712	0.2970	0.072*
C12	0.7189 (5)	0.3073 (4)	−0.0066 (3)	0.0301 (10)
C13	0.7077 (5)	0.2853 (4)	−0.1057 (3)	0.0314 (10)
C14	0.8150 (6)	0.3260 (5)	−0.1483 (4)	0.0387 (12)
H14	0.9026	0.3749	−0.1183	0.046*
C15	0.7639 (7)	0.2787 (5)	−0.2438 (4)	0.0483 (15)
H15	0.8120	0.2900	−0.2881	0.058*
C16	0.6262 (7)	0.2108 (5)	−0.2599 (4)	0.0459 (14)
H16	0.5685	0.1701	−0.3170	0.055*
C17	0.5908 (6)	0.2146 (5)	−0.1762 (4)	0.0403 (12)
H17	0.5061	0.1776	−0.1681	0.048*
C18	0.6875 (9)	0.0107 (6)	−0.1635 (7)	0.068 (2)
H18	0.6154	−0.0170	−0.1383	0.082*
C19	0.6858 (10)	−0.0179 (7)	−0.2583 (7)	0.077 (3)
H19	0.6132	−0.0672	−0.3065	0.092*
C20	0.8156 (10)	0.0431 (7)	−0.2648 (5)	0.070 (2)
H20	0.8440	0.0413	−0.3189	0.084*
C21	0.8948 (7)	0.1067 (6)	−0.1768 (5)	0.0547 (16)
H21	0.9849	0.1540	−0.1621	0.066*
C22	0.8153 (8)	0.0872 (6)	−0.1148 (5)	0.0521 (16)
H22	0.8431	0.1198	−0.0514	0.062*
C23	0.7722 (5)	0.5336 (4)	0.2103 (3)	0.0316 (10)
C24	0.7895 (6)	0.6546 (5)	0.2447 (4)	0.0390 (12)
C25	0.9056 (7)	0.7480 (6)	0.3031 (5)	0.0557 (17)
H25	0.9856	0.7444	0.3231	0.067*
C26	0.8796 (7)	0.8480 (6)	0.3260 (6)	0.064 (2)
H26	0.9389	0.9211	0.3636	0.076*
C27	0.7461 (8)	0.8160 (6)	0.2810 (5)	0.0613 (18)
H27	0.7026	0.8646	0.2835	0.074*
C28	0.6914 (7)	0.6974 (6)	0.2318 (5)	0.0517 (15)
H28	0.6050	0.6543	0.1967	0.062*
C29	0.7967 (13)	0.7074 (11)	0.4817 (7)	0.1035 (17)
H29	0.8765	0.7039	0.5022	0.124*
C30	0.7749 (13)	0.8055 (11)	0.5033 (7)	0.1035 (17)
H30	0.8348	0.8789	0.5398	0.124*
C31	0.6402 (13)	0.7706 (11)	0.4575 (7)	0.1035 (17)
H31	0.5955	0.8181	0.4589	0.124*
C32	0.5877 (13)	0.6540 (11)	0.4106 (7)	0.1035 (17)
H32	0.5019	0.6094	0.3749	0.124*
C33	0.6860 (13)	0.6156 (12)	0.4263 (7)	0.1035 (17)
H33	0.6779	0.5406	0.4032	0.124*
C35	0.6934 (8)	−0.0006 (5)	0.0838 (5)	0.0558 (17)
H35A	0.7419	−0.0080	0.1331	0.084*
H35B	0.7273	−0.0232	0.0298	0.084*
H35C	0.6005	−0.0483	0.0720	0.084*
C36	1.1219 (7)	0.3952 (6)	0.0992 (6)	0.0590 (18)
H36	1.0569	0.3571	0.0452	0.071*
C37	1.3472 (11)	0.4908 (11)	0.1742 (10)	0.112 (2)
H37A	1.3168	0.4657	0.2218	0.168*
H37B	1.3659	0.5703	0.1923	0.168*
H37C	1.4268	0.4784	0.1638	0.168*
C38	1.2905 (11)	0.4134 (11)	0.0096 (9)	0.112 (2)
H38A	1.2170	0.3662	−0.0420	0.168*
H38B	1.3532	0.3784	0.0093	0.168*
H38C	1.3336	0.4865	0.0060	0.168*
C34	0.7101 (6)	0.1220 (5)	0.1097 (4)	0.0373 (12)
C40	0.1239 (11)	0.1510 (11)	0.1034 (10)	0.112 (2)
H40A	0.1700	0.1690	0.0579	0.168*
H40B	0.0466	0.1691	0.1017	0.168*
H40C	0.0967	0.0714	0.0913	0.168*
C41	0.1499 (11)	0.2274 (10)	0.2676 (9)	0.112 (2)
H41A	0.2151	0.2753	0.3237	0.168*
H41B	0.1043	0.1535	0.2691	0.168*
H41C	0.0867	0.2601	0.2606	0.168*
C39	0.3427 (8)	0.2540 (7)	0.1983 (6)	0.062 (2)
H39	0.3977	0.2924	0.2565	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0279 (3)	0.0294 (3)	0.0301 (3)	0.0118 (2)	0.0105 (2)	0.0119 (2)
Cu2	0.0276 (3)	0.0293 (3)	0.0285 (3)	0.0122 (3)	0.0081 (2)	0.0116 (2)
Fe2	0.0524 (5)	0.0332 (4)	0.0312 (4)	0.0214 (4)	0.0126 (3)	0.0154 (3)
Fe1	0.0448 (5)	0.0330 (4)	0.0328 (4)	0.0120 (4)	0.0073 (3)	0.0149 (3)
Fe3	0.0512 (5)	0.0473 (5)	0.0511 (5)	0.0241 (4)	0.0134 (4)	0.0103 (4)
O3	0.035 (2)	0.040 (2)	0.0288 (17)	0.0120 (17)	0.0066 (16)	0.0147 (16)
O7	0.041 (2)	0.0286 (18)	0.047 (2)	0.0154 (17)	0.0158 (18)	0.0137 (16)
O6	0.036 (2)	0.0304 (18)	0.0402 (19)	0.0146 (17)	0.0078 (17)	0.0113 (16)
O4	0.040 (2)	0.043 (2)	0.0296 (17)	0.0147 (18)	0.0102 (16)	0.0132 (16)
O5	0.043 (2)	0.0306 (19)	0.043 (2)	0.0169 (17)	0.0132 (18)	0.0111 (16)
O2	0.049 (2)	0.050 (2)	0.0316 (18)	0.021 (2)	0.0152 (18)	0.0183 (17)
O1	0.045 (2)	0.048 (2)	0.0312 (18)	0.0200 (19)	0.0103 (17)	0.0179 (17)
O8	0.039 (2)	0.0298 (19)	0.053 (2)	0.0129 (17)	0.0192 (19)	0.0176 (17)
O10	0.032 (2)	0.046 (2)	0.066 (3)	0.0177 (18)	0.020 (2)	0.023 (2)
O9	0.033 (2)	0.051 (2)	0.052 (2)	0.0152 (19)	0.0143 (19)	0.023 (2)
N1	0.044 (3)	0.069 (4)	0.108 (5)	0.027 (3)	0.039 (4)	0.047 (4)
N2	0.058 (4)	0.091 (5)	0.111 (6)	0.050 (4)	0.050 (4)	0.073 (5)
C1	0.045 (3)	0.031 (3)	0.030 (2)	0.016 (2)	0.007 (2)	0.014 (2)
C2	0.053 (3)	0.039 (3)	0.029 (2)	0.018 (3)	0.009 (2)	0.016 (2)
C3	0.053 (4)	0.029 (3)	0.046 (3)	0.003 (3)	0.000 (3)	0.019 (2)
C4	0.075 (5)	0.036 (3)	0.039 (3)	0.012 (3)	−0.006 (3)	0.011 (3)
C5	0.099 (6)	0.057 (4)	0.032 (3)	0.043 (4)	0.020 (3)	0.022 (3)
C6	0.073 (5)	0.066 (4)	0.041 (3)	0.045 (4)	0.024 (3)	0.028 (3)
C7	0.054 (4)	0.054 (4)	0.080 (5)	0.003 (4)	0.010 (4)	0.024 (4)
C8	0.102 (7)	0.045 (4)	0.059 (4)	0.018 (4)	0.015 (4)	0.029 (3)
C9	0.086 (6)	0.043 (4)	0.078 (5)	0.032 (4)	−0.001 (5)	0.019 (4)
C10	0.077 (5)	0.044 (4)	0.078 (5)	0.022 (4)	0.038 (4)	0.013 (4)
C11	0.071 (5)	0.043 (4)	0.042 (3)	0.009 (3)	−0.001 (3)	0.006 (3)
C12	0.040 (3)	0.024 (2)	0.031 (2)	0.017 (2)	0.010 (2)	0.0118 (19)
C13	0.041 (3)	0.033 (3)	0.028 (2)	0.018 (2)	0.009 (2)	0.016 (2)
C14	0.051 (3)	0.033 (3)	0.041 (3)	0.017 (3)	0.017 (3)	0.022 (2)
C15	0.080 (5)	0.048 (3)	0.040 (3)	0.036 (4)	0.029 (3)	0.030 (3)
C16	0.063 (4)	0.045 (3)	0.032 (3)	0.022 (3)	0.004 (3)	0.017 (2)
C17	0.044 (3)	0.040 (3)	0.041 (3)	0.018 (3)	0.008 (3)	0.019 (2)
C18	0.079 (5)	0.048 (4)	0.110 (7)	0.035 (4)	0.041 (5)	0.055 (4)
C19	0.090 (6)	0.042 (4)	0.088 (6)	0.036 (4)	−0.012 (5)	0.009 (4)
C20	0.123 (8)	0.074 (5)	0.049 (4)	0.071 (6)	0.038 (5)	0.026 (4)
C21	0.056 (4)	0.053 (4)	0.068 (4)	0.032 (3)	0.017 (3)	0.028 (3)
C22	0.078 (5)	0.056 (4)	0.051 (3)	0.045 (4)	0.024 (3)	0.034 (3)
C23	0.040 (3)	0.031 (3)	0.028 (2)	0.017 (2)	0.013 (2)	0.012 (2)
C24	0.046 (3)	0.027 (3)	0.044 (3)	0.016 (2)	0.015 (3)	0.010 (2)
C25	0.046 (4)	0.044 (4)	0.075 (5)	0.020 (3)	0.020 (3)	0.016 (3)
C26	0.055 (4)	0.036 (3)	0.092 (5)	0.013 (3)	0.021 (4)	0.017 (4)
C27	0.072 (5)	0.045 (4)	0.077 (5)	0.031 (4)	0.019 (4)	0.025 (4)
C28	0.056 (4)	0.048 (4)	0.053 (4)	0.026 (3)	0.009 (3)	0.017 (3)
C29	0.129 (4)	0.127 (4)	0.081 (3)	0.069 (4)	0.058 (3)	0.044 (3)
C30	0.129 (4)	0.127 (4)	0.081 (3)	0.069 (4)	0.058 (3)	0.044 (3)
C31	0.129 (4)	0.127 (4)	0.081 (3)	0.069 (4)	0.058 (3)	0.044 (3)
C32	0.129 (4)	0.127 (4)	0.081 (3)	0.069 (4)	0.058 (3)	0.044 (3)
C33	0.129 (4)	0.127 (4)	0.081 (3)	0.069 (4)	0.058 (3)	0.044 (3)
C35	0.072 (5)	0.034 (3)	0.072 (4)	0.026 (3)	0.029 (4)	0.024 (3)
C36	0.046 (4)	0.061 (4)	0.081 (5)	0.025 (3)	0.024 (4)	0.034 (4)
C37	0.088 (4)	0.122 (5)	0.184 (6)	0.067 (4)	0.074 (4)	0.091 (5)
C38	0.088 (4)	0.122 (5)	0.184 (6)	0.067 (4)	0.074 (4)	0.091 (5)
C34	0.052 (3)	0.028 (3)	0.032 (2)	0.014 (2)	0.014 (2)	0.014 (2)
C40	0.088 (4)	0.122 (5)	0.184 (6)	0.067 (4)	0.074 (4)	0.091 (5)
C41	0.088 (4)	0.122 (5)	0.184 (6)	0.067 (4)	0.074 (4)	0.091 (5)
C39	0.067 (4)	0.077 (5)	0.085 (5)	0.047 (4)	0.048 (4)	0.057 (4)

Geometric parameters (Å, º)

Cu1—O8	1.964 (4)	C7—C11	1.416 (11)
Cu1—O4	1.970 (4)	C7—H7	0.9300
Cu1—O6	1.978 (4)	C8—C9	1.377 (12)
Cu1—O2	1.987 (4)	C8—H8	0.9300
Cu1—O10	2.164 (4)	C9—C10	1.420 (12)
Cu1—Cu2	2.6183 (11)	C9—H9	0.9300
Cu2—O1	1.945 (4)	C10—C11	1.381 (11)
Cu2—O3	1.963 (4)	C10—H10	0.9300
Cu2—O5	1.973 (4)	C11—H11	0.9300
Cu2—O7	1.988 (4)	C12—C13	1.485 (7)
Cu2—O9	2.161 (4)	C13—C17	1.424 (8)
Fe2—C13	2.025 (5)	C13—C14	1.434 (7)
Fe2—C22	2.034 (6)	C14—C15	1.413 (8)
Fe2—C14	2.036 (6)	C14—H14	0.9300
Fe2—C18	2.036 (7)	C15—C16	1.416 (10)
Fe2—C20	2.042 (7)	C15—H15	0.9300
Fe2—C21	2.048 (7)	C16—C17	1.399 (8)
Fe2—C15	2.049 (6)	C16—H16	0.9300
Fe2—C19	2.049 (7)	C17—H17	0.9300
Fe2—C16	2.053 (6)	C18—C22	1.388 (11)
Fe2—C17	2.054 (6)	C18—C19	1.420 (12)
Fe1—C3	2.013 (6)	C18—H18	0.9300
Fe1—C10	2.014 (7)	C19—C20	1.405 (13)
Fe1—C2	2.025 (6)	C19—H19	0.9300
Fe1—C11	2.028 (7)	C20—C21	1.394 (11)
Fe1—C8	2.031 (7)	C20—H20	0.9300
Fe1—C7	2.037 (8)	C21—C22	1.391 (9)
Fe1—C9	2.039 (7)	C21—H21	0.9300
Fe1—C6	2.042 (7)	C22—H22	0.9300
Fe1—C5	2.046 (6)	C23—C24	1.486 (7)
Fe1—C4	2.055 (6)	C24—C28	1.416 (9)
Fe3—C31	2.000 (9)	C24—C25	1.416 (9)
Fe3—C29	2.018 (12)	C25—C26	1.419 (9)
Fe3—C28	2.019 (7)	C25—H25	0.9300
Fe3—C32	2.022 (11)	C26—C27	1.423 (11)
Fe3—C30	2.023 (10)	C26—H26	0.9300
Fe3—C24	2.033 (5)	C27—C28	1.411 (9)
Fe3—C25	2.037 (6)	C27—H27	0.9300
Fe3—C33	2.038 (12)	C28—H28	0.9300
Fe3—C27	2.040 (8)	C29—C33	1.364 (16)
Fe3—C26	2.046 (8)	C29—C30	1.371 (16)
O3—C12	1.249 (6)	C29—H29	0.9300
O7—C34	1.264 (7)	C30—C31	1.431 (16)
O6—C23	1.257 (6)	C30—H30	0.9300
O4—C12	1.261 (6)	C31—C32	1.384 (16)
O5—C23	1.255 (6)	C31—H31	0.9300
O2—C1	1.279 (7)	C32—C33	1.386 (15)
O1—C1	1.249 (6)	C32—H32	0.9300
O8—C34	1.250 (7)	C33—H33	0.9300
O10—C39	1.211 (7)	C35—C34	1.515 (8)
O9—C36	1.210 (8)	C35—H35A	0.9600
N1—C36	1.287 (8)	C35—H35B	0.9600
N1—C38	1.393 (12)	C35—H35C	0.9600
N1—C37	1.460 (15)	C36—H36	0.9300
N2—C39	1.319 (9)	C37—H37A	0.9600
N2—C41	1.389 (12)	C37—H37B	0.9600
N2—C40	1.472 (15)	C37—H37C	0.9600
C1—C2	1.474 (7)	C38—H38A	0.9600
C2—C6	1.416 (8)	C38—H38B	0.9600
C2—C3	1.423 (9)	C38—H38C	0.9600
C3—C4	1.408 (9)	C40—H40A	0.9600
C3—H3	0.9300	C40—H40B	0.9600
C4—C5	1.399 (11)	C40—H40C	0.9600
C4—H4	0.9300	C41—H41A	0.9600
C5—C6	1.420 (9)	C41—H41B	0.9600
C5—H5	0.9300	C41—H41C	0.9600
C6—H6	0.9300	C39—H39	0.9300
C7—C8	1.396 (12)
O8—Cu1—O4	89.37 (17)	C4—C5—H5	125.6
O8—Cu1—O6	167.62 (15)	C6—C5—H5	125.6
O4—Cu1—O6	89.89 (16)	Fe1—C5—H5	126.1
O8—Cu1—O2	88.57 (18)	C2—C6—C5	107.8 (6)
O4—Cu1—O2	167.40 (16)	C2—C6—Fe1	69.0 (3)
O6—Cu1—O2	89.46 (17)	C5—C6—Fe1	69.8 (4)
O8—Cu1—O10	95.06 (16)	C2—C6—H6	126.1
O4—Cu1—O10	96.20 (17)	C5—C6—H6	126.1
O6—Cu1—O10	97.31 (16)	Fe1—C6—H6	126.6
O2—Cu1—O10	96.36 (17)	C8—C7—C11	107.2 (7)
O8—Cu1—Cu2	84.26 (12)	C8—C7—Fe1	69.7 (4)
O4—Cu1—Cu2	84.55 (12)	C11—C7—Fe1	69.3 (4)
O6—Cu1—Cu2	83.36 (11)	C8—C7—H7	126.4
O2—Cu1—Cu2	82.87 (12)	C11—C7—H7	126.4
O10—Cu1—Cu2	178.98 (12)	Fe1—C7—H7	126.2
O1—Cu2—O3	168.23 (16)	C9—C8—C7	109.5 (7)
O1—Cu2—O5	89.34 (17)	C9—C8—Fe1	70.5 (4)
O3—Cu2—O5	89.81 (17)	C7—C8—Fe1	70.2 (4)
O1—Cu2—O7	88.32 (17)	C9—C8—H8	125.2
O3—Cu2—O7	90.03 (17)	C7—C8—H8	125.2
O5—Cu2—O7	167.72 (16)	Fe1—C8—H8	125.6
O1—Cu2—O9	99.92 (17)	C8—C9—C10	107.0 (8)
O3—Cu2—O9	91.85 (16)	C8—C9—Fe1	69.9 (4)
O5—Cu2—O9	96.55 (17)	C10—C9—Fe1	68.5 (4)
O7—Cu2—O9	95.72 (16)	C8—C9—H9	126.5
O1—Cu2—Cu1	85.06 (12)	C10—C9—H9	126.5
O3—Cu2—Cu1	83.17 (11)	Fe1—C9—H9	126.6
O5—Cu2—Cu1	84.36 (12)	C11—C10—C9	108.6 (7)
O7—Cu2—Cu1	83.44 (12)	C11—C10—Fe1	70.6 (4)
O9—Cu2—Cu1	174.93 (11)	C9—C10—Fe1	70.4 (4)
C13—Fe2—C22	106.6 (2)	C11—C10—H10	125.7
C13—Fe2—C14	41.3 (2)	C9—C10—H10	125.7
C22—Fe2—C14	115.7 (3)	Fe1—C10—H10	124.9
C13—Fe2—C18	116.4 (3)	C10—C11—C7	107.8 (7)
C22—Fe2—C18	39.9 (3)	C10—C11—Fe1	69.5 (4)
C14—Fe2—C18	148.9 (3)	C7—C11—Fe1	70.0 (4)
C13—Fe2—C20	166.1 (3)	C10—C11—H11	126.1
C22—Fe2—C20	67.1 (3)	C7—C11—H11	126.1
C14—Fe2—C20	128.8 (3)	Fe1—C11—H11	126.0
C18—Fe2—C20	67.4 (3)	O3—C12—O4	126.5 (5)
C13—Fe2—C21	127.6 (3)	O3—C12—C13	117.1 (4)
C22—Fe2—C21	39.8 (3)	O4—C12—C13	116.4 (5)
C14—Fe2—C21	107.1 (3)	C17—C13—C14	107.6 (5)
C18—Fe2—C21	67.1 (3)	C17—C13—C12	126.3 (5)
C20—Fe2—C21	39.9 (3)	C14—C13—C12	126.0 (5)
C13—Fe2—C15	68.7 (2)	C17—C13—Fe2	70.6 (3)
C22—Fe2—C15	149.3 (3)	C14—C13—Fe2	69.7 (3)
C14—Fe2—C15	40.5 (2)	C12—C13—Fe2	122.2 (3)
C18—Fe2—C15	169.9 (3)	C15—C14—C13	107.8 (5)
C20—Fe2—C15	109.9 (3)	C15—C14—Fe2	70.2 (3)
C21—Fe2—C15	117.7 (3)	C13—C14—Fe2	68.9 (3)
C13—Fe2—C19	150.7 (3)	C15—C14—H14	126.1
C22—Fe2—C19	67.7 (3)	C13—C14—H14	126.1
C14—Fe2—C19	167.7 (3)	Fe2—C14—H14	126.3
C18—Fe2—C19	40.7 (4)	C14—C15—C16	107.6 (5)
C20—Fe2—C19	40.2 (4)	C14—C15—Fe2	69.3 (3)
C21—Fe2—C19	67.5 (3)	C16—C15—Fe2	70.0 (3)
C15—Fe2—C19	131.0 (3)	C14—C15—H15	126.2
C13—Fe2—C16	68.0 (2)	C16—C15—H15	126.2
C22—Fe2—C16	167.9 (3)	Fe2—C15—H15	126.1
C14—Fe2—C16	67.9 (3)	C17—C16—C15	109.3 (5)
C18—Fe2—C16	131.6 (3)	C17—C16—Fe2	70.1 (3)
C20—Fe2—C16	120.6 (3)	C15—C16—Fe2	69.6 (4)
C21—Fe2—C16	151.9 (3)	C17—C16—H16	125.3
C15—Fe2—C16	40.4 (3)	C15—C16—H16	125.3
C19—Fe2—C16	111.4 (3)	Fe2—C16—H16	126.5
C13—Fe2—C17	40.9 (2)	C16—C17—C13	107.7 (5)
C22—Fe2—C17	129.2 (2)	C16—C17—Fe2	70.1 (3)
C14—Fe2—C17	68.7 (2)	C13—C17—Fe2	68.5 (3)
C18—Fe2—C17	109.5 (3)	C16—C17—H17	126.2
C20—Fe2—C17	152.5 (3)	C13—C17—H17	126.2
C21—Fe2—C17	166.4 (3)	Fe2—C17—H17	126.8
C15—Fe2—C17	68.1 (2)	C22—C18—C19	108.3 (7)
C19—Fe2—C17	119.2 (3)	C22—C18—Fe2	70.0 (4)
C16—Fe2—C17	39.8 (2)	C19—C18—Fe2	70.2 (4)
C3—Fe1—C10	108.2 (3)	C22—C18—H18	125.9
C3—Fe1—C2	41.3 (2)	C19—C18—H18	125.9
C10—Fe1—C2	114.7 (3)	Fe2—C18—H18	125.6
C3—Fe1—C11	130.4 (3)	C20—C19—C18	106.4 (8)
C10—Fe1—C11	40.0 (3)	C20—C19—Fe2	69.6 (4)
C2—Fe1—C11	107.5 (3)	C18—C19—Fe2	69.2 (4)
C3—Fe1—C8	148.2 (3)	C20—C19—H19	126.8
C10—Fe1—C8	67.6 (3)	C18—C19—H19	126.8
C2—Fe1—C8	170.3 (3)	Fe2—C19—H19	126.0
C11—Fe1—C8	67.7 (3)	C21—C20—C19	108.8 (7)
C3—Fe1—C7	169.9 (3)	C21—C20—Fe2	70.3 (4)
C10—Fe1—C7	67.8 (3)	C19—C20—Fe2	70.2 (4)
C2—Fe1—C7	130.9 (3)	C21—C20—H20	125.6
C11—Fe1—C7	40.8 (3)	C19—C20—H20	125.6
C8—Fe1—C7	40.1 (3)	Fe2—C20—H20	125.5
C3—Fe1—C9	116.1 (3)	C22—C21—C20	108.0 (7)
C10—Fe1—C9	41.0 (3)	C22—C21—Fe2	69.5 (4)
C2—Fe1—C9	147.8 (3)	C20—C21—Fe2	69.8 (4)
C11—Fe1—C9	68.0 (3)	C22—C21—H21	126.0
C8—Fe1—C9	39.6 (4)	C20—C21—H21	126.0
C7—Fe1—C9	67.5 (4)	Fe2—C21—H21	126.2
C3—Fe1—C6	68.5 (3)	C18—C22—C21	108.5 (7)
C10—Fe1—C6	147.1 (3)	C18—C22—Fe2	70.2 (4)
C2—Fe1—C6	40.8 (2)	C21—C22—Fe2	70.6 (4)
C11—Fe1—C6	115.9 (3)	C18—C22—H22	125.7
C8—Fe1—C6	132.6 (3)	C21—C22—H22	125.7
C7—Fe1—C6	109.5 (3)	Fe2—C22—H22	125.1
C9—Fe1—C6	170.7 (3)	O5—C23—O6	126.1 (5)
C3—Fe1—C5	67.9 (3)	O5—C23—C24	116.6 (5)
C10—Fe1—C5	170.6 (4)	O6—C23—C24	117.2 (5)
C2—Fe1—C5	68.5 (2)	C28—C24—C25	107.3 (5)
C11—Fe1—C5	149.0 (3)	C28—C24—C23	126.9 (5)
C8—Fe1—C5	110.9 (3)	C25—C24—C23	125.6 (5)
C7—Fe1—C5	117.5 (3)	C28—C24—Fe3	69.0 (3)
C9—Fe1—C5	132.0 (3)	C25—C24—Fe3	69.8 (3)
C6—Fe1—C5	40.7 (3)	C23—C24—Fe3	122.7 (4)
C3—Fe1—C4	40.5 (3)	C24—C25—C26	108.6 (6)
C10—Fe1—C4	131.7 (3)	C24—C25—Fe3	69.5 (3)
C2—Fe1—C4	68.7 (2)	C26—C25—Fe3	70.0 (4)
C11—Fe1—C4	169.5 (3)	C24—C25—H25	125.7
C8—Fe1—C4	117.5 (3)	C26—C25—H25	125.7
C7—Fe1—C4	148.9 (3)	Fe3—C25—H25	126.4
C9—Fe1—C4	109.7 (3)	C25—C26—C27	107.5 (6)
C6—Fe1—C4	68.0 (3)	C25—C26—Fe3	69.3 (4)
C5—Fe1—C4	39.9 (3)	C27—C26—Fe3	69.4 (4)
C31—Fe3—C29	67.2 (5)	C25—C26—H26	126.3
C31—Fe3—C28	122.9 (4)	C27—C26—H26	126.3
C29—Fe3—C28	159.9 (4)	Fe3—C26—H26	126.6
C31—Fe3—C32	40.2 (4)	C28—C27—C26	107.8 (6)
C29—Fe3—C32	66.7 (5)	C28—C27—Fe3	68.9 (4)
C28—Fe3—C32	108.6 (4)	C26—C27—Fe3	69.9 (4)
C31—Fe3—C30	41.7 (4)	C28—C27—H27	126.1
C29—Fe3—C30	39.7 (4)	C26—C27—H27	126.1
C28—Fe3—C30	159.1 (4)	Fe3—C27—H27	126.7
C32—Fe3—C30	68.7 (5)	C27—C28—C24	108.8 (6)
C31—Fe3—C24	158.7 (4)	C27—C28—Fe3	70.4 (4)
C29—Fe3—C24	123.7 (4)	C24—C28—Fe3	70.1 (4)
C28—Fe3—C24	40.9 (2)	C27—C28—H28	125.6
C32—Fe3—C24	123.1 (4)	C24—C28—H28	125.6
C30—Fe3—C24	158.1 (4)	Fe3—C28—H28	125.5
C31—Fe3—C25	159.4 (4)	C33—C29—C30	111.1 (13)
C29—Fe3—C25	108.3 (4)	C33—C29—Fe3	71.1 (7)
C28—Fe3—C25	68.4 (3)	C30—C29—Fe3	70.3 (7)
C32—Fe3—C25	158.6 (4)	C33—C29—H29	124.4
C30—Fe3—C25	121.8 (4)	C30—C29—H29	124.4
C24—Fe3—C25	40.7 (3)	Fe3—C29—H29	125.7
C31—Fe3—C33	67.2 (5)	C29—C30—C31	105.0 (12)
C29—Fe3—C33	39.3 (5)	C29—C30—Fe3	70.0 (6)
C28—Fe3—C33	124.6 (4)	C31—C30—Fe3	68.3 (6)
C32—Fe3—C33	39.9 (4)	C29—C30—H30	127.5
C30—Fe3—C33	67.5 (5)	C31—C30—H30	127.5
C24—Fe3—C33	108.5 (4)	Fe3—C30—H30	125.8
C25—Fe3—C33	123.0 (4)	C32—C31—C30	108.3 (12)
C31—Fe3—C27	107.9 (4)	C32—C31—Fe3	70.7 (6)
C29—Fe3—C27	158.3 (4)	C30—C31—Fe3	70.0 (6)
C28—Fe3—C27	40.7 (3)	C32—C31—H31	125.8
C32—Fe3—C27	124.1 (4)	C30—C31—H31	125.8
C30—Fe3—C27	122.4 (4)	Fe3—C31—H31	125.0
C24—Fe3—C27	68.7 (3)	C31—C32—C33	107.7 (13)
C25—Fe3—C27	68.4 (3)	C31—C32—Fe3	69.0 (7)
C33—Fe3—C27	160.4 (4)	C33—C32—Fe3	70.7 (7)
C31—Fe3—C26	123.3 (4)	C31—C32—H32	126.2
C29—Fe3—C26	122.8 (5)	C33—C32—H32	126.2
C28—Fe3—C26	68.6 (3)	Fe3—C32—H32	125.7
C32—Fe3—C26	159.9 (4)	C29—C33—C32	107.8 (12)
C30—Fe3—C26	106.4 (4)	C29—C33—Fe3	69.6 (7)
C24—Fe3—C26	68.7 (3)	C32—C33—Fe3	69.4 (7)
C25—Fe3—C26	40.7 (3)	C29—C33—H33	126.1
C33—Fe3—C26	158.0 (4)	C32—C33—H33	126.1
C27—Fe3—C26	40.8 (3)	Fe3—C33—H33	126.5
C12—O3—Cu2	121.8 (3)	C34—C35—H35A	109.5
C34—O7—Cu2	121.7 (3)	C34—C35—H35B	109.5
C23—O6—Cu1	121.6 (3)	H35A—C35—H35B	109.5
C12—O4—Cu1	120.3 (3)	C34—C35—H35C	109.5
C23—O5—Cu2	121.2 (4)	H35A—C35—H35C	109.5
C1—O2—Cu1	121.8 (3)	H35B—C35—H35C	109.5
C1—O1—Cu2	122.0 (4)	O9—C36—N1	128.0 (8)
C34—O8—Cu1	122.4 (3)	O9—C36—H36	116.0
C39—O10—Cu1	124.8 (5)	N1—C36—H36	116.0
C36—O9—Cu2	121.0 (5)	N1—C37—H37A	109.5
C36—N1—C38	128.2 (9)	N1—C37—H37B	109.5
C36—N1—C37	116.8 (8)	H37A—C37—H37B	109.5
C38—N1—C37	114.9 (8)	N1—C37—H37C	109.5
C39—N2—C41	127.3 (9)	H37A—C37—H37C	109.5
C39—N2—C40	117.3 (7)	H37B—C37—H37C	109.5
C41—N2—C40	115.2 (8)	N1—C38—H38A	109.5
O1—C1—O2	125.2 (5)	N1—C38—H38B	109.5
O1—C1—C2	117.1 (5)	H38A—C38—H38B	109.5
O2—C1—C2	117.6 (5)	N1—C38—H38C	109.5
C6—C2—C3	107.0 (5)	H38A—C38—H38C	109.5
C6—C2—C1	128.6 (6)	H38B—C38—H38C	109.5
C3—C2—C1	124.4 (5)	O8—C34—O7	125.3 (5)
C6—C2—Fe1	70.2 (3)	O8—C34—C35	117.8 (5)
C3—C2—Fe1	68.9 (3)	O7—C34—C35	116.9 (5)
C1—C2—Fe1	125.3 (4)	N2—C40—H40A	109.5
C4—C3—C2	108.8 (6)	N2—C40—H40B	109.5
C4—C3—Fe1	71.4 (4)	H40A—C40—H40B	109.5
C2—C3—Fe1	69.8 (3)	N2—C40—H40C	109.5
C4—C3—H3	125.6	H40A—C40—H40C	109.5
C2—C3—H3	125.6	H40B—C40—H40C	109.5
Fe1—C3—H3	124.8	N2—C41—H41A	109.5
C5—C4—C3	107.6 (6)	N2—C41—H41B	109.5
C5—C4—Fe1	69.7 (4)	H41A—C41—H41B	109.5
C3—C4—Fe1	68.2 (3)	N2—C41—H41C	109.5
C5—C4—H4	126.2	H41A—C41—H41C	109.5
C3—C4—H4	126.2	H41B—C41—H41C	109.5
Fe1—C4—H4	127.5	O10—C39—N2	127.7 (9)
C4—C5—C6	108.8 (6)	O10—C39—H39	116.2
C4—C5—Fe1	70.4 (4)	N2—C39—H39	116.2
C6—C5—Fe1	69.5 (4)