μ-Cyano-1:2κ²C:N-tetracyano-1κ⁴C-(5-methyl-5-nitro-3,7-diazanonane-1,9-diamine-2κ⁴N^1,3,7,9)-nitrosyl-1κN-copper(II)iron(II) dihydrate

The title binuclear complex, [CuFe(CN)₅(C₈H₂₁N₅O₂)(NO)]·2H₂O or [CuFe(nelin)(CN)₅(NO)]·2H₂O (nelin is 5-methyl-5-nitro-3,7-di­aza­nonane-1,9-di­amine) consists of discrete binuclear mixed-metal species, with a Cu centre linked to an Fe centre through a cyano bridge, and two water mol­ecules of crystallization. In the complex, the Cu^II ion is coordinated by five N atoms and has a distorted square-pyramidal geometry. The Fe^II centre is in a distorted octahedral environment.

S1. Comment

It is well known that the cyanide ion may coordinate through the C atom, acting as a monodentate ligand, or through both the C and N atoms, acting as a bridging ligand (Cramer et al., 1965). The preparation and study of polynuclear cyanide-bridged metal complexes, especially ferro- and ferricyanide complexes, have been of great interest in recent years due to the unusual electronic state, magnetic behaviour and photochemical properties of these compounds (Alcock et al., 1993; Entley & Giroloni, 1994; Clemente-Leon et al., 2001). Several studies have been made of the [Fe(CN)₅(NO)]^2- anion (Olabe et al., 1984; Zhan et al., 1999). Attempts have been made to clarify the structural correlation with the photochemical or magnetic properties of polynuclear complexes with the nitroprusside. We report here the preparation and structure of a new cyano-bridged Cu—Fe complex, namely [Cu(nelin)Fe(CN)₅(NO)]·2H₂O, (I). \sch

The dinuclear unit of (I) comprises one [Fe(CN)₅(NO)]^2- anion linked to one [Cu(nelin)]²⁺ cation through a CN^- ligand. As shown in Fig. 1, the coordination environment of the Cu atom can be described as distorted square-based pyramidal. The basal plane is constructed by the coordination of the four N atoms of the tetradentate nelin ligand, and the N atom of the cyanide group occupies the axial position. The Cu—N distances reveal a small tetragonal distortion of the Cu—N₄ plane, with the Cu—N bonds to the secondary amines being slightly longer than the Cu—N bonds to the primary amines, and this may be a consequence of steric differences for the N atoms. Within the Cu—N₄ plane, the N2—Cu—N3 angle of 92.11 (7)° is about 3.6° smaller than the N1—Cu—N4 angle because of the steric difference. This is different from the similar structure (name or formula?) studied by Bernhardt et al. (1990), in which the trans angles are almost the same. The axial Cu—N6 bond is elongated, as in the case of [Cu₂(oxpn)Fe(CN)₅(NO)]_n [oxpn is N,N'-bis(3-aminopropyl)oxamide; Chen et al., 1995] and [Cu(dmen)₂Fe(CN)₅(NO)] (dmen is 2-dimethylaminoethylamine; Mondal et al., 2000).

The Fe^II atom is in a deformed octahedral arrangement. The equatorial plane is defined by four C atoms of the cyanides, and the two axial sites are occupied by a cyanide C atom and the N atom of the nitrosyl group. The Fe—C, Fe—N, C—N and N—O bond lengths in the [Fe(CN)₅(NO)] moiety are comparable with those reported for other multinuclear complexes of [Fe(CN)₅(NO)]^2- (Shyu et al., 1997; Zhan et al., 1999). The Fe—N distance [1.651 (2) Å] is much shorter than the other five Fe—C distances, which lie between 1.939 (3) and 1.948 (2) Å. Hence, the NO ligand is perfectly localized in the structure.

According to molecular orbital theory, M—NO⁺ will be nearly linear, which is proved in (I) by the Fe—N—O bond angle of 179.1 (2)°. The Fe—C—N bond angles [in the range 176.7 (2) to 179.2 (2)°] are also nearly linear. The Cu—N6—C9 bond angle is 157.1 (2)°, indicating a nonlinear linkage between the N atom of the cyanide ligand and the Cu^II atom.

Hydrogen-bonding interactions play an important role in the solid-state structure of (I), as shown in Fig. 2. In the unit cell, the complex is linked by hydrogen bonds to form sheets which lie in the domain 0 < z < 1/2, and these sheets are then linked by the two water molecules via O—H···N hydrogen bonds to give a three-dimensional network.

S2. Experimental

To an aqueous solution (15 ml) of [Cu(nelin)(ClO₄)₂] (0.48 g, 1 mmol), an aqueous solution (15 ml) containing Na₂[Fe(CN)₅(NO)]·2H₂O (0.29 g, 1 mmol) was added dropwise. After stirring for 30 min at room temperature, the resulting precipitate was collected by suction filtration. Dark-purple single crystals of (I) were obtained by recrystallizing from water in the dark.

S3. Refinement

All H atoms were visible in difference maps. The water H atoms were refined with DFIX restraints (SHELXL97; Sheldrick 1997), with O—H = 0.82 (3) Å and H···H = 1.37 (3) Å. All other H atoms were allowed for as riding atoms, with C—H = 0.96 and 0.97 Å, and N—H = 0.90 and 0.91 Å. The nitro group (N5/O1/O2) showed some signs of disorder (one O atom markedly anisotropic), and this was allowed for by refining atom O2 over two closely adjacent sites with 0.5 occupancy and with N5—O2 and N5—O2' restrained to be 1.22 (1) Å.

Computing details

Data collection: XSCANS (Siemens, 1991); cell refinement: XSCANS; data reduction: SHELXTL-Plus (Sheldrick, 1990a); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus; software used to prepare material for publication: SHELXTL-Plus.

Figures

	Fig. 1. A view of the coordination environment in (I), shown with 35% probability displacement ellipsoids. Hydrogen bonds are illustrated as dotted lines.
	Fig. 2. The molecular packing diagram for (I). Atoms labelled with an asterisk (*), hash sign (#) or dollar sign () are at symmetry positions (x - 1, y, z), (x, y - 1, z) and (1 + x, y - 1, z), respectively.

µ-Cyano-1:2κ²C:N-tetracyano-1κ⁴C-(5-methyl-5-nitro-3,7-diazanonane- 1,9-diamine-2κ⁴N)-nitrosyl-1κN-copper(II)iron(II) dihydrate

Crystal data

[CuFe(C8H21N5O2)(CN)5(NO)]·2H2O	Z = 2
Mr = 534.83	F(000) = 550
Triclinic, P1	Dx = 1.613 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.470 (2) Å	Cell parameters from 31 reflections
b = 9.702 (2) Å	θ = 2.6–15.9°
c = 14.648 (3) Å	µ = 1.67 mm^−1
α = 85.55 (1)°	T = 291 K
β = 80.11 (2)°	Prism, dark purple
γ = 68.20 (1)°	0.58 × 0.54 × 0.40 mm
V = 1100.9 (4) Å^3

Data collection

Siemens P4 diffractometer	3436 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.008
Graphite monochromator	θmax = 25.0°, θmin = 2.3°
ω scans	h = 0→10
Absorption correction: empirical (using intensity measurements) (North et al., 1968)	k = −10→11
Tmin = 0.380, Tmax = 0.512	l = −17→17
4302 measured reflections	3 standard reflections every 97 reflections
3874 independent reflections	intensity decay: 0.5%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.067	w = 1/[σ^2(Fo^2) + (0.0379P)^2 + 0.3921P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
3874 reflections	Δρmax = 0.33 e Å^−3
307 parameters	Δρmin = −0.27 e Å^−3
7 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0042 (7)

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	Occ. (<1)
Cu	0.19133 (3)	0.20779 (3)	0.191616 (17)	0.02803 (9)
Fe	−0.18785 (4)	0.73472 (3)	0.32692 (2)	0.02823 (10)
O1	0.7112 (2)	0.3337 (2)	0.09481 (14)	0.0593 (5)
O2	0.7135 (14)	0.1735 (11)	0.1990 (12)	0.054 (2)	0.50
O4	0.2433 (3)	0.6895 (2)	0.59839 (14)	0.0542 (5)
O5	−0.6254 (3)	0.8399 (3)	0.04973 (14)	0.0566 (5)
N1	0.0791 (3)	0.1023 (2)	0.28877 (14)	0.0411 (5)
H1NA	−0.0275	0.1641	0.3113	0.049*
H1NB	0.0702	0.0241	0.2639	0.049*
N2	0.3421 (2)	0.20215 (18)	0.28489 (11)	0.0272 (4)
H2N	0.4425	0.1237	0.2708	0.033*
N3	0.3198 (2)	0.3044 (2)	0.09380 (12)	0.0301 (4)
H3N	0.4236	0.2349	0.0718	0.036*
N4	0.0977 (2)	0.1613 (2)	0.08578 (13)	0.0404 (5)
H4NA	0.1249	0.0627	0.0832	0.049*
H4NB	−0.0177	0.2054	0.0944	0.049*
N5	0.6355 (2)	0.2906 (2)	0.16278 (14)	0.0375 (4)
N6	−0.0187 (2)	0.4357 (2)	0.22588 (14)	0.0383 (5)
O3	−0.4086 (3)	0.6420 (2)	0.45856 (14)	0.0692 (6)
N8	0.0611 (3)	0.8285 (2)	0.17842 (15)	0.0464 (5)
N9	0.1116 (3)	0.6357 (3)	0.43963 (18)	0.0657 (7)
N10	−0.4574 (3)	0.8736 (2)	0.19694 (14)	0.0446 (5)
N11	−0.3116 (3)	1.0431 (2)	0.41346 (15)	0.0494 (5)
C1	0.1832 (3)	0.0516 (3)	0.36375 (18)	0.0487 (6)
H1A	0.2763	−0.0422	0.3479	0.058*
H1B	0.1128	0.0377	0.4206	0.058*
C2	0.2548 (3)	0.1685 (3)	0.37641 (16)	0.0422 (6)
H2A	0.1624	0.2578	0.4011	0.051*
H2B	0.3363	0.1330	0.4199	0.051*
C3	0.3868 (3)	0.3335 (2)	0.29182 (15)	0.0318 (5)
H3A	0.4719	0.3083	0.3331	0.038*
H3B	0.2847	0.4115	0.3211	0.038*
C4	0.4559 (3)	0.3972 (2)	0.20284 (15)	0.0312 (5)
C5	0.3478 (3)	0.4329 (2)	0.12536 (15)	0.0328 (5)
H5A	0.2368	0.5085	0.1465	0.039*
H5B	0.4037	0.4741	0.0730	0.039*
C6	0.2123 (3)	0.3470 (3)	0.01910 (16)	0.0457 (6)
H6A	0.2737	0.3769	−0.0362	0.055*
H6B	0.1067	0.4300	0.0384	0.055*
C7	0.1713 (3)	0.2153 (3)	−0.00112 (17)	0.0537 (7)
H7A	0.0898	0.2438	−0.0446	0.064*
H7B	0.2753	0.1373	−0.0286	0.064*
C8	0.4822 (3)	0.5369 (3)	0.2282 (2)	0.0486 (6)
H8A	0.3743	0.6072	0.2564	0.058*
H8B	0.5255	0.5802	0.1732	0.058*
H8C	0.5632	0.5106	0.2710	0.058*
C9	−0.0858 (3)	0.5470 (2)	0.26230 (15)	0.0309 (5)
N7	−0.3177 (3)	0.6788 (2)	0.40502 (13)	0.0380 (4)
C11	−0.0329 (3)	0.7968 (2)	0.23372 (16)	0.0337 (5)
C12	0.0015 (3)	0.6711 (3)	0.39785 (17)	0.0408 (5)
C13	−0.3552 (3)	0.8191 (2)	0.24329 (15)	0.0325 (5)
C14	−0.2636 (3)	0.9302 (2)	0.37982 (15)	0.0342 (5)
O2'	0.6747 (15)	0.1657 (10)	0.1960 (14)	0.068 (4)	0.50
H4OA	0.221 (5)	0.662 (4)	0.5513 (15)	0.105 (15)*
H4OB	0.270 (4)	0.764 (2)	0.5843 (19)	0.071 (11)*
H5OA	−0.586 (4)	0.853 (4)	0.0936 (15)	0.065 (10)*
H5OB	−0.706 (3)	0.815 (4)	0.072 (2)	0.068 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.03029 (15)	0.03079 (15)	0.02506 (15)	−0.01437 (11)	−0.00042 (10)	−0.00438 (10)
Fe	0.02927 (17)	0.02657 (17)	0.02740 (17)	−0.00988 (13)	0.00095 (13)	−0.00527 (12)
O1	0.0360 (10)	0.0706 (13)	0.0622 (12)	−0.0185 (9)	0.0076 (9)	0.0141 (10)
O2	0.018 (5)	0.052 (3)	0.078 (4)	−0.005 (2)	−0.002 (4)	0.031 (3)
O4	0.0621 (12)	0.0578 (12)	0.0510 (12)	−0.0318 (10)	−0.0077 (10)	−0.0001 (9)
O5	0.0446 (11)	0.0839 (15)	0.0422 (11)	−0.0244 (11)	−0.0038 (9)	−0.0080 (10)
N1	0.0459 (12)	0.0410 (11)	0.0428 (11)	−0.0267 (10)	0.0037 (9)	−0.0053 (9)
N2	0.0246 (8)	0.0279 (9)	0.0256 (9)	−0.0075 (7)	−0.0013 (7)	0.0030 (7)
N3	0.0236 (9)	0.0381 (10)	0.0254 (9)	−0.0078 (8)	−0.0040 (7)	0.0006 (7)
N4	0.0308 (10)	0.0463 (12)	0.0455 (11)	−0.0132 (9)	−0.0048 (9)	−0.0153 (9)
N5	0.0255 (10)	0.0426 (12)	0.0447 (12)	−0.0130 (9)	−0.0062 (9)	0.0022 (9)
N6	0.0337 (10)	0.0317 (10)	0.0452 (11)	−0.0105 (8)	0.0062 (9)	−0.0101 (9)
O3	0.0724 (14)	0.0677 (13)	0.0628 (13)	−0.0366 (12)	0.0283 (11)	−0.0036 (11)
N8	0.0441 (12)	0.0526 (13)	0.0474 (12)	−0.0271 (11)	0.0044 (10)	−0.0068 (10)
N9	0.0538 (15)	0.0768 (18)	0.0572 (15)	−0.0053 (13)	−0.0207 (13)	−0.0148 (13)
N10	0.0439 (12)	0.0485 (12)	0.0404 (12)	−0.0139 (10)	−0.0082 (10)	−0.0074 (10)
N11	0.0690 (15)	0.0354 (12)	0.0425 (12)	−0.0168 (11)	−0.0075 (11)	−0.0070 (10)
C1	0.0463 (14)	0.0451 (14)	0.0485 (15)	−0.0182 (12)	0.0052 (12)	0.0153 (12)
C2	0.0402 (13)	0.0610 (16)	0.0256 (11)	−0.0217 (12)	−0.0022 (10)	0.0090 (11)
C3	0.0304 (11)	0.0379 (12)	0.0287 (11)	−0.0135 (9)	−0.0049 (9)	−0.0041 (9)
C4	0.0238 (10)	0.0324 (11)	0.0377 (12)	−0.0113 (9)	−0.0037 (9)	0.0001 (9)
C5	0.0272 (11)	0.0345 (12)	0.0363 (12)	−0.0129 (9)	−0.0041 (9)	0.0095 (9)
C6	0.0390 (13)	0.0704 (18)	0.0273 (12)	−0.0191 (12)	−0.0115 (10)	0.0115 (11)
C7	0.0445 (15)	0.087 (2)	0.0307 (13)	−0.0222 (14)	−0.0082 (11)	−0.0149 (13)
C8	0.0453 (15)	0.0409 (14)	0.0672 (18)	−0.0242 (12)	−0.0081 (13)	−0.0042 (13)
C9	0.0272 (11)	0.0317 (12)	0.0329 (11)	−0.0118 (9)	0.0005 (9)	−0.0018 (9)
N7	0.0421 (11)	0.0309 (10)	0.0363 (11)	−0.0113 (9)	0.0043 (9)	−0.0067 (8)
C11	0.0347 (12)	0.0307 (11)	0.0380 (12)	−0.0134 (10)	−0.0046 (10)	−0.0087 (9)
C12	0.0415 (13)	0.0391 (13)	0.0365 (13)	−0.0084 (11)	−0.0028 (11)	−0.0097 (10)
C13	0.0347 (12)	0.0300 (11)	0.0329 (11)	−0.0141 (10)	0.0032 (10)	−0.0089 (9)
C14	0.0400 (12)	0.0338 (12)	0.0287 (11)	−0.0137 (10)	−0.0043 (9)	−0.0015 (9)
O2'	0.017 (5)	0.047 (4)	0.115 (6)	0.003 (3)	0.016 (4)	0.017 (4)

Geometric parameters (Å, º)

Cu—N1	2.0019 (19)	N5—O2'	1.217 (4)
Cu—N4	2.0076 (19)	N5—C4	1.532 (3)
Cu—N2	2.0093 (17)	N6—C9	1.141 (3)
Cu—N3	2.0322 (18)	O3—N7	1.135 (3)
Cu—N6	2.2915 (19)	N8—C11	1.143 (3)
Fe—N7	1.651 (2)	N9—C12	1.135 (3)
Fe—C13	1.939 (3)	N10—C13	1.139 (3)
Fe—C14	1.940 (2)	N11—C14	1.136 (3)
Fe—C12	1.941 (3)	C1—C2	1.507 (4)
Fe—C9	1.944 (2)	C1—H1A	0.97
Fe—C11	1.948 (2)	C1—H1B	0.97
O1—N5	1.222 (3)	C2—H2A	0.97
O2—N5	1.216 (4)	C2—H2B	0.97
O4—H4OA	0.83 (3)	C3—C4	1.518 (3)
O4—H4OB	0.84 (3)	C3—H3A	0.97
O5—H5OA	0.81 (3)	C3—H3B	0.97
O5—H5OB	0.82 (3)	C4—C5	1.519 (3)
N1—C1	1.467 (3)	C4—C8	1.535 (3)
N1—H1NA	0.90	C5—H5A	0.97
N1—H1NB	0.90	C5—H5B	0.97
N2—C3	1.473 (3)	C6—C7	1.505 (4)
N2—C2	1.490 (3)	C6—H6A	0.97
N2—H2N	0.91	C6—H6B	0.97
N3—C5	1.473 (3)	C7—H7A	0.97
N3—C6	1.480 (3)	C7—H7B	0.97
N3—H3N	0.91	C8—H8A	0.96
N4—C7	1.466 (3)	C8—H8B	0.96
N4—H4NA	0.90	C8—H8C	0.96
N4—H4NB	0.90
N1—Cu—N4	95.69 (8)	O1—N5—C4	117.11 (18)
N1—Cu—N2	85.80 (8)	C9—N6—Cu	157.02 (18)
N4—Cu—N2	163.66 (7)	N1—C1—C2	107.74 (19)
N1—Cu—N3	176.38 (8)	N1—C1—H1A	110.2
N4—Cu—N3	85.49 (8)	C2—C1—H1A	110.2
N2—Cu—N3	92.11 (7)	N1—C1—H1B	110.2
N1—Cu—N6	93.43 (8)	C2—C1—H1B	110.2
N4—Cu—N6	97.44 (8)	H1A—C1—H1B	108.5
N2—Cu—N6	98.71 (7)	N2—C2—C1	108.85 (19)
N3—Cu—N6	89.80 (7)	N2—C2—H2A	109.9
N7—Fe—C13	94.64 (10)	C1—C2—H2A	109.9
N7—Fe—C14	93.92 (9)	N2—C2—H2B	109.9
C13—Fe—C14	87.93 (9)	C1—C2—H2B	109.9
N7—Fe—C12	95.20 (10)	H2A—C2—H2B	108.3
C13—Fe—C12	169.74 (10)	N2—C3—C4	117.77 (17)
C14—Fe—C12	88.52 (10)	N2—C3—H3A	107.9
N7—Fe—C9	94.46 (9)	C4—C3—H3A	107.9
C13—Fe—C9	92.65 (9)	N2—C3—H3B	107.9
C14—Fe—C9	171.53 (9)	C4—C3—H3B	107.9
C12—Fe—C9	89.46 (9)	H3A—C3—H3B	107.2
N7—Fe—C11	178.87 (9)	C3—C4—C5	116.34 (17)
C13—Fe—C11	85.45 (9)	C3—C4—N5	110.60 (17)
C14—Fe—C11	87.21 (9)	C5—C4—N5	106.64 (17)
C12—Fe—C11	84.76 (10)	C3—C4—C8	107.39 (18)
C9—Fe—C11	84.41 (9)	C5—C4—C8	110.07 (19)
H4OA—O4—H4OB	109 (3)	N5—C4—C8	105.25 (17)
H5OA—O5—H5OB	106 (3)	N3—C5—C4	114.30 (17)
C1—N1—Cu	109.09 (14)	N3—C5—H5A	108.7
C1—N1—H1NA	109.9	C4—C5—H5A	108.7
Cu—N1—H1NA	109.9	N3—C5—H5B	108.7
C1—N1—H1NB	109.9	C4—C5—H5B	108.7
Cu—N1—H1NB	109.9	H5A—C5—H5B	107.6
H1NA—N1—H1NB	108.3	N3—C6—C7	108.4 (2)
C3—N2—C2	110.02 (17)	N3—C6—H6A	110.0
C3—N2—Cu	118.11 (13)	C7—C6—H6A	110.0
C2—N2—Cu	106.39 (13)	N3—C6—H6B	110.0
C3—N2—H2N	107.3	C7—C6—H6B	110.0
C2—N2—H2N	107.3	H6A—C6—H6B	108.4
Cu—N2—H2N	107.3	N4—C7—C6	108.85 (19)
C5—N3—C6	111.53 (18)	N4—C7—H7A	109.9
C5—N3—Cu	115.17 (13)	C6—C7—H7A	109.9
C6—N3—Cu	103.63 (13)	N4—C7—H7B	109.9
C5—N3—H3N	108.8	C6—C7—H7B	109.9
C6—N3—H3N	108.8	H7A—C7—H7B	108.3
Cu—N3—H3N	108.8	C4—C8—H8A	109.5
C7—N4—Cu	109.33 (14)	C4—C8—H8B	109.5
C7—N4—H4NA	109.8	H8A—C8—H8B	109.5
Cu—N4—H4NA	109.8	C4—C8—H8C	109.5
C7—N4—H4NB	109.8	H8A—C8—H8C	109.5
Cu—N4—H4NB	109.8	H8B—C8—H8C	109.5
H4NA—N4—H4NB	108.3	N6—C9—Fe	176.73 (19)
O2—N5—O2'	17.7 (12)	O3—N7—Fe	179.1 (2)
O2—N5—O1	118.0 (7)	N8—C11—Fe	177.8 (2)
O2'—N5—O1	127.7 (8)	N9—C12—Fe	179.2 (2)
O2—N5—C4	124.5 (8)	N10—C13—Fe	177.0 (2)
O2'—N5—C4	114.4 (7)	N11—C14—Fe	177.4 (2)
N4—Cu—N1—C1	152.24 (16)	C3—N2—C2—C1	170.19 (19)
N2—Cu—N1—C1	−11.42 (16)	Cu—N2—C2—C1	41.2 (2)
N6—Cu—N1—C1	−109.92 (16)	N1—C1—C2—N2	−52.2 (3)
N1—Cu—N2—C3	−140.67 (15)	C2—N2—C3—C4	−172.28 (18)
N4—Cu—N2—C3	123.4 (3)	Cu—N2—C3—C4	−49.9 (2)
N3—Cu—N2—C3	42.29 (15)	N2—C3—C4—C5	53.0 (3)
N6—Cu—N2—C3	−47.83 (15)	N2—C3—C4—N5	−68.8 (2)
N1—Cu—N2—C2	−16.51 (14)	N2—C3—C4—C8	176.85 (18)
N4—Cu—N2—C2	−112.4 (3)	O2—N5—C4—C3	−2.1 (10)
N3—Cu—N2—C2	166.46 (14)	O2'—N5—C4—C3	14.6 (10)
N6—Cu—N2—C2	76.33 (15)	O1—N5—C4—C3	−174.57 (19)
N4—Cu—N3—C5	148.07 (15)	O2—N5—C4—C5	−129.5 (10)
N2—Cu—N3—C5	−48.12 (14)	O2'—N5—C4—C5	−112.8 (10)
N6—Cu—N3—C5	50.59 (14)	O1—N5—C4—C5	58.0 (2)
N4—Cu—N3—C6	25.98 (15)	O2—N5—C4—C8	113.6 (10)
N2—Cu—N3—C6	−170.21 (15)	O2'—N5—C4—C8	130.3 (10)
N6—Cu—N3—C6	−71.50 (15)	O1—N5—C4—C8	−58.9 (3)
N1—Cu—N4—C7	−175.14 (17)	C6—N3—C5—C4	179.42 (18)
N2—Cu—N4—C7	−80.7 (3)	Cu—N3—C5—C4	61.7 (2)
N3—Cu—N4—C7	1.42 (16)	C3—C4—C5—N3	−59.4 (2)
N6—Cu—N4—C7	90.64 (17)	N5—C4—C5—N3	64.5 (2)
N1—Cu—N6—C9	89.6 (5)	C8—C4—C5—N3	178.14 (18)
N4—Cu—N6—C9	−174.2 (4)	C5—N3—C6—C7	−173.10 (19)
N2—Cu—N6—C9	3.3 (5)	Cu—N3—C6—C7	−48.6 (2)
N3—Cu—N6—C9	−88.8 (5)	Cu—N4—C7—C6	−28.8 (2)
Cu—N1—C1—C2	36.7 (2)	N3—C6—C7—N4	52.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4OA···N9	0.83 (3)	2.09 (3)	2.905 (4)	167 (4)
O4—H4OB···N11^i	0.84 (3)	2.03 (2)	2.847 (3)	165 (3)
O5—H5OA···N10	0.81 (3)	2.07 (3)	2.879 (3)	173 (3)
O5—H5OB···N8^ii	0.82 (3)	2.26 (3)	3.014 (4)	153 (3)
N1—H1NA···O4^iii	0.90	2.15	3.023 (3)	162
N1—H1NB···N8^iv	0.90	2.38	3.278 (3)	172
N2—H2N···N10^v	0.91	2.52	3.251 (3)	138
N3—H3N···O5^vi	0.91	2.20	2.996 (3)	145
N4—H4NA···O5^v	0.90	2.41	3.147 (3)	140
N4—H4NB···O1^ii	0.90	2.17	3.058 (3)	170

Symmetry codes: (i) −x, −y+2, −z+1; (ii) x−1, y, z; (iii) −x, −y+1, −z+1; (iv) x, y−1, z; (v) x+1, y−1, z; (vi) −x, −y+1, −z.