A cyano-bridged binuclear Cu–Fe complex based on nitro­prusside

The title compound, μ-cyano-1:2κ²C:N-tetra­cyano-1κC-[3,7-bis(2-amino­ethyl)-1,3,5,7-tetra­aza­bi­cyclo­[3,3,2]­decane-2κ⁴N^1,3,5,7]-nitro­syl-1κN-copper(II)­iron(II) monohydrate, [CuFe(CN)₅(C₁₀H₂₄N₆)(NO)]·H₂O, has been synthesized and structurally characterized; the Cu atom is five-coordinate and has a square pyramidal configuration. The [Fe(CN)₅(NO)]²⁻ anion uses the CN⁻ ligand cis to the NO⁺ ligand to link to the Cu atom. The Cu—N[triple bond]C—Fe linkage is nonlinear, similar to that in other cyano-bridged bimetallic complexes.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.041
• wR factor = 0.091
• Data-to-parameter ratio = 22.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_420  Alert C D-H Without Acceptor       N(12)  -   H(12C)            ?


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

It is well known that the cyanide ion may coordinate through the carbon atom acting as a monodentate ligand or through both the carbon and nitrogen atoms acting as a bridging ligand. Recently, using [Fe(CN)₅(NO)]^2- as a building block, some cyano-bridged polymeric complexes have been prepared for the investigation of photo-functional properties (Bellouard et al., 2001; Gu et al., 2001) and semipermeable membrane properties (Mullica et al., 1990) of nitroprusside. Also, there has been much interest in clarifying the structural correlation with magnetic properties of nitroprusside-bridged complexes. Magnetic studies show that the nitroprusside anion transmits very weak antiferromagnetic interaction. Tang and co-workers reported a two-dimensional cyano-bridged [Cu₂(oxpn)Fe(CN)₅(NO)]_n [H₂oxpn = N,N'-bis(3-aminopropyl)oxamide] complex, in which a nitrogen atom of the cyano group in [Fe(CN)₅(NO)]^2- is coordinated to one of the adjacent Cu^II ions in [Cu₂(oxpn)]²⁺ (Chen et al., 1995). The complexes M(en)₂Fe(CN)₅(NO).nH₂O (where en = ethylenediamine, M = Ni^II and Cu^II, n = 0 or 1) exhibit one-dimensional chain-like structure, in which weak antiferromagnetic coupling is present through the nitroprusside (Kou et al., 1998; Shyu et al., 1997), whereas Cu(L¹)₂Fe(CN)₅(NO).nH₂O (where L¹ = 2-dimethylaminoethylamine, 1-dimethylamino-2-propylamine, 3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12- hexaazacyclotetradecane and 1,2-diaminopropane) are cyano-bridged dinuclear complexes (Zhang et al., 2002). We have been interested in this versatile building block. Recently, we prepared a new tetraazabicycle–Cu^II complexes [CuL²](ClO₄)₂ [L² = 3,7-bis(2-aminoethyl)-1,3,5,7-tetraazabicyclo[3,3,2]decane], in which the Cu^II ion exhibits 4 + 2 coordination geometry (He et al., 2003). Reacting the precursor with [Fe(CN)₅(NO)]^2- is anticipated to generate cyano-bridged species.

A displacement ellipsoid plot of the title compound, (I), is illustrated in Fig. 1. The central Cu atom is coordinated by five N atoms leading to a distorted pyramidal structure with four N atoms from the L² ligand defining the equatorial plan and one N atom from the bridging CN^- ligand occupying the axial position. The Cu—N_equatorial bond lengths [range 1.998 (2)–2.032 (2) Å] is shorter than the Cu—N_axial bond lengths [2.303 (2) Å] due to the Jahn–Teller effect for the d⁹ configuration of the Cu^II ion in a pyramidal environment. The equatorial atoms (N7, N8, N11 and N12) show some deviation from coplanarity [largest deviation 0.129 (3) Å]. The coordination sphere of Cu^II shows the distortion from square pyramidal (SP) toward trigonal bipyrimidal (TBP), which can be defined by a τ value (where τ = 1.0 for a regular TBP and τ = 0.0 for a regular SP stereochemistry; Brophy et al., 1999). For the coordination environment of Cu in the present complex, a τ value of 0.19 is obtained, emphasizing that the metal centre geometry is much closer to SP rather than TBP. The bridging cyanide coordinates to the Cu^II ions in a bent fashion with the C1—N1—Cu bond angle of 141.37 (19)°, which is similar to that of related compounds (Kou et al., 1998; Zhang et al., 2002; Smekal et al., 2000; Mondal et al., 2000). The Fe···Cu distance through the cyano bridge is 5.027 (1) Å.

As usual, the [Fe(CN)₅(NO)]^2- moiety exhibits a distorted octahedral structure (C_4v), with the four equatorial CN^- ligands away from the NO⁺ ligand. This is due to the greater electronegativity of the nitrosyl group with respect to the cyanide groups. The C—Fe—NO angles are greater than 90°, and consequently the C—Fe—C5 angles are less than 90°. The mean Fe—C and C—N bond lengths are 1.938 (3) and 1.141 (3) Å, respectively. The Fe—N6 and N6—O11 bond distances are 1.657 (2) and 1.124 (3) Å. The Fe—C—N and Fe—N—O bonds are linear with the bond angles ranging from 174.8 (2) to 179.1 (3)°. These values are in good agreement with those of the previous reports (Mondal et al., 2000; Shyu et al., 1997). Like other dinuclear bimetallic nitroprussides, the cyanide ligand cis to the NO⁺ ligand serves as a bridging group to connect two metal ions with similar bridging bond angles (Ribas et al., 1984; Zhang et al., 2002).

The lattice water molecules are hydrogen bonded to the non-bridging cyanide N atom and to the primary amine atoms to produce a hydrogen-bonded three-dimensional network; details are available in Table 2.

S2. Experimental

Cu(L²)(ClO₄)₂ was synthesized as described in the literature (He et al., 2003). Slow evaporation of the aqueous solution of Cu(L²)(ClO₄)₂ and Na₂[Fe(CN)₅(NO)]·2H₂O (molar ratio, 1:1) at room temperature resulted in red crystals of (I) suitable for single-crystal analysis.

S3. Refinement

The H atoms of the water molecule were found from difference Fourier maps and refined isotropically. The H atoms bound to C and N atoms were also visible in difference maps and were placed using the HFIX commands in SHELXL97, and they were allowed for as riding atoms (C—H 0.97 Å and N—H 0.86 Å).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. A view of the title compound (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level for non-H atoms.

(I)

Crystal data

[CuFe(CN)5(C10H24N6)(NO)]·H2O	Z = 2
Mr = 525.87	F(000) = 542
Triclinic, P1	Dx = 1.568 Mg m^−3
a = 9.3360 (19) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.013 (2) Å	Cell parameters from 4565 reflections
c = 12.020 (2) Å	θ = 2.3–30°
α = 71.36 (3)°	µ = 1.65 mm^−1
β = 81.26 (3)°	T = 293 K
γ = 72.34 (3)°	Platelet, red
V = 1113.8 (4) Å^3	0.4 × 0.2 × 0.1 mm

Data collection

Bruker SMART CCD area-detector diffractometer	6292 independent reflections
Radiation source: fine-focus sealed tube	4956 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
Detector resolution: 15 × 15 microns pixels mm^-1	θmax = 30.0°, θmin = 2.3°
φ and ω scans	h = −13→8
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −15→15
Tmin = 0.566, Tmax = 0.848	l = −16→15
9026 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 0.91	w = 1/[σ^2(Fo^2) + (0.031P)^2 + 1P] where P = (Fo^2 + 2Fc^2)/3
6292 reflections	(Δ/σ)max = 0.001
280 parameters	Δρmax = 0.55 e Å^−3
0 restraints	Δρmin = −0.26 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu	0.77316 (3)	0.19966 (3)	0.23429 (2)	0.03550 (8)
Fe	0.74402 (4)	0.60421 (3)	0.35536 (3)	0.03773 (9)
N1	0.6564 (2)	0.3971 (2)	0.27783 (18)	0.0417 (4)
N11	0.8694 (2)	0.27642 (19)	0.07684 (17)	0.0378 (4)
N8	0.6274 (2)	0.17100 (19)	0.14188 (17)	0.0393 (4)
C12	0.7580 (3)	0.3966 (2)	0.0057 (2)	0.0434 (5)
H12A	0.7206	0.4602	0.0506	0.052*
H12B	0.8106	0.4382	−0.0655	0.052*
C8	0.5429 (3)	0.3037 (3)	0.0658 (2)	0.0434 (5)
H8A	0.4632	0.2910	0.0313	0.052*
H8B	0.4959	0.3613	0.1153	0.052*
N7	0.6639 (3)	0.1099 (2)	0.37816 (19)	0.0544 (6)
H7A	0.7092	0.0220	0.4022	0.065*
H7D	0.6606	0.1448	0.4371	0.065*
C1	0.6819 (3)	0.4770 (2)	0.30800 (19)	0.0360 (4)
N10	0.8183 (3)	0.1261 (2)	−0.0189 (2)	0.0481 (5)
N6	0.7541 (3)	0.5095 (3)	0.4939 (2)	0.0538 (6)
N9	0.6329 (3)	0.3697 (2)	−0.02646 (17)	0.0438 (5)
C2	0.9498 (3)	0.5218 (3)	0.3081 (2)	0.0458 (5)
C9	0.7156 (3)	0.0773 (3)	0.0710 (3)	0.0528 (6)
H9A	0.7710	−0.0042	0.1247	0.063*
H9B	0.6444	0.0547	0.0355	0.063*
N2	1.0699 (3)	0.4715 (3)	0.2814 (3)	0.0640 (7)
C14	0.9965 (3)	0.3178 (3)	0.1016 (3)	0.0554 (7)
H14A	1.0657	0.3296	0.0326	0.067*
H14B	0.9579	0.4022	0.1194	0.067*
C3	0.5399 (3)	0.7083 (3)	0.3780 (2)	0.0487 (6)
N12	0.9671 (3)	0.1821 (3)	0.3008 (2)	0.0580 (6)
H12C	0.9502	0.2378	0.3451	0.070*
H12D	1.0029	0.0983	0.3466	0.070*
C4	0.8154 (3)	0.7435 (3)	0.3749 (3)	0.0567 (7)
C13	0.9293 (3)	0.1690 (3)	0.0157 (3)	0.0521 (6)
H13A	0.9906	0.2015	−0.0538	0.063*
H13B	0.9946	0.0925	0.0678	0.063*
N3	0.4217 (3)	0.7724 (3)	0.3931 (3)	0.0702 (7)
C15	1.0775 (3)	0.2148 (3)	0.2030 (3)	0.0662 (9)
H15A	1.1328	0.1355	0.1801	0.079*
H15B	1.1488	0.2483	0.2273	0.079*
C10	0.6518 (4)	0.3376 (3)	−0.1377 (2)	0.0577 (7)
H10A	0.6893	0.4048	−0.1987	0.069*
H10B	0.5542	0.3409	−0.1590	0.069*
N4	0.8584 (4)	0.8253 (3)	0.3851 (3)	0.0897 (10)
O1	0.7584 (4)	0.4390 (3)	0.5854 (2)	0.0961 (10)
C7	0.5228 (4)	0.1047 (4)	0.2292 (3)	0.0657 (8)
H7B	0.4237	0.1351	0.1984	0.079*
H7C	0.5588	0.0091	0.2421	0.079*
C11	0.7594 (4)	0.2010 (3)	−0.1333 (3)	0.0691 (9)
H11A	0.7072	0.1495	−0.1561	0.083*
H11B	0.8431	0.2124	−0.1905	0.083*
C6	0.5117 (4)	0.1347 (4)	0.3421 (3)	0.0760 (10)
H6A	0.4564	0.2271	0.3332	0.091*
H6B	0.4579	0.0789	0.4018	0.091*
C5	0.7237 (3)	0.7078 (2)	0.1910 (2)	0.0428 (5)
N5	0.7078 (3)	0.7681 (3)	0.0943 (2)	0.0600 (6)
O2	0.1115 (3)	0.9018 (3)	0.4235 (3)	0.0776 (7)
H200	0.198 (6)	0.864 (5)	0.396 (4)	0.107 (16)*
H201	0.053 (6)	0.863 (5)	0.412 (5)	0.12 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.03836 (15)	0.03184 (14)	0.03338 (13)	−0.00707 (11)	−0.00449 (10)	−0.00680 (10)
Fe	0.04127 (18)	0.03947 (18)	0.03906 (17)	−0.01530 (14)	0.00197 (13)	−0.01824 (14)
N1	0.0477 (11)	0.0373 (10)	0.0424 (10)	−0.0130 (9)	−0.0019 (9)	−0.0138 (8)
N11	0.0369 (9)	0.0367 (9)	0.0421 (10)	−0.0102 (8)	0.0059 (8)	−0.0182 (8)
N8	0.0411 (10)	0.0364 (10)	0.0411 (10)	−0.0155 (8)	−0.0031 (8)	−0.0071 (8)
C12	0.0600 (15)	0.0315 (11)	0.0344 (11)	−0.0116 (10)	0.0040 (10)	−0.0078 (9)
C8	0.0366 (11)	0.0464 (13)	0.0427 (12)	−0.0007 (10)	−0.0071 (9)	−0.0146 (10)
N7	0.0823 (17)	0.0442 (12)	0.0361 (10)	−0.0247 (12)	0.0023 (11)	−0.0064 (9)
C1	0.0383 (11)	0.0355 (11)	0.0330 (10)	−0.0096 (9)	−0.0006 (8)	−0.0097 (8)
N10	0.0484 (12)	0.0442 (11)	0.0553 (13)	−0.0033 (9)	−0.0038 (10)	−0.0276 (10)
N6	0.0649 (15)	0.0696 (16)	0.0418 (12)	−0.0344 (13)	−0.0022 (10)	−0.0214 (11)
N9	0.0551 (12)	0.0373 (10)	0.0323 (9)	−0.0028 (9)	−0.0049 (9)	−0.0090 (8)
C2	0.0475 (14)	0.0478 (14)	0.0516 (14)	−0.0192 (11)	−0.0030 (11)	−0.0213 (11)
C9	0.0606 (17)	0.0370 (13)	0.0672 (17)	−0.0115 (12)	−0.0135 (14)	−0.0208 (12)
N2	0.0460 (13)	0.0764 (18)	0.0796 (18)	−0.0165 (13)	0.0020 (12)	−0.0392 (15)
C14	0.0440 (14)	0.0662 (18)	0.0704 (18)	−0.0274 (13)	0.0150 (13)	−0.0359 (15)
C3	0.0516 (15)	0.0555 (15)	0.0487 (14)	−0.0190 (12)	0.0072 (11)	−0.0288 (12)
N12	0.0521 (13)	0.0564 (14)	0.0639 (15)	−0.0003 (11)	−0.0234 (12)	−0.0199 (12)
C4	0.0544 (16)	0.0521 (16)	0.0747 (19)	−0.0162 (13)	−0.0044 (14)	−0.0313 (14)
C13	0.0432 (13)	0.0528 (15)	0.0657 (17)	−0.0052 (11)	0.0075 (12)	−0.0365 (13)
N3	0.0542 (15)	0.084 (2)	0.0781 (19)	−0.0118 (14)	0.0081 (14)	−0.0428 (16)
C15	0.0350 (13)	0.074 (2)	0.101 (3)	−0.0058 (13)	−0.0057 (15)	−0.050 (2)
C10	0.075 (2)	0.0601 (17)	0.0329 (12)	−0.0077 (15)	−0.0078 (12)	−0.0141 (12)
N4	0.085 (2)	0.0680 (19)	0.141 (3)	−0.0291 (17)	−0.017 (2)	−0.053 (2)
O1	0.143 (3)	0.122 (2)	0.0422 (12)	−0.080 (2)	−0.0177 (14)	−0.0022 (13)
C7	0.0629 (19)	0.075 (2)	0.0647 (18)	−0.0413 (17)	0.0024 (15)	−0.0088 (16)
C11	0.084 (2)	0.074 (2)	0.0493 (16)	−0.0012 (17)	−0.0066 (15)	−0.0364 (16)
C6	0.082 (2)	0.089 (3)	0.0613 (19)	−0.049 (2)	0.0243 (18)	−0.0159 (18)
C5	0.0447 (13)	0.0385 (12)	0.0481 (13)	−0.0179 (10)	0.0046 (10)	−0.0137 (10)
N5	0.0680 (16)	0.0538 (14)	0.0536 (14)	−0.0227 (12)	0.0039 (12)	−0.0071 (11)
O2	0.0551 (14)	0.0837 (18)	0.102 (2)	−0.0005 (13)	−0.0116 (14)	−0.0514 (16)

Geometric parameters (Å, º)

Cu—N7	1.998 (2)	N6—O1	1.124 (3)
Cu—N11	2.006 (2)	N9—C10	1.462 (3)
Cu—N12	2.021 (2)	C2—N2	1.138 (4)
Cu—N8	2.032 (2)	C9—H9A	0.9700
Cu—N1	2.303 (2)	C9—H9B	0.9700
Fe—N6	1.657 (2)	C14—C15	1.490 (5)
Fe—C1	1.931 (2)	C14—H14A	0.9700
Fe—C3	1.933 (3)	C14—H14B	0.9700
Fe—C4	1.937 (3)	C3—N3	1.139 (4)
Fe—C2	1.944 (3)	N12—H12C	0.9000
Fe—C5	1.945 (3)	N12—H12D	0.9000
N1—C1	1.149 (3)	C4—N4	1.136 (4)
N11—C14	1.492 (3)	C13—H13A	0.9700
N11—C12	1.509 (3)	C13—H13B	0.9700
N11—C13	1.511 (3)	C15—H15A	0.9700
N8—C7	1.490 (3)	C15—H15B	0.9700
N8—C8	1.503 (3)	C10—C11	1.525 (4)
N8—C9	1.517 (3)	C10—H10A	0.9700
C12—N9	1.422 (3)	C10—H10B	0.9700
C12—H12A	0.9700	C7—C6	1.478 (5)
C12—H12B	0.9700	C7—H7B	0.9700
C8—N9	1.427 (3)	C7—H7C	0.9700
C8—H8A	0.9700	C11—H11A	0.9700
C8—H8B	0.9700	C11—H11B	0.9700
N7—C6	1.469 (4)	C6—H6A	0.9700
N7—H7A	0.9000	C6—H6B	0.9700
N7—H7D	0.9000	C5—N5	1.146 (3)
N10—C9	1.415 (4)	O2—H200	0.86 (5)
N10—C13	1.423 (3)	O2—H201	0.83 (5)
N10—C11	1.450 (4)
N7—Cu—N11	171.25 (9)	C12—N9—C10	116.3 (2)
N7—Cu—N12	100.91 (11)	C8—N9—C10	116.8 (2)
N11—Cu—N12	85.99 (10)	N2—C2—Fe	178.8 (3)
N7—Cu—N8	86.10 (9)	N10—C9—N8	116.0 (2)
N11—Cu—N8	85.68 (8)	N10—C9—H9A	108.3
N12—Cu—N8	160.36 (9)	N8—C9—H9A	108.3
N7—Cu—N1	87.62 (9)	N10—C9—H9B	108.3
N11—Cu—N1	97.56 (8)	N8—C9—H9B	108.3
N12—Cu—N1	92.26 (9)	H9A—C9—H9B	107.4
N8—Cu—N1	106.46 (8)	C15—C14—N11	110.1 (2)
N6—Fe—C1	91.91 (10)	C15—C14—H14A	109.6
N6—Fe—C3	94.37 (13)	N11—C14—H14A	109.6
C1—Fe—C3	93.64 (10)	C15—C14—H14B	109.6
N6—Fe—C4	97.24 (13)	N11—C14—H14B	109.6
C1—Fe—C4	170.32 (12)	H14A—C14—H14B	108.2
C3—Fe—C4	88.84 (12)	N3—C3—Fe	177.4 (3)
N6—Fe—C2	94.77 (13)	C15—N12—Cu	108.84 (18)
C1—Fe—C2	88.05 (10)	C15—N12—H12C	109.9
C3—Fe—C2	170.64 (12)	Cu—N12—H12C	109.9
C4—Fe—C2	88.03 (12)	C15—N12—H12D	109.9
N6—Fe—C5	175.86 (10)	Cu—N12—H12D	109.9
C1—Fe—C5	84.12 (10)	H12C—N12—H12D	108.3
C3—Fe—C5	84.74 (12)	N4—C4—Fe	179.1 (3)
C4—Fe—C5	86.79 (12)	N10—C13—N11	115.5 (2)
C2—Fe—C5	86.28 (12)	N10—C13—H13A	108.4
C1—N1—Cu	141.37 (19)	N11—C13—H13A	108.4
C14—N11—C12	109.5 (2)	N10—C13—H13B	108.4
C14—N11—C13	110.0 (2)	N11—C13—H13B	108.4
C12—N11—C13	112.30 (19)	H13A—C13—H13B	107.5
C14—N11—Cu	105.93 (16)	N12—C15—C14	109.0 (2)
C12—N11—Cu	110.24 (14)	N12—C15—H15A	109.9
C13—N11—Cu	108.67 (16)	C14—C15—H15A	109.9
C7—N8—C8	111.0 (2)	N12—C15—H15B	109.9
C7—N8—C9	108.3 (2)	C14—C15—H15B	109.9
C8—N8—C9	112.57 (19)	H15A—C15—H15B	108.3
C7—N8—Cu	107.10 (17)	N9—C10—C11	113.4 (2)
C8—N8—Cu	108.99 (14)	N9—C10—H10A	108.9
C9—N8—Cu	108.70 (15)	C11—C10—H10A	108.9
N9—C12—N11	115.04 (19)	N9—C10—H10B	108.9
N9—C12—H12A	108.5	C11—C10—H10B	108.9
N11—C12—H12A	108.5	H10A—C10—H10B	107.7
N9—C12—H12B	108.5	C6—C7—N8	110.9 (2)
N11—C12—H12B	108.5	C6—C7—H7B	109.5
H12A—C12—H12B	107.5	N8—C7—H7B	109.5
N9—C8—N8	114.8 (2)	C6—C7—H7C	109.5
N9—C8—H8A	108.6	N8—C7—H7C	109.5
N8—C8—H8A	108.6	H7B—C7—H7C	108.1
N9—C8—H8B	108.6	N10—C11—C10	114.1 (2)
N8—C8—H8B	108.6	N10—C11—H11A	108.7
H8A—C8—H8B	107.6	C10—C11—H11A	108.7
C6—N7—Cu	104.88 (18)	N10—C11—H11B	108.7
C6—N7—H7A	110.8	C10—C11—H11B	108.7
Cu—N7—H7A	110.8	H11A—C11—H11B	107.6
C6—N7—H7D	110.8	N7—C6—C7	109.2 (3)
Cu—N7—H7D	110.8	N7—C6—H6A	109.8
H7A—N7—H7D	108.8	C7—C6—H6A	109.8
N1—C1—Fe	174.8 (2)	N7—C6—H6B	109.8
C9—N10—C13	116.7 (2)	C7—C6—H6B	109.8
C9—N10—C11	116.7 (3)	H6A—C6—H6B	108.3
C13—N10—C11	116.5 (3)	N5—C5—Fe	178.0 (2)
O1—N6—Fe	175.3 (2)	H200—O2—H201	105 (4)
C12—N9—C8	117.52 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7A···N4^i	0.90	2.25	3.092 (4)	156
N7—H7D···N3^ii	0.90	2.42	3.295 (4)	163
N12—H12D···O2^iii	0.90	2.06	2.947 (4)	169
O2—H200···N3	0.86 (5)	2.02 (5)	2.838 (4)	158 (4)
O2—H201···N4^iv	0.83 (5)	2.08 (5)	2.881 (4)	162 (5)
N12—H12C···O2^ii	0.90	2.78	3.174 (4)	108

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