Crystal structures of tetra-methyl-ammonium (2,2'-bi-pyridine)-tetra-cyanidoferrate(III) trihydrate and poly[[(2,2'-bi-pyridine-κ(2) N,N')di-μ2-cyanido-dicyanido(μ-ethyl-enedi-amine)(ethyl-enedi-amine-κ(2) N,N')-cadmium(II)iron(II)] monohydrate].

The crystal structures of the building block tetra-methyl-ammonium (2,2'-bi-pyridine-κ(2) N,N')tetra-cyanidoferrate(III) trihydrate, [N(CH3)4][Fe(CN)4(C10H8N2)]·3H2O, (I), and a new two-dimensional cyanide-bridged bimetallic coordination polymer, poly[[(2,2'-bi-pyridine-κ(2) N,N')di-μ2-cyanido-dicyanido(μ-ethyl-enedi-amine-κ(2) N:N')(ethyl-enedi-amine-κ(2) N,N')cadmium(II)iron(II)] monohydrate], [CdFe(CN)4(C10H8N2)(C2H8N2)2]·H2O, (II), are reported. In the crystal of (I), pairs of [Fe(2,2'-bipy)(CN)4](-) units (2,2'-bipy is 2,2'-bi-pyri-dine) are linked together through π-π stacking between the pyridyl rings of the 2,2'-bipy ligands to form a graphite-like structure parallel to the ab plane. The three independent water mol-ecules are hydrogen-bonded alternately with each other, forming a ladder chain structure with R 4 (4)(8) and R 6 (6)(12) graph-set ring motifs, while the disordered [N(CH3)4](+) cations lie above and below the water chains, and the packing is stabilized by weak C-H⋯O hydrogen bonds. The water chains are further linked with adjacent sheets into a three-dimensional network via O-H⋯O hydrogen bonds involving the lattice water mol-ecules and the N atoms of terminal cyanide groups of the [Fe(2,2'-bipy)(CN)4](-) building blocks, forming an R 4 (4)(12) ring motif. Compound (II) features a two-dimensional {[Fe(2,2'-bipy)(CN)4Cd(en)2]} n layer structure (en is ethyl-enedi-amine) extending parallel to (010) and constructed from {[Fe(2,2'-bipy)(CN)4Cd(en)]} n chains inter-linked by bridging en ligands at the Cd atoms. Classical O-H⋯N and N-H⋯O hydrogen bonds involving the lattice water mol-ecule and N atoms of terminal cyanide groups and the N-H groups of the en ligands are observed within the layers. The layers are further connected via π-π stacking inter-actions between adjacent pyridine rings of the 2,2'-bipy ligands, completing a three-dimensional supra-molecular structure.

Chemical context

Over the past several decades, hexa­cyanido­metallate anions, [M(CN)6] (n = 2–4), have been used extensively as building blocks for the design and construction of a large number of high-dimensional cyanide-bridged bimetallic coordination polymers because of their ability to act as multidentate ligands to link numerous metal atoms through all six cyanide groups (Ohba & Ōkawa, 2000 ▸; Smith et al., 2000 ▸; Berlinguette et al., 2005 ▸). The highly insoluble three-dimensional Prussian blue and its more soluble Prussian blue analogues are perhaps the best known examples of this class of compounds, which are obtained by reacting the building block [M(CN)6]3– with octa­hedrally coordinated transition metal ions (Buser et al., 1977 ▸). The inclusion of a bidentate chelating ligand (L) such as 2,2′-bi­pyridine (2,2′-bipy) or 1,10-phenanthroline (1,10-phen) in cyanide-containing building blocks of general formula [M(L)(CN)4] (n = 2, 3) instead of [M(CN)6] has been a recent development in the field of low-dimensionality cyanide-bridged bimetallic coordination compounds (Lescouëzec et al., 2001 ▸; Laza­rides et al., 2007 ▸). The aromatic ligand L does not just block two coordination sites of the central atom, to yield one- and two-dimensional polymeric compounds, but also helps to stabilize the assembly as well as stabilizing the dimensionality of the three-dimensional supra­molecular structures through aromatic π–π stacking inter­actions (Lescouëzec et al., 2002 ▸; Toma et al., 2004 ▸). It is also known that the non-coordinating nitro­gen atoms of the cyanide groups can act as hydrogen-bond acceptors to self-assemble into various supra­molecular architectures (Xiang et al., 2009 ▸).

As part of our search for novel cyanide-bridged bimetallic coordination polymers, we herein describe the synthesis and crystal structure of [N(CH3)4][Fe(CN)4(C10H8N2)]·3H2O (I) building block and a new two-dimensional cyanide-bridged cadmium–iron(II) bimetallic coordination polymer, [CdFe(CN4)(C10H8N2)(C2H8N2)2]·H2O (II), in which ethylenedi­amine (en) adopts both bridging and chelating coordination modes.

Structural commentary

The asymmetric unit of (I) consists of one [Fe(2,2′-bipy)(CN)4]− anion, one disordered tetra­methyl­ammonium cation, [N(CH3)4]+ and three water mol­ecules, as displayed in Fig. 1 ▸. The FeIII ion is coordinated by two nitro­gen atoms from one 2,2′-bipy ligand and four cyanide carbon atoms in a distorted octa­hedral geometry. This distortion around the metal atom is defined by the sum of the octa­hedral angular deviations from 90° (Σ), in which the trigonal distortion angle = 0 for a perfect octa­hedron (Marchivie et al., 2005 ▸). In (I), Σ for twelve bond angles, viz, 5C—Fe—C, 6C—Fe—N and 1N—Fe—N, is 41.03°, confirming a distorted octa­hedral geometry around the central FeIII ion. Another factor accounting for the distortion form ideal octa­hedral geometry of the FeIII atom is the acute angle subtended by the chelating 2,2′-bipy ligand, viz. N5—Fe1—N6 = 81.14 (11)°. The three trans angles [viz. C1—Fe1—N5 = 175.01 (15), C2—Fe1—N6 = 175.52 (14) and C3—Fe1—C4 = 178.06 (15)°] are bent slightly from the ideal value of 180°. The iron atom and terminal cyanido groups, viz. [Fe1—C3≡N3 = 178.7 (3) and Fe1—C4≡N4 = 179.8 (4)°] are almost linear compared to the iron atom and the corresponding equatorial cyano groups [viz. Fe1—C1—N1 = 175.8 (4) and Fe1—C2—N2 = 176.6 (4)°]. This difference is probably caused by hydrogen bonding (see below). The Fe—C bond lengths range from 1.917 (4) to 1.969 (4) Å, whereas the Fe—N bond lengths are 1.981 (3) and 1.985 (3) Å. The whole mol­ecule of 2,2′-bipy ligand is planar with an r.m.s. deviation of 0.016 Å; the dihedral angle between the two pyridyl rings is 1.57 (18)°. Bond lengths and angles within the [Fe(2,2′-bipy)(CN)4]− anion in (I) are in agreement with those reported for other cyanido and 2,2′-bipy-containing mononuclear iron(III) complexes such as K[Fe(2,2′-bipy)(CN)4]·H2O (Toma et al., 2002 ▸), PPh4[Fe(2,2′-bipy)(CN)4]·H2O (Lescouëzec et al., 2002 ▸) and AsPPh4[Fe(2,2′-bipy)(CN)4]·CH3CN (Toma et al., 2007 ▸).

Figure 1

The asymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 35% probability level. Dashed lines indicate O—H⋯O hydrogen bonds. Covalent bonds in the major and minor parts of the disordered are shaded differently and H atoms have been omitted for clarity. The labelling scheme A and B applied to the aromatic rings is used to identify the rings in the subsequent discussion.

Compound (II) is a new cyanido-bridged Fe–Cd bimetallic coordination polymer synthesized using the precursor complex (I) as building block in which the FeIII precursor was reduced to FeII under the crystallization conditions. The asymmetric unit contains half each of an [Fe(2,2′-bipy)(CN)4]− anion and a [Cd(en)2]2+ cation, with the mol­ecules lying across twofold rotation axes, Fig. 2 ▸. The coordination polyhedron of FeII ion is a distorted octa­hedron with a Σ of 28.90°. The Fe—C—N angles for both bridging [Fe1—C1—N1 = 178.15 (14)°] and terminal [Fe1—C2—N2 = 176.85 (16)°] cyanide groups deviate slightly from strict linearity. The Fe—Ccyanide bond lengths at 1.8950 (16) and 1.9363 (17) Å are slightly shorter than the Fe—N2,2′-bipy bond length, 1.9976 (14) Å. The CdII ion is six-coordinated by two N atoms from two cyanide groups, two N atoms from a chelating en ligand and two N atoms from two different bridging en ligands in a highly distorted octa­hedral geometry with a Σ of 108.08°. The Cd—N bond lengths and the N—Cd—N bond angles in (II) are in the range 2.3980 (15)–2.5046 (14) Å and 73.24 (5)–157.20 (5)°, respectively. These values are comparable to those observed in compounds (Et4N)[{Fe(CN)6}3{Cd(en)}4] (Maľarová et al., 2003 ▸), [Fe(CN)6Cd(en)2] (Fu & Wang, 2005 ▸) and [{Fe(CN)6}2{Cd(en)}3]·4H2O (Maľarová et al., 2006 ▸). Each [Fe(2,2′-bipy)(CN)4]2– anion uses two cyanide groups to link [Cd(en)]2+cations, forming a chain of [Fe(2,2′-bipy)(CN)4Cd(en)] units running parallel to the a axis. Along the b axis, adjacent chains are then inter­connected through the N atoms of the bridging en ligands at the Cd atoms into a two-dimensional layer of [Fe(2,2′-bipy)(CN)4Cd(en)2], as shown in Fig. 3 ▸. The layer contains hexa­nuclear cyclic [{Fe(CN)2}2{Cd(en)}2] units with an Fe⋯Cd distance through the cyanide bridge and a Cd⋯Cd distance through the en bridge of 5.1292 (7) and 7.6692 (12) Å, respectively. The M⋯M distances across the cyclic windows vary from 5.5614 (10) to 14.0061 (10) Å.

Figure 2

The structures of the molecular entities in (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 35% probability level. The pyridine ring labelled C is discussed in the text. [Symmetry codes: (i) 1 − x, y,  − z; (ii) −x, y,  − z.]

Figure 3

A view of the layer structure of (II) along the b axis. 2,2′-Bipy mol­ecules and H atoms bonded to C and N atoms of the en ligands have been omitted for clarity.

Supra­molecular features

The three-dimensional supra­molecular structure in (I) is the result of combinations of inter­molecular inter­actions including aromatic π–π stacking and hydrogen bonds. As can be seen in Fig. 4 ▸, pairs of [Fe(2,2′-bipy)(CN)4]− mol­ecules are linked together through the parallel pyridyl rings of the 2,2′-bipy ligands to generate a graphite-like layers parallel to the ab plane. Within the sheets, the neighbouring pyridyl moieties related by an inversion centre are in a head-to-head arrangement with centroid (C g) to centroid distances of 4.005 (3) Å [inter­planar angle = 0.0 (4)°] and 3.903 (3) Å [inter­planar angle = 0.0 (3)°] for rings A⋯A i and B⋯B ii [symmetry codes: (i) −x, 2 − y, 1 − z; (ii) 1 − x, 1 − y, 1 − z], respectively. The FeIII⋯FeIII separations along the π–π stacking of parallel rings A⋯A i and rings B⋯B ii are 8.2821 (12) and 8.4572 (13) Å, respectively. The adjacent pyridyl rings A and B iii [symmetry code: (iii) x − 1, y, z] related by translation parallel to the a axis are arranged alternately in a head-to-tail manner with a C g⋯C g distance of 3.865 (2) Å [inter­planar angle = 1.51 (12)°] and an FeIII⋯FeIII separation of 6.8690 (9) Å.

Figure 4

A view of the two-dimensional anionic [Fe(2,2′-bipy)(CN)4]− graphite-like sheet structure in (I), parallel to the ab plane, with π–π inter­actions shown as dashed lines. H atoms have been omitted for clarity.

A notable feature of (I) is the self-assembly of the tetra­meric (H2O)4 and hexa­meric (H2O)6 subunits into (H2O)10 units [the dihedral angle between the best plane of the (H2O)4 and (H2O)6 subunits is 55.2 (2)°]; neighbouring units are further joined together, giving rise to ladder-like water chains running parallel to the a axis. As can be seen from Fig. 5 ▸, the water mol­ecules at O1, O1i, O2, and O2i (for symmetry code see Table 1 ▸) form centrosymmetric cyclic tetra­meric units through classical O—H⋯O hydrogen bonds with an (8) ring motif according to graph-set notation. In this unit, each water monomer acts as a single donor and a single acceptor of hydrogen bonds, and the four water mol­ecules are perfectly coplanar (mean deviation of all non-hydrogen atoms = 0.00 Å). The average O⋯O distance in (I) is 2.805 Å. This value is comparable to the average distances for the gas-phase water tetra­mer (D2O)4 (2.78 Å; Liu et al., 1996 ▸), liquid water (2.85 Å; Belch & Rice, 1987 ▸) and other tetra­meric water units in the solid state (2.81 Å; Tao et al., 2004 ▸, and 2.83 Å; Long et al., 2004 ▸). The average O⋯O⋯O angle is 90°, which is similar to those of the cyclic water tetra­mer found in liquid water and in the crystal host of metal–organic frameworks, [Cu(adipate)(4,4-bipy)]·2H2O (Long et al., 2004 ▸) and [Cd3(pbtz)3(DMF)4(H2O)2]·4DMF·4H2O (Tao et al., 2004 ▸).

Figure 5

Self-assembly of the water tetra­mer (H2O)4 and hexa­mer (H2O)6 by O—H⋯O hydrogen bonds into the ladder-like chain, and representation of O—H⋯N hydrogen bonds between the water chain and anionic [Fe(2,2′-bipy)(CN)4]− units. See Table 1 ▸ for symmetry codes.

Table 1

Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17A—H17C⋯O2i	0.96	2.50	3.112 (11)	122
O3—H3A⋯N4	0.84 (1)	2.00 (1)	2.841 (5)	178 (5)
O1—H1A⋯N1	0.84 (1)	2.03 (1)	2.859 (5)	176 (7)
O3—H3B⋯O1ii	0.85 (1)	1.89 (1)	2.736 (6)	174 (7)
O2—H2A⋯O3	0.84 (1)	1.87 (2)	2.709 (6)	172 (7)
O2—H2B⋯O1	0.84 (1)	1.98 (1)	2.818 (7)	177 (14)
O1—H1B⋯O2iii	0.84 (1)	2.02 (6)	2.792 (8)	152 (11)

Symmetry codes: (i) ; (ii) ; (iii) .

The hexa­meric water unit has crystallographically imposed inversion symmetry. The six water mol­ecules O1i, O1ii, O2, O2iii, O3, and O3iii (for symmetry codes, see Table 1 ▸) are almost coplanar with a mean deviation of 0.025 Å. Similar to the situation in the tetra­meric water unit, each water mol­ecule acts as both a single hydrogen-bond donor and acceptor, and is simultaneously involved in classical O—H⋯O inter­actions, leading to a cyclic (12) hydrogen-bonding motif with an average O⋯O distance of 2.786 Å. This value is slightly shorter than the average distance for the tetra­meric unit and liquid water; however, it is comparable with the distance in ice I h (2.74 Å; Eisenberg & Kauzmann, 1969 ▸) and water trapped in a metal–organic framework (2.78 Å; Ghosh & Bharadwaj, 2003 ▸). The average O⋯O⋯O angle in the planar hexa­meric unit is 120°, deviating considerably from the corresponding value of 109.3° in hexa­gonal ice (Fletcher, 1970 ▸). Another remarkable feature in (I) is that the ladder-like water chains are incorporated with the aromatic π–π stacking graphite-like layers through classical O—H⋯N hydrogen bonds involving the lattice water mol­ecules (O1 and O3) and the N atoms of the cyanido groups (N1 and N4), forming an (12) ring motif. In addition, the [N(CH3)]+ cations lie above and below the water chains and take part in the formation of weak C—H⋯O hydrogen bonds with the water mol­ecule.

For (II), classical O—H⋯N and N—H⋯O hydrogen bonds involving the lattice water mol­ecules and N atoms of terminal cyanide groups and the N—H group of the en ligands are observed within a layer, Table 2 ▸. The layers are further linked together into a three-dimensional network via π–π stacking between adjacent pyridyl rings with C g⋯C g distances of 4.2925 (18) [inter­planar angle = 1.55 (18)°] and 4.0642 (18) Å [inter­planar angle = 0.0 (3)°] for rings C⋯C iv and C⋯C v [symmetry codes: (iv) 2 − x, y,  − z; (v)  − x,  − y, 1 − z], respectively, Fig. 6 ▸.

Table 2

Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯O1i	0.89	2.20	3.0726 (18)	167
O1—H1⋯N2	0.87 (1)	1.99 (1)	2.8045 (19)	156 (2)

Symmetry code: (i) .

Figure 6

A portion of the crystal packing in (II) viewed in the bc plane showing π–π stacking inter­actions (dashed lines).

Synthesis and crystallization

The building block N(CH3)4[Fe(2,2′-bipy)(CN)4]·3H2O (I) was prepared following the procedure described for PPh4[Fe(2,2′-bipy)(CN)4]·H2O (Lescouëzec et al., 2002 ▸), except that tetra­methyl­ammonium chloride was used instead of tetra­phenyl­phospho­nium chloride. Dark-red single crystals of (I) suitable for structure determination were obtained by recrystallization from water and methanol (1:1, v/v). Analysis calculated for C18H26FeN7O: C, 48.66; H, 5.90; N, 22.07%. Found: C, 48.66; H, 5.90; N, 22.07%.

For the synthesis of (II), Cd(NO3)2·4H2O (0.062 g, 0.2 mmol) and ethyl­enedi­amine (stock solution, 0.01 ml, 0.2 mmol) were dissolved in distilled H2O (4 ml), and this was pipetted into one side of an H-tube. N(CH3)4[Fe(2,2′-bipy)(CN)4]·3H2O (0.089 g, 0.2 mmol) was dissolved in distilled H2O (4 ml), and this was pipetted into the other side arm of the H-tube. The H-tube (15 ml capacity) was then carefully filled with distilled H2O. Slow diffusion in the dark for three weeks yielded dark-yellow plate-shaped crystals of (II) suitable for X-ray crystallographic analysis. Analysis calculated for C18H26CdFeN10O: C, 38.15; H, 4.62; N, 24.72%. Found: C, 38.18; H, 4.60; N, 24.68%.

Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 3 ▸. H atoms bonded to C and N atoms were placed at calculated positions and refined using a riding-model approximation, with C—H = 0.93 (aromatic), 0.96 (meth­yl) or 0.97 (methyl­ene) Å and N—H = 0.89 Å, and with U iso(H) = 1.5U eq(C) for methyl groups and 1.2U eq(C, N) otherwise. For (I), the water-H atoms were located in a difference Fourier map and refined with distance restraints: O—H = 0.84 (1) Å and H⋯H = 1.39 (2) Å with U iso(H) = 1.5U eq(O). For (II), the water-H atoms were refined with restraints of O—H = 0.82 (1) Å with U iso(H) = 1.5U eq(O). The tetra­metyl­ammonium cation in (I) exhibits rotational positional disorder in three of the methyl groups, and was refined with occupancy factors of 0.440 (6) for C16A, C17A and C18A, and 0.560 (6) for atoms C16B, C17B, and C18B. Anisotropic displacement parameters of all atoms were restrained using enhanced rigid-bond restraints (RIGU command, s.u.’s 0.001 Å2; Thorn et al., 2012 ▸). The restraint SADI was also used for the disordered tetra­metyl­ammonium cation.

Table 3

Experimental details

	(I)	(II)
Crystal data
Chemical formula	(C4H12N)[Fe(CN)4(C10H8N2)]·3H2O	[CdFe(CN)4(C10H8N2)(C2H8N2)2]·H2O
M r	444.31	566.74
Crystal system, space group	Triclinic, P	Monoclinic, C2/c
Temperature (K)	296	296
a, b, c (Å)	6.8690 (9), 11.9405 (16), 14.2731 (17)	7.4184 (14), 28.534 (5), 11.094 (2)
α, β, γ (°)	104.107 (4), 99.695 (4), 92.235 (4)	90, 109.143 (6), 90
V (Å3)	1115.2 (2)	2218.3 (7)
Z	2	4
Radiation type	Mo Kα	Mo Kα
μ (mm−1)	0.71	1.65
Crystal size (mm)	0.22 × 0.16 × 0.08	0.30 × 0.26 × 0.14
Data collection
Diffractometer	Bruker APEXII D8 QUEST CMOS	Bruker APEXII D8 QUEST CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 ▸)	Multi-scan (SADABS; Bruker, 2014 ▸)
T min, T max	0.691, 0.745	0.633, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	20120, 3982, 3015	51158, 2757, 2478
R int	0.072	0.038
(sin θ/λ)max (Å−1)	0.599	0.667
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.053, 0.142, 1.04	0.020, 0.046, 1.07
No. of reflections	3982	2757
No. of parameters	321	146
No. of restraints	87	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.72, −0.59	0.47, −0.47

Computer programs: APEX2 and SAINT (Bruker, 2014 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL2014 (Sheldrick, 2015b ▸), OLEX2 (Dolomanov et al., 2009 ▸), publCIF (Westrip, 2010 ▸) and enCIFer (Allen et al., 2004 ▸).

Crystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989016006848/bg2584sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016006848/bg2584Isup2.hkl

Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989016006848/bg2584IIsup3.hkl

CCDC references: 1476008, 1476007

Additional supporting information: crystallographic information; 3D view; checkCIF report

(C4H12N)[Fe(CN)4(C10H8N2)]·3H2O	Z = 2
Mr = 444.31	F(000) = 466
Triclinic, P1	Dx = 1.323 Mg m−3
a = 6.8690 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.9405 (16) Å	Cell parameters from 9941 reflections
c = 14.2731 (17) Å	θ = 3.0–36.4°
α = 104.107 (4)°	µ = 0.71 mm−1
β = 99.695 (4)°	T = 296 K
γ = 92.235 (4)°	Block, orange
V = 1115.2 (2) Å3	0.22 × 0.16 × 0.08 mm

Bruker APEXII D8 QUEST CMOS diffractometer	3982 independent reflections
Radiation source: microfocus sealed x-ray tube, Incoatec Iµus	3015 reflections with I > 2σ(I)
GraphiteDouble Bounce Multilayer Mirror monochromator	Rint = 0.072
Detector resolution: 10.5 pixels mm-1	θmax = 25.2°, θmin = 3.0°
ω and φ scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −14→14
Tmin = 0.691, Tmax = 0.745	l = −16→17
20120 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.142	w = 1/[σ2(Fo2) + (0.0712P)2 + 0.9213P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
3982 reflections	Δρmax = 0.72 e Å−3
321 parameters	Δρmin = −0.59 e Å−3
87 restraints

Experimental. Absorption correction: SADABS-2014/4 (Bruker,2014/4) was used for absorption correction. wR2(int) was 0.0760 before and 0.0587 after correction. The Ratio of minimum to maximum transmission is 0.9266. The λ/2 correction factor is 0.00150.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Fe1	0.66815 (7)	0.18786 (4)	0.33212 (4)	0.03351 (19)
N1	0.3698 (6)	0.2365 (4)	0.1661 (3)	0.0673 (11)
N2	0.8300 (7)	0.0198 (4)	0.1707 (3)	0.0754 (12)
N3	0.4210 (6)	−0.0265 (3)	0.3445 (3)	0.0589 (9)
N4	0.9261 (6)	0.3973 (3)	0.3139 (3)	0.0596 (10)
N5	0.8717 (4)	0.1745 (2)	0.4441 (2)	0.0316 (6)
N6	0.5553 (4)	0.2840 (2)	0.4410 (2)	0.0329 (6)
C1	0.4755 (6)	0.2152 (3)	0.2280 (3)	0.0458 (9)
C2	0.7745 (6)	0.0849 (4)	0.2313 (3)	0.0467 (10)
C3	0.5079 (5)	0.0512 (3)	0.3399 (2)	0.0353 (8)
C4	0.8320 (6)	0.3212 (4)	0.3207 (3)	0.0415 (9)
C5	1.0370 (5)	0.1194 (3)	0.4385 (3)	0.0368 (8)
H5	1.0615	0.0823	0.3768	0.044*
C6	1.1713 (5)	0.1153 (3)	0.5197 (3)	0.0420 (9)
H6	1.2849	0.0764	0.5132	0.050*
C7	1.1364 (6)	0.1694 (3)	0.6109 (3)	0.0456 (9)
H7	1.2248	0.1668	0.6672	0.055*
C8	0.9667 (6)	0.2285 (3)	0.6182 (3)	0.0449 (9)
H8	0.9404	0.2664	0.6793	0.054*
C9	0.8387 (5)	0.2298 (3)	0.5336 (3)	0.0341 (8)
C10	0.6566 (5)	0.2913 (3)	0.5321 (3)	0.0346 (8)
C11	0.5933 (6)	0.3533 (3)	0.6147 (3)	0.0460 (9)
H11	0.6665	0.3583	0.6769	0.055*
C12	0.4214 (6)	0.4078 (3)	0.6046 (3)	0.0495 (10)
H12	0.3767	0.4498	0.6597	0.059*
C13	0.3164 (6)	0.3992 (3)	0.5119 (3)	0.0458 (10)
H13	0.1994	0.4353	0.5034	0.055*
C14	0.3861 (5)	0.3368 (3)	0.4321 (3)	0.0388 (8)
H14	0.3139	0.3308	0.3696	0.047*
N7	0.7782 (5)	0.1799 (3)	0.9466 (2)	0.0597 (8)
C15	0.7397 (8)	0.0530 (4)	0.9254 (4)	0.0789 (12)
H15A	0.7621	0.0296	0.9859	0.118*
H15B	0.8272	0.0161	0.8838	0.118*
H15C	0.6048	0.0307	0.8928	0.118*
C16A	0.901 (2)	0.1995 (11)	0.8753 (9)	0.078 (2)	0.440 (6)
H16A	0.8350	0.1608	0.8099	0.116*	0.440 (6)
H16B	1.0272	0.1693	0.8889	0.116*	0.440 (6)
H16C	0.9202	0.2811	0.8809	0.116*	0.440 (6)
C16B	0.7816 (19)	0.2208 (9)	0.8579 (6)	0.081 (2)	0.560 (6)
H16D	0.6484	0.2199	0.8237	0.121*	0.560 (6)
H16E	0.8551	0.1709	0.8158	0.121*	0.560 (6)
H16F	0.8436	0.2984	0.8760	0.121*	0.560 (6)
C17A	0.5779 (14)	0.2172 (11)	0.9193 (10)	0.085 (2)	0.440 (6)
H17A	0.4813	0.1690	0.9361	0.128*	0.440 (6)
H17B	0.5497	0.2105	0.8499	0.128*	0.440 (6)
H17C	0.5729	0.2964	0.9542	0.128*	0.440 (6)
C17B	0.6394 (16)	0.2374 (9)	1.0058 (8)	0.091 (2)	0.560 (6)
H17D	0.6423	0.3177	1.0052	0.137*	0.560 (6)
H17E	0.6766	0.2312	1.0721	0.137*	0.560 (6)
H17F	0.5079	0.2011	0.9789	0.137*	0.560 (6)
C18A	0.846 (2)	0.2542 (10)	1.0479 (6)	0.080 (2)	0.440 (6)
H18A	0.8136	0.3322	1.0500	0.120*	0.440 (6)
H18B	0.9863	0.2531	1.0664	0.120*	0.440 (6)
H18C	0.7803	0.2253	1.0927	0.120*	0.440 (6)
C18B	0.9780 (11)	0.1987 (8)	1.0119 (7)	0.0764 (19)	0.560 (6)
H18D	1.0251	0.2790	1.0273	0.115*	0.560 (6)
H18E	1.0690	0.1522	0.9787	0.115*	0.560 (6)
H18F	0.9678	0.1770	1.0715	0.115*	0.560 (6)
O3	1.0432 (6)	0.5315 (3)	0.1904 (3)	0.0675 (9)
O1	0.3484 (7)	0.4452 (4)	0.1018 (4)	0.0881 (12)
O2	0.6905 (8)	0.5827 (5)	0.1007 (4)	0.1151 (16)
H3A	1.007 (7)	0.491 (3)	0.226 (3)	0.076 (16)*
H1A	0.360 (10)	0.384 (3)	0.120 (4)	0.12 (2)*
H3B	1.134 (9)	0.500 (6)	0.162 (5)	0.19 (4)*
H2A	0.795 (6)	0.561 (6)	0.129 (5)	0.15 (3)*
H2B	0.588 (7)	0.543 (9)	0.103 (9)	0.28 (7)*
H1B	0.296 (16)	0.432 (6)	0.042 (2)	0.23 (6)*

	U11	U22	U33	U12	U13	U23
Fe1	0.0330 (3)	0.0381 (3)	0.0315 (3)	0.0052 (2)	0.0066 (2)	0.0119 (2)
N1	0.064 (3)	0.084 (3)	0.055 (2)	0.008 (2)	−0.008 (2)	0.031 (2)
N2	0.082 (3)	0.089 (3)	0.053 (2)	0.024 (2)	0.025 (2)	0.003 (2)
N3	0.055 (2)	0.056 (2)	0.066 (2)	−0.0004 (19)	0.0092 (19)	0.0178 (19)
N4	0.054 (2)	0.060 (2)	0.077 (3)	0.0019 (19)	0.019 (2)	0.035 (2)
N5	0.0305 (15)	0.0323 (15)	0.0343 (15)	0.0044 (12)	0.0081 (13)	0.0111 (13)
N6	0.0304 (15)	0.0314 (16)	0.0389 (16)	0.0045 (12)	0.0072 (13)	0.0119 (13)
C1	0.047 (2)	0.051 (2)	0.041 (2)	0.0047 (19)	0.0058 (19)	0.0161 (19)
C2	0.048 (2)	0.053 (2)	0.036 (2)	0.0061 (19)	0.0045 (19)	0.0080 (19)
C3	0.0358 (19)	0.039 (2)	0.0297 (18)	0.0055 (17)	0.0033 (15)	0.0075 (16)
C4	0.038 (2)	0.052 (2)	0.038 (2)	0.0141 (18)	0.0082 (17)	0.0172 (18)
C5	0.0346 (19)	0.037 (2)	0.042 (2)	0.0053 (15)	0.0102 (16)	0.0131 (16)
C6	0.0337 (19)	0.041 (2)	0.057 (2)	0.0072 (16)	0.0088 (18)	0.0224 (19)
C7	0.041 (2)	0.053 (2)	0.046 (2)	0.0026 (18)	−0.0016 (18)	0.026 (2)
C8	0.045 (2)	0.054 (2)	0.037 (2)	0.0031 (18)	0.0056 (18)	0.0144 (18)
C9	0.0322 (18)	0.0364 (19)	0.0345 (18)	0.0009 (15)	0.0042 (15)	0.0121 (15)
C10	0.0330 (18)	0.0348 (19)	0.0382 (19)	0.0023 (15)	0.0096 (16)	0.0116 (16)
C11	0.050 (2)	0.050 (2)	0.037 (2)	0.0049 (19)	0.0113 (18)	0.0074 (18)
C12	0.048 (2)	0.046 (2)	0.054 (3)	0.0067 (19)	0.024 (2)	0.0024 (19)
C13	0.037 (2)	0.037 (2)	0.067 (3)	0.0083 (17)	0.017 (2)	0.0128 (19)
C14	0.0310 (18)	0.039 (2)	0.049 (2)	0.0039 (16)	0.0074 (17)	0.0156 (17)
N7	0.0690 (19)	0.0535 (17)	0.0545 (17)	0.0007 (15)	0.0077 (15)	0.0133 (14)
C15	0.089 (3)	0.0683 (19)	0.078 (3)	0.0004 (17)	0.014 (2)	0.0188 (17)
C16A	0.092 (4)	0.069 (4)	0.074 (4)	0.003 (3)	0.023 (3)	0.018 (3)
C16B	0.100 (5)	0.076 (4)	0.067 (3)	−0.001 (4)	0.010 (3)	0.024 (3)
C17A	0.084 (3)	0.085 (4)	0.079 (4)	0.012 (3)	0.006 (2)	0.012 (3)
C17B	0.100 (4)	0.097 (4)	0.081 (4)	0.024 (3)	0.024 (3)	0.023 (3)
C18A	0.086 (5)	0.081 (4)	0.065 (2)	−0.006 (3)	0.010 (2)	0.008 (2)
C18B	0.082 (3)	0.068 (4)	0.074 (3)	0.002 (2)	0.004 (2)	0.015 (3)
O3	0.075 (2)	0.068 (2)	0.070 (2)	0.0046 (18)	0.0206 (19)	0.0325 (18)
O1	0.083 (3)	0.089 (3)	0.116 (4)	0.025 (2)	0.035 (3)	0.058 (3)
O2	0.078 (3)	0.146 (4)	0.142 (4)	0.012 (3)	0.006 (3)	0.084 (4)

Fe1—N5	1.981 (3)	N7—C16B	1.468 (6)
Fe1—N6	1.985 (3)	N7—C17A	1.482 (7)
Fe1—C1	1.917 (4)	N7—C17B	1.460 (7)
Fe1—C2	1.917 (4)	N7—C18A	1.486 (7)
Fe1—C3	1.969 (4)	N7—C18B	1.498 (6)
Fe1—C4	1.969 (4)	C15—H15A	0.9600
N1—C1	1.132 (5)	C15—H15B	0.9600
N2—C2	1.142 (5)	C15—H15C	0.9600
N3—C3	1.105 (5)	C16A—H16A	0.9600
N4—C4	1.127 (5)	C16A—H16B	0.9600
N5—C5	1.339 (4)	C16A—H16C	0.9600
N5—C9	1.349 (4)	C16B—H16D	0.9600
N6—C10	1.348 (4)	C16B—H16E	0.9600
N6—C14	1.346 (4)	C16B—H16F	0.9600
C5—H5	0.9300	C17A—H17A	0.9600
C5—C6	1.367 (5)	C17A—H17B	0.9600
C6—H6	0.9300	C17A—H17C	0.9600
C6—C7	1.370 (5)	C17B—H17D	0.9600
C7—H7	0.9300	C17B—H17E	0.9600
C7—C8	1.391 (5)	C17B—H17F	0.9600
C8—H8	0.9300	C18A—H18A	0.9600
C8—C9	1.372 (5)	C18A—H18B	0.9600
C9—C10	1.475 (5)	C18A—H18C	0.9600
C10—C11	1.379 (5)	C18B—H18D	0.9600
C11—H11	0.9300	C18B—H18E	0.9600
C11—C12	1.373 (6)	C18B—H18F	0.9600
C12—H12	0.9300	O3—H3A	0.840 (10)
C12—C13	1.374 (6)	O3—H3B	0.847 (10)
C13—H13	0.9300	O1—H1A	0.836 (10)
C13—C14	1.371 (5)	O1—H1B	0.838 (10)
C14—H14	0.9300	O2—H2A	0.842 (10)
N7—C15	1.475 (5)	O2—H2B	0.840 (10)
N7—C16A	1.481 (7)
N5—Fe1—N6	81.14 (11)	C15—N7—C17A	102.4 (6)
C1—Fe1—N5	175.01 (15)	C15—N7—C18A	122.6 (6)
C1—Fe1—N6	95.97 (14)	C15—N7—C18B	101.2 (5)
C1—Fe1—C2	86.42 (17)	C16A—N7—C17A	108.8 (8)
C1—Fe1—C3	92.47 (15)	C16A—N7—C18A	114.0 (8)
C1—Fe1—C4	87.33 (16)	C16B—N7—C15	112.9 (5)
C2—Fe1—N5	96.73 (14)	C16B—N7—C18B	111.8 (7)
C2—Fe1—N6	175.52 (14)	C17A—N7—C18A	102.4 (8)
C2—Fe1—C3	86.72 (16)	C17B—N7—C15	110.2 (6)
C2—Fe1—C4	91.34 (17)	C17B—N7—C16B	112.9 (7)
C3—Fe1—N5	91.57 (13)	C17B—N7—C18B	107.1 (6)
C3—Fe1—N6	89.39 (13)	N7—C15—H15A	109.5
C4—Fe1—N5	88.73 (13)	N7—C15—H15B	109.5
C4—Fe1—N6	92.55 (13)	N7—C15—H15C	109.5
C4—Fe1—C3	178.06 (15)	H15A—C15—H15B	109.5
C5—N5—Fe1	126.4 (2)	H15A—C15—H15C	109.5
C5—N5—C9	118.4 (3)	H15B—C15—H15C	109.5
C9—N5—Fe1	115.1 (2)	N7—C16A—H16A	109.5
C10—N6—Fe1	115.3 (2)	N7—C16A—H16B	109.5
C14—N6—Fe1	126.3 (3)	N7—C16A—H16C	109.5
C14—N6—C10	118.3 (3)	H16A—C16A—H16B	109.5
N1—C1—Fe1	175.8 (4)	H16A—C16A—H16C	109.5
N2—C2—Fe1	176.6 (4)	H16B—C16A—H16C	109.5
N3—C3—Fe1	178.7 (3)	N7—C16B—H16D	109.5
N4—C4—Fe1	179.8 (4)	N7—C16B—H16E	109.5
N5—C5—H5	118.7	N7—C16B—H16F	109.5
N5—C5—C6	122.7 (3)	H16D—C16B—H16E	109.5
C6—C5—H5	118.7	H16D—C16B—H16F	109.5
C5—C6—H6	120.5	H16E—C16B—H16F	109.5
C5—C6—C7	119.1 (3)	N7—C17A—H17A	109.5
C7—C6—H6	120.5	N7—C17A—H17B	109.5
C6—C7—H7	120.5	N7—C17A—H17C	109.5
C6—C7—C8	119.1 (4)	H17A—C17A—H17B	109.5
C8—C7—H7	120.5	H17A—C17A—H17C	109.5
C7—C8—H8	120.6	H17B—C17A—H17C	109.5
C9—C8—C7	118.8 (4)	N7—C17B—H17D	109.5
C9—C8—H8	120.6	N7—C17B—H17E	109.5
N5—C9—C8	121.9 (3)	N7—C17B—H17F	109.5
N5—C9—C10	114.4 (3)	H17D—C17B—H17E	109.5
C8—C9—C10	123.7 (3)	H17D—C17B—H17F	109.5
N6—C10—C9	114.0 (3)	H17E—C17B—H17F	109.5
N6—C10—C11	121.6 (3)	N7—C18A—H18A	109.5
C11—C10—C9	124.4 (3)	N7—C18A—H18B	109.5
C10—C11—H11	120.2	N7—C18A—H18C	109.5
C12—C11—C10	119.5 (4)	H18A—C18A—H18B	109.5
C12—C11—H11	120.2	H18A—C18A—H18C	109.5
C11—C12—H12	120.5	H18B—C18A—H18C	109.5
C11—C12—C13	119.0 (4)	N7—C18B—H18D	109.5
C13—C12—H12	120.5	N7—C18B—H18E	109.5
C12—C13—H13	120.4	N7—C18B—H18F	109.5
C14—C13—C12	119.2 (4)	H18D—C18B—H18E	109.5
C14—C13—H13	120.4	H18D—C18B—H18F	109.5
N6—C14—C13	122.4 (4)	H18E—C18B—H18F	109.5
N6—C14—H14	118.8	H3A—O3—H3B	109 (3)
C13—C14—H14	118.8	H1A—O1—H1B	112 (3)
C15—N7—C16A	105.4 (6)	H2A—O2—H2B	112 (3)
Fe1—N5—C5—C6	179.2 (3)	C6—C7—C8—C9	0.5 (6)
Fe1—N5—C9—C8	−179.9 (3)	C7—C8—C9—N5	0.8 (6)
Fe1—N5—C9—C10	−0.3 (4)	C7—C8—C9—C10	−178.8 (3)
Fe1—N6—C10—C9	2.4 (4)	C8—C9—C10—N6	178.2 (3)
Fe1—N6—C10—C11	−178.8 (3)	C8—C9—C10—C11	−0.5 (6)
Fe1—N6—C14—C13	178.2 (3)	C9—N5—C5—C6	1.2 (5)
N5—C5—C6—C7	0.1 (5)	C9—C10—C11—C12	179.7 (3)
N5—C9—C10—N6	−1.4 (4)	C10—N6—C14—C13	1.4 (5)
N5—C9—C10—C11	179.8 (3)	C10—C11—C12—C13	−0.1 (6)
N6—C10—C11—C12	1.0 (6)	C11—C12—C13—C14	−0.1 (6)
C5—N5—C9—C8	−1.7 (5)	C12—C13—C14—N6	−0.5 (6)
C5—N5—C9—C10	178.0 (3)	C14—N6—C10—C9	179.6 (3)
C5—C6—C7—C8	−1.0 (6)	C14—N6—C10—C11	−1.6 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C17A—H17C···O2i	0.96	2.50	3.112 (11)	122
O3—H3A···N4	0.84 (1)	2.00 (1)	2.841 (5)	178 (5)
O1—H1A···N1	0.84 (1)	2.03 (1)	2.859 (5)	176 (7)
O3—H3B···O1ii	0.85 (1)	1.89 (1)	2.736 (6)	174 (7)
O2—H2A···O3	0.84 (1)	1.87 (2)	2.709 (6)	172 (7)
O2—H2B···O1	0.84 (1)	1.98 (1)	2.818 (7)	177 (14)
O1—H1B···O2iii	0.84 (1)	2.02 (6)	2.792 (8)	152 (11)

[CdFe(CN)4(C10H8N2)(C2H8N2)2]·H2O	F(000) = 1144
Mr = 566.74	Dx = 1.697 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.4184 (14) Å	Cell parameters from 9748 reflections
b = 28.534 (5) Å	θ = 3.0–30.3°
c = 11.094 (2) Å	µ = 1.65 mm−1
β = 109.143 (6)°	T = 296 K
V = 2218.3 (7) Å3	Block, dark red
Z = 4	0.3 × 0.26 × 0.14 mm

Bruker APEXII D8 QUEST CMOS diffractometer	2757 independent reflections
Radiation source: microfocus sealed x-ray tube, Incoatec Iµus	2478 reflections with I > 2σ(I)
GraphiteDouble Bounce Multilayer Mirror monochromator	Rint = 0.038
Detector resolution: 10.5 pixels mm-1	θmax = 28.3°, θmin = 3.0°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −38→37
Tmin = 0.633, Tmax = 0.746	l = −14→14
51158 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.020	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.046	w = 1/[σ2(Fo2) + (0.0207P)2 + 2.0817P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.004
2757 reflections	Δρmax = 0.47 e Å−3
146 parameters	Δρmin = −0.47 e Å−3
2 restraints

Experimental. SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0955 before and 0.0483 after correction. The Ratio of minimum to maximum transmission is 0.8480. The λ/2 correction factor is 0.00150.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
Cd1	1.0000	0.49884 (2)	0.7500	0.02579 (6)
Fe1	0.5000	0.37467 (2)	0.7500	0.02273 (7)
N4	0.75926 (17)	0.48296 (5)	0.56872 (12)	0.0267 (3)
H4A	0.7937	0.4917	0.5024	0.032*
H4B	0.7400	0.4521	0.5632	0.032*
N3	0.3184 (2)	0.32132 (5)	0.68950 (13)	0.0302 (3)
N1	0.8094 (2)	0.44919 (5)	0.85021 (13)	0.0322 (3)
N5	0.9225 (2)	0.56629 (5)	0.85229 (14)	0.0366 (3)
H5A	0.7964	0.5699	0.8271	0.044*
H5B	0.9639	0.5621	0.9365	0.044*
C8	0.5794 (2)	0.50634 (5)	0.56058 (14)	0.0268 (3)
H8A	0.5983	0.5400	0.5636	0.032*
H8B	0.5425	0.4975	0.6336	0.032*
C1	0.6899 (2)	0.42120 (5)	0.81322 (14)	0.0247 (3)
N2	0.5958 (3)	0.37056 (6)	0.49974 (16)	0.0510 (4)
C2	0.5568 (2)	0.37319 (5)	0.59168 (15)	0.0304 (3)
C7	0.3972 (3)	0.27812 (6)	0.71567 (17)	0.0359 (4)
C3	0.1298 (3)	0.32437 (7)	0.62837 (18)	0.0397 (4)
H3	0.0746	0.3539	0.6117	0.048*
C4	0.0142 (3)	0.28557 (8)	0.5892 (2)	0.0524 (5)
H4	−0.1158	0.2891	0.5466	0.063*
C9	1.0114 (3)	0.60852 (6)	0.82011 (18)	0.0441 (4)
H9A	1.1459	0.6092	0.8702	0.053*
H9B	0.9517	0.6363	0.8406	0.053*
C6	0.2860 (3)	0.23784 (7)	0.6780 (2)	0.0531 (5)
H6	0.3422	0.2084	0.6963	0.064*
C5	0.0941 (4)	0.24163 (8)	0.6142 (2)	0.0593 (6)
H5	0.0193	0.2150	0.5883	0.071*
O1	0.5000	0.40519 (9)	0.2500	0.0599 (6)
H1	0.510 (5)	0.3877 (6)	0.3156 (11)	0.093 (10)*

	U11	U22	U33	U12	U13	U23
Cd1	0.01948 (8)	0.02751 (9)	0.02482 (9)	0.000	−0.00030 (6)	0.000
Fe1	0.02656 (15)	0.01792 (14)	0.02166 (14)	0.000	0.00513 (11)	0.000
N4	0.0199 (6)	0.0310 (7)	0.0259 (6)	0.0007 (5)	0.0030 (5)	−0.0003 (5)
N3	0.0388 (8)	0.0243 (6)	0.0276 (7)	−0.0063 (6)	0.0111 (6)	−0.0029 (5)
N1	0.0300 (7)	0.0325 (7)	0.0321 (7)	−0.0047 (6)	0.0074 (6)	0.0002 (6)
N5	0.0442 (9)	0.0326 (8)	0.0365 (8)	0.0031 (6)	0.0178 (7)	0.0032 (6)
C8	0.0190 (7)	0.0330 (8)	0.0239 (7)	0.0019 (6)	0.0009 (6)	−0.0024 (6)
C1	0.0270 (7)	0.0246 (7)	0.0214 (7)	0.0042 (6)	0.0066 (6)	0.0024 (6)
N2	0.0791 (13)	0.0434 (9)	0.0369 (9)	0.0018 (9)	0.0277 (9)	0.0007 (7)
C2	0.0373 (8)	0.0218 (7)	0.0292 (8)	−0.0003 (6)	0.0072 (7)	0.0009 (6)
C7	0.0507 (10)	0.0233 (8)	0.0370 (9)	−0.0040 (7)	0.0188 (8)	−0.0015 (7)
C3	0.0390 (10)	0.0344 (9)	0.0411 (10)	−0.0077 (8)	0.0069 (8)	−0.0013 (7)
C4	0.0465 (11)	0.0498 (12)	0.0560 (13)	−0.0194 (9)	0.0100 (10)	−0.0085 (10)
C9	0.0634 (13)	0.0291 (9)	0.0427 (11)	−0.0014 (8)	0.0213 (9)	−0.0030 (7)
C6	0.0699 (15)	0.0250 (9)	0.0675 (14)	−0.0094 (9)	0.0265 (12)	−0.0060 (9)
C5	0.0670 (15)	0.0395 (11)	0.0710 (15)	−0.0264 (10)	0.0222 (12)	−0.0154 (10)
O1	0.0733 (15)	0.0704 (15)	0.0342 (11)	0.000	0.0151 (11)	0.000

Cd1—N4i	2.2546 (13)	N5—H5B	0.8900
Cd1—N4	2.2547 (13)	N5—C9	1.473 (2)
Cd1—N1i	2.5046 (14)	C8—C8iii	1.512 (3)
Cd1—N1	2.5045 (14)	C8—H8A	0.9700
Cd1—N5i	2.3981 (15)	C8—H8B	0.9700
Cd1—N5	2.3980 (15)	N2—C2	1.150 (2)
Fe1—N3	1.9976 (14)	C7—C7ii	1.465 (4)
Fe1—N3ii	1.9976 (14)	C7—C6	1.396 (3)
Fe1—C1ii	1.8951 (16)	C3—H3	0.9300
Fe1—C1	1.8950 (16)	C3—C4	1.380 (3)
Fe1—C2ii	1.9362 (17)	C4—H4	0.9300
Fe1—C2	1.9363 (17)	C4—C5	1.376 (3)
N4—H4A	0.8900	C9—C9i	1.509 (4)
N4—H4B	0.8900	C9—H9A	0.9700
N4—C8	1.4681 (19)	C9—H9B	0.9700
N3—C7	1.354 (2)	C6—H6	0.9300
N3—C3	1.343 (2)	C6—C5	1.370 (3)
N1—C1	1.163 (2)	C5—H5	0.9300
N5—H5A	0.8900	O1—H1	0.865 (9)
N4i—Cd1—N4	156.82 (7)	C3—N3—C7	118.18 (15)
N4i—Cd1—N1i	83.39 (5)	C1—N1—Cd1	135.03 (12)
N4i—Cd1—N1	83.56 (5)	Cd1—N5—H5A	109.6
N4—Cd1—N1	83.39 (5)	Cd1—N5—H5B	109.6
N4—Cd1—N1i	83.56 (5)	H5A—N5—H5B	108.1
N4i—Cd1—N5	88.96 (5)	C9—N5—Cd1	110.25 (11)
N4—Cd1—N5i	88.96 (5)	C9—N5—H5A	109.6
N4—Cd1—N5	109.92 (5)	C9—N5—H5B	109.6
N4i—Cd1—N5i	109.91 (5)	N4—C8—C8iii	111.91 (16)
N1—Cd1—N1i	111.12 (7)	N4—C8—H8A	109.2
N5—Cd1—N1i	157.20 (5)	N4—C8—H8B	109.2
N5i—Cd1—N1i	89.20 (5)	C8iii—C8—H8A	109.2
N5i—Cd1—N1	157.20 (5)	C8iii—C8—H8B	109.2
N5—Cd1—N1	89.20 (5)	H8A—C8—H8B	107.9
N5—Cd1—N5i	73.24 (7)	N1—C1—Fe1	178.15 (14)
N3—Fe1—N3ii	80.69 (8)	N2—C2—Fe1	176.85 (16)
C1ii—Fe1—N3	94.13 (6)	N3—C7—C7ii	114.47 (10)
C1—Fe1—N3ii	94.12 (6)	N3—C7—C6	120.93 (18)
C1ii—Fe1—N3ii	174.82 (6)	C6—C7—C7ii	124.60 (13)
C1—Fe1—N3	174.81 (6)	N3—C3—H3	118.5
C1—Fe1—C1ii	91.06 (9)	N3—C3—C4	122.95 (19)
C1ii—Fe1—C2	92.07 (6)	C4—C3—H3	118.5
C1—Fe1—C2	89.69 (7)	C3—C4—H4	120.5
C1ii—Fe1—C2ii	89.69 (7)	C5—C4—C3	119.0 (2)
C1—Fe1—C2ii	92.07 (7)	C5—C4—H4	120.5
C2ii—Fe1—N3ii	90.11 (6)	N5—C9—C9i	110.03 (14)
C2—Fe1—N3ii	87.98 (6)	N5—C9—H9A	109.7
C2—Fe1—N3	90.11 (6)	N5—C9—H9B	109.7
C2ii—Fe1—N3	87.98 (6)	C9i—C9—H9A	109.7
C2ii—Fe1—C2	177.49 (9)	C9i—C9—H9B	109.7
Cd1—N4—H4A	108.8	H9A—C9—H9B	108.2
Cd1—N4—H4B	108.8	C7—C6—H6	120.0
H4A—N4—H4B	107.7	C5—C6—C7	120.1 (2)
C8—N4—Cd1	113.68 (9)	C5—C6—H6	120.0
C8—N4—H4A	108.8	C4—C5—H5	120.6
C8—N4—H4B	108.8	C6—C5—C4	118.82 (19)
C7—N3—Fe1	115.19 (12)	C6—C5—H5	120.6
C3—N3—Fe1	126.62 (12)
Cd1—N4—C8—C8iii	−178.38 (14)	C7—N3—C3—C4	−1.2 (3)
Cd1—N5—C9—C9i	43.1 (2)	C7ii—C7—C6—C5	179.9 (2)
Fe1—N3—C7—C7ii	0.1 (2)	C7—C6—C5—C4	−0.5 (4)
Fe1—N3—C7—C6	−179.70 (15)	C3—N3—C7—C7ii	−179.03 (18)
Fe1—N3—C3—C4	179.74 (15)	C3—N3—C7—C6	1.2 (3)
N3—C7—C6—C5	−0.3 (3)	C3—C4—C5—C6	0.4 (4)
N3—C3—C4—C5	0.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O1iii	0.89	2.20	3.0726 (18)	167
O1—H1···N2	0.87 (1)	1.99 (1)	2.8045 (19)	156 (2)