One-dimensional structure of catena-poly[tetra­ethyl­ammonium [tetra­cyano­iron(III)-μ-cyano-[bis­(ethyl­ene­diamine)­cadmium(II)]-μ-cyano] tetra­hydrate]

The title compound, {(C₈H₂₀N)[CdFe(CN)₆(C₂H₈N₂)₂]·4H₂O}_n, was isolated from the aqueous system Cd²⁺/ethyl­ene­diamine (en)/[Fe(CN)₆]³⁻ in the presence of [Et₄N]Br. The crystal structure is dominated by a one-dimensional motif, viz. a negatively charged 2,2-CT (cis–trans) [–Cd(en)₂—NC—Fe(CN)₄—CN–]_nⁿ⁻ chain. The Cd and Fe atoms of the anion and the N atom of the cation all lie on twofold axes. The ethyl groups of the cation are equally disordered over two orientations. The cationic building block of the chain consists of a Cd^II atom coordinated by two chelating en ligands, and the distorted octa­hedral coordination is completed by two bridging cyano ligands in cis positions. The anionic building block is an [Fe(CN)₆]³⁻ anion in which the Fe^III atom is octa­hedrally coordinated by six cyano ligands; two of the cyano ligands, in trans positions, are bridging. The uncoordinated water mol­ecules link neighbouring chains through O—H...N and N—H...O hydrogen bonds.

S1. Comment

Cyano complexes have been considered attractive subjects for study because of their ability to form host–guest and mineralomimetic systems (Iwamoto, 1996; Iwamoto et al., 1997; Hoskins & Robson, 1990; Dunbar & Heintz, 1997), and also because of their uses in such diverse areas as heterogeneous catalysis and sorption processes (Boellaard et al., 2002; Ayrault et al., 1998; Loos-Neskovic & Fedoroff, 1989). At present, oligomeric and polymeric cyano complexes attract the interest of both chemists and physicists from the point of view of magnetic properties (Larionova et al., 2000; Verdaguer et al., 1999; Bernhardt et al., 2005; Sato et al., 1996).

Polymeric cyano complexes can be built up of cationic and anionic building blocks linked via bridging cyano ligands; the cationic block is a complex cation coordinated by suitable, mainly N-donor, ligands (blocking ligands) and the anionic block is a complex cyano anion. The dimensionality of the cyano complex formed can be tuned to some extent by the number and type of the blocking ligands coordinated to the cationic central atom (Willett or Willet et al., 1993). Following this approach, we have investigated the system Cd²⁺/ethylenediamine/[Fe(CN)₆]³⁻ in the presence of [Et₄N]Br (Et is ethyl) for compensation of charge differences between the respective building blocks and have occasionally isolated the title compound, [Et₄N][Cd(en)₂Fe(CN)₆]·4H₂O (en is ethylenediamine), (I), along with the main crystalline product [Et₄N][Cd(en)]₄[Fe(CN)₆]₃, (II). Compound (II) formed at all Cd:en ratios up to 1:6. It exhibits a three-dimensional crystal structure with [Et₄N]⁺ cations placed in octahedral cavities of the cyano complex skeleton (Maĺarová et al., 2003). Our further attempts to prepare (I) were unsuccessful, but we were able to determine its structure; the results are reported here.

The structure of (I) consists of anionic chains [–Cd(en)₂—NC—Fe(CN)₄—CN–]_n^n-, [Et₄N]⁺ cations (the Cd atom, the Fe atom and the N atom of the cation occupy special positions), and two crystalographically independent uncoordinated water molecules, which are located between the chains (Figs. 1, 2 and 3). Heretofore, besides (II), only one crystal structure based on a Cd^II central atom and an [Fe(CN)₆]³⁻ anion has been reported. [Me₄N][CdFe(CN)₆]·3H₂O exhibits a three-dimensional crystal structure, and is built up of [CdN₄(OH₂)₂]²⁺ octahedra and [CdN₅]²⁺ square pyramids linked via [Fe(CN)₆]³⁻ octahedra; tetramethylammonium cations and water molecules are located in the cavities formed (Witzel et al., 2000).

The Cd^II atoms in (I) are six-coordinated by two chelating en molecules and two N-bound µ₂-bridging cyano groups placed in cis (C) positions. As the bridging cyano ligands are in trans (T) positions in the anion, and the connectivities of both building blocks are 2, the chain is of the 2,2-CT type [for details of notation see Černák et al. (2002)]. The Cd—N bond distances are in the range 2.339 (2)–2.376 (2) Å (Table 1). Similar bond distances and N—Cd—N angles were found in the one-dimensional compound [Cd{tet}]₂[Fe(CN)₆]·3H₂O (tet is ?; Zhang, Tong et al., 2000). The Cd—N1—C1 angle is 145.0 (2)°; such a deviation from linearity is usual in this type of structure (Zhang, Cai et al., 2000; Zhang, Tong et al., 2000). Both en ligands are in the δ conformation and exhibit typical values of geometric parameters (Yuge et al., 1995).

The Fe^III atom is six-coordinated by six cyano ligands, of which two, located in trans positions, are bridging (Fig. 1). The [FeC₆] octahedron is regular and the observed geometric parameters are in line with those reported for other hexacyanoferrates(III) (Witzel et al., 2000).

The tetraethylammonium cations are located between the chains; the cation is disordered about the twofold axis upon which atom N6 lies. Two crystallographically independent water molecules are interconnected via hydrogen bonds of the O—H···O type; moreover, they link neighbouring chains via O—H···N and N—H···O hydrogen bonds (Fig. 3 and Table 2). N—H···N hydrogen bonds between the chains contribute to the stability of the structure (Fig. 4 and Table 2).

S2. Experimental

Compound (I) crystallized from the same reaction mixture as (II). To an aqueous solution of CdCl₂2.5H₂O (0.23 g, 1 mmol), aqueous solutions of en (0.136 ml, 2 mmol) and [Et₄N]Br (0.15 g, 1 mmol) were added, and the mixture was stirred at room temperature for 10 min. To this colourless solution was added an aqueous solution of K₃[Fe(CN)₆] (0.33 g, 1 mmol). The resulting yellow solution was left to crystallize at two temperatures. From the solution kept at room temperature, red prismatic crystals of (II) were obtained after two days, and from the second solution, kept within the temperature range 281–286 K, yellow prismatic crystals of (I) separated after two weeks (yield 30%). Analysis calculated for C₁₈H₄₄CdFeN₁₁O₄ (Mr = 646.9): C 23.70, H 6.89, N 33.05%; found: C 23.82, H 6.86, N 33.42%. IR (cm⁻¹; Nicolet Magna 750 spectrometer, KBr disc): 3430, 3358, 3295, 2934, 2122, 1604, 1463, 1186, 1001, 961, 415, 398.

S3. Refinement

In the tetraethylammonium cation the ethyl groups are disordered over two positions related by a twofold axis parallel to [110]. Accordingly, the site occupation factors of all atoms of the relevant ethyl groups were set to 0.5. Owing to the observed disorder, the N—C bonds in the cation were restrained to be the same, and the anisotropic displacement parameters of the C atoms of methyl groups were assumed to have the same values. The H atoms of the water molecules were located in a difference Fourier map; their positional parameters were refined, while their U_iso(H) values were set at 1.5U_eq(O). For the remaining H atoms, a riding model was used with constrained displacement parameters [C—H = 0.98 and 0.99 Å, and U_iso(H) = 1.2U_eq(C,N) and 1.5U_eq(C_methyl)].

Computing details

Data collection: WinExpose in X-AREA (Stoe & Cie, 2002); cell refinement: WinCell in X-AREA; data reduction: WinIntegrate in X-AREA; program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Crystal Impact, 2000).

Figures

Fig. 1. The structure of the anion of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (A) y, x, −z; (B) 1 − y, 1 − x, 1/2 − z.] Fig. 2. A view of the [Et4N]^+ cation (only one disordered congener shown). Fig. 3. Packing diagram of (I), displaying its one-dimensional character. Large black balls: Fe; large white balls: Cd; medium white balls: O; small black balls: N; small white balls: C. For the sake of clarity, the [Et4N]^+ cations are represented only by N atoms (medium grey balls); H atoms have been omitted. Fig. 4. Hydrogen bonds in (I). [Et4N]^+ cations and H atoms not involved in hydrogen-bond formation have been omitted for clarity. [Symmetry codes: (A) 1 − y, 1 − x, 1/2 − z; (b) 1/2 − y, 1/2 + x, −1/4 + z; (C) 1/2 − x, 1/2 + y, 3/4 − z; (D) −y, 1 − x, 1/2 − z; (E) x, 1 + y, z; (F) y, x, 1 − z; (G) 1 − x, 1 − y, 1/2 + z; (H) y, x, −z; (I) 1 − x, 1 − y, z − 1/2; (J) 1/2 − y, 1/2 + x, 3/4 + z; (K) 1/2 − x, 1/2 + y, −1/4 − z.]

catena-poly[tetraethylammonium [tetracyanoiron(III)-µ-cyano-[bis(ethylenediamine)cadmium(II)]-µ-cyano] tetrahydrate]

Crystal data

(C8H20N)[CdFe(CN)6(C2H8N2)2]·4H2O	Dx = 1.414 Mg m^−3 Dm = 1.390 Mg m^−3 Dm measured by flotation in what?
Mr = 646.89	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P43212	Cell parameters from 29777 reflections
Hall symbol: P 4nw 2abw	θ = 1.9–29.4°
a = 13.0444 (5) Å	µ = 1.22 mm^−1
c = 17.8599 (9) Å	T = 173 K
V = 3039.0 (2) Å^3	Prism, yellow
Z = 4	0.2 × 0.18 × 0.1 mm
F(000) = 1340

Data collection

Stoe IPDS-II diffractometer	4164 independent reflections
Radiation source: fine-focus sealed tube	4043 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 150 pixels mm^-1	θmax = 29.4°, θmin = 1.9°
ω scans	h = −16→17
Absorption correction: numerical (XPREP in SHELXTL; Sheldrick, 1996)	k = −17→18
Tmin = 0.610, Tmax = 0.701	l = −24→24
29777 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.023	w = 1/[σ^2(Fo^2) + (0.0383P)^2 + 1.3052P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.063	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 0.46 e Å^−3
4164 reflections	Δρmin = −0.42 e Å^−3
191 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
6 restraints	Extinction coefficient: 0.0026 (6)
Primary atom site location: structure-invariant direct methods	Absolute structure: refinement of absolute structure parameter (Flack, 1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.02 (2)

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)
Cd	0.360847 (10)	0.360847 (10)	0.0000	0.02790 (7)
Fe	0.519498 (18)	0.480502 (18)	0.2500	0.02141 (8)
O1	−0.04027 (17)	0.4925 (3)	0.17663 (14)	0.0674 (8)
H11	−0.095 (4)	0.496 (4)	0.192 (3)	0.101*
H12	0.008 (5)	0.485 (4)	0.213 (3)	0.101*
O2	0.04976 (17)	0.57278 (15)	0.05274 (11)	0.0442 (4)
H21	0.036 (3)	0.644 (3)	0.046 (2)	0.066*
H22	0.003 (3)	0.563 (3)	0.092 (2)	0.066*
N1	0.48289 (18)	0.4216 (2)	0.08508 (12)	0.0439 (5)
N2	0.28563 (17)	0.48589 (19)	0.27826 (15)	0.0478 (5)
N3	0.5128 (2)	0.24732 (18)	0.27864 (14)	0.0489 (5)
C1	0.49676 (17)	0.44742 (18)	0.14588 (12)	0.0309 (4)
C2	0.37320 (16)	0.48426 (16)	0.26827 (12)	0.0299 (4)
C3	0.51689 (18)	0.33468 (16)	0.26844 (11)	0.0302 (4)
C4	0.2616 (2)	0.2747 (2)	0.14962 (14)	0.0455 (6)
H4C	0.3066	0.3077	0.1872	0.055*
H4D	0.2235	0.2189	0.1749	0.055*
C5	0.1867 (2)	0.3523 (2)	0.12002 (14)	0.0463 (6)
H5C	0.1391	0.3186	0.0846	0.056*
H5D	0.1459	0.3804	0.1620	0.056*
N4	0.3249 (2)	0.23100 (17)	0.08950 (13)	0.0477 (5)
H4A	0.2906	0.1777	0.0669	0.057*
H4B	0.3852	0.2060	0.1091	0.057*
N5	0.24030 (18)	0.43599 (17)	0.08185 (12)	0.0409 (5)
H5A	0.2730	0.4772	0.1162	0.049*
H5B	0.1945	0.4754	0.0553	0.049*
N6	0.68909 (13)	0.68909 (13)	0.0000	0.0344 (5)
C6	0.6950 (4)	0.6864 (4)	−0.08420 (19)	0.0428 (10)	0.50
H61A	0.7478	0.6353	−0.0982	0.051*	0.50
H61B	0.6285	0.6607	−0.1032	0.051*	0.50
C10	0.7189 (6)	0.7838 (10)	−0.1248 (6)	0.0552 (9)	0.50
H10A	0.6945	0.7788	−0.1766	0.083*	0.50
H10B	0.7931	0.7952	−0.1247	0.083*	0.50
H10C	0.6847	0.8413	−0.0998	0.083*	0.50
C7	0.6479 (4)	0.5908 (3)	0.0311 (3)	0.0465 (11)	0.50
H71A	0.5809	0.5752	0.0076	0.056*	0.50
H71B	0.6370	0.5979	0.0857	0.056*	0.50
C11	0.7243 (6)	0.5013 (8)	0.0157 (4)	0.0552 (9)	0.50
H11A	0.6871	0.4360	0.0161	0.083*	0.50
H11B	0.7772	0.5005	0.0546	0.083*	0.50
H11C	0.7565	0.5112	−0.0333	0.083*	0.50
C8	0.6044 (4)	0.7705 (4)	0.0169 (3)	0.0434 (11)	0.50
H81A	0.5907	0.7696	0.0714	0.052*	0.50
H81B	0.6323	0.8390	0.0045	0.052*	0.50
C12	0.5042 (8)	0.7584 (6)	−0.0230 (4)	0.0552 (9)	0.50
H12A	0.5072	0.6980	−0.0555	0.083*	0.50
H12B	0.4908	0.8195	−0.0533	0.083*	0.50
H12C	0.4492	0.7497	0.0138	0.083*	0.50
C9	0.7843 (4)	0.7331 (5)	0.0350 (3)	0.0481 (12)	0.50
H91A	0.7979	0.8011	0.0125	0.058*	0.50
H91B	0.8431	0.6881	0.0228	0.058*	0.50
C13	0.7778 (11)	0.7451 (6)	0.1206 (6)	0.0552 (9)	0.50
H13A	0.8438	0.7693	0.1398	0.083*	0.50
H13B	0.7612	0.6787	0.1433	0.083*	0.50
H13C	0.7242	0.7949	0.1331	0.083*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd	0.02974 (8)	0.02974 (8)	0.02420 (9)	−0.00288 (7)	0.00028 (6)	−0.00028 (6)
Fe	0.02232 (11)	0.02232 (11)	0.01961 (15)	−0.00077 (11)	−0.00003 (10)	−0.00003 (10)
O1	0.0320 (9)	0.119 (2)	0.0518 (12)	0.0075 (12)	0.0093 (9)	0.0267 (14)
O2	0.0546 (11)	0.0333 (9)	0.0446 (9)	0.0056 (7)	0.0088 (9)	0.0052 (7)
N1	0.0439 (11)	0.0608 (13)	0.0269 (9)	−0.0147 (10)	−0.0019 (8)	−0.0011 (9)
N2	0.0297 (10)	0.0459 (12)	0.0678 (15)	−0.0026 (9)	0.0093 (9)	−0.0137 (10)
N3	0.0614 (14)	0.0297 (10)	0.0557 (13)	0.0050 (10)	0.0077 (11)	0.0038 (9)
C1	0.0309 (9)	0.0379 (10)	0.0241 (9)	−0.0049 (8)	−0.0032 (7)	0.0027 (7)
C2	0.0276 (9)	0.0262 (8)	0.0358 (10)	−0.0012 (7)	0.0020 (7)	−0.0032 (7)
C3	0.0343 (10)	0.0271 (9)	0.0291 (9)	0.0011 (7)	0.0009 (7)	−0.0004 (7)
C4	0.0592 (17)	0.0406 (13)	0.0368 (11)	−0.0070 (11)	0.0114 (11)	−0.0010 (9)
C5	0.0400 (12)	0.0589 (16)	0.0400 (12)	−0.0067 (12)	0.0102 (10)	−0.0052 (12)
N4	0.0642 (15)	0.0313 (10)	0.0475 (12)	−0.0001 (9)	0.0127 (11)	0.0032 (9)
N5	0.0422 (11)	0.0405 (10)	0.0399 (11)	0.0074 (9)	−0.0025 (9)	−0.0029 (8)
N6	0.0369 (7)	0.0369 (7)	0.0294 (11)	−0.0085 (10)	0.0016 (9)	−0.0016 (9)
C6	0.050 (3)	0.052 (3)	0.0267 (18)	−0.007 (2)	0.0037 (19)	−0.0069 (19)
C10	0.059 (2)	0.0537 (18)	0.0531 (14)	−0.012 (3)	−0.0061 (16)	0.0124 (16)
C7	0.048 (3)	0.039 (2)	0.052 (3)	−0.008 (2)	0.005 (2)	0.008 (2)
C11	0.059 (2)	0.0537 (18)	0.0531 (14)	−0.012 (3)	−0.0061 (16)	0.0124 (16)
C8	0.042 (2)	0.043 (2)	0.045 (3)	0.0018 (19)	−0.0012 (19)	−0.008 (2)
C12	0.059 (2)	0.0537 (18)	0.0531 (14)	−0.012 (3)	−0.0061 (16)	0.0124 (16)
C9	0.046 (3)	0.055 (3)	0.044 (3)	−0.013 (2)	−0.003 (2)	0.009 (2)
C13	0.059 (2)	0.0537 (18)	0.0531 (14)	−0.012 (3)	−0.0061 (16)	0.0124 (16)

Geometric parameters (Å, º)

Cd—N1	2.339 (2)	N6—C6	1.506 (3)
Cd—N5	2.360 (2)	N6—C8	1.562 (4)
Cd—N4	2.376 (2)	C6—C10	1.496 (13)
Fe—C3	1.931 (2)	C6—H61A	0.9900
Fe—C1	1.932 (2)	C6—H61B	0.9900
Fe—C2	1.937 (2)	C10—H10A	0.9800
O1—H11	0.77 (6)	C10—H10B	0.9800
O1—H12	0.91 (6)	C10—H10C	0.9800
O2—H21	0.95 (4)	C7—C11	1.559 (11)
O2—H22	0.94 (4)	C7—H71A	0.9900
N1—C1	1.151 (3)	C7—H71B	0.9900
N2—C2	1.156 (3)	C11—H11A	0.9800
N3—C3	1.155 (3)	C11—H11B	0.9800
C4—N4	1.470 (3)	C11—H11C	0.9800
C4—C5	1.502 (4)	C8—C12	1.496 (12)
C4—H4C	0.9900	C8—H81A	0.9900
C4—H4D	0.9900	C8—H81B	0.9900
C5—N5	1.464 (4)	C12—H12A	0.9800
C5—H5C	0.9900	C12—H12B	0.9800
C5—H5D	0.9900	C12—H12C	0.9800
N4—H4A	0.9200	C9—C13	1.539 (12)
N4—H4B	0.9200	C9—H91A	0.9900
N5—H5A	0.9200	C9—H91B	0.9900
N5—H5B	0.9200	C13—H13A	0.9800
N6—C7	1.497 (4)	C13—H13B	0.9800
N6—C9	1.504 (4)	C13—H13C	0.9800
N1—Cd—N1^i	87.74 (11)	C7—N6—C8	104.9 (3)
N1—Cd—N5^i	110.21 (8)	C9—N6—C8	104.1 (3)
N1—Cd—N5	84.86 (8)	C6—N6—C8	104.2 (3)
N5^i—Cd—N5	159.56 (11)	N6—C6—C10	118.4 (5)
N1—Cd—N4^i	171.56 (9)	N6—C6—H61A	107.7
N1—Cd—N4	86.50 (9)	C10—C6—H61A	107.7
N5^i—Cd—N4	91.36 (8)	N6—C6—H61B	107.7
N5—Cd—N4	75.40 (8)	C10—C6—H61B	107.7
N4^i—Cd—N4	99.86 (14)	H61A—C6—H61B	107.1
C3^ii—Fe—C3	93.66 (14)	C6—C10—H10A	109.5
C3^ii—Fe—C1	89.49 (9)	C6—C10—H10B	109.5
C3—Fe—C1	86.64 (9)	H10A—C10—H10B	109.5
C1—Fe—C1^ii	174.34 (14)	C6—C10—H10C	109.5
C3^ii—Fe—C2	177.54 (9)	H10A—C10—H10C	109.5
C3—Fe—C2	88.79 (9)	H10B—C10—H10C	109.5
C1—Fe—C2	90.95 (9)	N6—C7—C11	110.2 (5)
C1—Fe—C2^ii	93.10 (9)	N6—C7—H71A	109.6
C2—Fe—C2^ii	88.77 (12)	C11—C7—H71A	109.6
H11—O1—H12	113 (5)	N6—C7—H71B	109.6
H21—O2—H22	97 (3)	C11—C7—H71B	109.6
C1—N1—Cd	145.0 (2)	H71A—C7—H71B	108.1
N1—C1—Fe	175.9 (2)	C7—C11—H11A	109.5
N2—C2—Fe	179.1 (2)	C7—C11—H11B	109.5
N3—C3—Fe	178.2 (2)	H11A—C11—H11B	109.5
N4—C4—C5	111.7 (2)	C7—C11—H11C	109.5
N4—C4—H4C	109.3	H11A—C11—H11C	109.5
C5—C4—H4C	109.3	H11B—C11—H11C	109.5
N4—C4—H4D	109.3	C12—C8—N6	117.0 (5)
C5—C4—H4D	109.3	C12—C8—H81A	108.1
H4C—C4—H4D	107.9	N6—C8—H81A	108.1
N5—C5—C4	110.9 (2)	C12—C8—H81B	108.1
N5—C5—H5C	109.5	N6—C8—H81B	108.1
C4—C5—H5C	109.5	H81A—C8—H81B	107.3
N5—C5—H5D	109.5	C8—C12—H12A	109.5
C4—C5—H5D	109.5	C8—C12—H12B	109.5
H5C—C5—H5D	108.1	H12A—C12—H12B	109.5
C4—N4—Cd	109.03 (16)	C8—C12—H12C	109.5
C4—N4—H4A	109.9	H12A—C12—H12C	109.5
Cd—N4—H4A	109.9	H12B—C12—H12C	109.5
C4—N4—H4B	109.9	N6—C9—C13	114.0 (6)
Cd—N4—H4B	109.9	N6—C9—H91A	108.8
H4A—N4—H4B	108.3	C13—C9—H91A	108.8
C5—N5—Cd	107.25 (16)	N6—C9—H91B	108.8
C5—N5—H5A	110.3	C13—C9—H91B	108.8
Cd—N5—H5A	110.3	H91A—C9—H91B	107.7
C5—N5—H5B	110.3	C9—C13—H13A	109.5
Cd—N5—H5B	110.3	C9—C13—H13B	109.5
H5A—N5—H5B	108.5	H13A—C13—H13B	109.5
C7—N6—C9	118.0 (3)	C9—C13—H13C	109.5
C7—N6—C6	111.6 (3)	H13A—C13—H13C	109.5
C9—N6—C6	112.4 (3)	H13B—C13—H13C	109.5

Symmetry codes: (i) y, x, −z; (ii) −y+1, −x+1, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11···N3^iii	0.77 (6)	2.06 (6)	2.817 (3)	171 (6)
O1—H12···O2^iv	0.91 (6)	1.87 (6)	2.748 (3)	162 (5)
O2—H21···N2^v	0.95 (4)	1.90 (4)	2.849 (3)	178 (4)
O2—H22···O1	0.94 (4)	1.86 (4)	2.715 (3)	152 (4)
N4—H4A···N3^vi	0.92	2.31	3.190 (4)	160
N5—H5B···O2	0.92	2.28	3.103 (3)	150

Symmetry codes: (iii) −y, −x+1, −z+1/2; (iv) y−1/2, −x+1/2, z+1/4; (v) −y+1/2, x+1/2, z−1/4; (vi) −y+1/2, x−1/2, z−1/4.