Luminescent properties of three structures built from 3-cyano-4-dicyano­methyl­ene-5-oxo-4,5-dihydro-1H-pyrrol-2-olate and cadmium

Yellow–orange tetra­aqua­bis(3-cyano-4-dicyano­methyl­ene-5-oxo-4,5-dihydro-1H-pyrrol-2-olato-κN³)cadmium(II) dihydrate, [Cd(C₈HN₄O₂)₂(H₂O)₄]·2H₂O, (I), and yellow tetra­aqua­bis­(3-cyano-4-dicyano­methyl­ene-5-oxo-4,5-dihydro-1H-pyrrol-2-ol­ato-κN³)­cadmium(II) 1,4-dioxane solvate, [Cd(C₈HN₄O₂)₂(H₂O)₄]·C₄H₈O₂, (II), contain centrosymmetric mononuclear Cd²⁺ coordination complex mol­ecules in different conformations. Dark-red poly[[deca­aquabis­(μ₂-3-cyano-4-dicyano­methyl­ene-5-oxo-4,5-dihydro-1H-pyrrol-2-olato-κ²N:N′)bis­(μ₂-3-cyano-4-dicyano­methyl­ene-1H-pyrrole-2,5-diolato-κ²N:N′)­tricadmium] hemihydrate], [Cd₃(C₈HN₄O₂)₂(C₈N₄O₂)₂(H₂O)₁₀]·0.5H₂O, (III), has a polymeric two-dimensional structure, the building block of which includes two cadmium cations (one of them located on an inversion centre), and both singly and doubly charged anions. The cathodoluminescence spectra of the crystals are different and cover the wavelength range from UV to red, with emission peaks at 377 and 620 nm for (III), and at 583 and 580 nm for (I) and (II), respectively.

S1. Comment

Optical, transport and magnetic properties of organic and metal-organic molecular crystals are actively studied nowadays because of potential application of these materials as molecular switches, information storage devices, sensors and active components of OLED displays. An important feature of such molecular systems is a pronounced hierarchy of interatomic interactions; bonding within the molecular complex has strong covalent or ionic character, while intermolecular interactions are much weaker. As a result, some physical properties have a local origin (local single molecule characteristics) while others depend on intermolecular contacts of a cooperative nature. An ideal target-oriented and property-directed design of molecular crystals may therefore be subdivided into the synthesis of a molecular unit carrying necessary electronic properties and the packing of molecular units to provide a required collective behavior and macroscopic properties of interest. Some types of intermolecular contacts were found to be of a special importance for conductivity, optics and magnetism (Rochefort et al., 2002; Zheng et al., 2003; Zhao et al., 1999; Inabe et al., 2003; Enoki et al., 2003). In particular, side-by-side contacts (SS, e.g. in the case of conjugated polymers) and face-by-face contacts (FF, stacking molecular arrangements) are recognized as important factors in control of electron transport, optical and magnetic properties of molecular crystals (Epstein, 2000; Matsumoto et al., 2002). Although numerous examples of such contacts can be found among photoconducting, superconducting or magnetically ordered organic polymers, crystals and thin films (see Law, 1993, and references therein), control of the properties is often difficult because of the complex schemes of intermolecular interactions. Thus, for the most novel materials, this crystal-engineering scenario is still a challenge.

Recently, on the basis of the organic anion 3-cyano-4-dicyanomethylene-5-oxo-4,5-dihydro-1H-pyrrol-2-olate, (A) (Tafeenko et al., 2003; Tafeenko, Peschar et al., 2004; Tafeenko, Nikolaev et al., 2004; Tafeenko et al., 2005), we synthesized a novel type of coordination polymer (Tafeenko & Chernyshev, 2005). Coordination polymers containing cyano-based anions are of high interest because some of them exhibit long-range magnetic ordering (Kurmoo & Kepert, 1998, 1999; Batten et al., 1998). Organic salts based on anion (A) show not only SS and FF types of molecular contacts but also a rich polymorphism, indicating that the molecular unit can be packed in various ways, so giving the opportunity for a controlled crystal engineering in relation to optics, conductivity and magnetism. The non-H atoms of the planar anion (A) supply π electrons for π–π (FF) stacking interaction between anions in solids, while the dicyanomethylene unit and the nitrile group at the 3-position of the pyrrole cycle, acting as a bridge between metals, enable the SS interaction in the polymer. On the basis of the previous structural data and the calculated charge distribution for the atoms of (A), we can assign the intrinsic intermolecular interactions of the anion: (a) Every outer (non-H) atom of the anion can be involved in coordination with a metal. (b) Every outer atom can be involved in hydrogen bonding. (c) Every cyano group can be involved in inter-molecular cyano–cyano interaction. (d) Every atom of the anion can be involved in π–π stacking interaction. This finding gives us a convenient way for comparison and description of the novel coordination structures formed with anion (A). The objective of our present investigation was to develop novel coordination compounds based on anion (A) in combination with the Cd²⁺ cation, and to analyze both coordination modes of the anion and the packing of the molecular unit, and relay these to their luminescent properties.

The synthesis of the cadmium coordination compounds was carried out by the exchange reaction of cadmium sulfate and barium 3-cyano-4-dicyanomethylene-5-oxo-4,5-dihydro-1H-pyrrole-2-olate. Three types of crystals suitable for X-ray single-crystal investigation were extracted from the precipitate of a slowly evaporated dioxane–water (1:1) solution, namely yellow-orange (I), yellow (II) and dark-red (III). The crystal structures of (I) and (III) contain solvent water molecules, while the solvent molecule in (II) is a dioxane. Both (I) and (II) contain tetraaquabis(3-cyano-4-dicyanomethylene-5-oxo -4,5-dihydro-1H-pyrrol-2-olato-κN)cadmium(II) with the Cd²⁺ cation located on an inversion centre. For both samples the coordination environment consists of four water molecules and two cyano groups (Figs. 1 and 2). The geometric parameters of the coordination mode are similar for the two substances (Tables 1 and 3). The basal angles N—Cd—O and O—Cd—O are in the range 86.31 (9)–93.69 (9)° for (I) and 85.77 (14)–94.23 (14)° for (II), so the octahedral geometry is nearly ideal. There are some deviations in the metal–ligand distances; in (I), the Cd–ligand distances differ somewhat more (Table 1) than in (II) (Table 3). Taking into account that every coordinated water molecule participates in intra- and intermolecular hydrogen bonding, it is possible that the minor changes in pure octahedral parameters could be considered a consequence of a packing effect.

Although anion (A) is inflexible, its coordination through the cyano group to the metal may lead to different conformations, as is the case here in (I) and (II); the Cd1—N4—C9—C3 dihedral angles differ by 61 (1)°. As a result, the shortest intramolecular distances between anions (A) and the coordinated water molecules are substantially different in (I) and (II). We find an intramolecular hydrogen bond (O4—H41···N2^v) only in (I) (see Fig.1 and Table 2). The relevant distances in (II) are 4.268 (5) Å (O4···N2) and 4.192 (6) Å (O3···N2) (Fig. 2).

As the packing motifs in (I) and (II) are similar, only packing figures for (I) are presented. Molecules in both (I) and (II) are involved in hydrogen bonding (symmetry codes and other parameters are given in Tables 2 and 4) using mainly two types of hydrogen bonds. The hydrogen bonds O3—H31···O2ⁱⁱ in (I) or O3—H31···O2ⁱⁱⁱ in (II) are complementary to the π–π stacking interactions between anions, and the [Cd²⁺(A^-)₂(H₂O)₄] molecules are arranged in a ···ZZZ··· fashion (Tafeenko & Chernyshev, 2005); thus infinite [Cd²⁺(A^-)₂(H₂O)₄]_n rods (Fig. 4) are formed. Neighbouring rods are linked by centrosymmetric N1—H1···O1ⁱ hydrogen bonds to give rise to the formation of an infinite layer (Fig. 5). π–π stacking interactions between rods (Fig. 6) and hydrogen bonding through solvent molecules complete the three-dimensional crystal structure. The distances between the mean-square planes through atoms of adjacent anions in (I), representing the π–π stacking interaction, are 3.277 (3) Å (Figs. 4 and 6), while in (II) they differ, viz. 3.106 (7) Å between anions of adjacent rods and 3.349 (7) Å between anions in the rods.

In (III), the pyrrole H atom of the anion can be replaced by a metal atom, giving the polymer poly[[heptaaqua(µ₂-3-cyano-4-dicyanomethylene-5-oxo-4,5-dihydro-1H- pyrrol-2-olato-κN)tris(µ₂-3-cyano-4-dicyanomethylene-3H-pyrrole-2,5-diolate-κ²N:N')dicadmium] 0.5-hydrate] (Fig. 3). This structure shows both novel properties of the anion in question and a novel type of polymeric crystal structure where simultaneously singly and doubly negatively charged anions are present. The polymeric undulated layer of (III), as shown in Fig. 7, can be described as follows: the chains consist of Cd2-based [Cd²⁺(A^2-)(H₂O)₃] building blocks that are linked head-to-tail by (A^2-) ligands through the pyrrole N atom (N1A) and the nitrile N atom (N3Aⁱⁱ) (Figs. 3 and 7) of the dicyanomethylene unit. Cd1-based [Cd²⁺(A^-)₂(H₂O)₄] building blocks cross-link neighbouring chains through coordination of the cadmium cation in the chain (Cd2) by atom N3 of the monovalent anion, so that the octahedral environment of atom Cd2 in the chain is completed. Hydrogen bonds involving coordinated and uncoordinated water molecules complement the π–π stacking interactions between the anions (Fig. 8), linking adjacent layers into a continuous framework (Table 6).

Atom Cd1 is located on an inversion centre and it is coordinated by four water molecules and two (A^-) ligands, displaying ideally octahedral geometry, which is similar to that found in (I) (see Table 5). All O—Cd1—O and O—Cd1—N angles lie in the range 88.33 (17)–91.67 (17)°. As in (I), the intramolecular O3—H3···N2ⁱ hydrogen bond (Fig. 3 and Table 6) occurs. By contrast, atom Cd2 has a distorted octahedral coordination, being bonded to three water molecules and atoms N3, N3Aⁱⁱ and N1A (symmetry code as in Table 5). The octahedral distortion results primarily from the coordination through atom N1A, the N1A—Cd2 distance being the shortest among all Cd–ligand distances in the three crystals (see Table 5). Moreover, all the equatorial atoms are bent towards the apical atom N3Aⁱⁱ, with all the (O,N)—Cd2—N3Aⁱⁱ angles smaller than 90° (Fig. 3). The shortest Cd1···Cd2 distance between cations is 5.548 (1) Å.

The cathodoluminescence (CL) spectra of (I) and (II) are similar, so only the spectra of (I) and (III) are represented in Fig. 9. The CL spectrum of (I) shows a broad peak at 583 nm. The CL spectrum of (III) differs drastically and exhibits two emission bands with maxima at 377 and 620 nm. The UV emission of 377 nm may be attributed to a doublly charged anion, while the emission peaks at 583 and 620 nm can be related to the charge recombination through the singly charged anion. To be sure that the luminescence originates from the anions, we further measured the emission spectra of the ammonium salt of (A). We chose the ammonium salt because of the common features (hydrogen-bonding dimersa and π–π stacking motifs) of the packing of the anions in (I) and in the ammonium salt (Tafeenko, Peschar et al., 2005). Figs. 9 and 10 illustrate that the luminescence spectra of the ammonium salt and (I) are similar, and thus the key role of the anions as the origin of the luminescence of the salts in question is proved, i.e. we are able to exclude the influence of the metal on the luminescence.

In conclusion, we emphasize that (a) an arrrangement of the octahedral (A)-containing complexes, in a ···ZZZ···fashion (Tafeenko & Chernyshev, 2005), is a major factor in the formation of their crystal structures; (b) the luminescence of compounds based on (A) covers the wavelength range from UV to red. Tuning of the emission photon energy can be carried out on the basis of controllable intermolecular interactions of a cooperative nature. We illustrate this by comparing the luminescence spectrum of the ammonium salt in solution and the CL spectrum of the solid (Fig. 10). The maximum of the emission band of the ammonium salt in the solid is at 620 nm, while in water it is at 520 nm, implying that the intermolecular interaction in the crystal structure leads to a spectral shift of about 100 nm.

Related literature

For related literature, see: Batten et al. (1998); Enoki et al. (2003); Epstein (2000); Inabe et al. (2003); Law (1993); Kurmoo & Kepert (1998, 1999); Matsumoto et al. (2002); Rochefort et al. (2002); Tafeenko & Chernyshev (2005); Tafeenko et al. (2003); Tafeenko, Peschar, Kajukov, Kornilov & Aslanov (2005); Zhao et al. (1999); Zheng et al. (2003).

S2. Experimental

The synthesis of the cadmium salts was carried out by slow addition of a cadmium sulfate solution (1.5 mmol of CdSO₄ in 10 ml of a 1:1 mixture of dioxane and water) to a 10 ml solution of barium 3-cyano-4-(dicyanomethylene)-5-oxo-4,5-dihydro-1H-pyrrol-2-olate (1.1 mmol of salt in 10 ml of 1:1 dioxane–water). A white precipitate formed immediately and was filtered off after 3 h. The clear yellow solution was left aside for crystallization at room temperature. Within four weeks, yellow and then red crystals were formed. The crystals were filtered off, washed with a small portion of cool water and dried in air. Red, orange and yellow crystals suitable for X-ray investigation were separated mechanically. (See the supplementary materials for the CL and PL spectral analysis details.)

S3. Refinement

For (I), (II) and (III), the positions of the H atoms were determined from a difference Fourier map and these atoms were allowed to ride on their parent atoms with U_iso(H) values set at 1.2 (for nitrogen) and 1.5 (for oxygen) times U_eq of the attached atoms. The solvent water molecule in (III) is disordered near to a twofold axis. The displacement parameter of this water molecule (O10) was refined isotropically and fixed at 0.067 Ų; the final value of the site occupancy of (O10) was 0.25 for the lowest agreement factor.

Computing details

For all compounds, data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. A view of (I), with displacement ellipsoids drawn at the 50% probability level. Intramolecular hydrogen bonds are shown as dashed lines. [Symmetry code: (v) -x + 1, -y + 1, -z + 2.]
	Fig. 2. A view of (II) including the solvent dioxane molecule located at an inversion centre, with displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (iv) -x, -y + 1, -z; (v) -x = 1, -y, -z.]
	Fig. 3. A view of (III) including the solvent water molecule (O10, occupancy factor 1/4) located near a twofold axis, with displacement ellipsoids drawn at the 50% probability level. Atom Cd1 is located on an inversion centre. The intra-molecular hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) -x + 1/2, -y + 1/2, -z; (ii) x - 1/2, -y + 3/2, z - 1/2.]
	Fig. 4. Part of the crystal structure of (I), showing the arrangement of the complexes in a ···ZZZ··· fashion. [Symmetry codes: (ii) -x, -y + 1, -z + 1; (v) -x + 1, -y + 1, -z + 2; (vi) -x - 1, -y + 1, -z; (vii) x + 1, y, z + 1.]
	Fig. 5. Adjacent blocks in each rod of (I) are connected by centrosymmetric N1—H1···O1^i hydrogen bonding, thus forming a layer. [Symmetry code: (i) -x + 1, -y + 2, -z + 1.]
	Fig. 6. A view of (I), showing how π–π stacking interaction between rods links adjacent layers. The shortest distances between atoms which reflect this π–π interaction are shown as thin lines. [Symmetry code: (viii) -x + 1, -y + 1, -z + 1.]
	Fig. 7. Part of the crystal structure of (III), showing the chains running along the a axis and the resulting undulated layers. [Symmetry codes: (i) -x + 1/2, -y + 1/2, -z; (ii) x - 1/2, -y + 3/2, z - 1/2.]
	Fig. 8. The anions of adjacent layers in (III) are connected by π–π interaction to form the three-dimensional structure. The shortest distances between atoms which reflected this π-π interaction are shown as thin lines. The hydrogen bonds are shown as dashed lines. [Symmetry codes: (v) -x + 1/2, -y + 3/2, -z; (vii) -x + 1/2, y - 1/2, -z + 1/2; (ix) x, -y + 1, z + 1/2.]
	Fig. 9. C L s pectra of (I), with a peak at 583 nm, and (III), with peaks at 377 and 620 nm.
	Fig. 10. The CL spectrum of the ammonium salt in the solid state, with a peak at 620 nm, and the photoluminescence spectrum of its water solution, with a peak at 520 nm.

(I) tetraaquabis(3-cyano-4-dicyanomethylene-5-oxo-4,5-dihydro-1H-pyrrol-2-olato)cadmium(II) dihydrate

Crystal data

[Cd(C8HN4O2)2(H2O)4]·2H2O	Z = 1
Mr = 590.76	F(000) = 294
Triclinic, P1	Dx = 1.751 Mg m^−3
Hall symbol: -P 1	Melting point: 190 K
a = 6.987 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.645 (2) Å	Cell parameters from 25 reflections
c = 10.567 (3) Å	θ = 14–18°
α = 105.48 (2)°	µ = 1.05 mm^−1
β = 97.08 (2)°	T = 295 K
γ = 110.28 (3)°	Prism, orange
V = 560.3 (3) Å^3	0.10 × 0.10 × 0.05 mm

Data collection

Enraf–Nonius CAD-4 diffractometr	2503 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.012
Graphite monochromator	θmax = 28.0°, θmin = 2.1°
non–profiled ω scan	h = −9→9
Absorption correction: ψ scan (North et al., 1968)	k = −11→10
Tmin = 0.903, Tmax = 0.950	l = 0→13
2838 measured reflections	2 standard reflections every 120 min
2693 independent reflections	intensity decay: none

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.071	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0363P)^2 + 0.2027P] where P = (Fo^2 + 2Fc^2)/3
2693 reflections	(Δ/σ)max = 0.005
166 parameters	Δρmax = 0.42 e Å^−3
9 restraints	Δρmin = −0.39 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
Cd1	0.5000	0.5000	1.0000	0.03556 (10)
O1	0.5587 (3)	0.9360 (2)	0.64762 (17)	0.0408 (4)
O2	0.0764 (3)	0.5289 (3)	0.26638 (17)	0.0439 (4)
O3	0.1451 (3)	0.3930 (3)	0.9348 (2)	0.0603 (6)
H3	0.0939	0.3115	0.9626	0.090*
H31	0.0783	0.4154	0.8818	0.090*
O4	0.5013 (4)	0.7512 (3)	1.1319 (2)	0.0663 (7)
H4	0.4237	0.7822	1.0894	0.099*
H41	0.6063	0.8321	1.1955	0.099*
O5	0.2138 (5)	0.8888 (3)	1.0657 (2)	0.0657 (6)
H51	0.208	0.909	0.993	0.099*
H5	0.251	0.981	1.130	0.099*
N1	0.3211 (3)	0.7656 (3)	0.4415 (2)	0.0347 (4)
H1	0.3319	0.8465	0.4066	0.042*
N2	0.1956 (4)	0.1716 (3)	0.6116 (3)	0.0551 (7)
N3	−0.1005 (5)	0.1132 (4)	0.2058 (3)	0.0704 (9)
N4	0.5019 (4)	0.5979 (3)	0.8151 (2)	0.0461 (6)
C2	0.4311 (4)	0.7943 (3)	0.5707 (2)	0.0303 (5)
C3	0.3646 (3)	0.6266 (3)	0.5914 (2)	0.0277 (4)
C4	0.2261 (3)	0.4979 (3)	0.4741 (2)	0.0263 (4)
C5	0.1943 (4)	0.5933 (3)	0.3774 (2)	0.0309 (5)
C6	0.1291 (4)	0.3193 (3)	0.4400 (2)	0.0300 (5)
C7	0.0020 (4)	0.2080 (3)	0.3089 (3)	0.0413 (6)
C8	0.1637 (4)	0.2352 (3)	0.5346 (3)	0.0352 (5)
C9	0.4397 (4)	0.6098 (3)	0.7143 (2)	0.0314 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.04323 (16)	0.03715 (15)	0.02502 (13)	0.01425 (11)	−0.00093 (10)	0.01470 (10)
O1	0.0518 (11)	0.0306 (9)	0.0319 (9)	0.0077 (8)	0.0013 (8)	0.0134 (7)
O2	0.0475 (11)	0.0484 (11)	0.0302 (9)	0.0134 (9)	−0.0060 (8)	0.0189 (8)
O3	0.0475 (12)	0.0782 (16)	0.0614 (13)	0.0202 (11)	0.0020 (10)	0.0440 (12)
O4	0.0730 (15)	0.0497 (13)	0.0544 (13)	0.0281 (12)	−0.0195 (11)	−0.0057 (10)
O5	0.0896 (18)	0.0621 (15)	0.0411 (12)	0.0308 (14)	0.0039 (12)	0.0148 (11)
N1	0.0418 (11)	0.0342 (10)	0.0294 (10)	0.0115 (9)	0.0036 (8)	0.0197 (9)
N2	0.0689 (17)	0.0406 (13)	0.0469 (14)	0.0123 (12)	−0.0063 (12)	0.0224 (11)
N3	0.092 (2)	0.0466 (15)	0.0416 (14)	0.0055 (15)	−0.0164 (14)	0.0093 (12)
N4	0.0556 (14)	0.0441 (13)	0.0316 (11)	0.0112 (11)	−0.0034 (10)	0.0194 (10)
C2	0.0344 (12)	0.0326 (12)	0.0285 (11)	0.0140 (10)	0.0079 (9)	0.0163 (9)
C3	0.0285 (11)	0.0304 (11)	0.0259 (10)	0.0110 (9)	0.0033 (8)	0.0144 (9)
C4	0.0251 (10)	0.0333 (11)	0.0253 (10)	0.0129 (9)	0.0060 (8)	0.0154 (9)
C5	0.0301 (11)	0.0390 (13)	0.0275 (11)	0.0138 (10)	0.0053 (9)	0.0179 (10)
C6	0.0280 (11)	0.0331 (11)	0.0267 (10)	0.0097 (9)	0.0013 (9)	0.0120 (9)
C7	0.0454 (15)	0.0371 (13)	0.0360 (13)	0.0100 (12)	0.0026 (11)	0.0154 (11)
C8	0.0362 (13)	0.0273 (11)	0.0359 (12)	0.0071 (10)	0.0019 (10)	0.0113 (10)
C9	0.0343 (12)	0.0294 (11)	0.0284 (11)	0.0089 (9)	0.0035 (9)	0.0133 (9)

Geometric parameters (Å, º)

Cd1—O4^i	2.242 (2)	N1—C5	1.365 (3)
Cd1—O4	2.242 (2)	N1—C2	1.394 (3)
Cd1—O3^i	2.264 (2)	N1—H1	0.8600
Cd1—O3	2.264 (2)	N2—C8	1.137 (3)
Cd1—N4^i	2.327 (2)	N3—C7	1.139 (4)
Cd1—N4	2.327 (2)	N4—C9	1.144 (3)
O1—C2	1.220 (3)	C2—C3	1.446 (3)
O2—C5	1.208 (3)	C3—C4	1.390 (3)
O3—H3	0.8200	C3—C9	1.404 (3)
O3—H31	0.7907	C4—C6	1.374 (3)
O4—H4	0.8200	C4—C5	1.515 (3)
O4—H41	0.8665	C6—C7	1.423 (3)
O5—H51	0.83	C6—C8	1.428 (3)
O5—H5	0.83
O4^i—Cd1—O4	180.000 (1)	C5—N1—C2	111.62 (19)
O4^i—Cd1—O3^i	89.47 (10)	C5—N1—H1	124.2
O4—Cd1—O3^i	90.53 (10)	C2—N1—H1	124.2
O4^i—Cd1—O3	90.53 (10)	C9—N4—Cd1	158.7 (2)
O4—Cd1—O3	89.47 (10)	O1—C2—N1	124.7 (2)
O3^i—Cd1—O3	180.0	O1—C2—C3	128.6 (2)
O4^i—Cd1—N4^i	90.89 (9)	N1—C2—C3	106.7 (2)
O4—Cd1—N4^i	89.11 (9)	C4—C3—C9	129.0 (2)
O3^i—Cd1—N4^i	86.31 (9)	C4—C3—C2	109.39 (19)
O3—Cd1—N4^i	93.69 (9)	C9—C3—C2	121.6 (2)
O4^i—Cd1—N4	89.11 (9)	C6—C4—C3	132.0 (2)
O4—Cd1—N4	90.89 (9)	C6—C4—C5	122.4 (2)
O3^i—Cd1—N4	93.69 (9)	C3—C4—C5	105.64 (19)
O3—Cd1—N4	86.31 (9)	O2—C5—N1	127.1 (2)
N4^i—Cd1—N4	180.000 (1)	O2—C5—C4	126.4 (2)
Cd1—O3—H3	109.5	N1—C5—C4	106.53 (18)
Cd1—O3—H31	126.6	C4—C6—C7	123.1 (2)
H3—O3—H31	122.9	C4—C6—C8	120.4 (2)
Cd1—O4—H4	109.5	C7—C6—C8	116.4 (2)
Cd1—O4—H41	125.6	N3—C7—C6	177.2 (3)
H4—O4—H41	117.4	N2—C8—C6	178.4 (3)
H51—O5—H5	110.4	N4—C9—C3	179.3 (3)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^ii	0.86	2.03	2.870 (3)	164
O4—H4···O5	0.82	2.01	2.773 (4)	155
O3—H31···O2^iii	0.79	2.05	2.837 (3)	175
O5—H51···N3^iii	0.83	2.08	2.874 (4)	161
O3—H3···O5^iv	0.82	2.17	2.825 (4)	137
O5—H5···O1^v	0.83	2.34	2.949 (3)	131
O4—H41···N2^i	0.87	2.33	2.986 (3)	132

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

(II) tetraaquabis(3-cyano-4-dicyanomethylene-5-oxo-4,5-dihydro-1H-pyrrol-2-olato)cadmium(II) 1,4-dioxane solvate

Crystal data

[Cd(C8HN4O2)2(H2O)4]·C4H8O2	Z = 1
Mr = 642.83	F(000) = 322
Triclinic, P1	Dx = 1.698 Mg m^−3
Hall symbol: -P 1	Melting point: 200 K
a = 6.9511 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.4052 (12) Å	Cell parameters from 25 reflections
c = 11.3293 (16) Å	θ = 12–17°
α = 84.61 (2)°	µ = 0.94 mm^−1
β = 72.523 (10)°	T = 295 K
γ = 88.34 (1)°	Prism, yellow
V = 628.57 (16) Å^3	0.12 × 0.10 × 0.06 mm

Data collection

Enraf–Nonius CAD-4 diffractometr	2239 reflections with > σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.018
Graphite monochromator	θmax = 28.0°, θmin = 1.9°
non–profiled ω scan	h = −8→9
Absorption correction: ψ scan (North et al., 1968)	k = −10→11
Tmin = 0.912, Tmax = 0.955	l = 0→14
3173 measured reflections	2 standard reflections every 120 min
3022 independent reflections	intensity decay: none

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0463P)^2] where P = (Fo^2 + 2Fc^2)/3
3022 reflections	(Δ/σ)max < 0.001
178 parameters	Δρmax = 0.61 e Å^−3
0 restraints	Δρmin = −0.59 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-CONSTR 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
Cd1	0.5000	0.0000	0.0000	0.03332 (17)
O3	0.3370 (6)	−0.2322 (5)	0.0978 (3)	0.0579 (11)
H3	0.2477	−0.2510	0.0676	0.087*
H31	0.2876	−0.2518	0.1721	0.087*
O4	0.2291 (5)	0.0481 (4)	−0.0705 (3)	0.0468 (9)
H4	0.2630	0.0423	−0.1458	0.070*
H41	0.1421	0.1041	−0.0290	0.070*
O1	0.5446 (5)	0.3899 (4)	0.3587 (3)	0.0418 (9)
O2	−0.0541 (5)	0.3671 (4)	0.6675 (3)	0.0408 (8)
O5	0.0097 (6)	0.3353 (4)	−0.0179 (3)	0.0541 (10)
N1	0.2619 (5)	0.4037 (4)	0.5291 (3)	0.0325 (9)
H1	0.3106	0.4648	0.5698	0.039*
N2	−0.1640 (7)	0.0189 (6)	0.3015 (4)	0.0586 (13)
N3	−0.4517 (6)	0.1976 (6)	0.6624 (4)	0.0557 (13)
N4	0.3521 (6)	0.1407 (5)	0.1661 (4)	0.0441 (11)
C2	0.3692 (7)	0.3535 (5)	0.4139 (4)	0.0311 (10)
C3	0.2333 (6)	0.2555 (5)	0.3777 (4)	0.0275 (9)
C4	0.0468 (6)	0.2481 (5)	0.4687 (4)	0.0255 (9)
C5	0.0723 (6)	0.3449 (5)	0.5693 (4)	0.0287 (9)
C6	−0.1317 (6)	0.1765 (5)	0.4772 (4)	0.0309 (10)
C7	−0.3077 (7)	0.1891 (6)	0.5807 (5)	0.0385 (11)
C8	−0.1516 (7)	0.0885 (6)	0.3808 (5)	0.0365 (11)
C9	0.2952 (6)	0.1913 (5)	0.2616 (4)	0.0312 (10)
C10	0.1645 (9)	0.4441 (7)	−0.0896 (6)	0.0581 (16)
H10A	0.2231	0.4081	−0.1717	0.070*
H10B	0.2704	0.4453	−0.0500	0.070*
C11	−0.0832 (10)	0.3915 (7)	0.1012 (5)	0.0615 (17)
H11A	0.0152	0.3911	0.1465	0.074*
H11B	−0.1919	0.3199	0.1481	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0316 (3)	0.0416 (3)	0.0273 (3)	−0.0017 (2)	−0.0055 (2)	−0.0164 (2)
O3	0.069 (3)	0.061 (3)	0.041 (2)	−0.021 (2)	−0.0107 (19)	−0.0009 (19)
O4	0.0417 (19)	0.063 (2)	0.041 (2)	0.0131 (17)	−0.0167 (16)	−0.0197 (18)
O1	0.0326 (17)	0.059 (2)	0.0311 (18)	−0.0125 (16)	−0.0006 (14)	−0.0183 (16)
O2	0.0361 (18)	0.053 (2)	0.0296 (17)	−0.0089 (16)	0.0006 (14)	−0.0165 (16)
O5	0.065 (3)	0.040 (2)	0.045 (2)	−0.0070 (18)	0.0026 (19)	−0.0060 (17)
N1	0.032 (2)	0.043 (2)	0.0238 (19)	−0.0101 (17)	−0.0064 (16)	−0.0133 (17)
N2	0.066 (3)	0.071 (3)	0.049 (3)	−0.019 (3)	−0.026 (2)	−0.020 (3)
N3	0.033 (2)	0.084 (4)	0.045 (3)	−0.006 (2)	−0.003 (2)	−0.009 (3)
N4	0.040 (2)	0.056 (3)	0.036 (2)	−0.001 (2)	−0.0063 (19)	−0.020 (2)
C2	0.032 (2)	0.033 (2)	0.027 (2)	−0.0028 (19)	−0.0040 (19)	−0.0112 (19)
C3	0.026 (2)	0.031 (2)	0.027 (2)	−0.0025 (18)	−0.0061 (18)	−0.0115 (18)
C4	0.026 (2)	0.028 (2)	0.023 (2)	−0.0001 (17)	−0.0072 (17)	−0.0055 (17)
C5	0.031 (2)	0.031 (2)	0.024 (2)	−0.0018 (19)	−0.0070 (18)	−0.0066 (18)
C6	0.029 (2)	0.037 (3)	0.027 (2)	−0.0038 (19)	−0.0081 (18)	−0.0069 (19)
C7	0.039 (3)	0.045 (3)	0.036 (3)	−0.007 (2)	−0.017 (2)	−0.003 (2)
C8	0.032 (2)	0.040 (3)	0.039 (3)	−0.009 (2)	−0.012 (2)	−0.002 (2)
C9	0.028 (2)	0.037 (3)	0.029 (2)	−0.0013 (19)	−0.0072 (19)	−0.006 (2)
C10	0.050 (3)	0.054 (4)	0.054 (4)	0.004 (3)	0.008 (3)	−0.001 (3)
C11	0.071 (4)	0.055 (4)	0.044 (3)	0.002 (3)	0.003 (3)	0.002 (3)

Geometric parameters (Å, º)

Cd1—O4^i	2.269 (3)	N2—C8	1.142 (6)
Cd1—O4	2.269 (3)	N3—C7	1.147 (6)
Cd1—N4	2.276 (4)	N4—C9	1.153 (5)
Cd1—N4^i	2.276 (4)	C2—C3	1.442 (6)
Cd1—O3^i	2.300 (4)	C3—C4	1.392 (5)
Cd1—O3	2.300 (4)	C3—C9	1.409 (6)
O3—H3	0.8200	C4—C6	1.368 (6)
O3—H31	0.8104	C4—C5	1.515 (6)
O4—H4	0.8200	C6—C8	1.417 (6)
O4—H41	0.8137	C6—C7	1.427 (6)
O1—C2	1.224 (5)	C10—C11^ii	1.488 (8)
O2—C5	1.219 (5)	C10—H10A	0.9700
O5—C11	1.428 (6)	C10—H10B	0.9700
O5—C10	1.431 (6)	C11—C10^ii	1.488 (8)
N1—C5	1.350 (5)	C11—H11A	0.9700
N1—C2	1.392 (5)	C11—H11B	0.9700
N1—H1	0.8600
O4^i—Cd1—O4	180.0 (2)	N1—C2—C3	106.4 (4)
O4^i—Cd1—N4	90.01 (13)	C4—C3—C9	129.9 (4)
O4—Cd1—N4	89.99 (13)	C4—C3—C2	109.7 (4)
O4^i—Cd1—N4^i	89.99 (13)	C9—C3—C2	120.3 (4)
O4—Cd1—N4^i	90.01 (13)	C6—C4—C3	132.6 (4)
N4—Cd1—N4^i	180.0 (3)	C6—C4—C5	122.4 (4)
O4^i—Cd1—O3^i	85.77 (14)	C3—C4—C5	105.0 (3)
O4—Cd1—O3^i	94.23 (14)	O2—C5—N1	126.3 (4)
N4—Cd1—O3^i	87.34 (14)	O2—C5—C4	126.8 (4)
N4^i—Cd1—O3^i	92.66 (14)	N1—C5—C4	106.9 (3)
O4^i—Cd1—O3	94.23 (14)	C4—C6—C8	121.0 (4)
O4—Cd1—O3	85.77 (14)	C4—C6—C7	122.4 (4)
N4—Cd1—O3	92.66 (14)	C8—C6—C7	116.6 (4)
N4^i—Cd1—O3	87.34 (14)	N3—C7—C6	178.4 (5)
O3^i—Cd1—O3	180.00 (18)	N2—C8—C6	178.6 (5)
Cd1—O3—H3	109.5	N4—C9—C3	177.8 (5)
Cd1—O3—H31	126.0	O5—C10—C11^ii	111.2 (5)
H3—O3—H31	105.1	O5—C10—H10A	109.4
Cd1—O4—H4	109.5	C11^ii—C10—H10A	109.4
Cd1—O4—H41	115.1	O5—C10—H10B	109.4
H4—O4—H41	128.4	C11^ii—C10—H10B	109.4
C11—O5—C10	109.6 (4)	H10A—C10—H10B	108.0
C5—N1—C2	111.9 (3)	O5—C11—C10^ii	111.3 (5)
C5—N1—H1	124.0	O5—C11—H11A	109.4
C2—N1—H1	124.0	C10^ii—C11—H11A	109.4
C9—N4—Cd1	167.1 (4)	O5—C11—H11B	109.4
O1—C2—N1	124.2 (4)	C10^ii—C11—H11B	109.4
O1—C2—C3	129.4 (4)	H11A—C11—H11B	108.0

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O5	0.81	2.12	2.831 (5)	145
N1—H1···O1^iii	0.86	1.98	2.831 (5)	172
O3—H3···O5^iv	0.82	2.18	2.993 (6)	169
O4—H4···N2^iv	0.82	2.18	2.893 (5)	145
O3—H31···O2^v	0.81	2.21	2.940 (5)	151

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

(III) poly[[decaaqua-bis(µ₂-3-cyano-4-dicyanomethylene-5-oxo-4,5-dihydro-1H- pyrrol-2-olato-κ²N:N')bis(µ₂-3-cyano-4-dicyanomethylene-3H-pyrrole- 2,5-diolate-κ²N:N')dicadmium] 0.5-hydrate]

Crystal data

[Cd3(C8HN4O2)2(C8N4O2)2(H2O)10]·0.5H2O	F(000) = 2472
Mr = 2527.77	Dx = 1.954 Mg m^−3
Monoclinic, C2/c	Melting point: 260 K
Hall symbol: -C 2yc	Cu Kα radiation, λ = 1.54184 Å
a = 18.3348 (12) Å	Cell parameters from 25 reflections
b = 19.9640 (15) Å	θ = 22–46°
c = 13.5231 (11) Å	µ = 12.64 mm^−1
β = 119.77 (2)°	T = 295 K
V = 4296.7 (10) Å^3	Prism, dark-red
Z = 2	0.20 × 0.15 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometr	3473 reflections with > σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 72.0°, θmin = 3.6°
non–profiled ω scan	h = −22→19
Absorption correction: ψ scan (North et al., 1968)	k = 0→24
Tmin = 0.150, Tmax = 0.385	l = 0→16
4312 measured reflections	2 standard reflections every 120 min
4123 independent reflections	intensity decay: none

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)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.118	w = 1/[σ^2(Fo^2) + (0.0731P)^2 + 11.5086P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.004
4123 reflections	Δρmax = 0.76 e Å^−3
324 parameters	Δρmin = −0.98 e Å^−3
9 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.000105 (18)

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)
Cd1	0.2500	0.2500	0.0000	0.03482 (16)
Cd2	0.10498 (2)	0.737626 (16)	0.02973 (3)	0.03098 (15)
O1	0.5019 (2)	0.41175 (19)	0.3751 (4)	0.0441 (10)
O2	0.3910 (3)	0.62098 (18)	0.2707 (4)	0.0429 (10)
O3	0.3781 (3)	0.1987 (2)	0.0672 (5)	0.0651 (14)
H3	0.3725	0.1581	0.0692	0.098*
H31	0.4091	0.2125	0.0385	0.098*
O4	0.2663 (4)	0.3050 (2)	−0.1343 (4)	0.0598 (14)
H4	0.2898	0.2804	−0.1584	0.090*
H41	0.2921	0.3435	−0.1119	0.090*
N1	0.4642 (3)	0.5235 (2)	0.3454 (4)	0.0320 (10)
H1	0.5092	0.5403	0.4009	0.038*
N2	0.1443 (3)	0.4426 (3)	−0.0141 (5)	0.0464 (12)
N3	0.2027 (3)	0.6530 (2)	0.0594 (5)	0.0460 (13)
N4	0.3122 (3)	0.3358 (2)	0.1280 (4)	0.0419 (11)
C2	0.4517 (3)	0.4549 (2)	0.3214 (5)	0.0288 (10)
C3	0.3684 (3)	0.4489 (2)	0.2209 (4)	0.0260 (10)
C4	0.3322 (3)	0.5117 (2)	0.1888 (4)	0.0238 (9)
C5	0.3972 (3)	0.5604 (2)	0.2708 (5)	0.0288 (10)
C6	0.2532 (3)	0.5316 (2)	0.1053 (4)	0.0265 (10)
C7	0.2280 (3)	0.5998 (3)	0.0838 (5)	0.0321 (11)
C8	0.1917 (3)	0.4832 (3)	0.0363 (5)	0.0325 (11)
C9	0.3367 (3)	0.3867 (2)	0.1695 (4)	0.0288 (10)
O1A	0.0974 (2)	0.89774 (19)	−0.0133 (4)	0.0474 (11)
O2A	0.3193 (2)	0.77993 (18)	0.2511 (4)	0.0441 (10)
O5	0.0900 (3)	0.6887 (2)	0.1731 (4)	0.0618 (13)
H5	0.0861	0.6480	0.1641	0.093*
H51	0.1373	0.6972	0.2361	0.093*
O6	0.0815 (3)	0.7688 (2)	−0.1508 (4)	0.0514 (11)
H6	0.1192	0.7538	−0.1604	0.077*
H61	0.0898	0.8132	−0.1481	0.077*
N1A	0.1943 (2)	0.82165 (18)	0.1092 (4)	0.0271 (9)
N2A	0.4176 (4)	1.0451 (2)	0.3231 (6)	0.0579 (16)
N3A	0.5037 (3)	0.8422 (2)	0.4191 (5)	0.0476 (13)
N4A	0.2056 (3)	1.0596 (2)	0.0999 (5)	0.0397 (11)
C2A	0.1671 (3)	0.8857 (2)	0.0677 (5)	0.0281 (10)
C3A	0.2336 (3)	0.9341 (2)	0.1324 (4)	0.0221 (9)
C4A	0.3031 (3)	0.8992 (2)	0.2096 (4)	0.0229 (9)
C5A	0.2747 (3)	0.8259 (2)	0.1931 (4)	0.0255 (10)
C6A	0.3837 (3)	0.9196 (2)	0.2893 (4)	0.0272 (10)
C7A	0.4489 (3)	0.8752 (2)	0.3600 (5)	0.0318 (11)
C8A	0.4037 (3)	0.9890 (3)	0.3081 (5)	0.0335 (12)
C9A	0.2204 (3)	1.0035 (2)	0.1148 (4)	0.0254 (10)
O10	0.5038 (17)	0.2720 (10)	0.2798 (18)	0.067 (6)*	0.25
O11	−0.0201 (3)	0.7944 (2)	−0.0054 (5)	0.0525 (12)
H11	−0.013	0.805	0.0571	0.079*
H111	−0.029	0.824	−0.051	0.079*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0391 (3)	0.0170 (2)	0.0392 (3)	−0.00586 (19)	0.0125 (2)	−0.00553 (19)
Cd2	0.01977 (19)	0.01864 (19)	0.0413 (2)	−0.00369 (12)	0.00510 (15)	−0.00036 (13)
O1	0.0287 (19)	0.034 (2)	0.054 (3)	0.0050 (16)	0.0093 (18)	0.0058 (18)
O2	0.044 (2)	0.0198 (17)	0.056 (3)	−0.0086 (16)	0.018 (2)	−0.0033 (17)
O3	0.041 (2)	0.045 (3)	0.098 (4)	−0.005 (2)	0.026 (3)	−0.015 (3)
O4	0.101 (4)	0.0211 (19)	0.081 (3)	−0.010 (2)	0.062 (3)	−0.008 (2)
N1	0.022 (2)	0.0220 (19)	0.041 (2)	−0.0096 (16)	0.0068 (18)	−0.0054 (17)
N2	0.028 (2)	0.044 (3)	0.057 (3)	−0.011 (2)	0.013 (2)	−0.012 (2)
N3	0.034 (2)	0.025 (2)	0.063 (3)	0.007 (2)	0.012 (2)	0.001 (2)
N4	0.045 (3)	0.022 (2)	0.047 (3)	−0.001 (2)	0.014 (2)	−0.003 (2)
C2	0.023 (2)	0.025 (2)	0.039 (3)	−0.0032 (19)	0.015 (2)	0.000 (2)
C3	0.022 (2)	0.021 (2)	0.036 (3)	−0.0028 (18)	0.014 (2)	−0.0019 (19)
C4	0.020 (2)	0.018 (2)	0.032 (3)	−0.0061 (17)	0.013 (2)	−0.0058 (18)
C5	0.027 (2)	0.023 (2)	0.036 (3)	−0.0088 (19)	0.016 (2)	−0.004 (2)
C6	0.023 (2)	0.018 (2)	0.037 (3)	−0.0020 (18)	0.014 (2)	−0.0040 (19)
C7	0.022 (2)	0.028 (3)	0.040 (3)	0.000 (2)	0.011 (2)	0.000 (2)
C8	0.025 (2)	0.030 (2)	0.038 (3)	0.002 (2)	0.012 (2)	−0.003 (2)
C9	0.030 (2)	0.017 (2)	0.036 (3)	−0.0016 (18)	0.014 (2)	−0.0016 (19)
O1A	0.0220 (18)	0.0293 (19)	0.060 (3)	0.0041 (15)	−0.0034 (17)	0.0061 (18)
O2A	0.029 (2)	0.0174 (16)	0.063 (3)	0.0046 (14)	0.0062 (19)	0.0108 (17)
O5	0.087 (4)	0.035 (2)	0.050 (3)	−0.002 (2)	0.024 (3)	0.005 (2)
O6	0.056 (3)	0.043 (2)	0.056 (3)	−0.009 (2)	0.028 (2)	0.000 (2)
N1A	0.0199 (18)	0.0150 (17)	0.037 (2)	0.0014 (15)	0.0065 (17)	0.0037 (16)
N2A	0.049 (3)	0.023 (2)	0.080 (4)	−0.007 (2)	0.015 (3)	−0.008 (2)
N3A	0.028 (2)	0.031 (2)	0.057 (3)	0.006 (2)	0.001 (2)	0.000 (2)
N4A	0.043 (3)	0.018 (2)	0.059 (3)	0.0051 (19)	0.026 (2)	0.0076 (19)
C2A	0.021 (2)	0.018 (2)	0.041 (3)	0.0034 (18)	0.012 (2)	0.0033 (19)
C3A	0.017 (2)	0.015 (2)	0.031 (2)	0.0001 (16)	0.0104 (19)	−0.0005 (17)
C4A	0.020 (2)	0.016 (2)	0.032 (2)	0.0024 (17)	0.0119 (19)	0.0019 (17)
C5A	0.025 (2)	0.0123 (19)	0.037 (3)	0.0010 (17)	0.013 (2)	−0.0003 (18)
C6A	0.023 (2)	0.016 (2)	0.035 (3)	−0.0005 (17)	0.009 (2)	0.0006 (18)
C7A	0.022 (2)	0.021 (2)	0.041 (3)	0.0018 (19)	0.007 (2)	−0.001 (2)
C8A	0.024 (2)	0.024 (3)	0.043 (3)	−0.001 (2)	0.010 (2)	−0.003 (2)
C9A	0.020 (2)	0.021 (2)	0.034 (3)	0.0024 (17)	0.013 (2)	−0.0002 (18)
O11	0.032 (2)	0.033 (2)	0.079 (3)	−0.0009 (18)	0.016 (2)	0.002 (2)

Geometric parameters (Å, º)

Cd1—O4^i	2.265 (5)	C4—C6	1.381 (6)
Cd1—O4	2.265 (5)	C4—C5	1.510 (6)
Cd1—N4^i	2.296 (5)	C6—C7	1.421 (6)
Cd1—N4	2.296 (5)	C6—C8	1.425 (7)
Cd1—O3	2.296 (5)	O1A—C2A	1.224 (6)
Cd1—O3^i	2.296 (5)	O2A—C5A	1.221 (6)
Cd2—N1A	2.214 (4)	O5—H5	0.8200
Cd2—O5	2.306 (5)	O5—H51	0.8793
Cd2—N3A^ii	2.338 (5)	O6—H6	0.8200
Cd2—O6	2.343 (5)	O6—H61	0.8960
Cd2—N3	2.347 (5)	N1A—C5A	1.344 (6)
Cd2—O11	2.384 (4)	N1A—C2A	1.386 (6)
O1—C2	1.205 (6)	N2A—C8A	1.145 (7)
O2—C5	1.214 (6)	N3A—C7A	1.134 (7)
O3—H3	0.8200	N3A—Cd2^iii	2.338 (5)
O3—H31	0.8773	N4A—C9A	1.147 (6)
O4—H4	0.8200	C2A—C3A	1.458 (6)
O4—H41	0.8757	C3A—C4A	1.369 (6)
N1—C5	1.357 (7)	C3A—C9A	1.406 (6)
N1—C2	1.400 (6)	C4A—C6A	1.390 (6)
N1—H1	0.8600	C4A—C5A	1.532 (6)
N2—C8	1.136 (7)	C6A—C7A	1.411 (7)
N3—C7	1.140 (7)	C6A—C8A	1.423 (6)
N4—C9	1.140 (7)	O10—O10^iv	0.75 (4)
C2—C3	1.461 (7)	O11—H11	0.82
C3—C4	1.385 (6)	O11—H111	0.82
C3—C9	1.399 (6)
O4^i—Cd1—O4	180.00 (17)	C4—C3—C2	109.5 (4)
O4^i—Cd1—N4^i	91.67 (17)	C9—C3—C2	121.3 (4)
O4—Cd1—N4^i	88.33 (17)	C6—C4—C3	131.4 (4)
O4^i—Cd1—N4	88.33 (17)	C6—C4—C5	122.7 (4)
O4—Cd1—N4	91.67 (17)	C3—C4—C5	105.9 (4)
N4^i—Cd1—N4	180.00 (14)	O2—C5—N1	126.2 (5)
O4^i—Cd1—O3	89.0 (2)	O2—C5—C4	127.0 (5)
O4—Cd1—O3	91.0 (2)	N1—C5—C4	106.8 (4)
N4^i—Cd1—O3	89.60 (18)	C4—C6—C7	123.1 (4)
N4—Cd1—O3	90.40 (18)	C4—C6—C8	120.6 (4)
O4^i—Cd1—O3^i	91.0 (2)	C7—C6—C8	116.3 (4)
O4—Cd1—O3^i	89.0 (2)	N3—C7—C6	175.0 (6)
N4^i—Cd1—O3^i	90.40 (18)	N2—C8—C6	176.6 (6)
N4—Cd1—O3^i	89.60 (18)	N4—C9—C3	178.9 (6)
O3—Cd1—O3^i	180.00 (15)	Cd2—O5—H5	109.5
N1A—Cd2—O5	106.30 (17)	Cd2—O5—H51	105.1
N1A—Cd2—N3A^ii	171.08 (17)	H5—O5—H51	107.9
O5—Cd2—N3A^ii	82.02 (19)	Cd2—O6—H6	109.5
N1A—Cd2—O6	90.77 (16)	Cd2—O6—H61	106.2
O5—Cd2—O6	162.13 (17)	H6—O6—H61	103.2
N3A^ii—Cd2—O6	80.67 (18)	C5A—N1A—C2A	107.8 (4)
N1A—Cd2—N3	98.32 (16)	C5A—N1A—Cd2	134.0 (3)
O5—Cd2—N3	87.18 (19)	C2A—N1A—Cd2	118.1 (3)
N3A^ii—Cd2—N3	85.12 (17)	C7A—N3A—Cd2^iii	172.6 (4)
O6—Cd2—N3	95.70 (19)	O1A—C2A—N1A	123.3 (4)
N1A—Cd2—O11	98.23 (14)	O1A—C2A—C3A	126.6 (4)
O5—Cd2—O11	82.23 (18)	N1A—C2A—C3A	110.0 (4)
N3A^ii—Cd2—O11	79.43 (16)	C4A—C3A—C9A	130.3 (4)
O6—Cd2—O11	90.28 (18)	C4A—C3A—C2A	107.8 (4)
N3—Cd2—O11	162.31 (16)	C9A—C3A—C2A	121.9 (4)
Cd1—O3—H3	109.5	C3A—C4A—C6A	132.2 (4)
Cd1—O3—H31	116.4	C3A—C4A—C5A	104.7 (4)
H3—O3—H31	116.5	C6A—C4A—C5A	123.1 (4)
Cd1—O4—H4	109.5	O2A—C5A—N1A	126.8 (4)
Cd1—O4—H41	114.4	O2A—C5A—C4A	123.7 (4)
H4—O4—H41	111.2	N1A—C5A—C4A	109.5 (4)
C5—N1—C2	112.0 (4)	C4A—C6A—C7A	124.0 (4)
C5—N1—H1	124.0	C4A—C6A—C8A	120.2 (4)
C2—N1—H1	124.0	C7A—C6A—C8A	115.7 (4)
C7—N3—Cd2	152.4 (5)	N3A—C7A—C6A	176.7 (6)
C9—N4—Cd1	164.4 (5)	N2A—C8A—C6A	177.9 (6)
O1—C2—N1	124.8 (5)	N4A—C9A—C3A	176.4 (5)
O1—C2—C3	129.4 (5)	Cd2—O11—H11	106.3
N1—C2—C3	105.8 (4)	Cd2—O11—H111	107.8
C4—C3—C9	129.2 (5)	H11—O11—H111	117.3

Symmetry codes: (i) −x+1/2, −y+1/2, −z; (ii) x−1/2, −y+3/2, z−1/2; (iii) x+1/2, −y+3/2, z+1/2; (iv) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N2^i	0.82	2.11	2.889 (7)	158
N1—H1···O1A^iii	0.86	1.91	2.730 (5)	160
O11—H11···O1^v	0.82	2.29	2.851 (6)	127
O11—H111···O2^ii	0.82	2.38	3.127 (6)	153
O6—H61···O2^vi	0.90	2.28	2.922 (6)	129
O4—H41···N4A^vi	0.88	1.94	2.749 (6)	153
O4—H4···O2A^vii	0.82	1.98	2.779 (6)	166
O5—H5···N2A^viii	0.82	2.06	2.871 (7)	168
O3—H31···O11^ix	0.88	2.34	3.149 (7)	154
O5—H51···O4^x	0.88	2.13	2.980 (8)	162
O6—H6···O2A^vi	0.82	2.15	2.922 (7)	158

Symmetry codes: (i) −x+1/2, −y+1/2, −z; (ii) x−1/2, −y+3/2, z−1/2; (iii) x+1/2, −y+3/2, z+1/2; (v) −x+1/2, y+1/2, −z+1/2; (vi) −x+1/2, −y+3/2, −z; (vii) x, −y+1, z−1/2; (viii) −x+1/2, y−1/2, −z+1/2; (ix) x+1/2, y−1/2, z; (x) x, −y+1, z+1/2.