Cobalt(II) and cadmium(II) square grids supported with 4,4′-bipyrazole and accommodating 3-carb­oxy­adamantane-1-carboxyl­ate

In poly[[bis­(μ-4,4′-bi-1H-pyrazole-κ²N²:N^2′)bis­(3-carb­oxy­ada­mantane-1-carboxyl­ato-κO¹)cobalt(II)] dihydrate], {[Co(C₁₂H₁₅O₄)₂(C₆H₆N₄)₂]·2H₂O}_n, (I), the Co²⁺ cation lies on an inversion centre and the 4,4′-bipyrazole (4,4′-bpz) ligands are also situated across centres of inversion. In its non-isomorphous cadmium analogue, {[Cd(C₁₂H₁₅O₄)₂(C₆H₆N₄)₂]·2H₂O}_n, (II), the Cd²⁺ cation lies on a twofold axis. In both compounds, the metal cations adopt an octa­hedral coordination, with four pyrazole N atoms in the equatorial plane [Co—N = 2.156 (2) and 2.162 (2) Å; Cd—N = 2.298 (2) and 2.321 (2) Å] and two axial carboxyl­ate O atoms [Co—O = 2.1547 (18) Å and Cd—O = 2.347 (2) Å]. In both structures, inter­ligand hydrogen bonding [N...O = 2.682 (3)–2.819 (3) Å] is essential for stabilization of the MN₄O₂ environment with its unusually high (for bulky adamantane­carboxyl­ates) number of coordinated N-donor co-ligands. The compounds adopt two-dimensional coordination connectivities and exist as square-grid [M(4,4′-bpz)₂]_n networks accommodating monodentate carboxyl­ate ligands. The interlayer linkage is provided by hydrogen bonds from the carboxylic acid groups via the solvent water molecules [O...O = 2.565 (3) and 2.616 (3) Å] to the carboxylate groups in the next layer [O...O = 2.717 (3)–2.841 (3) Å], thereby extending the structures in the third dimension.

S1. Comment

Adamantane-1,3-dicarboxylate (ADC^2-) is a paradigmatic ligand used for the generation of metal–organic frameworks (MOFs), providing such important features as multivalence and geometrically rigid angular configuration of binding sites at the entirely aliphatic `nanodiamond scaffold'. These issues are particularly significant for the elegant three-dimensional frameworks adopted by Eu³⁺ (Millange et al., 2004) and Ca²⁺ cations (Nielsen et al., 2012), the layered network in Mg(ADC) (Plonka et al., 2011), and one-dimensional polymers of UO₂²⁺ (Rusanova et al., 2010) and Th⁴⁺ (Nazarenko et al., 2010). From the perspective of crystal design, even more versatile possibilities may be found for transition metal complexes when combining anionic ADC^2- or HADC^- and exo-bidentate neutral N-donor co-ligands. Following this methodology, two groups have developed a variety of heteroligand Ag⁺, Co²⁺, Zn²⁺ and Cd²⁺ frameworks based on bipyridine (Jin et al., 2009, 2010) and bis(1,2,4-triazole) linkers (Ren et al., 2011). However, in these cases the local coordination geometries were suggestive of steric influence of the bulky adamantane scaffold, mitigating against coordination of more than two N-atom donors, irrespective of the nature of the metal cation. In this context, we have examined the prototypical linker 4,4'-bipyrazole (H₂bpz). Unlike the more common pyridine and N-substituted imidazole and 1,2,4-triazole species, coordination of the pyrazole N-atom site is complemented by the strong hydrogen-bond-donor ability of the adjacent NH site. This dual function of pyrazole could be especially important for dense interaction between the coordinated pyrazole and anionic groups, in effect stabilizing higher ligand/M ratios and providing wider possibilities for the generation of highly connected coordination frameworks (Rusanov et al., 2003). We have prepared the title coordination polymers of Co, (I), and Cd, (II), supported with 4,4'-bipyrazole and mediated by singly charged HADC^- anions, and we report their structures here.

The Co^II compound, (I), and its Cd^II analogue, (II), are not isostructural, although they possess similar compositions and very closely related structures. In triclinic (I), the Co²⁺ cation is situated on an inversion centre and two independent bipyrazole ligands are situated across a centre of inversion (Fig. 1). In monoclinic (II), the Cd²⁺ cation lies on a twofold axis (Fig. 2). In both structures, the central atoms adopt a typical sixfold coordination [MN₄O₂] in a slightly distorted octahedral geometry. Their coordination environments comprise four pyrazole N-atom donors in the equatorial planes and two carboxylate O atoms in axial positions (Tables 1 and 3). The appreciably longer Cd–ligand bonds are responsible for the greater volume per formula unit in (II) [916.3 ų in (I) and 965.2 ų in (II)] and the lower packing index [68.7 in (I) and 65.4 in (II)]. Thus, the H₂bpz ligands act as bitopic connectors, while HADC^- represents a monodentate carboxylate ligand retaining a noncoordinated neutral carboxylic acid group. It is worth noting that bridging of HADC^- is also possible, as shown by the structures [Co(HADC)₂(H₂O)₂] (Tang et al., 2009) and [Th(HADC)₄] (Nazarenko et al., 2010).

The most striking feature of the coordination environments of (I) and (II) is self-complementary hydrogen bonding between four pyrazole NH donors and four carboxylate O atoms. There are two kinds of bonding patterns, leading to the organization of five- and seven-membered pseudo-chelate cycles (Figs. 1 and 2), with coordinated O1 and carbonyl O2 atoms, respectively. The corresponding N···O separations [2.682 (3)–2.819 (3) Å; Tables 2 and 4] are characteristic of relatively strong hydrogen bonding. The mutual orientation of these rings provides the primary structural difference for (I) and (II). Two pyrazole groups, constituting either five- or seven-membered rings, adopt a trans configuration in the Co²⁺ complex (Fig. 1) and a cis configuration in the Cd²⁺ analogue (Fig. 2). With respect to the overall structures, this variation appears to be very subtle; it does not affect either the composition of the compounds or the topology of the coordination and hydrogen bonding. Isomerism of the hydrogen-bonding patterns adopted by pyrazole and carboxylate co-ligands is also known for simpler molecular species, such as [Ni(Hpz)₄(AcO)₂] (Hpz = pyrazole; Papánková et al., 2005) and [Ni(Hpz)₄(AcO)₂].H₂O (Döring et al., 1994).

The metal–bipyrazole part of the two structures exists in the form of two-dimensional square-grid networks, which are parallel to the bc plane in (I) and parallel to the ab plane in (II). This topology was also observed for [Cu(H₂bpz)₂(NO₃)₂] (Pettinari et al., 2012), while [Cd(H₂bpz)₂(NO₃)₂] exhibits a three-dimensional array of polycatenated square grids (Boldog et al., 2002). The ligands act as simple bitopic linkers and connect the Co²⁺ cations at distances of 10.1568 (8) and 10.2186 (8) Å [parameters b and c of the unit cell of (I), respectively]. For the Cd analogue, (II), this distance is slightly longer [Cd1···Cd1ⁱⁱⁱ = 10.4390 (6) Å; symmetry code: (iii) x - 1/2, y + 1/2, z]. The planar arrangement of the H₂bpz ligands in (I) or the nearly planar arrangement in (II) [torsion angle C3—C2—C5—C4 = -6.7 (6)°], and the anti configuration of the two N—M bonds, are responsible for the collinear orientation of the M—H₂bpz links and the generation of flat coordination layers. The singly charged HADC^- anions are accommodated on both axial sides of these layers (Fig. 3) and the presence of the bulky adamantane groups is appreciable for the relatively large interlayer separations of 8.8287 (9) and 8.8613 (5) Å for (I) and (II), respectively (Fig. 4). Since all the metal cations of a single layer are coplanar in both structures, the latter parameters are defined as the deviation of the metal cation from the neighbouring plane. These interlayer separations significantly exceed the usual values for square-grid polymers adopted by H₂bpz (4.7–7.0 Å; Boldog et al., 2002).

Thus, the monodentate HADC^- anions terminate the coordination connectivity, which is restricted to the M/H₂bpz linkage. However, the noncoordinated carboxylic acid groups of the HADC^- anions are important for crosslinking of the layers by means of hydrogen bonding. In both structures, the bonds formed by the solvent water molecules lead to the assembly of typical anion/aqua dimers [O···O = 2.717 (3)–2.841 (3) Å] joining the coordinated carboxylate groups of successive layers (Fig. 4). Considering these dimers as links between the coordination layers, three-dimensional six-connected hybrid coordination and hydrogen-bonded frameworks (primitive cubic net) are found for both compounds. The carboxylic acid group is involved in strong hydrogen bonding with the solvent water molecules, i.e. COOH···OH₂ [for (I), O3···O5^iv = 2.565 (3) Å; symmetry code: (iv) -x + 1, -y + 1, -z + 1]; for (II), O3···O5^iv = 2.616 (3) Å; symmetry code: (iv) -x + 1/2, -y + 1/2, -z + 1] (Tables 2 and 4), providing further integration of the dimers. Similar bonding was observed in [Ag(4,4'-bipy)(HADC)].H₂O (4,4'-bipy is 4,4'-bipyridine), with the same O···O separation of 2.565 (4) Å (Jin et al., 2009). The carbonyl O atom of the carboxylic acid group maintains only one weak C—H···O hydrogen bond with the pyrazole ring [for (I), C···O = 3.407 (4) Å; symmetry code: -x + 1, -y, -z + 1; for (II), C···O = 3.465 (4) Å; symmetry code: x + 1/2, -y + 1/2, z - 1/2], whereas the C7═O2 carboxylate group accepts three strong hydrogen bonds from a pyrazole NH donor and two solvent water molecules (Tables 2 and 4). Such a functionality of coordinated carboxylate is relatively rare; a related pattern involving triple hydrogen bonding, together with the formation of COO^-/aqua dimers, was observed in hydrated bis(pyridazine-3-carboxylato)zinc(II) (Gryz et al., 2003).

In brief, the title compounds demonstrate the special potential of bipyrazole species as efficient bridging co-ligands for coordination polymers formed by bulky adamantanecarboxylates. This approach, relying on a synergism of coordination and hydrogen bonding, could be particularly important for the stabilization of the inner coordination sphere and may find wider applications in developing frameworks based on polyfunctionalized adamantanes.

Related literature

For related literature, see: Boldog et al. (2001, 2002); Döring et al. (1994); Gryz et al. (2003); Jin et al. (2009, 2010); Millange et al. (2004); Nazarenko et al. (2010); Nielsen et al. (2012); Papánková et al. (2005); Pettinari et al. (2012); Plonka et al. (2011); Ren et al. (2011); Rusanov et al. (2003); Rusanova et al. (2010); Stetter & Wulff (1960); Tang et al. (2009).

S2. Experimental

Adamantane-1,3-dicarboxylic acid (H₂ADC) was synthesized by the Koch–Haaf carboxylation of adamantane-1,3-diol (Stetter & Wulff, 1960) and 4,4'-bipyrazole (H₂bpz) was prepared by a multistage synthesis starting from butyne-1,4-diol (Boldog et al., 2001).

For the preparation of (I), a mixture of H₂ADC (17.9 mg, 0.080 mmol), Co(AcO)₂.4H₂O (10.2 mg, 0.041 mmol) and H₂bpz (10.8 mg, 0.081 mmol) in water (4 ml) was sealed in a 15 ml Pyrex tube, heated at 423 K for 24 h and then cooled to room temperature at a rate of 2 K h^-1. Pink crystals of (I) were collected by filtration (yield 19 mg, 60%).

The Cd analogue, (II) (colourless prisms; yield 19 mg, 55%), was prepared in a similar manner starting with Cd(AcO)₂.2H₂O (10.6 mg, 0.040 mmol).

Elemental analysis for (I), calculated: C 53.40, H 5.73, N 13.84%; found: C 53.57, H 5.68, N 14.03%. Elemental analysis for (II), calculated: C 50.09, H 5.37, N 12.98%; found: C 50.43, H 5.31, N 13.18%.

S3. Refinement

All H atoms were located from difference maps and then refined as riding, with the angles constrained and with distance restraints of O—H = 0.85 Å, N—H = 0.86 Å, methylene C—H = 0.97 Å, adamantane C—H = 0.98 Å and pyrazole C—H = 0.93 Å, and with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(O,N).

Computing details

For both compounds, data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-NT (Bruker, 1999); data reduction: SAINT-NT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures

	Fig. 1. The structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. N and O atoms are shaded grey and dashed lines indicate hydrogen bonding. [Symmetry codes: (i) -x + 2, -y, -z; (ii) -x + 2, -y + 1, -z; (iii) -x + 2, -y, -z + 1.]
	Fig. 2. The structure of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. N and O atoms are shaded grey and dashed lines indicate hydrogen bonding. [Symmetry codes: (i) -x + 1, y, -z + 1/2; (ii) -x + 3/2, y + 1/2, -z + 1/2; (iii) x - 1/2, y + 1/2, z.]
	Fig. 3. A projection of the structure of (I) on the bc plane, showing the Co^2+/H2bpz layer (indicated as a grey grid) accommodating HADC^- anions by coordination and hydrogen bonding (dashed lines). The carbocyclic skeletons are shown as grey wires, and O and N atoms are shaded grey.
	Fig. 4. The interconnection of successive coordination layers in (I) (which are nearly orthogonal to the drawing plane) by hydrogen bonding (dashed lines) involving either coordinated carboxylate or carboxy groups and water molecules. Note the location of bulky adamantane ligands in the interlayer space (the carbocyclic skeletons are shown as grey wires). [Symmetry codes: (i) -x + 2, -y, -z; (iv) -x + 1, -y + 1, -z + 1, (v) -x + 1, -y, -z + 1.]

(I) Poly[[bis(µ-4,4'-bi-1H-pyrazole-κ²N²:N^2')bis(3-carboxyadamantane-1-carboxylato-κO¹)cobalt(II)] dihydrate]

Crystal data

[Co(C12H15O4)2(C6H6N4)2]·2H2O	Z = 1
Mr = 809.74	F(000) = 425
Triclinic, P1	Dx = 1.467 Mg m^−3
a = 10.0002 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.1568 (8) Å	Cell parameters from 16309 reflections
c = 10.2186 (8) Å	θ = 2.1–26.8°
α = 89.906 (6)°	µ = 0.54 mm^−1
β = 66.363 (5)°	T = 296 K
γ = 75.805 (5)°	Prism, pink
V = 916.32 (13) Å^3	0.22 × 0.22 × 0.18 mm

Data collection

Bruker APEXII area-detector diffractometer	3857 independent reflections
Radiation source: fine-focus sealed tube	3006 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
ω scans	θmax = 26.8°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.891, Tmax = 0.909	k = −12→12
16309 measured reflections	l = −12→12

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.125	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0632P)^2 + 0.3148P] where P = (Fo^2 + 2Fc^2)/3
3857 reflections	(Δ/σ)max < 0.001
250 parameters	Δρmax = 1.20 e Å^−3
0 restraints	Δρmin = −0.33 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
Co1	1.0000	0.0000	0.0000	0.01857 (16)
O1	0.7623 (2)	0.10514 (19)	0.08758 (19)	0.0291 (4)
O2	0.6465 (2)	0.01954 (19)	0.2881 (2)	0.0339 (5)
O3	0.4723 (3)	0.6279 (2)	0.3208 (3)	0.0605 (7)
H1O	0.4860	0.6984	0.3526	0.091*
O4	0.2746 (3)	0.6306 (3)	0.5213 (3)	0.0637 (8)
O5	0.5378 (3)	0.1396 (2)	0.5727 (2)	0.0531 (7)
H1W	0.5745	0.1077	0.4849	0.080*
H2W	0.4784	0.0935	0.6223	0.080*
N1	1.0309 (2)	0.2026 (2)	−0.0276 (2)	0.0229 (5)
N2	1.1426 (3)	0.2249 (2)	−0.1442 (2)	0.0297 (5)
H1N	1.2075	0.1619	−0.2111	0.045*
N3	1.0226 (2)	−0.0046 (2)	0.2018 (2)	0.0237 (5)
N4	1.1443 (3)	−0.1002 (3)	0.1982 (2)	0.0357 (6)
H2N	1.2121	−0.1507	0.1218	0.054*
C1	0.9562 (3)	0.3252 (3)	0.0465 (3)	0.0247 (6)
H1	0.8712	0.3414	0.1334	0.030*
C2	1.0226 (3)	0.4263 (2)	−0.0235 (3)	0.0217 (5)
C3	1.1419 (3)	0.3571 (3)	−0.1453 (3)	0.0313 (7)
H3	1.2102	0.3948	−0.2159	0.038*
C4	0.9484 (3)	0.0473 (3)	0.3382 (3)	0.0254 (6)
H4	0.8582	0.1164	0.3735	0.030*
C5	1.0220 (3)	−0.0144 (3)	0.4229 (3)	0.0232 (6)
C6	1.1475 (4)	−0.1072 (3)	0.3273 (3)	0.0387 (8)
H6	1.2223	−0.1652	0.3484	0.046*
C7	0.6456 (3)	0.1019 (3)	0.1966 (3)	0.0227 (6)
C8	0.3607 (3)	0.5777 (3)	0.4030 (4)	0.0364 (7)
C9	0.4962 (3)	0.2089 (3)	0.2225 (3)	0.0257 (6)
C10	0.5017 (3)	0.3397 (3)	0.2947 (3)	0.0253 (6)
H10A	0.5870	0.3710	0.2307	0.030*
H10B	0.5151	0.3201	0.3823	0.030*
C11	0.3527 (3)	0.4524 (3)	0.3301 (3)	0.0291 (6)
C12	0.3383 (4)	0.4845 (3)	0.1885 (3)	0.0386 (7)
H12A	0.2466	0.5565	0.2079	0.046*
H12B	0.4240	0.5161	0.1259	0.046*
C13	0.3335 (4)	0.3563 (3)	0.1148 (4)	0.0450 (8)
H13	0.3238	0.3772	0.0248	0.054*
C14	0.4808 (4)	0.2433 (3)	0.0821 (3)	0.0386 (7)
H14A	0.4791	0.1622	0.0333	0.046*
H14B	0.5671	0.2740	0.0192	0.046*
C15	0.3576 (3)	0.1627 (3)	0.3218 (3)	0.0360 (7)
H15A	0.3540	0.0806	0.2764	0.043*
H15B	0.3662	0.1415	0.4112	0.043*
C16	0.2125 (3)	0.2752 (3)	0.3530 (4)	0.0445 (8)
H16	0.1251	0.2444	0.4162	0.053*
C17	0.2187 (3)	0.4023 (3)	0.4275 (4)	0.0397 (8)
H17A	0.1256	0.4737	0.4507	0.048*
H17B	0.2282	0.3810	0.5165	0.048*
C18	0.1981 (4)	0.3083 (4)	0.2132 (4)	0.0551 (10)
H18A	0.1935	0.2276	0.1662	0.066*
H18B	0.1054	0.3792	0.2333	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0251 (3)	0.0158 (3)	0.0166 (3)	−0.0062 (2)	−0.0099 (2)	0.00106 (19)
O1	0.0257 (10)	0.0330 (11)	0.0231 (10)	−0.0050 (8)	−0.0061 (8)	0.0037 (8)
O2	0.0319 (11)	0.0266 (11)	0.0307 (11)	−0.0009 (9)	−0.0044 (9)	0.0062 (9)
O3	0.0529 (15)	0.0441 (14)	0.0732 (18)	−0.0244 (12)	−0.0081 (13)	−0.0107 (13)
O4	0.0625 (17)	0.0596 (17)	0.0521 (16)	−0.0141 (14)	−0.0078 (14)	−0.0238 (14)
O5	0.0844 (18)	0.0401 (13)	0.0414 (13)	−0.0331 (13)	−0.0233 (13)	0.0073 (11)
N1	0.0258 (12)	0.0180 (11)	0.0247 (12)	−0.0080 (9)	−0.0091 (10)	0.0000 (9)
N2	0.0323 (13)	0.0192 (12)	0.0262 (12)	−0.0049 (10)	−0.0017 (10)	−0.0038 (10)
N3	0.0271 (12)	0.0255 (12)	0.0201 (11)	−0.0058 (9)	−0.0121 (9)	0.0020 (9)
N4	0.0351 (14)	0.0408 (15)	0.0203 (12)	0.0113 (11)	−0.0128 (11)	−0.0058 (11)
C1	0.0233 (14)	0.0214 (13)	0.0269 (14)	−0.0053 (11)	−0.0081 (11)	−0.0039 (11)
C2	0.0248 (13)	0.0187 (13)	0.0234 (13)	−0.0056 (11)	−0.0118 (11)	0.0003 (11)
C3	0.0347 (16)	0.0239 (14)	0.0292 (16)	−0.0120 (12)	−0.0047 (13)	0.0020 (12)
C4	0.0275 (14)	0.0267 (14)	0.0223 (14)	−0.0048 (11)	−0.0121 (11)	−0.0004 (11)
C5	0.0296 (14)	0.0254 (14)	0.0175 (13)	−0.0100 (11)	−0.0111 (11)	0.0020 (11)
C6	0.0392 (17)	0.0470 (19)	0.0251 (15)	0.0058 (15)	−0.0186 (14)	−0.0005 (14)
C7	0.0238 (13)	0.0208 (13)	0.0214 (13)	−0.0057 (11)	−0.0074 (11)	−0.0038 (11)
C8	0.0335 (16)	0.0274 (16)	0.0452 (19)	0.0005 (13)	−0.0182 (15)	−0.0040 (14)
C9	0.0249 (14)	0.0241 (14)	0.0274 (15)	−0.0078 (11)	−0.0096 (12)	0.0014 (11)
C10	0.0197 (13)	0.0248 (14)	0.0300 (15)	−0.0053 (11)	−0.0091 (11)	−0.0006 (11)
C11	0.0252 (14)	0.0264 (15)	0.0343 (16)	−0.0031 (12)	−0.0132 (12)	0.0002 (12)
C12	0.0357 (17)	0.0324 (17)	0.0448 (19)	−0.0004 (13)	−0.0188 (15)	0.0031 (14)
C13	0.049 (2)	0.049 (2)	0.0448 (19)	−0.0014 (16)	−0.0344 (17)	−0.0012 (16)
C14	0.0470 (19)	0.0364 (17)	0.0322 (16)	−0.0032 (14)	−0.0208 (15)	−0.0033 (14)
C15	0.0293 (16)	0.0304 (16)	0.0480 (19)	−0.0118 (13)	−0.0133 (14)	0.0058 (14)
C16	0.0237 (15)	0.046 (2)	0.062 (2)	−0.0128 (14)	−0.0139 (15)	0.0032 (17)
C17	0.0224 (15)	0.0410 (18)	0.0454 (19)	−0.0016 (13)	−0.0078 (14)	−0.0010 (15)
C18	0.044 (2)	0.049 (2)	0.087 (3)	−0.0076 (17)	−0.045 (2)	−0.003 (2)

Geometric parameters (Å, º)

Co1—O1	2.1547 (18)	C6—H6	0.9300
Co1—O1^i	2.1547 (18)	C7—C9	1.541 (4)
Co1—N1	2.156 (2)	C8—C11	1.510 (4)
Co1—N1^i	2.156 (2)	C9—C14	1.534 (4)
Co1—N3	2.162 (2)	C9—C15	1.536 (4)
Co1—N3^i	2.162 (2)	C9—C10	1.544 (4)
O1—C7	1.257 (3)	C10—C11	1.547 (4)
O2—C7	1.254 (3)	C10—H10A	0.9700
O3—C8	1.318 (4)	C10—H10B	0.9700
O3—H1O	0.8500	C11—C17	1.519 (4)
O4—C8	1.196 (4)	C11—C12	1.537 (4)
O5—H1W	0.8500	C12—C13	1.526 (4)
O5—H2W	0.8500	C12—H12A	0.9700
N1—C1	1.332 (3)	C12—H12B	0.9700
N1—N2	1.332 (3)	C13—C18	1.521 (5)
N2—C3	1.341 (3)	C13—C14	1.542 (4)
N2—H1N	0.8600	C13—H13	0.9800
N3—C4	1.324 (3)	C14—H14A	0.9700
N3—N4	1.345 (3)	C14—H14B	0.9700
N4—C6	1.333 (4)	C15—C16	1.526 (4)
N4—H2N	0.8600	C15—H15A	0.9700
C1—C2	1.399 (4)	C15—H15B	0.9700
C1—H1	0.9300	C16—C18	1.521 (5)
C2—C3	1.366 (4)	C16—C17	1.527 (4)
C2—C2^ii	1.475 (5)	C16—H16	0.9800
C3—H3	0.9300	C17—H17A	0.9700
C4—C5	1.403 (4)	C17—H17B	0.9700
C4—H4	0.9300	C18—H18A	0.9700
C5—C6	1.363 (4)	C18—H18B	0.9700
C5—C5^iii	1.464 (5)
O1—Co1—O1^i	180.00 (6)	C14—C9—C10	107.9 (2)
O1—Co1—N1	84.13 (8)	C15—C9—C10	109.6 (2)
O1^i—Co1—N1	95.87 (8)	C7—C9—C10	105.8 (2)
O1—Co1—N1^i	95.87 (8)	C9—C10—C11	109.7 (2)
O1^i—Co1—N1^i	84.13 (8)	C9—C10—H10A	109.7
N1—Co1—N1^i	180.00 (12)	C11—C10—H10A	109.7
O1—Co1—N3	96.61 (7)	C9—C10—H10B	109.7
O1^i—Co1—N3	83.39 (7)	C11—C10—H10B	109.7
N1—Co1—N3	93.21 (8)	H10A—C10—H10B	108.2
N1^i—Co1—N3	86.79 (8)	C8—C11—C17	110.6 (2)
O1—Co1—N3^i	83.39 (7)	C8—C11—C12	110.3 (2)
O1^i—Co1—N3^i	96.61 (7)	C17—C11—C12	109.5 (2)
N1—Co1—N3^i	86.79 (8)	C8—C11—C10	108.3 (2)
N1^i—Co1—N3^i	93.21 (8)	C17—C11—C10	109.8 (2)
N3—Co1—N3^i	180.0	C12—C11—C10	108.3 (2)
C7—O1—Co1	136.67 (18)	C13—C12—C11	109.6 (3)
C8—O3—H1O	119.8	C13—C12—H12A	109.7
H1W—O5—H2W	108.4	C11—C12—H12A	109.7
C1—N1—N2	105.1 (2)	C13—C12—H12B	109.7
C1—N1—Co1	134.55 (18)	C11—C12—H12B	109.7
N2—N1—Co1	120.33 (16)	H12A—C12—H12B	108.2
N1—N2—C3	112.1 (2)	C18—C13—C12	109.4 (3)
N1—N2—H1N	123.9	C18—C13—C14	109.7 (3)
C3—N2—H1N	123.9	C12—C13—C14	109.4 (3)
C4—N3—N4	104.4 (2)	C18—C13—H13	109.4
C4—N3—Co1	141.30 (19)	C12—C13—H13	109.4
N4—N3—Co1	113.90 (16)	C14—C13—H13	109.4
C6—N4—N3	112.0 (2)	C9—C14—C13	109.8 (2)
C6—N4—H2N	124.0	C9—C14—H14A	109.7
N3—N4—H2N	124.0	C13—C14—H14A	109.7
N1—C1—C2	111.1 (2)	C9—C14—H14B	109.7
N1—C1—H1	124.5	C13—C14—H14B	109.7
C2—C1—H1	124.5	H14A—C14—H14B	108.2
C3—C2—C1	104.3 (2)	C16—C15—C9	110.2 (2)
C3—C2—C2^ii	127.3 (3)	C16—C15—H15A	109.6
C1—C2—C2^ii	128.3 (3)	C9—C15—H15A	109.6
N2—C3—C2	107.4 (2)	C16—C15—H15B	109.6
N2—C3—H3	126.3	C9—C15—H15B	109.6
C2—C3—H3	126.3	H15A—C15—H15B	108.1
N3—C4—C5	111.9 (2)	C18—C16—C15	109.8 (3)
N3—C4—H4	124.1	C18—C16—C17	109.8 (3)
C5—C4—H4	124.1	C15—C16—C17	108.9 (3)
C6—C5—C4	103.7 (2)	C18—C16—H16	109.4
C6—C5—C5^iii	127.5 (3)	C15—C16—H16	109.4
C4—C5—C5^iii	128.8 (3)	C17—C16—H16	109.4
N4—C6—C5	108.0 (3)	C11—C17—C16	110.1 (2)
N4—C6—H6	126.0	C11—C17—H17A	109.6
C5—C6—H6	126.0	C16—C17—H17A	109.6
O2—C7—O1	123.2 (2)	C11—C17—H17B	109.6
O2—C7—C9	118.6 (2)	C16—C17—H17B	109.6
O1—C7—C9	118.2 (2)	H17A—C17—H17B	108.2
O4—C8—O3	121.9 (3)	C13—C18—C16	109.7 (3)
O4—C8—C11	125.2 (3)	C13—C18—H18A	109.7
O3—C8—C11	112.9 (3)	C16—C18—H18A	109.7
C14—C9—C15	109.1 (2)	C13—C18—H18B	109.7
C14—C9—C7	112.5 (2)	C16—C18—H18B	109.7
C15—C9—C7	111.8 (2)	H18A—C18—H18B	108.2
N1—Co1—O1—C7	−133.0 (3)	O1—C7—C9—C14	35.8 (3)
N1^i—Co1—O1—C7	47.0 (3)	O2—C7—C9—C15	−23.9 (3)
N3—Co1—O1—C7	−40.4 (3)	O1—C7—C9—C15	159.0 (2)
N3^i—Co1—O1—C7	139.6 (3)	O2—C7—C9—C10	95.3 (3)
O1—Co1—N1—C1	34.9 (2)	O1—C7—C9—C10	−81.8 (3)
O1^i—Co1—N1—C1	−145.1 (2)	C14—C9—C10—C11	61.4 (3)
N3—Co1—N1—C1	−61.4 (3)	C15—C9—C10—C11	−57.3 (3)
N3^i—Co1—N1—C1	118.6 (3)	C7—C9—C10—C11	−178.0 (2)
O1—Co1—N1—N2	−141.6 (2)	O4—C8—C11—C17	0.3 (4)
O1^i—Co1—N1—N2	38.4 (2)	O3—C8—C11—C17	−177.8 (3)
N3—Co1—N1—N2	122.05 (19)	O4—C8—C11—C12	121.6 (4)
N3^i—Co1—N1—N2	−57.95 (19)	O3—C8—C11—C12	−56.5 (3)
C1—N1—N2—C3	0.7 (3)	O4—C8—C11—C10	−120.1 (3)
Co1—N1—N2—C3	178.20 (18)	O3—C8—C11—C10	61.8 (3)
O1—Co1—N3—C4	−11.2 (3)	C9—C10—C11—C8	178.9 (2)
O1^i—Co1—N3—C4	168.8 (3)	C9—C10—C11—C17	58.1 (3)
N1—Co1—N3—C4	73.3 (3)	C9—C10—C11—C12	−61.5 (3)
N1^i—Co1—N3—C4	−106.7 (3)	C8—C11—C12—C13	178.9 (2)
O1—Co1—N3—N4	159.88 (18)	C17—C11—C12—C13	−59.1 (3)
O1^i—Co1—N3—N4	−20.12 (18)	C10—C11—C12—C13	60.6 (3)
N1—Co1—N3—N4	−115.66 (19)	C11—C12—C13—C18	59.9 (3)
N1^i—Co1—N3—N4	64.34 (19)	C11—C12—C13—C14	−60.4 (3)
C4—N3—N4—C6	−0.7 (3)	C15—C9—C14—C13	58.5 (3)
Co1—N3—N4—C6	−174.9 (2)	C7—C9—C14—C13	−176.9 (2)
N2—N1—C1—C2	−0.6 (3)	C10—C9—C14—C13	−60.5 (3)
Co1—N1—C1—C2	−177.53 (18)	C18—C13—C14—C9	−59.4 (3)
N1—C1—C2—C3	0.3 (3)	C12—C13—C14—C9	60.6 (4)
N1—C1—C2—C2^ii	−178.5 (3)	C14—C9—C15—C16	−58.8 (3)
N1—N2—C3—C2	−0.6 (3)	C7—C9—C15—C16	176.2 (2)
C1—C2—C3—N2	0.2 (3)	C10—C9—C15—C16	59.2 (3)
C2^ii—C2—C3—N2	179.0 (3)	C9—C15—C16—C18	59.6 (3)
N4—N3—C4—C5	0.1 (3)	C9—C15—C16—C17	−60.6 (3)
Co1—N3—C4—C5	171.7 (2)	C8—C11—C17—C16	−179.6 (3)
N3—C4—C5—C6	0.5 (3)	C12—C11—C17—C16	58.6 (3)
N3—C4—C5—C5^iii	179.3 (3)	C10—C11—C17—C16	−60.1 (3)
N3—N4—C6—C5	1.0 (4)	C18—C16—C17—C11	−59.1 (3)
C4—C5—C6—N4	−0.9 (3)	C15—C16—C17—C11	61.1 (4)
C5^iii—C5—C6—N4	−179.7 (3)	C12—C13—C18—C16	−60.3 (4)
Co1—O1—C7—O2	−2.4 (4)	C14—C13—C18—C16	59.8 (3)
Co1—O1—C7—C9	174.57 (17)	C15—C16—C18—C13	−59.9 (3)
O2—C7—C9—C14	−147.0 (2)	C17—C16—C18—C13	59.8 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1O···O5^iv	0.85	1.74	2.565 (3)	164
O5—H1W···O2	0.85	1.97	2.820 (3)	174
O5—H2W···O2^v	0.85	1.87	2.717 (3)	174
N2—H1N···O2^i	0.86	1.98	2.781 (3)	155
N4—H2N···O1^i	0.86	2.11	2.682 (3)	123
C4—H4···O4^iv	0.93	2.59	3.407 (4)	147

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

(II) Poly[[bis(µ-4,4'-bi-1H-pyrazole-κ²N²:N^2')bis(3-carboxyadamantane-1-carboxylato-κO¹)cadmium(II)] dihydrate]

Crystal data

[Cd(C12H15O4)2(C6H6N4)2]·2H2O	F(000) = 1784
Mr = 863.21	Dx = 1.485 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.5363 (12) Å	Cell parameters from 12693 reflections
b = 14.9862 (13) Å	θ = 2.1–26.4°
c = 18.3813 (17) Å	µ = 0.63 mm^−1
β = 105.384 (7)°	T = 296 K
V = 3860.8 (6) Å^3	Prism, colourless
Z = 4	0.23 × 0.22 × 0.19 mm

Data collection

Bruker APEXII area-detector diffractometer	3945 independent reflections
Radiation source: fine-focus sealed tube	3056 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
ω scans	θmax = 26.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→18
Tmin = 0.868, Tmax = 0.889	k = −18→18
12693 measured reflections	l = −22→18

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.077	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0264P)^2 + 1.6268P] where P = (Fo^2 + 2Fc^2)/3
3945 reflections	(Δ/σ)max < 0.001
249 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.43 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	0.209765 (19)	0.2500	0.02024 (10)
O1	0.52757 (16)	0.24394 (13)	0.37859 (12)	0.0329 (6)
O2	0.52525 (16)	0.11352 (13)	0.43394 (12)	0.0354 (6)
O3	0.28963 (19)	0.40998 (18)	0.51619 (15)	0.0666 (9)
H1O	0.2328	0.4291	0.5087	0.100*
O4	0.2789 (2)	0.3313 (2)	0.61387 (16)	0.0695 (9)
O5	0.37647 (16)	0.02616 (14)	0.47978 (14)	0.0518 (7)
H1W	0.4186	0.0545	0.4646	0.078*
H2W	0.4033	−0.0175	0.5066	0.078*
N1	0.61043 (18)	0.09640 (16)	0.27108 (15)	0.0299 (7)
N2	0.61718 (19)	0.04162 (16)	0.33006 (15)	0.0340 (7)
H1N	0.5875	0.0494	0.3643	0.051*
N3	0.88300 (19)	−0.18159 (16)	0.23721 (15)	0.0322 (7)
N4	0.8645 (2)	−0.13287 (17)	0.17452 (16)	0.0386 (7)
H2N	0.8902	−0.1418	0.1380	0.058*
C1	0.6657 (2)	0.0608 (2)	0.23276 (18)	0.0297 (8)
H1	0.6747	0.0847	0.1884	0.036*
C2	0.7095 (2)	−0.01746 (18)	0.26681 (17)	0.0241 (7)
C3	0.6760 (2)	−0.0265 (2)	0.32876 (18)	0.0335 (8)
H3	0.6913	−0.0722	0.3641	0.040*
C4	0.8292 (2)	−0.1464 (2)	0.27713 (18)	0.0365 (9)
H4	0.8269	−0.1677	0.3241	0.044*
C5	0.7762 (2)	−0.0740 (2)	0.24144 (17)	0.0266 (7)
C6	0.8013 (3)	−0.0684 (2)	0.1751 (2)	0.0410 (9)
H6	0.7783	−0.0270	0.1369	0.049*
C7	0.5296 (2)	0.19788 (19)	0.43565 (17)	0.0243 (7)
C8	0.3238 (3)	0.3549 (2)	0.5714 (2)	0.0381 (9)
C9	0.5325 (2)	0.24696 (19)	0.50917 (18)	0.0250 (7)
C10	0.4302 (2)	0.2778 (2)	0.50451 (17)	0.0278 (7)
H10A	0.4080	0.3170	0.4614	0.033*
H10B	0.3882	0.2264	0.4975	0.033*
C11	0.4266 (2)	0.3272 (2)	0.57656 (17)	0.0307 (8)
C12	0.4627 (3)	0.2660 (2)	0.64389 (18)	0.0406 (9)
H12A	0.4593	0.2966	0.6896	0.049*
H12B	0.4224	0.2134	0.6382	0.049*
C13	0.5646 (3)	0.2382 (3)	0.65038 (19)	0.0472 (10)
H13	0.5870	0.1992	0.6943	0.057*
C14	0.5676 (3)	0.1874 (2)	0.57865 (17)	0.0407 (9)
H14A	0.6324	0.1682	0.5824	0.049*
H14B	0.5276	0.1347	0.5735	0.049*
C15	0.5961 (3)	0.3306 (2)	0.5186 (2)	0.0437 (10)
H15A	0.6613	0.3133	0.5215	0.052*
H15B	0.5739	0.3694	0.4753	0.052*
C16	0.5929 (3)	0.3806 (3)	0.5906 (2)	0.0535 (11)
H16	0.6338	0.4335	0.5961	0.064*
C17	0.6298 (3)	0.3201 (3)	0.6587 (2)	0.0665 (13)
H17A	0.6300	0.3520	0.7047	0.080*
H17B	0.6946	0.3015	0.6617	0.080*
C18	0.4910 (3)	0.4099 (2)	0.5856 (2)	0.0441 (10)
H18A	0.4685	0.4494	0.5427	0.053*
H18B	0.4892	0.4421	0.6309	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02006 (17)	0.01415 (15)	0.0288 (2)	0.000	0.01052 (14)	0.000
O1	0.0489 (15)	0.0285 (11)	0.0259 (13)	−0.0042 (10)	0.0181 (12)	0.0015 (11)
O2	0.0550 (16)	0.0239 (11)	0.0352 (14)	0.0058 (10)	0.0259 (13)	0.0009 (10)
O3	0.0598 (19)	0.092 (2)	0.0531 (19)	0.0411 (17)	0.0240 (16)	0.0213 (17)
O4	0.0523 (19)	0.102 (2)	0.066 (2)	0.0201 (17)	0.0364 (17)	0.0163 (18)
O5	0.0382 (15)	0.0416 (14)	0.081 (2)	0.0156 (11)	0.0253 (15)	0.0188 (14)
N1	0.0290 (16)	0.0292 (14)	0.0373 (17)	0.0117 (12)	0.0191 (14)	0.0040 (13)
N2	0.0451 (18)	0.0319 (14)	0.0337 (17)	0.0147 (13)	0.0254 (15)	0.0100 (14)
N3	0.0370 (17)	0.0356 (15)	0.0267 (16)	0.0188 (13)	0.0130 (14)	0.0065 (13)
N4	0.0496 (19)	0.0405 (16)	0.0347 (18)	0.0196 (15)	0.0269 (15)	0.0099 (15)
C1	0.0307 (19)	0.0335 (17)	0.028 (2)	0.0068 (15)	0.0140 (16)	0.0030 (16)
C2	0.0215 (17)	0.0249 (16)	0.0267 (19)	0.0045 (13)	0.0078 (15)	0.0001 (15)
C3	0.045 (2)	0.0312 (18)	0.029 (2)	0.0148 (16)	0.0191 (18)	0.0099 (16)
C4	0.044 (2)	0.046 (2)	0.0232 (19)	0.0240 (17)	0.0163 (17)	0.0114 (17)
C5	0.0270 (18)	0.0281 (16)	0.0251 (19)	0.0077 (14)	0.0074 (16)	−0.0031 (15)
C6	0.053 (2)	0.0328 (18)	0.042 (2)	0.0228 (17)	0.021 (2)	0.0121 (18)
C7	0.0227 (16)	0.0271 (17)	0.0264 (18)	0.0015 (13)	0.0124 (14)	0.0027 (15)
C8	0.041 (2)	0.045 (2)	0.030 (2)	0.0056 (18)	0.0141 (19)	−0.0088 (18)
C9	0.0257 (18)	0.0269 (15)	0.0246 (18)	0.0018 (13)	0.0104 (15)	−0.0013 (14)
C10	0.0319 (18)	0.0293 (17)	0.0219 (17)	0.0051 (14)	0.0066 (15)	−0.0019 (15)
C11	0.0295 (19)	0.0430 (18)	0.0219 (19)	0.0037 (15)	0.0109 (16)	−0.0061 (16)
C12	0.046 (2)	0.055 (2)	0.0210 (19)	0.0015 (18)	0.0092 (17)	−0.0030 (17)
C13	0.055 (3)	0.065 (3)	0.019 (2)	0.023 (2)	0.0047 (19)	0.0045 (18)
C14	0.045 (2)	0.051 (2)	0.0240 (19)	0.0199 (17)	0.0052 (17)	0.0007 (17)
C15	0.038 (2)	0.051 (2)	0.048 (2)	−0.0172 (18)	0.0231 (19)	−0.016 (2)
C16	0.047 (3)	0.062 (3)	0.053 (3)	−0.027 (2)	0.017 (2)	−0.029 (2)
C17	0.031 (2)	0.110 (4)	0.049 (3)	0.002 (2)	−0.005 (2)	−0.037 (3)
C18	0.052 (3)	0.040 (2)	0.044 (2)	−0.0037 (18)	0.021 (2)	−0.0141 (19)

Geometric parameters (Å, º)

Cd1—N1^i	2.298 (2)	C6—H6	0.9300
Cd1—N1	2.298 (2)	C7—C9	1.529 (4)
Cd1—N3^ii	2.321 (2)	C8—C11	1.530 (4)
Cd1—N3^iii	2.321 (2)	C9—C14	1.530 (4)
Cd1—O1^i	2.347 (2)	C9—C10	1.538 (4)
Cd1—O1	2.347 (2)	C9—C15	1.540 (4)
O1—C7	1.249 (3)	C10—C11	1.530 (4)
O2—C7	1.266 (3)	C10—H10A	0.9700
O3—C8	1.300 (4)	C10—H10B	0.9700
O3—H1O	0.8500	C11—C12	1.518 (4)
O4—C8	1.196 (4)	C11—C18	1.536 (4)
O5—H1W	0.8500	C12—C13	1.514 (5)
O5—H2W	0.8500	C12—H12A	0.9700
N1—C1	1.314 (4)	C12—H12B	0.9700
N1—N2	1.343 (3)	C13—C17	1.532 (5)
N2—C3	1.336 (4)	C13—C14	1.533 (5)
N2—H1N	0.8600	C13—H13	0.9800
N3—C4	1.316 (4)	C14—H14A	0.9700
N3—N4	1.330 (3)	C14—H14B	0.9700
N3—Cd1^iv	2.321 (2)	C15—C16	1.533 (5)
N4—C6	1.335 (4)	C15—H15A	0.9700
N4—H2N	0.8600	C15—H15B	0.9700
C1—C2	1.401 (4)	C16—C18	1.523 (5)
C1—H1	0.9300	C16—C17	1.524 (5)
C2—C3	1.359 (4)	C16—H16	0.9800
C2—C5	1.455 (4)	C17—H17A	0.9700
C3—H3	0.9300	C17—H17B	0.9700
C4—C5	1.390 (4)	C18—H18A	0.9700
C4—H4	0.9300	C18—H18B	0.9700
C5—C6	1.365 (4)
N1^i—Cd1—N1	84.69 (13)	C7—C9—C15	111.5 (3)
N1^i—Cd1—N3^ii	174.76 (9)	C14—C9—C15	108.9 (3)
N1—Cd1—N3^ii	92.36 (9)	C10—C9—C15	107.7 (3)
N1^i—Cd1—N3^iii	92.36 (9)	C11—C10—C9	110.6 (2)
N1—Cd1—N3^iii	174.76 (9)	C11—C10—H10A	109.5
N3^ii—Cd1—N3^iii	90.90 (14)	C9—C10—H10A	109.5
N1^i—Cd1—O1^i	93.81 (8)	C11—C10—H10B	109.5
N1—Cd1—O1^i	104.84 (8)	C9—C10—H10B	109.5
N3^ii—Cd1—O1^i	82.75 (8)	H10A—C10—H10B	108.1
N3^iii—Cd1—O1^i	79.64 (8)	C12—C11—C8	109.6 (3)
N1^i—Cd1—O1	104.84 (8)	C12—C11—C10	109.3 (3)
N1—Cd1—O1	93.81 (8)	C8—C11—C10	109.6 (3)
N3^ii—Cd1—O1	79.64 (8)	C12—C11—C18	109.3 (3)
N3^iii—Cd1—O1	82.75 (8)	C8—C11—C18	110.2 (3)
O1^i—Cd1—O1	154.79 (10)	C10—C11—C18	108.9 (3)
C7—O1—Cd1	133.21 (19)	C13—C12—C11	110.5 (3)
C8—O3—H1O	119.7	C13—C12—H12A	109.6
H1W—O5—H2W	108.4	C11—C12—H12A	109.6
C1—N1—N2	105.1 (2)	C13—C12—H12B	109.6
C1—N1—Cd1	135.1 (2)	C11—C12—H12B	109.6
N2—N1—Cd1	119.10 (18)	H12A—C12—H12B	108.1
C3—N2—N1	111.3 (3)	C12—C13—C17	110.7 (3)
C3—N2—H1N	124.4	C12—C13—C14	108.6 (3)
N1—N2—H1N	124.4	C17—C13—C14	109.0 (3)
C4—N3—N4	104.5 (2)	C12—C13—H13	109.5
C4—N3—Cd1^iv	138.8 (2)	C17—C13—H13	109.5
N4—N3—Cd1^iv	116.56 (18)	C14—C13—H13	109.5
N3—N4—C6	111.8 (3)	C9—C14—C13	110.4 (3)
N3—N4—H2N	124.1	C9—C14—H14A	109.6
C6—N4—H2N	124.1	C13—C14—H14A	109.6
N1—C1—C2	111.7 (3)	C9—C14—H14B	109.6
N1—C1—H1	124.1	C13—C14—H14B	109.6
C2—C1—H1	124.1	H14A—C14—H14B	108.1
C3—C2—C1	103.7 (3)	C16—C15—C9	109.9 (3)
C3—C2—C5	128.9 (3)	C16—C15—H15A	109.7
C1—C2—C5	127.4 (3)	C9—C15—H15A	109.7
N2—C3—C2	108.2 (3)	C16—C15—H15B	109.7
N2—C3—H3	125.9	C9—C15—H15B	109.7
C2—C3—H3	125.9	H15A—C15—H15B	108.2
N3—C4—C5	112.7 (3)	C18—C16—C17	110.2 (3)
N3—C4—H4	123.6	C18—C16—C15	109.9 (3)
C5—C4—H4	123.6	C17—C16—C15	109.5 (3)
C6—C5—C4	102.9 (3)	C18—C16—H16	109.1
C6—C5—C2	127.6 (3)	C17—C16—H16	109.1
C4—C5—C2	129.5 (3)	C15—C16—H16	109.1
N4—C6—C5	108.1 (3)	C16—C17—C13	108.7 (3)
N4—C6—H6	126.0	C16—C17—H17A	109.9
C5—C6—H6	126.0	C13—C17—H17A	109.9
O1—C7—O2	122.8 (3)	C16—C17—H17B	109.9
O1—C7—C9	117.7 (3)	C13—C17—H17B	109.9
O2—C7—C9	119.5 (3)	H17A—C17—H17B	108.3
O4—C8—O3	122.4 (4)	C16—C18—C11	109.2 (3)
O4—C8—C11	124.9 (3)	C16—C18—H18A	109.8
O3—C8—C11	112.7 (3)	C11—C18—H18A	109.8
C7—C9—C14	112.5 (2)	C16—C18—H18B	109.8
C7—C9—C10	107.2 (2)	C11—C18—H18B	109.8
C14—C9—C10	109.0 (3)	H18A—C18—H18B	108.3
N1^i—Cd1—O1—C7	34.2 (3)	O2—C7—C9—C10	−97.8 (3)
N1—Cd1—O1—C7	−51.3 (3)	O1—C7—C9—C15	−38.3 (4)
N3^ii—Cd1—O1—C7	−143.0 (3)	O2—C7—C9—C15	144.6 (3)
N3^iii—Cd1—O1—C7	124.8 (3)	C7—C9—C10—C11	179.5 (2)
O1^i—Cd1—O1—C7	170.6 (3)	C14—C9—C10—C11	57.6 (3)
N1^i—Cd1—N1—C1	104.4 (3)	C15—C9—C10—C11	−60.4 (3)
N3^ii—Cd1—N1—C1	−71.3 (3)	O4—C8—C11—C12	−0.4 (5)
O1^i—Cd1—N1—C1	11.8 (3)	O3—C8—C11—C12	177.8 (3)
O1—Cd1—N1—C1	−151.1 (3)	O4—C8—C11—C10	119.5 (4)
N1^i—Cd1—N1—N2	−64.6 (2)	O3—C8—C11—C10	−62.3 (4)
N3^ii—Cd1—N1—N2	119.7 (2)	O4—C8—C11—C18	−120.7 (4)
O1^i—Cd1—N1—N2	−157.2 (2)	O3—C8—C11—C18	57.5 (4)
O1—Cd1—N1—N2	39.9 (2)	C9—C10—C11—C12	−58.4 (3)
C1—N1—N2—C3	0.4 (4)	C9—C10—C11—C8	−178.5 (3)
Cd1—N1—N2—C3	172.4 (2)	C9—C10—C11—C18	60.9 (3)
C4—N3—N4—C6	0.4 (4)	C8—C11—C12—C13	−179.6 (3)
Cd1^iv—N3—N4—C6	−175.6 (2)	C10—C11—C12—C13	60.3 (4)
N2—N1—C1—C2	−0.3 (4)	C18—C11—C12—C13	−58.8 (4)
Cd1—N1—C1—C2	−170.4 (2)	C11—C12—C13—C17	58.7 (4)
N1—C1—C2—C3	0.2 (4)	C11—C12—C13—C14	−61.0 (4)
N1—C1—C2—C5	−179.0 (3)	C7—C9—C14—C13	−177.2 (3)
N1—N2—C3—C2	−0.3 (4)	C10—C9—C14—C13	−58.5 (4)
C1—C2—C3—N2	0.0 (4)	C15—C9—C14—C13	58.7 (4)
C5—C2—C3—N2	179.2 (3)	C12—C13—C14—C9	60.3 (4)
N4—N3—C4—C5	−0.7 (4)	C17—C13—C14—C9	−60.5 (4)
Cd1^iv—N3—C4—C5	173.8 (2)	C7—C9—C15—C16	176.9 (3)
N3—C4—C5—C6	0.8 (4)	C14—C9—C15—C16	−58.4 (4)
N3—C4—C5—C2	−179.6 (3)	C10—C9—C15—C16	59.6 (4)
C3—C2—C5—C6	172.8 (4)	C9—C15—C16—C18	−60.7 (4)
C1—C2—C5—C6	−8.3 (5)	C9—C15—C16—C17	60.5 (4)
C3—C2—C5—C4	−6.7 (6)	C18—C16—C17—C13	59.5 (4)
C1—C2—C5—C4	172.3 (3)	C15—C16—C17—C13	−61.5 (4)
N3—N4—C6—C5	0.1 (4)	C12—C13—C17—C16	−58.3 (4)
C4—C5—C6—N4	−0.5 (4)	C14—C13—C17—C16	61.2 (4)
C2—C5—C6—N4	179.9 (3)	C17—C16—C18—C11	−60.6 (4)
Cd1—O1—C7—O2	7.7 (5)	C15—C16—C18—C11	60.1 (4)
Cd1—O1—C7—C9	−169.26 (18)	C12—C11—C18—C16	59.5 (4)
O1—C7—C9—C14	−161.0 (3)	C8—C11—C18—C16	180.0 (3)
O2—C7—C9—C14	21.9 (4)	C10—C11—C18—C16	−59.8 (4)
O1—C7—C9—C10	79.3 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1O···O5^v	0.85	1.79	2.616 (3)	164
O5—H1W···O2	0.85	1.99	2.841 (3)	175
O5—H2W···O2^vi	0.85	1.93	2.781 (3)	175
N2—H1N···O2	0.86	2.00	2.819 (3)	159
N4—H2N···O1^vii	0.86	2.16	2.763 (3)	127
C1—H1···O4^viii	0.93	2.62	3.465 (4)	151

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