The supra­molecular structure of a cadmium complex with the new functionalized terpyridine ligand 4'-[4-(pyrimidin-5-yl)phen­yl]-2,2':6',2''-terpyridine (L1): aqua­(L1-[kappa]³N,N',N'')(nitrato-[kappa]²O,O')(nitrato-[kappa]O)cadmium(II) dihydrate

The monomeric title compound, aqua­(nitrato-[kappa]²O,O')(nitrato-[kappa]O){4'-[4-(pyrimidin-5-yl)phen­yl]-2,2':6',2''-terpyridine-[kappa]³N,N',N''}cadmium(II) dihydrate, [Cd(NO₃)₂(C₂₅H₁₇N₅)(H₂O)]·2H₂O, consists of a seven-coordinated Cd^II centre bound to the novel 4'-[4-(pyrimidin-5-yl)phen­yl]-2,2':6',2''-terpyridine (L1) ligand (behaving as a tridentate chelate), two nitrate anions (as chelating-bidentate and monodentate ligands) and a water O atom. Both chelating groups define the base of a slightly deformed penta­gonal bipyramid, while the monocoordinated ligands occupy the apices. The four heterocycles in L1 form a planar skeleton, while the central benzene ring is rotated from this planar geometry by more than 30°, probably because of packing effects. Noncovalent inter­actions lead to the formation of columnar arrays parallel to [100].

S1. Introduction

Considerable attention has been drawn recently to the derivatives of 2,2':6',2''-terpyridine which have been synthesized with the aim of giving new supra­molecular properties to the ligand and its metal complexes (Constable, 2007; Wild et al., 2011). A diverse range of easy synthetic methods have allowed the introduction of a large selection of substituents at different positions (Wild et al., 2011; Heller & Schubert, 2003). The 4'-position of terpyridine has usually been the preferred one to introduce N-donor substituents like pyridyl-based groups, which has enabled the diversification of the types of noncovalent inter­action present, such as hydrogen bonding, π–π stacking etc. In this regard, the insertion of the heteroaromatic pyrimidine group has led to the formation of the π-conjugated terpyridine 4'-(pyrimidin-5-yl)-2,2':6',2''- terpyridine (L2), which was reacted with iron(II) and ruthenium(II) to give the cationic homoleptic species [M(L2)]²⁺ (M = Fe, Ru; Beves et al., 2008). Only the X-ray crystal structure of the ruthenium(II) complex was reported, showing that L2 is bonded in a tridentate manner using its terpyridine fragment and that the expected noncovalent π–π inter­actions are weak compared with those in related systems (Beves et al., 2008). As an extension of the supra­molecular study of this class of ligand with pyrimidine–terpyridine arrays, we have decided to modify the structure of L2 by introducing a benzene ring between the pyrimidine and terpyridine portions. Under this premise, the ligand 4'-[4-(pyrimidin-5-yl)phenyl]-2,2':6',2''-terpyridine (L1) was synthesized and characterized spectroscopically. The coordinating properties of L1 were tested by reacting it with cadmium(II) nitrate to form the title neutral complex, (I), the supra­molecular motif of which is dominated by a significant number of π–π inter­actions involving all the aromatic rings.

S2. Synthesis and crystallization

4'-[4-(Pyrimidin-5-yl)phenyl]-2,2':6',2''-terpyridine (L1) was prepared according to the method of Wang & Hanan (2005). 2-Acetyl­pyridine (0.61 g, 5.0 mmol) and KOH (039 g, 5.0 mmol) were added to a solution of 4-(pyrimidin-5-yl)benzaldehyde (0.46 g, 2.5 mmol) in ethanol (22 ml). The mixture was stirred over a period of 12 h, then an excess of aqueous NH₃ (8.6 ml, 25%, 115 mmol) was added and the stirring was continued for a further 24 h. The solid was filtered off, and washed with water (5 × 10 ml) and ethanol (3 × 10 ml). The product was disolved in CHCl₃ (20 ml) and the addition of methanol (60 ml) afforded a crystalline solid, which was washed with methanol (3 × 10 ml). The crude product was purified by column chromatography over alumina (EtOAc–CH₃OH 10%) to give needle-like crystals (yield 0.42 g, 43%; m.p. 502–504 K). Analysis, calculated for C₂₅H₁₇N₅: C 77.50, H 4.42, N 18.08%; found: C77.25, H 4.40, N 18.36%.

For the preparation of complex (I), an excess of Cd(NO₃)₂ (140.0 mg, 0.454 mmol) was added to a hot solution (using an oil bath at 331–335 K) of L1 (4.7 mg, 0.012 mmol) in MeOH (2.5 ml) contained in a closed volumetric flask (10 ml). The resultant solution was heated in the oil bath for 2 h. Prismatic light-yellow crystals of (I) were obtained after the removal of the hot solvent, and were washed with MeOH (2 × 4 ml) and dried in air (yield 3.5 mg, 43%).

S3. Refinement

The two solvent water molecules appeared disordered over three sites. Their site-occupancy factors were refined in the initial stages, but showed a small oscilatory behaviour (amplitude < 0.05) which precluded convergence of the refinement process. Thus, water O-atom occupancies were kept fixed at the mean values obtained during cycling. H atoms pertaining to the water molecules could not be reliably determined from a difference map and were not included in the model. All remaining H atoms on undisordered parents were found in a difference Fourier map but were treated differently in the refinement. Those attached to C atoms were further idealized and refined as riding, with aromatic C—H = 0.93 Å. Those attached to atom O1W were refined with O—H and H···H distances restrained to 0.85 (1) and 1.35 (1) Å. respectively. In all cases, U_iso(H) = 1.2U_eq(host).

S4. Results and discussion

The monomeric structure of (I) (Fig. 1) consists of a seven-coordinated Cd^II centre (Table 2), which is bound to a tridentate chelating L1 ligand, one water O atom and two nitrate groups. One of the nitrate groups acts in a bidentate chelating fashion and the other as just a monodentate ligand (see below for a discussion of its coordination character). The environment of atom Cd1 is a slightly deformed penta­gonal bipyramid, with the two chelating ligands defining the CdN₃O₂ base [Cd—N = 2.327 (4)-=2.379 (4)Å and Cd—O = 2.400 (5)–2.540 (5) Å]. The two chelates bind in a slightly noncoplanar fashion [dihedral angle between the CdN₃ and CdO₂ coordination planes = 12.8 (2)°], leading to a maximum deviation from the least-squares plane of 0.192 (2)Å for atom O22. The monocoordinated ligands occupy the apical positions, with the Cd1—O1W [2.324 (4) Å] and Cd1—O23 [2.354 (5)Å] bonds forming an angle of 160.0 (2)° with each other, and angles of 3.4 (2) and 17.5 (2)°, respectively, with the normal to the plane. The bond-valence sum (BVS) for Cd1, with standard parameters taken from Brown (2009), led to a BVS of 1.994 valence units (v.u.) (expected value = 2.000 v.u.).

An inter­esting situation is posed by the nitrate anions Nit2 (atoms N12/O12/O22/O32) and Nit3 (atoms N13/O13/O23/O33). Even if at first glance only Nit2 appears as definitely bidentate, the relative orientation of Nit3 towards the cation suggests the possible existence of a weak Cd—O33 inter­action in Nit3, in spite of the rather large Cd1···O33 distance [3.008 (4) Å].

When the inter­nal geometries of both nitrate anions are compared, many small deviations from an ideal threefold symmetry appear which may support this hypothesis, viz. the O—N—O angle facing atom Cd1 is much smaller than the remaining two in the anion, a usual characteristic of chelation [115.6 (6) versus 120.7 (6)–123.7 (6)° in Nit2, and 116.3 (7) versus 121.2 (8)–122.4 (7)° in Nit3], complemented by a `hint' of shortening of the third N—O bond [1.218 (7) versus 1.222 (7)–1.237 (7) Å in Nit2, and 1.205 (7) versus 1.213 (7)–1.216 (7) Å in Nit3]. Admittedly this is a weak argument, since these differences are barely significant on a statistical level and, in the case of Nit3, could be partially caused by libration effects.

The BVS for such a hypothetical Cd—O bond would be very much on the borderline of significance (~0.05 v.u.), so the situation could be described, at most, as a `semicoordination'.

The L1 ligand presents an essentially planar substructure made up of the four N-containing groups. The four heterocycles (Cg1–Cg4 in Fig. 1) adopt a collective flattened disposition, with a mean deviation from the least-squares plane of 0.05 Å and a maximum distance of 0.173 (2) Å for atom C91. However, the central phenyl ring (Cg5) protrudes significantly from this planar geometry through a rotation of 31.4 (2)° around the C161···C221 axis, forced by packing requirements, as we shall discuss below.

Noncovalent inter­actions in (I) are of various types and strengths, and are presented in Table 3 (hydrogen bonding) and Table 4 (π–π inter­actions). For the sake of simplicity, in what follows we shall use a shorthand notation, viz. `[Tn(m)]' to denote `Table n (mth entry)'.

In addition to the contacts presented in Table 3, there are a few O···O short contacts involving disordered water molecules (to which no H atoms could be assigned, as explained in the Refinement section) and which are obviously due to hydrogen-bonding inter­actions. The most significant ones are O2W···O3W = 2.706 (15) Å and O2W···O22(-x + 1, -y + 1, -z + 1) = 2.789 (10) Å.

The most noticeable packing motif that the noncovalent inter­actions give rise to in (I) is a dimeric unit (shown between square brackets in Fig. 2), built up around an inversion centre (A in Fig. 2) by one strong hydrogen bond [T3(1)] and two π–π inter­actions [T4(1,2)], together with their symmetry-related counterparts. These dimers inter­act with their symmetric equivalents by the inversion centre B in Fig. 2, via two further π–π bonds [T4(3,4)] and a weak C—H···O hydrogen bond [T3(2)], to form columnar arrays parallel to [100] (Fig. 2). Inspection of Fig. 2 and Table 4 shows that benzene ring 5 is involved in both types of inter­action, and in order to comply with this double role the group needs to rotate out of plane of the other four heterocycles of the L1 ligand.

It is perhaps worth noting that the only symmetry elements involved in the formation of these columns are inversion centres (types A or B, as defined in Fig. 2). The remaining ones (c-glide planes and a twofold screw axis) serve to generate symmetry-related columns. A detailed view of the way in which the resulting [100] columns are arranged in space is shown in Fig. 3. In particular, the cross inter­actions are provided by a π–π inter­action [T4(5)]. [T3(3-7)] present inter­actions involving the disordered water molecules, shown in the central part of Fig. 3.

Even though a comparison of the noncovalent inter­actions and packing geometries in the present CdL1 complex, (I), with those of related structures would be highly desirable, any attempt to do so with its closest relative, the above referenced Ru-L2 complex, (II), would be inappropriate, due to intrinsic differences between the two monomeric complexes. While (I) is electrically neutral and the linkage between molecules is thus mainly provided by hydrogen-bonding and π–π inter­actions, structure (II) is ionic, the molecular assembly being a 2+ cation balanced by hexa­fluoro­phosphate anions in 1:2 ratio. In this latter complex, direct inter­actions between molecules not mediated by the anions are rather weak or non-existent, so a comparison must be postponed until further work on the subject is available.

Related literature

For related literature, see: Beves et al. (2008); Brown (2009); Constable (2007); Heller & Schubert (2003); Wang & Hanan (2005); Wild et al. (2011).

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of (I), showing the atom and ring labelling. Displacement ellipsoids are drawn at the 30% probability level. The broken open bond corresponds to a weak semi-coodination.
	Fig. 2. A packing diagram for (I), showing the way in which the [100] columns build up. The square brackets indicate the hydrogen-bonded dimer, which is the building block of the columns. [Symmetry codes: (i) -x + 1, -y, -z + 1; (ii) -x, -y, -z + 1.]
	Fig. 3. A packing view of (I), projected down [100] (the direction of the columns), showing the interactions linking the columns. [Symmetry code: (vii) x, -y + 1/2, z - 1/2.]

Aqua(nitrato-κ²O,O')(nitrato-κO){4'-[4-(pyrimidin-5-yl)phenyl]-2,2':6',2''-terpyridine-κ³N,N',N''}cadmium(II) dihydrate

Crystal data

[Cd(NO3)2(C25H17N5)(H2O)]·2H2O	Z = 4
Mr = 677.90	F(000) = 1368
Monoclinic, P21/c	Dx = 1.657 Mg m^−3
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.9422 (4) Å	µ = 0.87 mm^−1
b = 22.0793 (11) Å	T = 294 K
c = 15.5923 (7) Å	Prism, light yellow
β = 96.281 (4)°	0.36 × 0.12 × 0.10 mm
V = 2717.8 (2) Å^3

Data collection

Oxford Gemini S Ultra CCD area-detector diffractometer	6278 independent reflections
Radiation source: fine-focus sealed tube	3447 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
ω scans, thick slices	θmax = 28.7°, θmin = 3.5°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −10→10
Tmin = 0.88, Tmax = 0.92	k = −25→28
14498 measured reflections	l = −20→19

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0478P)^2] where P = (Fo^2 + 2Fc^2)/3
6278 reflections	(Δ/σ)max = 0.001
394 parameters	Δρmax = 0.56 e Å^−3
14 restraints	Δρmin = −0.56 e Å^−3

Special details

Experimental. IR (KBr, ν, cm^-1): 1586, 1412, 1383, 831, 789. ¹H NMR (300 MHz, CDCl₃, 298 K, δ, p.p.m.): 9.25 (s, 1H), 9.04 (s, 2H), 8.80 (s, 2H), 8.75 (ddd, 2H, J = 4.8, 1.7 and 0.6 Hz), 8.7 (dt, 2H, J = 7.9 and 1.1 Hz), 8.08 (d, 2H, J = 8.4 Hz), 7.91 (td, 2H, J = 7.9 and 1.7 Hz), 7.75 (d, 2H, J = 8.4 Hz), 7.38 (ddd, 2H, J = 7.9, 4.8 and 1.1 Hz). ¹³C-PND and ¹³C-DEPT NMR (75 MHz, CDCl₃, 298 K, δ, p.p.m.): 157.7 (1 CH), 156.1 (3 Cquat), 156.0 (2 Cquat), 154.9 (2 CH), 149.1 (2 CH), 139.2 (1 Cquat), 136.9 (2 CH), 134.8 (1 Cquat), 133.7 (1 Cquat), 128.4 (2 CH), 127.4 (2 CH), 123.9 (2 CH), 121.4 (2 CH), 118.7 (2 CH). MS (EI+, 70eV) for C₂₅H₁₇N₅ ([M⁺]) 387 (100%).

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cd1	0.45706 (5)	0.332305 (18)	0.34623 (3)	0.04502 (16)
N11	0.5691 (5)	0.2572 (2)	0.2589 (3)	0.0419 (11)
N21	0.4013 (5)	0.23553 (19)	0.3951 (3)	0.0373 (10)
N31	0.3283 (6)	0.3378 (2)	0.4749 (3)	0.0500 (12)
N41	0.1268 (5)	−0.2189 (2)	0.5714 (3)	0.0478 (12)
N51	0.0042 (6)	−0.1683 (2)	0.6832 (3)	0.0526 (12)
C11	0.6514 (7)	0.2706 (3)	0.1915 (4)	0.0495 (14)
H11	0.6755	0.3111	0.1813	0.059*
C21	0.7024 (8)	0.2277 (3)	0.1365 (4)	0.0553 (16)
H21	0.7631	0.2385	0.0911	0.066*
C31	0.6622 (7)	0.1690 (3)	0.1497 (4)	0.0514 (15)
H31	0.6926	0.1390	0.1124	0.062*
C41	0.5760 (7)	0.1538 (3)	0.2190 (3)	0.0450 (14)
H41	0.5477	0.1138	0.2290	0.054*
C51	0.5323 (6)	0.1997 (2)	0.2733 (3)	0.0347 (12)
C61	0.4454 (6)	0.1870 (2)	0.3506 (3)	0.0339 (11)
C71	0.4155 (6)	0.1289 (2)	0.3807 (3)	0.0375 (12)
H71	0.4453	0.0953	0.3497	0.045*
C81	0.3415 (6)	0.1208 (2)	0.4566 (3)	0.0345 (12)
C91	0.3005 (6)	0.1727 (2)	0.5011 (3)	0.0390 (12)
H91	0.2527	0.1693	0.5528	0.047*
C101	0.3313 (6)	0.2291 (2)	0.4679 (3)	0.0353 (12)
C111	0.2811 (6)	0.2861 (2)	0.5106 (3)	0.0383 (12)
C121	0.1982 (7)	0.2866 (3)	0.5823 (4)	0.0531 (15)
H121	0.1682	0.2502	0.6065	0.064*
C131	0.1584 (8)	0.3405 (3)	0.6195 (4)	0.0607 (17)
H131	0.1007	0.3412	0.6683	0.073*
C141	0.2055 (9)	0.3924 (3)	0.5828 (4)	0.0696 (19)
H141	0.1799	0.4297	0.6058	0.084*
C151	0.2908 (9)	0.3895 (3)	0.5120 (4)	0.0661 (18)
H151	0.3245	0.4256	0.4882	0.079*
C161	0.3035 (6)	0.0601 (2)	0.4894 (3)	0.0339 (12)
C171	0.2946 (6)	0.0496 (2)	0.5762 (4)	0.0436 (13)
H171	0.3232	0.0806	0.6155	0.052*
C181	0.2447 (6)	−0.0052 (3)	0.6060 (3)	0.0433 (13)
H181	0.2408	−0.0108	0.6649	0.052*
C191	0.1995 (6)	−0.0528 (2)	0.5489 (3)	0.0346 (12)
C201	0.2112 (7)	−0.0430 (2)	0.4611 (3)	0.0428 (13)
H201	0.1827	−0.0739	0.4217	0.051*
C211	0.2649 (6)	0.0120 (3)	0.4329 (3)	0.0434 (13)
H211	0.2757	0.0173	0.3746	0.052*
C221	0.1416 (6)	−0.1113 (2)	0.5808 (3)	0.0342 (12)
C231	0.1740 (6)	−0.1655 (3)	0.5426 (3)	0.0419 (13)
H231	0.2320	−0.1649	0.4939	0.050*
C241	0.0435 (7)	−0.2170 (3)	0.6405 (4)	0.0513 (16)
H241	0.0090	−0.2540	0.6612	0.062*
C251	0.0540 (6)	−0.1161 (3)	0.6518 (3)	0.0444 (13)
H251	0.0280	−0.0806	0.6796	0.053*
O12	0.6046 (7)	0.4094 (2)	0.2593 (3)	0.0863 (14)
O22	0.4395 (7)	0.4408 (2)	0.3442 (4)	0.1045 (18)
N12	0.5409 (7)	0.4529 (3)	0.2918 (4)	0.0640 (15)
O32	0.5704 (6)	0.5053 (2)	0.2741 (3)	0.0795 (14)
O23	0.2574 (7)	0.3285 (3)	0.2231 (3)	0.0920 (17)
O33	0.0883 (9)	0.3624 (3)	0.3024 (5)	0.134 (2)
N13	0.1169 (9)	0.3481 (3)	0.2301 (4)	0.0697 (16)
O13	0.0075 (6)	0.3499 (3)	0.1702 (4)	0.110 (2)
O1W	0.7171 (6)	0.3363 (2)	0.4303 (4)	0.0774 (14)
H1WA	0.791 (3)	0.3615 (19)	0.418 (4)	0.093*
H1WB	0.770 (4)	0.3037 (9)	0.443 (4)	0.093*
O2W	0.8116 (13)	0.4759 (4)	0.6262 (7)	0.125 (4)	0.60
O3W	0.8423 (11)	0.4462 (3)	0.4602 (6)	0.138 (3)	0.75
O4W	1.0571 (12)	0.5145 (4)	0.7217 (7)	0.131 (4)	0.65

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0645 (3)	0.0310 (2)	0.0411 (2)	0.0020 (2)	0.01241 (18)	0.00396 (19)
N11	0.052 (3)	0.037 (3)	0.038 (3)	−0.001 (2)	0.010 (2)	0.003 (2)
N21	0.044 (2)	0.033 (3)	0.036 (2)	0.004 (2)	0.004 (2)	0.001 (2)
N31	0.077 (3)	0.033 (3)	0.042 (3)	0.012 (2)	0.014 (2)	−0.002 (2)
N41	0.056 (3)	0.031 (3)	0.056 (3)	−0.004 (2)	0.006 (2)	0.005 (2)
N51	0.052 (3)	0.054 (4)	0.054 (3)	−0.007 (3)	0.014 (2)	0.015 (3)
C11	0.067 (4)	0.037 (4)	0.047 (4)	−0.003 (3)	0.019 (3)	0.004 (3)
C21	0.076 (4)	0.055 (4)	0.039 (3)	0.007 (3)	0.024 (3)	0.009 (3)
C31	0.071 (4)	0.044 (4)	0.042 (3)	0.006 (3)	0.020 (3)	−0.001 (3)
C41	0.058 (3)	0.036 (3)	0.042 (3)	0.000 (3)	0.010 (3)	−0.001 (2)
C51	0.038 (3)	0.038 (3)	0.029 (3)	−0.003 (2)	0.005 (2)	0.005 (2)
C61	0.033 (2)	0.031 (3)	0.038 (3)	0.002 (2)	0.004 (2)	0.001 (2)
C71	0.039 (3)	0.033 (3)	0.042 (3)	0.002 (2)	0.009 (2)	−0.002 (2)
C81	0.038 (3)	0.031 (3)	0.035 (3)	0.004 (2)	0.003 (2)	0.002 (2)
C91	0.049 (3)	0.037 (3)	0.032 (3)	0.000 (3)	0.010 (2)	0.002 (2)
C101	0.040 (3)	0.031 (3)	0.035 (3)	0.002 (2)	0.004 (2)	−0.002 (2)
C111	0.044 (3)	0.036 (3)	0.036 (3)	0.008 (2)	0.007 (2)	0.000 (2)
C121	0.069 (4)	0.043 (4)	0.051 (4)	−0.002 (3)	0.022 (3)	0.001 (3)
C131	0.075 (4)	0.055 (5)	0.057 (4)	0.007 (3)	0.027 (3)	−0.005 (3)
C141	0.099 (5)	0.050 (5)	0.062 (5)	0.017 (4)	0.022 (4)	−0.012 (4)
C151	0.104 (5)	0.034 (4)	0.064 (4)	0.012 (4)	0.030 (4)	0.007 (3)
C161	0.038 (3)	0.027 (3)	0.037 (3)	−0.001 (2)	0.007 (2)	0.001 (2)
C171	0.055 (3)	0.031 (3)	0.045 (3)	−0.005 (3)	0.006 (3)	−0.002 (3)
C181	0.058 (3)	0.041 (3)	0.031 (3)	−0.004 (3)	0.005 (2)	0.006 (3)
C191	0.036 (3)	0.029 (3)	0.040 (3)	0.000 (2)	0.007 (2)	0.006 (2)
C201	0.060 (3)	0.031 (3)	0.038 (3)	−0.005 (3)	0.009 (3)	0.000 (2)
C211	0.060 (3)	0.041 (4)	0.031 (3)	0.001 (3)	0.014 (3)	0.001 (2)
C221	0.037 (3)	0.032 (3)	0.033 (3)	−0.001 (2)	0.000 (2)	0.005 (2)
C231	0.047 (3)	0.038 (3)	0.042 (3)	−0.002 (3)	0.008 (2)	0.003 (3)
C241	0.054 (3)	0.044 (4)	0.053 (4)	−0.011 (3)	−0.004 (3)	0.014 (3)
C251	0.047 (3)	0.045 (4)	0.042 (3)	0.000 (3)	0.010 (3)	0.006 (3)
O12	0.123 (4)	0.045 (3)	0.093 (4)	0.009 (3)	0.022 (3)	0.008 (3)
O22	0.142 (5)	0.056 (3)	0.126 (5)	0.003 (3)	0.062 (4)	0.027 (3)
N12	0.083 (4)	0.046 (4)	0.063 (4)	−0.003 (3)	0.010 (3)	0.011 (3)
O32	0.116 (4)	0.034 (3)	0.089 (3)	−0.012 (3)	0.015 (3)	0.015 (3)
O23	0.084 (3)	0.110 (5)	0.077 (4)	0.037 (3)	−0.011 (3)	−0.008 (3)
O33	0.179 (7)	0.134 (6)	0.094 (5)	0.009 (5)	0.033 (5)	−0.019 (4)
N13	0.097 (5)	0.060 (4)	0.054 (4)	0.004 (3)	0.014 (4)	0.012 (3)
O13	0.072 (3)	0.145 (6)	0.106 (5)	0.007 (3)	−0.019 (3)	0.034 (4)
O1W	0.090 (3)	0.054 (3)	0.084 (3)	0.004 (2)	−0.008 (3)	−0.004 (3)
O2W	0.163 (9)	0.082 (7)	0.138 (9)	0.053 (6)	0.059 (7)	0.022 (6)
O3W	0.161 (7)	0.066 (6)	0.173 (9)	−0.025 (5)	−0.042 (7)	0.013 (6)
O4W	0.128 (7)	0.098 (8)	0.181 (10)	0.016 (6)	0.084 (7)	0.007 (7)

Geometric parameters (Å, º)

Cd1—O1W	2.324 (4)	C101—C111	1.497 (7)
Cd1—N21	2.327 (4)	C111—C121	1.358 (7)
Cd1—N31	2.352 (5)	C121—C131	1.374 (8)
Cd1—O23	2.354 (5)	C121—H121	0.9300
Cd1—N11	2.379 (4)	C131—C141	1.352 (9)
Cd1—O22	2.400 (5)	C131—H131	0.9300
Cd1—O12	2.540 (5)	C141—C151	1.358 (9)
N11—C51	1.328 (6)	C141—H141	0.9300
N11—C11	1.330 (7)	C151—H151	0.9300
N21—C101	1.325 (6)	C161—C171	1.382 (7)
N21—C61	1.343 (6)	C161—C211	1.392 (7)
N31—C151	1.328 (7)	C171—C181	1.371 (7)
N31—C111	1.343 (7)	C171—H171	0.9300
N41—C241	1.325 (7)	C181—C191	1.398 (7)
N41—C231	1.329 (6)	C181—H181	0.9300
N51—C241	1.318 (7)	C191—C201	1.398 (7)
N51—C251	1.331 (7)	C191—C221	1.475 (7)
C11—C21	1.370 (8)	C201—C211	1.376 (7)
C11—H11	0.9300	C201—H201	0.9300
C21—C31	1.356 (8)	C211—H211	0.9300
C21—H21	0.9300	C221—C231	1.375 (7)
C31—C41	1.382 (7)	C221—C251	1.375 (7)
C31—H31	0.9300	C231—H231	0.9300
C41—C51	1.388 (7)	C241—H241	0.9300
C41—H41	0.9300	C251—H251	0.9300
C51—C61	1.481 (7)	O12—N12	1.222 (7)
C61—C71	1.395 (7)	O22—N12	1.237 (7)
C71—C81	1.389 (7)	O32—N12	1.218 (7)
C71—H71	0.9300	O23—N13	1.213 (7)
C81—C91	1.397 (7)	O33—N13	1.216 (7)
C81—C161	1.478 (7)	O13—N13	1.205 (7)
C91—C101	1.381 (7)	O1W—H1WA	0.846 (10)
C91—H91	0.9300	O1W—H1WB	0.847 (10)
Cd1···O33	3.008 (4)
O1W—Cd1—N21	92.25 (15)	N21—C101—C111	116.6 (5)
O1W—Cd1—N31	87.67 (18)	C91—C101—C111	121.6 (5)
N21—Cd1—N31	69.67 (15)	N31—C111—C121	121.1 (5)
O1W—Cd1—O23	160.0 (2)	N31—C111—C101	115.5 (5)
N21—Cd1—O23	95.66 (17)	C121—C111—C101	123.4 (5)
N31—Cd1—O23	112.35 (18)	C111—C121—C131	120.6 (6)
O1W—Cd1—N11	89.08 (17)	C111—C121—H121	119.7
N21—Cd1—N11	69.15 (15)	C131—C121—H121	119.7
N31—Cd1—N11	138.52 (16)	C141—C131—C121	117.9 (6)
O23—Cd1—N11	76.66 (17)	C141—C131—H131	121.1
O1W—Cd1—O22	90.95 (18)	C121—C131—H131	121.1
N21—Cd1—O22	155.24 (18)	C131—C141—C151	119.4 (6)
N31—Cd1—O22	85.95 (18)	C131—C141—H141	120.3
O23—Cd1—O22	89.5 (2)	C151—C141—H141	120.3
N11—Cd1—O22	135.46 (18)	N31—C151—C141	123.3 (6)
O1W—Cd1—O12	80.93 (18)	N31—C151—H151	118.4
N21—Cd1—O12	154.84 (17)	C141—C151—H151	118.4
N31—Cd1—O12	133.55 (17)	C171—C161—C211	117.4 (5)
O23—Cd1—O12	84.14 (19)	C171—C161—C81	121.7 (5)
N11—Cd1—O12	86.45 (17)	C211—C161—C81	120.7 (5)
O22—Cd1—O12	49.73 (17)	C181—C171—C161	121.8 (5)
C51—N11—C11	118.8 (5)	C181—C171—H171	119.1
C51—N11—Cd1	117.8 (3)	C161—C171—H171	119.1
C11—N11—Cd1	123.0 (4)	C171—C181—C191	120.7 (5)
C101—N21—C61	120.9 (5)	C171—C181—H181	119.6
C101—N21—Cd1	119.4 (3)	C191—C181—H181	119.6
C61—N21—Cd1	119.6 (3)	C201—C191—C181	117.9 (5)
C151—N31—C111	117.7 (5)	C201—C191—C221	121.4 (5)
C151—N31—Cd1	123.7 (4)	C181—C191—C221	120.7 (5)
C111—N31—Cd1	118.5 (4)	C211—C201—C191	120.4 (5)
C241—N41—C231	115.6 (5)	C211—C201—H201	119.8
C241—N51—C251	115.1 (5)	C191—C201—H201	119.8
N11—C11—C21	123.1 (6)	C201—C211—C161	121.7 (5)
N11—C11—H11	118.5	C201—C211—H211	119.2
C21—C11—H11	118.5	C161—C211—H211	119.2
C31—C21—C11	118.4 (6)	C231—C221—C251	114.6 (5)
C31—C21—H21	120.8	C231—C221—C191	122.5 (5)
C11—C21—H21	120.8	C251—C221—C191	122.9 (5)
C21—C31—C41	119.7 (5)	N41—C231—C221	123.6 (5)
C21—C31—H31	120.1	N41—C231—H231	118.2
C41—C31—H31	120.1	C221—C231—H231	118.2
C31—C41—C51	118.6 (5)	N51—C241—N41	127.1 (6)
C31—C41—H41	120.7	N51—C241—H241	116.5
C51—C41—H41	120.7	N41—C241—H241	116.5
N11—C51—C41	121.4 (5)	N51—C251—C221	124.1 (5)
N11—C51—C61	116.7 (5)	N51—C251—H251	118.0
C41—C51—C61	121.9 (5)	C221—C251—H251	118.0
N21—C61—C71	119.8 (5)	N12—O12—Cd1	94.0 (4)
N21—C61—C51	116.2 (5)	N12—O22—Cd1	100.6 (4)
C71—C61—C51	124.0 (5)	O32—N12—O12	123.7 (6)
C81—C71—C61	120.5 (5)	O32—N12—O22	120.7 (6)
C81—C71—H71	119.7	O12—N12—O22	115.6 (6)
C61—C71—H71	119.7	N13—O23—Cd1	117.3 (5)
C71—C81—C91	117.5 (5)	O13—N13—O23	122.4 (7)
C71—C81—C161	122.3 (5)	O13—N13—O33	121.2 (8)
C91—C81—C161	120.3 (5)	O23—N13—O33	116.3 (7)
C101—C91—C81	119.5 (5)	Cd1—O1W—H1WA	119 (3)
C101—C91—H91	120.2	Cd1—O1W—H1WB	119 (3)
C81—C91—H91	120.2	H1WA—O1W—H1WB	105.9 (17)
N21—C101—C91	121.7 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···N41^i	0.85 (3)	2.07 (2)	2.875 (6)	160 (6)
C241—H241···O33^ii	0.93	2.60	3.521 (9)	172
O1W—H1WA···O3W	0.85 (4)	2.01 (4)	2.644 (8)	131 (4)
C41—H41···O32^iii	0.93	2.57	3.484 (8)	168
C121—H121···O23^iv	0.93	2.56	3.358 (9)	144
C131—H131···N51^v	0.93	2.55	3.470 (8)	168
C201—H201···O13^vi	0.93	2.59	3.467 (8)	158

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