Poly[[aqua­bis(μ₂-isonicotinato-κ³N:O,O′)cadmium(II)] 1,4-di-3-pyridyl-2,3-diaza-1,3-butadiene hemisolvate]

The title compound, {[Cd(C₆H₄NO₂)₂(H₂O)]·0.5C₁₂H₁₀N₄}_n, presents an intricate three-dimensional network with cavities traversing it in three orthogonal directions, where the (disordered) guest mol­ecules lodge. The compound is a member of a series of coordination polymers presenting the same main host framework but with guests of variable size and geometry, to which the flexible skeleton seems to adapt. The disorder in the structure is explained in terms of an apparently well defined specificity in the position/orientation of the guest mol­ecules, as determined by the main framework.

S1. Comment

Isonicotinate is a versatile ligand, taking part in many coordination polymers with interesting structural features. In particular, {[Cd(isonicotinate)₂(H₂O)].X}_n (X = guest molecules) defines an isostructural family presenting a three-dimensional [Cd(isonicotinate)₂(H₂O)]_n porous framework (Pbca symmetry), with two interpenetrating diamondoid substructures (P2₁2₁2₁ symmetry) related to each other by an inversion centre. The empty space in the framework is occupied by X guest molecules. Already reported structures in the series correspond to X = dimethylformamide (Liao et al., 2004), (1); pyrazine, (2) (Evans et al., 1999) and biformyl, (3) (Liu et al., 2006). We present here a slightly different assembly with a metal–guest ratio of 1:0.5, the title complex, {[Cd(isonicotinate)₂(H₂O)].0.5(3pa)}_n, (4) [3pa is 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene], where the porous host network contains the large bipyridyl guest molecule 3pa in a disordered fashion (see discussion below, and Experimental section for refinement details).

As in the rest of the series, the elemental link in (4) (Fig. 1) is composed of Cd^II ions bridged to four nearest neighbours by isonicotinate ligands, each of which uses both carboxylate O atoms to chelate to one side of the bridge and the pyridyl N atom to bind to the other. Thus, each Cd^II ion is seven-coordinated in the form of a pentagonal bipyramid, with four carboxylate O atoms from two isonicotinate ligands and one pyridyl N atom from a third isonicotinate ligand defining the equatorial plane, while the N atom from a fourth isonicotinate ligand and the aqua molecule determine the apical axis (Table 1). This results in the formation of two interpenetrated P2₁2₁2₁ substructures defining the main Pbca framework, with large tunnels traversing it in three orthogonal directions (Fig. 2).

Stabilization of the framework is modestly enhanced by four non-conventional hydrogen bonds involving the four C—H groups of one single ligand (isonicotinate 1) as donors and the carboxylate O atoms of both ligands as acceptors, as well as by two strong hydrogen bonds formed by the aqua molecule: that involving atom H1WA is directed towards the main framework, while the second, involving atom H1WB, is a diffuse interaction with the disordered 3pa molecule (Table 2).

Though interpenetration reduces the volume of the overall empty space amenable to filling by guest species, it appears that the framework is flexible enough to adapt to the requirements of a diversity of guests. This can be inferred from the variations in cell dimensions displayed by the four known structures in the series, where a direct correlation with the guest size and geometry can be detected (Table 3).

Finally, it is interesting to compare the present structure, (4), with the pyrazine analogue, (2). For convenience, we will describe this latter structure with the aromatic guests disposed along those channels parallel to the b axis, with their planar face nearly perpendicular to a, and with two rings per cell in each of the four available channels. Fig. 3(a) depicts this situation, with the left-hand side showing the column contents and the rightmost part of the figure displaying a view down a, with the pyrazine rings highlighted. In (4), the much longer 3pa units dispose along b in such a way as to have the orientation of the aromatic rings also perpendicular to a [and thus parallel to the pyrazines in (2)]. Surprisingly, if only the rings in the 3pa molecule are considered, disregarding the connecting chains in between, the packing of these disordered guests (with individual site occupancy factors of 1/4) e nd s up in two conglomerates per column within each cell. These groups are made up of four rings each, nearly parallel to each other and almost overlapping [maximum deviation of the centre of gravity from the centroid = 0.60 (2) Å].

In addition, the group presents a (global) population of 4 × 0.25 = 1.00, the equivalent of a complete ring. The locations in which these groups fall, as measured by their centroids, are almost coincident with those in (2) [differences in fractional coordinates between the centres of gravity of pyrazine and the centroid of 3pa: Δ(x) 0.03695; Δ(y) 0.00609; Δ(z) 0.00348]. Fig. 3(b) illustrates this state of affairs, in parallel to that shown for (2). Thus, the left-hand side presents the (disordered) column content, drawn in full so as to visualize the way in which the guests dispose, while the right-hand side exhibits, in turn, the view down a, with only the aromatic rings highlighted in order to emphasize the similarities with the pyrazine case.

In summary, the highly disordered 3pa structure, (4), reproduces, on average but with a surprising spatial match, the ordered pyrazine structure, and the leading factor in this similarity seems to be the planar aromatic rings lodged in the cavities. The conclusion which can be inferred from this is that the guest positions are not weakly defined, but instead appear to be firmly determined by the host environment in combination with the particular guest shape, in this case the planar aromatic ring, irrespective of its being isolated [pyrazine in (2)] or being part of a more complex molecule [3pa in (4)].

Related literature

For related literature, see: Dong et al. (2000); Evans et al. (1999); Liao et al. (2004); Liu et al. (2006).

S2. Experimental

For the synthesis of the title compound, Cd(NO₃)₂·4H₂O (0.15 4 g, 0.5 mmol), isonicotinic acid (0.123 g, 1.0 mmol), 3pa (0.053 g, 0.25 mmol) and 0.1 M NaOH solution (10.0 ml, 1.0 mmol) were placed in a Parr Teflon-lined stainless steel vessel (23 ml). The vessel was sealed and heated to 383 K for 24 h, and then the reactor was cooled slowly to ambient temperature. The resultant yellow block-shaped crystals of (I), suitable for X-ray structure analysis, were filtered off and dried (yield: 80%, based on Cd).

S3. Refinement

H atoms attached to carbon were placed in geometrically idealized positions, with C—H = 0.93 Å; those in the water molecule were found in a difference map and refined with restrained distances of O—H 0.85 (3) and H···H 1.35 (4) Å. In all cases, U_iso(H) = 1.2U_eq(carrier).

The 3pa molecule appeared disordered over two sites, shifted along the crystallographic b axis direction (Fig. 1) and defining a kind of chain. Due to difficulties in the handling of the guest molecules (both moieties tended to deform on refinement), each of the two independent images was treated as a rigid body to which the coordinates of the free moiety (as taken from Dong et al., 2000) were fitted. Their occupancy factors, when freely refined, converged very nearly to 0.25; they were then all fixed at this value in the final stages of refinement. This treatment appears justified by the acceptably low maximum residual electron density found around the guest molecules after convergence (~0.68 e Å^-3).

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: MSC/AFC Diffractometer Control Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT (Sheldrick, 2000); software used to prepare material for publication: SHELXTL-NT and PLATON (Spek, 2003).

Figures

	Fig. 1. The structure of (4), showing the Cd environment and the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. H atoms have been omitted for clarity. Also shown is the uncoordinated 3pa molecule, which was modelled isotropically due to disorder. Symmetry codes are as in Table 1.
	Fig. 2. A schematic view of the main framework along the a axis, showing the two interpenetrating networks. The guest molecules (omitted for clarity) are disordered along the b axis (top to bottom).
	Fig. 3. A comparison of (a) structure (2) [guest = one full ordered pyrazine per Cd atom] and (b) (4) [guest = one half of a disordered 3pa per Cd atom]. See Comment for details.

Poly[[aquabis(µ₂-isonicotinato-κ³N:O,O')cadmium(II)] 1,4-di-3-pyridyl-2,3-diaza-1,3-butadiene hemisolvate]

Crystal data

[Cd(C6H4NO2)2(H2O)]·0.5C12H10N4	F(000) = 1912
Mr = 1919.00	Dx = 1.675 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 11.882 (7) Å	θ = 10–12.5°
b = 15.518 (5) Å	µ = 1.19 mm^−1
c = 20.637 (8) Å	T = 294 K
V = 3805 (3) Å^3	Block, yellow
Z = 2	0.32 × 0.24 × 0.20 mm

Data collection

Rigaku AFC-6S diffractometer	1889 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.064
Graphite monochromator	θmax = 26.0°, θmin = 2.0°
ω/2θ scans	h = −1→14
Absorption correction: ψ scan (North et al., 1968)	k = −1→19
Tmin = 0.72, Tmax = 0.79	l = −1→25
4656 measured reflections	3 standard reflections every 150 reflections
3735 independent reflections	intensity decay: <2%

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.186	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0902P)^2 + 8.6P] where P = (Fo^2 + 2Fc^2)/3
3735 reflections	(Δ/σ)max < 0.001
217 parameters	Δρmax = 0.82 e Å^−3
23 restraints	Δρmin = −1.45 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1'	0.750 (2)	0.9259 (9)	0.3433 (9)	0.059 (7)*	0.25
H1'	0.7501	0.8834	0.3095	0.071*	0.25
C2'	0.754 (3)	1.0118 (9)	0.3281 (11)	0.081 (8)*	0.25
H2'	0.7568	1.0302	0.2837	0.097*	0.25
C3'	0.753 (2)	1.0718 (8)	0.3782 (12)	0.073 (8)*	0.25
H3'	0.7574	1.1319	0.3672	0.088*	0.25
N4'	0.748 (2)	1.0500 (8)	0.4404 (11)	0.074 (7)*	0.25
C5'	0.7435 (19)	0.9659 (8)	0.4541 (10)	0.057 (7)*	0.25
H5'	0.7394	0.9494	0.4988	0.069*	0.25
C6'	0.7445 (15)	0.9004 (8)	0.4077 (9)	0.045 (7)*	0.25
C7'	0.7401 (14)	0.8112 (8)	0.4281 (8)	0.036 (6)*	0.25
H7'	0.7347	0.7984	0.4736	0.043*	0.25
N8'	0.7431 (14)	0.7486 (8)	0.3875 (7)	0.044 (7)*	0.25
N9'	0.7388 (12)	0.6674 (8)	0.4186 (7)	0.057 (8)*	0.25
C10'	0.7418 (15)	0.6048 (8)	0.3780 (7)	0.064 (8)*	0.25
H10'	0.7471	0.6175	0.3326	0.076*	0.25
C11'	0.7374 (13)	0.5156 (8)	0.3984 (8)	0.051 (7)*	0.25
C12'	0.738 (2)	0.4501 (8)	0.3521 (8)	0.036 (6)*	0.25
H12'	0.7424	0.4666	0.3073	0.043*	0.25
N13'	0.7341 (19)	0.3659 (8)	0.3657 (9)	0.034 (5)*	0.25
C14'	0.7285 (16)	0.3441 (8)	0.4280 (10)	0.037 (6)*	0.25
H14'	0.7244	0.2841	0.4389	0.045*	0.25
C15'	0.728 (2)	0.4042 (9)	0.4780 (9)	0.033 (5)*	0.25
H15'	0.7251	0.3858	0.5224	0.039*	0.25
C16'	0.7323 (17)	0.4901 (8)	0.4629 (8)	0.035 (6)*	0.25
H16'	0.7317	0.5325	0.4967	0.042*	0.25
C1"	0.7916 (19)	−0.0177 (9)	0.4546 (10)	0.059 (7)*	0.25
H1"	0.7899	0.0217	0.4904	0.071*	0.25
C2"	0.804 (2)	−0.1043 (10)	0.4655 (12)	0.081 (8)*	0.25
H2"	0.8106	−0.1262	0.5088	0.097*	0.25
C3"	0.8069 (18)	−0.1599 (9)	0.4127 (13)	0.073 (8)*	0.25
H3"	0.8168	−0.2204	0.4206	0.088*	0.25
N4"	0.797 (2)	−0.1333 (9)	0.3517 (12)	0.074 (7)*	0.25
C5"	0.784 (2)	−0.0486 (9)	0.3422 (11)	0.057 (7)*	0.25
H5"	0.7768	−0.0286	0.2984	0.069*	0.25
C6"	0.7815 (14)	0.0128 (9)	0.3916 (10)	0.045 (7)*	0.25
C7"	0.7682 (14)	0.1031 (9)	0.3756 (8)	0.036 (6)*	0.25
H7"	0.7598	0.1193	0.3310	0.043*	0.25
N8"	0.7674 (12)	0.1621 (9)	0.4191 (7)	0.044 (7)*	0.25
N9"	0.7546 (12)	0.2454 (9)	0.3921 (7)	0.057 (8)*	0.25
C10"	0.7537 (13)	0.3045 (9)	0.4356 (7)	0.064 (8)*	0.25
H10"	0.7621	0.2883	0.4802	0.076*	0.25
C11"	0.7405 (12)	0.3948 (9)	0.4196 (7)	0.051 (7)*	0.25
C12"	0.7377 (19)	0.4561 (9)	0.4690 (8)	0.036 (6)*	0.25
H12"	0.7452	0.4362	0.5129	0.043*	0.25
N13"	0.7253 (19)	0.5408 (9)	0.4595 (9)	0.034 (5)*	0.25
C14"	0.7151 (16)	0.5674 (9)	0.3986 (9)	0.037 (6)*	0.25
H14"	0.7052	0.6279	0.3906	0.045*	0.25
C15"	0.718 (2)	0.5118 (9)	0.3457 (8)	0.033 (5)*	0.25
H15"	0.7113	0.5337	0.3024	0.039*	0.25
C16"	0.7304 (18)	0.4253 (9)	0.3566 (7)	0.035 (6)*	0.25
H16"	0.7321	0.3858	0.3208	0.042*	0.25
Cd1	0.81706 (5)	0.23570 (4)	0.17417 (3)	0.0294 (2)
O11	1.1848 (6)	0.1689 (5)	−0.1078 (3)	0.0501 (18)
O12	1.0120 (7)	0.6696 (4)	0.2676 (4)	0.059 (2)
N11	0.9225 (8)	0.2304 (5)	0.0768 (4)	0.045 (2)
C21	0.9747 (10)	0.1616 (7)	0.0546 (5)	0.053 (3)
H21	0.9656	0.1104	0.0774	0.064*
C31	1.0416 (9)	0.1599 (6)	0.0005 (5)	0.044 (3)
H31	1.0768	0.1088	−0.0115	0.052*
C41	1.0568 (9)	0.2310 (6)	−0.0351 (5)	0.044 (3)
C51	0.9979 (11)	0.3078 (8)	−0.0158 (6)	0.070 (4)
H51	1.0001	0.3575	−0.0409	0.084*
C61	0.9382 (11)	0.3047 (8)	0.0413 (6)	0.073 (4)
H61	0.9067	0.3555	0.0568	0.087*
C71	1.1373 (10)	0.2351 (7)	−0.0905 (5)	0.048 (3)
O21	1.1626 (7)	0.3107 (5)	−0.1134 (4)	0.065 (2)
O22	1.1421 (6)	0.5888 (4)	0.3106 (3)	0.0447 (18)
N12	0.8929 (6)	0.3642 (5)	0.2131 (4)	0.0333 (18)
C22	0.8700 (8)	0.4449 (6)	0.1867 (4)	0.039 (2)
H22	0.8180	0.4479	0.1531	0.047*
C32	0.9185 (8)	0.5197 (6)	0.2066 (5)	0.041 (2)
H32	0.9001	0.5719	0.1873	0.049*
C42	0.9945 (8)	0.5159 (6)	0.2557 (5)	0.038 (2)
C52	1.0229 (8)	0.4369 (6)	0.2854 (4)	0.034 (2)
H52	1.0750	0.4334	0.3189	0.041*
C62	0.9673 (8)	0.3642 (6)	0.2611 (5)	0.042 (2)
H62	0.9838	0.3114	0.2802	0.050*
C72	1.0545 (8)	0.5955 (6)	0.2794 (5)	0.040 (2)
O1W	0.7024 (8)	0.2344 (5)	0.2630 (4)	0.073 (3)
H1WA	0.651 (7)	0.196 (6)	0.261 (3)	0.088*
H1WB	0.708 (5)	0.2477 (12)	0.3025 (8)	0.088*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0328 (4)	0.0191 (3)	0.0363 (4)	0.0001 (3)	−0.0030 (3)	0.0009 (3)
O11	0.043 (4)	0.053 (5)	0.055 (4)	0.001 (4)	0.018 (4)	−0.012 (3)
O12	0.070 (5)	0.020 (4)	0.088 (6)	−0.003 (4)	−0.028 (5)	−0.002 (4)
N11	0.054 (6)	0.026 (4)	0.056 (5)	0.002 (4)	0.017 (4)	0.003 (4)
C21	0.059 (8)	0.044 (7)	0.058 (7)	−0.001 (6)	0.017 (6)	0.018 (5)
C31	0.049 (6)	0.033 (6)	0.049 (6)	0.013 (5)	0.002 (5)	0.003 (4)
C41	0.044 (6)	0.040 (5)	0.048 (6)	0.003 (5)	0.029 (5)	0.005 (5)
C51	0.078 (9)	0.070 (9)	0.062 (8)	0.008 (7)	0.041 (7)	0.020 (7)
C61	0.088 (10)	0.050 (7)	0.081 (9)	0.024 (7)	0.042 (8)	0.012 (7)
C71	0.049 (6)	0.050 (6)	0.045 (6)	0.005 (6)	0.007 (5)	−0.015 (6)
O21	0.078 (6)	0.064 (6)	0.055 (5)	−0.002 (5)	0.027 (4)	0.015 (4)
O22	0.033 (4)	0.018 (3)	0.083 (5)	−0.007 (3)	−0.013 (4)	−0.013 (3)
N12	0.030 (4)	0.022 (4)	0.048 (5)	−0.004 (3)	0.002 (4)	−0.005 (4)
C22	0.027 (5)	0.042 (6)	0.048 (6)	−0.007 (4)	−0.014 (5)	0.004 (5)
C32	0.048 (6)	0.032 (5)	0.042 (6)	−0.007 (5)	−0.011 (5)	−0.016 (4)
C42	0.047 (6)	0.020 (4)	0.046 (6)	0.003 (4)	0.002 (5)	0.003 (4)
C52	0.034 (5)	0.023 (5)	0.046 (6)	0.006 (4)	−0.010 (5)	−0.004 (4)
C62	0.041 (6)	0.021 (5)	0.063 (7)	0.002 (4)	−0.010 (5)	0.006 (4)
C72	0.033 (6)	0.020 (5)	0.067 (7)	−0.009 (4)	0.000 (5)	−0.003 (4)
O1W	0.102 (7)	0.048 (5)	0.070 (5)	−0.024 (5)	0.031 (5)	−0.025 (4)

Geometric parameters (Å, º)

C1'—C2'	1.3697	C11"—C12"	1.3955
C1'—C6'	1.3888	C12"—N13"	1.3367
C1'—H1'	0.9599	C12"—H12"	0.9600
C2'—C3'	1.3910	N13"—C14"	1.3303
C2'—H2'	0.9599	C14"—C15"	1.3909
C3'—N4'	1.3300	C14"—H14"	0.9600
C3'—H3'	0.9601	C15"—C16"	1.3697
N4'—C5'	1.3366	C15"—H15"	0.9600
C5'—C6'	1.3958	C16"—H16"	0.9599
C5'—H5'	0.9598	Cd1—O1W	2.285 (8)
C6'—C7'	1.4481	Cd1—N12	2.331 (7)
C7'—N8'	1.2833	Cd1—O22^i	2.352 (6)
C7'—H7'	0.9599	Cd1—O21^ii	2.336 (8)
N8'—N9'	1.4149	Cd1—N11	2.370 (8)
N9'—C10'	1.2832	Cd1—O11^ii	2.557 (7)
C10'—C11'	1.4481	Cd1—O12^i	2.574 (7)
C10'—H10'	0.9599	O11—C71	1.225 (11)
C11'—C16'	1.3888	O12—C72	1.279 (11)
C11'—C12'	1.3956	N11—C21	1.317 (13)
C12'—N13'	1.3367	N11—C61	1.379 (13)
C12'—H12'	0.9598	C21—C31	1.371 (13)
N13'—C14'	1.3300	C21—H21	0.9300
C14'—C15'	1.3910	C31—C41	1.338 (13)
C14'—H14'	0.9601	C31—H31	0.9300
C15'—C16'	1.3697	C41—C51	1.438 (15)
C15'—H15'	0.9599	C41—C71	1.492 (13)
C16'—H16'	0.9598	C51—C61	1.376 (14)
C1"—C2"	1.3698	C51—H51	0.9300
C1"—C6"	1.3890	C61—H61	0.9300
C1"—H1"	0.9598	C71—O21	1.300 (13)
C2"—C3"	1.3911	O22—C72	1.229 (11)
C2"—H2"	0.9599	N12—C62	1.327 (11)
C3"—N4"	1.3303	N12—C22	1.392 (12)
C3"—H3"	0.9601	C22—C32	1.359 (12)
N4"—C5"	1.3366	C22—H22	0.9300
C5"—C6"	1.3955	C32—C42	1.357 (12)
C5"—H5"	0.9598	C32—H32	0.9300
C6"—C7"	1.4480	C42—C52	1.411 (12)
C7"—N8"	1.2833	C42—C72	1.509 (13)
C7"—H7"	0.9599	C52—C62	1.401 (12)
N8"—N9"	1.4148	C52—H52	0.9300
N9"—C10"	1.2834	C62—H62	0.9300
C10"—C11"	1.4482	O1W—H1WA	0.85 (5)
C10"—H10"	0.9601	O1W—H1WB	0.84 (2)
C11"—C16"	1.3886
C2'—C1'—C6'	119.8	O22^i—Cd1—O21^ii	86.3 (3)
C1'—C2'—C3'	118.8	O1W—Cd1—N11	174.7 (3)
N4'—C3'—C2'	123.2	N12—Cd1—N11	96.8 (3)
C3'—N4'—C5'	117.0	O22^i—Cd1—N11	88.3 (3)
N4'—C5'—C6'	124.5	O21^ii—Cd1—N11	87.1 (3)
C1'—C6'—C5'	116.7	O1W—Cd1—O11^ii	93.9 (3)
C1'—C6'—C7'	123.5	N12—Cd1—O11^ii	85.8 (2)
C5'—C6'—C7'	119.8	O22^i—Cd1—O11^ii	139.4 (2)
N8'—C7'—C6'	122.2	O21^ii—Cd1—O11^ii	53.7 (3)
C7'—N8'—N9'	112.2	N11—Cd1—O11^ii	83.7 (3)
C10'—N9'—N8'	112.2	O1W—Cd1—O12^i	95.3 (3)
N9'—C10'—C11'	122.2	N12—Cd1—O12^i	82.8 (2)
C16'—C11'—C12'	116.7	O22^i—Cd1—O12^i	52.3 (2)
C16'—C11'—C10'	123.5	O21^ii—Cd1—O12^i	138.4 (3)
C12'—C11'—C10'	119.8	N11—Cd1—O12^i	88.0 (3)
N13'—C12'—C11'	124.5	O11^ii—Cd1—O12^i	165.0 (2)
C14'—N13'—C12'	117.0	C71—O11—Cd1^iii	87.4 (7)
N13'—C14'—C15'	123.2	C72—O12—Cd1^iv	87.6 (6)
C16'—C15'—C14'	118.8	C21—N11—C61	115.5 (9)
C15'—C16'—C11'	119.8	C21—N11—Cd1	124.9 (7)
C2"—C1"—C6"	119.8	C61—N11—Cd1	119.5 (7)
C2"—C1"—H1"	120.1	N11—C21—C31	124.9 (10)
C6"—C1"—H1"	120.1	N11—C21—H21	117.6
C1"—C2"—C3"	118.8	C31—C21—H21	117.6
C1"—C2"—H2"	120.6	C41—C31—C21	120.6 (10)
C3"—C2"—H2"	120.6	C41—C31—H31	119.7
N4"—C3"—C2"	123.2	C21—C31—H31	119.7
N4"—C3"—H3"	118.4	C31—C41—C51	117.8 (9)
C2"—C3"—H3"	118.4	C31—C41—C71	122.8 (10)
C3"—N4"—C5"	117.0	C51—C41—C71	119.3 (9)
N4"—C5"—C6"	124.5	C61—C51—C41	117.3 (10)
N4"—C5"—H5"	117.7	C61—C51—H51	121.3
C6"—C5"—H5"	117.7	C41—C51—H51	121.3
C1"—C6"—C5"	116.7	C51—C61—N11	123.6 (11)
C1"—C6"—C7"	123.5	C51—C61—H61	118.2
C5"—C6"—C7"	119.8	N11—C61—H61	118.2
N8"—C7"—C6"	122.2	O11—C71—O21	122.9 (10)
N8"—C7"—H7"	118.9	O11—C71—C41	118.9 (10)
C6"—C7"—H7"	118.9	O21—C71—C41	117.7 (9)
C7"—N8"—N9"	112.2	C71—O21—Cd1^iii	95.7 (6)
C10"—N9"—N8"	112.2	C72—O22—Cd1^iv	99.4 (6)
N9"—C10"—C11"	122.2	C62—N12—C22	115.0 (8)
N9"—C10"—H10"	118.9	C62—N12—Cd1	120.9 (6)
C11"—C10"—H10"	118.9	C22—N12—Cd1	124.0 (6)
C16"—C11"—C12"	116.7	C32—C22—N12	124.5 (9)
C16"—C11"—C10"	123.5	C32—C22—H22	117.8
C12"—C11"—C10"	119.8	N12—C22—H22	117.8
N13"—C12"—C11"	124.5	C42—C32—C22	118.1 (10)
N13"—C12"—H12"	117.7	C42—C32—H32	121.0
C11"—C12"—H12"	117.8	C22—C32—H32	121.0
C14"—N13"—C12"	117.0	C32—C42—C52	121.4 (9)
N13"—C14"—C15"	123.2	C32—C42—C72	121.4 (9)
N13"—C14"—H14"	118.4	C52—C42—C72	117.2 (9)
C15"—C14"—H14"	118.4	C42—C52—C62	115.5 (9)
C16"—C15"—C14"	118.8	C42—C52—H52	122.2
C16"—C15"—H15"	120.6	C62—C52—H52	122.2
C14"—C15"—H15"	120.6	N12—C62—C52	125.5 (9)
C15"—C16"—C11"	119.8	N12—C62—H62	117.2
C15"—C16"—H16"	120.1	C52—C62—H62	117.2
C11"—C16"—H16"	120.1	O22—C72—O12	120.7 (9)
O1W—Cd1—N12	87.8 (3)	O22—C72—C42	120.1 (9)
O1W—Cd1—O22^i	90.4 (3)	O12—C72—C42	119.2 (9)
N12—Cd1—O22^i	134.7 (3)	Cd1—O1W—H1WA	113 (4)
O1W—Cd1—O21^ii	87.7 (3)	Cd1—O1W—H1WB	136 (3)
N12—Cd1—O21^ii	138.8 (3)	H1WA—O1W—H1WB	106 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O12^v	0.85 (5)	1.98 (6)	2.739 (12)	148 (11)
O1W—H1WB···N4′′^vi	0.84 (2)	2.11 (4)	2.751 (17)	133 (2)
O1W—H1WB···N8′^v	0.84 (2)	1.85 (4)	2.66 (3)	161 (5)
O1W—H1WB···N9′′	0.84 (2)	1.93 (4)	2.741 (17)	161 (4)
O1W—H1WB···N13′	0.84 (2)	2.27 (4)	2.968 (18)	140 (2)
C22—H22···O11^ii	0.93	2.58	3.258 (11)	130
C32—H32···O21^vii	0.93	2.49	3.400 (13)	166
C52—H52···O11^viii	0.93	2.55	3.356 (11)	145
C62—H62···O12^i	0.93	2.41	3.087 (11)	129

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