Crystal structure of bis-(μ-3-nitro-benzoato)-κ3O,O':O;κ3O:O,O'-bis-[bis-(3-cyano-pyridine-κN1)(3-nitro-benzoato-κ2O,O')cadmium].

The asymmetric unit of the title compound, [Cd2(C7H4NO4)4(C6H4N2)4], contains one CdII atom, two 3-nitro-benzoate (NB) anions and two 3-cyano-pyridine (CPy) ligands. The two CPy ligands act as monodentate N(pyridine)-bonding ligands, while the two NB anions act as bidentate ligands through the carboxyl-ate O atoms. The centrosymmetric dinuclear complex is generated by application of inversion symmetry, whereby the CdII atoms are bridged by the carboxyl-ate O atoms of two symmetry-related NB anions, thus completing the distorted N2O5 penta-gonal-bipyramidal coordination sphere of each CdII atom. The benzene and pyridine rings are oriented at dihedral angles of 10.02 (7) and 5.76 (9)°, respectively. In the crystal, C-H⋯N hydrogen bonds link the mol-ecules, enclosing R22(26) ring motifs, in which they are further linked via C-H⋯O hydrogen bonds, resulting in a three-dimensional network. In addition, π-π stacking inter-actions between parallel benzene rings and between parallel pyridine rings of adjacent mol-ecules [shortest centroid-to-centroid distances = 3.885 (1) and 3.712 (1) Å, respectively], as well as a weak C-H⋯π inter-action, may further stabilize the crystal structure.

Chemical context

In the last two decades, research on metal–organic frameworks (MOFs) has received considerable attention due to their extensive structural chemistry (Li et al., 2016 ▸) and their potential applications, including gas storage, nonlinear optics and ion exchange (Carlucci et al., 2003 ▸). In the syntheses of compounds having MOF structures, various carboxyl­ate ligands have been used (Li et al., 2004 ▸).

On the other hand, transition-metal complexes with biochemically active mol­ecules show inter­esting physical and/or chemical properties, through which they may find applications in biological systems (Antolini et al., 1982 ▸). Some n class="Chemical">benzoic acid derivatives, such as 4-amino­benzoic acid, have been extensively reported in coordination chemistry, as bifunctional organic ligands, due to the varieties of their coordination modes (Chen & Chen, 2002 ▸; Amiraslanov et al., 1979 ▸; Hauptmann et al., 2000 ▸).

The structure–function–coordination relationships of aryl­carboxyl­ate ions in ZnII complexes of benzoic acid derivatives change depending on the nature and position of the substituted groups on the n class="Chemical">benzene ring, the nature of the additional ligand mol­ecule or solvent, and the pH range and temperature of the synthesis (Shnulin et al., 1981 ▸; Nadzhafov et al., 1981 ▸; Antsyshkina et al., 1980 ▸; Adiwidjaja et al., 1978 ▸). When pyridine and its derivatives are used instead of water mol­ecules, the structure is completely different (Catterick et al., 1974 ▸).

The structures of some dinuclear complexes obtained from the reactions of transition metal(II) ions with nicotinamide (n class="Chemical">NA; C6H6N2O) and some benzoic acid derivatives as ligands, e.g. [Zn2(C7H4FO2)4(C6H6N2O)2]·C7H5FO2 [(II); Hökelek et al., 2009 ▸], [Cu2(C8H7O3)4(C6H6N2O)2(H2O)2] [(III); Hökelek et al., 2010 ▸], [Cu2(C8H5O3)4(C6H6N2O)4] [(IV); Sertçelik et al., 2013 ▸], [Mn2(C7H4BrO2)4(C6H6N2O)2(H2O)2] [(V); Necefoğlu et al., 2011 ▸] and [Cd2(C7H4ClO2)4(C6H6N2O)2(H2O)2] [(VI); Bozkurt et al., 2013 ▸], have been determined previously. In this context, we have synthesized the CdII-containing title compound, bis(μ-3-nitro­benzoato)-κ3 O,O′:O;κ3 O:O,O′-bis­[bis­(3-cyano­pyridine-κN)(3-nitro­benzoato-κ2 O,O′)cadmium], [Cd2(C7H4NO4)4(C6H4N2)4], and report herein its crystal structure.

Structural commentary

The asymmetric unit of the title complex contains one CdII atom, two 3-nitro­benzoate (n class="Chemical">NB) anions and two 3-cyano­pyridine (CPy) ligands. The two CPy ligands are monodentate (through the pyridine N atoms), while both NB anions act as bidentate ligands through their carboxyl­ate O atoms (Fig. 1 ▸). The centrosymmetric dinuclear mol­ecule is completed by application of inversion symmerty. The CdII atoms are bridged by the carboxyl­ate O atoms of one NB anions (O6 and O5) and its symmetry-related counterpart [symmetry code: (i) −x, −y + 1, −z + 1]. Hence, this carboxyl­ate group not only chelates to one CdII atom but also bridges two CdII atoms (Fig. 2 ▸). Thus, each CdII atom is surrounded by three NB anions and two CPy ligands. The overall coordination sphere of the CdII atom is defined by the bridging/chelating NB anions (O5, O5i and O6), one chelating NB anion (O1 and O2) and two 3-cyano­pyridine (CPy) ligands (N3 and N5), resulting in a distorted penta­gonal–bipyramidal environment. The five carboxyl­ate O atoms (O1, O2, O5, O5i and O6) of the three NB anions around the CdII atom form a distorted penta­gonal arrangement, with an average Cd1—O bond length of 2.42 Å (Table 1 ▸). The distorted penta­gonal–bipyramidal coordination is completed by pyridine atoms N3 and N5 of the CPy ligands at distances of 2.3186 (17) and 2.3435 (17) Å, respectively, in the axial positions (Table 1 ▸; Figs. 1 ▸ and 2 ▸). The Cd1 atom lies 0.1252 (1) Å above and 0.0326 (1) Å below of planar O1/O2/C1 and O5/O6/C8 carboxyl­ate groups, respectively. The Cd1⋯Cd1i separation in the binuclear mol­ecule is 3.9360 (15) Å and is comparable to the corresponding M—M distances (M is a metal) in the structurally related transition metal(II) complexes [7.1368 (3) Å in (III), 4.1554 (8) Å in (IV), 7.180 (2) Å in (V) and 7.1647 (3) Å in (VI)]. The metal atoms are bridged by two NA ligand N and O atoms in (III), (V) and (VI), while they are bridged by two carboxyl­ate O atoms in (IV).

Figure 1

The asymmetric unit of the title mol­ecule, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2

The mol­ecular structure of the binuclear title mol­ecule. Symmetry-related atoms are related by the symmetry code (−x, −y + 1, −z + 1). H atoms have been omitted for clarity.

Table 1

Selected bond lengths (Å)

Cd1—O1	2.3017 (15)	Cd1—O6	2.3264 (15)
Cd1—O2	2.5072 (18)	Cd1—N3	2.3186 (17)
Cd1—O5	2.5367 (16)	Cd1—N5	2.3435 (17)
Cd1—O5i	2.4716 (16)

Symmetry code: (i) .

The near equalities of the C1—O1 [1.264 (3) Å], C1—O2 [1.241 (3) Å], C8—O5 [1.256 (3) Å] and C8—O6 [1.253 (3) Å] bonds in the carboxyl­ate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The O1—Cd1—n class="Chemical">O2 and O5—Cd1—O6 bite angles are reduced to 54.33 (5) and 53.47 (5)°, respectively. The corresponding O—M—O (M is a divalent metal) angles are 60.92 (12)° in (II), 53.50 (14)° in (IV), 57.61 (8)° in (V), and 54.22 (4) and 53.32 (5)° in (VI). The dihedral angles between the planar carboxyl­ate groups (O1/O2/C1 and O5/O6/C8) and the adjacent benzene [A (C2–C7) and B (C9–C14)] rings in the title structure are 17.18 (13) and 3.36 (12)°, respectively, while the benzene (A and B) and pyridine [C (N3/C15–C19) and D (N5/C21–C25)] rings are oriented at dihedral angles of A/B = 10.02 (7)°, A/C = 72.70 (7)°, A/D = 74.72 (7)°, B/C = 82.28 (7)°, B/D = 84.54 (8)° and C/D = 5.76 (9)°.

Supra­molecular features

Intra­molecular C—Hcpy⋯Oc (n class="Chemical">cpy = cyano­pyridine and c = carboxyl­ate) and C—Hnb⋯Oc (nb = nitro­benzoate) hydrogen bonds (Table 2 ▸) link the cyano­pyridine and nitro­benzoate ligands to the carboxyl­ate O atoms. In the crystal, C—Hcpy⋯Ncpy hydrogen bonds (Table 2 ▸) link the mol­ecules, enclosing (26) ring motifs (Bernstein et al., 1995 ▸) (Fig. 3 ▸), in which they are further linked via additional C—Hcpy⋯Onb (nb = nitro­benzoate) hydrogen bonds (Table 2 ▸), resulting in a three-dimensional network. The π–π contacts between parallel benzene rings and between parallel pyridine rings of adjacent mol­ecules, Cg1–Cg2i and Cg3–Cg4ii [symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) −x, −y + 1, −z + 1; Cg1, Cg2, Cg3 and Cg4 are the centroids of the rings A (atoms C2–C7), B (C9–C14), C (N3/C15–C19) and D (N5/C21–C25)] may further stabilize the structure, with centroid–centroid distances of 3.885 (1) and 3.712 (1) Å, respectively. A weak C—H⋯π inter­action (Table 2 ▸) is also observed.

Table 2

Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the N3/C15–C19 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯O1i	0.93	2.20	3.108 (3)	167
C15—H15⋯O2ii	0.93	2.32	3.111 (3)	143
C23—H23⋯N4iii	0.93	2.38	3.236 (5)	154
C25—H25⋯O6	0.93	2.58	3.242 (3)	128
C10—H10⋯Cg3ii	0.93	3.26	4.186 (3)	176

Symmetry codes: (i) ; (ii) ; (iii) .

Figure 3

Part of the crystal structure. Intra­molecular (C—Hcpy⋯Oc and C—Hnb⋯Oc) and inter­molecular (C—Hcpy⋯Ncpy and C—Hcpy⋯Onb) (cpy = cyano­pyridine, c = carboxyl­ate and nb = nitro­benzoate) hydrogen bonds are shown as dashed lines. Nonbonding H atoms have been omitted for clarity.

Refinement

The experimental details including the crystal data, data collection and refinement are summarized in Table 3 ▸. Aromatic H atoms were positioned geometrically, with C—H = 0.93 Å, and constrained to ride on their parent atoms, with U iso(H) = 1.2U eq(C). The maximum and minimum electron densities were found at 1.43 and 0.80 Å from atoms O2 and Cd1, respectively.

Table 3

Experimental details

Crystal data
Chemical formula	[Cd2(C7H4NO4)4(C6H4N2)4]
M r	1305.72
Crystal system, space group	Triclinic, P
Temperature (K)	296
a, b, c (Å)	8.5237 (3), 12.7145 (4), 13.0583 (5)
α, β, γ (°)	105.022 (3), 97.347 (3), 104.866 (2)
V (Å3)	1292.12 (8)
Z	1
Radiation type	Mo Kα
μ (mm−1)	0.91
Crystal size (mm)	0.28 × 0.20 × 0.18
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 ▸)
T min, T max	0.615, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	65471, 6414, 5828
R int	0.029
(sin θ/λ)max (Å−1)	0.668
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.029, 0.072, 1.22
No. of reflections	6414
No. of parameters	370
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	1.01, −0.75

Computer programs: APEX2 (Bruker, 2012 ▸), SAINT (Bruker, 2012 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL97 (Sheldrick, 2008 ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸), WinGX (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸).

Synthesis and crystallization

The title compound was prepared by the reaction of 3CdSO4·8H2O (0.64 g, 2.5 mmol) in n class="Chemical">H2O (50 ml) and 3-cyano­pyridine (0.52 g, 5 mmol) in H2O (50 ml) with sodium 3-nitro­benzoate (0.95 g, 5 mmol) in H2O (100 ml) at 333 K. The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving colourless single crystals.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017002675/wm5366sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017002675/wm5366Isup2.hkl

CCDC reference: 1533101

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Cd2(C7H4NO4)4(C6H4N2)4]	Z = 1
Mr = 1305.72	F(000) = 652
Triclinic, P1	Dx = 1.678 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5237 (3) Å	Cell parameters from 9607 reflections
b = 12.7145 (4) Å	θ = 3.1–28.3°
c = 13.0583 (5) Å	µ = 0.91 mm−1
α = 105.022 (3)°	T = 296 K
β = 97.347 (3)°	Prism, colourless
γ = 104.866 (2)°	0.28 × 0.20 × 0.18 mm
V = 1292.12 (8) Å3

Bruker APEXII CCD diffractometer	6414 independent reflections
Radiation source: fine-focus sealed tube	5828 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ and ω scans	θmax = 28.3°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −11→11
Tmin = 0.615, Tmax = 0.746	k = −16→16
65471 measured reflections	l = −17→17

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072	H-atom parameters constrained
S = 1.22	w = 1/[σ2(Fo2) + (0.0277P)2 + 0.8651P] where P = (Fo2 + 2Fc2)/3
6414 reflections	(Δ/σ)max = 0.001
370 parameters	Δρmax = 1.01 e Å−3
0 restraints	Δρmin = −0.75 e Å−3

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.

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 > 2sigma(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.

	x	y	z	Uiso*/Ueq
Cd1	0.151839 (18)	0.436274 (11)	0.419807 (11)	0.03200 (6)
O1	0.0821 (2)	0.25149 (13)	0.30752 (14)	0.0448 (4)
O2	0.3355 (2)	0.35240 (13)	0.30991 (15)	0.0480 (4)
O3	−0.0992 (3)	−0.15593 (16)	0.12938 (19)	0.0675 (6)
O4	0.0033 (3)	−0.22812 (15)	−0.00392 (17)	0.0646 (5)
O5	0.1364 (2)	0.61626 (13)	0.55320 (14)	0.0431 (4)
O6	0.3515 (2)	0.61460 (13)	0.47720 (13)	0.0414 (3)
O7	0.8058 (3)	0.9744 (2)	0.5573 (3)	0.1093 (12)
O8	0.7807 (3)	1.13029 (18)	0.6485 (3)	0.0928 (9)
N1	0.0007 (3)	−0.14806 (16)	0.07056 (17)	0.0435 (4)
N2	0.7303 (3)	1.02738 (18)	0.6099 (2)	0.0537 (5)
N3	0.2275 (2)	0.37248 (14)	0.56414 (14)	0.0320 (3)
N4	0.6329 (5)	0.5371 (3)	0.8932 (3)	0.1256 (18)
N5	0.0320 (2)	0.48389 (15)	0.27322 (14)	0.0358 (4)
N6	−0.3803 (3)	0.2705 (2)	−0.0491 (2)	0.0685 (7)
C1	0.2174 (3)	0.26302 (16)	0.27548 (16)	0.0324 (4)
C2	0.2308 (3)	0.16188 (17)	0.19015 (17)	0.0322 (4)
C3	0.1160 (3)	0.05585 (17)	0.17155 (17)	0.0330 (4)
H3	0.0350	0.0469	0.2127	0.040*
C4	0.1244 (3)	−0.03626 (17)	0.09058 (17)	0.0347 (4)
C5	0.2408 (3)	−0.0262 (2)	0.0267 (2)	0.0459 (5)
H5	0.2429	−0.0892	−0.0279	0.055*
C6	0.3544 (4)	0.0798 (2)	0.0456 (2)	0.0535 (6)
H6	0.4340	0.0886	0.0034	0.064*
C7	0.3498 (3)	0.1736 (2)	0.1279 (2)	0.0447 (5)
H7	0.4274	0.2445	0.1410	0.054*
C8	0.2760 (2)	0.66594 (16)	0.53913 (16)	0.0315 (4)
C9	0.3550 (2)	0.79211 (16)	0.59657 (16)	0.0312 (4)
C10	0.5053 (3)	0.84920 (17)	0.57676 (18)	0.0346 (4)
H10	0.5592	0.8106	0.5294	0.042*
C11	0.5721 (3)	0.96539 (17)	0.62989 (19)	0.0384 (5)
C12	0.4989 (3)	1.02590 (19)	0.7024 (2)	0.0491 (6)
H12	0.5479	1.1036	0.7373	0.059*
C13	0.3506 (4)	0.9677 (2)	0.7217 (2)	0.0565 (7)
H13	0.2988	1.0064	0.7706	0.068*
C14	0.2785 (3)	0.8520 (2)	0.6685 (2)	0.0453 (5)
H14	0.1776	0.8140	0.6811	0.054*
C15	0.3517 (3)	0.43881 (18)	0.64654 (18)	0.0360 (4)
H15	0.4061	0.5123	0.6466	0.043*
C16	0.4023 (3)	0.4017 (2)	0.73219 (19)	0.0414 (5)
C17	0.3240 (3)	0.2918 (2)	0.7327 (2)	0.0479 (6)
H17	0.3567	0.2653	0.7894	0.058*
C18	0.1962 (3)	0.2229 (2)	0.6465 (2)	0.0503 (6)
H18	0.1411	0.1486	0.6437	0.060*
C19	0.1517 (3)	0.26648 (19)	0.56478 (19)	0.0417 (5)
H19	0.0649	0.2200	0.5072	0.050*
C20	0.5330 (4)	0.4779 (3)	0.8215 (3)	0.0706 (10)
C21	−0.0872 (3)	0.40583 (18)	0.19319 (17)	0.0375 (4)
H21	−0.1240	0.3318	0.1971	0.045*
C22	−0.1584 (3)	0.43099 (19)	0.10448 (17)	0.0373 (4)
C23	−0.1049 (3)	0.5416 (2)	0.09792 (19)	0.0462 (5)
H23	−0.1512	0.5609	0.0397	0.055*
C24	0.0186 (4)	0.6213 (2)	0.1803 (2)	0.0541 (7)
H24	0.0579	0.6960	0.1787	0.065*
C25	0.0835 (3)	0.58913 (19)	0.26552 (19)	0.0460 (6)
H25	0.1675	0.6438	0.3204	0.055*
C26	−0.2833 (3)	0.3418 (2)	0.0192 (2)	0.0484 (6)

	U11	U22	U33	U12	U13	U23
Cd1	0.03932 (9)	0.02142 (7)	0.02841 (8)	0.00423 (6)	0.00100 (6)	0.00389 (5)
O1	0.0451 (9)	0.0315 (8)	0.0489 (9)	0.0062 (7)	0.0178 (7)	−0.0009 (7)
O2	0.0433 (9)	0.0304 (8)	0.0549 (10)	−0.0010 (7)	0.0077 (8)	0.0003 (7)
O3	0.0779 (14)	0.0390 (10)	0.0778 (14)	0.0002 (9)	0.0284 (12)	0.0163 (10)
O4	0.0769 (14)	0.0324 (9)	0.0658 (13)	0.0110 (9)	0.0042 (10)	−0.0060 (8)
O5	0.0372 (8)	0.0272 (7)	0.0521 (9)	−0.0040 (6)	0.0057 (7)	0.0061 (7)
O6	0.0422 (8)	0.0266 (7)	0.0437 (8)	0.0026 (6)	0.0061 (7)	0.0000 (6)
O7	0.0819 (17)	0.0595 (14)	0.155 (3)	−0.0138 (12)	0.0739 (19)	−0.0093 (16)
O8	0.0713 (15)	0.0345 (10)	0.141 (2)	−0.0190 (10)	0.0299 (15)	0.0046 (13)
N1	0.0528 (11)	0.0276 (9)	0.0451 (11)	0.0108 (8)	−0.0003 (9)	0.0091 (8)
N2	0.0436 (11)	0.0353 (10)	0.0650 (14)	−0.0075 (9)	0.0087 (10)	0.0070 (10)
N3	0.0325 (8)	0.0287 (8)	0.0325 (8)	0.0070 (7)	0.0044 (7)	0.0091 (7)
N4	0.136 (3)	0.085 (2)	0.103 (3)	−0.028 (2)	−0.077 (2)	0.050 (2)
N5	0.0488 (10)	0.0272 (8)	0.0279 (8)	0.0093 (7)	0.0024 (7)	0.0072 (7)
N6	0.0717 (16)	0.0507 (14)	0.0597 (15)	−0.0003 (12)	−0.0179 (13)	0.0112 (12)
C1	0.0396 (10)	0.0240 (9)	0.0312 (9)	0.0086 (8)	0.0033 (8)	0.0072 (7)
C2	0.0361 (10)	0.0269 (9)	0.0346 (10)	0.0122 (8)	0.0055 (8)	0.0093 (8)
C3	0.0373 (10)	0.0282 (9)	0.0332 (10)	0.0105 (8)	0.0056 (8)	0.0092 (8)
C4	0.0411 (11)	0.0259 (9)	0.0348 (10)	0.0110 (8)	0.0006 (8)	0.0081 (8)
C5	0.0548 (14)	0.0371 (11)	0.0464 (13)	0.0196 (10)	0.0167 (11)	0.0048 (10)
C6	0.0565 (15)	0.0471 (14)	0.0628 (16)	0.0197 (12)	0.0313 (13)	0.0136 (12)
C7	0.0437 (12)	0.0347 (11)	0.0540 (14)	0.0086 (9)	0.0183 (10)	0.0098 (10)
C8	0.0323 (9)	0.0236 (9)	0.0298 (9)	0.0016 (7)	−0.0040 (7)	0.0055 (7)
C9	0.0303 (9)	0.0221 (8)	0.0321 (9)	0.0004 (7)	−0.0020 (7)	0.0045 (7)
C10	0.0331 (10)	0.0246 (9)	0.0387 (11)	0.0027 (7)	0.0041 (8)	0.0047 (8)
C11	0.0321 (10)	0.0261 (9)	0.0452 (12)	−0.0034 (8)	−0.0006 (9)	0.0071 (8)
C12	0.0485 (13)	0.0230 (10)	0.0587 (15)	0.0004 (9)	0.0032 (11)	−0.0023 (10)
C13	0.0547 (15)	0.0342 (12)	0.0656 (17)	0.0061 (11)	0.0202 (13)	−0.0062 (11)
C14	0.0387 (11)	0.0332 (11)	0.0509 (13)	−0.0005 (9)	0.0118 (10)	0.0007 (10)
C15	0.0334 (10)	0.0317 (10)	0.0388 (11)	0.0042 (8)	0.0001 (8)	0.0128 (8)
C16	0.0376 (11)	0.0411 (12)	0.0431 (12)	0.0086 (9)	−0.0002 (9)	0.0162 (10)
C17	0.0519 (14)	0.0486 (13)	0.0483 (13)	0.0137 (11)	0.0059 (11)	0.0269 (11)
C18	0.0567 (15)	0.0351 (12)	0.0568 (15)	0.0034 (10)	0.0089 (12)	0.0222 (11)
C19	0.0432 (12)	0.0323 (10)	0.0411 (12)	0.0017 (9)	0.0021 (9)	0.0095 (9)
C20	0.0715 (19)	0.0570 (17)	0.0665 (19)	−0.0031 (14)	−0.0272 (16)	0.0329 (15)
C21	0.0454 (12)	0.0296 (10)	0.0336 (10)	0.0072 (9)	0.0035 (9)	0.0093 (8)
C22	0.0408 (11)	0.0361 (11)	0.0310 (10)	0.0106 (9)	0.0019 (8)	0.0070 (8)
C23	0.0601 (15)	0.0393 (12)	0.0379 (11)	0.0157 (11)	−0.0025 (10)	0.0148 (10)
C24	0.0765 (18)	0.0296 (11)	0.0472 (13)	0.0060 (11)	−0.0058 (12)	0.0155 (10)
C25	0.0605 (15)	0.0284 (10)	0.0369 (11)	0.0030 (10)	−0.0055 (10)	0.0075 (9)
C26	0.0533 (14)	0.0412 (12)	0.0430 (12)	0.0080 (11)	−0.0028 (11)	0.0123 (10)

Cd1—O1	2.3017 (15)	C7—H7	0.9300
Cd1—O2	2.5072 (18)	C8—C9	1.511 (3)
Cd1—O5	2.5367 (16)	C9—C10	1.393 (3)
Cd1—O5i	2.4716 (16)	C9—C14	1.389 (3)
Cd1—O6	2.3264 (15)	C10—C11	1.387 (3)
Cd1—N3	2.3186 (17)	C10—H10	0.9300
Cd1—N5	2.3435 (17)	C11—N2	1.470 (3)
Cd1—C1	2.733 (2)	C11—C12	1.377 (3)
O1—C1	1.264 (3)	C12—C13	1.381 (4)
O5—Cd1i	2.4716 (16)	C12—H12	0.9300
O5—C8	1.256 (3)	C13—H13	0.9300
O6—C8	1.253 (3)	C14—C13	1.386 (3)
O8—N2	1.210 (3)	C14—H14	0.9300
N1—O3	1.220 (3)	C15—C16	1.384 (3)
N1—O4	1.219 (3)	C15—H15	0.9300
N1—C4	1.472 (3)	C16—C17	1.387 (3)
N2—O7	1.198 (3)	C16—C20	1.438 (4)
N3—C15	1.330 (3)	C17—H17	0.9300
N3—C19	1.339 (3)	C18—C17	1.381 (4)
N4—C20	1.127 (4)	C18—H18	0.9300
N5—C21	1.335 (3)	C19—C18	1.379 (3)
N5—C25	1.331 (3)	C19—H19	0.9300
C1—O2	1.241 (3)	C21—C22	1.387 (3)
C1—C2	1.508 (3)	C21—H21	0.9300
C2—C7	1.381 (3)	C22—C23	1.391 (3)
C3—C2	1.388 (3)	C22—C26	1.443 (3)
C3—C4	1.384 (3)	C23—C24	1.375 (3)
C3—H3	0.9300	C23—H23	0.9300
C4—C5	1.378 (3)	C24—H24	0.9300
C5—C6	1.382 (4)	C25—C24	1.380 (3)
C5—H5	0.9300	C25—H25	0.9300
C6—H6	0.9300	C26—N6	1.144 (3)
C7—C6	1.397 (3)
O1—Cd1—O2	54.33 (5)	C4—C5—H5	120.8
O1—Cd1—O5	161.73 (6)	C6—C5—H5	120.8
O1—Cd1—O5i	85.39 (6)	C5—C6—C7	120.1 (2)
O1—Cd1—O6	144.74 (6)	C5—C6—H6	120.0
O1—Cd1—N3	88.63 (6)	C7—C6—H6	120.0
O1—Cd1—N5	87.92 (6)	C2—C7—C6	120.5 (2)
O1—Cd1—C1	27.40 (6)	C2—C7—H7	119.7
O2—Cd1—O5	143.94 (5)	C6—C7—H7	119.7
O2—Cd1—C1	26.95 (6)	O5—C8—C9	119.48 (19)
O5i—Cd1—O2	139.57 (5)	O6—C8—O5	122.10 (18)
O5i—Cd1—O5	76.40 (5)	O6—C8—C9	118.41 (18)
O5—Cd1—C1	170.87 (6)	C10—C9—C8	119.84 (19)
O5i—Cd1—C1	112.66 (6)	C14—C9—C8	120.56 (19)
O6—Cd1—O2	90.60 (5)	C14—C9—C10	119.60 (18)
O6—Cd1—O5	53.47 (5)	C9—C10—H10	121.0
O6—Cd1—O5i	129.14 (5)	C11—C10—C9	117.9 (2)
O6—Cd1—N5	89.46 (6)	C11—C10—H10	121.0
O6—Cd1—C1	117.41 (6)	C10—C11—N2	118.8 (2)
N3—Cd1—O2	93.62 (6)	C12—C11—N2	117.92 (19)
N3—Cd1—O5	89.29 (6)	C12—C11—C10	123.3 (2)
N3—Cd1—O5i	88.16 (6)	C11—C12—C13	118.0 (2)
N3—Cd1—O6	98.23 (6)	C11—C12—H12	121.0
N3—Cd1—N5	170.84 (6)	C13—C12—H12	121.0
N3—Cd1—C1	92.02 (6)	C12—C13—C14	120.3 (2)
N5—Cd1—O2	91.25 (6)	C12—C13—H13	119.8
N5—Cd1—O5	91.33 (6)	C14—C13—H13	119.8
N5—Cd1—O5i	83.11 (6)	C9—C14—H14	119.6
N5—Cd1—C1	88.81 (6)	C13—C14—C9	120.9 (2)
C1—O1—Cd1	95.65 (12)	C13—C14—H14	119.6
C1—O2—Cd1	86.70 (13)	N3—C15—C16	121.9 (2)
Cd1i—O5—Cd1	103.60 (5)	N3—C15—H15	119.0
C8—O5—Cd1i	165.65 (15)	C16—C15—H15	119.0
C8—O5—Cd1	87.27 (13)	C15—C16—C17	119.8 (2)
C8—O6—Cd1	97.16 (12)	C15—C16—C20	119.9 (2)
O3—N1—C4	118.33 (19)	C17—C16—C20	120.3 (2)
O4—N1—O3	123.3 (2)	C16—C17—H17	120.9
O4—N1—C4	118.4 (2)	C18—C17—C16	118.1 (2)
O7—N2—O8	122.4 (2)	C18—C17—H17	120.9
O7—N2—C11	119.0 (2)	C17—C18—H18	120.7
O8—N2—C11	118.6 (2)	C19—C18—C17	118.7 (2)
C15—N3—Cd1	120.77 (14)	C19—C18—H18	120.7
C15—N3—C19	118.26 (19)	N3—C19—C18	123.2 (2)
C19—N3—Cd1	120.93 (14)	N3—C19—H19	118.4
C21—N5—Cd1	121.21 (14)	C18—C19—H19	118.4
C25—N5—Cd1	121.09 (15)	N4—C20—C16	178.3 (5)
C25—N5—C21	117.68 (19)	N5—C21—C22	122.5 (2)
O1—C1—Cd1	56.96 (10)	N5—C21—H21	118.7
O1—C1—C2	116.79 (18)	C22—C21—H21	118.7
O2—C1—Cd1	66.35 (12)	C21—C22—C23	119.3 (2)
O2—C1—O1	123.24 (19)	C21—C22—C26	119.7 (2)
O2—C1—C2	120.0 (2)	C23—C22—C26	121.0 (2)
C2—C1—Cd1	172.89 (15)	C22—C23—H23	121.1
C3—C2—C1	118.64 (19)	C24—C23—C22	117.9 (2)
C7—C2—C1	121.51 (19)	C24—C23—H23	121.1
C7—C2—C3	119.80 (19)	C23—C24—C25	119.2 (2)
C2—C3—H3	120.6	C23—C24—H24	120.4
C4—C3—C2	118.7 (2)	C25—C24—H24	120.4
C4—C3—H3	120.6	N5—C25—C24	123.4 (2)
C3—C4—N1	118.3 (2)	N5—C25—H25	118.3
C5—C4—N1	119.2 (2)	C24—C25—H25	118.3
C5—C4—C3	122.4 (2)	N6—C26—C22	178.8 (3)
C4—C5—C6	118.5 (2)
O2—Cd1—O1—C1	−1.60 (12)	Cd1—O1—C1—C2	−176.08 (15)
O5—Cd1—O1—C1	179.36 (16)	Cd1—O5—C8—O6	−0.7 (2)
O5i—Cd1—O1—C1	174.69 (14)	Cd1i—O5—C8—O6	−140.5 (5)
O6—Cd1—O1—C1	5.3 (2)	Cd1—O5—C8—C9	178.05 (16)
N3—Cd1—O1—C1	−97.04 (14)	Cd1i—O5—C8—C9	38.3 (7)
N5—Cd1—O1—C1	91.44 (14)	Cd1—O6—C8—O5	0.8 (2)
O1—Cd1—O2—C1	1.62 (12)	Cd1—O6—C8—C9	−177.99 (15)
O5—Cd1—O2—C1	−178.89 (11)	O3—N1—C4—C3	−3.3 (3)
O5i—Cd1—O2—C1	−4.09 (18)	O3—N1—C4—C5	178.5 (2)
O6—Cd1—O2—C1	−174.39 (13)	O4—N1—C4—C3	176.7 (2)
N3—Cd1—O2—C1	87.33 (13)	O4—N1—C4—C5	−1.5 (3)
N5—Cd1—O2—C1	−84.92 (14)	Cd1—N3—C15—C16	−178.18 (17)
O1—Cd1—O5—Cd1i	−4.8 (2)	C19—N3—C15—C16	−0.7 (3)
O1—Cd1—O5—C8	−175.30 (18)	Cd1—N3—C19—C18	177.4 (2)
O2—Cd1—O5—Cd1i	176.53 (8)	C15—N3—C19—C18	0.0 (4)
O2—Cd1—O5—C8	6.03 (18)	Cd1—N5—C21—C22	−178.82 (17)
O5i—Cd1—O5—Cd1i	0.0	C25—N5—C21—C22	−0.5 (3)
O5i—Cd1—O5—C8	−170.51 (16)	Cd1—N5—C25—C24	179.2 (2)
O6—Cd1—O5—Cd1i	170.93 (10)	C21—N5—C25—C24	0.8 (4)
O6—Cd1—O5—C8	0.42 (12)	O1—C1—O2—Cd1	−2.9 (2)
N3—Cd1—O5—Cd1i	−88.28 (7)	C2—C1—O2—Cd1	176.33 (17)
N3—Cd1—O5—C8	101.21 (13)	O1—C1—C2—C3	−15.8 (3)
N5—Cd1—O5—Cd1i	82.58 (7)	O1—C1—C2—C7	161.6 (2)
N5—Cd1—O5—C8	−87.92 (13)	O2—C1—C2—C3	164.9 (2)
O1—Cd1—O6—C8	177.25 (12)	O2—C1—C2—C7	−17.6 (3)
O2—Cd1—O6—C8	−177.13 (13)	C1—C2—C7—C6	−176.7 (2)
O5—Cd1—O6—C8	−0.42 (12)	C3—C2—C7—C6	0.7 (4)
O5i—Cd1—O6—C8	10.98 (16)	C4—C3—C2—C1	177.69 (18)
N3—Cd1—O6—C8	−83.38 (13)	C4—C3—C2—C7	0.2 (3)
N5—Cd1—O6—C8	91.63 (13)	C2—C3—C4—N1	−179.25 (18)
C1—Cd1—O6—C8	−179.99 (12)	C2—C3—C4—C5	−1.1 (3)
O1—Cd1—N3—C15	146.88 (17)	N1—C4—C5—C6	179.1 (2)
O1—Cd1—N3—C19	−30.50 (17)	C3—C4—C5—C6	0.9 (4)
O2—Cd1—N3—C15	92.75 (17)	C4—C5—C6—C7	0.1 (4)
O2—Cd1—N3—C19	−84.63 (17)	C2—C7—C6—C5	−0.9 (4)
O5—Cd1—N3—C15	−51.27 (16)	O5—C8—C9—C10	−176.4 (2)
O5i—Cd1—N3—C15	−127.69 (17)	O5—C8—C9—C14	3.1 (3)
O5—Cd1—N3—C19	131.34 (17)	O6—C8—C9—C10	2.4 (3)
O5i—Cd1—N3—C19	54.93 (17)	O6—C8—C9—C14	−178.1 (2)
O6—Cd1—N3—C15	1.62 (17)	C8—C9—C10—C11	178.96 (19)
O6—Cd1—N3—C19	−175.77 (17)	C14—C9—C10—C11	−0.6 (3)
C1—Cd1—N3—C15	119.69 (17)	C8—C9—C14—C13	179.8 (2)
C1—Cd1—N3—C19	−57.69 (17)	C10—C9—C14—C13	−0.6 (4)
O1—Cd1—N5—C21	25.91 (17)	C9—C10—C11—N2	−179.8 (2)
O1—Cd1—N5—C25	−152.4 (2)	C9—C10—C11—C12	1.4 (4)
O2—Cd1—N5—C21	80.15 (18)	C10—C11—N2—O7	−7.6 (4)
O2—Cd1—N5—C25	−98.16 (19)	C10—C11—N2—O8	173.3 (3)
O5—Cd1—N5—C21	−135.83 (17)	C12—C11—N2—O7	171.3 (3)
O5—Cd1—N5—C25	45.86 (19)	C12—C11—N2—O8	−7.7 (4)
O5i—Cd1—N5—C25	122.0 (2)	N2—C11—C12—C13	−179.7 (3)
O5i—Cd1—N5—C21	−59.69 (17)	C10—C11—C12—C13	−0.9 (4)
O6—Cd1—N5—C25	−7.57 (19)	C11—C12—C13—C14	−0.4 (5)
O6—Cd1—N5—C21	170.74 (18)	C9—C14—C13—C12	1.2 (5)
C1—Cd1—N5—C21	53.30 (18)	N3—C15—C16—C17	0.9 (4)
C1—Cd1—N5—C25	−125.0 (2)	N3—C15—C16—C20	−177.6 (3)
O1—Cd1—C1—O2	−177.1 (2)	C15—C16—C17—C18	−0.2 (4)
O2—Cd1—C1—O1	177.1 (2)	C20—C16—C17—C18	178.2 (3)
O5i—Cd1—C1—O1	−5.74 (15)	C19—C18—C17—C16	−0.4 (4)
O5i—Cd1—C1—O2	177.13 (13)	N3—C19—C18—C17	0.6 (4)
O6—Cd1—C1—O1	−176.54 (13)	N5—C21—C22—C23	−0.3 (4)
O6—Cd1—C1—O2	6.33 (15)	N5—C21—C22—C26	178.2 (2)
N3—Cd1—C1—O1	83.11 (14)	C21—C22—C23—C24	0.6 (4)
N3—Cd1—C1—O2	−94.02 (14)	C26—C22—C23—C24	−177.8 (3)
N5—Cd1—C1—O1	−87.76 (14)	C22—C23—C24—C25	−0.3 (4)
N5—Cd1—C1—O2	95.10 (14)	N5—C25—C24—C23	−0.5 (5)
Cd1—O1—C1—O2	3.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O1i	0.93	2.20	3.108 (3)	167
C15—H15···O2ii	0.93	2.32	3.111 (3)	143
C23—H23···N4iii	0.93	2.38	3.236 (5)	154
C25—H25···O6	0.93	2.58	3.242 (3)	128
C10—H10···Cg3ii	0.93	3.26	4.186 (3)	176