A two-dimensional CdII coordination polymer: poly[di-aqua-[μ3-5,6-bis-(pyridin-2-yl)pyrazine-2,3-di-carboxyl-ato-κ5O2:O3:O3,N4,N5]cadmium].

The reaction of 5,6-bis-(pyridin-2-yl)pyrazine-2,3-di-carb-oxy-lic acid with cadmium dichloride leads to the formation of the title two-dimensional coordination polymer, [Cd(C16H8N4O4)(H2O)2] n . The metal atom is sevenfold coordinated by one pyrazine and one pyridine N atom, two water O atoms, and by two carboxyl-ate O atoms, one of which bridges two CdII atoms to form a Cd2O2 unit situated about a centre of inversion. Hence, the ligand coordinates to the cadmium atom in an N,N',O-tridentate and an O-monodentate manner. Within the polymer network, there are a number of O-H⋯O hydrogen bonds present, involving the water mol-ecules and the carboxyl-ate O atoms. There are also C-H⋯N and C-H⋯O hydrogen bonds present. In the crystal, the polymer networks lie parallel to the bc plane. They are aligned back-to-back along the a axis with the non-coordinating pyridine rings directed into the space between the networks.

Chemical context

The crystal structure of the ligand 5,6-bis­(pyridin-2-yl)pyrazine-2,3-di­carb­oxy­lic acid (H) and the chloride, perchlorate and hexa­fluoro­phosphate salts, have been reported on previously (Alfonso et al., 2001 ▸). Inter­estingly, the ligand crystallizes as a zwitterion in all four compounds. The reaction of H with CuBr2 (ratio 1:2) leads to the formation of a one-dimensional coordination polymer. On exposure to air, the compound loses the solvent of crystallization and four water mol­ecules, transforming into a two-dimensional coordination polymer (Neels et al., 2003 ▸). In both cases, there are two crystallographically independent fivefold-coordinated copper atoms present and they all have almost perfect square-pyramidal geometry. Recently, we have reported on the crystal structures of the dimethyl and diethyl ester of the H ligand (Alfonso & Stoeckli-Evans, 2016a ▸). The reaction of the dimethyl ester of H with CdCl2 and HgCl2 leads to the formation of isotypic one-dimensional coordination polymers (Alfonso & Stoeckli-Evans, 2016b ▸). There the ligand coordin­ates to the metal atom via the pyridine N atoms, and they have MN2Cl2 fourfold bis­phenoidal coordination geometry.

Structural commentary

The reaction of 5,6-bis­(pyridin-2-yl)pyrazine-2,3-di­carb­oxy­lic acid with cadmium dichloride leads to the formation of the title two-dimensional coordination polymer (Fig. 1 ▸). Here the metal atom is sevenfold coordinated by one pyrazine N atom (N1), one pyridine N atom (N3) and two water O atoms (O1W and O2W), and by two carboxyl­ate O atoms (O1 and O3). Atom O1 bridges two cadmium atoms to form a Cd2O2 unit situated about a centre of inversion; the Cd1⋯Cd1ii distance is 3.8753 (8) Å, while the Cd—O1 and Cd—O1ii bonds are, respectively, 2.371 (4) and 2.427 (4) Å, and the Cd1—O1⋯Cd1ii and O1—Cd⋯O1ii bond angles are 107.74 (13) and 72.26 (13)°, respectively. As can be seen in Fig. 1 ▸, the ligand coordinates to the cadmium atom in a tridentate (N,N,O) and a monodentate manner (O). It can be seen from the carboxyl­ate C—O bond lengths [C15—O1 and C15—O2 are 1.255 (6) and 1.253 (6) Å, respectively, while C16—O3 and C16—O4 are 1.258 (6) and 1.227 (6) Å, respectively] that the negative charge is distributed over the O–C–O group for the first, but located on atom O3 for the second.

Figure 1

A view of the mol­ecular structure of the title coordination polymer, showing the atom labelling [symmetry codes: (i) x, −y + , z − ; (ii) −x + 1, −y + 1, −z + 1; (iii) x, −y + , z + ]. Displacement ellipsoids are drawn at the 50% probability level.

Selected bond lengths and angles involving atom Cd1 are given in Table 1 ▸. The Cd—Npyrazine (Cd1—N1) and the Cd—Npyridine (Cd1—N3) bond lengths are the same within 3 s.u.s. [2.418 (4) cf. 2.430 (4) Å]. The Cd—Owater bond lengths [2.301 (4) and 2.317 (3) Å] are shorter than the Cd—Ocarboxyl­ate bond lengths [2.371 (4) and 2.377 (4) Å], while the bridging Cd1⋯O1ii distance is the longest at 2.427 (4) Å. The geometry of the sevenfold-coordinated cadmium atom can best be described as a distorted penta­gonal bipyramid, with atoms O1,N1,N3,O2W,O1ii in the basal plane and atoms O1W,O3i in the apical positions with an O1W—Cd1—O3i bond angle of 157.41 (15)° (Table 1 ▸).

Table 1

Selected geometric parameters (Å, °)

Cd1—O1	2.371 (4)	Cd1—N3	2.430 (4)
Cd1—O3i	2.377 (4)	Cd1—O1W	2.301 (4)
Cd1—N1	2.418 (4)	Cd1—O2W	2.317 (3)
Cd1—O1ii	2.427 (4)
Cd1—O1—Cd1ii	107.74 (13)	O1W—Cd1—N1	91.62 (16)
O1W—Cd1—O3i	157.41 (15)	O1W—Cd1—N3	87.87 (15)
O1—Cd1—O1ii	72.26 (13)	O1W—Cd1—O1ii	76.59 (15)
O1—Cd1—N1	67.98 (13)	O2W—Cd1—O3i	87.05 (13)
N1—Cd1—N3	65.40 (14)	O1—Cd1—O3i	80.38 (12)
O2W—Cd1—N3	78.01 (13)	O3i—Cd1—N1	91.67 (13)
O2W—Cd1—O1ii	80.65 (13)	O3i—Cd1—O1ii	86.60 (12)
O1W—Cd1—O2W	104.67 (16)	O3i—Cd1—N3	113.74 (13)
O1W—Cd1—O1	80.18 (15)

Symmetry codes: (i) ; (ii) .

The coordinated pyridine ring (N3/C5-C9) and the carboxyl­ate group (O1/O2/C15) are inclined to the pyrazine ring (r.m.s. deviation = 0.03 Å) by 16.9 (2) and 1.9 (6)°, respectively. The non-coordinating pyridine ring (N4/C10–C14) and the second coordinating carboxyl­ate group (O3/O4/C16) are inclined to the pyrazine ring by 60.2 (3) and 89.1 (11)°, respectively. The two pyridine rings are inclined to one another by 75.4 (3) °.

Supra­molecular features

In the crystal, the two-dimensional polymer networks lie parallel to the bc plane, as illustrated in Figs. 2 ▸ and 3 ▸. The networks are aligned back-to-back along the a axis, with the non-coordinating pyridine rings directed into the space between the networks (Fig. 4 ▸). Within the networks there are a number of O—H⋯O hydrogen bonds present, involving the water mol­ecules and the carboxyl­ate O atoms (Table 2 ▸ and Fig. 5 ▸). There are also C—H⋯O and C—H⋯N hydrogen bonds present within the network (Table 2 ▸).

Figure 2

A view along the a axis of the title two-dimensional coordination polymer. The C-bound H atoms have been omitted for clarity.

Figure 3

A view along the c axis of the title two-dimensional coordination polymer. The C-bound H atoms have been omitted for clarity.

Figure 4

A view in projection down the c axis of the crystal packing of the title two-dimensional coordination polymer. The C-bound H atoms have been omitted for clarity.

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O3iii	0.82 (2)	2.22 (3)	2.974 (6)	152 (5)
O1W—H1WB⋯O2iv	0.84 (2)	2.05 (4)	2.805 (6)	150 (7)
O2W—H2WA⋯O4i	0.85 (2)	1.88 (3)	2.630 (6)	146 (5)
O2W—H2WB⋯O2ii	0.85 (2)	1.88 (2)	2.692 (5)	159 (5)
C9—H9⋯O3v	0.94	2.52	3.245 (6)	134
C14—H14⋯N4vi	0.94	2.62	3.372 (8)	137

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Figure 5

A view normal to plane (10) of the O—H⋯O hydrogen bonds (dashed lines; see Table 2 ▸) within the polymer network, involving the carboxyl­ate O atoms (red balls) and the coordinating water mol­ecules. The C atoms and C-bound H atoms of the ligand have been omitted for clarity.

Database survey

A search of the Cambridge Structural Database (CSD, Version 5.37, last update May 2016; Groom et al., 2016 ▸) for the ligand H gave eight hits. All of these structures have been mentioned in the Chemical context above. A search for cadmium complexes with the Cd atom coordinated by two N atoms, two water mol­ecules and three O atoms, two of which are carboxyl­ate O atoms, gave seven hits. One of these compounds, catena-[(μ2-1,1′-(butane-1,4-di­yl)bis­(5,6-dimethyl-1H-benzimidazole)]bis­(μ2-pyridine-2,6-di­carboxyl­ato)tetra­aqua­dicadmium dihydrate) [CSD refcode: FAVHIV; Jiao et al., 2012 ▸] has a Cd2O2 unit formed about an inversion centre as in the title compound. In FAVHIV, the Cd⋯Cd distance and the angles Cd—O⋯Cd and O—Cd⋯O are, respectively, 4.0408 (5) Å, and 111.05 (8) and 68.95 (7)°, compared to 3.8753 (8) Å, and 107.74 (13) and 72.26 (13) °, respectively, in the title compound. However, such an arrangement is extremely common for cadmium(II) complexes (over 600 hits in the CSD) and the bond lengths and angles vary enormously; for example the Cd⋯Cd distance varies from ca 3.0 to 4.3 Å, the Cd—O⋯Cd angle varies from ca 82 to 119° and the O—Cd⋯O angle from ca 60 to 90°.

Synthesis and crystallization

The synthesis of the ligand 5,6-bis­(pyridin-2-yl)pyrazine-2,3-di­carb­oxy­lic acid (H) has been reported previously (Alfonso et al., 2001 ▸).

Synthesis of the title coordination polymer: H (32 mg, 0.10 mmol) was added to an aqueous solution (25 ml) of CdCl2·2H2O (22 mg, 0.10 mmol). The colourless solution immediately obtained was stirred for 1 h at room temperature. The reaction mixture was then filtered and the filtrate allowed to evaporate slowly at room temperature. After two weeks, small colourless plate-like crystals of the title compound were obtained, separated by filtration and dried in air (yield: 40 mg, 42.5%). Selected IR bands (KBr pellet, cm−1): ν 1630(m), 1598(vs), 1533(m), 1469(m), 1442(m), 1414(m), 1362(s), 1301(m), 1273(m), 1176(m), 1165(m), 1119(m), 1043(w), 992(w), 829(m), 789(m), 759(m), 675(m), 562(m), 513(m). Analysis for C16H12N4O6Cd (468.71): calculated: C 41.00, H 2.58, N 11.95%; found: C 40.70, H 2.43, N 11.80%.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. The water H atoms were located in a difference Fourier map and refined with distance restraints: O—H = 0.84 (2) and H⋯H = 1.35 (2) Å, with U iso(H) = 1.5U eq(O). The C-bound H atoms were included in calculated positions and treated as riding atoms: C—H = 0.94 Å with U iso(H) = 1.2U eq(C). The best crystal available was extremely thin (0.01 mm) and as the shape of the crystal was irregular it was not possible to carry out a numerical absorption correction. The displacement ellipsoids for two carboxyl­ate O atoms (O2 and O4) and a water O atom (OW1) are large but attempts to split these atoms were not successful.

Table 3

Experimental details

Crystal data
Chemical formula	[Cd(C16H8N4O4)(H2O)2]
M r	468.70
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	223
a, b, c (Å)	16.6854 (12), 7.0799 (6), 13.4537 (10)
β (°)	96.236 (9)
V (Å3)	1579.9 (2)
Z	4
Radiation type	Mo Kα
μ (mm−1)	1.43
Crystal size (mm)	0.30 × 0.20 × 0.01
Data collection
Diffractometer	Stoe IPDS 1 image plate
Absorption correction	Multi-scan (MULABS; Spek, 2009 ▸)
T min, T max	0.900, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	11782, 3056, 1781
R int	0.129
(sin θ/λ)max (Å−1)	0.615
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.038, 0.063, 0.75
No. of reflections	3056
No. of parameters	257
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.53, −0.59

Computer programs: EXPOSE, CELL and INTEGRATE in IPDS-I (Stoe & Cie, 2004 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸), Mercury (Macrae et al., 2008 ▸), PLATON (Spek, 2009 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989016012858/pk2589sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016012858/pk2589Isup2.hkl

CCDC reference: 1498382

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

[Cd(C16H8N4O4)(H2O)2]	F(000) = 928
Mr = 468.70	Dx = 1.970 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.6854 (12) Å	Cell parameters from 5000 reflections
b = 7.0799 (6) Å	θ = 1.7–26.1°
c = 13.4537 (10) Å	µ = 1.43 mm−1
β = 96.236 (9)°	T = 223 K
V = 1579.9 (2) Å3	Plate, colourless
Z = 4	0.30 × 0.20 × 0.01 mm

Stoe IPDS 1 image plate diffractometer	3056 independent reflections
Radiation source: fine-focus sealed tube	1781 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.129
φ rotation scans	θmax = 25.9°, θmin = 2.5°
Absorption correction: multi-scan (MULABS; Spek, 2009)	h = −20→20
Tmin = 0.900, Tmax = 1.00	k = −8→8
11782 measured reflections	l = −16→16

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.063	w = 1/[σ2(Fo2) + (0.0062P)2] where P = (Fo2 + 2Fc2)/3
S = 0.75	(Δ/σ)max = 0.001
3056 reflections	Δρmax = 0.53 e Å−3
257 parameters	Δρmin = −0.59 e Å−3
6 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00055 (16)

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.

	x	y	z	Uiso*/Ueq
Cd1	0.39911 (3)	0.63678 (6)	0.47689 (3)	0.01231 (13)
O1	0.4663 (2)	0.3932 (6)	0.5741 (2)	0.0160 (9)
O2	0.4579 (2)	0.1638 (6)	0.6875 (3)	0.0266 (10)
O3	0.3636 (2)	0.1259 (6)	0.8712 (2)	0.0207 (9)
O4	0.3010 (3)	−0.0413 (6)	0.7454 (3)	0.0436 (14)
O1W	0.4770 (3)	0.8162 (6)	0.5928 (3)	0.0412 (13)
H1WA	0.520 (2)	0.780 (9)	0.623 (4)	0.062*
H1WB	0.457 (3)	0.898 (7)	0.628 (4)	0.062*
O2W	0.3837 (2)	0.8219 (5)	0.3341 (2)	0.0189 (10)
H2WA	0.355 (2)	0.766 (7)	0.287 (3)	0.028*
H2WB	0.4295 (16)	0.833 (8)	0.312 (3)	0.028*
N1	0.3193 (3)	0.5188 (6)	0.6031 (3)	0.0130 (10)
N2	0.2284 (3)	0.3495 (7)	0.7347 (3)	0.0156 (10)
N3	0.2853 (2)	0.8351 (6)	0.5067 (3)	0.0131 (10)
N4	0.0603 (3)	0.5341 (6)	0.6152 (3)	0.0222 (12)
C1	0.2472 (3)	0.5920 (7)	0.6161 (3)	0.0096 (12)
C2	0.2003 (3)	0.4982 (7)	0.6816 (4)	0.0128 (13)
C3	0.3478 (3)	0.3673 (9)	0.6546 (3)	0.0100 (10)
C4	0.3025 (3)	0.2842 (7)	0.7250 (4)	0.0102 (13)
C5	0.2290 (3)	0.7774 (7)	0.5650 (4)	0.0122 (13)
C6	0.1657 (3)	0.8955 (8)	0.5818 (3)	0.0186 (14)
H6	0.1260	0.8536	0.6211	0.022*
C7	0.1608 (4)	1.0747 (7)	0.5410 (4)	0.0196 (14)
H7	0.1174	1.1544	0.5516	0.024*
C8	0.2194 (3)	1.1351 (9)	0.4850 (3)	0.0166 (11)
H8	0.2175	1.2573	0.4576	0.020*
C9	0.2815 (3)	1.0138 (7)	0.4696 (4)	0.0156 (13)
H9	0.3224	1.0560	0.4322	0.019*
C10	0.1146 (4)	0.5462 (7)	0.6958 (4)	0.0179 (14)
C11	0.0946 (4)	0.5917 (8)	0.7907 (4)	0.0249 (15)
H11	0.1347	0.6018	0.8453	0.030*
C12	0.0141 (4)	0.6216 (10)	0.8025 (4)	0.0285 (14)
H12	−0.0016	0.6492	0.8660	0.034*
C13	−0.0426 (4)	0.6106 (9)	0.7204 (5)	0.0333 (16)
H13	−0.0974	0.6328	0.7263	0.040*
C14	−0.0169 (4)	0.5661 (8)	0.6298 (5)	0.0294 (17)
H14	−0.0560	0.5574	0.5741	0.035*
C15	0.4309 (3)	0.3025 (7)	0.6364 (4)	0.0140 (14)
C16	0.3259 (3)	0.1061 (8)	0.7857 (4)	0.0146 (13)

	U11	U22	U33	U12	U13	U23
Cd1	0.0136 (2)	0.01131 (19)	0.01235 (19)	0.0013 (3)	0.00290 (13)	0.0012 (2)
O1	0.015 (2)	0.019 (2)	0.0148 (18)	−0.001 (2)	0.0050 (16)	0.0052 (18)
O2	0.023 (2)	0.026 (3)	0.034 (2)	0.013 (2)	0.0159 (18)	0.021 (2)
O3	0.032 (2)	0.019 (2)	0.0108 (18)	0.011 (2)	0.0008 (17)	−0.002 (2)
O4	0.064 (4)	0.015 (2)	0.042 (3)	−0.011 (2)	−0.039 (3)	0.003 (2)
O1W	0.029 (3)	0.032 (3)	0.057 (3)	0.010 (2)	−0.018 (2)	−0.031 (2)
O2W	0.017 (2)	0.023 (3)	0.017 (2)	−0.003 (2)	−0.0011 (17)	0.0062 (17)
N1	0.012 (3)	0.017 (3)	0.010 (2)	0.003 (2)	0.003 (2)	−0.0037 (19)
N2	0.018 (3)	0.015 (2)	0.014 (2)	0.005 (3)	−0.0004 (19)	0.002 (2)
N3	0.014 (3)	0.007 (3)	0.018 (2)	0.002 (2)	0.0006 (19)	0.0031 (19)
N4	0.012 (3)	0.027 (3)	0.028 (3)	0.004 (2)	0.004 (2)	0.002 (2)
C1	0.005 (3)	0.017 (3)	0.008 (2)	0.001 (2)	0.004 (2)	−0.002 (2)
C2	0.010 (3)	0.014 (3)	0.014 (3)	−0.007 (3)	−0.002 (2)	−0.002 (2)
C3	0.013 (3)	0.010 (2)	0.007 (2)	−0.004 (3)	0.001 (2)	0.001 (3)
C4	0.012 (3)	0.010 (3)	0.009 (3)	−0.005 (3)	0.002 (2)	−0.003 (2)
C5	0.008 (3)	0.017 (3)	0.013 (3)	0.000 (3)	0.004 (2)	−0.001 (2)
C6	0.019 (3)	0.021 (4)	0.016 (3)	0.004 (3)	0.007 (2)	0.003 (3)
C7	0.023 (4)	0.015 (3)	0.021 (3)	0.011 (3)	0.003 (3)	−0.004 (2)
C8	0.027 (3)	0.007 (2)	0.016 (3)	0.004 (3)	0.003 (2)	0.001 (3)
C9	0.020 (4)	0.017 (3)	0.011 (3)	−0.002 (3)	0.006 (3)	0.001 (2)
C10	0.020 (4)	0.014 (3)	0.020 (3)	0.002 (3)	0.003 (3)	0.006 (2)
C11	0.025 (4)	0.024 (4)	0.026 (3)	0.002 (3)	0.009 (3)	0.004 (3)
C12	0.032 (4)	0.021 (3)	0.037 (3)	0.003 (4)	0.021 (3)	0.004 (3)
C13	0.021 (4)	0.022 (4)	0.060 (4)	0.003 (4)	0.017 (3)	0.002 (4)
C14	0.013 (4)	0.028 (4)	0.045 (4)	0.003 (3)	−0.004 (3)	0.006 (3)
C15	0.015 (4)	0.015 (3)	0.012 (3)	−0.003 (3)	0.002 (3)	−0.006 (2)
C16	0.016 (3)	0.012 (3)	0.017 (3)	0.005 (3)	0.005 (2)	0.002 (3)

Cd1—O1	2.371 (4)	N4—C14	1.344 (7)
Cd1—O3i	2.377 (4)	C1—C2	1.407 (7)
Cd1—N1	2.418 (4)	C1—C5	1.498 (7)
Cd1—O1ii	2.427 (4)	C2—C10	1.502 (8)
Cd1—N3	2.430 (4)	C3—C4	1.403 (7)
Cd1—O1W	2.301 (4)	C3—C15	1.506 (7)
Cd1—O2W	2.317 (3)	C4—C16	1.530 (7)
O1—C15	1.255 (6)	C5—C6	1.384 (7)
O1—Cd1ii	2.427 (3)	C6—C7	1.381 (7)
O2—C15	1.253 (6)	C6—H6	0.9400
O3—C16	1.258 (6)	C7—C8	1.366 (7)
O3—Cd1iii	2.377 (4)	C7—H7	0.9400
O4—C16	1.227 (6)	C8—C9	1.378 (7)
O1W—H1WA	0.82 (2)	C8—H8	0.9400
O1W—H1WB	0.837 (19)	C9—H9	0.9400
O2W—H2WA	0.847 (19)	C10—C11	1.392 (7)
O2W—H2WB	0.852 (19)	C11—C12	1.386 (8)
N1—C3	1.335 (7)	C11—H11	0.9400
N1—C1	1.339 (6)	C12—C13	1.376 (8)
N2—C2	1.328 (7)	C12—H12	0.9400
N2—C4	1.341 (7)	C13—C14	1.373 (8)
N3—C5	1.351 (6)	C13—H13	0.9400
N3—C9	1.359 (6)	C14—H14	0.9400
N4—C10	1.338 (7)
Cd1—O1—Cd1ii	107.74 (13)	C1—C2—C10	125.1 (5)
O1W—Cd1—O3i	157.41 (15)	N1—C3—C4	120.0 (5)
O1—Cd1—O1ii	72.26 (13)	N1—C3—C15	116.3 (4)
O1—Cd1—N1	67.98 (13)	C4—C3—C15	123.6 (5)
N1—Cd1—N3	65.40 (14)	N2—C4—C3	119.4 (5)
O2W—Cd1—N3	78.01 (13)	N2—C4—C16	114.6 (4)
O2W—Cd1—O1ii	80.65 (13)	C3—C4—C16	125.6 (5)
O1W—Cd1—O2W	104.67 (16)	N3—C5—C6	120.2 (5)
O1W—Cd1—O1	80.18 (15)	N3—C5—C1	114.3 (5)
O1W—Cd1—N1	91.62 (16)	C6—C5—C1	125.1 (5)
O1W—Cd1—N3	87.87 (15)	C7—C6—C5	120.3 (5)
O1W—Cd1—O1ii	76.59 (15)	C7—C6—H6	119.9
O2W—Cd1—O3i	87.05 (13)	C5—C6—H6	119.9
O1—Cd1—O3i	80.38 (12)	C8—C7—C6	119.4 (5)
O3i—Cd1—N1	91.67 (13)	C8—C7—H7	120.3
O3i—Cd1—O1ii	86.60 (12)	C6—C7—H7	120.3
O3i—Cd1—N3	113.74 (13)	C7—C8—C9	118.9 (5)
O2W—Cd1—N1	139.31 (15)	C7—C8—H8	120.6
O2W—Cd1—O1	150.65 (13)	C9—C8—H8	120.6
N1—Cd1—O1ii	139.91 (14)	N3—C9—C8	122.1 (5)
O1—Cd1—N3	131.34 (12)	N3—C9—H9	119.0
O1ii—Cd1—N3	149.40 (14)	C8—C9—H9	119.0
C15—O1—Cd1	120.8 (3)	N4—C10—C11	123.3 (5)
C15—O1—Cd1ii	131.4 (4)	N4—C10—C2	116.9 (5)
C16—O3—Cd1iii	121.8 (4)	C11—C10—C2	119.7 (5)
Cd1—O1W—H1WA	124 (4)	C12—C11—C10	118.2 (6)
Cd1—O1W—H1WB	122 (4)	C12—C11—H11	120.9
H1WA—O1W—H1WB	109 (3)	C10—C11—H11	120.9
Cd1—O2W—H2WA	111 (4)	C13—C12—C11	119.3 (5)
Cd1—O2W—H2WB	109 (4)	C13—C12—H12	120.4
H2WA—O2W—H2WB	104 (3)	C11—C12—H12	120.4
C3—N1—C1	121.2 (4)	C14—C13—C12	118.2 (6)
C3—N1—Cd1	116.7 (3)	C14—C13—H13	120.9
C1—N1—Cd1	121.9 (3)	C12—C13—H13	120.9
C2—N2—C4	119.7 (4)	N4—C14—C13	124.4 (6)
C5—N3—C9	119.1 (4)	N4—C14—H14	117.8
C5—N3—Cd1	121.8 (3)	C13—C14—H14	117.8
C9—N3—Cd1	118.9 (3)	O2—C15—O1	126.9 (5)
C10—N4—C14	116.5 (5)	O2—C15—C3	115.6 (5)
N1—C1—C2	117.9 (5)	O1—C15—C3	117.5 (5)
N1—C1—C5	114.8 (4)	O4—C16—O3	127.6 (5)
C2—C1—C5	127.0 (5)	O4—C16—C4	114.3 (5)
N2—C2—C1	121.6 (5)	O3—C16—C4	118.0 (5)
N2—C2—C10	113.3 (4)
C3—N1—C1—C2	−3.4 (7)	C6—C7—C8—C9	1.0 (8)
Cd1—N1—C1—C2	171.5 (3)	C5—N3—C9—C8	−3.6 (7)
C3—N1—C1—C5	171.2 (4)	Cd1—N3—C9—C8	−178.9 (4)
Cd1—N1—C1—C5	−13.9 (6)	C7—C8—C9—N3	1.2 (8)
C4—N2—C2—C1	−1.1 (8)	C14—N4—C10—C11	−0.9 (8)
C4—N2—C2—C10	176.2 (5)	C14—N4—C10—C2	176.1 (5)
N1—C1—C2—N2	4.7 (7)	N2—C2—C10—N4	−117.2 (5)
C5—C1—C2—N2	−169.2 (5)	C1—C2—C10—N4	60.0 (7)
N1—C1—C2—C10	−172.3 (5)	N2—C2—C10—C11	59.9 (7)
C5—C1—C2—C10	13.8 (8)	C1—C2—C10—C11	−122.9 (6)
C1—N1—C3—C4	−1.2 (7)	N4—C10—C11—C12	1.5 (8)
Cd1—N1—C3—C4	−176.3 (4)	C2—C10—C11—C12	−175.3 (5)
C1—N1—C3—C15	−177.7 (4)	C10—C11—C12—C13	−1.7 (9)
Cd1—N1—C3—C15	7.1 (5)	C11—C12—C13—C14	1.3 (10)
C2—N2—C4—C3	−3.6 (7)	C10—N4—C14—C13	0.4 (9)
C2—N2—C4—C16	−176.7 (5)	C12—C13—C14—N4	−0.7 (10)
N1—C3—C4—N2	4.8 (8)	Cd1—O1—C15—O2	175.2 (4)
C15—C3—C4—N2	−178.9 (5)	Cd1ii—O1—C15—O2	−2.5 (8)
N1—C3—C4—C16	177.2 (5)	Cd1—O1—C15—C3	−6.1 (6)
C15—C3—C4—C16	−6.5 (8)	Cd1ii—O1—C15—C3	176.2 (3)
C9—N3—C5—C6	3.7 (7)	N1—C3—C15—O2	177.9 (4)
Cd1—N3—C5—C6	178.9 (4)	C4—C3—C15—O2	1.5 (8)
C9—N3—C5—C1	−169.7 (4)	N1—C3—C15—O1	−0.9 (7)
Cd1—N3—C5—C1	5.5 (6)	C4—C3—C15—O1	−177.3 (5)
N1—C1—C5—N3	5.2 (6)	Cd1iii—O3—C16—O4	1.6 (8)
C2—C1—C5—N3	179.3 (5)	Cd1iii—O3—C16—C4	177.4 (3)
N1—C1—C5—C6	−167.8 (5)	N2—C4—C16—O4	82.7 (6)
C2—C1—C5—C6	6.3 (9)	C3—C4—C16—O4	−90.0 (7)
N3—C5—C6—C7	−1.5 (8)	N2—C4—C16—O3	−93.7 (6)
C1—C5—C6—C7	171.1 (5)	C3—C4—C16—O3	93.6 (6)
C5—C6—C7—C8	−0.8 (8)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O3iv	0.82 (2)	2.22 (3)	2.974 (6)	152 (5)
O1W—H1WB···O2v	0.84 (2)	2.05 (4)	2.805 (6)	150 (7)
O2W—H2WA···O4i	0.85 (2)	1.88 (3)	2.630 (6)	146 (5)
O2W—H2WB···O2ii	0.85 (2)	1.88 (2)	2.692 (5)	159 (5)
C9—H9···O3vi	0.94	2.52	3.245 (6)	134
C14—H14···N4vii	0.94	2.62	3.372 (8)	137