A new chain-like cadmium(II) coordination polymer containing chains of water mol­ecules

The title cadmium(II) polymer, catena-poly[[[bis­(4-amino­pyridine-κN)­aqua­cadmium(II)]-μ-1,4-phenyl­enediacetato-κ⁴O,O′:O′′,O′′′] dihydrate], {[Cd(C₁₀H₈O₄)(C₅H₆N₂)₂(H₂O)]·2H₂O}_n, comprises one-dimensional wave-like chains, in which the Cd atom is coordinated by 1,4-phenyl­enediacetate and 4-amino­pyridine molecules. The 1,4-phenylenediacetate ligands lie about inversion centres. Extensive hydrogen-bonding inter­actions between the chains lead to a three-dimensional structure. Free water mol­ecules form chains in the structure.

S1. Comment

Various rigid benzenedicarboxylic acids, such as 1,2-benzenedicarboxylic acid and 1,4-benzenedicarboxylic acid, which have been demonstrated to be excellent candidates for bridging metal centers and metal clusters and form architectures of various dimensions, have been used in numerous reactions to produce metal-organic frameworks (Li et al., 2004). However, phenylenediacetic acids, for example, 1,4-phenylenediacetic acid (H₂PDA), derived from benzenedicarboxylic acid, have more flexible carboxylic acid groups which do not tend to take part in reactions; hence, there are only a few examples of polymeric compounds containing these acids (Pan et al., 2003). In this context, we introduced a secondary building unit (4-aminopyridine) for the design of metal-organic carboxylate frameworks, to improve the activity of the carboxylate group coordination with transition metal ions. Remarkably and fortunately, a three-dimensional complex was obtained containing the two ligands. The other significant observation is that free water molecules form hydrogen-bonded chains in the structure, a phenomenon that is of current interest (Ghosh & Bharadwaj, 2004).

As shown in Fig. 1, the chain consists of [Cd^II(4-aminopyridine)(PDA)H₂O] building blocks that are linked head-to-tail by PDA²⁻ ligands through M—O bonds. The Cd atom has a distorted decahedral environment, with the equatorial plane occupied by five O atoms, four (O1, O2, O3 and O4) from two deprotonated PDA²⁻ molecules and one (O5) from the coordinated water molecule. Two N atoms from two 4-aminopyridine molecules fill the two axial positions, with bond lengths of 2.276 (3) Å (Cd—N3) and 2.296 (3) Å (Cd—N2). The 4-aminopyridine ligand uses its pyridine ring N atom to coordinate with the metal ion and its amine N atom is uncoordinated. The two deprotonated PDA²⁻ moieties act as bridges, linking three Cd^II ions through carboxylate groups and using their carboxylate groups to chelate with Cd^II ions. The M—O(PDA²⁻) distances range from 2.378 (2) to 2.651 (3) Å. The M—O_water distance is 2.335 (3) Å. Hence, each metal centre connects two PDA²⁻ ligands to form a one-dimensional chain in a step-like shape with metal–metal distances of 11.644 (s.u.?) Å.

In the structure, different kinds of hydrogen bonds are observed: (i) hydrogen bonds between free water molecules [O6···O7 = 2.827 (5) Å], (ii) hydrogen bonding of free water and carboxyl O atoms [O7···O4 = 2.771 (5) Å], (iii) hydrogen bonding of coordinated water and carboxyl O atoms [O5···O2 = 2.745 (4) Å and O5···O3 = 2.780 (4) Å], (iv) hydrogen bonding between the amine N atoms in the 4-aminopyridine molecules and free water molecules [N4···O7 = 3.178 (5) Å and N1···O6 = 3.020 (6) Å], and (v) hydrogen bonding betweem the amine N atoms and carboxyl O atoms [N4···O4 = 3.234 (5) Å]. Through these hydrogen-bonding interactions, each Cd^II polymer chain links to other chains to form a three-dimensional structure (Fig. 2a) in a layer-chain grid construction (for clarity, 4-aminopyridine molecules were omitted from the plot). These central parts are linked by hydrogen bonds to form two-dimensional layers (Fig. 2b). The supramolecular layers are connected by the PDA²⁻ molecules of the step-like chains (Fig. 2a) to form the final three-dimensional supramolecular structure. Moreover, the uncoordinated amine N atoms of 4-aminepyridine molecules are hydrogen-bonded to O atoms of water molecules and carboxyl groups to stabilize the conformation.

Free water molecules play an interesting role in the structure, forming infinite chains by supramolecular assembly (Fig. 3). Through hydrogen bonds, the water chains further organize the coordination polymer chains to distribute alternately side by side and constitute the two-dimensional structure (Fig. 2b).

S2. Experimental

The title compound, (I), was produced in hydrothermal conditions. Cadmium nitrate tetrahydrate (0.119 g), 1,4-phenylenediacetic acid (97%, 0.040 g), 4-aminopyridine (98%, 0.020 g) and H₂O (15 ml) were added to a teflon-lined steel autoclave vessel. The mixture was heated at 438 K for 3 d and then slowly cooled over a period of 2 d to room temperature. The resulting product consisted of white crystals of the title complex in 40% yield.

S3. Refinement

H atoms were included in calculated positions and their parameters were refined isotropically [C—H = 0.87 (5)–1.07 (5) Å, O—H = 0.71 (5)–0.94 (6) Å and N—H = 0.78 (6)–0.96 (6) Å].

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1994)?; software used to prepare material for publication: SHELXTL?.

Figures

	Fig. 1. The one-dimensional chain structure of the title compound, showing the local coordination environment around the Cd^II ions; H atoms have been omitted for clarity.
	Fig. 2. (a) The two-dimensional layer in the title compound, showing hydrogen-bonding interactions along the b axis. H atoms and 4-aminopyridine molecules have been omitted. (b) The two-dimensional layer of the title compound, showing hydrogen-bond interactions along the a axis. Phenyl rings and 4-aminopyridine molecules have been omitted.
	Fig. 3. The chain of water molecules in the title structure.

catena-Poly[[[bis(4-aminopyridine-κN)aquacadmium(II)]-µ-1,4- phenylenediacetato-κ⁴O,O':O'',O'''] dihydrate]

Crystal data

[Cd(C10H8O4)(C5H6N2)2(H2O)]·2H2O	Dx = 1.624 Mg m^−3
Mr = 546.85	Melting point: not measured K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.1668 (12) Å	Cell parameters from 5000 reflections
b = 13.6273 (10) Å	θ = 3.1–27.5°
c = 9.2692 (7) Å	µ = 1.03 mm^−1
β = 102.998 (3)°	T = 293 K
V = 2235.9 (3) Å^3	Prism, white
Z = 4	0.30 × 0.16 × 0.15 mm
F(000) = 1112

Data collection

Mercury 70 (2x2 bin mode) diffractometer	5117 independent reflections
Radiation source: fine-focus sealed tube	4579 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
Detector resolution: 14.6306 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
dtprofit.ref scans	h = −23→23
Absorption correction: multi-scan [empirical (using intensity measurements) from equivalent reflections (XEMP in SHELXTL; Siemens, 1994)]	k = −8→17
Tmin = 0.757, Tmax = 0.857	l = −12→12
16963 measured reflections

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.148	All H-atom parameters refined
S = 1.07	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
5117 reflections	(Δ/σ)max < 0.001
393 parameters	Δρmax = 0.60 e Å^−3
3 restraints	Δρmin = −0.51 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Cd1	0.246375 (13)	0.88862 (2)	0.22610 (3)	0.03511 (14)
O1	0.28542 (18)	1.0281 (2)	0.1002 (4)	0.0549 (8)
O2	0.27566 (18)	0.8925 (2)	−0.0260 (4)	0.0489 (7)
O3	0.22066 (18)	0.8988 (2)	0.4661 (3)	0.0480 (7)
O4	0.19881 (18)	1.0415 (2)	0.3567 (3)	0.0547 (8)
O5	0.2493 (3)	0.7174 (3)	0.2193 (4)	0.0823 (15)
H21	0.257 (3)	0.673 (5)	0.293 (6)	0.064 (16)*
H22	0.241 (3)	0.684 (4)	0.159 (6)	0.059 (17)*
O6	0.3027 (2)	1.2222 (3)	0.1582 (4)	0.0623 (8)
H25	0.281 (2)	1.237 (4)	0.223 (4)	0.063 (15)*
H26	0.310 (4)	1.1630 (13)	0.156 (9)	0.11 (3)*
O7	0.2138 (2)	1.2438 (3)	0.3700 (4)	0.0614 (8)
H23	0.190 (4)	1.182 (4)	0.353 (7)	0.081 (19)*
H24	0.238 (2)	1.253 (4)	0.455 (2)	0.10 (3)*
N1	0.6044 (3)	0.8491 (5)	0.4997 (6)	0.0743 (14)
H3	0.620 (4)	0.865 (5)	0.587 (8)	0.09 (2)*
H4	0.628 (3)	0.817 (4)	0.457 (7)	0.075 (19)*
N2	0.37255 (19)	0.8706 (3)	0.3327 (4)	0.0426 (8)
N3	0.12142 (19)	0.8709 (2)	0.1194 (4)	0.0407 (7)
N4	−0.1115 (2)	0.8605 (4)	−0.0467 (6)	0.0650 (12)
H9	−0.128 (3)	0.888 (3)	−0.126 (7)	0.054 (16)*
H10	−0.137 (3)	0.835 (4)	0.025 (6)	0.066 (15)*
C1	0.4039 (3)	0.8931 (4)	0.4729 (5)	0.0541 (12)
H1	0.371 (3)	0.919 (4)	0.521 (6)	0.069 (16)*
C2	0.4798 (3)	0.8870 (4)	0.5325 (6)	0.0594 (13)
H2	0.496 (4)	0.916 (5)	0.629 (8)	0.10 (2)*
C3	0.5285 (2)	0.8540 (4)	0.4464 (5)	0.0498 (10)
C4	0.4954 (2)	0.8293 (3)	0.3006 (4)	0.0444 (9)
H5	0.527 (2)	0.811 (3)	0.237 (5)	0.053 (12)*
C5	0.4196 (2)	0.8374 (3)	0.2509 (5)	0.0470 (9)
H6	0.395 (3)	0.814 (4)	0.158 (6)	0.065 (14)*
C6	0.0899 (3)	0.8946 (3)	−0.0212 (5)	0.0455 (10)
H7	0.124 (3)	0.916 (4)	−0.077 (7)	0.080 (18)*
C7	0.0133 (3)	0.8916 (3)	−0.0813 (5)	0.0508 (11)
H8	−0.004 (3)	0.924 (4)	−0.179 (6)	0.055 (13)*
C8	−0.0360 (2)	0.8630 (3)	0.0060 (5)	0.0426 (9)
C9	−0.0034 (2)	0.8360 (3)	0.1506 (5)	0.0445 (9)
H11	−0.035 (2)	0.816 (3)	0.209 (5)	0.041 (11)*
C10	0.0734 (2)	0.8418 (3)	0.2014 (4)	0.0436 (9)
H12	0.096 (2)	0.816 (3)	0.290 (4)	0.030 (9)*
C11	0.29581 (18)	0.9796 (3)	−0.0079 (4)	0.0368 (8)
C12	0.3380 (2)	1.0270 (3)	−0.1144 (4)	0.0411 (8)
H13	0.327 (3)	1.104 (3)	−0.118 (6)	0.062 (16)*
H14	0.321 (2)	0.995 (3)	−0.221 (5)	0.040 (10)*
C13	0.42261 (18)	1.0132 (3)	−0.0560 (4)	0.0347 (7)
C14	0.4643 (2)	1.0835 (3)	0.0360 (5)	0.0409 (8)
H16	0.438 (2)	1.145 (3)	0.062 (4)	0.038 (10)*
C15	0.4583 (2)	0.9310 (3)	−0.0902 (4)	0.0401 (8)
H15	0.431 (3)	0.884 (3)	−0.138 (6)	0.052 (15)*
C16	0.19790 (18)	0.9855 (3)	0.4623 (4)	0.0373 (8)
C17	0.1642 (2)	1.0220 (3)	0.5897 (4)	0.0406 (8)
H17	0.179 (3)	1.095 (3)	0.607 (6)	0.053 (14)*
H18	0.184 (3)	0.981 (4)	0.684 (6)	0.069 (15)*
C18	0.07845 (18)	1.0109 (3)	0.5448 (3)	0.0345 (7)
C19	0.0331 (2)	1.0905 (3)	0.4921 (5)	0.0429 (9)
H19	0.061 (3)	1.149 (4)	0.489 (5)	0.052 (13)*
C20	0.0449 (2)	0.9202 (3)	0.5525 (4)	0.0406 (8)
H20	0.083 (2)	0.865 (3)	0.590 (4)	0.029 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.03007 (19)	0.0407 (2)	0.0359 (2)	−0.00054 (9)	0.01040 (12)	0.00076 (10)
O1	0.0634 (19)	0.0514 (17)	0.0618 (18)	0.0035 (15)	0.0389 (15)	−0.0013 (15)
O2	0.0490 (17)	0.0545 (18)	0.0439 (16)	−0.0100 (13)	0.0116 (14)	0.0004 (12)
O3	0.0426 (16)	0.0612 (18)	0.0425 (16)	0.0138 (13)	0.0146 (13)	−0.0010 (12)
O4	0.0632 (19)	0.0601 (19)	0.0460 (15)	−0.0098 (15)	0.0235 (13)	0.0009 (14)
O5	0.150 (5)	0.0380 (19)	0.046 (2)	0.0062 (19)	−0.006 (2)	0.0016 (16)
O6	0.067 (2)	0.063 (2)	0.062 (2)	−0.0102 (18)	0.0255 (17)	−0.0078 (18)
O7	0.062 (2)	0.065 (2)	0.058 (2)	−0.0025 (17)	0.0158 (16)	−0.0074 (18)
N1	0.040 (2)	0.106 (4)	0.072 (3)	0.018 (2)	−0.001 (2)	−0.011 (3)
N2	0.0312 (16)	0.056 (2)	0.0416 (18)	0.0051 (14)	0.0097 (13)	0.0024 (15)
N3	0.0320 (16)	0.0498 (18)	0.0407 (18)	−0.0088 (14)	0.0092 (13)	0.0007 (14)
N4	0.038 (2)	0.086 (3)	0.065 (3)	−0.010 (2)	−0.0020 (19)	0.009 (3)
C1	0.037 (2)	0.085 (4)	0.042 (2)	0.009 (2)	0.0123 (18)	−0.005 (2)
C2	0.044 (3)	0.089 (4)	0.044 (2)	0.009 (2)	0.009 (2)	−0.006 (2)
C3	0.038 (2)	0.056 (2)	0.054 (2)	0.0126 (19)	0.0070 (17)	0.005 (2)
C4	0.0405 (19)	0.053 (2)	0.043 (2)	0.0119 (18)	0.0174 (16)	0.0094 (19)
C5	0.040 (2)	0.059 (3)	0.043 (2)	0.0092 (19)	0.0109 (16)	0.001 (2)
C6	0.044 (2)	0.058 (3)	0.037 (2)	−0.0078 (18)	0.0122 (17)	0.0002 (17)
C7	0.048 (2)	0.062 (3)	0.039 (2)	−0.0081 (19)	0.0024 (18)	0.0046 (18)
C8	0.0347 (19)	0.045 (2)	0.045 (2)	−0.0081 (16)	0.0034 (16)	−0.0056 (17)
C9	0.0392 (19)	0.049 (2)	0.048 (2)	−0.0115 (18)	0.0177 (16)	−0.0041 (19)
C10	0.043 (2)	0.051 (2)	0.0353 (19)	−0.0084 (18)	0.0050 (15)	0.0039 (17)
C11	0.0261 (15)	0.047 (2)	0.0382 (18)	0.0026 (15)	0.0089 (13)	0.0067 (16)
C12	0.0285 (16)	0.057 (2)	0.0402 (19)	0.0005 (16)	0.0117 (14)	0.0103 (17)
C13	0.0260 (15)	0.0459 (19)	0.0360 (17)	−0.0004 (14)	0.0151 (13)	0.0046 (15)
C14	0.0347 (19)	0.044 (2)	0.048 (2)	0.0030 (16)	0.0179 (16)	−0.0071 (17)
C15	0.0334 (18)	0.044 (2)	0.0439 (19)	−0.0041 (16)	0.0101 (15)	−0.0121 (17)
C16	0.0222 (15)	0.056 (2)	0.0359 (17)	−0.0018 (15)	0.0101 (12)	−0.0042 (16)
C17	0.0318 (17)	0.053 (2)	0.0384 (18)	0.0005 (16)	0.0116 (14)	−0.0029 (17)
C18	0.0310 (16)	0.048 (2)	0.0277 (15)	0.0031 (15)	0.0127 (12)	0.0011 (14)
C19	0.0350 (19)	0.042 (2)	0.054 (2)	0.0019 (16)	0.0165 (17)	0.0009 (18)
C20	0.0326 (18)	0.043 (2)	0.048 (2)	0.0109 (16)	0.0129 (15)	0.0103 (17)

Geometric parameters (Å, º)

Cd1—O1	2.418 (3)	C4—C5	1.356 (6)
Cd1—O2	2.511 (3)	C4—H5	0.95 (4)
Cd1—O3	2.378 (3)	C5—H6	0.93 (5)
Cd1—O4	2.651 (3)	C6—C7	1.378 (7)
Cd1—O5	2.334 (4)	C6—H7	0.93 (6)
Cd1—N2	2.296 (3)	C7—C8	1.391 (6)
Cd1—N3	2.276 (3)	C7—H8	0.99 (5)
O1—C11	1.250 (5)	C8—C9	1.388 (6)
O2—C11	1.243 (5)	C9—C10	1.371 (5)
O3—C16	1.250 (5)	C9—H11	0.92 (4)
O4—C16	1.244 (5)	C10—H12	0.91 (4)
O5—H21	0.90 (6)	C11—C12	1.523 (5)
O5—H22	0.71 (5)	C12—C13	1.521 (5)
O6—H25	0.814 (10)	C12—H13	1.07 (5)
O6—H26	0.819 (10)	C12—H14	1.06 (4)
O7—H23	0.94 (6)	C13—C14	1.388 (5)
O7—H24	0.819 (10)	C13—C15	1.367 (5)
N1—C3	1.356 (6)	C14—C15^i	1.395 (5)
N1—H3	0.82 (7)	C14—H16	1.02 (4)
N1—H4	0.78 (6)	C15—C14^i	1.395 (5)
N2—C1	1.332 (6)	C15—H15	0.87 (5)
N2—C5	1.342 (5)	C16—C17	1.529 (5)
N3—C6	1.340 (6)	C17—C18	1.527 (5)
N3—C10	1.340 (5)	C17—H17	1.04 (5)
N4—C8	1.348 (6)	C17—H18	1.03 (5)
N4—H9	0.82 (6)	C18—C19	1.383 (5)
N4—H10	0.96 (6)	C18—C20	1.387 (5)
C1—C2	1.367 (7)	C19—C20^ii	1.391 (5)
C1—H1	0.89 (5)	C19—H19	0.95 (5)
C2—C3	1.394 (7)	C20—C19^ii	1.391 (5)
C2—H2	0.96 (7)	C20—H20	1.03 (4)
C3—C4	1.391 (6)
N3—Cd1—N2	167.79 (14)	N2—C5—C4	124.3 (4)
N3—Cd1—O5	84.77 (14)	N2—C5—H6	114 (3)
N2—Cd1—O5	83.02 (14)	C4—C5—H6	121 (3)
N3—Cd1—O3	91.49 (12)	N3—C6—C7	123.9 (4)
N2—Cd1—O3	89.47 (12)	N3—C6—H7	115 (4)
O5—Cd1—O3	95.40 (12)	C7—C6—H7	121 (4)
N3—Cd1—O1	104.22 (12)	C6—C7—C8	119.8 (4)
N2—Cd1—O1	85.35 (12)	C6—C7—H8	116 (3)
O5—Cd1—O1	139.58 (13)	C8—C7—H8	123 (3)
O3—Cd1—O1	123.10 (10)	N4—C8—C9	121.4 (4)
N3—Cd1—O2	89.84 (12)	N4—C8—C7	122.1 (4)
N2—Cd1—O2	90.16 (12)	C9—C8—C7	116.5 (4)
O5—Cd1—O2	89.13 (12)	C10—C9—C8	119.7 (4)
O3—Cd1—O2	175.37 (10)	C10—C9—H11	123 (3)
O1—Cd1—O2	52.27 (9)	C8—C9—H11	118 (3)
N3—Cd1—O4	83.45 (11)	N3—C10—C9	124.4 (4)
N2—Cd1—O4	106.49 (11)	N3—C10—H12	114 (2)
O5—Cd1—O4	144.06 (13)	C9—C10—H12	121 (2)
O3—Cd1—O4	51.23 (9)	O2—C11—O1	121.3 (3)
O1—Cd1—O4	76.34 (11)	O2—C11—C12	119.6 (3)
O2—Cd1—O4	124.60 (9)	O1—C11—C12	119.0 (4)
C11—O1—Cd1	94.9 (2)	C13—C12—C11	109.5 (3)
C11—O2—Cd1	90.7 (2)	C13—C12—H13	107 (3)
C16—O3—Cd1	99.3 (2)	C11—C12—H13	109 (3)
C16—O4—Cd1	86.6 (2)	C13—C12—H14	110 (2)
Cd1—O5—H21	131 (4)	C11—C12—H14	110 (2)
Cd1—O5—H22	132 (4)	H13—C12—H14	111 (4)
H21—O5—H22	98 (6)	C15—C13—C14	119.0 (3)
H25—O6—H26	112 (6)	C15—C13—C12	120.8 (3)
H23—O7—H24	115 (6)	C14—C13—C12	120.2 (3)
C3—N1—H3	116 (5)	C13—C14—C15^i	119.4 (3)
C3—N1—H4	118 (5)	C13—C14—H16	119 (2)
H3—N1—H4	123 (7)	C15^i—C14—H16	121 (2)
C1—N2—C5	116.2 (4)	C13—C15—C14^i	121.6 (4)
C1—N2—Cd1	124.2 (3)	C13—C15—H15	118 (3)
C5—N2—Cd1	119.6 (3)	C14^i—C15—H15	120 (3)
C6—N3—C10	115.6 (4)	O4—C16—O3	122.6 (3)
C6—N3—Cd1	124.3 (3)	O4—C16—C17	119.1 (4)
C10—N3—Cd1	119.9 (3)	O3—C16—C17	118.2 (3)
C8—N4—H9	117 (4)	C18—C17—C16	108.6 (3)
C8—N4—H10	111 (3)	C18—C17—H17	110 (3)
H9—N4—H10	131 (5)	C16—C17—H17	108 (3)
N2—C1—C2	123.5 (4)	C18—C17—H18	109 (3)
N2—C1—H1	113 (4)	C16—C17—H18	111 (3)
C2—C1—H1	123 (4)	H17—C17—H18	111 (4)
C1—C2—C3	120.1 (5)	C19—C18—C20	118.9 (3)
C1—C2—H2	115 (4)	C19—C18—C17	120.6 (4)
C3—C2—H2	124 (4)	C20—C18—C17	120.5 (3)
N1—C3—C4	121.6 (4)	C18—C19—C20^ii	120.6 (4)
N1—C3—C2	122.1 (5)	C18—C19—H19	113 (3)
C4—C3—C2	116.3 (4)	C20^ii—C19—H19	127 (3)
C5—C4—C3	119.6 (4)	C18—C20—C19^ii	120.5 (4)
C5—C4—H5	122 (3)	C18—C20—H20	113 (2)
C3—C4—H5	119 (3)	C19^ii—C20—H20	126 (2)
N3—Cd1—O3—C16	−77.8 (2)	Cd1—O4—C16—O3	4.4 (4)
N2—Cd1—O3—C16	114.3 (2)	Cd1—O4—C16—C17	−172.6 (3)
O5—Cd1—O3—C16	−162.7 (2)	Cd1—O3—C16—O4	−5.0 (4)
O1—Cd1—O3—C16	30.2 (3)	Cd1—O3—C16—C17	172.0 (3)
O2—Cd1—O3—C16	28.8 (11)	C1—N2—C5—C4	−2.6 (7)
O4—Cd1—O3—C16	2.5 (2)	Cd1—N2—C5—C4	176.1 (4)
N3—Cd1—O2—C11	113.2 (2)	O2—C11—O1—Cd1	9.4 (4)
N2—Cd1—O2—C11	−79.0 (2)	C12—C11—O1—Cd1	−167.1 (3)
O5—Cd1—O2—C11	−162.0 (2)	N3—Cd1—O1—C11	−83.5 (2)
O3—Cd1—O2—C11	6.5 (12)	N2—Cd1—O1—C11	88.8 (2)
O1—Cd1—O2—C11	5.0 (2)	O5—Cd1—O1—C11	15.3 (3)
O4—Cd1—O2—C11	31.3 (3)	O3—Cd1—O1—C11	175.1 (2)
N2—Cd1—N3—C6	−110.2 (6)	O2—Cd1—O1—C11	−5.0 (2)
O5—Cd1—N3—C6	−109.3 (4)	O4—Cd1—O1—C11	−163.0 (3)
O3—Cd1—N3—C6	155.4 (3)	C6—N3—C10—C9	−0.5 (6)
O1—Cd1—N3—C6	30.6 (4)	Cd1—N3—C10—C9	174.9 (3)
O2—Cd1—N3—C6	−20.2 (3)	C5—N2—C1—C2	2.4 (7)
O4—Cd1—N3—C6	104.7 (3)	Cd1—N2—C1—C2	−176.3 (4)
N2—Cd1—N3—C10	74.8 (6)	N3—C10—C9—C8	−1.2 (7)
O5—Cd1—N3—C10	75.6 (3)	N3—C6—C7—C8	0.2 (7)
O3—Cd1—N3—C10	−19.6 (3)	O2—C11—C12—C13	−90.7 (4)
O1—Cd1—N3—C10	−144.4 (3)	O1—C11—C12—C13	85.9 (4)
O2—Cd1—N3—C10	164.8 (3)	C10—C9—C8—N4	−178.4 (5)
O4—Cd1—N3—C10	−70.3 (3)	C10—C9—C8—C7	2.3 (6)
Cd1—O2—C11—O1	−9.0 (4)	C6—C7—C8—N4	178.9 (5)
Cd1—O2—C11—C12	167.4 (3)	C6—C7—C8—C9	−1.8 (6)
N3—Cd1—O4—C16	94.7 (2)	N2—C1—C2—C3	−1.4 (8)
N2—Cd1—O4—C16	−78.0 (2)	N1—C3—C2—C1	178.4 (5)
O5—Cd1—O4—C16	23.1 (3)	C4—C3—C2—C1	0.4 (8)
O3—Cd1—O4—C16	−2.5 (2)	N2—C5—C4—C3	1.7 (7)
O1—Cd1—O4—C16	−158.9 (3)	N1—C3—C4—C5	−178.6 (5)
O2—Cd1—O4—C16	180.0 (2)	C2—C3—C4—C5	−0.5 (7)
C10—N3—C6—C7	1.1 (6)	C19^ii—C20—C18—C19	0.0 (6)
Cd1—N3—C6—C7	−174.1 (3)	C19^ii—C20—C18—C17	−178.3 (3)
N3—Cd1—N2—C1	−111.8 (6)	C11—C12—C13—C15	87.7 (4)
O5—Cd1—N2—C1	−112.7 (4)	C11—C12—C13—C14	−90.8 (4)
O3—Cd1—N2—C1	−17.2 (4)	C20—C18—C19—C20^ii	0.0 (6)
O1—Cd1—N2—C1	106.1 (4)	C17—C18—C19—C20^ii	178.3 (3)
O2—Cd1—N2—C1	158.2 (4)	C14—C13—C15—C14^i	−0.6 (6)
O4—Cd1—N2—C1	31.8 (4)	C12—C13—C15—C14^i	−179.1 (3)
N3—Cd1—N2—C5	69.6 (6)	C15—C13—C14—C15^i	0.5 (6)
O5—Cd1—N2—C5	68.7 (3)	C12—C13—C14—C15^i	179.1 (3)
O3—Cd1—N2—C5	164.2 (3)	C19—C18—C17—C16	−99.2 (4)
O1—Cd1—N2—C5	−72.5 (3)	C20—C18—C17—C16	79.1 (4)
O2—Cd1—N2—C5	−20.4 (3)	O4—C16—C17—C18	82.0 (4)
O4—Cd1—N2—C5	−146.8 (3)	O3—C16—C17—C18	−95.1 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H9···O4^iii	0.82 (6)	2.44 (6)	3.241 (6)	170 (5)
O5—H21···O2^iv	0.90 (6)	1.86 (5)	2.745 (5)	166 (5)
O5—H22···O3^v	0.71 (5)	2.07 (5)	2.782 (5)	172 (6)
N4—H10···O7^vi	0.96 (6)	2.25 (6)	3.168 (6)	161 (5)
N1—H4···O6^vii	0.78 (6)	2.23 (6)	3.015 (7)	178 (6)
O6—H26···O1	0.82 (1)	1.94 (3)	2.703 (5)	156 (8)
O6—H25···O7	0.81 (1)	2.03 (2)	2.825 (6)	166 (5)
O7—H23···O4	0.94 (6)	1.92 (6)	2.770 (5)	149 (6)
O7—H24···O6^viii	0.82 (1)	2.01 (1)	2.832 (6)	177 (5)

Symmetry codes: (iii) −x, −y+2, −z; (iv) x, −y+3/2, z+1/2; (v) x, −y+3/2, z−1/2; (vi) −x, y−1/2, −z+1/2; (vii) −x+1, y−1/2, −z+1/2; (viii) x, −y+5/2, z+1/2.