catena-Poly[[bis­(dimethyl­ammonium) [cadmate(II)-bis­(μ-1,1′:4′,1′′-terphenyl-3,3′′-dicarboxyl­ato)]] dimethyl­formamide disolvate]

Abstract

In the title compound, {(C₂H₈N)₂[Cd(C₂₀H₁₂O₄)₂]·2C₃H₇NO}_n, the Cd^II ion lies on a twofold rotation axis and is in a distorted octa­hedral CdO₆ environment, defined by four O atoms of two μ²-coordinated 1,1′:4′,1′′-terphenyl-3,3′′-dicarboxyl­ate (DCT) ligands and two O atoms of two μ¹-coordinated DCT ligands. Both types of DCT ligands act as bridging, forming a one-dimensional polymeric structure propagating parallel to [10].

Related literature

For background information on metal-organic frameworks (MOFs), see: Li & Zhou (2009 ▶); Huh et al. (2009 ▶, 2010 ▶); Youm et al. (2004 ▶); Gu et al. (2010 ▶).

Experimental

Crystal data

• (C₂H₈N)₂[Cd(C₂₀H₁₂O₄)₂]·2C₃H₇NO

• M _r = 983.37

• Monoclinic,

• a = 28.525 (4) Å

• b = 9.3267 (13) Å

• c = 20.580 (3) Å

• β = 114.752 (2)°

• V = 4972.1 (11) ų

• Z = 4

• Mo Kα radiation

• μ = 0.50 mm⁻¹

• T = 293 K

• 0.08 × 0.08 × 0.05 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• 13515 measured reflections

• 4888 independent reflections

• 2861 reflections with I > 2σ(I)

• R _int = 0.068

Refinement

• R[F ² > 2σ(F ²)] = 0.046

• wR(F ²) = 0.116

• S = 0.90

• 4888 reflections

• 298 parameters

• H-atom parameters constrained

• Δρ_max = 1.47 e Å⁻³

• Δρ_min = −0.76 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; 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: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

The role of bridging ligands in the formation of structurally interesting metal-organic frameworks (MOFs) is of significant importance for the design of multi-functional MOFs and coordination polymers (Li & Zhou, 2009; Huh et al., 2010; Huh et al., 2009; Youm et al., 2004). For instance, the reaction between a Zn(II) ion and a new C_{2 h}-symmetric bridging ligand, 3,3"-dicarboxy-1,1':4',1"-terphenyl (DCT), in the presence of 1,4-diazacyclo[2,2,2]octane (DABCO) afforded a new nanoporous Zn-MOF containing DABCO ligands with an uncoordinated nitrogen atom towards one-dimensional channels. The resulting DABCO-functionalized Zn-MOF showed a better adsorption of CO₂ over H₂ and N₂ with an exceptionally high CO₂ adsorption enthalpy (Gu et al., 2010).

To prepare new functional MOFs and coordination polymers, a reaction between Cd(NO₃)₂.H₂O and the DCT ligand was investigated. A new one-dimensional coordination polymer, [H₂N(CH₃)₂]₂[Cd(DCT)₂].2DMF (I), was obtained as colorless crystals and the crystal structure of (I) is reported herein. In the crystal structure of the title compound the Cd atom is coordinated by four oxygen atoms of two µ²-coordinated DCT ligands and two oxygen atoms of two µ¹-coordinated DCT ligands (Fig. 1). Two DCT ligands bridging two Cd atoms and the title compound forms an extended one-dimensional coordination polymer (Fig. 2). The overall coordination environment of a Cd atom is a distorted octahedral geometry. The title compound possesses periodically arranged Cd^II ions with two negative charges per Cd center because of the charge mismatching between Cd^II ions and the DCT ligands. Therefore two dimethylammonium cations are required for charge balancing. In addtion there are two dimethylformamide solvent molecules in the formula unit.

Experimental

The reaction mixture of Cd(NO₃)₂.H₂O (30.8 mg, 0.1 mmol) and 3,3"-dicarboxy-1,1':4',1"-terphenyl (DCT, 32 mg, 0.1 mmol) in 10 ml of DMF was heated at 130 °C for 4 d. The resulting clear solution was storedat room temperature for few days gave colorless crystals.

Refinement

H atoms were placed incalculated positions with C—H distances of 0.93 Å (phenyl) 0.96 Å (methyl) and N—H distances of 0.90 Å (ammonium). They were included in the refinement in riding-motion approximation with U_iso(H) = 1.2U_eq(C and N) and 1.5U_eq(C).

Figures

Fig. 1.

The asymmetric unit of the title compound's anion with labeling scheme. Displacement ellipsoids are shown at the 50% probability level.

Fig. 2.

One-dimensional chain of the title compound. The dimethylammonium cations and DMF solvent molecules are omitted for clarity.

Crystal data

(C2H8N)2[Cd(C20H12O4)2]·2C3H7NO	F(000) = 2040
Mr = 983.37	Dx = 1.314 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2049 reflections
a = 28.525 (4) Å	θ = 2.3–27.0°
b = 9.3267 (13) Å	µ = 0.50 mm−1
c = 20.580 (3) Å	T = 293 K
β = 114.752 (2)°	Block, colorless
V = 4972.1 (11) Å3	0.08 × 0.08 × 0.05 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2861 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.068
graphite	θmax = 26.0°, θmin = 1.6°
φ and ω scans	h = −35→32
13515 measured reflections	k = −8→11
4888 independent reflections	l = −25→18

Refinement

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H-atom parameters constrained
S = 0.90	w = 1/[σ2(Fo2) + (0.0481P)2] where P = (Fo2 + 2Fc2)/3
4888 reflections	(Δ/σ)max < 0.001
298 parameters	Δρmax = 1.47 e Å−3
0 restraints	Δρmin = −0.76 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	1.0000	0.22586 (5)	0.7500	0.03992 (17)
O1	1.08028 (11)	0.3209 (3)	0.77314 (16)	0.0572 (9)
O2	1.01785 (11)	0.4040 (3)	0.67570 (16)	0.0621 (9)
O3	0.95903 (10)	0.0827 (3)	0.65658 (14)	0.0505 (8)
O4	1.03902 (12)	0.0114 (4)	0.68232 (16)	0.0719 (10)
C1	1.06411 (17)	0.4007 (5)	0.7194 (2)	0.0449 (11)
C2	1.10258 (15)	0.4955 (4)	0.7074 (2)	0.0389 (10)
C3	1.15225 (14)	0.5095 (4)	0.7608 (2)	0.0390 (10)
H3	1.1610	0.4619	0.8040	0.047*
C4	1.18932 (14)	0.5936 (4)	0.7510 (2)	0.0382 (10)
C5	1.17464 (16)	0.6611 (5)	0.6854 (2)	0.0482 (12)
H5	1.1987	0.7164	0.6770	0.058*
C6	1.12548 (16)	0.6485 (5)	0.6323 (2)	0.0534 (12)
H6	1.1167	0.6951	0.5888	0.064*
C7	1.08924 (16)	0.5672 (5)	0.6433 (2)	0.0471 (11)
H7	1.0558	0.5605	0.6077	0.056*
C8	0.74239 (14)	−0.1084 (4)	0.3083 (2)	0.0377 (10)
C9	0.76565 (15)	0.0007 (5)	0.3571 (2)	0.0452 (11)
H9	0.7467	0.0827	0.3560	0.054*
C10	0.81649 (16)	−0.0094 (5)	0.4076 (2)	0.0465 (11)
H10	0.8308	0.0657	0.4395	0.056*
C11	0.84628 (15)	−0.1288 (5)	0.4114 (2)	0.0379 (10)
C12	0.82222 (15)	−0.2418 (5)	0.3648 (2)	0.0443 (11)
H12	0.8404	−0.3260	0.3677	0.053*
C13	0.77171 (15)	−0.2300 (5)	0.3145 (2)	0.0463 (11)
H13	0.7569	−0.3066	0.2837	0.056*
C14	0.90158 (15)	−0.1368 (4)	0.4619 (2)	0.0385 (10)
C15	0.92021 (15)	−0.0652 (4)	0.5273 (2)	0.0408 (10)
H15	0.8975	−0.0131	0.5400	0.049*
C16	0.97212 (15)	−0.0706 (4)	0.5738 (2)	0.0396 (10)
C17	1.00572 (16)	−0.1481 (5)	0.5552 (2)	0.0506 (12)
H17	1.0406	−0.1523	0.5861	0.061*
C18	0.98748 (16)	−0.2195 (5)	0.4906 (2)	0.0541 (12)
H18	1.0102	−0.2724	0.4782	0.065*
C19	0.93633 (16)	−0.2132 (5)	0.4445 (2)	0.0480 (11)
H19	0.9248	−0.2609	0.4009	0.058*
C20	0.99169 (17)	0.0116 (5)	0.6434 (2)	0.0473 (11)
N21	0.1478 (2)	0.4189 (6)	0.9596 (2)	0.0814 (14)
O21	0.16600 (16)	0.1981 (4)	0.9324 (2)	0.0925 (13)
C21	0.1350 (2)	0.2929 (7)	0.9302 (3)	0.0737 (16)
H21	0.1000	0.2727	0.9057	0.088*
C22	0.2015 (3)	0.4610 (9)	0.9988 (4)	0.146 (3)
H22A	0.2235	0.3826	0.9996	0.220*
H22B	0.2077	0.4863	1.0469	0.220*
H22C	0.2088	0.5420	0.9757	0.220*
C23	0.1082 (3)	0.5226 (8)	0.9496 (3)	0.126 (3)
H23A	0.1143	0.6068	0.9275	0.189*
H23B	0.1088	0.5475	0.9952	0.189*
H23C	0.0752	0.4828	0.9196	0.189*
N31	0.12647 (13)	1.0202 (4)	0.80646 (18)	0.0537 (10)
H31A	0.1302	1.0770	0.8436	0.064*
H31B	0.0943	1.0331	0.7724	0.064*
C31	0.16355 (19)	1.0657 (7)	0.7781 (3)	0.0912 (19)
H31C	0.1980	1.0579	0.8149	0.137*
H31D	0.1568	1.1634	0.7623	0.137*
H31E	0.1601	1.0055	0.7385	0.137*
C32	0.1320 (2)	0.8719 (6)	0.8299 (3)	0.101 (2)
H32A	0.1310	0.8107	0.7919	0.152*
H32B	0.1042	0.8471	0.8426	0.152*
H32C	0.1643	0.8599	0.8708	0.152*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cd1	0.0305 (2)	0.0450 (3)	0.0417 (3)	0.000	0.01258 (19)	0.000
O1	0.0486 (19)	0.058 (2)	0.060 (2)	−0.0061 (16)	0.0182 (16)	0.0137 (17)
O2	0.0367 (18)	0.067 (2)	0.072 (2)	−0.0066 (16)	0.0126 (17)	0.0110 (17)
O3	0.0426 (18)	0.061 (2)	0.0476 (18)	0.0010 (15)	0.0182 (15)	−0.0085 (15)
O4	0.0410 (19)	0.101 (3)	0.055 (2)	0.0050 (19)	0.0016 (16)	−0.0156 (19)
C1	0.042 (3)	0.041 (3)	0.051 (3)	0.002 (2)	0.019 (2)	−0.003 (2)
C2	0.037 (2)	0.035 (3)	0.047 (3)	0.0023 (19)	0.020 (2)	0.002 (2)
C3	0.038 (2)	0.038 (3)	0.040 (2)	0.005 (2)	0.015 (2)	0.0036 (19)
C4	0.033 (2)	0.037 (3)	0.044 (3)	0.0013 (19)	0.015 (2)	0.000 (2)
C5	0.040 (3)	0.053 (3)	0.053 (3)	−0.004 (2)	0.020 (2)	0.014 (2)
C6	0.043 (3)	0.064 (3)	0.048 (3)	0.002 (2)	0.014 (2)	0.016 (2)
C7	0.035 (2)	0.048 (3)	0.051 (3)	0.004 (2)	0.011 (2)	0.007 (2)
C8	0.035 (2)	0.036 (3)	0.042 (2)	0.000 (2)	0.016 (2)	0.001 (2)
C9	0.041 (3)	0.041 (3)	0.052 (3)	0.006 (2)	0.017 (2)	−0.006 (2)
C10	0.046 (3)	0.042 (3)	0.045 (3)	−0.002 (2)	0.013 (2)	−0.006 (2)
C11	0.039 (2)	0.042 (3)	0.034 (2)	0.002 (2)	0.0158 (19)	0.002 (2)
C12	0.044 (2)	0.040 (3)	0.048 (3)	0.006 (2)	0.018 (2)	−0.002 (2)
C13	0.045 (2)	0.040 (3)	0.052 (3)	−0.003 (2)	0.018 (2)	−0.011 (2)
C14	0.040 (2)	0.040 (3)	0.034 (2)	0.001 (2)	0.014 (2)	0.001 (2)
C15	0.037 (2)	0.042 (3)	0.044 (3)	0.001 (2)	0.018 (2)	0.002 (2)
C16	0.038 (2)	0.040 (3)	0.038 (2)	0.002 (2)	0.012 (2)	−0.001 (2)
C17	0.038 (3)	0.057 (3)	0.051 (3)	0.009 (2)	0.012 (2)	−0.001 (2)
C18	0.048 (3)	0.056 (3)	0.060 (3)	0.010 (2)	0.024 (2)	−0.008 (3)
C19	0.045 (3)	0.051 (3)	0.045 (3)	0.002 (2)	0.015 (2)	−0.010 (2)
C20	0.047 (3)	0.046 (3)	0.045 (3)	−0.002 (2)	0.015 (2)	0.003 (2)
N21	0.092 (4)	0.076 (4)	0.074 (3)	−0.010 (3)	0.034 (3)	−0.021 (3)
O21	0.095 (3)	0.086 (3)	0.078 (3)	0.011 (2)	0.018 (2)	−0.011 (2)
C21	0.090 (4)	0.067 (4)	0.054 (3)	−0.016 (4)	0.020 (3)	−0.010 (3)
C22	0.108 (6)	0.159 (8)	0.171 (7)	−0.055 (5)	0.057 (5)	−0.080 (6)
C23	0.151 (7)	0.092 (6)	0.130 (6)	0.007 (5)	0.054 (5)	−0.012 (4)
N31	0.046 (2)	0.060 (3)	0.049 (2)	0.010 (2)	0.0142 (19)	−0.0055 (19)
C31	0.069 (4)	0.108 (5)	0.113 (5)	0.000 (3)	0.055 (4)	−0.002 (4)
C32	0.134 (6)	0.064 (4)	0.127 (5)	0.021 (4)	0.075 (5)	0.014 (4)

Geometric parameters (Å, °)

Cd1—O3	2.228 (3)	C12—H12	0.9300
Cd1—O3i	2.228 (3)	C13—H13	0.9300
Cd1—O1	2.312 (3)	C14—C19	1.383 (5)
Cd1—O1i	2.312 (3)	C14—C15	1.394 (5)
Cd1—O2	2.451 (3)	C15—C16	1.387 (5)
Cd1—O2i	2.451 (3)	C15—H15	0.9300
Cd1—C1i	2.714 (4)	C16—C17	1.376 (5)
Cd1—C1	2.714 (4)	C16—C20	1.510 (6)
O1—C1	1.250 (5)	C17—C18	1.380 (6)
O2—C1	1.248 (4)	C17—H17	0.9300
O3—C20	1.262 (5)	C18—C19	1.369 (5)
O4—C20	1.249 (5)	C18—H18	0.9300
C1—C2	1.508 (6)	C19—H19	0.9300
C2—C7	1.383 (5)	N21—C21	1.302 (6)
C2—C3	1.389 (5)	N21—C23	1.434 (7)
C3—C4	1.397 (5)	N21—C22	1.455 (7)
C3—H3	0.9300	O21—C21	1.238 (6)
C4—C5	1.386 (5)	C21—H21	0.9300
C4—C8ii	1.485 (5)	C22—H22A	0.9600
C5—C6	1.375 (5)	C22—H22B	0.9600
C5—H5	0.9300	C22—H22C	0.9600
C6—C7	1.375 (5)	C23—H23A	0.9600
C6—H6	0.9300	C23—H23B	0.9600
C7—H7	0.9300	C23—H23C	0.9600
C8—C13	1.383 (5)	N31—C32	1.452 (6)
C8—C9	1.388 (5)	N31—C31	1.469 (6)
C8—C4iii	1.485 (5)	N31—H31A	0.9000
C9—C10	1.389 (5)	N31—H31B	0.9000
C9—H9	0.9300	C31—H31C	0.9600
C10—C11	1.383 (5)	C31—H31D	0.9600
C10—H10	0.9300	C31—H31E	0.9600
C11—C12	1.396 (5)	C32—H32A	0.9600
C11—C14	1.484 (5)	C32—H32B	0.9600
C12—C13	1.383 (5)	C32—H32C	0.9600
O3—Cd1—O3i	106.36 (15)	C10—C11—C14	121.9 (4)
O3—Cd1—O1	121.60 (10)	C12—C11—C14	121.0 (4)
O3i—Cd1—O1	86.31 (11)	C13—C12—C11	120.9 (4)
O3—Cd1—O1i	86.31 (11)	C13—C12—H12	119.6
O3i—Cd1—O1i	121.60 (10)	C11—C12—H12	119.6
O1—Cd1—O1i	134.91 (16)	C12—C13—C8	122.3 (4)
O3—Cd1—O2	92.22 (10)	C12—C13—H13	118.9
O3i—Cd1—O2	140.68 (10)	C8—C13—H13	118.9
O1—Cd1—O2	54.70 (10)	C19—C14—C15	118.1 (4)
O1i—Cd1—O2	93.34 (10)	C19—C14—C11	120.8 (4)
O3—Cd1—O2i	140.68 (10)	C15—C14—C11	121.0 (4)
O3i—Cd1—O2i	92.22 (10)	C16—C15—C14	121.0 (4)
O1—Cd1—O2i	93.34 (11)	C16—C15—H15	119.5
O1i—Cd1—O2i	54.69 (10)	C14—C15—H15	119.5
O2—Cd1—O2i	94.67 (15)	C17—C16—C15	119.6 (4)
O3—Cd1—C1i	113.54 (12)	C17—C16—C20	120.4 (4)
O3i—Cd1—C1i	108.72 (12)	C15—C16—C20	120.0 (4)
O1—Cd1—C1i	115.31 (12)	C16—C17—C18	119.7 (4)
O1i—Cd1—C1i	27.33 (10)	C16—C17—H17	120.1
O2—Cd1—C1i	94.22 (11)	C18—C17—H17	120.1
O2i—Cd1—C1i	27.36 (10)	C19—C18—C17	120.6 (4)
O3—Cd1—C1	108.72 (12)	C19—C18—H18	119.7
O3i—Cd1—C1	113.54 (12)	C17—C18—H18	119.7
O1—Cd1—C1	27.34 (10)	C18—C19—C14	121.0 (4)
O1i—Cd1—C1	115.31 (12)	C18—C19—H19	119.5
O2—Cd1—C1	27.36 (10)	C14—C19—H19	119.5
O2i—Cd1—C1	94.22 (11)	O4—C20—O3	124.1 (4)
C1i—Cd1—C1	106.12 (18)	O4—C20—C16	118.6 (4)
C1—O1—Cd1	94.5 (3)	O3—C20—C16	117.2 (4)
C1—O2—Cd1	88.1 (3)	C21—N21—C23	119.5 (6)
C20—O3—Cd1	109.4 (3)	C21—N21—C22	121.7 (6)
O2—C1—O1	122.7 (4)	C23—N21—C22	118.7 (6)
O2—C1—C2	119.3 (4)	O21—C21—N21	124.9 (6)
O1—C1—C2	118.0 (4)	O21—C21—H21	117.5
O2—C1—Cd1	64.5 (2)	N21—C21—H21	117.5
O1—C1—Cd1	58.1 (2)	N21—C22—H22A	109.5
C2—C1—Cd1	176.1 (3)	N21—C22—H22B	109.5
C7—C2—C3	119.4 (4)	H22A—C22—H22B	109.5
C7—C2—C1	120.8 (4)	N21—C22—H22C	109.5
C3—C2—C1	119.8 (4)	H22A—C22—H22C	109.5
C2—C3—C4	121.4 (4)	H22B—C22—H22C	109.5
C2—C3—H3	119.3	N21—C23—H23A	109.5
C4—C3—H3	119.3	N21—C23—H23B	109.5
C5—C4—C3	117.2 (4)	H23A—C23—H23B	109.5
C5—C4—C8ii	121.5 (4)	N21—C23—H23C	109.5
C3—C4—C8ii	121.3 (4)	H23A—C23—H23C	109.5
C6—C5—C4	121.8 (4)	H23B—C23—H23C	109.5
C6—C5—H5	119.1	C32—N31—C31	114.3 (4)
C4—C5—H5	119.1	C32—N31—H31A	108.7
C7—C6—C5	120.2 (4)	C31—N31—H31A	108.7
C7—C6—H6	119.9	C32—N31—H31B	108.7
C5—C6—H6	119.9	C31—N31—H31B	108.7
C6—C7—C2	119.9 (4)	H31A—N31—H31B	107.6
C6—C7—H7	120.1	N31—C31—H31C	109.5
C2—C7—H7	120.1	N31—C31—H31D	109.5
C13—C8—C9	116.6 (4)	H31C—C31—H31D	109.5
C13—C8—C4iii	121.7 (4)	N31—C31—H31E	109.5
C9—C8—C4iii	121.7 (4)	H31C—C31—H31E	109.5
C8—C9—C10	121.6 (4)	H31D—C31—H31E	109.5
C8—C9—H9	119.2	N31—C32—H32A	109.5
C10—C9—H9	119.2	N31—C32—H32B	109.5
C11—C10—C9	121.5 (4)	H32A—C32—H32B	109.5
C11—C10—H10	119.3	N31—C32—H32C	109.5
C9—C10—H10	119.3	H32A—C32—H32C	109.5
C10—C11—C12	117.0 (4)	H32B—C32—H32C	109.5
O3—Cd1—O1—C1	68.3 (3)	C2—C3—C4—C5	−0.8 (6)
O3i—Cd1—O1—C1	175.3 (3)	C2—C3—C4—C8ii	180.0 (4)
O1i—Cd1—O1—C1	−52.1 (2)	C3—C4—C5—C6	1.1 (6)
O2—Cd1—O1—C1	0.6 (2)	C8ii—C4—C5—C6	−179.6 (4)
O2i—Cd1—O1—C1	−92.7 (3)	C4—C5—C6—C7	0.0 (7)
C1i—Cd1—O1—C1	−75.8 (3)	C5—C6—C7—C2	−1.4 (7)
O3—Cd1—O2—C1	−128.6 (3)	C3—C2—C7—C6	1.7 (6)
O3i—Cd1—O2—C1	−9.1 (3)	C1—C2—C7—C6	−177.4 (4)
O1—Cd1—O2—C1	−0.6 (2)	C13—C8—C9—C10	2.6 (6)
O1i—Cd1—O2—C1	145.0 (3)	C4iii—C8—C9—C10	−175.6 (4)
O2i—Cd1—O2—C1	90.1 (3)	C8—C9—C10—C11	0.1 (6)
C1i—Cd1—O2—C1	117.6 (3)	C9—C10—C11—C12	−3.3 (6)
O3i—Cd1—O3—C20	−64.4 (3)	C9—C10—C11—C14	175.9 (4)
O1—Cd1—O3—C20	31.4 (3)	C10—C11—C12—C13	3.7 (6)
O1i—Cd1—O3—C20	173.7 (3)	C14—C11—C12—C13	−175.5 (4)
O2—Cd1—O3—C20	80.5 (3)	C11—C12—C13—C8	−1.0 (6)
O2i—Cd1—O3—C20	−179.4 (2)	C9—C8—C13—C12	−2.2 (6)
C1i—Cd1—O3—C20	176.1 (3)	C4iii—C8—C13—C12	176.1 (4)
C1—Cd1—O3—C20	58.2 (3)	C10—C11—C14—C19	−148.1 (4)
Cd1—O2—C1—O1	1.1 (4)	C12—C11—C14—C19	31.1 (6)
Cd1—O2—C1—C2	−179.3 (3)	C10—C11—C14—C15	30.5 (6)
Cd1—O1—C1—O2	−1.2 (5)	C12—C11—C14—C15	−150.4 (4)
Cd1—O1—C1—C2	179.2 (3)	C19—C14—C15—C16	−0.1 (6)
O3—Cd1—C1—O2	55.5 (3)	C11—C14—C15—C16	−178.7 (4)
O3i—Cd1—C1—O2	173.7 (2)	C14—C15—C16—C17	−0.2 (6)
O1—Cd1—C1—O2	178.9 (4)	C14—C15—C16—C20	178.1 (4)
O1i—Cd1—C1—O2	−39.3 (3)	C15—C16—C17—C18	0.0 (7)
O2i—Cd1—C1—O2	−92.0 (3)	C20—C16—C17—C18	−178.3 (4)
C1i—Cd1—C1—O2	−66.9 (2)	C16—C17—C18—C19	0.5 (7)
O3—Cd1—C1—O1	−123.3 (3)	C17—C18—C19—C14	−0.8 (7)
O3i—Cd1—C1—O1	−5.2 (3)	C15—C14—C19—C18	0.6 (6)
O1i—Cd1—C1—O1	141.8 (2)	C11—C14—C19—C18	179.2 (4)
O2—Cd1—C1—O1	−178.9 (4)	Cd1—O3—C20—O4	7.4 (5)
O2i—Cd1—C1—O1	89.1 (3)	Cd1—O3—C20—C16	−168.7 (3)
C1i—Cd1—C1—O1	114.2 (3)	C17—C16—C20—O4	2.3 (6)
O2—C1—C2—C7	−10.8 (6)	C15—C16—C20—O4	−176.0 (4)
O1—C1—C2—C7	168.7 (4)	C17—C16—C20—O3	178.6 (4)
O2—C1—C2—C3	170.1 (4)	C15—C16—C20—O3	0.4 (6)
O1—C1—C2—C3	−10.3 (6)	C23—N21—C21—O21	176.3 (6)
C7—C2—C3—C4	−0.6 (6)	C22—N21—C21—O21	0.3 (9)
C1—C2—C3—C4	178.5 (4)

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