A one-dimensional coordination polymer with a three-dimensional supra­molecular framework: catena-poly[[[(3,4,7,8-tetra­methyl-1,10-phenanthroline)cadmium(II)]-[mu]₃-4,4'-sulfonyl­dibenzoato] trihydrate]

In the title mixed-ligand metal-organic polymeric compound, {[Cd(C₁₄H₈O₆S)(C₁₆H₁₆N₂)]·3H₂O}_n, the asymmetric unit contains a crystallographically unique Cd^II atom, one doubly deprotonated 4,4'-sulfonyl­dibenzoic acid (H₂SDBA) ligand, one 3,4,7,8-tetra­methyl-1,10-phenanthroline (TMPHEN) mol­ecule and three solvent water mol­ecules. Each Cd^II centre is six-coordinated by two O atoms from a chelating carboxyl­ate group of a SDBA^2- ligand, two O atoms from monodentate carboxyl­ate groups of two different SDBA^2- ligands and two N atoms from a chelating TMPHEN ligand. There are two coordination patterns for the carboxyl­ate groups of the SDBA^2- ligand, with one in a [mu]₁-[eta]¹:[eta]¹ chelating mode and the other in a [mu]₂-[eta]¹:[eta]¹ bis-monodentate mode. Single-crystal X-ray diffraction analysis revealed that the title compound is a one-dimensional double-chain polymer containing 28-membered rings based on the [Cd₂(CO₂)₂] rhomboid subunit. More inter­estingly, a chair-shaped water hexa­mer cluster is observed in the compound.

S1. Comment

The design and synthesis of metal–organic compounds has been flourishing in recent years, not only due to their diverse topology and intriguing structures but also owing to their potential applications in areas such as gas storage, ion exchange and catalysis (Kitagawa et al., 2004; Ferey et al., 2005; Roy et al., 2009; Zhang et al., 2009; Jiang et al., 2009). It is well known that the construction of metal–organic compounds is usually influenced by several factors in the self-assembly process, such as the solvent system, temperature, the organic ligands and the metal atoms (Kan et al., 2012; Liu et al., 2012). Among these factors, the organic ligands play a key role in determining the final architectures. The main method for constructing coordination polymers is to utilize carboxylate-containing ligands, since the carboxylate groups have an excellent coordination capability and flexible coordination patterns. As an important family of multidentate O-donor ligands, semi-rigid V-shaped dicarboxylate ligands, such as 4,4'-oxybis(benzoic acid) (H₂OBA), 4,4'-(hexafluoroisopropylidene)bis(benzoic acid) (H₂FA), 4,4'-sulfonyldibenzoic acid (H₂SDBA), have been used extensively in constructing new metal–organic compounds (Zhuang et al., 2007; Lian et al., 2008; Xiao et al., 2008; Chen et al., 2009; Liu et al., 2009; Li et al., 2010). However, to the best of our knowledge, coordination polymers constructed from 4,4'-sulfonyldibenzoic acid (H₂SDBA) and 3,4,7,8-tetramethyl-1,10-phenanthroline (TMPHEN) ligands have not been reported so far. We report here the structure of the Cd^II coordination polymer {[Cd(SDBA)(TMPHEN)].3H₂O}_n, (I) (Fig. 1).

Compound (I) crystallizes in the monoclinic space group P2₁/c, and the asymmetric unit contains a crystallographically unique Cd^II atom, one fully deprotonated H₂SDBA ligand, one TMPHEN molecule and three solvent water molecules. Each Cd^II centre is six-coordinated by two O atoms from a chelating carboxylate group of a SDBA^2- ligand, two O atoms from monodentate carboxylate groups of two different SDBA^2- ligands and two N atoms from a chelating TMPHEN ligand (Table 1). The average Cd—O and Cd—N distances (Table 1) in (I) are comparable with those in other reported Cd^II-based compounds (Wang et al., 2011, 2012).

In the SDBA^2- ligand in (I), the dihedral angle between the two benzene rings is 86.0 (3)° and the C23–S1–C24 angle is 104.8 (2)°. The dihedral angles between the carboxylate groups and their adjacent benzene rings are 159.8(s.u.?) and 6.2(s.u.?)°. It is worth noting that the SDBA^2- ligand links three Cd^II atoms and there are two coordination patterns for the carboxylate groups, with one in a µ₁-η¹:η¹ chelating mode and the other in a µ₂-η¹:η¹ bis-monodentate mode. Two crystallographically equivalent Cd^II atoms are bridged by atoms O5, O6 and C30 to form a binuclear [Cd₂(CO₂)₂] motif; the Cd···Cd separation is 3.1383 (7) Å. The [Cd₂(CO₂)₂] rhomboid subunit is further bridged by an SDBA² ligand into a one-dimensional double chain containing 28-membered rings, with SDBA^2- ligands as bridges arranged parallel to the a direction (Fig. 2). The TMPHEN ligands are extended on both sides of the chain. In addition, the chains are connected by two types of the hydrogen bonds (O—H···O and C—H···O) and by π–π and S═O···π interactions to form a three-dimensional supramolecular structure (Fig. 3). Approximately 12.2% of the crystal volume is occupied by the solvent molecules, with a volume of ~353.0 ų in each unit cell (2883.4 ų), based on a PLATON calculation (Spek, 2009).

Interestingly, six lattice water molecules [O7, O7^v, O8, O8^v, O9 and O9^v; symmetry code: (v) -x+1, -y+1, -z+1] related by a twofold axis form a chair-shaped water hexamer via hydrogen bonds (Table 2). The average O···O distance within the hexamer is 2.96 Å, which is significantly longer than the corresponding value of 2.85 Å in liquid water. The O···O···O angles range from 63.7(s.u.?) to 125.9(s.u.?)°, deviating considerably from the preferred ideal tetrahedral geometry of water (Fig. 4). Such hexamers are fixed to the framework through numerous hydrogen bonds involving solvent water O atoms and carboxylate (O2 and O5) and sulfonyl (O3 and O4) O atoms.

In conclusion, we have synthesized a one-dimensional double-chain polymer containing 28-membered rings based on the [Cd₂(CO₂)₂] rhomboid subunit. More interestingly, there exists a chair-shaped water hexamer cluster.

Related literature

For related literature, see: Chen (2009); Ferey et al. (2005); Jiang (2009); Kan et al. (2012); Kitagawa et al. (2004); Li et al. (2010); Lian et al. (2008); Liu et al. (2009, 2012); Roy et al. (2009); Spek (2009); Wang et al. (2011, 2012); Xiao et al. (2008); Zhang et al. (2009); Zhuang et al. (2007).

S2. Experimental

A mixture of Cd(NO₃)₂.6H₂O (34.5 mg, 0.1 mmol), H₂SDBA (30.6 mg, 0.1 mmol), TMPHEN (35.4 mg, 0.15 mmol) and NaOH (6.0 mg, 0.15 mmol) in H₂O (10 ml) was sealed in a 16 ml Teflon-lined stainless steel container and heated at 453 K for 72 h. After cooling to room temperature, white block-shaped crystals of (I) were collected by filtration and washed water water and ethanol several times (yield 7.3%, based on H₂SDBA). Elemental analysis for C₃₀H₃₀CdN₂O₉S: C 50.96, N 3.96, H 4.28%; found: C 51.08, N 3.97, H 4.31%.

S3. Refinement

H atoms bonded to C atoms were placed in calculated positions and treated using a riding-model approximation, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, and C—H = 0.98 Å and U_iso(H) = 1.2U_eq(C) for the tert-butyl H atoms. Water H atoms were located in difference Fourier maps and were refined with a distance restraint of O—H = 0.85 Å and with U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. A view of the local coordination of the Cd^II cations in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y, -z.]
	Fig. 2. A view of one-dimensional double-chain framework in (I).
	Fig. 3. A perspective view of the three-dimensional supramolecular structure of (I), incorporating S═O···π and C—H···π interactions (dashed lines).
	Fig. 4. Perspective view of the hexameric water cluster in (I), showing the hydrogen bonding. [Symmetry code: (v) -x+1, -y+1, -z+1.]

catena-Poly[[[(3,4,7,8-tetramethyl-1,10-phenanthroline)cadmium(II)]-µ₃-4,4'-sulfonyldibenzoato] trihydrate]

Crystal data

[Cd(C14H8O6S)(C16H16N2)]·3H2O	F(000) = 1440
Mr = 707.04	Dx = 1.629 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2821 reflections
a = 13.5444 (14) Å	θ = 2.4–22.9°
b = 11.9489 (13) Å	µ = 0.89 mm^−1
c = 18.518 (2) Å	T = 173 K
β = 105.826 (1)°	Block, white
V = 2883.4 (5) Å^3	0.23 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	5135 independent reflections
Radiation source: fine-focus sealed tube	3389 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.073
phi and ω scans	θmax = 25.1°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −16→14
Tmin = 0.815, Tmax = 0.852	k = −11→14
15734 measured reflections	l = −21→22

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0424P)^2] where P = (Fo^2 + 2Fc^2)/3
5135 reflections	(Δ/σ)max < 0.001
392 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.68 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	0.94398 (3)	0.15673 (3)	0.01535 (2)	0.03252 (14)
C1	1.0405 (4)	0.2585 (5)	−0.1159 (3)	0.0380 (13)
H1	1.0686	0.1853	−0.1133	0.046*
C2	1.0679 (4)	0.3352 (5)	−0.1645 (3)	0.0398 (14)
C3	1.1362 (5)	0.2969 (5)	−0.2113 (3)	0.0564 (17)
H3A	1.1012	0.3081	−0.2645	0.085*
H3B	1.1520	0.2173	−0.2019	0.085*
H3C	1.2001	0.3402	−0.1979	0.085*
C4	1.0315 (4)	0.4420 (5)	−0.1669 (3)	0.0387 (14)
C5	1.0595 (5)	0.5286 (5)	−0.2171 (3)	0.0570 (17)
H5A	1.1328	0.5229	−0.2136	0.085*
H5B	1.0446	0.6035	−0.2011	0.085*
H5C	1.0194	0.5159	−0.2691	0.085*
C6	0.9643 (4)	0.4696 (4)	−0.1222 (3)	0.0345 (13)
C7	0.9393 (4)	0.3845 (4)	−0.0777 (3)	0.0314 (12)
C8	0.8659 (4)	0.4066 (4)	−0.0349 (3)	0.0320 (12)
C9	0.9193 (4)	0.5774 (5)	−0.1209 (3)	0.0441 (15)
H9	0.9374	0.6362	−0.1493	0.053*
C10	0.8520 (4)	0.5986 (5)	−0.0808 (3)	0.0445 (15)
H10	0.8234	0.6714	−0.0823	0.053*
C11	0.8224 (4)	0.5141 (4)	−0.0361 (3)	0.0379 (13)
C12	0.7495 (4)	0.5319 (5)	0.0055 (3)	0.0429 (14)
C13	0.7015 (5)	0.6461 (5)	0.0062 (3)	0.0576 (17)
H13A	0.6555	0.6444	0.0389	0.086*
H13B	0.6623	0.6662	−0.0449	0.086*
H13C	0.7556	0.7017	0.0250	0.086*
C14	0.6456 (5)	0.4514 (6)	0.0880 (4)	0.075 (2)
H14A	0.6654	0.5115	0.1252	0.113*
H14B	0.6433	0.3802	0.1138	0.113*
H14C	0.5778	0.4676	0.0542	0.113*
C15	0.7234 (4)	0.4437 (5)	0.0431 (3)	0.0485 (16)
C16	0.7713 (4)	0.3418 (5)	0.0412 (3)	0.0490 (15)
H16	0.7523	0.2815	0.0681	0.059*
C17	0.8401 (5)	0.0875 (6)	0.1140 (4)	0.0481 (16)
C18	0.7704 (4)	0.0540 (5)	0.1622 (3)	0.0406 (14)
C19	0.7058 (4)	−0.0363 (5)	0.1433 (3)	0.0473 (15)
H19	0.7057	−0.0792	0.1001	0.057*
C20	0.6407 (4)	−0.0656 (5)	0.1865 (3)	0.0483 (15)
H20	0.5968	−0.1287	0.1737	0.058*
C21	0.7713 (4)	0.1161 (5)	0.2249 (3)	0.0441 (15)
H21	0.8174	0.1771	0.2391	0.053*
C22	0.7045 (4)	0.0891 (5)	0.2672 (3)	0.0419 (14)
H22	0.7029	0.1336	0.3094	0.050*
C23	0.6409 (4)	−0.0016 (5)	0.2481 (3)	0.0363 (13)
C24	0.4325 (4)	−0.0131 (4)	0.2411 (3)	0.0328 (12)
C25	0.4014 (4)	0.0952 (5)	0.2221 (3)	0.0408 (14)
H25	0.4458	0.1562	0.2411	0.049*
C26	0.3045 (4)	0.1136 (5)	0.1750 (3)	0.0406 (14)
H26	0.2830	0.1880	0.1609	0.049*
C27	0.3683 (4)	−0.1023 (5)	0.2146 (3)	0.0451 (15)
H27	0.3906	−0.1768	0.2276	0.054*
C28	0.2707 (4)	−0.0814 (5)	0.1688 (3)	0.0445 (14)
H28	0.2252	−0.1422	0.1514	0.053*
C29	0.2384 (4)	0.0257 (4)	0.1480 (3)	0.0290 (12)
C30	0.1323 (4)	0.0472 (5)	0.0983 (3)	0.0318 (12)
N1	0.9788 (3)	0.2800 (4)	−0.0735 (2)	0.0346 (10)
N2	0.8417 (3)	0.3211 (4)	0.0049 (2)	0.0398 (11)
O1	0.9131 (3)	0.1514 (4)	0.1399 (2)	0.0547 (11)
O2	0.8159 (3)	0.0532 (3)	0.0472 (2)	0.0579 (11)
O3	0.5725 (3)	0.0429 (3)	0.36227 (19)	0.0498 (10)
O4	0.5655 (3)	−0.1540 (3)	0.3190 (2)	0.0505 (10)
O5	0.1095 (3)	0.1462 (3)	0.0778 (2)	0.0431 (10)
O6	0.0711 (2)	−0.0331 (3)	0.08092 (18)	0.0378 (9)
O7	0.5072 (7)	0.2427 (7)	0.4235 (5)	0.219 (4)
H7A	0.5383	0.1922	0.4059	0.263*
H7B	0.5450	0.3006	0.4328	0.263*
O8	0.5974 (5)	0.4537 (8)	0.4635 (4)	0.190 (4)
H8A	0.6605	0.4580	0.4872	0.228*
H8B	0.5738	0.5196	0.4540	0.228*
O9	0.4977 (8)	0.6674 (8)	0.4236 (6)	0.250 (5)
H9A	0.4947	0.7323	0.4042	0.300*
H9B	0.4584	0.6652	0.4524	0.300*
S1	0.55609 (10)	−0.03595 (13)	0.30184 (7)	0.0389 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0322 (2)	0.0300 (2)	0.0350 (2)	0.00160 (19)	0.00865 (16)	0.00311 (19)
C1	0.039 (3)	0.032 (3)	0.044 (3)	0.002 (3)	0.012 (3)	−0.001 (3)
C2	0.035 (3)	0.051 (4)	0.033 (3)	−0.004 (3)	0.008 (2)	0.000 (3)
C3	0.062 (4)	0.065 (4)	0.048 (4)	0.004 (4)	0.025 (3)	0.004 (3)
C4	0.040 (3)	0.039 (4)	0.032 (3)	−0.006 (3)	0.002 (2)	0.003 (3)
C5	0.069 (4)	0.054 (4)	0.052 (4)	−0.008 (4)	0.022 (3)	0.009 (3)
C6	0.038 (3)	0.028 (3)	0.032 (3)	−0.003 (3)	0.001 (2)	0.004 (2)
C7	0.033 (3)	0.027 (3)	0.031 (3)	0.001 (3)	0.002 (2)	−0.001 (2)
C8	0.034 (3)	0.025 (3)	0.033 (3)	0.001 (3)	0.001 (2)	−0.001 (2)
C9	0.057 (4)	0.028 (3)	0.039 (3)	−0.003 (3)	0.000 (3)	0.004 (3)
C10	0.049 (4)	0.028 (3)	0.046 (4)	0.009 (3)	−0.005 (3)	0.001 (3)
C11	0.039 (3)	0.031 (3)	0.036 (3)	0.004 (3)	−0.002 (2)	−0.006 (3)
C12	0.045 (3)	0.041 (4)	0.036 (3)	0.010 (3)	0.000 (3)	−0.007 (3)
C13	0.065 (4)	0.054 (4)	0.050 (4)	0.020 (4)	0.009 (3)	−0.010 (3)
C14	0.069 (5)	0.082 (6)	0.086 (5)	0.023 (4)	0.040 (4)	0.003 (4)
C15	0.043 (4)	0.052 (4)	0.050 (4)	0.015 (3)	0.012 (3)	−0.003 (3)
C16	0.045 (3)	0.057 (4)	0.049 (4)	0.010 (3)	0.019 (3)	0.009 (3)
C17	0.048 (4)	0.048 (4)	0.054 (4)	0.019 (3)	0.023 (3)	0.020 (3)
C18	0.032 (3)	0.045 (4)	0.045 (3)	0.009 (3)	0.011 (3)	0.016 (3)
C19	0.054 (4)	0.048 (4)	0.046 (3)	0.008 (3)	0.023 (3)	−0.001 (3)
C20	0.050 (4)	0.045 (4)	0.052 (4)	−0.006 (3)	0.017 (3)	−0.001 (3)
C21	0.038 (3)	0.052 (4)	0.041 (3)	−0.004 (3)	0.008 (3)	0.007 (3)
C22	0.038 (3)	0.050 (4)	0.036 (3)	0.002 (3)	0.008 (3)	0.000 (3)
C23	0.028 (3)	0.043 (4)	0.039 (3)	0.005 (3)	0.009 (2)	0.010 (3)
C24	0.028 (3)	0.034 (3)	0.036 (3)	0.005 (3)	0.008 (2)	0.006 (3)
C25	0.033 (3)	0.030 (3)	0.055 (4)	−0.005 (3)	0.005 (3)	0.000 (3)
C26	0.037 (3)	0.025 (3)	0.057 (4)	0.005 (3)	0.006 (3)	0.010 (3)
C27	0.044 (4)	0.026 (3)	0.061 (4)	0.008 (3)	0.008 (3)	0.009 (3)
C28	0.040 (3)	0.031 (3)	0.057 (4)	−0.004 (3)	0.005 (3)	0.001 (3)
C29	0.028 (3)	0.026 (3)	0.034 (3)	0.003 (3)	0.010 (2)	0.004 (2)
C30	0.035 (3)	0.033 (3)	0.028 (3)	0.001 (3)	0.010 (2)	−0.002 (2)
N1	0.037 (3)	0.030 (3)	0.037 (2)	0.003 (2)	0.010 (2)	0.001 (2)
N2	0.041 (3)	0.037 (3)	0.042 (3)	0.004 (2)	0.013 (2)	0.003 (2)
O1	0.046 (3)	0.069 (3)	0.054 (3)	0.000 (2)	0.023 (2)	0.020 (2)
O2	0.065 (3)	0.058 (3)	0.063 (3)	−0.004 (2)	0.039 (2)	0.005 (2)
O3	0.045 (2)	0.067 (3)	0.036 (2)	0.004 (2)	0.0073 (17)	−0.001 (2)
O4	0.047 (2)	0.050 (3)	0.054 (2)	0.010 (2)	0.0107 (19)	0.024 (2)
O5	0.032 (2)	0.033 (2)	0.058 (2)	−0.0011 (19)	0.0008 (17)	0.009 (2)
O6	0.037 (2)	0.035 (2)	0.041 (2)	−0.0051 (19)	0.0098 (17)	−0.0061 (18)
O7	0.225 (9)	0.155 (8)	0.287 (12)	0.042 (7)	0.087 (9)	0.017 (8)
O8	0.145 (6)	0.289 (11)	0.132 (6)	−0.008 (7)	0.033 (5)	−0.048 (7)
O9	0.240 (11)	0.263 (13)	0.275 (13)	−0.069 (9)	0.119 (10)	−0.027 (9)
S1	0.0312 (8)	0.0459 (9)	0.0389 (8)	0.0062 (7)	0.0086 (6)	0.0105 (7)

Geometric parameters (Å, º)

Cd1—O5^i	2.228 (3)	C16—N2	1.333 (6)
Cd1—O6^ii	2.281 (3)	C16—H16	0.9500
Cd1—O2	2.334 (4)	C17—O1	1.238 (7)
Cd1—N1	2.351 (4)	C17—O2	1.259 (7)
Cd1—N2	2.380 (4)	C17—C18	1.519 (7)
Cd1—O1	2.455 (4)	C18—C19	1.373 (8)
C1—N1	1.318 (6)	C18—C21	1.374 (7)
C1—C2	1.404 (7)	C19—C20	1.388 (7)
C1—H1	0.9500	C19—H19	0.9500
C2—C4	1.365 (7)	C20—C23	1.372 (7)
C2—C3	1.500 (7)	C20—H20	0.9500
C3—H3A	0.9800	C21—C22	1.387 (7)
C3—H3B	0.9800	C21—H21	0.9500
C3—H3C	0.9800	C22—C23	1.370 (7)
C4—C6	1.427 (7)	C22—H22	0.9500
C4—C5	1.506 (7)	C23—S1	1.761 (5)
C5—H5A	0.9800	C24—C25	1.377 (7)
C5—H5B	0.9800	C24—C27	1.378 (7)
C5—H5C	0.9800	C24—S1	1.765 (5)
C6—C7	1.407 (7)	C25—C26	1.380 (7)
C6—C9	1.427 (7)	C25—H25	0.9500
C7—N1	1.352 (6)	C26—C29	1.382 (7)
C7—C8	1.454 (7)	C26—H26	0.9500
C8—N2	1.352 (6)	C27—C28	1.385 (7)
C8—C11	1.411 (7)	C27—H27	0.9500
C9—C10	1.347 (7)	C28—C29	1.373 (7)
C9—H9	0.9500	C28—H28	0.9500
C10—C11	1.431 (7)	C29—C30	1.503 (6)
C10—H10	0.9500	C30—O6	1.251 (6)
C11—C12	1.424 (7)	C30—O5	1.255 (6)
C12—C15	1.363 (8)	O3—S1	1.433 (4)
C12—C13	1.512 (7)	O4—S1	1.443 (4)
C13—H13A	0.9800	O5—Cd1^iii	2.228 (3)
C13—H13B	0.9800	O6—Cd1^ii	2.281 (3)
C13—H13C	0.9800	O7—H7A	0.8500
C14—C15	1.513 (8)	O7—H7B	0.8500
C14—H14A	0.9800	O8—H8A	0.8501
C14—H14B	0.9800	O8—H8B	0.8500
C14—H14C	0.9800	O9—H9A	0.8500
C15—C16	1.384 (8)	O9—H9B	0.8500
O5^i—Cd1—O6^ii	103.42 (13)	H14B—C14—H14C	109.5
O5^i—Cd1—O2	123.44 (14)	C12—C15—C16	118.7 (5)
O6^ii—Cd1—O2	86.56 (14)	C12—C15—C14	123.4 (6)
O5^i—Cd1—N1	91.88 (13)	C16—C15—C14	118.0 (6)
O6^ii—Cd1—N1	81.45 (14)	N2—C16—C15	125.5 (6)
O2—Cd1—N1	144.53 (14)	N2—C16—H16	117.2
O5^i—Cd1—N2	124.71 (14)	C15—C16—H16	117.2
O6^ii—Cd1—N2	123.00 (13)	O1—C17—O2	123.3 (6)
O2—Cd1—N2	90.11 (15)	O1—C17—C18	119.6 (6)
N1—Cd1—N2	69.47 (15)	O2—C17—C18	117.0 (6)
O5^i—Cd1—O1	85.19 (14)	C19—C18—C21	119.8 (5)
O6^ii—Cd1—O1	135.70 (14)	C19—C18—C17	120.8 (6)
O2—Cd1—O1	54.53 (14)	C21—C18—C17	119.3 (6)
N1—Cd1—O1	142.39 (15)	C18—C19—C20	120.8 (5)
N2—Cd1—O1	81.57 (14)	C18—C19—H19	119.6
N1—C1—C2	125.2 (5)	C20—C19—H19	119.6
N1—C1—H1	117.4	C23—C20—C19	118.8 (5)
C2—C1—H1	117.4	C23—C20—H20	120.6
C4—C2—C1	118.3 (5)	C19—C20—H20	120.6
C4—C2—C3	122.7 (5)	C18—C21—C22	119.7 (5)
C1—C2—C3	118.9 (5)	C18—C21—H21	120.1
C2—C3—H3A	109.5	C22—C21—H21	120.1
C2—C3—H3B	109.5	C23—C22—C21	119.9 (5)
H3A—C3—H3B	109.5	C23—C22—H22	120.0
C2—C3—H3C	109.5	C21—C22—H22	120.0
H3A—C3—H3C	109.5	C22—C23—C20	120.9 (5)
H3B—C3—H3C	109.5	C22—C23—S1	120.0 (4)
C2—C4—C6	118.7 (5)	C20—C23—S1	119.1 (4)
C2—C4—C5	120.9 (5)	C25—C24—C27	121.0 (5)
C6—C4—C5	120.5 (5)	C25—C24—S1	118.6 (4)
C4—C5—H5A	109.5	C27—C24—S1	120.3 (4)
C4—C5—H5B	109.5	C24—C25—C26	118.9 (5)
H5A—C5—H5B	109.5	C24—C25—H25	120.5
C4—C5—H5C	109.5	C26—C25—H25	120.5
H5A—C5—H5C	109.5	C25—C26—C29	121.2 (5)
H5B—C5—H5C	109.5	C25—C26—H26	119.4
C7—C6—C4	117.8 (5)	C29—C26—H26	119.4
C7—C6—C9	118.1 (5)	C24—C27—C28	118.9 (5)
C4—C6—C9	124.1 (5)	C24—C27—H27	120.5
N1—C7—C6	123.1 (5)	C28—C27—H27	120.5
N1—C7—C8	117.1 (5)	C29—C28—C27	121.1 (5)
C6—C7—C8	119.8 (5)	C29—C28—H28	119.4
N2—C8—C11	122.3 (5)	C27—C28—H28	119.4
N2—C8—C7	117.6 (5)	C28—C29—C26	118.8 (5)
C11—C8—C7	120.1 (5)	C28—C29—C30	120.6 (5)
C10—C9—C6	122.3 (5)	C26—C29—C30	120.6 (5)
C10—C9—H9	118.8	O6—C30—O5	123.6 (5)
C6—C9—H9	118.8	O6—C30—C29	118.9 (5)
C9—C10—C11	121.6 (5)	O5—C30—C29	117.5 (5)
C9—C10—H10	119.2	C1—N1—C7	116.8 (4)
C11—C10—H10	119.2	C1—N1—Cd1	125.1 (4)
C8—C11—C12	118.5 (5)	C7—N1—Cd1	117.8 (3)
C8—C11—C10	118.0 (5)	C16—N2—C8	116.6 (5)
C12—C11—C10	123.5 (5)	C16—N2—Cd1	126.4 (4)
C15—C12—C11	118.3 (5)	C8—N2—Cd1	116.5 (3)
C15—C12—C13	121.5 (5)	C17—O1—Cd1	88.5 (4)
C11—C12—C13	120.2 (5)	C17—O2—Cd1	93.6 (4)
C12—C13—H13A	109.5	C30—O5—Cd1^iii	109.9 (3)
C12—C13—H13B	109.5	C30—O6—Cd1^ii	127.5 (3)
H13A—C13—H13B	109.5	H7A—O7—H7B	108.8
C12—C13—H13C	109.5	H8A—O8—H8B	108.6
H13A—C13—H13C	109.5	H9A—O9—H9B	109.1
H13B—C13—H13C	109.5	O3—S1—O4	119.0 (2)
C15—C14—H14A	109.5	O3—S1—C23	107.6 (3)
C15—C14—H14B	109.5	O4—S1—C23	108.7 (2)
H14A—C14—H14B	109.5	O3—S1—C24	108.3 (2)
C15—C14—H14C	109.5	O4—S1—C24	107.6 (2)
H14A—C14—H14C	109.5	C23—S1—C24	104.8 (2)
N1—C1—C2—C4	2.5 (8)	C26—C29—C30—O5	5.5 (7)
N1—C1—C2—C3	−177.9 (5)	C2—C1—N1—C7	0.0 (7)
C1—C2—C4—C6	−2.3 (7)	C2—C1—N1—Cd1	−174.5 (4)
C3—C2—C4—C6	178.0 (5)	C6—C7—N1—C1	−2.6 (7)
C1—C2—C4—C5	179.0 (5)	C8—C7—N1—C1	176.0 (4)
C3—C2—C4—C5	−0.7 (8)	C6—C7—N1—Cd1	172.4 (4)
C2—C4—C6—C7	0.0 (7)	C8—C7—N1—Cd1	−9.0 (5)
C5—C4—C6—C7	178.7 (5)	O5^i—Cd1—N1—C1	58.1 (4)
C2—C4—C6—C9	−178.6 (5)	O6^ii—Cd1—N1—C1	−45.2 (4)
C5—C4—C6—C9	0.1 (8)	O2—Cd1—N1—C1	−116.8 (4)
C4—C6—C7—N1	2.6 (7)	N2—Cd1—N1—C1	−175.3 (4)
C9—C6—C7—N1	−178.7 (5)	O1—Cd1—N1—C1	142.6 (4)
C4—C6—C7—C8	−176.0 (4)	O5^i—Cd1—N1—C7	−116.4 (3)
C9—C6—C7—C8	2.7 (7)	O6^ii—Cd1—N1—C7	140.3 (3)
N1—C7—C8—N2	−0.8 (7)	O2—Cd1—N1—C7	68.7 (4)
C6—C7—C8—N2	177.8 (4)	N2—Cd1—N1—C7	10.2 (3)
N1—C7—C8—C11	179.3 (4)	O1—Cd1—N1—C7	−31.9 (4)
C6—C7—C8—C11	−2.1 (7)	C15—C16—N2—C8	−1.9 (8)
C7—C6—C9—C10	−2.2 (8)	C15—C16—N2—Cd1	169.9 (4)
C4—C6—C9—C10	176.5 (5)	C11—C8—N2—C16	2.5 (7)
C6—C9—C10—C11	0.8 (8)	C7—C8—N2—C16	−177.4 (5)
N2—C8—C11—C12	−1.0 (7)	C11—C8—N2—Cd1	−170.1 (4)
C7—C8—C11—C12	178.9 (4)	C7—C8—N2—Cd1	10.0 (6)
N2—C8—C11—C10	−179.2 (4)	O5^i—Cd1—N2—C16	−104.7 (5)
C7—C8—C11—C10	0.7 (7)	O6^ii—Cd1—N2—C16	113.4 (4)
C9—C10—C11—C8	−0.1 (8)	O2—Cd1—N2—C16	27.4 (5)
C9—C10—C11—C12	−178.2 (5)	N1—Cd1—N2—C16	177.8 (5)
C8—C11—C12—C15	−1.3 (7)	O1—Cd1—N2—C16	−26.6 (4)
C10—C11—C12—C15	176.8 (5)	O5^i—Cd1—N2—C8	67.0 (4)
C8—C11—C12—C13	179.6 (5)	O6^ii—Cd1—N2—C8	−74.8 (4)
C10—C11—C12—C13	−2.3 (8)	O2—Cd1—N2—C8	−160.8 (4)
C11—C12—C15—C16	2.0 (8)	N1—Cd1—N2—C8	−10.5 (3)
C13—C12—C15—C16	−179.0 (5)	O1—Cd1—N2—C8	145.1 (4)
C11—C12—C15—C14	−178.9 (5)	O2—C17—O1—Cd1	2.0 (6)
C13—C12—C15—C14	0.1 (9)	C18—C17—O1—Cd1	−173.6 (5)
C12—C15—C16—N2	−0.4 (9)	O5^i—Cd1—O1—C17	−138.7 (3)
C14—C15—C16—N2	−179.6 (5)	O6^ii—Cd1—O1—C17	−34.4 (4)
O1—C17—C18—C19	−163.7 (5)	O2—Cd1—O1—C17	−1.1 (3)
O2—C17—C18—C19	20.5 (8)	N1—Cd1—O1—C17	134.4 (3)
O1—C17—C18—C21	17.2 (8)	N2—Cd1—O1—C17	95.1 (3)
O2—C17—C18—C21	−158.6 (5)	O1—C17—O2—Cd1	−2.1 (6)
C21—C18—C19—C20	0.4 (8)	C18—C17—O2—Cd1	173.6 (4)
C17—C18—C19—C20	−178.7 (5)	O5^i—Cd1—O2—C17	54.7 (4)
C18—C19—C20—C23	0.9 (8)	O6^ii—Cd1—O2—C17	158.5 (3)
C19—C18—C21—C22	−2.1 (8)	N1—Cd1—O2—C17	−131.5 (4)
C17—C18—C21—C22	177.0 (5)	N2—Cd1—O2—C17	−78.5 (3)
C18—C21—C22—C23	2.5 (8)	O1—Cd1—O2—C17	1.1 (3)
C21—C22—C23—C20	−1.2 (8)	O6—C30—O5—Cd1^iii	4.4 (6)
C21—C22—C23—S1	179.9 (4)	C29—C30—O5—Cd1^iii	−174.0 (3)
C19—C20—C23—C22	−0.5 (8)	O5—C30—O6—Cd1^ii	96.5 (5)
C19—C20—C23—S1	178.4 (4)	C29—C30—O6—Cd1^ii	−85.1 (5)
C27—C24—C25—C26	−0.8 (8)	C22—C23—S1—O3	−1.5 (5)
S1—C24—C25—C26	−179.6 (4)	C20—C23—S1—O3	179.6 (4)
C24—C25—C26—C29	1.2 (8)	C22—C23—S1—O4	−131.6 (4)
C25—C24—C27—C28	−0.6 (8)	C20—C23—S1—O4	49.6 (5)
S1—C24—C27—C28	178.1 (4)	C22—C23—S1—C24	113.6 (4)
C24—C27—C28—C29	1.8 (9)	C20—C23—S1—C24	−65.2 (5)
C27—C28—C29—C26	−1.4 (8)	C25—C24—S1—O3	44.1 (5)
C27—C28—C29—C30	−180.0 (5)	C27—C24—S1—O3	−134.7 (4)
C25—C26—C29—C28	−0.1 (8)	C25—C24—S1—O4	174.0 (4)
C25—C26—C29—C30	178.5 (5)	C27—C24—S1—O4	−4.8 (5)
C28—C29—C30—O6	5.5 (7)	C25—C24—S1—C23	−70.4 (5)
C26—C29—C30—O6	−173.0 (5)	C27—C24—S1—C23	110.8 (5)
C28—C29—C30—O5	−176.0 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O3	0.85	2.06	2.883 (10)	162
O7—H7B···O8	0.85	1.99	2.811 (13)	163
O8—H8B···O9	0.85	2.05	2.889 (14)	172
C22—H22···O3	0.95	2.49	2.884 (6)	105
C27—H27···O4	0.95	2.52	2.905 (6)	104
O8—H8A···O2^iv	0.85	2.10	2.944 (8)	173
O9—H9A···O4^v	0.85	2.47	3.182 (11)	142
O9—H9B···O7^vi	0.85	2.48	3.046 (13)	125
O9—H9B···O8^vi	0.85	2.38	3.096 (12)	143
C10—H10···O5^vii	0.95	2.35	3.092 (7)	134
C13—H13B···O4^viii	0.98	2.51	3.454 (7)	162
C20—H20···O7^ix	0.95	2.49	3.344 (10)	150
C25—H25···O4^x	0.95	2.51	3.155 (7)	125

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