Bis(μ-5-sulfonatosalicylato)bis­[bis­(1,10-phenanthroline)cadmium(II)] monohydrate

In the title compound, [Cd₂(C₇H₄O₆S)₂(C₁₂H₈N₂)₄]·H₂O, the Cd^II atoms are bridged by two 5-sulfonatosalicylate dianions, forming a centrosymmetric dinuclear complex. Each Cd atom is coordinated by four N atoms from two 1,10-phenanthroline mol­ecules and two O atoms from two 5-sulfonatosalicylate ligands in a distorted octa­hedral environment. A strong π–π stacking inter­action occurs between 1,10-phenanthroline ligands from neighboring dimers. Extensive hydrogen bonds give rise to a two-dimensional network and enhance the stability of the crystal packing.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• Disorder in solvent or counterion
• R factor = 0.031
• wR factor = 0.072
• Data-to-parameter ratio = 12.1

checkCIF/PLATON results

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Alert level C
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      50.00 Perc.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

5-Sulfosalicylic acid (5-H₃ssal) has three functional groups, viz. hydroxy, carboxyl and sulfonic acid groups, and can be partly or fully deprotonated in the formation of metal complexes. Therefore, 5-sulfonatosalicylate metal complexes can exhibit interesting assembly structures (Fan, Cai et al., 2005; Fan & Zhu, 2005a,b), among which only one cyclic dimer was reported (Li et al., 2004). We present here the second 5-sulfonatosalicylate cyclic dimer, (I).

The title Cd^II complex is a centrosymmetric cyclic dimer, in which each Cd atom adopts a distorted octahedral geometry defined by four N atoms from two 1,10-phenanthroline ligands and two O atoms from one sulfonate and one carboxylate group of two 5-Hssal²⁻ ligands (Fig. 1 and Table 1). The Cd—O(SO₃) and Cd—N bond distances are similar to those in the cyclic dimer of bis[diaqua(1,10-phenanthroline)(µ-4-sulfonatobenzoato)cadmium(II)], (II) (Fan, Zhang et al., 2005). 5-Sulfosalicylic acid is doubly deprotonated and acts as a bridging ligand through its sulfonate and carboxylate groups. The Cd···Cd separation in the dimer is 8.1153 (5) Å, which is significantly shorter than 9.931 (1) Å in (II). In neighboring dimers, there is a strong π–π stacking interaction between symmetry-related N3/N4/C13–C24 1,10-phenanthroline groups (symmetry code: 1 − x, 1 − y, 2 − z), with an interplanar distance of 3.29 (2) Å. Moreover, intra- and intermolecular hydrogen bonds generate a two-dimensional extended network (Fig. 2 and Table 2) and stabilize the crystal packing.

S2. Experimental

A mixture of Cd(CH₃COO)₂·2H₂O (0.053 g, 0.2 mmol), 5-sulfosalicylic acid dihydrate (0.050 g, 0.2 mmol) and 1,10-phenanthroline hydrate (0.040 g, 0.2 mmol) in an aqueous solution (10 ml) was stirred for 2 h, and then sealed in a 20 ml stainless steel reactor with a Teflon liner. The mixture was heated for 72 h at 423 K. Colorless plate-shaped crystals of (I) were obtained after cooling to room temperature and these were separated by suction filtration. Thermogravimetric measurement showed 1.35% weight loss between 377 and 441 K, which corresponds to one water molecule per Cd complex.

S3. Refinement

H atoms on C atoms were placed geometrically and refined as riding atoms with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). The water and hydroxy H atoms were located from a difference Fourier map and were refined with a distance restraint of O—H = 0.85 (1) Å, and with U_iso(H) = 0.08 Ų. The occupancy of the water molecule O1w was initially refined and converged to 0.595 (12), and was then fixed at 0.5 in the final cycles of refinement.

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. ORTEP-3 (Farrugia, 1997) view of (I). Displacement ellipsoids are drawn at the 40% probability level. H atoms are not shown for clarity [symmetry code (i): 1 − x, −y, 2 − z].
	Fig. 2. A view of the two-dimensional hydrogen-bonding network in (I). Hydrogen bonds are shown as dashed lines. 1,10-Phenanthroline ligands have been omitted for clarity.

Bis(µ-5-sulfonatosalicylato)bis[bis(1,10-phenanthroline)cadmium(II)] monohydrate

Crystal data

[Cd2(C7H4O6S)2(C12H8N2)4]·H2O	F(000) = 1404
Mr = 1395.96	Dx = 1.663 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7178 reflections
a = 15.1984 (7) Å	θ = 2.3–27.9°
b = 9.8340 (4) Å	µ = 0.91 mm^−1
c = 18.9902 (8) Å	T = 296 K
β = 100.778 (1)°	Plate, colorless
V = 2788.2 (2) Å^3	0.31 × 0.21 × 0.15 mm
Z = 2

Data collection

Bruker APEX area-detector diffractometer	4905 independent reflections
Radiation source: fine-focus sealed tube	4600 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ϕ and ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −18→17
Tmin = 0.765, Tmax = 0.875	k = −11→11
14180 measured reflections	l = −22→19

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.072	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0314P)^2 + 2.1742P] where P = (Fo^2 + 2Fc^2)/3
4905 reflections	(Δ/σ)max = 0.001
406 parameters	Δρmax = 0.39 e Å^−3
4 restraints	Δρmin = −0.33 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	Occ. (<1)
Cd1	0.716876 (12)	0.22732 (2)	0.980272 (10)	0.03252 (8)
S1	0.58041 (4)	0.11818 (7)	0.80855 (4)	0.03517 (16)
N1	0.85396 (15)	0.3304 (3)	1.03881 (12)	0.0399 (6)
N2	0.83530 (14)	0.1325 (2)	0.93496 (12)	0.0375 (5)
N3	0.70536 (14)	0.4285 (2)	0.90958 (12)	0.0360 (5)
N4	0.64130 (15)	0.3972 (2)	1.03419 (12)	0.0368 (5)
O1	0.34167 (14)	−0.0890 (2)	0.94857 (11)	0.0465 (5)
O2	0.20607 (14)	−0.0316 (3)	0.89132 (13)	0.0652 (7)
O3	0.18930 (16)	0.1432 (4)	0.79092 (15)	0.0816 (9)
O4	0.61524 (13)	0.1302 (2)	0.88582 (10)	0.0491 (5)
O5	0.60269 (13)	−0.0135 (2)	0.78217 (11)	0.0484 (5)
O6	0.60394 (15)	0.2308 (2)	0.76750 (13)	0.0546 (6)
O1W	0.0108 (4)	0.2434 (6)	0.7480 (5)	0.101 (2)	0.50
C1	0.8636 (2)	0.4279 (3)	1.08740 (17)	0.0505 (8)
H1	0.8125	0.4615	1.1016	0.061*
C2	0.9460 (2)	0.4834 (4)	1.11854 (18)	0.0585 (9)
H2	0.9496	0.5518	1.1528	0.070*
C3	1.0205 (2)	0.4356 (4)	1.09788 (19)	0.0612 (10)
H3	1.0762	0.4707	1.1185	0.073*
C4	1.0147 (2)	0.3338 (4)	1.04569 (17)	0.0492 (8)
C5	1.0899 (2)	0.2803 (4)	1.0206 (2)	0.0631 (10)
H5	1.1467	0.3131	1.0399	0.076*
C6	1.0815 (2)	0.1845 (4)	0.9702 (2)	0.0613 (10)
H6	1.1323	0.1521	0.9550	0.074*
C7	0.99501 (19)	0.1302 (3)	0.93883 (17)	0.0481 (8)
C8	0.9828 (2)	0.0300 (4)	0.88617 (19)	0.0571 (9)
H8	1.0320	−0.0046	0.8695	0.069*
C9	0.8995 (2)	−0.0177 (4)	0.85898 (18)	0.0552 (9)
H9	0.8909	−0.0850	0.8240	0.066*
C10	0.8268 (2)	0.0372 (3)	0.88506 (16)	0.0455 (7)
H10	0.7697	0.0049	0.8663	0.055*
C11	0.92857 (18)	0.2831 (3)	1.01692 (16)	0.0395 (7)
C12	0.91869 (18)	0.1798 (3)	0.96226 (15)	0.0391 (7)
C13	0.73720 (19)	0.4448 (3)	0.84968 (15)	0.0433 (7)
H13	0.7634	0.3704	0.8314	0.052*
C14	0.7333 (2)	0.5678 (4)	0.81273 (16)	0.0492 (8)
H14	0.7572	0.5751	0.7712	0.059*
C15	0.6940 (2)	0.6771 (4)	0.83823 (17)	0.0504 (8)
H15	0.6902	0.7597	0.8139	0.060*
C16	0.65929 (18)	0.6645 (3)	0.90134 (16)	0.0417 (7)
C17	0.6172 (2)	0.7747 (3)	0.93158 (19)	0.0532 (8)
H17	0.6134	0.8594	0.9095	0.064*
C18	0.5831 (2)	0.7577 (3)	0.99141 (19)	0.0535 (9)
H18	0.5547	0.8302	1.0093	0.064*
C19	0.58975 (19)	0.6304 (3)	1.02798 (16)	0.0420 (7)
C20	0.5548 (2)	0.6082 (3)	1.09024 (17)	0.0515 (8)
H20	0.5244	0.6776	1.1088	0.062*
C21	0.5652 (2)	0.4855 (4)	1.12357 (17)	0.0514 (8)
H21	0.5430	0.4708	1.1653	0.062*
C22	0.60952 (19)	0.3823 (3)	1.09446 (16)	0.0449 (7)
H22	0.6173	0.2992	1.1181	0.054*
C23	0.66689 (17)	0.5372 (3)	0.93577 (14)	0.0345 (6)
C24	0.63275 (17)	0.5197 (3)	1.00127 (14)	0.0347 (6)
C25	0.28959 (19)	−0.0286 (3)	0.89914 (16)	0.0404 (7)
C26	0.33121 (18)	0.0502 (3)	0.84613 (14)	0.0363 (6)
C27	0.27890 (19)	0.1348 (4)	0.79563 (17)	0.0503 (8)
C28	0.3187 (2)	0.2132 (4)	0.75002 (17)	0.0540 (9)
H28	0.2837	0.2704	0.7172	0.065*
C29	0.4099 (2)	0.2075 (3)	0.75268 (15)	0.0434 (7)
H29	0.4361	0.2605	0.7217	0.052*
C30	0.46250 (17)	0.1222 (3)	0.80172 (13)	0.0329 (6)
C31	0.42321 (17)	0.0449 (3)	0.84784 (14)	0.0328 (6)
H31	0.4587	−0.0118	0.8807	0.039*
H1A	0.0659 (12)	0.265 (6)	0.755 (5)	0.080*	0.50
H1B	−0.021 (3)	0.315 (4)	0.744 (4)	0.080*	0.50
H3A	0.178 (3)	0.088 (3)	0.8223 (17)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02807 (12)	0.03403 (13)	0.03711 (13)	0.00127 (8)	0.01030 (8)	−0.00059 (8)
S1	0.0325 (3)	0.0374 (4)	0.0364 (4)	−0.0036 (3)	0.0086 (3)	0.0014 (3)
N1	0.0365 (13)	0.0475 (15)	0.0347 (13)	−0.0009 (11)	0.0037 (10)	−0.0011 (11)
N2	0.0317 (12)	0.0420 (14)	0.0393 (13)	0.0051 (10)	0.0077 (10)	0.0012 (11)
N3	0.0309 (12)	0.0394 (14)	0.0384 (13)	−0.0019 (10)	0.0081 (10)	−0.0011 (10)
N4	0.0368 (12)	0.0357 (13)	0.0397 (13)	0.0034 (10)	0.0119 (10)	0.0008 (10)
O1	0.0479 (12)	0.0440 (12)	0.0515 (13)	−0.0013 (10)	0.0197 (10)	0.0090 (10)
O2	0.0370 (12)	0.0904 (19)	0.0733 (16)	−0.0040 (12)	0.0236 (11)	0.0074 (14)
O3	0.0346 (13)	0.125 (3)	0.085 (2)	0.0196 (15)	0.0099 (12)	0.0356 (18)
O4	0.0386 (11)	0.0644 (15)	0.0419 (12)	−0.0079 (10)	0.0012 (9)	−0.0022 (10)
O5	0.0435 (11)	0.0461 (13)	0.0581 (13)	0.0042 (10)	0.0160 (10)	−0.0050 (10)
O6	0.0501 (13)	0.0550 (14)	0.0615 (15)	−0.0096 (10)	0.0172 (11)	0.0162 (11)
O1W	0.064 (4)	0.067 (4)	0.160 (7)	0.015 (3)	−0.005 (4)	0.007 (4)
C1	0.0532 (19)	0.053 (2)	0.0433 (18)	−0.0021 (15)	0.0036 (14)	−0.0004 (15)
C2	0.067 (2)	0.058 (2)	0.0448 (19)	−0.0137 (18)	−0.0053 (17)	−0.0012 (16)
C3	0.0462 (19)	0.070 (2)	0.059 (2)	−0.0201 (18)	−0.0122 (16)	0.0145 (19)
C4	0.0368 (16)	0.060 (2)	0.0463 (18)	−0.0074 (15)	−0.0031 (13)	0.0152 (16)
C5	0.0260 (16)	0.086 (3)	0.074 (3)	−0.0052 (16)	0.0004 (16)	0.019 (2)
C6	0.0291 (16)	0.084 (3)	0.073 (2)	0.0095 (17)	0.0156 (16)	0.019 (2)
C7	0.0352 (16)	0.058 (2)	0.0540 (19)	0.0133 (14)	0.0142 (14)	0.0167 (16)
C8	0.0461 (19)	0.068 (2)	0.063 (2)	0.0188 (17)	0.0249 (16)	0.0054 (18)
C9	0.059 (2)	0.056 (2)	0.054 (2)	0.0146 (17)	0.0195 (16)	−0.0045 (16)
C10	0.0399 (16)	0.0473 (18)	0.0496 (18)	0.0082 (14)	0.0091 (13)	−0.0024 (15)
C11	0.0316 (15)	0.0442 (17)	0.0416 (16)	−0.0004 (12)	0.0039 (12)	0.0152 (13)
C12	0.0297 (14)	0.0474 (17)	0.0407 (16)	0.0047 (12)	0.0083 (12)	0.0115 (13)
C13	0.0379 (15)	0.0508 (19)	0.0428 (17)	−0.0041 (13)	0.0115 (13)	−0.0042 (14)
C14	0.0454 (17)	0.064 (2)	0.0401 (17)	−0.0110 (16)	0.0141 (14)	0.0074 (15)
C15	0.0459 (18)	0.051 (2)	0.0526 (19)	−0.0078 (15)	0.0055 (15)	0.0147 (16)
C16	0.0364 (15)	0.0387 (17)	0.0477 (17)	−0.0044 (13)	0.0021 (13)	0.0033 (14)
C17	0.060 (2)	0.0339 (17)	0.063 (2)	0.0020 (15)	0.0041 (17)	0.0042 (15)
C18	0.064 (2)	0.0328 (18)	0.062 (2)	0.0084 (15)	0.0052 (17)	−0.0096 (15)
C19	0.0441 (16)	0.0366 (17)	0.0441 (17)	0.0001 (13)	0.0048 (13)	−0.0099 (13)
C20	0.060 (2)	0.046 (2)	0.0489 (19)	0.0083 (15)	0.0128 (15)	−0.0164 (15)
C21	0.0568 (19)	0.063 (2)	0.0389 (17)	0.0030 (16)	0.0194 (14)	−0.0082 (15)
C22	0.0461 (17)	0.0492 (19)	0.0412 (17)	0.0028 (14)	0.0129 (14)	0.0038 (14)
C23	0.0289 (13)	0.0339 (15)	0.0387 (15)	−0.0019 (11)	0.0017 (11)	−0.0014 (12)
C24	0.0306 (13)	0.0351 (15)	0.0377 (15)	−0.0006 (11)	0.0046 (11)	−0.0036 (12)
C25	0.0418 (17)	0.0401 (17)	0.0418 (17)	−0.0010 (13)	0.0143 (13)	−0.0060 (13)
C26	0.0368 (15)	0.0385 (16)	0.0345 (15)	0.0012 (12)	0.0086 (12)	−0.0028 (12)
C27	0.0353 (16)	0.068 (2)	0.0459 (18)	0.0107 (15)	0.0040 (13)	0.0062 (16)
C28	0.0484 (19)	0.067 (2)	0.0435 (18)	0.0166 (16)	0.0017 (15)	0.0174 (16)
C29	0.0489 (18)	0.0489 (18)	0.0326 (15)	0.0039 (14)	0.0085 (13)	0.0069 (13)
C30	0.0339 (14)	0.0348 (15)	0.0301 (14)	−0.0002 (11)	0.0064 (11)	−0.0029 (11)
C31	0.0363 (14)	0.0311 (15)	0.0309 (14)	0.0042 (11)	0.0057 (11)	−0.0003 (11)

Geometric parameters (Å, º)

Cd1—O1^i	2.2177 (19)	C7—C12	1.405 (4)
Cd1—O4	2.3407 (19)	C8—C9	1.358 (5)
Cd1—N1	2.395 (2)	C8—H8	0.9300
Cd1—N2	2.330 (2)	C9—C10	1.400 (4)
Cd1—N3	2.379 (2)	C9—H9	0.9300
Cd1—N4	2.366 (2)	C10—H10	0.9300
S1—O4	1.469 (2)	C11—C12	1.440 (4)
S1—O5	1.451 (2)	C13—C14	1.394 (4)
S1—O6	1.437 (2)	C13—H13	0.9300
S1—C30	1.773 (3)	C14—C15	1.362 (5)
N1—C1	1.320 (4)	C14—H14	0.9300
N1—C11	1.360 (4)	C15—C16	1.402 (4)
N2—C10	1.322 (4)	C15—H15	0.9300
N2—C12	1.359 (4)	C16—C23	1.407 (4)
N3—C13	1.327 (4)	C16—C17	1.432 (4)
N3—C23	1.356 (3)	C17—C18	1.344 (5)
N4—C22	1.331 (4)	C17—H17	0.9300
N4—C24	1.353 (4)	C18—C19	1.425 (4)
O1—C25	1.258 (3)	C18—H18	0.9300
O1—Cd1^i	2.2177 (19)	C19—C20	1.401 (4)
O2—C25	1.251 (3)	C19—C24	1.412 (4)
O3—C27	1.351 (4)	C20—C21	1.358 (5)
O3—H3A	0.85 (3)	C20—H20	0.9300
O1W—H1A	0.850 (10)	C21—C22	1.388 (4)
O1W—H1B	0.849 (10)	C21—H21	0.9300
C1—C2	1.392 (5)	C22—H22	0.9300
C1—H1	0.9300	C23—C24	1.445 (4)
C2—C3	1.350 (5)	C25—C26	1.500 (4)
C2—H2	0.9300	C26—C31	1.394 (4)
C3—C4	1.400 (5)	C26—C27	1.400 (4)
C3—H3	0.9300	C27—C28	1.381 (5)
C4—C11	1.411 (4)	C28—C29	1.378 (4)
C4—C5	1.420 (5)	C28—H28	0.9300
C5—C6	1.332 (5)	C29—C30	1.389 (4)
C5—H5	0.9300	C29—H29	0.9300
C6—C7	1.440 (5)	C30—C31	1.377 (4)
C6—H6	0.9300	C31—H31	0.9300
C7—C8	1.392 (5)
O1^i—Cd1—O4	86.23 (8)	N2—C10—H10	118.3
O1^i—Cd1—N1	112.96 (8)	C9—C10—H10	118.3
O1^i—Cd1—N2	113.91 (8)	N1—C11—C4	121.8 (3)
O1^i—Cd1—N3	149.14 (8)	N1—C11—C12	118.7 (2)
O1^i—Cd1—N4	83.50 (8)	C4—C11—C12	119.5 (3)
O4—Cd1—N1	156.97 (8)	N2—C12—C7	121.8 (3)
O4—Cd1—N2	89.91 (8)	N2—C12—C11	118.7 (2)
O4—Cd1—N3	86.47 (8)	C7—C12—C11	119.5 (3)
O4—Cd1—N4	108.38 (8)	N3—C13—C14	123.2 (3)
N1—Cd1—N2	71.08 (8)	N3—C13—H13	118.4
N1—Cd1—N3	82.87 (8)	C14—C13—H13	118.4
N1—Cd1—N4	87.20 (8)	C15—C14—C13	119.1 (3)
N2—Cd1—N3	96.01 (8)	C15—C14—H14	120.4
N2—Cd1—N4	155.99 (8)	C13—C14—H14	120.4
N3—Cd1—N4	70.53 (8)	C14—C15—C16	119.6 (3)
O5—S1—O4	110.67 (13)	C14—C15—H15	120.2
O6—S1—O4	113.57 (14)	C16—C15—H15	120.2
O6—S1—O5	113.74 (13)	C15—C16—C23	117.7 (3)
O6—S1—C30	107.08 (13)	C15—C16—C17	122.9 (3)
O5—S1—C30	107.02 (12)	C23—C16—C17	119.4 (3)
O4—S1—C30	103.99 (12)	C18—C17—C16	121.1 (3)
C1—N1—C11	118.1 (3)	C18—C17—H17	119.5
C1—N1—Cd1	127.3 (2)	C16—C17—H17	119.5
C11—N1—Cd1	114.58 (19)	C17—C18—C19	121.2 (3)
C10—N2—C12	118.4 (2)	C17—C18—H18	119.4
C10—N2—Cd1	124.76 (19)	C19—C18—H18	119.4
C12—N2—Cd1	116.88 (19)	C20—C19—C24	117.2 (3)
C13—N3—C23	118.1 (3)	C20—C19—C18	123.0 (3)
C13—N3—Cd1	125.7 (2)	C24—C19—C18	119.8 (3)
C23—N3—Cd1	116.08 (17)	C21—C20—C19	120.2 (3)
C22—N4—C24	118.4 (2)	C21—C20—H20	119.9
C22—N4—Cd1	125.3 (2)	C19—C20—H20	119.9
C24—N4—Cd1	116.19 (17)	C20—C21—C22	119.1 (3)
C25—O1—Cd1^i	118.44 (18)	C20—C21—H21	120.4
C27—O3—H3A	105 (3)	C22—C21—H21	120.4
S1—O4—Cd1	149.48 (13)	N4—C22—C21	122.9 (3)
H1A—O1W—H1B	109.8 (18)	N4—C22—H22	118.5
N1—C1—C2	123.8 (3)	C21—C22—H22	118.5
N1—C1—H1	118.1	N3—C23—C16	122.3 (3)
C2—C1—H1	118.1	N3—C23—C24	118.1 (2)
C3—C2—C1	118.5 (3)	C16—C23—C24	119.6 (3)
C3—C2—H2	120.8	N4—C24—C19	122.1 (3)
C1—C2—H2	120.8	N4—C24—C23	119.0 (2)
C2—C3—C4	120.6 (3)	C19—C24—C23	118.9 (3)
C2—C3—H3	119.7	O2—C25—O1	124.1 (3)
C4—C3—H3	119.7	O2—C25—C26	118.6 (3)
C3—C4—C11	117.2 (3)	O1—C25—C26	117.3 (2)
C3—C4—C5	123.7 (3)	C31—C26—C27	118.5 (3)
C11—C4—C5	119.1 (3)	C31—C26—C25	120.8 (2)
C6—C5—C4	121.9 (3)	C27—C26—C25	120.7 (3)
C6—C5—H5	119.1	O3—C27—C28	118.6 (3)
C4—C5—H5	119.1	O3—C27—C26	121.2 (3)
C5—C6—C7	121.1 (3)	C28—C27—C26	120.1 (3)
C5—C6—H6	119.4	C29—C28—C27	120.7 (3)
C7—C6—H6	119.4	C29—C28—H28	119.7
C8—C7—C12	117.8 (3)	C27—C28—H28	119.7
C8—C7—C6	123.3 (3)	C28—C29—C30	119.8 (3)
C12—C7—C6	118.9 (3)	C28—C29—H29	120.1
C9—C8—C7	120.5 (3)	C30—C29—H29	120.1
C9—C8—H8	119.8	C31—C30—C29	119.7 (3)
C7—C8—H8	119.8	C31—C30—S1	119.6 (2)
C8—C9—C10	118.3 (3)	C29—C30—S1	120.6 (2)
C8—C9—H9	120.9	C30—C31—C26	121.1 (2)
C10—C9—H9	120.9	C30—C31—H31	119.4
N2—C10—C9	123.3 (3)	C26—C31—H31	119.4
O1^i—Cd1—N1—C1	−73.2 (3)	Cd1—N2—C12—C7	−179.9 (2)
N2—Cd1—N1—C1	178.1 (3)	C10—N2—C12—C11	−179.7 (3)
O4—Cd1—N1—C1	142.3 (2)	Cd1—N2—C12—C11	0.4 (3)
N4—Cd1—N1—C1	8.5 (3)	C8—C7—C12—N2	0.0 (4)
N3—Cd1—N1—C1	79.2 (3)	C6—C7—C12—N2	−179.8 (3)
O1^i—Cd1—N1—C11	108.56 (19)	C8—C7—C12—C11	179.7 (3)
N2—Cd1—N1—C11	−0.10 (18)	C6—C7—C12—C11	−0.1 (4)
O4—Cd1—N1—C11	−35.9 (3)	N1—C11—C12—N2	−0.5 (4)
N4—Cd1—N1—C11	−169.7 (2)	C4—C11—C12—N2	−179.8 (3)
N3—Cd1—N1—C11	−99.0 (2)	N1—C11—C12—C7	179.8 (3)
O1^i—Cd1—N2—C10	72.5 (2)	C4—C11—C12—C7	0.5 (4)
O4—Cd1—N2—C10	−13.3 (2)	C23—N3—C13—C14	0.2 (4)
N4—Cd1—N2—C10	−153.8 (2)	Cd1—N3—C13—C14	−176.0 (2)
N3—Cd1—N2—C10	−99.8 (2)	N3—C13—C14—C15	−0.9 (5)
N1—Cd1—N2—C10	179.9 (3)	C13—C14—C15—C16	0.7 (5)
O1^i—Cd1—N2—C12	−107.6 (2)	C14—C15—C16—C23	0.0 (4)
O4—Cd1—N2—C12	166.6 (2)	C14—C15—C16—C17	179.9 (3)
N4—Cd1—N2—C12	26.1 (3)	C15—C16—C17—C18	178.6 (3)
N3—Cd1—N2—C12	80.2 (2)	C23—C16—C17—C18	−1.5 (5)
N1—Cd1—N2—C12	−0.17 (19)	C16—C17—C18—C19	1.7 (5)
O1^i—Cd1—N3—C13	−146.6 (2)	C17—C18—C19—C20	−179.7 (3)
N2—Cd1—N3—C13	19.6 (2)	C17—C18—C19—C24	0.0 (5)
O4—Cd1—N3—C13	−70.0 (2)	C24—C19—C20—C21	1.9 (5)
N4—Cd1—N3—C13	179.1 (2)	C18—C19—C20—C21	−178.4 (3)
N1—Cd1—N3—C13	89.6 (2)	C19—C20—C21—C22	−1.0 (5)
O1^i—Cd1—N3—C23	37.2 (3)	C24—N4—C22—C21	2.4 (4)
N2—Cd1—N3—C23	−156.68 (18)	Cd1—N4—C22—C21	−179.7 (2)
O4—Cd1—N3—C23	113.78 (18)	C20—C21—C22—N4	−1.2 (5)
N4—Cd1—N3—C23	2.87 (17)	C13—N3—C23—C16	0.5 (4)
N1—Cd1—N3—C23	−86.67 (18)	Cd1—N3—C23—C16	177.1 (2)
O1^i—Cd1—N4—C22	16.5 (2)	C13—N3—C23—C24	−179.6 (2)
N2—Cd1—N4—C22	−121.8 (3)	Cd1—N3—C23—C24	−3.0 (3)
O4—Cd1—N4—C22	100.3 (2)	C15—C16—C23—N3	−0.6 (4)
N3—Cd1—N4—C22	179.5 (2)	C17—C16—C23—N3	179.5 (3)
N1—Cd1—N4—C22	−97.0 (2)	C15—C16—C23—C24	179.5 (3)
O1^i—Cd1—N4—C24	−165.6 (2)	C17—C16—C23—C24	−0.4 (4)
N2—Cd1—N4—C24	56.2 (3)	C22—N4—C24—C19	−1.4 (4)
O4—Cd1—N4—C24	−81.7 (2)	Cd1—N4—C24—C19	−179.5 (2)
N3—Cd1—N4—C24	−2.47 (18)	C22—N4—C24—C23	−179.9 (2)
N1—Cd1—N4—C24	80.95 (19)	Cd1—N4—C24—C23	1.9 (3)
O6—S1—O4—Cd1	−19.5 (3)	C20—C19—C24—N4	−0.7 (4)
O5—S1—O4—Cd1	109.8 (3)	C18—C19—C24—N4	179.6 (3)
C30—S1—O4—Cd1	−135.6 (3)	C20—C19—C24—C23	177.8 (3)
O1^i—Cd1—O4—S1	−175.6 (3)	C18—C19—C24—C23	−1.9 (4)
N2—Cd1—O4—S1	−61.7 (3)	N3—C23—C24—N4	0.8 (4)
N4—Cd1—O4—S1	102.5 (3)	C16—C23—C24—N4	−179.4 (2)
N3—Cd1—O4—S1	34.4 (3)	N3—C23—C24—C19	−177.8 (2)
N1—Cd1—O4—S1	−28.1 (4)	C16—C23—C24—C19	2.0 (4)
C11—N1—C1—C2	−1.3 (5)	Cd1^i—O1—C25—O2	6.8 (4)
Cd1—N1—C1—C2	−179.4 (2)	Cd1^i—O1—C25—C26	−172.38 (18)
N1—C1—C2—C3	0.3 (5)	O2—C25—C26—C31	−173.0 (3)
C1—C2—C3—C4	0.8 (5)	O1—C25—C26—C31	6.2 (4)
C2—C3—C4—C11	−0.8 (5)	O2—C25—C26—C27	9.5 (4)
C2—C3—C4—C5	179.0 (3)	O1—C25—C26—C27	−171.3 (3)
C3—C4—C5—C6	−179.2 (4)	C31—C26—C27—O3	179.4 (3)
C11—C4—C5—C6	0.6 (5)	C25—C26—C27—O3	−3.1 (5)
C4—C5—C6—C7	−0.2 (6)	C31—C26—C27—C28	−1.5 (5)
C5—C6—C7—C8	−179.9 (4)	C25—C26—C27—C28	176.0 (3)
C5—C6—C7—C12	−0.1 (5)	O3—C27—C28—C29	−179.7 (3)
C12—C7—C8—C9	−0.2 (5)	C26—C27—C28—C29	1.1 (5)
C6—C7—C8—C9	179.6 (3)	C27—C28—C29—C30	−0.1 (5)
C7—C8—C9—C10	0.3 (5)	C28—C29—C30—C31	−0.6 (4)
C12—N2—C10—C9	0.1 (5)	C28—C29—C30—S1	−177.5 (2)
Cd1—N2—C10—C9	−180.0 (2)	O6—S1—C30—C31	−166.0 (2)
C8—C9—C10—N2	−0.3 (5)	O5—S1—C30—C31	71.7 (2)
C1—N1—C11—C4	1.2 (4)	O4—S1—C30—C31	−45.5 (2)
Cd1—N1—C11—C4	179.6 (2)	O6—S1—C30—C29	10.9 (3)
C1—N1—C11—C12	−178.0 (3)	O5—S1—C30—C29	−111.4 (2)
Cd1—N1—C11—C12	0.4 (3)	O4—S1—C30—C29	131.4 (2)
C3—C4—C11—N1	−0.2 (4)	C29—C30—C31—C26	0.2 (4)
C5—C4—C11—N1	−180.0 (3)	S1—C30—C31—C26	177.1 (2)
C3—C4—C11—C12	179.0 (3)	C27—C26—C31—C30	0.9 (4)
C5—C4—C11—C12	−0.8 (4)	C25—C26—C31—C30	−176.7 (2)
C10—N2—C12—C7	0.0 (4)

Symmetry code: (i) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1B···O5^ii	0.85 (1)	2.10 (2)	2.940 (6)	172 (8)
O1w—H1A···O3	0.85 (1)	2.22 (5)	2.858 (7)	131 (5)
O3—H3A···O2	0.85 (3)	1.75 (2)	2.545 (4)	154 (4)

Symmetry code: (ii) −x+1/2, y+1/2, −z+3/2.