catena-Poly[[bis­[5-(4-pyridyl-κN)-2-(2-pyridylmethyl­sulfan­yl)-1,3,4-oxa­diazole]cadmium(II)]-di-μ-thio­cyan­ato-κ²N:S;κ²S:N]

The title compound, [Cd(NCS)₂(C₁₃H₁₀N₄OS)₂]_n, contains SCN⁻ anions acting as end-to-end bridging ligands which utilize both S and N atoms to link cadmium(II) centers into one-dimensional double chains. The multidentate 5-(4-pyrid­yl)-2-(2-pyridylmethyl­sulfan­yl)-1,3,4-oxadiazole ligands behave as monodentate terminal ligands, binding metal centers only through the N atoms of the 4-pyridyl groups. Two types of eight-membered rings are formed by two SCN⁻ anions bridging Cd^II centers, viz. planar and chair conformation, which are alternately disposed along the same chain. Finally, chains define a two-dimensional array through two different inter­chain π–π stacking inter­actions.

S1. Comment

The formation of coordination polymers has attracted great attention in recent years for their potential applications in separation and selective inclusion, and their ion exchange, catalysis, magnetism and nonlinear optical properties (Moulton & Zaworotko, 2001). 1,3,4-Oxadiazole exhibits the corresponding biological properties, such as antiphlogosis and antisepsis, which has given rise to an extensive variety of applications in both medicine and agriculture. Although many compounds containing symmetrical organic ligands bearing oxadiazole rings have been prepared (Du et al., 2006), as far as is known coordination compounds relative to asymmetrical ligands with oxadiazole groups are uncommon. We purposely synthesized the pyridyl-containing asymmetrical oxadiazole ligand 5-(4-pyridyl-κN)-2-(2-pyridylmethylsulfanyl)-1,3,4-oxadiazole (pmpo). The asymmetrical configuration, coordination variety and flexibility of pmpo are expected to meet metal coordination requirements (Du & Zhao, 2004). The heterocyclic groups in the ligand usually favor packing arrangements via π–π stacking interactions in the solid state (Atoub et al., 2007). Furthermore, thiocyanate, well known for its versatile coordination modes such as monodentate, end bridge and end-to-end bridge, was used in this research. We present here a new Cd^II thiocyanate complex of the asymmetrical pmpo ligand, [Cd(pmpo)₂(SCN)₂]_n, (I).

The main structural feature of (I) is that the SCN⁻ anions act as end-to-end bridging spacers, linking Cd^II centers into a double chain structure, with the pmpo ligands bound edgeways; this structure is very similar to those of several reported cadmium(II) thiocyanate complexes with pyridyl-containing oxadiazole ligands (Marsh et al., 2002). The Cd^II atom in (I) adopts an octahedral coordination geometry, with two S-bonded and two N-bonded thiocyanate ligands in the equatorial plane and two N-bonded 4-pyridyl rings of different pmpo ligands at the axial sites (Fig. 1).

The average Cd—N and Cd—S bond lengths in the equatorial plane are 2.323 (11) and 2.77 (5) Å, respectively, and the average Cd—N_pyridyl distance at the axial sites is 2.359 (4) Å, slightly longer than that of Cd—N_NCS in the equatorial plane. The average Cd—N_pyridyl length is almost the same as that of {is there a value missing here?} {[Cd(bpo)(SCN)₂]·(CH₃CN)}_n [bpo is 2,5-bis(4-pyridyl)-1,3,4-oxodiazole; Du et al. 2002] and slightly shorter than that of 2.463 (2) Å in [Cd(bpo)₂(SCN)₂] (Du et al., 2006). Furthermore, it is longer than that of 2.2749 (16) Å in [Cd(imH)₂(NCS)(SCN)]_n (imH is imidazole; Bose et al. 2004). The N—Cd—N bond angles around each Cd^II center are very close to 90° [mean 90.3 (15)°]; the N—Cd—S angles range from 82.45 (5) to 97.05 (5)°. The multidentate pmpo ligand behaves as a terminal ligand, with the 4-pyridyl group binding the metal center, and its two pyridyl rings subtending to each other a dihedral angle of 20.7°, deviating from the central oxadiazole plane by 14.3 and 6.7°.

Neighboring Cd···Cd distances in a chain are 5.863 (1)–6.019 (1) Å, slightly shorter than previously reported values [e.g. 6.067 (1) Å; Second et al., 2000]. There are two types of eight-membered rings formed by the SCN⁻ anions bridging Cd^II centers in the same chain. As clearly portrayed in Fig. 1, the ring formed by the two SCN⁻ anions bridging atoms Cd1 and Cd1ⁱ is nearly planar, with a mean deviation from the least-square plane of 0.045 Å, while the other ring, constructed by the SCN⁻ anions binding atoms Cd1 and Cd1ⁱⁱ, displays a chair conformation with the corresponding value of 0.222 Å.

Adjacent one-dimensional polymeric chains are linked via two types of interchain π–π stacking interactions (Fig. 2). Type 1 takes place between the oxadiazole and 2-pyridyl rings, with homologous centroid-to-centroid separations of 3.603 (2) and 3.616 (2) Å, while type 2 occurs between two contiguous 4-pyridyl and 2-pyridyl rings, with a similar separation of 3.834 (2) Å. Through these interchain interactions, the one-dimensional polymeric chains stack to form a two-dimensional array.

Related literature

For related literature, see: Atoub et al. (2007); Bose et al. (2004); Dodd & Nishi (1997); Du & Zhao (2004); Du et al. (2002, 2006); Marsh et al. (2002); Moulton & Zaworotko (2001).

S2. Experimental

The pmpo ligand was synthesized following a procedure reported previously (Dodd & Nishi, 1997). At room temperature, to a solution of Cd(NO₃)·4H₂O (0.0308 g, 0.1 mmol) in CH₃OH (5 ml) was added a solution of pmpo (0.0540 g, 0.2 mmol) in CH₃CN (5 ml) with vigorous stirring for 10 min, and then potassium thiocyanate (0.0194 g, 0.2 mmol) in aqueous solution (5 ml) was added slowly to the above mixed solution under reflux condition. The reaction mixture was filtered and left to stand at room temperature. Well shaped prismatic colourless single crystals suitable for X-ray analysis were obtained after several days by slow evaporation of the solvent (yield 34%).

S3. Refinement

All H atoms were positioned geometrically, with C—H distances of 0.93 (CH) and 0.97 Å (CH₂), and constrained to ride on their parent atoms [U_iso(H) = 1.2U_eq(C)].

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994); 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: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme, showing two types of eight-membered rings (30% probability displacement ellipsoids for all non-H atoms). Symmetry codes as in Table 1.
	Fig. 2. View of interchain array showing the two-types of π–π stacking interactions in (I).

catena-Poly[[bis[5-(4-pyridyl-κN)-2-(2-pyridylmethylsulfanyl)-1,3,4-oxadiazole]cadmium(II)]-diµ-thiocyanato-κ²N:S;κ²S:N]

Crystal data

[Cd(NCS)2(C13H10N4OS)2]	Z = 2
Mr = 769.18	F(000) = 772
Triclinic, P1	Dx = 1.657 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8868 (13) Å	Cell parameters from 1434 reflections
b = 11.1060 (18) Å	θ = 2.5–28.3°
c = 19.050 (4) Å	µ = 1.03 mm^−1
α = 104.686 (4)°	T = 291 K
β = 93.920 (5)°	Prism, colourless
γ = 105.202 (3)°	0.50 × 0.21 × 0.12 mm
V = 1541.2 (5) Å^3

Data collection

Siemens SMART CCD diffractometer	5756 independent reflections
Radiation source: fine-focus sealed tube	4955 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
ω scans	θmax = 25.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.628, Tmax = 0.887	k = −13→13
11469 measured reflections	l = −23→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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.054	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0215P)^2 + 0.5618P] where P = (Fo^2 + 2Fc^2)/3
5695 reflections	(Δ/σ)max = 0.001
406 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.30 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	0.28131 (2)	0.238922 (14)	0.494519 (8)	0.03671 (6)
S1	0.63962 (8)	−0.16775 (6)	0.02115 (3)	0.04457 (14)
S2	0.14998 (8)	0.69266 (6)	1.00176 (3)	0.04411 (14)
S3	0.05369 (8)	−0.16342 (6)	0.57902 (3)	0.04660 (15)
S4	0.36063 (8)	0.66414 (6)	0.43973 (4)	0.04900 (15)
O1	0.5671 (2)	−0.07891 (14)	0.15504 (8)	0.0401 (4)
O2	0.1917 (2)	0.60210 (14)	0.86397 (8)	0.0396 (3)
N1	0.3880 (2)	0.10997 (17)	0.39976 (9)	0.0385 (4)
N2	0.5591 (3)	−0.23645 (18)	0.20743 (10)	0.0457 (5)
N3	0.6006 (3)	−0.27639 (18)	0.13600 (10)	0.0460 (5)
N4	0.6614 (3)	−0.2659 (2)	−0.12716 (11)	0.0547 (5)
N5	0.2303 (2)	0.37982 (17)	0.60142 (9)	0.0391 (4)
N6	0.1883 (3)	0.75943 (18)	0.81254 (10)	0.0467 (5)
N7	0.1723 (3)	0.80373 (18)	0.88757 (10)	0.0476 (5)
N8	0.1027 (3)	0.77607 (19)	1.14823 (11)	0.0482 (5)
N9	0.2141 (3)	0.07060 (18)	0.54816 (10)	0.0463 (5)
N10	0.3172 (3)	0.40427 (18)	0.43687 (10)	0.0473 (5)
C1	0.4569 (3)	0.1603 (2)	0.34775 (13)	0.0496 (6)
H1	0.4687	0.2476	0.3524	0.059*
C2	0.5112 (3)	0.0899 (2)	0.28772 (13)	0.0479 (6)
H2	0.5584	0.1292	0.2528	0.057*
C3	0.4947 (3)	−0.0399 (2)	0.28003 (11)	0.0357 (5)
C4	0.4280 (3)	−0.0923 (2)	0.33454 (12)	0.0427 (5)
H4	0.4178	−0.1788	0.3318	0.051*
C5	0.3770 (3)	−0.0150 (2)	0.39294 (12)	0.0424 (5)
H5	0.3328	−0.0512	0.4293	0.051*
C6	0.5414 (3)	−0.1218 (2)	0.21601 (11)	0.0368 (5)
C7	0.6034 (3)	−0.1814 (2)	0.10807 (12)	0.0384 (5)
C8	0.6399 (3)	−0.3348 (2)	−0.01680 (13)	0.0493 (6)
H8A	0.7298	−0.3538	0.0124	0.059*
H8B	0.5254	−0.3932	−0.0155	0.059*
C9	0.6775 (3)	−0.3560 (2)	−0.09465 (12)	0.0414 (5)
C10	0.7233 (3)	−0.4657 (2)	−0.12957 (14)	0.0536 (6)
H10	0.7364	−0.5256	−0.1048	0.064*
C11	0.7489 (4)	−0.4846 (3)	−0.20202 (15)	0.0667 (8)
H11	0.7769	−0.5587	−0.2272	0.080*
C12	0.7329 (4)	−0.3936 (3)	−0.23641 (15)	0.0669 (8)
H12	0.7501	−0.4041	−0.2852	0.080*
C13	0.6909 (4)	−0.2863 (3)	−0.19721 (14)	0.0662 (8)
H13	0.6823	−0.2236	−0.2206	0.079*
C14	0.1740 (3)	0.4841 (2)	0.60249 (12)	0.0463 (6)
H14	0.1413	0.4978	0.5580	0.056*
C15	0.1623 (3)	0.5719 (2)	0.66606 (12)	0.0459 (6)
H15	0.1233	0.6434	0.6644	0.055*
C16	0.2097 (3)	0.5517 (2)	0.73299 (11)	0.0357 (5)
C17	0.2673 (3)	0.4439 (2)	0.73271 (12)	0.0399 (5)
H17	0.2996	0.4275	0.7765	0.048*
C18	0.2756 (3)	0.3614 (2)	0.66618 (12)	0.0418 (5)
H18	0.3146	0.2894	0.6663	0.050*
C19	0.1975 (3)	0.6422 (2)	0.80140 (11)	0.0372 (5)
C20	0.1738 (3)	0.7084 (2)	0.91447 (11)	0.0389 (5)
C21	0.1475 (4)	0.8584 (2)	1.04240 (12)	0.0491 (6)
H21A	0.2644	0.9178	1.0457	0.059*
H21B	0.0638	0.8807	1.0119	0.059*
C22	0.0945 (3)	0.8708 (2)	1.11793 (12)	0.0412 (5)
C23	0.0405 (3)	0.9770 (2)	1.15250 (13)	0.0498 (6)
H23	0.0338	1.0400	1.1291	0.060*
C24	−0.0031 (3)	0.9878 (3)	1.22224 (13)	0.0546 (7)
H24	−0.0372	1.0592	1.2471	0.066*
C25	0.0047 (3)	0.8915 (3)	1.25428 (13)	0.0542 (7)
H25	−0.0245	0.8961	1.3012	0.065*
C26	0.0566 (3)	0.7878 (3)	1.21532 (14)	0.0552 (7)
H26	0.0597	0.7221	1.2370	0.066*
C27	0.1457 (3)	−0.0266 (2)	0.55996 (11)	0.0337 (5)
C28	0.3365 (3)	0.5119 (2)	0.43828 (11)	0.0359 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.04687 (10)	0.02825 (9)	0.03274 (9)	0.00628 (7)	0.00983 (7)	0.00831 (6)
S1	0.0550 (4)	0.0423 (3)	0.0390 (3)	0.0150 (3)	0.0140 (3)	0.0130 (3)
S2	0.0556 (4)	0.0455 (3)	0.0360 (3)	0.0197 (3)	0.0120 (3)	0.0132 (3)
S3	0.0468 (3)	0.0389 (3)	0.0555 (4)	0.0063 (3)	0.0001 (3)	0.0238 (3)
S4	0.0499 (4)	0.0337 (3)	0.0625 (4)	0.0110 (3)	0.0040 (3)	0.0143 (3)
O1	0.0466 (9)	0.0400 (8)	0.0388 (8)	0.0171 (7)	0.0130 (7)	0.0135 (7)
O2	0.0500 (9)	0.0383 (8)	0.0346 (8)	0.0180 (7)	0.0119 (7)	0.0107 (7)
N1	0.0411 (11)	0.0363 (10)	0.0363 (10)	0.0092 (8)	0.0075 (8)	0.0086 (8)
N2	0.0592 (13)	0.0458 (11)	0.0394 (11)	0.0232 (10)	0.0135 (9)	0.0148 (9)
N3	0.0586 (13)	0.0443 (11)	0.0410 (11)	0.0227 (10)	0.0148 (9)	0.0123 (9)
N4	0.0714 (15)	0.0547 (13)	0.0437 (12)	0.0235 (11)	0.0118 (10)	0.0174 (10)
N5	0.0452 (11)	0.0391 (10)	0.0350 (10)	0.0131 (9)	0.0092 (8)	0.0120 (8)
N6	0.0681 (14)	0.0397 (11)	0.0382 (11)	0.0214 (10)	0.0161 (10)	0.0132 (9)
N7	0.0688 (14)	0.0428 (11)	0.0371 (10)	0.0245 (10)	0.0157 (10)	0.0111 (9)
N8	0.0525 (12)	0.0531 (12)	0.0460 (12)	0.0224 (10)	0.0147 (10)	0.0169 (10)
N9	0.0463 (12)	0.0417 (11)	0.0474 (11)	0.0025 (9)	0.0008 (9)	0.0186 (9)
N10	0.0596 (13)	0.0342 (11)	0.0425 (11)	0.0013 (9)	0.0056 (9)	0.0138 (9)
C1	0.0627 (16)	0.0336 (12)	0.0535 (15)	0.0112 (11)	0.0234 (12)	0.0132 (11)
C2	0.0576 (15)	0.0408 (13)	0.0498 (14)	0.0123 (11)	0.0248 (12)	0.0182 (11)
C3	0.0311 (11)	0.0398 (12)	0.0368 (11)	0.0116 (9)	0.0056 (9)	0.0105 (10)
C4	0.0558 (15)	0.0383 (12)	0.0404 (13)	0.0193 (11)	0.0093 (11)	0.0156 (10)
C5	0.0550 (15)	0.0405 (13)	0.0358 (12)	0.0161 (11)	0.0097 (11)	0.0146 (10)
C6	0.0353 (12)	0.0407 (12)	0.0369 (12)	0.0123 (10)	0.0055 (9)	0.0140 (10)
C7	0.0369 (12)	0.0391 (12)	0.0381 (12)	0.0120 (10)	0.0081 (10)	0.0072 (10)
C8	0.0620 (16)	0.0429 (13)	0.0476 (14)	0.0180 (12)	0.0159 (12)	0.0158 (11)
C9	0.0381 (13)	0.0395 (12)	0.0420 (13)	0.0081 (10)	0.0063 (10)	0.0068 (10)
C10	0.0562 (16)	0.0428 (14)	0.0556 (16)	0.0130 (12)	0.0062 (12)	0.0052 (12)
C11	0.0673 (19)	0.0601 (18)	0.0564 (17)	0.0156 (15)	0.0129 (14)	−0.0100 (14)
C12	0.0611 (18)	0.080 (2)	0.0378 (14)	0.0021 (15)	0.0067 (13)	−0.0032 (14)
C13	0.080 (2)	0.074 (2)	0.0424 (15)	0.0130 (16)	0.0065 (14)	0.0222 (14)
C14	0.0586 (16)	0.0521 (14)	0.0367 (12)	0.0241 (12)	0.0099 (11)	0.0180 (11)
C15	0.0602 (16)	0.0480 (14)	0.0404 (13)	0.0284 (12)	0.0124 (11)	0.0168 (11)
C16	0.0365 (12)	0.0356 (11)	0.0379 (12)	0.0122 (9)	0.0124 (9)	0.0117 (9)
C17	0.0490 (14)	0.0425 (13)	0.0333 (11)	0.0177 (11)	0.0074 (10)	0.0146 (10)
C18	0.0536 (14)	0.0387 (12)	0.0398 (13)	0.0197 (11)	0.0123 (11)	0.0147 (10)
C19	0.0403 (12)	0.0394 (12)	0.0357 (12)	0.0132 (10)	0.0105 (9)	0.0142 (10)
C20	0.0433 (13)	0.0389 (12)	0.0360 (12)	0.0159 (10)	0.0096 (10)	0.0082 (10)
C21	0.0648 (17)	0.0458 (14)	0.0427 (13)	0.0234 (12)	0.0146 (12)	0.0136 (11)
C22	0.0393 (13)	0.0456 (13)	0.0368 (12)	0.0120 (10)	0.0052 (10)	0.0088 (10)
C23	0.0575 (16)	0.0459 (14)	0.0443 (14)	0.0185 (12)	0.0040 (12)	0.0068 (11)
C24	0.0533 (16)	0.0557 (16)	0.0459 (14)	0.0174 (13)	0.0078 (12)	−0.0032 (12)
C25	0.0468 (15)	0.0722 (18)	0.0390 (13)	0.0136 (13)	0.0107 (11)	0.0100 (13)
C26	0.0578 (16)	0.0673 (17)	0.0498 (15)	0.0212 (14)	0.0150 (13)	0.0278 (13)
C27	0.0329 (11)	0.0389 (12)	0.0289 (11)	0.0115 (10)	0.0031 (9)	0.0079 (9)
C28	0.0364 (12)	0.0399 (13)	0.0279 (11)	0.0038 (10)	0.0063 (9)	0.0106 (9)

Geometric parameters (Å, º)

Cd1—N9	2.3115 (19)	C2—H2	0.9300
Cd1—N10	2.3348 (19)	C3—C4	1.383 (3)
Cd1—N1	2.3550 (17)	C3—C6	1.458 (3)
Cd1—N5	2.3630 (18)	C4—C5	1.377 (3)
Cd1—S3^i	2.7172 (7)	C4—H4	0.9300
Cd1—S4^ii	2.8180 (8)	C5—H5	0.9300
S1—C7	1.736 (2)	C8—C9	1.504 (3)
S1—C8	1.813 (2)	C8—H8A	0.9700
S2—C20	1.733 (2)	C8—H8B	0.9700
S2—C21	1.813 (2)	C9—C10	1.382 (3)
S3—C27	1.644 (2)	C10—C11	1.380 (4)
S3—Cd1^i	2.7172 (7)	C10—H10	0.9300
S4—C28	1.644 (2)	C11—C12	1.363 (4)
S4—Cd1^ii	2.8180 (8)	C11—H11	0.9300
O1—C7	1.366 (2)	C12—C13	1.370 (4)
O1—C6	1.371 (2)	C12—H12	0.9300
O2—C20	1.367 (2)	C13—H13	0.9300
O2—C19	1.373 (2)	C14—C15	1.375 (3)
N1—C1	1.336 (3)	C14—H14	0.9300
N1—C5	1.340 (3)	C15—C16	1.393 (3)
N2—C6	1.287 (3)	C15—H15	0.9300
N2—N3	1.409 (2)	C16—C17	1.386 (3)
N3—C7	1.293 (3)	C16—C19	1.457 (3)
N4—C9	1.330 (3)	C17—C18	1.380 (3)
N4—C13	1.343 (3)	C17—H17	0.9300
N5—C18	1.341 (3)	C18—H18	0.9300
N5—C14	1.341 (3)	C21—C22	1.509 (3)
N6—C19	1.287 (3)	C21—H21A	0.9700
N6—N7	1.415 (2)	C21—H21B	0.9700
N7—C20	1.290 (3)	C22—C23	1.383 (3)
N8—C22	1.335 (3)	C23—C24	1.379 (3)
N8—C26	1.337 (3)	C23—H23	0.9300
N9—C27	1.158 (3)	C24—C25	1.371 (4)
N10—C28	1.158 (3)	C24—H24	0.9300
C1—C2	1.375 (3)	C25—C26	1.379 (3)
C1—H1	0.9300	C25—H25	0.9300
C2—C3	1.382 (3)	C26—H26	0.9300
N9—Cd1—N10	173.99 (7)	H8A—C8—H8B	108.2
N9—Cd1—N1	90.09 (7)	N4—C9—C10	123.0 (2)
N10—Cd1—N1	91.76 (7)	N4—C9—C8	116.7 (2)
N9—Cd1—N5	89.47 (7)	C10—C9—C8	120.3 (2)
N10—Cd1—N5	89.80 (7)	C11—C10—C9	118.5 (3)
N1—Cd1—N5	169.02 (6)	C11—C10—H10	120.7
N9—Cd1—S3^i	91.71 (5)	C9—C10—H10	120.7
N10—Cd1—S3^i	82.45 (5)	C12—C11—C10	119.4 (3)
N1—Cd1—S3^i	93.93 (5)	C12—C11—H11	120.3
N5—Cd1—S3^i	97.05 (5)	C10—C11—H11	120.3
N9—Cd1—S4^ii	94.70 (5)	C11—C12—C13	118.2 (3)
N10—Cd1—S4^ii	91.17 (5)	C11—C12—H12	120.9
N1—Cd1—S4^ii	84.64 (5)	C13—C12—H12	120.9
N5—Cd1—S4^ii	84.46 (5)	N4—C13—C12	124.1 (3)
S3^i—Cd1—S4^ii	173.430 (18)	N4—C13—H13	118.0
C7—S1—C8	95.82 (10)	C12—C13—H13	118.0
C20—S2—C21	96.03 (10)	N5—C14—C15	123.3 (2)
C27—S3—Cd1^i	102.98 (8)	N5—C14—H14	118.3
C28—S4—Cd1^ii	96.46 (8)	C15—C14—H14	118.3
C7—O1—C6	101.94 (16)	C14—C15—C16	118.7 (2)
C20—O2—C19	102.03 (16)	C14—C15—H15	120.6
C1—N1—C5	117.10 (19)	C16—C15—H15	120.6
C1—N1—Cd1	119.43 (15)	C17—C16—C15	118.56 (19)
C5—N1—Cd1	123.41 (14)	C17—C16—C19	121.25 (19)
C6—N2—N3	106.57 (17)	C15—C16—C19	120.19 (19)
C7—N3—N2	105.71 (17)	C18—C17—C16	118.6 (2)
C9—N4—C13	116.8 (2)	C18—C17—H17	120.7
C18—N5—C14	117.37 (19)	C16—C17—H17	120.7
C18—N5—Cd1	117.87 (14)	N5—C18—C17	123.4 (2)
C14—N5—Cd1	124.47 (14)	N5—C18—H18	118.3
C19—N6—N7	106.45 (17)	C17—C18—H18	118.3
C20—N7—N6	105.78 (17)	N6—C19—O2	112.60 (18)
C22—N8—C26	116.8 (2)	N6—C19—C16	128.50 (19)
C27—N9—Cd1	162.39 (17)	O2—C19—C16	118.88 (18)
C28—N10—Cd1	151.60 (17)	N7—C20—O2	113.12 (18)
N1—C1—C2	123.5 (2)	N7—C20—S2	130.68 (17)
N1—C1—H1	118.2	O2—C20—S2	116.17 (15)
C2—C1—H1	118.2	C22—C21—S2	109.31 (16)
C1—C2—C3	119.0 (2)	C22—C21—H21A	109.8
C1—C2—H2	120.5	S2—C21—H21A	109.8
C3—C2—H2	120.5	C22—C21—H21B	109.8
C2—C3—C4	118.0 (2)	S2—C21—H21B	109.8
C2—C3—C6	121.88 (19)	H21A—C21—H21B	108.3
C4—C3—C6	120.07 (19)	N8—C22—C23	123.1 (2)
C5—C4—C3	119.3 (2)	N8—C22—C21	117.0 (2)
C5—C4—H4	120.4	C23—C22—C21	119.9 (2)
C3—C4—H4	120.4	C24—C23—C22	118.8 (2)
N1—C5—C4	123.0 (2)	C24—C23—H23	120.6
N1—C5—H5	118.5	C22—C23—H23	120.6
C4—C5—H5	118.5	C25—C24—C23	118.9 (2)
N2—C6—O1	112.66 (18)	C25—C24—H24	120.5
N2—C6—C3	127.78 (19)	C23—C24—H24	120.5
O1—C6—C3	119.53 (18)	C24—C25—C26	118.4 (2)
N3—C7—O1	113.12 (19)	C24—C25—H25	120.8
N3—C7—S1	130.00 (17)	C26—C25—H25	120.8
O1—C7—S1	116.85 (16)	N8—C26—C25	123.9 (2)
C9—C8—S1	109.86 (16)	N8—C26—H26	118.1
C9—C8—H8A	109.7	C25—C26—H26	118.1
S1—C8—H8A	109.7	N9—C27—S3	178.1 (2)
C9—C8—H8B	109.7	N10—C28—S4	179.1 (2)
S1—C8—H8B	109.7
N9—Cd1—N1—C1	−177.81 (18)	C6—O1—C7—N3	0.1 (2)
N10—Cd1—N1—C1	7.92 (18)	C6—O1—C7—S1	178.42 (15)
N5—Cd1—N1—C1	−90.1 (4)	C8—S1—C7—N3	7.3 (2)
S3^i—Cd1—N1—C1	90.47 (17)	C8—S1—C7—O1	−170.74 (17)
S4^ii—Cd1—N1—C1	−83.10 (17)	C7—S1—C8—C9	−177.55 (18)
N9—Cd1—N1—C5	5.12 (18)	C13—N4—C9—C10	0.4 (4)
N10—Cd1—N1—C5	−169.16 (18)	C13—N4—C9—C8	−178.5 (2)
N5—Cd1—N1—C5	92.8 (3)	S1—C8—C9—N4	−15.5 (3)
S3^i—Cd1—N1—C5	−86.60 (17)	S1—C8—C9—C10	165.63 (19)
S4^ii—Cd1—N1—C5	99.83 (17)	N4—C9—C10—C11	−1.7 (4)
C6—N2—N3—C7	−0.2 (2)	C8—C9—C10—C11	177.1 (2)
N9—Cd1—N5—C18	34.99 (17)	C9—C10—C11—C12	1.6 (4)
N10—Cd1—N5—C18	−150.97 (17)	C10—C11—C12—C13	−0.2 (4)
N1—Cd1—N5—C18	−52.8 (4)	C9—N4—C13—C12	1.1 (4)
S3^i—Cd1—N5—C18	126.66 (16)	C11—C12—C13—N4	−1.2 (5)
S4^ii—Cd1—N5—C18	−59.77 (16)	C18—N5—C14—C15	0.5 (3)
N9—Cd1—N5—C14	−151.28 (19)	Cd1—N5—C14—C15	−173.29 (18)
N10—Cd1—N5—C14	22.75 (19)	N5—C14—C15—C16	−0.5 (4)
N1—Cd1—N5—C14	121.0 (3)	C14—C15—C16—C17	0.1 (3)
S3^i—Cd1—N5—C14	−59.62 (18)	C14—C15—C16—C19	−179.5 (2)
S4^ii—Cd1—N5—C14	113.95 (18)	C15—C16—C17—C18	0.2 (3)
C19—N6—N7—C20	0.1 (3)	C19—C16—C17—C18	179.8 (2)
N1—Cd1—N9—C27	−73.5 (6)	C14—N5—C18—C17	−0.1 (3)
N5—Cd1—N9—C27	117.5 (6)	Cd1—N5—C18—C17	174.04 (18)
S3^i—Cd1—N9—C27	20.4 (6)	C16—C17—C18—N5	−0.2 (4)
S4^ii—Cd1—N9—C27	−158.1 (6)	N7—N6—C19—O2	−1.0 (3)
N1—Cd1—N10—C28	−156.8 (4)	N7—N6—C19—C16	178.0 (2)
N5—Cd1—N10—C28	12.3 (4)	C20—O2—C19—N6	1.3 (2)
S3^i—Cd1—N10—C28	109.4 (4)	C20—O2—C19—C16	−177.73 (19)
S4^ii—Cd1—N10—C28	−72.2 (4)	C17—C16—C19—N6	161.9 (2)
C5—N1—C1—C2	1.8 (4)	C15—C16—C19—N6	−18.5 (4)
Cd1—N1—C1—C2	−175.4 (2)	C17—C16—C19—O2	−19.2 (3)
N1—C1—C2—C3	0.0 (4)	C15—C16—C19—O2	160.4 (2)
C1—C2—C3—C4	−1.7 (4)	N6—N7—C20—O2	0.8 (3)
C1—C2—C3—C6	176.9 (2)	N6—N7—C20—S2	−176.95 (18)
C2—C3—C4—C5	1.6 (3)	C19—O2—C20—N7	−1.3 (2)
C6—C3—C4—C5	−177.0 (2)	C19—O2—C20—S2	176.79 (15)
C1—N1—C5—C4	−1.9 (3)	C21—S2—C20—N7	−5.8 (3)
Cd1—N1—C5—C4	175.20 (17)	C21—S2—C20—O2	176.55 (17)
C3—C4—C5—N1	0.3 (4)	C20—S2—C21—C22	169.84 (17)
N3—N2—C6—O1	0.2 (3)	C26—N8—C22—C23	−0.3 (4)
N3—N2—C6—C3	178.5 (2)	C26—N8—C22—C21	179.6 (2)
C7—O1—C6—N2	−0.2 (2)	S2—C21—C22—N8	16.0 (3)
C7—O1—C6—C3	−178.63 (19)	S2—C21—C22—C23	−163.99 (19)
C2—C3—C6—N2	168.0 (2)	N8—C22—C23—C24	1.5 (4)
C4—C3—C6—N2	−13.4 (4)	C21—C22—C23—C24	−178.4 (2)
C2—C3—C6—O1	−13.8 (3)	C22—C23—C24—C25	−1.4 (4)
C4—C3—C6—O1	164.8 (2)	C23—C24—C25—C26	0.2 (4)
N2—N3—C7—O1	0.1 (3)	C22—N8—C26—C25	−1.0 (4)
N2—N3—C7—S1	−178.03 (17)	C24—C25—C26—N8	1.0 (4)

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