Di-μ₂-sulfito-κ⁸O,O′:O′,O′′-bis[(2,4,6-tri-2-pyrid­yl-1,3,5-triazine-κ³N²,N¹,N⁶)cadmium(II)] octa­hydrate

The title compound, [Cd₂(SO₃)₂(C₁₈H₁₂N₆)₂]·8H₂O, is a dimer built up around a symmetry center, where the sulfite anion displays a so far unreported coordination mode in metal-organic complexes; the anion binds as a μ₂-sulfite-κ⁴O,O′:O′,O′′ ligand to two symmetry-related seven-coordinate Cd^II cations, binding through its three O atoms by way of two chelate bites with an O atom in common, which acts as a bridge. The cation coordination is completed by a 2,4,6-tri-2-pyridyl-1,3,5-triazine ligand acting in its usual tridentate mode.

S1. Comment

The sulfite anion has proved to be a very versatile ligand, both in sulfite salts, where it displays an amazingly complex diversity of coordination modes, and in coordination compounds with organic ligands, where the variety is not so ample but still important. A search of the November 2005 release of the Cambridge Structural Database (CSD; Allen, 2002) shows eight different coordination modes for the anion, presented in the first scheme below. When attached to a single cation the ligand appears to bind through S in a µ-κS mode (Type 1), through one O atom (Type 2) or through two O atoms in a µ-κ² O,O' mode (Type 3). When two different cationic sites are involved, the anion binds in three alternative modes, viz. via its S and one O atom, as µ₂-κ² S:O (Type 4), through two O atoms, as µ₂-κ²O:O' (Type 5), or with its three O atoms, in a µ₂-κ³O,O':O" mode (Type 6). Finally, when binding to three cations, it always does so via its three O atoms, either as a µ₃-κ² O:O':O' mode (Type 7) or a µ₃-κ³O:O':O" mode (Type 8). Type 1 compounds are the most common (29 entries in the CSD, mostly Co^III complexes). The geometry of the sulfite unit in this type of coordination is quite regular, with all angles around 110° and S—O distances not significantly different [mean value 1.467 (2) Å] except in the case when the O atom is involved in hydorgen bonds, which seems to lengthen the S—O bonds [mean value 1.474 (6) Å; CSD refcodes STEDCOI10, VEBJAN, VEBJER, VEBJIV and XUFVEZ). The mean S—O bond length is considerably shorter than those in ionic sulfite salts [1.529 (7) Å (Battelle & Trueblood, 1965) and 1.536 (7) Å (Baggio & Becka, 1969)]. In other cases when O atoms are involved in coordination, S—O bonds show a characteristic lengthening for S—O_coord as compared with S—O_non-coord ones. This effect can be seen in the following cases, referred to by their CSD reference codes (mean distances are mentioned as S—O_coord/S—O_non-coord): BERXUR [Type 2, 1.591 (1)/1.504 (1) Å]; AVAZAY, FIFBAX, KIRBOC and YAPMOR [Type 3, 1.545 (17)/1.364 (16) Å]; FEYNUS, KAJCON, LAMBIK, LOQCAV, SOQXUR, YIQFOT and YIQFUZ [Type 4, 1.519 (2)/1.460 (3) Å]; and ALELUY, KAVJIA and ZETXEB [Type 5, 1.548 (3)/1.489 (1) Å]. Angles are quite regular, all around the expected tetrahedral values, except in the case of the constraints introduced by chelation, leading to angles as small as 90° (FIFBAX and YAPMOR) or 98° (IHIWOL and GAKTES, Type 6). There are only two entries showing an O atom acting as a bridge between two metal centres (Type 7, GAKTIW and HOFCEK). In these cases, the S—O_bridge bond length [mean value 1.563 (1) Å] is considerably longer than the other S—O bonds [S—O_non-coord = 1.507 (2) Å and S—O_coord = 1.521 (1) Å].

The title complex, (I), is a dimer built up around a symmetry center (Fig. 1), with two symmetry-related seven-coordinate Cd^II cations bound to a tridentate 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tpt) ligand and a sulfite anion acting in a so far unreported (in metallorganic compounds) µ₂-κ³O,O':O',O" mode (Type 9 in scheme above, and Fig. 2). Both chelating O—S—O angles are almost equal within the determined s.u. values [102.60 (12) and 102.16 (12)°], while the remaining one is larger [106.54 (12)°]. However, the chelates are not completely symmetrical, their S—O distances differing by some 1.5%.

Coordination around the Cd^II centres generates a dimeric centrosymmetric structure where both monomers are doubly linked via the Cd1—O2—S1—O1—Cd1ⁱ and Cd1—O3—Cd1ⁱ loops (see Fig. 2 for symmetry codes). The general disposition of the dimer resembles that of an Mn(tpt) complex that we have recently reported {viz. [Mn₂(C₁₆H₁₂N₆)₂(SO₄)2(H₂O)₂]·4H₂O; Diaz de Vivar et al., 2006}, where a sulfate group played the role of the actual sulfite. The two structures both have dimeric character and share many other coordination features. The main difference resides in the central O atom, which in the present structure bridges to two symmetry-related cations, while in the sulfate analogue it `breaks' one of these bonds, the O atom leaning towards the remaining cation. The vacant site left in the sevenfold Mn coordination polyhedron is occupied by one aqua molecule.

The organic ligand coordinates via three N-atom donors (N1 and N3 from two pyridine rings and N2 from the triazine ring), leaving the third pyridyl group uncoordinated and rotated by 4.6 (2)° to the central core mean plane. The latter is not strictly planar, the deformation being mainly due to the misalignment of the individual pyridyl and triazine components [the range of interplanar angles is 0.2 (2)–10.4 (2)°]. The coordination mode displayed by tpt is its most common one; a search of the CSD showed that 89% of the reported complexes containing the ligand adopt this tridentated bite to the cation.

Only four structures with tpt coordinating to group 12 metals appear in the CSD, viz. two with Zn^II (EYIMUU and PAHTEY), one with Cd^II (GADLON) and one with Hg^II (BEJFUR). As in all other reported group 12 t pt complexes, the central metal–N distance [2.353 (2) Å] is shorter than the lateral ones [the mean is 2.434 (20) Å], owing to chelation constraints and the rigid character of the ligand.

The elongated dimer presents a prolate profile with principal axes of very different lengths, viz. 23.9 (1), 11.2 (1) and 4.8 (1) Å, and dimers stack along their shortest direction, in the form of columns oriented parallel to [100] (in heavy lines in Fig. 3). The link between succesive units in the column is the water molecule O3W, through the two hydrogen bonds in which it takes part (entries 1 and 2 in Table 2, and Fig 3). These chains, in turn, interact laterally with neighbouring chains through two different mechanisms, viz. a very long hydrogen-bonding chain [8.54 (2) Å between extreme O2 and O2^iv acceptors] involving all four water molecules and their symmetry related counterparts (entries 3 to 7 in Table 2, and Fig 3), and a Cg···Cg interaction between pyridyl groups of the interdigitated tpt ligands (Table 3). The result is a broad two-dimensional structure expanding parallel to the (010) plane. The interaction between these planes is achieved mainly through the strong interaction involving O1W and N6 (entry 8 in Table 2); these are directed straight out of the paper and are therefore not represented in Fig. 3.

S2. Experimental

2,4,6-Tris(2-pyridyl)-1,3,5-triazine and Cd acetate were dissolved in 95% ethanol and left to diffuse over an aqueous solution of potassium pyrosulfite. The Metal–tpt–K₂S₂O₅ molar ratio was 1:1:2. After five months, irregular colorless crystals suitable for X-ray analysis were obtained.

S3. Refinement

Hydrogen atoms attached to carbon were included at their calculated positions with d(C—H), 0.93 Å and allowed to ride both in position as in their CH Isotropic displacement parameters (U_isot(H) = 1.2*U_eq(C)). Those attached to water molecules were found in the difference Fourier synthesis and refined with restrained O—H:0.82 (1) Å, H···H:1.30 (2) Å, but free U_isot(H).

Computing details

Data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 2000); data reduction: SAINT-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT (Sheldrick, 2000); software used to prepare material for publication: SHELXTL-NT and PLATON (Spek, 2005).

Figures

	Fig. 1. : An ellipsoid plot for the dimeric unit and its environment. Full displacement ellipsoids (for the independent moiety) and open ones (for the symmetry-related part) are drawn at the 30% probability level. [Symmetry codes as in Tables 1 and 2.]
	Fig. 2. : The centrosymmetric cage built up by the sulfite anion around the cadmium centers. [Symmetry code as in Table 1.]
	Fig. 3. : A view of the packing, showing the different hydrogen-bonded columnar units evolving vertically along [100]. The central column is presented in heavy lines, in order to distinguish it from its neighbours. Hydrogen bonds are shown as broken lines. The planar array, presented here in a slightly slanted fashion for clarity, evolves parallel to (010).

Di-µ₂-sulfito-κ⁴O,O':κ⁴O',O''-[2,4,6-tris(2-pyridyl)- 1,3,5-triazine-κ³N²,N¹,N⁶]cadmium(II) octahydrate

Crystal data

[Cd2(SO3)2(C18H12N6)2]·8H2O	V = 1085.0 (3) Å^3
Mr = 1153.72	Z = 1
Triclinic, P1	F(000) = 580
Hall symbol: -P 1	Dx = 1.766 Mg m^−3
a = 8.5826 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.5117 (14) Å	µ = 1.16 mm^−1
c = 13.1078 (17) Å	T = 295 K
α = 103.902 (2)°	Blocks, colorless
β = 107.988 (2)°	0.26 × 0.18 × 0.12 mm
γ = 91.639 (2)°

Data collection

Bruker SMART CCD area-detector diffractometer	4665 independent reflections
Radiation source: fine-focus sealed tube	4289 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ϕ and ω scans	θmax = 28.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −11→11
Tmin = 0.74, Tmax = 0.88	k = −13→13
9107 measured reflections	l = −16→17

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 0.84	w = 1/[σ^2(Fo^2) + (0.0703P)^2 + 0.6306P] where P = (Fo^2 + 2Fc^2)/3
4665 reflections	(Δ/σ)max = 0.002
331 parameters	Δρmax = 1.13 e Å^−3
12 restraints	Δρmin = −0.38 e Å^−3

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

	x	y	z	Uiso*/Ueq
Cd1	0.51459 (2)	0.596554 (17)	0.641740 (14)	0.03450 (8)
S1	0.69658 (9)	0.36093 (7)	0.57426 (5)	0.03723 (15)
O1	0.7434 (3)	0.3759 (2)	0.47503 (17)	0.0477 (5)
O2	0.7513 (2)	0.4936 (2)	0.66154 (16)	0.0440 (5)
O3	0.5088 (2)	0.3598 (2)	0.53321 (16)	0.0432 (4)
N1	0.6839 (3)	0.8109 (2)	0.71068 (18)	0.0369 (5)
N2	0.5413 (3)	0.7031 (2)	0.82694 (17)	0.0347 (5)
N3	0.3430 (3)	0.4824 (2)	0.71436 (18)	0.0362 (5)
N4	0.4820 (3)	0.7009 (2)	0.98974 (18)	0.0371 (5)
N5	0.6551 (3)	0.8803 (2)	0.98680 (19)	0.0384 (5)
N6	0.6872 (3)	0.9952 (3)	1.2021 (2)	0.0464 (6)
C1	0.7557 (4)	0.8613 (3)	0.6501 (2)	0.0429 (6)
H1B	0.7319	0.8178	0.5755	0.051*
C2	0.8636 (4)	0.9750 (3)	0.6936 (3)	0.0499 (7)
H2A	0.9113	1.0072	0.6487	0.060*
C3	0.9001 (4)	1.0403 (3)	0.8032 (3)	0.0520 (8)
H3A	0.9747	1.1161	0.8342	0.062*
C4	0.8243 (4)	0.9918 (3)	0.8671 (2)	0.0437 (6)
H4B	0.8440	1.0357	0.9413	0.052*
C5	0.7187 (3)	0.8768 (3)	0.8181 (2)	0.0348 (5)
C6	0.6347 (3)	0.8171 (3)	0.8818 (2)	0.0339 (5)
C7	0.5751 (3)	0.8164 (3)	1.0366 (2)	0.0350 (5)
C8	0.4653 (3)	0.6493 (3)	0.8837 (2)	0.0338 (5)
C9	0.3518 (3)	0.5281 (3)	0.8207 (2)	0.0338 (5)
C10	0.2536 (4)	0.4707 (3)	0.8676 (3)	0.0433 (6)
H10A	0.2650	0.5020	0.9424	0.052*
C11	0.1387 (4)	0.3657 (3)	0.8002 (3)	0.0491 (7)
H11A	0.0700	0.3256	0.8288	0.059*
C12	0.1266 (4)	0.3211 (3)	0.6902 (3)	0.0473 (7)
H12A	0.0486	0.2513	0.6433	0.057*
C13	0.2316 (4)	0.3812 (3)	0.6505 (2)	0.0428 (6)
H13A	0.2244	0.3497	0.5764	0.051*
C14	0.5919 (3)	0.8798 (3)	1.1547 (2)	0.0363 (6)
C15	0.5113 (4)	0.8197 (3)	1.2102 (2)	0.0443 (6)
H15A	0.4450	0.7400	1.1744	0.053*
C16	0.5315 (4)	0.8808 (3)	1.3198 (3)	0.0501 (7)
H16A	0.4796	0.8424	1.3594	0.060*
C17	0.6287 (4)	0.9984 (3)	1.3695 (2)	0.0511 (8)
H17A	0.6446	1.0412	1.4434	0.061*
C18	0.7029 (5)	1.0524 (3)	1.3075 (3)	0.0536 (8)
H18A	0.7675	1.1332	1.3413	0.064*
O1W	1.1519 (4)	0.7983 (3)	0.8610 (2)	0.0656 (7)
H1WA	1.108 (5)	0.754 (3)	0.7968 (14)	0.066 (13)*
H1WB	1.195 (5)	0.870 (2)	0.863 (3)	0.076 (14)*
O2W	0.7897 (4)	0.4772 (3)	0.8799 (2)	0.0662 (7)
H2WA	0.859 (6)	0.541 (4)	0.912 (3)	0.13 (2)*
H2WB	0.773 (5)	0.458 (4)	0.8130 (10)	0.082 (14)*
O3W	1.0118 (3)	0.6592 (3)	0.6336 (3)	0.0638 (6)
H3WA	0.950 (5)	0.603 (3)	0.641 (4)	0.097 (18)*
H3WB	1.065 (5)	0.625 (4)	0.594 (3)	0.077 (14)*
O4W	1.0274 (4)	0.6911 (3)	1.0013 (2)	0.0685 (7)
H4WA	1.065 (4)	0.715 (4)	0.958 (3)	0.062 (12)*
H4WB	1.094 (5)	0.654 (7)	1.040 (5)	0.16 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.04067 (13)	0.03593 (12)	0.02733 (12)	−0.00239 (8)	0.01467 (8)	0.00512 (8)
S1	0.0434 (4)	0.0376 (3)	0.0325 (3)	0.0032 (3)	0.0139 (3)	0.0105 (3)
O1	0.0474 (11)	0.0636 (13)	0.0390 (10)	0.0083 (10)	0.0236 (9)	0.0135 (10)
O2	0.0437 (11)	0.0468 (11)	0.0343 (10)	−0.0007 (9)	0.0089 (8)	0.0029 (8)
O3	0.0408 (10)	0.0505 (11)	0.0384 (10)	−0.0059 (9)	0.0147 (8)	0.0106 (9)
N1	0.0435 (12)	0.0362 (11)	0.0332 (11)	0.0001 (9)	0.0170 (10)	0.0073 (9)
N2	0.0424 (12)	0.0332 (11)	0.0301 (11)	−0.0010 (9)	0.0161 (9)	0.0061 (9)
N3	0.0411 (12)	0.0372 (11)	0.0317 (11)	−0.0004 (9)	0.0147 (9)	0.0081 (9)
N4	0.0445 (12)	0.0375 (11)	0.0313 (11)	0.0008 (10)	0.0156 (10)	0.0084 (9)
N5	0.0459 (13)	0.0358 (11)	0.0330 (11)	−0.0018 (10)	0.0162 (10)	0.0048 (9)
N6	0.0580 (15)	0.0458 (13)	0.0333 (12)	−0.0039 (12)	0.0187 (11)	0.0027 (10)
C1	0.0519 (16)	0.0437 (15)	0.0374 (14)	−0.0006 (13)	0.0229 (13)	0.0081 (12)
C2	0.0607 (19)	0.0467 (16)	0.0522 (17)	−0.0035 (14)	0.0317 (15)	0.0150 (14)
C3	0.0588 (19)	0.0415 (15)	0.0556 (18)	−0.0137 (14)	0.0242 (15)	0.0077 (14)
C4	0.0515 (17)	0.0380 (14)	0.0388 (15)	−0.0049 (12)	0.0182 (13)	0.0016 (12)
C5	0.0380 (13)	0.0333 (12)	0.0349 (13)	0.0014 (10)	0.0155 (11)	0.0076 (10)
C6	0.0373 (13)	0.0349 (12)	0.0289 (12)	0.0031 (10)	0.0115 (10)	0.0066 (10)
C7	0.0398 (14)	0.0372 (13)	0.0290 (12)	0.0058 (11)	0.0120 (10)	0.0091 (10)
C8	0.0382 (13)	0.0344 (12)	0.0313 (12)	0.0038 (10)	0.0145 (11)	0.0093 (10)
C9	0.0389 (13)	0.0328 (12)	0.0332 (12)	0.0034 (10)	0.0163 (11)	0.0094 (10)
C10	0.0536 (17)	0.0418 (14)	0.0434 (15)	0.0009 (13)	0.0277 (13)	0.0124 (12)
C11	0.0532 (17)	0.0414 (15)	0.0618 (19)	−0.0016 (13)	0.0325 (15)	0.0133 (14)
C12	0.0429 (15)	0.0399 (14)	0.0550 (18)	−0.0036 (12)	0.0157 (14)	0.0060 (13)
C13	0.0477 (16)	0.0398 (14)	0.0371 (14)	−0.0033 (12)	0.0131 (12)	0.0048 (11)
C14	0.0417 (14)	0.0387 (13)	0.0296 (12)	0.0072 (11)	0.0139 (11)	0.0074 (11)
C15	0.0545 (17)	0.0434 (15)	0.0387 (14)	0.0026 (13)	0.0209 (13)	0.0104 (12)
C16	0.067 (2)	0.0521 (17)	0.0407 (16)	0.0077 (15)	0.0285 (15)	0.0148 (13)
C17	0.072 (2)	0.0526 (17)	0.0322 (14)	0.0117 (16)	0.0242 (14)	0.0081 (13)
C18	0.068 (2)	0.0468 (17)	0.0394 (16)	−0.0073 (15)	0.0189 (15)	−0.0018 (13)
O1W	0.0848 (19)	0.0587 (15)	0.0609 (17)	0.0043 (14)	0.0258 (15)	0.0276 (13)
O2W	0.0746 (18)	0.085 (2)	0.0417 (13)	−0.0008 (15)	0.0244 (13)	0.0165 (13)
O3W	0.0599 (15)	0.0549 (14)	0.0780 (18)	−0.0028 (12)	0.0353 (14)	0.0043 (13)
O4W	0.099 (2)	0.0547 (15)	0.0590 (16)	0.0002 (14)	0.0379 (16)	0.0132 (13)

Geometric parameters (Å, º)

Cd1—O1^i	2.342 (2)	C4—H4B	0.9300
Cd1—O2	2.302 (2)	C5—C6	1.486 (4)
Cd1—O3	2.543 (2)	C7—C14	1.491 (4)
Cd1—O3^i	2.395 (2)	C8—C9	1.477 (4)
Cd1—N1	2.455 (2)	C9—C10	1.386 (4)
Cd1—N2	2.353 (2)	C10—C11	1.379 (4)
Cd1—N3	2.414 (2)	C10—H10A	0.9300
S1—O1	1.515 (2)	C11—C12	1.374 (5)
S1—O2	1.529 (2)	C11—H11A	0.9300
S1—O3	1.532 (2)	C12—C13	1.378 (4)
N1—C1	1.332 (4)	C12—H12A	0.9300
N1—C5	1.346 (3)	C13—H13A	0.9300
N2—C6	1.331 (3)	C14—C15	1.383 (4)
N2—C8	1.334 (3)	C15—C16	1.379 (4)
N3—C13	1.329 (4)	C15—H15A	0.9300
N3—C9	1.338 (3)	C16—C17	1.366 (5)
N4—C8	1.325 (3)	C16—H16A	0.9300
N4—C7	1.331 (4)	C17—C18	1.382 (5)
N5—C6	1.331 (3)	C17—H17A	0.9300
N5—C7	1.345 (4)	C18—H18A	0.9300
N6—C18	1.330 (4)	O1W—H1WA	0.82 (2)
N6—C14	1.339 (4)	O1W—H1WB	0.82 (3)
C1—C2	1.377 (4)	O2W—H2WA	0.82 (5)
C1—H1B	0.9300	O2W—H2WB	0.82 (2)
C2—C3	1.367 (5)	O3W—H3WA	0.83 (4)
C2—H2A	0.9300	O3W—H3WB	0.82 (4)
C3—C4	1.381 (4)	O4W—H4WA	0.81 (4)
C3—H3A	0.9300	O4W—H4WB	0.82 (5)
C4—C5	1.379 (4)
O2—Cd1—O1^i	148.00 (7)	C3—C2—H2A	120.3
O2—Cd1—N2	102.30 (7)	C1—C2—H2A	120.3
O1^i—Cd1—N2	109.26 (8)	C2—C3—C4	118.9 (3)
O2—Cd1—O3^i	97.32 (7)	C2—C3—H3A	120.5
O1^i—Cd1—O3^i	60.25 (7)	C4—C3—H3A	120.5
N2—Cd1—O3^i	141.88 (7)	C5—C4—C3	118.3 (3)
O2—Cd1—N3	106.51 (8)	C5—C4—H4B	120.9
O1^i—Cd1—N3	81.46 (7)	C3—C4—H4B	120.9
N2—Cd1—N3	67.59 (7)	N1—C5—C4	123.2 (2)
O3^i—Cd1—N3	136.23 (7)	N1—C5—C6	115.3 (2)
O2—Cd1—N1	89.26 (7)	C4—C5—C6	121.5 (2)
O1^i—Cd1—N1	107.68 (8)	N5—C6—N2	124.9 (2)
N2—Cd1—N1	66.77 (7)	N5—C6—C5	119.0 (2)
O3^i—Cd1—N1	81.29 (7)	N2—C6—C5	116.1 (2)
N3—Cd1—N1	133.89 (7)	N4—C7—N5	125.8 (2)
O2—Cd1—O3	58.63 (7)	N4—C7—C14	116.8 (2)
O1^i—Cd1—O3	93.89 (7)	N5—C7—C14	117.4 (2)
N2—Cd1—O3	135.42 (7)	N4—C8—N2	123.9 (2)
O3^i—Cd1—O3	82.66 (7)	N4—C8—C9	119.8 (2)
N3—Cd1—O3	79.44 (7)	N2—C8—C9	116.3 (2)
N1—Cd1—O3	141.63 (7)	N3—C9—C10	122.5 (3)
O2—Cd1—S1^i	123.66 (5)	N3—C9—C8	115.8 (2)
O1^i—Cd1—S1^i	29.88 (5)	C10—C9—C8	121.6 (2)
N2—Cd1—S1^i	131.50 (6)	C11—C10—C9	118.2 (3)
O3^i—Cd1—S1^i	30.48 (5)	C11—C10—H10A	120.9
N3—Cd1—S1^i	108.36 (6)	C9—C10—H10A	120.9
N1—Cd1—S1^i	96.83 (6)	C12—C11—C10	119.3 (3)
O3—Cd1—S1^i	86.26 (5)	C12—C11—H11A	120.3
O1—S1—O2	106.54 (12)	C10—C11—H11A	120.3
O1—S1—O3	102.60 (12)	C11—C12—C13	119.0 (3)
O2—S1—O3	102.16 (12)	C11—C12—H12A	120.5
O1—S1—Cd1^i	50.36 (8)	C13—C12—H12A	120.5
O2—S1—Cd1^i	109.41 (8)	N3—C13—C12	122.4 (3)
O3—S1—Cd1^i	52.46 (8)	N3—C13—H13A	118.8
S1—O1—Cd1^i	99.76 (10)	C12—C13—H13A	118.8
S1—O2—Cd1	104.31 (10)	N6—C14—C15	123.0 (3)
S1—O3—Cd1^i	97.06 (9)	N6—C14—C7	116.7 (2)
S1—O3—Cd1	94.14 (9)	C15—C14—C7	120.2 (3)
Cd1^i—O3—Cd1	97.34 (7)	C16—C15—C14	118.4 (3)
C1—N1—C5	117.4 (2)	C16—C15—H15A	120.8
C1—N1—Cd1	123.55 (18)	C14—C15—H15A	120.8
C5—N1—Cd1	118.77 (17)	C17—C16—C15	119.3 (3)
C6—N2—C8	116.3 (2)	C17—C16—H16A	120.4
C6—N2—Cd1	122.73 (17)	C15—C16—H16A	120.4
C8—N2—Cd1	120.96 (17)	C16—C17—C18	118.5 (3)
C13—N3—C9	118.6 (2)	C16—C17—H17A	120.7
C13—N3—Cd1	122.27 (18)	C18—C17—H17A	120.7
C9—N3—Cd1	119.00 (17)	N6—C18—C17	123.6 (3)
C8—N4—C7	115.3 (2)	N6—C18—H18A	118.2
C6—N5—C7	113.8 (2)	C17—C18—H18A	118.2
C18—N6—C14	117.2 (3)	H1WA—O1W—H1WB	111 (4)
N1—C1—C2	122.7 (3)	H2WA—O2W—H2WB	111 (4)
N1—C1—H1B	118.6	H3WA—O3W—H3WB	110 (4)
C2—C1—H1B	118.6	H4WA—O4W—H4WB	111 (4)
C3—C2—C1	119.5 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O3W	0.82 (2)	2.02 (2)	2.838 (4)	174 (3)
O1W—H1WB···N6^ii	0.82 (3)	2.19 (3)	2.950 (4)	154 (4)
O2W—H2WA···O4W	0.82 (5)	1.97 (4)	2.785 (4)	175 (5)
O2W—H2WB···O2	0.82 (2)	2.06 (2)	2.827 (3)	156 (4)
O3W—H3WA···O2	0.83 (4)	2.15 (4)	2.958 (3)	166 (4)
O3W—H3WB···O1^iii	0.82 (4)	2.11 (4)	2.867 (3)	154 (4)
O4W—H4WA···O1W	0.82 (4)	2.01 (4)	2.817 (4)	173 (4)
O4W—H4WB···O2W^iv	0.82 (5)	2.03 (5)	2.827 (5)	165 (7)

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