Inter­actions of thia­mine with polymeric halogenocadmate anions in the organic–inorganic hybrid compound (thia­minium)[Cd₃Br_4.4Cl_3.6]

The structure of poly[3-[(4-amino-2-methylpyrimidin-1-ium-5-yl)meth­yl]-5-(2-hydroxy­ethyl)-4-methyl­thia­zolium octa-μ-bromo/chloro­(4.4/3.6)-tricadmate(II)], {(C₁₂H₁₈N₄OS)[Cd₃ Br_4.41Cl_3.59]}_n consists of hydrogen-bonded thia­mine mol­ecules and polymeric cadmium bromide/chloride anions in an organic–inorganic hybrid fashion. The one-dimensional anion ribbons are formed by edge-sharing octa­hedra and vertex-sharing tetra­hedra. Thia­mine mol­ecules adopting the S conformation are linked to anions via three types of inter­actions, namely an N(amino)—H...anion...thia­zolium bridging inter­action, an N(pyrimidine)—H...anion hydrogen bond and an O(hydr­oxy)—H...anion hydrogen bond.

S1. Comment

Interest in the interactions of thiamine (vitamin B₁) with anions has been prompted by their relevance to biologically catalytic processes because the enzymatic action of the coenzyme, thiamine pyrophosphate, involves a direct reaction of a substrate anion such as pyruvate at the C2 site of the thiazolium moiety (Breslow, 1958; Krampitz, 1969). Structural studies have revealed that the manner in which the thiamine is associated with the anions is closely related to the molecular conformation (Cramer et al., 1988; Aoki et al., 1993). There are two distinct types of anion bridging interactions, which link the thiazolium and pyrimidine rings of a thiamine molecule via hydrogen bonds and electrostatic contacts. They are of the forms C2—H···anion···pyrimidine ring and N(amino)—H···anion···thiazolium ring and are defined as type I and II anion bridges, respectively (Hu et al., 1999). The interaction of thiamine with discrete anions, from `simple' anions such as halogen (Thompson & Richardson, 1977; Lee & Richardson, 1976), SCN⁻, BF₄⁻ (Aoki et al., 1990), ClO₄⁻ or PF₆⁻ (Aoki et al., 1988), to metal complex anions such as [PtCl₄]²⁻ (Cramer et al., 1988), [PtCl₆]²⁻ (Aoki et al., 1993), [Pt(NO₂)₄]²⁻ (Hu et al., 2001b) and [Pt(SCN)₆]²⁻ (Aoki et al., 1999), have been widely investigated. However, reports describing thiamine compounds containing infinite polymeric anions are very rare. In our previous work, we have examined the interaction of thiamine monophosphate (TMP) with polymeric halogenomercurate anions in (TMP)(Hg₂Br₅)·0.5H₂O and (TMP)₂(Hg₃I₈) (Hu et al., 2002). Both compounds show organic–inorganic hybrid layered structures, consisting of sheets of polymeric mercury halide separated by hydrogen-bonded TMP cation layers. The TMP molecule adopting the usual F conformation (torsion angles ϕ_T = C5'—C35'—N3—C2 is approximately 0° and ϕ_P = N3—C35'—C5'—C4' is approximately ±90°) (Pletcher et al., 1977) is attached to the anion layer through a type I anion bridge, i.e. a C2—H···Br(or I)···pyrimidine-ring interaction. As an extension of these studies, we were interested in examining how thiamine interacts with polymeric halogenometal anions and whether the anions impose effects on the conformation of thiamine. We report here the structure of (thiaminium)(Cd₃Br_4.4Cl_3.6), (I), in which thiamine adopts the S conformation (ϕ_T is approximately ±100° and ϕ_P ±150°) and interacts with one-dimensional halogenocadmate anions in a manner different from that found in the TMP halogenomercurate compounds.

The structure of (I) consists of hydrogen-bonded thiamine molecules and polymeric cadmium bromide/chloride anions in an organic–inorganic hybrid fashion (Mitzi et al., 1995). Fig. 1 shows the molecular structure of thiamine and three crystallographically independent Cd²⁺ centres. The crystal structure analysis indicated that Br and Cl atoms share the halogen sites. The atom names in the atomic numbering scheme are assigned as the major disordered component. As shown in Table 1, the average Cd—µ₃-Cl7 bond length is 2.711 (7) Å, apparently shorter than the average value of Cd—µ₃-Br6 [2.80 (2) Å]. This is also the case for the Cd1—µ₂-Cl2 and Cd1—µ₂-Br1 bond lengths and for Cd3—µ₂-Cl2 and Cd2—µ₂-Br1 bond lengths (Table 1), consistent with the result that Cl is the major component at the Cl2 and Cl7 sites. Both atoms Cd2 and Cd3 are coordinated in an octahedral geometry, each by three µ₃-Br/Cl atoms and three µ₂-Br/Cl atoms. Each octahedral unit is connected to the four neighbouring units by sharing edges. These edge-sharing octahedra propagate in the [100] direction to form a one-dimensional ribbon. Atom Cd1 is tetrahedral and attached to the ribbon by sharing a vertex with Cd2 and Cd3 octahedra, respectively. The Cd1 tetrahedron acts as a tooth, with terminal atoms Br3 and Br4 pointing outside of the ribbon, thus producing a saw-like anion structure (Fig. 2). The anion ribbons are further arranged in the ac plane into layers at b = 0 and 1/2.

The thiamine molecule exists as a divalent cation with N2 protonated; the H atom at N2 was clearly visible in a difference map and the C10—N2—C11 angle of 121.3 (4)° is larger than the corresponding value of the unprotonated pyrimidine ring (about 115°; Aoki et al., 1990). The molecular dimensions are comparable with those of the reported divalent thiamine cation (Hu et al., 2001a). The torsion angles, ϕ_T = 90.3 (5)° and ϕ_P = 179.8 (4)°, indicate that thiamine adopts the unusual S conformation. The S conformation makes the C11—H bond point over the N1 atom of the thiazolium ring (Fig. 1), while the F conformation is characterized by the C1—H bond pointing over the C8 atom of the pyrimidine ring. For C1-unsubstituted thiamine, the F-form is overwhelmingly preferable to the S-form (Shin et al., 1993). Cramer et al. (1988) have pointed out that the polychlorometal anion can affect the conformation of thiamine through a bridging interaction (i.e. anion bridge II), and thus the F conformation is favoured by smaller anions and the S conformation by larger anions. Aoki et al. (1991) have further noticed that, for the F conformation, the type II anion bridge formed by a smaller anion is a one-point attachment, being of the form N(amino)—H···X···thiazolium ring, while for the S conformation, the type II anion bridge formed by a larger anion is a two-point attachment, being of the form N(amino)—H···X—M—X···thiazolium ring (X is an electronegative atom and M is a metal). This `two-point' anion bridge has been observed again in the present structure containing thiamine in the S conformation, i.e. an N4—H···Cl7—Cd3—Cl2···thiazolium ring interaction, where the closest contact between Cl2 and the thiazolium ring is Cl2···N1 = 3.386 (3) Å. In contrast, the TMP molecule adopts the F conformation in (TMP)(Hg₂Br₅)·0.5H₂O and (TMP)₂(Hg₃I₈), despite the existence of large halogenometal anions. This is due to the anionic phosphate group of the TMP molecule, which is evidently smaller than the halogenometal anion measured by the non-bonded X···X distance and taking part in the formation of a 'one-point' anion bridge. Interestingly, in (I), strongly electronegative Cl atoms compete with Br atoms for the two-point anion bridge, as Cl is the major component at the Cl2 and Cl7 sites (Fig. 1).

Fig. 3 shows that the crystal packing of (I) exhibits a layer-like structure consisting of alternating cationic sheets of the hydrogen-bonded thiamine molecules and anionic sheets of the polymeric halogenocadmate. Thiamine molecules self-associate through N4—H···O1 hydrogen bonds into a chain structure (Fig. 4), which is tilted relative to the anion ribbon at an angle of 54.0 (4)°. Each thiamine molecule is bound to three anion ribbons. As seen in Fig. 4, the thiamine molecule at (x, y, z) is attached to one anion ribbon through the type II anion bridge described above. Atom O1 of this molecule acts as hydrogen-bond donor to atom Br4 at (−x, 1 − y, −z) of a second ribbon, and the pyrimidine ring of this molecule is located between the teeth of a third ribbon lying in the above layer to form an N2—H···Cl2(−x, y − 1/2, 1/2 − z) hydrogen bond (Table 2). This binding mode is quite different from that observed in the structures of (TMP)(Hg₂Br₅)·0.5H₂O and (TMP)₂(Hg₃I₈), where the TMP molecule binds to the polymeric anions mainly through the characteristic type I anion bridge for the F conformation. Therefore, the sole existence of large halogenocadmate anions results in the S conformation of thiamine and thus determines the binding mode of thiamine to the anions.

S2. Experimental

Compound (I) was prepared by reacting thiamine chloride hydrochloride (0.2 mmol) and cadmium bromide (0.4 mmol) in water (20 ml). The solution was set aside to crystallize at ambient temperature and the resulting crystals were washed with water and methanol.

S3. Refinement

Preliminary structure refinements were carried out with all halogen sites assigned to Br atoms (R₁ = 0.080). Examination of the refined structure using PLATON (Spek, 2003) showed large differences between the U_eq values of these atoms and a residual density minimum larger than expected, which might be caused by wrongly assigned atom types. This implies that the halogen sites might be statistically occupied by Br and Cl. Thus, the refinements of the structure were carried out again using an algorithm to refine the occupancy factors of Br and Cl and to keep the summation of the two components to 1 for each site. The refinements led to a markedly reduced R₁ of 0.027. The final occupancy factors correspond in total to 4.41 Br atoms and 3.59 Cl atoms per molecular formula unit. All H atoms were treated as riding atoms, with C—H distances of 0.98 (CH₃), 0.99 (CH₂) or 0.95 Å (CH), and N—H distances of 0.88 Å, and with U_iso(H) = U_eq(parent).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of (I), showing the atom-labelling scheme and the two-point anion bridge. The dashed line denotes the hydrogen bond and the dotted line denotes the close contact. Displacement ellipsoids are drawn at the 30% probability level. Occupancy factors for Br/Cl: 0.683 (3):0.317 (3) for the Br1 site, 0.169 (3):0.831 (3) for the Cl2 site, 0.834 (3):0.166 (3) for the Br3 site, 0.810 (4):0.190 (4) for the Br4 site, 0.571 (3):0.429 (3) for the Br5 site, 0.635 (3):0.365 (3) for the Br6 site, 0.066 (3):0.934 (3) for the Cl7 site and 0.641 (3):0.359 (3) for the Br8 site.
	Fig. 2. A view of the one-dimensional anion ribbon in (I).
	Fig. 3. A view of the organic–inorganic hybrid layered structure. H atoms have been omitted.
	Fig. 4. Part of the crystal structure of (I), showing the formation of a molecular chain of thiamine and the interactions of a thiamine molecule with three anion ribbons around it. For the sake of clarity, H atoms have been omitted.

poly[3-[(4-amino-2-methyl-5-pyrimidin-1-io)methyl]-5-(2-hydroxyethyl)-4- methylthiazolium octa-µ-bromochloro(4.4/3.6)-tricadmate(II)

Crystal data

(C12H18N4OS)[Cd3Br4.41Cl3.59]	F(000) = 2005.4
Mr = 1083.23	Dx = 2.720 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4585 reflections
a = 7.7492 (4) Å	θ = 2.5–26.0°
b = 18.3881 (10) Å	µ = 9.51 mm^−1
c = 18.6756 (11) Å	T = 187 K
β = 96.187 (1)°	Tabular, colourless
V = 2645.6 (3) Å^3	0.21 × 0.15 × 0.09 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	5211 independent reflections
Radiation source: fine-focus sealed tube	4331 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ϕ and ω scans	θmax = 26.0°, θmin = 1.6°
Absorption correction: multi-scan (SAINT; Bruker, 2003)	h = −9→9
Tmin = 0.202, Tmax = 0.431	k = −22→21
13339 measured reflections	l = −23→13

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.060	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0272P)^2 + 0.1435P] where P = (Fo^2 + 2Fc^2)/3
5211 reflections	(Δ/σ)max = 0.008
275 parameters	Δρmax = 0.64 e Å^−3
0 restraints	Δρmin = −0.51 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cd1	0.30884 (4)	0.569695 (18)	0.215635 (17)	0.02643 (9)
Cd2	0.60424 (4)	0.542343 (16)	0.411088 (16)	0.02057 (9)
Cd3	0.10261 (4)	0.549992 (16)	0.418010 (16)	0.02150 (9)
Br1	0.56862 (7)	0.49317 (3)	0.27415 (3)	0.0268 (2)	0.683 (3)
Cl1	0.56862 (7)	0.49317 (3)	0.27415 (3)	0.0268 (2)	0.317 (3)
Br2	0.06970 (10)	0.51008 (4)	0.28039 (4)	0.0234 (3)	0.169 (3)
Cl2	0.06970 (10)	0.51008 (4)	0.28039 (4)	0.0234 (3)	0.831 (3)
Br3	0.32331 (7)	0.70570 (3)	0.20343 (3)	0.0352 (2)	0.834 (3)
Cl3	0.32331 (7)	0.70570 (3)	0.20343 (3)	0.0352 (2)	0.166 (3)
Br4	0.21937 (7)	0.52181 (3)	0.08904 (3)	0.0380 (2)	0.810 (4)
Cl4	0.21937 (7)	0.52181 (3)	0.08904 (3)	0.0380 (2)	0.190 (4)
Br5	0.84269 (7)	0.64316 (3)	0.39898 (3)	0.0252 (2)	0.571 (3)
Cl5	0.84269 (7)	0.64316 (3)	0.39898 (3)	0.0252 (2)	0.429 (3)
Br6	0.86437 (6)	0.43620 (3)	0.43434 (3)	0.0223 (2)	0.635 (3)
Cl6	0.86437 (6)	0.43620 (3)	0.43434 (3)	0.0223 (2)	0.365 (3)
Br7	0.35648 (11)	0.44824 (5)	0.44283 (5)	0.0197 (3)	0.066 (3)
Cl7	0.35648 (11)	0.44824 (5)	0.44283 (5)	0.0197 (3)	0.934 (3)
Br8	0.35518 (7)	0.64303 (3)	0.39959 (3)	0.0253 (2)	0.641 (3)
Cl8	0.35518 (7)	0.64303 (3)	0.39959 (3)	0.0253 (2)	0.359 (3)
S1	−0.17280 (14)	0.34295 (7)	0.16056 (7)	0.0326 (3)
O1	−0.2852 (4)	0.31980 (17)	0.01252 (18)	0.0394 (8)
H1	−0.3034	0.3589	−0.0104	0.039*
N1	0.1011 (5)	0.33057 (18)	0.24359 (19)	0.0267 (8)
N2	0.1797 (4)	0.11933 (19)	0.31734 (19)	0.0267 (8)
H2	0.1315	0.0842	0.2902	0.027*
N3	0.3515 (4)	0.15350 (19)	0.42105 (18)	0.0252 (8)
N4	0.4258 (5)	0.27130 (19)	0.44129 (19)	0.0325 (9)
H4A	0.4873	0.2566	0.4810	0.032*
H4B	0.4228	0.3178	0.4300	0.032*
C1	−0.0683 (6)	0.3397 (2)	0.2437 (2)	0.0320 (11)
H1A	−0.1244	0.3438	0.2864	0.032*
C2	0.1567 (6)	0.3280 (2)	0.1753 (2)	0.0271 (10)
C3	0.0209 (5)	0.3340 (2)	0.1228 (2)	0.0264 (10)
C4	0.3437 (5)	0.3205 (3)	0.1661 (3)	0.0379 (12)
H4C	0.3572	0.3141	0.1149	0.038*
H4D	0.3915	0.2782	0.1932	0.038*
H4E	0.4058	0.3644	0.1840	0.038*
C5	0.0243 (6)	0.3355 (3)	0.0431 (2)	0.0355 (11)
H5A	0.1376	0.3164	0.0318	0.035*
H5B	0.0158	0.3867	0.0267	0.035*
C6	−0.1189 (6)	0.2921 (2)	0.0009 (2)	0.0363 (12)
H6A	−0.1045	0.2945	−0.0511	0.036*
H6B	−0.1104	0.2405	0.0160	0.036*
C7	0.2137 (6)	0.3226 (2)	0.3117 (2)	0.0313 (11)
H7A	0.1637	0.3504	0.3499	0.031*
H7B	0.3295	0.3432	0.3061	0.031*
C8	0.2333 (5)	0.2441 (2)	0.3339 (2)	0.0223 (9)
C9	0.3389 (5)	0.2241 (2)	0.3991 (2)	0.0216 (9)
C10	0.2734 (5)	0.1027 (2)	0.3801 (2)	0.0238 (9)
C11	0.1583 (5)	0.1892 (2)	0.2952 (2)	0.0260 (10)
H11	0.0888	0.1995	0.2513	0.026*
C12	0.2820 (6)	0.0257 (2)	0.4039 (2)	0.0306 (10)
H12A	0.3917	0.0172	0.4340	0.031*
H12B	0.2752	−0.0062	0.3617	0.031*
H12C	0.1847	0.0153	0.4318	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02455 (17)	0.03074 (19)	0.02370 (17)	0.00062 (13)	0.00133 (13)	0.00451 (15)
Cd2	0.01777 (16)	0.02497 (17)	0.01866 (16)	−0.00011 (12)	0.00061 (13)	0.00112 (13)
Cd3	0.01782 (16)	0.02717 (17)	0.01933 (16)	0.00092 (12)	0.00116 (13)	0.00319 (13)
Br1	0.0240 (3)	0.0374 (4)	0.0184 (3)	0.0043 (2)	−0.0002 (2)	−0.0013 (2)
Cl1	0.0240 (3)	0.0374 (4)	0.0184 (3)	0.0043 (2)	−0.0002 (2)	−0.0013 (2)
Br2	0.0217 (5)	0.0298 (5)	0.0183 (5)	−0.0002 (3)	0.0000 (3)	0.0034 (4)
Cl2	0.0217 (5)	0.0298 (5)	0.0183 (5)	−0.0002 (3)	0.0000 (3)	0.0034 (4)
Br3	0.0422 (4)	0.0301 (3)	0.0338 (3)	−0.0019 (2)	0.0057 (2)	0.0008 (2)
Cl3	0.0422 (4)	0.0301 (3)	0.0338 (3)	−0.0019 (2)	0.0057 (2)	0.0008 (2)
Br4	0.0480 (4)	0.0421 (4)	0.0229 (3)	−0.0055 (3)	−0.0006 (2)	−0.0016 (3)
Cl4	0.0480 (4)	0.0421 (4)	0.0229 (3)	−0.0055 (3)	−0.0006 (2)	−0.0016 (3)
Br5	0.0200 (3)	0.0239 (3)	0.0314 (4)	−0.0005 (2)	0.0016 (2)	0.0050 (3)
Cl5	0.0200 (3)	0.0239 (3)	0.0314 (4)	−0.0005 (2)	0.0016 (2)	0.0050 (3)
Br6	0.0201 (3)	0.0290 (3)	0.0178 (3)	0.0017 (2)	0.0017 (2)	0.0022 (2)
Cl6	0.0201 (3)	0.0290 (3)	0.0178 (3)	0.0017 (2)	0.0017 (2)	0.0022 (2)
Br7	0.0196 (5)	0.0210 (5)	0.0179 (5)	−0.0002 (3)	−0.0004 (4)	0.0004 (4)
Cl7	0.0196 (5)	0.0210 (5)	0.0179 (5)	−0.0002 (3)	−0.0004 (4)	0.0004 (4)
Br8	0.0210 (3)	0.0257 (3)	0.0292 (3)	0.0008 (2)	0.0022 (2)	0.0017 (2)
Cl8	0.0210 (3)	0.0257 (3)	0.0292 (3)	0.0008 (2)	0.0022 (2)	0.0017 (2)
S1	0.0267 (6)	0.0395 (7)	0.0303 (6)	−0.0005 (5)	−0.0037 (5)	0.0049 (6)
O1	0.038 (2)	0.040 (2)	0.037 (2)	−0.0013 (15)	−0.0151 (16)	0.0091 (17)
N1	0.033 (2)	0.0200 (18)	0.025 (2)	0.0012 (15)	−0.0086 (17)	0.0013 (16)
N2	0.027 (2)	0.0241 (19)	0.028 (2)	−0.0033 (15)	−0.0014 (17)	−0.0073 (17)
N3	0.029 (2)	0.0241 (19)	0.0213 (19)	−0.0012 (16)	−0.0005 (16)	0.0010 (16)
N4	0.043 (2)	0.028 (2)	0.023 (2)	0.0017 (17)	−0.0148 (18)	−0.0009 (17)
C1	0.037 (3)	0.032 (3)	0.026 (3)	−0.001 (2)	−0.001 (2)	−0.001 (2)
C2	0.033 (3)	0.018 (2)	0.028 (2)	−0.0040 (18)	−0.007 (2)	0.000 (2)
C3	0.028 (2)	0.021 (2)	0.029 (2)	−0.0031 (18)	−0.005 (2)	0.002 (2)
C4	0.025 (3)	0.045 (3)	0.041 (3)	−0.002 (2)	−0.008 (2)	−0.004 (3)
C5	0.036 (3)	0.041 (3)	0.028 (3)	−0.010 (2)	−0.002 (2)	0.006 (2)
C6	0.045 (3)	0.034 (3)	0.027 (3)	−0.005 (2)	−0.010 (2)	0.004 (2)
C7	0.044 (3)	0.025 (2)	0.021 (2)	−0.001 (2)	−0.012 (2)	−0.006 (2)
C8	0.022 (2)	0.023 (2)	0.020 (2)	−0.0029 (17)	−0.0041 (18)	0.0018 (19)
C9	0.023 (2)	0.024 (2)	0.017 (2)	0.0015 (17)	0.0025 (18)	−0.0044 (18)
C10	0.023 (2)	0.026 (2)	0.024 (2)	0.0006 (18)	0.0086 (19)	−0.001 (2)
C11	0.031 (2)	0.027 (2)	0.020 (2)	0.0048 (19)	−0.0017 (19)	0.000 (2)
C12	0.037 (3)	0.026 (2)	0.030 (3)	−0.002 (2)	0.007 (2)	0.002 (2)

Geometric parameters (Å, º)

Cd1—Br3	2.5148 (6)	N3—C9	1.362 (5)
Cd1—Br4	2.5480 (6)	N4—C9	1.309 (5)
Cd1—Cl2	2.5654 (9)	N4—H4A	0.8800
Cd1—Br1	2.5986 (6)	N4—H4B	0.8800
Cd2—Br5	2.6442 (6)	C1—H1A	0.9500
Cd2—Br8	2.6663 (6)	C2—C3	1.363 (6)
Cd2—Cl7	2.6976 (9)	C2—C4	1.484 (6)
Cd2—Br1	2.6985 (6)	C3—C5	1.491 (6)
Cd2—Cl7^i	2.7178 (9)	C4—H4C	0.9800
Cd2—Br6	2.8058 (6)	C4—H4D	0.9800
Cd3—Br5^ii	2.6389 (6)	C4—H4E	0.9800
Cd3—Br8	2.6497 (6)	C5—C6	1.517 (6)
Cd3—Cl2	2.6585 (9)	C5—H5A	0.9900
Cd3—Cl7	2.7183 (9)	C5—H5B	0.9900
Cd3—Br6^i	2.7535 (6)	C6—H6A	0.9900
Cd3—Br6^ii	2.8285 (6)	C6—H6B	0.9900
S1—C1	1.674 (4)	C7—C8	1.506 (6)
S1—C3	1.734 (5)	C7—H7A	0.9900
O1—C6	1.424 (5)	C7—H7B	0.9900
O1—H1	0.8400	C8—C11	1.337 (5)
N1—C1	1.324 (5)	C8—C9	1.439 (5)
N1—C2	1.389 (6)	C10—C12	1.483 (6)
N1—C7	1.470 (5)	C11—H11	0.9500
N2—C10	1.346 (5)	C12—H12A	0.9800
N2—C11	1.355 (5)	C12—H12B	0.9800
N2—H2	0.8800	C12—H12C	0.9800
N3—C10	1.313 (5)
Br3—Cd1—Br4	105.66 (2)	C9—N4—H4A	120.0
Br3—Cd1—Cl2	120.61 (3)	C9—N4—H4B	120.0
Br4—Cd1—Cl2	98.72 (2)	H4A—N4—H4B	120.0
Br3—Cd1—Br1	122.45 (2)	N1—C1—S1	112.5 (4)
Br4—Cd1—Br1	108.91 (2)	N1—C1—H1A	123.7
Cl2—Cd1—Br1	97.85 (2)	S1—C1—H1A	123.7
Br5—Cd2—Br8	90.730 (19)	C3—C2—N1	111.5 (4)
Br5—Cd2—Cl7	171.47 (3)	C3—C2—C4	127.6 (4)
Br8—Cd2—Cl7	86.39 (2)	N1—C2—C4	120.9 (4)
Br5—Cd2—Br1	98.91 (2)	C2—C3—C5	128.7 (4)
Br8—Cd2—Br1	99.040 (19)	C2—C3—S1	110.5 (4)
Cl7—Cd2—Br1	89.47 (2)	C5—C3—S1	120.9 (3)
Br5—Cd2—Cl7^i	92.15 (2)	C2—C4—H4C	109.5
Br8—Cd2—Cl7^i	92.20 (2)	C2—C4—H4D	109.5
Cl7—Cd2—Cl7^i	79.96 (3)	H4C—C4—H4D	109.5
Br1—Cd2—Cl7^i	164.07 (3)	C2—C4—H4E	109.5
Br5—Cd2—Br6	90.224 (18)	H4C—C4—H4E	109.5
Br8—Cd2—Br6	175.70 (2)	H4D—C4—H4E	109.5
Cl7—Cd2—Br6	92.08 (2)	C3—C5—C6	114.8 (4)
Br1—Cd2—Br6	84.950 (18)	C3—C5—H5A	108.6
Cl7^i—Cd2—Br6	83.58 (2)	C6—C5—H5A	108.6
Br5^ii—Cd3—Br8	97.306 (19)	C3—C5—H5B	108.6
Br5^ii—Cd3—Cl2	93.25 (2)	C6—C5—H5B	108.6
Br8—Cd3—Cl2	92.75 (2)	H5A—C5—H5B	107.6
Br5^ii—Cd3—Cl7	176.08 (3)	O1—C6—C5	110.9 (4)
Br8—Cd3—Cl7	86.29 (2)	O1—C6—H6A	109.5
Cl2—Cd3—Cl7	88.11 (3)	C5—C6—H6A	109.5
Br5^ii—Cd3—Br6^i	93.567 (19)	O1—C6—H6B	109.5
Br8—Cd3—Br6^i	94.604 (19)	C5—C6—H6B	109.5
Cl2—Cd3—Br6^i	169.26 (2)	H6A—C6—H6B	108.1
Cl7—Cd3—Br6^i	84.56 (2)	N1—C7—C8	111.5 (3)
Br5^ii—Cd3—Br6^ii	89.837 (18)	N1—C7—H7A	109.3
Br8—Cd3—Br6^ii	172.493 (19)	C8—C7—H7A	109.3
Cl2—Cd3—Br6^ii	84.51 (2)	N1—C7—H7B	109.3
Cl7—Cd3—Br6^ii	86.63 (2)	C8—C7—H7B	109.3
Br6^i—Cd3—Br6^ii	87.221 (18)	H7A—C7—H7B	108.0
Cd1—Br1—Cd2	102.27 (2)	C11—C8—C9	116.1 (4)
Cd1—Cl2—Cd3	109.81 (3)	C11—C8—C7	123.3 (4)
Cd3^iii—Br5—Cd2	93.65 (2)	C9—C8—C7	120.6 (4)
Cd3^i—Br6—Cd2	94.503 (18)	N4—C9—N3	115.8 (4)
Cd3^i—Br6—Cd3^iii	92.776 (18)	N4—C9—C8	123.3 (4)
Cd2—Br6—Cd3^iii	86.280 (17)	N3—C9—C8	120.9 (4)
Cd2—Cl7—Cd2^i	100.04 (3)	N3—C10—N2	121.1 (4)
Cd2—Cl7—Cd3	92.30 (3)	N3—C10—C12	120.1 (4)
Cd2^i—Cl7—Cd3	97.36 (3)	N2—C10—C12	118.8 (4)
Cd3—Br8—Cd2	94.569 (19)	C8—C11—N2	121.2 (4)
C1—S1—C3	91.2 (2)	C8—C11—H11	119.4
C6—O1—H1	109.5	N2—C11—H11	119.4
C1—N1—C2	114.3 (4)	C10—C12—H12A	109.5
C1—N1—C7	120.5 (4)	C10—C12—H12B	109.5
C2—N1—C7	125.2 (4)	H12A—C12—H12B	109.5
C10—N2—C11	121.3 (4)	C10—C12—H12C	109.5
C10—N2—H2	119.4	H12A—C12—H12C	109.5
C11—N2—H2	119.4	H12B—C12—H12C	109.5
C10—N3—C9	119.3 (3)
C2—N1—C1—S1	1.9 (5)	C2—N1—C7—C8	−88.3 (5)
C7—N1—C1—S1	−176.8 (3)	N1—C7—C8—C11	0.9 (6)
C3—S1—C1—N1	−1.5 (3)	N1—C7—C8—C9	179.8 (4)
C1—N1—C2—C3	−1.3 (5)	C10—N3—C9—N4	−177.4 (4)
C7—N1—C2—C3	177.4 (4)	C10—N3—C9—C8	3.7 (6)
C1—N1—C2—C4	178.0 (4)	C11—C8—C9—N4	177.4 (4)
C7—N1—C2—C4	−3.4 (6)	C7—C8—C9—N4	−1.6 (7)
N1—C2—C3—C5	178.5 (4)	C11—C8—C9—N3	−3.7 (6)
C4—C2—C3—C5	−0.7 (8)	C7—C8—C9—N3	177.3 (4)
N1—C2—C3—S1	0.1 (4)	C9—N3—C10—N2	−0.8 (6)
C4—C2—C3—S1	−179.1 (4)	C9—N3—C10—C12	−178.5 (4)
C1—S1—C3—C2	0.8 (3)	C11—N2—C10—N3	−2.0 (6)
C1—S1—C3—C5	−177.7 (4)	C11—N2—C10—C12	175.7 (4)
C2—C3—C5—C6	138.9 (5)	C9—C8—C11—N2	1.0 (6)
S1—C3—C5—C6	−42.9 (6)	C7—C8—C11—N2	180.0 (4)
C3—C5—C6—O1	61.3 (5)	C10—N2—C11—C8	1.8 (6)
C1—N1—C7—C8	90.3 (5)

Symmetry codes: (i) −x+1, −y+1, −z+1; (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
N4—H4A···O1^iv	0.88	2.28	2.991 (5)	138
N4—H4B···Cl7	0.88	2.47	3.298 (4)	157
N2—H2···Cl2^v	0.88	2.36	3.216 (3)	164
O1—H1···Br4^vi	0.84	2.76	3.542 (3)	156

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