The first salt of an isolated penta­chloro­plumbate(II) trianion

The title compound, tris(cyclo­hexane-1,2-diamine-κ²N,N′)cobalt penta­chloro­plum­bate sesquihydrate, [Co(C₆H₁₄N₂)₃][PbCl₅]·1.5H₂O, crystallizes in the monoclinic space group C2/c, with a tricationic cobalt complex, a penta­chloro­plumbate trianion, one water mol­ecule in a general position and a second water mol­ecule on a crystallographic twofold axis. The compound is the first example of an isolated [PbCl₅]³⁻ moiety; the Pb atom is coordinated in a square-pyramidal fashion, with four longer bonds to Cl atoms in the basal plane and a shorter distance to the apex. The ionic constituents and the solvent mol­ecules form a three-dimensional network of hydrogen bonds.

S1. Comment

Pentachlorometallates containing isolated MCl₅ⁿ⁻ anions have been documented for both main group (M = In, Tl, Ge, Sn and Sb) and transition metals (M = V, Mn, Fe, Cu, Pt and Hg). For these elements, the Cambridge Structural Database (CSD. Version of August 2005; Allen, 2002) contains at least one error-free example, without disorder, for which three-dimensional atomic coordinates are available. The prototypic PbCl₅³⁻ anion, presumably a simple building block, has not yet been structurally characterized; we communicate here the synthesis and first X-ray diffraction study on such a pentachloroplumbate. In the context of a systematic comparison of homo- and heterochiral crystals we performed a cocrystallization experiment on tris(trans-1,2-diaminocyclohexane)cobalttrichloride and PbCl₂ in aqueous solution. The tricationic cobalt species represented the enantiomeric mixture of the thermodynamically stable isomers, namely the Δ configured complex of the (R,R)-diamine and its Λ-(S,S) mirror image (Kalf et al., 2002). From a solution containing both starting materials, a red crystalline product precipitates according to equation (1). Single-crystal X-ray diffraction showed that the solid (I) contains the expected complex cations (Fig. 1) and isolated PbCl₅³⁻ (Fig. 2) anions. To the best of our knowledge, the latter moiety has not yet been documented in the solid. Earlier reports on `pentachloroplumbates' do not refer to structures with isolated PbCl₅³⁻ building blocks but rather to compounds with chains of corner-sharing octahedra (Mousdis et al., 1998; Ng, 2000). We note that the formation of (I) necessarily competes with reprecipitation of lead(II) chloride, which is only sparingly soluble in cold water.

Fig. 2 shows that the pentachloroplumbate anion adopts an essentially square-pyramidal geometry, with a shorter apical bond and four longer coordination distances to the chloro substituents in the tetragonal plane. The metal atom lies 0.0368 (4) Å above this plane, in the direction of the apical ligand. Building blocks of an extended solid cannot be considered `isolated' in a strict sense. In the present case, however, this description of the anion as being `isolated' rather than being part of an extended moiety is justified: Additional neighbors of the central Pb atom are located at much longer distances and involve two C-bonded H atoms at 3.287 (3) and 3.485 (3) Å as well as a hydrate O atom at 3.5487 (17) Å. Our solid (I) contains a cation, an anion and a water molecule in a general position of the space group C2/c, and an additional water molecule on the twofold crystallographic axis; the compound is a sesquihydrate. All potential hydrogen-bond donors, viz. six NH and three symmetrically independent OH groups, are involved in moderate-to-weak hydrogen bonding, the acceptor atoms being either the plumbate Cl or the hydrate O atoms. Table 2 summarizes the hydrogen-bond geometry. To which structures should the new PbCl₅³⁻ anion be compared? The apical Pb^II—Cl distance is almost as short as those in chloro complexes of Pb^IV (Olafsson et al., 2000; Cashin et al., 2002), whereas the longer bonds in the base closely match the mean Pb—Cl distance for more than 200 structures in the CSD: For 202 error-free observations of Pb—Cl distances, the mean value is 2.873 and the median is 2.864 Å. Distances and angles in the structurally characterized pentachloroantimonates cover a wide range. Several SbCl₅²⁻ groups in the earlier literature (Zaleski and Pietraszko, 1995; Li et al., 1995; Derwahl et al., 1996; Ohta & Yamashita, 1997) not only adopt a square-pyramidal geometry but also match the metal–halide distance pattern of one shorter apical and four longer bonds. However, in these antimonates, the metal atom and the apical ligand are situated on opposite faces of the square plane, whereas in our pentachloroplumbate, the metal is slightly displaced towards the apex. In crystalline (I), loss of crystal water occurs at 443 K, and decomposition starts at ca 553 K. We have no direct evidence about the species present in solution, but ²⁰⁷Pb NMR data provide some insight: An aqueous solution of the tris(diaminocyclohexane)cobaltpentachloroplumbate shows a signal at −2224 p.p.m. This single resonance shifts to −1902 p.p.m. upon addition of LiCl (5 equivalents), i.e. when the Cl/Pb ratio is increased. Under the same conditions, a saturated solution of PbCl₂, with a lower Cl/Pb ratio, shows a resonance at −2383 p.p.m. The `hydrated Pb²⁺ cation' is found at ca −2800 p.p.m. (Harrison et al., 1983). These numbers, which will surely depend on concentration or supersaturation and should not be overinterpreted, are in agreement with the presence of Pb²⁺ cations with variable numbers of solvent water molecules and chloride ions in the coordination environment.

Originally, our interest in homo- and heterochiral crystals had induced us to perform reaction (1), and we conclude our short report with the negative outcome of a closely related experiment. Our new pentachloroplumbate (I) exists in the form of racemic crystals. Their formation is obviously preferred over the statistically less popular crystallization alternative, namely a conglomerate, whereas the nitrate of the same cationic complex shows spontaneous resolution (Morooka et al., 1991). We therefore expected that the enantiomerically pure cobalt complex as a starting material would enforce a chiral space group and hence an independent second example for a solid of the chemical composition [Co(chxn)₃]PbCl₅ with the pentachloroplumbate in a different packing environment. However, when aqueous solutions of enantiomerically pure [Co(chxn)₃]Cl₃ and PbCl₂ were mixed and evaporated under the same conditions, no precipitation of an analogous, necessarily homochiral compound is observed; after prolonged evaporation, PbCl₂ reprecipitates. We conclude that the competition between (I) and lead chloride is a close one, and that the formation of further pentachloroplumbate derivatives will not be trivial.

S2. Experimental

From a solution containing [Co(chxn)₃]Cl₃·2H₂O and PbCl₂, the red crystalline product precipitates according to equation (1). [Co(chxn)₃]Cl₃·2H₂O (0.272 g) [for the synthesis and structure of this compound see Kalf et al. (2002)] and PbCl₂ (0.5 mmol, 0.139 g) were separately dissolved in water (10 ml each) at 318 K. The orange-coloured mixture was stirred for 30 min at 318 K and then allowed to cool to room temperature; after 2 d, the precipitation of dark-red crystals of [Co(chxn)₃]PbCl₅·1.5H₂O began (yield 89%). The saturated solution should not be exposed to lower temperatures; cooling of a saturated solution of compound (I) to 279 K resulted in the formation of PbCl₂. Analysis calculated for C₃₆H₉₀N₁₂O₃Cl₁₀Co₂Pb₂: C, 26.59; H, 5.58; N, 10.34. Found: C, 26.23; H, 5.98; N, 10.17. ²⁰⁷Pb NMR spectra were recorded on a Varian Unity 500 instrument, 105 MHz, in D₂O and externally referenced to Pb(CH₃)₄.

S3. Refinement

All H atoms were introduced in idealized positions (C—H = 0.98 Å, N—H = 0.92 Å, O—H = 0.80 Å) and treated as riding.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A displacement ellipsoid plot [PLATON (Spek, 2003); 50% probability, H atoms with arbitrary radii] of the cation and the solvent water molecules in (I). The solvent molecule associated with atom O2 is located on a twofold crystallographic axis in space group C2/c.
	Fig. 2. A displacement ellipsoid plot [PLATON (Spek, 2003); 50% probability) of the pentachloroplumbate anion in (I).

Tris(cyclohexane-1,2-diamine-κ²N,N')cobalt pentachloroplumbate sesquihydrate, [Co(C₆H₁₄N₂)₃][PbCl₅]·1.5H₂O

Crystal data

[Co(C6H14N2)3][PbCl5]·1.5H2O	F(000) = 3208
Mr = 812.97	Dx = 1.854 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6549 reflections
a = 27.066 (2) Å	θ = 2.5–29.8°
b = 12.4657 (11) Å	µ = 6.83 mm^−1
c = 21.3066 (19) Å	T = 110 K
β = 125.889 (1)°	Fragment, orange
V = 5824.0 (8) Å^3	0.39 × 0.28 × 0.17 mm
Z = 8

Data collection

Bruker SMART CCD area-detector diffractometer	8402 independent reflections
Radiation source: fine-focus sealed tube	6901 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.066
ω scans	θmax = 30.0°, θmin = 2.4°
Absorption correction: analytical (PLATON; Spek, 2003)	h = −37→38
Tmin = 0.084, Tmax = 0.357	k = −17→17
42820 measured reflections	l = −29→29

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.048	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.007P)^2] where P = (Fo^2 + 2Fc^2)/3
8402 reflections	(Δ/σ)max = 0.001
294 parameters	Δρmax = 1.46 e Å^−3
0 restraints	Δρmin = −1.19 e Å^−3

Special details

Experimental. ²⁰⁷Pb NMR spectra were recorded on a Varian Unity 500 instrument, 105 MHz, in D₂O and externally referenced to Pb(CH₃)₄.

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
Co1	0.135742 (17)	0.68974 (3)	0.05905 (2)	0.01518 (8)
N1	0.18198 (10)	0.82202 (18)	0.07312 (13)	0.0172 (5)
H1A	0.1779	0.8709	0.1021	0.021*
H1B	0.2227	0.8061	0.0991	0.021*
N2	0.08336 (11)	0.72956 (18)	−0.05093 (13)	0.0184 (5)
H2A	0.0946	0.6918	−0.0778	0.022*
H2B	0.0433	0.7137	−0.0717	0.022*
N3	0.19030 (10)	0.60252 (17)	0.04742 (13)	0.0163 (5)
H3A	0.1845	0.6189	0.0014	0.020*
H3B	0.2303	0.6168	0.0873	0.020*
N4	0.08743 (10)	0.55766 (17)	0.03306 (13)	0.0170 (5)
H4A	0.0929	0.5301	0.0768	0.020*
H4B	0.0467	0.5725	−0.0026	0.020*
N5	0.18574 (10)	0.65689 (18)	0.17074 (13)	0.0176 (5)
H5A	0.1849	0.5842	0.1776	0.021*
H5B	0.2255	0.6765	0.1929	0.021*
N6	0.08289 (10)	0.76716 (19)	0.07947 (13)	0.0181 (5)
H6A	0.0917	0.8393	0.0853	0.022*
H6B	0.0426	0.7583	0.0386	0.022*
C1	0.15798 (12)	0.8692 (2)	−0.00485 (15)	0.0166 (6)
H1	0.1772	0.8318	−0.0258	0.020*
C2	0.09038 (13)	0.8468 (2)	−0.05696 (16)	0.0172 (6)
H2	0.0710	0.8854	−0.0366	0.021*
C3	0.06140 (13)	0.8839 (2)	−0.13933 (16)	0.0208 (6)
H3C	0.0174	0.8697	−0.1711	0.025*
H3D	0.0790	0.8445	−0.1616	0.025*
C4	0.07287 (13)	1.0042 (2)	−0.13875 (17)	0.0229 (6)
H4C	0.0565	1.0279	−0.1914	0.028*
H4D	0.0516	1.0436	−0.1214	0.028*
C5	0.14062 (13)	1.0291 (2)	−0.08535 (16)	0.0214 (6)
H5C	0.1465	1.1068	−0.0843	0.026*
H5D	0.1610	0.9955	−0.1060	0.026*
C6	0.17023 (13)	0.9892 (2)	−0.00264 (16)	0.0189 (6)
H6C	0.2143	1.0024	0.0289	0.023*
H6D	0.1532	1.0280	0.0207	0.023*
C7	0.17669 (12)	0.4873 (2)	0.04842 (16)	0.0161 (6)
H7	0.1933	0.4676	0.1019	0.019*
C8	0.10796 (12)	0.4784 (2)	0.00043 (16)	0.0163 (6)
H8	0.0911	0.4994	−0.0529	0.020*
C9	0.08688 (13)	0.3653 (2)	−0.00048 (16)	0.0190 (6)
H9A	0.0423	0.3620	−0.0353	0.023*
H9B	0.0998	0.3457	0.0517	0.023*
C10	0.11387 (13)	0.2859 (2)	−0.02770 (18)	0.0217 (6)
H10A	0.1029	0.2126	−0.0236	0.026*
H10B	0.0966	0.2997	−0.0822	0.026*
C11	0.18317 (13)	0.2964 (2)	0.02111 (18)	0.0228 (7)
H11A	0.1992	0.2469	0.0014	0.027*
H11B	0.2006	0.2762	0.0748	0.027*
C12	0.20258 (13)	0.4108 (2)	0.01934 (17)	0.0194 (6)
H12A	0.2472	0.4158	0.0522	0.023*
H12B	0.1875	0.4299	−0.0337	0.023*
C13	0.16269 (12)	0.7147 (2)	0.20960 (15)	0.0170 (6)
H13	0.1795	0.7875	0.2215	0.020*
C14	0.09400 (13)	0.7231 (2)	0.15146 (16)	0.0186 (6)
H14	0.0768	0.6506	0.1405	0.022*
C15	0.06615 (14)	0.7894 (2)	0.18399 (17)	0.0236 (7)
H15A	0.0217	0.7910	0.1467	0.028*
H15B	0.0813	0.8633	0.1934	0.028*
C16	0.08386 (15)	0.7383 (3)	0.26005 (19)	0.0275 (7)
H16A	0.0679	0.7823	0.2826	0.033*
H16B	0.0654	0.6670	0.2494	0.033*
C17	0.15304 (14)	0.7285 (3)	0.31792 (17)	0.0280 (7)
H17A	0.1629	0.6938	0.3652	0.034*
H17B	0.1712	0.8004	0.3317	0.034*
C18	0.18039 (14)	0.6632 (2)	0.28438 (16)	0.0220 (6)
H18A	0.2249	0.6613	0.3214	0.026*
H18B	0.1651	0.5894	0.2746	0.026*
Pb1	0.114580 (5)	0.272844 (9)	0.230932 (6)	0.01924 (3)
Cl1	0.18149 (3)	0.07962 (6)	0.28765 (4)	0.02208 (15)
Cl2	0.04703 (3)	0.17369 (6)	0.08105 (4)	0.02275 (15)
Cl3	0.20126 (3)	0.35868 (6)	0.22727 (4)	0.02552 (16)
Cl4	0.03941 (3)	0.45312 (6)	0.13972 (4)	0.02687 (16)
Cl5	0.17754 (4)	0.34501 (7)	0.38838 (4)	0.03137 (18)
O1	0.36516 (10)	0.48067 (16)	0.37283 (12)	0.0293 (5)
H1O	0.3948	0.5171	0.3917	0.038*
H2O	0.3421	0.5043	0.3299	0.038*
O2	0.0000	0.3656 (3)	0.2500	0.0850 (16)
H3O	−0.0014	0.4027	0.2795	0.110*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01478 (19)	0.01641 (19)	0.01275 (18)	−0.00002 (15)	0.00717 (16)	−0.00044 (14)
N1	0.0151 (12)	0.0168 (12)	0.0149 (12)	−0.0005 (9)	0.0061 (11)	−0.0029 (9)
N2	0.0188 (12)	0.0151 (11)	0.0173 (12)	−0.0017 (10)	0.0084 (11)	−0.0007 (10)
N3	0.0195 (13)	0.0175 (12)	0.0118 (11)	−0.0018 (9)	0.0090 (11)	−0.0012 (9)
N4	0.0167 (12)	0.0186 (12)	0.0161 (12)	0.0010 (10)	0.0099 (11)	−0.0007 (9)
N5	0.0170 (12)	0.0197 (13)	0.0171 (12)	0.0015 (10)	0.0105 (11)	−0.0004 (10)
N6	0.0156 (12)	0.0197 (12)	0.0156 (12)	0.0008 (10)	0.0073 (10)	−0.0012 (10)
C1	0.0183 (14)	0.0166 (14)	0.0144 (14)	−0.0002 (11)	0.0093 (12)	0.0002 (11)
C2	0.0207 (15)	0.0127 (14)	0.0174 (14)	−0.0002 (11)	0.0107 (13)	0.0006 (11)
C3	0.0195 (15)	0.0209 (15)	0.0175 (15)	−0.0014 (12)	0.0084 (13)	0.0017 (12)
C4	0.0226 (16)	0.0213 (16)	0.0197 (15)	0.0003 (12)	0.0095 (14)	0.0045 (12)
C5	0.0254 (17)	0.0185 (15)	0.0214 (15)	−0.0018 (12)	0.0143 (14)	0.0009 (12)
C6	0.0204 (15)	0.0177 (15)	0.0191 (15)	−0.0023 (11)	0.0119 (13)	−0.0008 (11)
C7	0.0179 (15)	0.0168 (14)	0.0145 (14)	−0.0014 (11)	0.0100 (12)	0.0003 (11)
C8	0.0169 (14)	0.0167 (14)	0.0158 (14)	0.0017 (11)	0.0099 (12)	0.0003 (11)
C9	0.0185 (15)	0.0177 (15)	0.0191 (15)	0.0000 (11)	0.0102 (13)	0.0003 (11)
C10	0.0261 (16)	0.0168 (15)	0.0242 (16)	−0.0021 (12)	0.0158 (14)	−0.0023 (12)
C11	0.0223 (16)	0.0183 (16)	0.0274 (17)	0.0027 (12)	0.0143 (14)	−0.0009 (12)
C12	0.0199 (15)	0.0188 (15)	0.0203 (15)	−0.0003 (12)	0.0122 (13)	−0.0021 (12)
C13	0.0185 (14)	0.0188 (15)	0.0140 (13)	−0.0017 (11)	0.0098 (12)	−0.0036 (11)
C14	0.0199 (15)	0.0174 (14)	0.0182 (14)	−0.0010 (12)	0.0110 (13)	−0.0021 (12)
C15	0.0210 (16)	0.0266 (18)	0.0254 (16)	−0.0004 (12)	0.0149 (14)	−0.0056 (13)
C16	0.0320 (18)	0.0293 (18)	0.0336 (18)	−0.0009 (14)	0.0261 (17)	−0.0046 (14)
C17	0.0342 (18)	0.0356 (18)	0.0179 (15)	0.0030 (15)	0.0174 (15)	−0.0010 (14)
C18	0.0270 (17)	0.0241 (16)	0.0158 (14)	0.0024 (13)	0.0130 (14)	0.0003 (12)
Pb1	0.01684 (5)	0.02238 (6)	0.01659 (5)	0.00008 (5)	0.00872 (4)	0.00000 (5)
Cl1	0.0206 (4)	0.0241 (4)	0.0175 (3)	0.0015 (3)	0.0090 (3)	0.0015 (3)
Cl2	0.0193 (4)	0.0238 (4)	0.0188 (4)	0.0003 (3)	0.0076 (3)	−0.0005 (3)
Cl3	0.0206 (4)	0.0341 (4)	0.0219 (4)	0.0000 (3)	0.0125 (3)	0.0034 (3)
Cl4	0.0221 (4)	0.0210 (4)	0.0264 (4)	0.0017 (3)	0.0080 (3)	0.0013 (3)
Cl5	0.0375 (5)	0.0387 (5)	0.0222 (4)	−0.0149 (4)	0.0199 (4)	−0.0096 (3)
O1	0.0352 (14)	0.0246 (12)	0.0239 (12)	−0.0052 (10)	0.0150 (11)	0.0041 (9)
O2	0.113 (4)	0.052 (3)	0.148 (5)	0.000	0.109 (4)	0.000

Geometric parameters (Å, º)

Co1—N2	1.963 (2)	C7—C8	1.513 (4)
Co1—N3	1.963 (2)	C7—C12	1.515 (4)
Co1—N4	1.969 (2)	C7—H7	0.9800
Co1—N5	1.971 (2)	C8—C9	1.518 (4)
Co1—N6	1.974 (2)	C8—H8	0.9800
Co1—N1	1.984 (2)	C9—C10	1.532 (4)
N1—C1	1.504 (3)	C9—H9A	0.9800
N1—H1A	0.9200	C9—H9B	0.9800
N1—H1B	0.9200	C10—C11	1.526 (4)
N2—C2	1.489 (3)	C10—H10A	0.9800
N2—H2A	0.9200	C10—H10B	0.9800
N2—H2B	0.9200	C11—C12	1.528 (4)
N3—C7	1.486 (3)	C11—H11A	0.9800
N3—H3A	0.9200	C11—H11B	0.9800
N3—H3B	0.9200	C12—H12A	0.9800
N4—C8	1.490 (3)	C12—H12B	0.9800
N4—H4A	0.9200	C13—C18	1.512 (4)
N4—H4B	0.9200	C13—C14	1.517 (4)
N5—C13	1.483 (3)	C13—H13	0.9800
N5—H5A	0.9200	C14—C15	1.531 (4)
N5—H5B	0.9200	C14—H14	0.9800
N6—C14	1.485 (3)	C15—C16	1.533 (4)
N6—H6A	0.9200	C15—H15A	0.9800
N6—H6B	0.9200	C15—H15B	0.9800
C1—C2	1.509 (4)	C16—C17	1.528 (4)
C1—C6	1.528 (4)	C16—H16A	0.9800
C1—H1	0.9800	C16—H16B	0.9800
C2—C3	1.515 (4)	C17—C18	1.530 (4)
C2—H2	0.9800	C17—H17A	0.9800
C3—C4	1.530 (4)	C17—H17B	0.9800
C3—H3C	0.9800	C18—H18A	0.9800
C3—H3D	0.9800	C18—H18B	0.9800
C4—C5	1.519 (4)	Pb1—Cl3	2.6211 (7)
C4—H4C	0.9800	Pb1—Cl1	2.8241 (7)
C4—H4D	0.9800	Pb1—Cl2	2.8677 (7)
C5—C6	1.529 (4)	Pb1—Cl5	2.8748 (8)
C5—H5C	0.9800	Pb1—Cl4	2.8863 (7)
C5—H5D	0.9800	O1—H1O	0.80
C6—H6C	0.9800	O1—H2O	0.80
C6—H6D	0.9800	O2—H3O	0.80
N2—Co1—N3	93.43 (9)	C5—C6—H6D	109.9
N2—Co1—N4	88.85 (9)	H6C—C6—H6D	108.3
N3—Co1—N4	85.76 (9)	N3—C7—C8	106.2 (2)
N2—Co1—N5	176.34 (10)	N3—C7—C12	115.1 (2)
N3—Co1—N5	90.14 (9)	C8—C7—C12	111.0 (2)
N4—Co1—N5	92.21 (10)	N3—C7—H7	108.1
N2—Co1—N6	91.71 (10)	C8—C7—H7	108.1
N3—Co1—N6	174.04 (9)	C12—C7—H7	108.1
N4—Co1—N6	91.33 (9)	N4—C8—C7	106.4 (2)
N5—Co1—N6	84.76 (9)	N4—C8—C9	112.4 (2)
N2—Co1—N1	85.44 (9)	C7—C8—C9	112.4 (2)
N3—Co1—N1	91.43 (9)	N4—C8—H8	108.5
N4—Co1—N1	173.47 (9)	C7—C8—H8	108.5
N5—Co1—N1	93.69 (9)	C9—C8—H8	108.5
N6—Co1—N1	91.99 (9)	C8—C9—C10	110.2 (2)
C1—N1—Co1	109.40 (16)	C8—C9—H9A	109.6
C1—N1—H1A	109.8	C10—C9—H9A	109.6
Co1—N1—H1A	109.8	C8—C9—H9B	109.6
C1—N1—H1B	109.8	C10—C9—H9B	109.6
Co1—N1—H1B	109.8	H9A—C9—H9B	108.1
H1A—N1—H1B	108.2	C11—C10—C9	110.8 (2)
C2—N2—Co1	108.17 (16)	C11—C10—H10A	109.5
C2—N2—H2A	110.1	C9—C10—H10A	109.5
Co1—N2—H2A	110.1	C11—C10—H10B	109.5
C2—N2—H2B	110.1	C9—C10—H10B	109.5
Co1—N2—H2B	110.1	H10A—C10—H10B	108.1
H2A—N2—H2B	108.4	C10—C11—C12	111.5 (2)
C7—N3—Co1	108.81 (16)	C10—C11—H11A	109.3
C7—N3—H3A	109.9	C12—C11—H11A	109.3
Co1—N3—H3A	109.9	C10—C11—H11B	109.3
C7—N3—H3B	109.9	C12—C11—H11B	109.3
Co1—N3—H3B	109.9	H11A—C11—H11B	108.0
H3A—N3—H3B	108.3	C7—C12—C11	109.2 (2)
C8—N4—Co1	108.51 (16)	C7—C12—H12A	109.8
C8—N4—H4A	110.0	C11—C12—H12A	109.8
Co1—N4—H4A	110.0	C7—C12—H12B	109.8
C8—N4—H4B	110.0	C11—C12—H12B	109.8
Co1—N4—H4B	110.0	H12A—C12—H12B	108.3
H4A—N4—H4B	108.4	N5—C13—C18	113.9 (2)
C13—N5—Co1	110.93 (16)	N5—C13—C14	107.0 (2)
C13—N5—H5A	109.5	C18—C13—C14	111.7 (2)
Co1—N5—H5A	109.5	N5—C13—H13	108.0
C13—N5—H5B	109.5	C18—C13—H13	108.0
Co1—N5—H5B	109.5	C14—C13—H13	108.0
H5A—N5—H5B	108.0	N6—C14—C13	106.2 (2)
C14—N6—Co1	108.23 (17)	N6—C14—C15	114.4 (2)
C14—N6—H6A	110.1	C13—C14—C15	111.1 (2)
Co1—N6—H6A	110.1	N6—C14—H14	108.3
C14—N6—H6B	110.1	C13—C14—H14	108.3
Co1—N6—H6B	110.1	C15—C14—H14	108.3
H6A—N6—H6B	108.4	C14—C15—C16	108.8 (2)
N1—C1—C2	107.0 (2)	C14—C15—H15A	109.9
N1—C1—C6	113.8 (2)	C16—C15—H15A	109.9
C2—C1—C6	110.6 (2)	C14—C15—H15B	109.9
N1—C1—H1	108.4	C16—C15—H15B	109.9
C2—C1—H1	108.4	H15A—C15—H15B	108.3
C6—C1—H1	108.4	C17—C16—C15	111.2 (2)
N2—C2—C1	106.2 (2)	C17—C16—H16A	109.4
N2—C2—C3	113.2 (2)	C15—C16—H16A	109.4
C1—C2—C3	112.2 (2)	C17—C16—H16B	109.4
N2—C2—H2	108.4	C15—C16—H16B	109.4
C1—C2—H2	108.4	H16A—C16—H16B	108.0
C3—C2—H2	108.4	C16—C17—C18	111.4 (2)
C2—C3—C4	109.0 (2)	C16—C17—H17A	109.3
C2—C3—H3C	109.9	C18—C17—H17A	109.3
C4—C3—H3C	109.9	C16—C17—H17B	109.3
C2—C3—H3D	109.9	C18—C17—H17B	109.3
C4—C3—H3D	109.9	H17A—C17—H17B	108.0
H3C—C3—H3D	108.3	C13—C18—C17	109.0 (2)
C5—C4—C3	110.9 (2)	C13—C18—H18A	109.9
C5—C4—H4C	109.5	C17—C18—H18A	109.9
C3—C4—H4C	109.5	C13—C18—H18B	109.9
C5—C4—H4D	109.5	C17—C18—H18B	109.9
C3—C4—H4D	109.5	H18A—C18—H18B	108.3
H4C—C4—H4D	108.0	Cl3—Pb1—Cl1	90.01 (2)
C4—C5—C6	112.6 (2)	Cl3—Pb1—Cl2	98.06 (2)
C4—C5—H5C	109.1	Cl1—Pb1—Cl2	86.51 (2)
C6—C5—H5C	109.1	Cl3—Pb1—Cl5	88.76 (2)
C4—C5—H5D	109.1	Cl1—Pb1—Cl5	88.56 (2)
C6—C5—H5D	109.1	Cl2—Pb1—Cl5	171.57 (2)
H5C—C5—H5D	107.8	Cl3—Pb1—Cl4	87.25 (2)
C1—C6—C5	109.0 (2)	Cl1—Pb1—Cl4	166.97 (2)
C1—C6—H6C	109.9	Cl2—Pb1—Cl4	81.27 (2)
C5—C6—H6C	109.9	Cl5—Pb1—Cl4	104.11 (2)
C1—C6—H6D	109.9	H1O—O1—H2O	104.2
N2—Co1—N1—C1	−7.06 (17)	N2—C2—C3—C4	−178.3 (2)
N3—Co1—N1—C1	86.27 (18)	C1—C2—C3—C4	−58.1 (3)
N4—Co1—N1—C1	21.9 (9)	C2—C3—C4—C5	55.6 (3)
N5—Co1—N1—C1	176.50 (17)	C3—C4—C5—C6	−56.3 (3)
N6—Co1—N1—C1	−98.62 (18)	N1—C1—C6—C5	−176.7 (2)
N3—Co1—N2—C2	−113.01 (17)	C2—C1—C6—C5	−56.2 (3)
N4—Co1—N2—C2	161.31 (17)	C4—C5—C6—C1	55.6 (3)
N5—Co1—N2—C2	54.5 (16)	Co1—N3—C7—C8	41.4 (2)
N6—Co1—N2—C2	70.01 (17)	Co1—N3—C7—C12	164.61 (19)
N1—Co1—N2—C2	−21.85 (17)	Co1—N4—C8—C7	40.4 (2)
N2—Co1—N3—C7	−104.13 (17)	Co1—N4—C8—C9	163.94 (18)
N4—Co1—N3—C7	−15.54 (17)	N3—C7—C8—N4	−53.4 (3)
N5—Co1—N3—C7	76.66 (17)	C12—C7—C8—N4	−179.2 (2)
N6—Co1—N3—C7	45.4 (10)	N3—C7—C8—C9	−176.9 (2)
N1—Co1—N3—C7	170.36 (17)	C12—C7—C8—C9	57.3 (3)
N2—Co1—N4—C8	79.24 (18)	N4—C8—C9—C10	−175.0 (2)
N3—Co1—N4—C8	−14.28 (17)	C7—C8—C9—C10	−54.9 (3)
N5—Co1—N4—C8	−104.26 (17)	C8—C9—C10—C11	54.1 (3)
N6—Co1—N4—C8	170.93 (17)	C9—C10—C11—C12	−56.8 (3)
N1—Co1—N4—C8	50.4 (9)	N3—C7—C12—C11	−178.1 (2)
N2—Co1—N5—C13	9.2 (16)	C8—C7—C12—C11	−57.5 (3)
N3—Co1—N5—C13	176.71 (18)	C10—C11—C12—C7	57.9 (3)
N4—Co1—N5—C13	−97.52 (18)	Co1—N5—C13—C18	156.8 (2)
N6—Co1—N5—C13	−6.39 (18)	Co1—N5—C13—C14	32.9 (2)
N1—Co1—N5—C13	85.28 (18)	Co1—N6—C14—C13	45.4 (2)
N2—Co1—N6—C14	158.73 (18)	Co1—N6—C14—C15	168.33 (19)
N3—Co1—N6—C14	9.2 (10)	N5—C13—C14—N6	−50.7 (3)
N4—Co1—N6—C14	69.85 (18)	C18—C13—C14—N6	−176.0 (2)
N5—Co1—N6—C14	−22.25 (17)	N5—C13—C14—C15	−175.6 (2)
N1—Co1—N6—C14	−115.78 (18)	C18—C13—C14—C15	59.1 (3)
Co1—N1—C1—C2	34.0 (2)	N6—C14—C15—C16	−177.1 (2)
Co1—N1—C1—C6	156.47 (18)	C13—C14—C15—C16	−56.9 (3)
Co1—N2—C2—C1	45.9 (2)	C14—C15—C16—C17	56.2 (3)
Co1—N2—C2—C3	169.43 (19)	C15—C16—C17—C18	−57.4 (3)
N1—C1—C2—N2	−51.9 (3)	N5—C13—C18—C17	−178.9 (2)
C6—C1—C2—N2	−176.4 (2)	C14—C13—C18—C17	−57.5 (3)
N1—C1—C2—C3	−176.0 (2)	C16—C17—C18—C13	56.6 (3)
C6—C1—C2—C3	59.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1^i	0.92	2.06	2.931 (4)	157
N1—H1B···Cl5^i	0.92	2.60	3.399 (3)	146
N2—H2A···Cl5^ii	0.92	2.77	3.592 (3)	149
N2—H2B···Cl2^iii	0.92	2.73	3.416 (3)	133
N2—H2B···Cl4^iii	0.92	2.76	3.527 (3)	141
N3—H3A···Cl5^ii	0.92	2.35	3.265 (3)	175
N3—H3B···Cl1^i	0.92	2.36	3.190 (2)	150
N4—H4A···Cl4	0.92	2.66	3.466 (3)	146
N4—H4B···Cl4^iii	0.92	2.47	3.246 (2)	143
N5—H5A···Cl3	0.92	2.94	3.854 (2)	170
N5—H5B···Cl1^i	0.92	2.60	3.300 (3)	134
N6—H6A···O1^i	0.92	2.01	2.901 (3)	163
N6—H6B···Cl2^iii	0.92	2.42	3.241 (3)	149
O1—H1O···Cl2^i	0.80	2.36	3.109 (3)	158
O1—H2O···Cl1^i	0.80	2.38	3.122 (2)	153
O2—H3O···Cl4^iv	0.80	2.55	3.2845 (19)	154

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