Crystal structure of tetra­kis­[μ2-2-(di­methyl­amino)­ethano­lato-κ3N,O:O]di-μ3-hydroxido-di­thio­cyanato-κ2N-dichromium(III)dilead(II) di­thio­cyanate aceto­nitrile monosolvate

Rusanova, J.A.; Semenaka, V.V.; Omelchenko, I.V.

doi:10.1107/S2056989016003996

research communications

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ISSN: 2056-9890

Volume 72| Part 4| April 2016| Pages 489-491

https://doi.org/10.1107/S2056989016003996

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Crystal structure of tetrakis[μ₂-2-(dimethylamino)ethanolato-κ³N,O:O]di-μ₃-hydroxido-dithiocyanato-κ²N-dichromium(III)dilead(II) dithiocyanate acetonitrile monosolvate

Julia A. Rusanova,^a ^* Valentyna V. Semenaka ^a and Irina V. Omelchenko ^b

^aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, 64/13, Volodymyrska Street, Kyiv 01601, Ukraine, and ^bSSI "Institute for Single Crystals", National Academy of Sciences of Ukraine, 60 Lenina ave., Kharkiv 61072, Ukraine
^*Correspondence e-mail: rusanova.j@gmail.com

Edited by H. Ishida, Okayama University, Japan (Received 11 January 2016; accepted 9 March 2016; online 11 March 2016)

The tetranuclear complex cation of the title compound, [Cr₂Pb₂(NCS)₂(OH)₂(C₄H₁₀NO)₄](SCN)₂·CH₃CN, lies on an inversion centre. The main structural feature of the cation is a distorted seco-norcubane Pb₂Cr₂O₆ cage with a central four-membered Cr₂O₂ ring. The Cr^III ion is coordinated in a distorted octahedron, which involves two N atoms of one bidentate ligand and one thiocyanate anion, two μ₂-O atoms of 2-(dimethylamino)ethanolate ligands and two μ₃-O atoms of hydroxide ions. The coordination geometry of the Pb^II ion is a distorted disphenoid, which involves one N atom, two μ₂-O atoms and one μ₃-O atom. In addition, weak Pb⋯S interactions involving the coordinating and non-coordinating thiocyanate anions are observed. In the crystal, the complex cations are linked through the thiocyanate anions via the Pb⋯S interactions and O—H⋯N hydrogen bonds into chains along the c axis. The chains are further linked together via S⋯S contacts. The contribution of the disordered solvent acetonitrile molecule was removed with the SQUEEZE [Spek (2015 ). Acta Cryst. C71, 9–18] procedure in PLATON. The solvent is included in the reported molecular formula, weight and density.

Keywords: crystal structure; N,N′-dimethylethanolamine; heterometal Pb^II/Cr^III complex.

CCDC reference: 1460850

1. Chemical context

There is considerable interest in polynuclear heterometallic complexes as a result of their potential for interesting physicochemical properties such as magnetic (Gheorghe et al., 2010 ), catalytic (Trettenhahn et al., 2006 ) and useful light- and/or redox-induced functions (Balzani et al., 2009 ). The interest currently paid to the synthesis of polynuclear transition metal complexes is stimulated, in particular, by attempts to design and construct multicomponent systems. Despite of a lot of work already done in this field, a limited number of synthetic strategies have been developed to date. Spontaneous self-assembly of Schiff base ligands or rigid building blocks appears to be an extremely powerful tool for the construction of novel polynuclear assemblies incorporating metal atoms by utilizing the various coordination modes of small and flexible ligands (Buvaylo et al., 2005 ; Kirillov et al., 2005 ). Metal powders have been successfully applied in direct synthesis of coordination compounds to yield a number of novel monometallic (Babich et al., 1996 ) and heterometallic complexes (Buvaylo et al., 2005) of various composition, nuclearities and dimensionalities. This work is a continuation of our investigations in the field of direct synthesis of heterometallic coordination compounds based on spontaneous self-assembly, in which one of the metals is introduced as a powder (zero-valent state) and oxidized during the synthesis (Nesterov et al., 2011 ), in particular the application of Reinecke's salt in direct synthesis of heterometallic complexes (Nikitina et al., 2008 ).

2. Structural commentary

The complex cation with a distorted seco-norcubane Pb₂Cr₂O₆ framework is centrosymmetric, as shown in Fig. 1. The two crystallographically independent dimethylaminoethanol ligands form five-membered chelate rings with the Cr^III and Pb^II ions. The Cr^III ion adopts a distorted octahedral coordination environment with one N atom and two μ₂-O atoms from the dimethylaminoethanol ligands and one μ₃-O atom from the hydroxide ion in the equatorial plane, and one N atom of the thiocyanate ion and one μ₃-O atom of the second hydroxide ion in the axial positions. The Cr—O and Cr—N bond lengths are 1.950 (3)–1.993 (3) Å and 2.008 (4)–2.158 (4) Å, respectively, and the N—Cr—O and O—Cr—O angles are 79.10 (11)–93.48 (12)° for cis-positions and 168.63 (13)–173.46 (12)° for trans-positions. The Pb^II ion is tetracoordinated by the one μ₃-O atom of the hydroxide ion, one N atom and two μ₂-O atoms of the dimethylaminoethanol ligands and adopts a distorted disphenoidal coordination. There are additional weak Pb⋯S interactions [Pb1⋯S1 3.2749 (14) Å and Pb1⋯S2 3.4056 (16) Å], and thus the coordination geometry of the Pb^II ion can be considered as a strongly distorted trigonal prism, if these interactions are included. The Pb—O bond lengths [2.308 (3)–2.686 (3) Å] as well as the Pb—N distance [2.547 (4) Å] are in a good agreement with literature values. In general, all geometric parameters of the title complex cation are in good agreement with those in related aminoalcohol complexes (Shahid et al., 2011 ).

Figure 1
The molecular structure of the title compound, shown with 30% probability displacement ellipsoids. O—H⋯N hydrogen bonds are shown as dashed lines.

3. Supramolecular features

In the crystal, the tetranuclear complex cations are linked through thiocyanate anions with the above-mentioned intermolecular Pb⋯S interactions and by an O—H⋯N hydrogen bond (Table 1) into chains along the c axis (Fig. 2). The chains are further linked together by an S⋯S sigma-hole bond [S1⋯S2 3.585 (2) Å], where atom S2 acts as a lone-pair donor.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯N2	0.82	1.95	2.757 (6)	169

Figure 2
Crystal packing diagram of the title compound, viewed along the b axis. Pb⋯S contacts and O—H⋯N hydrogen bonds are shown as dashed lines.

4. Database survey

A search of the Cambridge Structural Database (Version 5.36; last update February 2015; Groom & Allen, 2014 ) for related complexes with 2-dimethylaminoethanol gave 260 hits, including some closely related structures with a distorted seco-norcubane cage with Ti (Hollingsworth et al., 2008 ), Ge(Sn)–Li (Khrustalev et al., 2004 , 2008 ) and Na(Li)–Al (Nöth et al., 2001 ).

5. Synthesis and crystallization

Lead monoxide (0,279 g, 1.25 mmol), NH₄[Cr(NCS)₄(NH₃)₂]·H₂O (0.443 g, 1.25 mmol), NH₄SCN (0.095 g, 1.25 mmol), 2-dimethylaminoethanol (0.5 ml, 5 mmol) and acetonitrile (20 ml) were heated in air at 323–333 K and stirred for 110 min until complete PbO dissolution occurred. Dark-grey crystals suitable for the crystallographic study were formed by slow evaporation of the resulting solution in air. The crystals were filtered off, washed with dry isopropyl alcohol and finally dried in vacuo at room temperature. Yield: 0.11 g, 10.3%.

The IR spectrum of the title compound (as KBr pellets) exhibited absorbance at 2250 cm⁻¹ assigned to υ(CN) of the solvent acetonitrile molecule, as well two additional bands at 2080 cm⁻¹ and 1610 cm⁻¹, which were assigned, respectively, to stretch and vibrational υ(CN) modes of the SCN anion. Analysis calculated for C₂₂H₄₅Cr₂N₉S₄Pb₂: C 22.43, H 3.85, N 10.69, S 10.88%; found: C 22.21, H 3.78, N 10.45, S 10.64%.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms were placed in idealized positions and refined as riding, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C,O) for methyl and hydroxyl groups.

Table 2
Experimental details

Crystal data
Chemical formula	[Cr₂Pb₂(NCS)₂(OH)₂(C₄H₁₀NO)₄](NCS)₂·C₂H₃N
M_r	1178.29
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	17.533 (1), 13.8815 (7), 16.6179 (8)
β (°)	104.771 (6)
V (Å³)	3910.9 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	9.39
Crystal size (mm)	0.4 × 0.1 × 0.1

Data collection
Diffractometer	Agilent Xcalibur Sapphire 3
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011 )
T_min, T_max	0.382, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	20193, 5680, 4133
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.058, 0.93
No. of reflections	5680
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.00, −0.69
Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), OLEX2 (Dolomanov et al., 2009 ) and PLATON (Spek, 2009).

During the refinement, several isolated electron density peaks were located, which were assignable to a solvent acetnitrile molecule(s) from the IR data and elementary analysis. Satisfactory results (R₁ = 0.045) were obtained modeling the disordered C and N atoms, but very large displacement parameters for them were observed. The SQUEEZE (Spek, 2015) procedure in PLATON (Spek, 2009 ) indicated solvent cavities of volume 118 Å³ centered at (0.5, 0, 0.25), (0.5, 0, 0.75), (0, 0.5, 0.75) and (0, 0.5, 0.25), each containing approximately 18 electrons. In the final refinement, this contribution was removed from the intensity data, producing better refinement results. We assumed full occupancy of the solvent molecule for each cavity, although the estimated 18 electrons are fewer than the 22 electrons expected for full occupancy. The solvent molecule is included in the reported molecular formula, weight and density.

Supporting information

CCDC reference: 1460850

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989016003996/is5439sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016003996/is5439Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 and PLATON (Spek, 2009).

Tetrakis[µ₂-2-(dimethylamino)ethanolato-κ³N,O:O]di-µ₃-hydroxido-dithiocyanato-κ²N-dichromium(III)dilead(II) dithiocyanate acetonitrile monosolvate top

Crystal data top

[Cr₂Pb₂(NCS)₂(OH)₂(C₄H₁₀NO)₄](NCS)₂·C₂H₃N	F(000) = 2256
M_r = 1178.29	D_x = 2.001 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.533 (1) Å	Cell parameters from 4335 reflections
b = 13.8815 (7) Å	θ = 2.9–32.5°
c = 16.6179 (8) Å	µ = 9.39 mm⁻¹
β = 104.771 (6)°	T = 298 K
V = 3910.9 (4) Å³	Block, metallic dark gray
Z = 4	0.4 × 0.1 × 0.1 mm

Data collection top

Agilent Xcalibur Sapphire 3 diffractometer	5680 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4133 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
Detector resolution: 16.1827 pixels mm^-1	θ_max = 30.0°, θ_min = 3.0°
ω scans	h = −24→24
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −19→18
T_min = 0.382, T_max = 1.000	l = −23→23
20193 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.058	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.0118P)²] where P = (F_o² + 2F_c²)/3
5680 reflections	(Δ/σ)_max = 0.001
190 parameters	Δρ_max = 1.00 e Å⁻³
0 restraints	Δρ_min = −0.69 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Å²) top

	x	y	z	U_iso*/U_eq
Pb1	0.369714 (9)	0.456817 (12)	0.330204 (9)	0.03296 (5)
Cr1	0.46177 (4)	0.59683 (5)	0.51003 (4)	0.02815 (15)
S1	0.33608 (10)	0.73222 (11)	0.70835 (8)	0.0651 (4)
S2	0.75622 (10)	0.58870 (14)	0.31923 (11)	0.0865 (6)
O1	0.35991 (16)	0.5544 (2)	0.44114 (16)	0.0327 (7)
O2	0.56441 (17)	0.6487 (2)	0.56837 (17)	0.0365 (7)
O3	0.50477 (15)	0.52564 (19)	0.42849 (15)	0.0294 (6)
H3	0.5314	0.5554	0.4027	0.044*
N1	0.4136 (2)	0.6465 (3)	0.5993 (2)	0.0412 (9)
N2	0.6095 (3)	0.6076 (4)	0.3499 (3)	0.0735 (14)
N3	0.2425 (2)	0.4171 (3)	0.3704 (2)	0.0385 (9)
N4	0.4503 (2)	0.7343 (3)	0.4474 (2)	0.0410 (9)
C1	0.3816 (3)	0.6803 (3)	0.6461 (3)	0.0395 (11)
C2	0.6716 (3)	0.6005 (4)	0.3384 (3)	0.0513 (13)
C3	0.2214 (3)	0.5127 (3)	0.3976 (3)	0.0441 (12)
H3A	0.1746	0.5067	0.4181	0.053*
H3B	0.2094	0.5561	0.3504	0.053*
C4	0.2877 (2)	0.5549 (3)	0.4655 (3)	0.0402 (11)
H4A	0.2746	0.6205	0.4770	0.048*
H4B	0.2939	0.5176	0.5161	0.048*
C5	0.2516 (3)	0.3465 (4)	0.4382 (3)	0.0536 (13)
H5A	0.2014	0.3357	0.4499	0.080*
H5B	0.2882	0.3708	0.4871	0.080*
H5C	0.2710	0.2870	0.4217	0.080*
C6	0.1806 (3)	0.3839 (4)	0.2987 (3)	0.0568 (14)
H6A	0.1336	0.3700	0.3160	0.085*
H6B	0.1980	0.3267	0.2762	0.085*
H6C	0.1697	0.4332	0.2568	0.085*
C7	0.5302 (3)	0.7792 (4)	0.4780 (3)	0.0604 (15)
H7A	0.5637	0.7591	0.4429	0.072*
H7B	0.5253	0.8488	0.4747	0.072*
C8	0.5662 (3)	0.7508 (3)	0.5642 (3)	0.0510 (13)
H8A	0.6202	0.7736	0.5813	0.061*
H8B	0.5371	0.7786	0.6010	0.061*
C9	0.4340 (4)	0.7257 (4)	0.3548 (3)	0.0702 (17)
H9A	0.4295	0.7889	0.3305	0.105*
H9B	0.3855	0.6913	0.3338	0.105*
H9C	0.4764	0.6916	0.3407	0.105*
C10	0.3883 (3)	0.7963 (4)	0.4640 (4)	0.0733 (18)
H10A	0.3869	0.8559	0.4344	0.110*
H10B	0.3992	0.8090	0.5226	0.110*
H10C	0.3382	0.7645	0.4459	0.110*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pb1	0.03289 (9)	0.03895 (10)	0.02546 (8)	−0.00140 (8)	0.00458 (6)	−0.00003 (8)
Cr1	0.0277 (4)	0.0296 (4)	0.0261 (3)	0.0001 (3)	0.0050 (3)	−0.0017 (3)
S1	0.0878 (12)	0.0615 (10)	0.0580 (8)	0.0261 (8)	0.0407 (8)	0.0061 (7)
S2	0.0671 (11)	0.1125 (15)	0.0917 (12)	−0.0349 (10)	0.0421 (10)	−0.0433 (11)
O1	0.0271 (15)	0.0382 (17)	0.0324 (14)	−0.0022 (12)	0.0070 (12)	−0.0052 (13)
O2	0.0353 (17)	0.0310 (17)	0.0376 (15)	−0.0028 (13)	−0.0009 (13)	0.0001 (13)
O3	0.0298 (15)	0.0320 (17)	0.0285 (13)	−0.0004 (12)	0.0111 (12)	0.0022 (12)
N1	0.044 (2)	0.044 (2)	0.0354 (19)	0.0010 (18)	0.0085 (18)	−0.0085 (18)
N2	0.075 (4)	0.085 (4)	0.069 (3)	−0.007 (3)	0.033 (3)	0.004 (3)
N3	0.032 (2)	0.044 (2)	0.0366 (19)	−0.0103 (17)	0.0048 (17)	−0.0009 (18)
N4	0.042 (2)	0.036 (2)	0.040 (2)	0.0025 (17)	0.0008 (18)	0.0030 (18)
C1	0.044 (3)	0.035 (3)	0.037 (2)	0.004 (2)	0.007 (2)	−0.004 (2)
C2	0.060 (4)	0.059 (4)	0.037 (2)	−0.017 (3)	0.015 (3)	−0.004 (2)
C3	0.031 (2)	0.052 (3)	0.047 (3)	0.002 (2)	0.007 (2)	0.002 (2)
C4	0.026 (2)	0.052 (3)	0.044 (2)	0.002 (2)	0.011 (2)	−0.008 (2)
C5	0.056 (3)	0.049 (3)	0.057 (3)	−0.007 (2)	0.018 (3)	0.007 (3)
C6	0.035 (3)	0.077 (4)	0.052 (3)	−0.017 (3)	−0.001 (2)	−0.006 (3)
C7	0.061 (4)	0.046 (3)	0.066 (3)	−0.015 (3)	0.001 (3)	0.011 (3)
C8	0.045 (3)	0.034 (3)	0.065 (3)	−0.011 (2)	−0.002 (3)	0.001 (2)
C9	0.086 (5)	0.068 (4)	0.048 (3)	0.009 (3)	0.003 (3)	0.019 (3)
C10	0.081 (4)	0.051 (4)	0.089 (4)	0.025 (3)	0.025 (4)	0.015 (3)

Geometric parameters (Å, º) top

Pb1—O2ⁱ	2.308 (3)	C3—H3A	0.9700
Pb1—O1	2.329 (3)	C3—H3B	0.9700
Pb1—N3	2.547 (4)	C4—H4A	0.9700
Pb1—O3	2.686 (3)	C4—H4B	0.9700
Cr1—O1	1.950 (3)	C5—H5A	0.9600
Cr1—O2	1.951 (3)	C5—H5B	0.9600
Cr1—O3	1.975 (3)	C5—H5C	0.9600
Cr1—O3ⁱ	1.993 (3)	C6—H6A	0.9600
Cr1—N1	2.008 (4)	C6—H6B	0.9600
Cr1—N4	2.158 (4)	C6—H6C	0.9600
S1—C1	1.627 (5)	C7—C8	1.465 (6)
S2—C2	1.603 (6)	C7—H7A	0.9700
O1—C4	1.424 (5)	C7—H7B	0.9700
O3—Cr1ⁱ	1.993 (3)	C8—O2	1.419 (5)
O3—H3	0.8211	C8—H8A	0.9700
N1—C1	1.167 (5)	C8—H8B	0.9700
N2—C2	1.157 (6)	C9—H9A	0.9600
N3—C6	1.467 (5)	C9—H9B	0.9600
N3—C5	1.471 (5)	C9—H9C	0.9600
N3—C3	1.479 (6)	C10—H10A	0.9600
N4—C10	1.466 (6)	C10—H10B	0.9600
N4—C9	1.497 (6)	C10—H10C	0.9600
N4—C7	1.498 (6)	O2—Pb1ⁱ	2.308 (3)
C3—C4	1.515 (6)

O2ⁱ—Pb1—O1	85.15 (10)	N3—C3—H3B	109.3
O2ⁱ—Pb1—N3	88.84 (11)	C4—C3—H3B	109.3
O1—Pb1—N3	70.85 (10)	H3A—C3—H3B	107.9
O2ⁱ—Pb1—O3	65.32 (9)	O1—C4—C3	110.8 (3)
O1—Pb1—O3	62.83 (8)	O1—C4—H4A	109.5
N3—Pb1—O3	127.79 (9)	C3—C4—H4A	109.5
O1—Cr1—O2	173.46 (12)	O1—C4—H4B	109.5
O1—Cr1—O3	84.20 (11)	C3—C4—H4B	109.5
O2—Cr1—O3	93.48 (12)	H4A—C4—H4B	108.1
O1—Cr1—O3ⁱ	98.58 (11)	N3—C5—H5A	109.5
O2—Cr1—O3ⁱ	86.94 (11)	N3—C5—H5B	109.5
O3—Cr1—O3ⁱ	79.10 (11)	H5A—C5—H5B	109.5
O1—Cr1—N1	92.45 (13)	N3—C5—H5C	109.5
O2—Cr1—N1	90.82 (14)	H5A—C5—H5C	109.5
O3—Cr1—N1	170.07 (13)	H5B—C5—H5C	109.5
O3ⁱ—Cr1—N1	92.21 (13)	N3—C6—H6A	109.5
O1—Cr1—N4	91.44 (13)	N3—C6—H6B	109.5
O2—Cr1—N4	82.75 (13)	H6A—C6—H6B	109.5
O3—Cr1—N4	96.70 (13)	N3—C6—H6C	109.5
O3ⁱ—Cr1—N4	168.63 (13)	H6A—C6—H6C	109.5
N1—Cr1—N4	92.71 (15)	H6B—C6—H6C	109.5
C4—O1—Cr1	125.4 (2)	C8—C7—N4	110.6 (4)
C4—O1—Pb1	118.6 (2)	C8—C7—H7A	109.5
Cr1—O1—Pb1	113.50 (12)	N4—C7—H7A	109.5
Cr1—O3—Cr1ⁱ	100.90 (11)	C8—C7—H7B	109.5
Cr1—O3—Pb1	99.42 (10)	N4—C7—H7B	109.5
Cr1ⁱ—O3—Pb1	96.14 (10)	H7A—C7—H7B	108.1
Cr1—O3—H3	118.3	O2—C8—C7	107.9 (4)
Cr1ⁱ—O3—H3	124.4	O2—C8—H8A	110.1
Pb1—O3—H3	113.0	C7—C8—H8A	110.1
C1—N1—Cr1	174.3 (4)	O2—C8—H8B	110.1
C6—N3—C5	109.0 (4)	C7—C8—H8B	110.1
C6—N3—C3	109.9 (4)	H8A—C8—H8B	108.4
C5—N3—C3	110.6 (3)	N4—C9—H9A	109.5
C6—N3—Pb1	111.8 (3)	N4—C9—H9B	109.5
C5—N3—Pb1	114.4 (3)	H9A—C9—H9B	109.5
C3—N3—Pb1	100.9 (2)	N4—C9—H9C	109.5
C10—N4—C9	106.5 (4)	H9A—C9—H9C	109.5
C10—N4—C7	111.4 (4)	H9B—C9—H9C	109.5
C9—N4—C7	107.4 (4)	N4—C10—H10A	109.5
C10—N4—Cr1	114.3 (3)	N4—C10—H10B	109.5
C9—N4—Cr1	113.3 (3)	H10A—C10—H10B	109.5
C7—N4—Cr1	103.9 (3)	N4—C10—H10C	109.5
N1—C1—S1	177.1 (4)	H10A—C10—H10C	109.5
N2—C2—S2	177.9 (5)	H10B—C10—H10C	109.5
N3—C3—C4	111.8 (4)	C8—O2—Cr1	111.9 (3)
N3—C3—H3A	109.3	C8—O2—Pb1ⁱ	131.0 (3)
C4—C3—H3A	109.3	Cr1—O2—Pb1ⁱ	110.78 (13)

O2—Cr1—O1—C4	−126.9 (10)	O1—Pb1—N3—C3	33.2 (2)
O3—Cr1—O1—C4	163.7 (3)	O3—Pb1—N3—C3	61.4 (3)
O3ⁱ—Cr1—O1—C4	85.6 (3)	O1—Cr1—N4—C10	68.5 (4)
N1—Cr1—O1—C4	−7.0 (3)	O2—Cr1—N4—C10	−114.5 (4)
N4—Cr1—O1—C4	−99.7 (3)	O3—Cr1—N4—C10	152.8 (3)
O2—Cr1—O1—Pb1	71.6 (11)	O3ⁱ—Cr1—N4—C10	−139.6 (6)
O3—Cr1—O1—Pb1	2.16 (13)	N1—Cr1—N4—C10	−24.0 (4)
O3ⁱ—Cr1—O1—Pb1	−75.86 (13)	O1—Cr1—N4—C9	−53.7 (3)
N1—Cr1—O1—Pb1	−168.47 (15)	O2—Cr1—N4—C9	123.3 (4)
N4—Cr1—O1—Pb1	98.76 (15)	O3—Cr1—N4—C9	30.6 (3)
O2ⁱ—Pb1—O1—C4	−100.0 (3)	O3ⁱ—Cr1—N4—C9	98.2 (7)
N3—Pb1—O1—C4	−9.5 (3)	N1—Cr1—N4—C9	−146.2 (3)
O3—Pb1—O1—C4	−164.7 (3)	O1—Cr1—N4—C7	−169.9 (3)
O2ⁱ—Pb1—O1—Cr1	62.91 (14)	O2—Cr1—N4—C7	7.1 (3)
N3—Pb1—O1—Cr1	153.37 (16)	O3—Cr1—N4—C7	−85.6 (3)
O3—Pb1—O1—Cr1	−1.78 (10)	O3ⁱ—Cr1—N4—C7	−18.0 (8)
O1—Cr1—O3—Cr1ⁱ	−99.92 (12)	N1—Cr1—N4—C7	97.6 (3)
O2—Cr1—O3—Cr1ⁱ	86.21 (12)	C6—N3—C3—C4	−173.7 (4)
O3ⁱ—Cr1—O3—Cr1ⁱ	0.0	C5—N3—C3—C4	65.9 (5)
N1—Cr1—O3—Cr1ⁱ	−29.3 (8)	Pb1—N3—C3—C4	−55.6 (4)
N4—Cr1—O3—Cr1ⁱ	169.31 (13)	Cr1—O1—C4—C3	−177.4 (3)
O1—Cr1—O3—Pb1	−1.74 (10)	Pb1—O1—C4—C3	−16.7 (5)
O2—Cr1—O3—Pb1	−175.61 (11)	N3—C3—C4—O1	52.2 (5)
O3ⁱ—Cr1—O3—Pb1	98.18 (12)	C10—N4—C7—C8	90.1 (5)
N1—Cr1—O3—Pb1	68.9 (8)	C9—N4—C7—C8	−153.7 (4)
N4—Cr1—O3—Pb1	−92.51 (12)	Cr1—N4—C7—C8	−33.4 (5)
O2ⁱ—Pb1—O3—Cr1	−95.92 (12)	N4—C7—C8—O2	52.8 (6)
O1—Pb1—O3—Cr1	1.63 (10)	C7—C8—O2—Cr1	−45.9 (5)
N3—Pb1—O3—Cr1	−28.53 (17)	C7—C8—O2—Pb1ⁱ	165.2 (3)
O2ⁱ—Pb1—O3—Cr1ⁱ	6.24 (9)	O1—Cr1—O2—C8	48.5 (12)
O1—Pb1—O3—Cr1ⁱ	103.79 (11)	O3—Cr1—O2—C8	117.4 (3)
N3—Pb1—O3—Cr1ⁱ	73.63 (15)	O3ⁱ—Cr1—O2—C8	−163.7 (3)
O2ⁱ—Pb1—N3—C6	−124.8 (3)	N1—Cr1—O2—C8	−71.6 (3)
O1—Pb1—N3—C6	149.9 (3)	N4—Cr1—O2—C8	21.1 (3)
O3—Pb1—N3—C6	178.2 (3)	O1—Cr1—O2—Pb1ⁱ	−156.1 (10)
O2ⁱ—Pb1—N3—C5	−0.3 (3)	O3—Cr1—O2—Pb1ⁱ	−87.20 (13)
O1—Pb1—N3—C5	−85.5 (3)	O3ⁱ—Cr1—O2—Pb1ⁱ	−8.32 (13)
O3—Pb1—N3—C5	−57.3 (3)	N1—Cr1—O2—Pb1ⁱ	83.85 (15)
O2ⁱ—Pb1—N3—C3	118.4 (2)	N4—Cr1—O2—Pb1ⁱ	176.47 (16)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N2	0.82	1.95	2.757 (6)	169

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