[S-Allyl-4-(4-hy­droxy-2-oxidobenzyl­idene-κO)-1-(2-oxidobenzyl­idene-κO)isothio­semicarbazidato-κ2N1,N4](ethanol-κO)dioxido­uranium(VI) ethanol monosolvate

Takjoo, R.; Dutkiewicz, G.; Kubicki, M.

doi:10.1107/S1600536811049579

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Pages m1824-m1825

https://doi.org/10.1107/S1600536811049579

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[S-Allyl-4-(4-hydroxy-2-oxidobenzylidene-κO)-1-(2-oxidobenzylidene-κO)isothiosemicarbazidato-κ²N¹,N⁴](ethanol-κO)dioxidouranium(VI) ethanol monosolvate

Reza Takjoo,^a Grzegorz Dutkiewicz ^b and Maciej Kubicki ^b ^*

^aDepartment of Chemistry, School of Sciences, Ferdowsi University of Mashhad, Mashhad 91775-1436, Iran, and ^bDepartment of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznań, Poland
^*Correspondence e-mail: mkubicki@amu.edu.pl

(Received 10 November 2011; accepted 20 November 2011; online 25 November 2011)

In the title compound, [U(C₁₈H₁₅N₃O₃S)O₂(C₂H₅OH)]·C₂H₅OH, the U^VI ion is in a distorted pentagonal–bipyramidal coordination geometry, with two oxide O atoms in axial sites. Two N and two O atoms of the tetradentate ligand and an O atom of an ethanol ligand form the equatorial plane. The dihedral angle between the mean planes of the two benzene rings is 34.8 (3)°. In the crystal, relatively strong O—H⋯O hydrogen bonds connect the complex and ethanol solvent molecules into alternating centrosymmetric R₂²(8) and R₄⁴(16) ring motifs, forming chains along [100]. Weak intermolecular C—H⋯O hydrogen bonds are also present.

Related literature

For background information on salicylaldehyde-S-alkyl-thiosemicarbazone compounds, see: Gerbeleu & Revenko (1971 ); Revenko et al. (1986 ); Simonov et al. (1985 ); Yampol'skaya et al. (1982 , 1983 ). For a related structure, see: Kawasaki & Kitazawa (2008 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

[U(C₁₈H₁₅N₃O₃S)O₂(C₂H₆O)]·C₂H₆O
M_r = 715.56
Monoclinic, P 2₁ /c
a = 12.0152 (4) Å
b = 17.6609 (4) Å
c = 13.1076 (3) Å
β = 109.195 (3)°
V = 2626.79 (12) Å³
Z = 4
Mo Kα radiation
μ = 6.30 mm⁻¹
T = 100 K
0.20 × 0.12 × 0.10 mm

Data collection

Agilent Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.424, T_max = 1.000
11844 measured reflections
5467 independent reflections
4148 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.120
S = 1.01
5467 reflections
309 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 2.48 e Å⁻³
Δρ_min = −1.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O8ⁱ	0.86	1.75	2.601 (7)	173
O29—H29⋯O1S	0.86	1.79	2.646 (9)	171
O1S—H1S1⋯O26ⁱⁱ	0.86	1.87	2.718 (8)	169
C23—H23⋯O2ⁱⁱⁱ	0.95	2.49	3.395 (9)	158
C27—H27⋯O1S	0.95	2.51	3.189 (10)	128
Symmetry codes: (i) -x+2, -y, -z; (ii) -x+1, -y, -z; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablock global. DOI: https://doi.org/10.1107/S1600536811049579/lh5378sup1.cif

checkCIF report

Comment top

Some salicylaldehyde-S-alkyl-thiosemicarbazones have been synthesized by template condensation of S-alkylisothiosemicarbazide with related aldehydes and ketones. These compounds were synthesized and characterized for the first time by Gerbeleu & Revenko (1971) and a few studies of these compounds have been carried out (e.g. Yampol'skaya et al., 1982, 1983; Simonov et al., 1985, Revenko et al., 1986). The fundamental investigations of the bonding and structure of uranium complexes provides important information on the field of backend chemistry (Kawasaki & Kitazawa, 2008). We report herein the synthesis and crystal structure of the title compound (I).

The molecular structure of (I) is shown in Fig. 1. The ligand takes part in the coordination to uranium as a double-deprotonated tetradentate N₂O₂ ligand (maximum deviation from the least-squares plane by four coordinating atoms is 0.35 Å). The coordination is a quite distorted pentagonal bipyramid with two oxo O atoms in the axial sites, and the pentagonal equatorial plane, which is relatively far from planarity, is completed by an ethanol ligand. The ligand molecule itself is slightly folded as the dihedral angle between the benzene ring planes is 34.8 (3)°; the C═CH₂ group is almost perpendicular to the mean ring plane (S18—C19—C20═C21 torsion angle = -100.9 (10)°).

In the crystal, relatively strong and directional O—H···O hydrogen bonds join the complex molecules into dimers which are further expanded into a chain. There are two different centrosymmetric dimers, one created by the O4—H4···O8(2 - x,-y,-z) interactions, with the graph set R²₂(8) (Bernstein et al., 1995) and the other formed by O29—H29···O1S and O1S—H1S···O26 (1-x,-y,-z), with the graph set R⁴₄(16). The sequence of these dimers creates a hydrogen-bonded chain (Fig. 2).

Related literature top

For background information on salicylaldehyde-S-alkyl-thiosemicarbazone compounds, see: Gerbeleu & Revenko (1971); Revenko et al. (1986); Simonov et al. (1985); Yampol'skaya et al. (1982, 1983). For a related structure, see: Kawasaki & Kitazawa (2008). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

UO₂(OAc)₂.2H₂O (0.42 g, 1.0 mmol) in 20 cm³ ethanol was added to a solution of salicylaldehyde mono-S-allylisothiosemicarbazone hydrobromide (0.32 g, 1.0 mmol), 2,4-dihydroxybenzaldehyde (0.14 g, 1.0 mmol) and 0.35 cm³ (2.5 mmol) triethylamine. This red solution was heated under reflux for 1 h at 343K. Red crystals appeared after 4 days then were collected by filtration, washed with ethanol, and dried in air.

Structure description top

For background information on salicylaldehyde-S-alkyl-thiosemicarbazone compounds, see: Gerbeleu & Revenko (1971); Revenko et al. (1986); Simonov et al. (1985); Yampol'skaya et al. (1982, 1983). For a related structure, see: Kawasaki & Kitazawa (2008). For hydrogen-bond motifs, see: Bernstein et al. (1995).

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: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Anisotropic ellipsoid representation of (I) with ellipsoids drawn at 50% probability level. Hydrogen atoms are depicted as spheres with arbitrary radii.
	Fig. 2. A hydrogen bonded (dotted lines) chain along [100].

[S-Allyl-4-(4-hydroxy-2-oxidobenzylidene-κO)-1-(2- oxidobenzylidene-κO)isothiosemicarbazidato- κ²N¹,N⁴](ethanol-κO)dioxidouranium(VI) ethanol monosolvate top

Crystal data top

[U(C₁₈H₁₅N₃O₃S)O₂(C₂H₆O)]·C₂H₆O	F(000) = 1376
M_r = 715.56	D_x = 1.809 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4645 reflections
a = 12.0152 (4) Å	θ = 2.8–28.2°
b = 17.6609 (4) Å	µ = 6.30 mm⁻¹
c = 13.1076 (3) Å	T = 100 K
β = 109.195 (3)°	Block, red
V = 2626.79 (12) Å³	0.2 × 0.12 × 0.1 mm
Z = 4

Data collection top

Agilent Xcalibur Eos diffractometer	5467 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4148 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 16.1544 pixels mm^-1	θ_max = 28.3°, θ_min = 2.9°
ω–scan	h = −15→15
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −22→21
T_min = 0.424, T_max = 1.000	l = −16→16
11844 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.070P)² + 2.0206P] where P = (F_o² + 2F_c²)/3
5467 reflections	(Δ/σ)_max = 0.001
309 parameters	Δρ_max = 2.48 e Å⁻³
1 restraint	Δρ_min = −1.18 e Å⁻³

Crystal data top

[U(C₁₈H₁₅N₃O₃S)O₂(C₂H₆O)]·C₂H₆O	V = 2626.79 (12) Å³
M_r = 715.56	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.0152 (4) Å	µ = 6.30 mm⁻¹
b = 17.6609 (4) Å	T = 100 K
c = 13.1076 (3) Å	0.2 × 0.12 × 0.1 mm
β = 109.195 (3)°

Data collection top

Agilent Xcalibur Eos diffractometer	5467 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	4148 reflections with I > 2σ(I)
T_min = 0.424, T_max = 1.000	R_int = 0.031
11844 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	1 restraint
wR(F²) = 0.120	H-atom parameters constrained
S = 1.01	Δρ_max = 2.48 e Å⁻³
5467 reflections	Δρ_min = −1.18 e Å⁻³
309 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
U1	0.85612 (2)	0.123346 (13)	−0.019954 (19)	0.02921 (11)
O2	0.7621 (4)	0.1424 (3)	−0.1531 (4)	0.0344 (11)
O3	0.9470 (4)	0.1011 (3)	0.1138 (4)	0.0347 (11)
O4	0.8352 (4)	−0.0092 (2)	−0.0602 (4)	0.0310 (10)
H4	0.8855	−0.0413	−0.0219	0.037*
C5	0.7523 (9)	−0.0468 (5)	−0.1482 (8)	0.084 (4)
H5A	0.7917	−0.0624	−0.2003	0.101*
H5B	0.6887	−0.0108	−0.1856	0.101*
C6	0.6985 (12)	−0.1151 (6)	−0.1151 (12)	0.122 (7)
H6A	0.7606	−0.1518	−0.0801	0.183*
H6B	0.6417	−0.1383	−0.1790	0.183*
H6C	0.6581	−0.1000	−0.0644	0.183*
C7	1.0608 (6)	0.1338 (4)	−0.1445 (6)	0.0354 (17)
O8	1.0218 (5)	0.1062 (3)	−0.0663 (4)	0.0356 (11)
C9	1.1165 (6)	0.0868 (4)	−0.1974 (6)	0.0384 (17)
H9	1.1250	0.0344	−0.1804	0.046*
C10	1.1594 (7)	0.1156 (4)	−0.2739 (7)	0.0441 (19)
H10	1.1980	0.0828	−0.3090	0.053*
C11	1.1473 (7)	0.1928 (5)	−0.3016 (6)	0.048 (2)
H11	1.1760	0.2120	−0.3560	0.057*
C12	1.0942 (7)	0.2394 (4)	−0.2495 (6)	0.0431 (19)
H12	1.0883	0.2918	−0.2666	0.052*
C13	1.0469 (6)	0.2121 (4)	−0.1696 (6)	0.0379 (17)
C14	0.9981 (6)	0.2648 (4)	−0.1165 (6)	0.0397 (18)
H14	1.0081	0.3165	−0.1315	0.048*
N15	0.9399 (5)	0.2520 (3)	−0.0483 (5)	0.0397 (15)
N16	0.9061 (6)	0.3185 (4)	−0.0119 (6)	0.0482 (17)
C17	0.8425 (7)	0.3098 (4)	0.0480 (6)	0.0363 (17)
S18	0.7961 (2)	0.39101 (11)	0.09995 (18)	0.0496 (5)
C19	0.8632 (9)	0.4648 (4)	0.0437 (8)	0.059 (2)
H19A	0.9477	0.4536	0.0582	0.070*
H19B	0.8241	0.4678	−0.0355	0.070*
C20	0.8496 (9)	0.5379 (5)	0.0953 (8)	0.057 (2)
H20	0.9020	0.5486	0.1658	0.068*
C21	0.7689 (9)	0.5878 (5)	0.0483 (8)	0.065 (3)
H21A	0.7155	0.5784	−0.0222	0.078*
H21B	0.7637	0.6336	0.0844	0.078*
N22	0.8004 (5)	0.2383 (3)	0.0693 (5)	0.0353 (14)
C23	0.7552 (6)	0.2332 (4)	0.1475 (6)	0.0395 (18)
H23	0.7568	0.2779	0.1883	0.047*
C24	0.7047 (7)	0.1687 (5)	0.1774 (6)	0.0411 (18)
C25	0.6751 (6)	0.1012 (4)	0.1140 (6)	0.0337 (16)
O26	0.6906 (4)	0.0979 (3)	0.0188 (4)	0.0325 (11)
C27	0.6239 (7)	0.0409 (4)	0.1483 (6)	0.0379 (17)
H27	0.6041	−0.0036	0.1056	0.046*
C28	0.6012 (7)	0.0454 (4)	0.2465 (6)	0.0431 (19)
O29	0.5576 (5)	−0.0114 (4)	0.2859 (5)	0.0623 (17)
H29	0.5365	−0.0487	0.2416	0.075*
C30	0.6283 (8)	0.1125 (5)	0.3084 (7)	0.054 (2)
H30	0.6127	0.1160	0.3747	0.065*
C31	0.6763 (7)	0.1708 (5)	0.2730 (6)	0.0443 (19)
H31	0.6919	0.2160	0.3146	0.053*
O1S	0.5141 (6)	−0.1238 (3)	0.1448 (6)	0.0641 (18)
H1S1	0.4504	−0.1215	0.0902	0.077*
C2S	0.5324 (11)	−0.1992 (7)	0.1650 (15)	0.131 (7)
H2S1	0.4597	−0.2228	0.1700	0.157*
H2S2	0.5958	−0.2066	0.2351	0.157*
C3S	0.5674 (15)	−0.2376 (10)	0.0748 (16)	0.187 (10)
H3S1	0.6259	−0.2064	0.0570	0.280*
H3S2	0.4975	−0.2434	0.0106	0.280*
H3S3	0.6011	−0.2876	0.0994	0.280*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
U1	0.03164 (17)	0.02203 (15)	0.03026 (15)	0.00084 (11)	0.00514 (11)	0.00180 (10)
O2	0.037 (3)	0.027 (2)	0.037 (3)	0.002 (2)	0.010 (2)	0.004 (2)
O3	0.037 (3)	0.027 (2)	0.038 (3)	0.001 (2)	0.010 (2)	0.002 (2)
O4	0.030 (3)	0.026 (2)	0.030 (2)	0.002 (2)	0.001 (2)	−0.001 (2)
C5	0.084 (8)	0.055 (6)	0.074 (7)	−0.001 (6)	−0.026 (6)	−0.012 (5)
C6	0.081 (10)	0.057 (7)	0.168 (16)	−0.022 (6)	−0.042 (10)	−0.001 (7)
C7	0.026 (4)	0.037 (4)	0.034 (4)	−0.006 (3)	−0.003 (3)	0.011 (3)
O8	0.033 (3)	0.030 (2)	0.043 (3)	−0.002 (2)	0.011 (2)	0.008 (2)
C9	0.036 (4)	0.034 (4)	0.043 (4)	0.006 (3)	0.010 (4)	0.002 (3)
C10	0.036 (4)	0.046 (5)	0.047 (5)	−0.004 (4)	0.009 (4)	0.010 (4)
C11	0.041 (5)	0.057 (5)	0.048 (5)	0.003 (4)	0.019 (4)	0.019 (4)
C12	0.036 (4)	0.040 (4)	0.044 (4)	−0.002 (4)	0.001 (4)	0.019 (4)
C13	0.035 (4)	0.033 (4)	0.042 (4)	0.000 (3)	0.008 (4)	0.008 (3)
C14	0.031 (4)	0.039 (4)	0.043 (4)	−0.005 (3)	0.004 (3)	0.012 (3)
N15	0.041 (4)	0.022 (3)	0.046 (4)	0.002 (3)	0.001 (3)	−0.003 (3)
N16	0.050 (4)	0.030 (3)	0.057 (4)	−0.001 (3)	0.006 (4)	0.002 (3)
C17	0.048 (5)	0.018 (3)	0.035 (4)	−0.004 (3)	0.003 (4)	0.001 (3)
S18	0.0659 (15)	0.0357 (10)	0.0487 (12)	0.0003 (10)	0.0211 (11)	−0.0008 (9)
C19	0.079 (7)	0.030 (4)	0.067 (6)	−0.003 (4)	0.025 (5)	−0.002 (4)
C20	0.067 (6)	0.038 (5)	0.064 (6)	−0.007 (4)	0.020 (5)	−0.004 (4)
C21	0.088 (8)	0.030 (4)	0.067 (6)	0.000 (5)	0.013 (6)	0.002 (4)
N22	0.042 (4)	0.026 (3)	0.033 (3)	0.001 (3)	0.006 (3)	−0.002 (3)
C23	0.038 (4)	0.036 (4)	0.037 (4)	0.008 (3)	0.002 (3)	−0.004 (3)
C24	0.044 (5)	0.049 (5)	0.028 (4)	0.008 (4)	0.008 (3)	−0.006 (3)
C25	0.032 (4)	0.036 (4)	0.032 (4)	0.011 (3)	0.008 (3)	0.007 (3)
O26	0.034 (3)	0.029 (2)	0.034 (3)	0.002 (2)	0.010 (2)	−0.002 (2)
C27	0.035 (4)	0.038 (4)	0.040 (4)	0.005 (3)	0.012 (3)	0.002 (3)
C28	0.044 (5)	0.040 (4)	0.042 (4)	−0.009 (4)	0.010 (4)	0.010 (4)
O29	0.061 (4)	0.073 (4)	0.048 (3)	−0.019 (3)	0.012 (3)	0.003 (3)
C30	0.052 (5)	0.077 (7)	0.032 (4)	−0.012 (5)	0.013 (4)	−0.013 (4)
C31	0.053 (5)	0.045 (5)	0.036 (4)	−0.002 (4)	0.017 (4)	−0.011 (4)
O1S	0.043 (4)	0.066 (4)	0.067 (4)	−0.005 (3)	−0.004 (3)	0.005 (3)
C2S	0.058 (8)	0.067 (8)	0.25 (2)	−0.008 (7)	0.020 (10)	0.049 (11)
C3S	0.118 (14)	0.139 (15)	0.23 (2)	0.061 (12)	−0.046 (14)	−0.079 (15)

Geometric parameters (Å, º) top

U1—O2	1.772 (5)	C17—S18	1.756 (7)
U1—O3	1.778 (5)	S18—C19	1.812 (9)
U1—O26	2.254 (5)	C19—C20	1.492 (11)
U1—O8	2.285 (5)	C19—H19A	0.9900
U1—O4	2.394 (4)	C19—H19B	0.9900
U1—N22	2.540 (6)	C20—C21	1.306 (12)
U1—N15	2.562 (6)	C20—H20	0.9500
O4—C5	1.417 (10)	C21—H21A	0.9500
O4—H4	0.8600	C21—H21B	0.9500
C5—C6	1.4995 (10)	N22—C23	1.310 (9)
C5—H5A	0.9900	C23—C24	1.406 (11)
C5—H5B	0.9900	C23—H23	0.9500
C6—H6A	0.9800	C24—C31	1.404 (10)
C6—H6B	0.9800	C24—C25	1.429 (10)
C6—H6C	0.9800	C25—O26	1.323 (8)
C7—O8	1.351 (9)	C25—C27	1.376 (10)
C7—C9	1.386 (10)	C27—C28	1.403 (10)
C7—C13	1.419 (9)	C27—H27	0.9500
C9—C10	1.367 (10)	C28—O29	1.314 (9)
C9—H9	0.9500	C28—C30	1.411 (11)
C10—C11	1.406 (10)	O29—H29	0.8600
C10—H10	0.9500	C30—C31	1.337 (11)
C11—C12	1.356 (11)	C30—H30	0.9500
C11—H11	0.9500	C31—H31	0.9500
C12—C13	1.429 (10)	O1S—C2S	1.362 (12)
C12—H12	0.9500	O1S—H1S1	0.8601
C13—C14	1.400 (10)	C2S—C3S	1.54 (2)
C14—N15	1.322 (9)	C2S—H2S1	0.9900
C14—H14	0.9500	C2S—H2S2	0.9900
N15—N16	1.378 (8)	C3S—H3S1	0.9800
N16—C17	1.273 (10)	C3S—H3S2	0.9800
C17—N22	1.422 (9)	C3S—H3S3	0.9800

O2—U1—O3	177.8 (2)	C14—N15—U1	124.7 (5)
O2—U1—O26	86.3 (2)	N16—N15—U1	122.1 (5)
O3—U1—O26	92.0 (2)	C17—N16—N15	114.5 (6)
O2—U1—O8	95.3 (2)	N16—C17—N22	123.6 (7)
O3—U1—O8	85.8 (2)	N16—C17—S18	118.2 (5)
O26—U1—O8	160.74 (18)	N22—C17—S18	118.1 (6)
O2—U1—O4	88.96 (18)	C17—S18—C19	100.9 (4)
O3—U1—O4	89.27 (19)	C20—C19—S18	107.9 (6)
O26—U1—O4	79.50 (16)	C20—C19—H19A	110.1
O8—U1—O4	81.34 (16)	S18—C19—H19A	110.1
O2—U1—N22	97.1 (2)	C20—C19—H19B	110.1
O3—U1—N22	83.8 (2)	S18—C19—H19B	110.1
O26—U1—N22	70.73 (18)	H19A—C19—H19B	108.4
O8—U1—N22	127.82 (19)	C21—C20—C19	123.0 (9)
O4—U1—N22	149.10 (18)	C21—C20—H20	118.5
O2—U1—N15	80.9 (2)	C19—C20—H20	118.5
O3—U1—N15	101.3 (2)	C20—C21—H21A	120.0
O26—U1—N15	128.91 (19)	C20—C21—H21B	120.0
O8—U1—N15	70.15 (18)	H21A—C21—H21B	120.0
O4—U1—N15	148.54 (18)	C23—N22—C17	118.7 (6)
N22—U1—N15	62.2 (2)	C23—N22—U1	123.0 (5)
C5—O4—U1	129.2 (5)	C17—N22—U1	117.0 (5)
C5—O4—H4	109.7	N22—C23—C24	127.0 (7)
U1—O4—H4	120.9	N22—C23—H23	116.5
O4—C5—C6	113.3 (8)	C24—C23—H23	116.5
O4—C5—H5A	108.9	C31—C24—C23	118.7 (7)
C6—C5—H5A	108.9	C31—C24—C25	117.0 (7)
O4—C5—H5B	108.9	C23—C24—C25	124.2 (7)
C6—C5—H5B	108.9	O26—C25—C27	119.4 (7)
H5A—C5—H5B	107.7	O26—C25—C24	120.0 (7)
C5—C6—H6A	109.5	C27—C25—C24	120.5 (7)
C5—C6—H6B	109.5	C25—O26—U1	127.8 (4)
H6A—C6—H6B	109.5	C25—C27—C28	119.9 (7)
C5—C6—H6C	109.5	C25—C27—H27	120.0
H6A—C6—H6C	109.5	C28—C27—H27	120.0
H6B—C6—H6C	109.5	O29—C28—C27	122.7 (7)
O8—C7—C9	120.6 (6)	O29—C28—C30	117.5 (7)
O8—C7—C13	118.9 (7)	C27—C28—C30	119.8 (7)
C9—C7—C13	120.5 (7)	C28—O29—H29	112.8
C7—O8—U1	134.8 (4)	C31—C30—C28	119.4 (7)
C10—C9—C7	120.3 (7)	C31—C30—H30	120.3
C10—C9—H9	119.8	C28—C30—H30	120.3
C7—C9—H9	119.8	C30—C31—C24	123.2 (7)
C9—C10—C11	121.2 (8)	C30—C31—H31	118.4
C9—C10—H10	119.4	C24—C31—H31	118.4
C11—C10—H10	119.4	C2S—O1S—H1S1	104.6
C12—C11—C10	119.0 (7)	O1S—C2S—C3S	110.5 (14)
C12—C11—H11	120.5	O1S—C2S—H2S1	109.6
C10—C11—H11	120.5	C3S—C2S—H2S1	109.6
C11—C12—C13	122.1 (7)	O1S—C2S—H2S2	109.6
C11—C12—H12	119.0	C3S—C2S—H2S2	109.6
C13—C12—H12	119.0	H2S1—C2S—H2S2	108.1
C14—C13—C7	124.7 (7)	C2S—C3S—H3S1	109.5
C14—C13—C12	118.2 (7)	C2S—C3S—H3S2	109.5
C7—C13—C12	116.9 (7)	H3S1—C3S—H3S2	109.5
N15—C14—C13	128.6 (7)	C2S—C3S—H3S3	109.5
N15—C14—H14	115.7	H3S1—C3S—H3S3	109.5
C13—C14—H14	115.7	H3S2—C3S—H3S3	109.5
C14—N15—N16	111.7 (6)

O2—U1—O4—C5	−14.1 (7)	N16—C17—S18—C19	−0.2 (7)
O3—U1—O4—C5	164.5 (7)	N22—C17—S18—C19	−176.1 (6)
O26—U1—O4—C5	72.3 (7)	C17—S18—C19—C20	−170.4 (7)
O8—U1—O4—C5	−109.6 (7)	S18—C19—C20—C21	−100.9 (10)
N22—U1—O4—C5	87.9 (8)	N16—C17—N22—C23	167.0 (7)
N15—U1—O4—C5	−84.7 (8)	S18—C17—N22—C23	−17.3 (9)
U1—O4—C5—C6	−134.3 (8)	N16—C17—N22—U1	−0.5 (9)
C9—C7—O8—U1	−138.9 (6)	S18—C17—N22—U1	175.2 (3)
C13—C7—O8—U1	42.9 (10)	O2—U1—N22—C23	120.5 (6)
O2—U1—O8—C7	29.9 (6)	O3—U1—N22—C23	−57.4 (6)
O3—U1—O8—C7	−152.1 (6)	O26—U1—N22—C23	36.9 (5)
O26—U1—O8—C7	123.9 (7)	O8—U1—N22—C23	−137.2 (5)
O4—U1—O8—C7	118.0 (6)	O4—U1—N22—C23	20.7 (8)
N22—U1—O8—C7	−73.3 (7)	N15—U1—N22—C23	−163.7 (6)
N15—U1—O8—C7	−48.5 (6)	O2—U1—N22—C17	−72.5 (5)
O8—C7—C9—C10	−177.8 (7)	O3—U1—N22—C17	109.6 (5)
C13—C7—C9—C10	0.4 (11)	O26—U1—N22—C17	−156.1 (5)
C7—C9—C10—C11	−0.6 (12)	O8—U1—N22—C17	29.8 (6)
C9—C10—C11—C12	1.4 (12)	O4—U1—N22—C17	−172.4 (4)
C10—C11—C12—C13	−2.0 (12)	N15—U1—N22—C17	3.3 (5)
O8—C7—C13—C14	2.1 (11)	C17—N22—C23—C24	177.0 (7)
C9—C7—C13—C14	−176.2 (7)	U1—N22—C23—C24	−16.3 (10)
O8—C7—C13—C12	177.2 (6)	N22—C23—C24—C31	170.9 (7)
C9—C7—C13—C12	−1.0 (11)	N22—C23—C24—C25	−12.0 (12)
C11—C12—C13—C14	177.3 (7)	C31—C24—C25—O26	174.5 (7)
C11—C12—C13—C7	1.8 (11)	C23—C24—C25—O26	−2.7 (11)
C7—C13—C14—N15	−12.0 (13)	C31—C24—C25—C27	−1.7 (11)
C12—C13—C14—N15	172.9 (7)	C23—C24—C25—C27	−178.9 (7)
C13—C14—N15—N16	179.5 (7)	C27—C25—O26—U1	−130.7 (6)
C13—C14—N15—U1	−14.2 (11)	C24—C25—O26—U1	53.1 (8)
O2—U1—N15—C14	−68.2 (6)	O2—U1—O26—C25	−155.6 (6)
O3—U1—N15—C14	112.1 (6)	O3—U1—O26—C25	25.9 (6)
O26—U1—N15—C14	−146.0 (5)	O8—U1—O26—C25	108.9 (7)
O8—U1—N15—C14	30.8 (5)	O4—U1—O26—C25	114.8 (5)
O4—U1—N15—C14	4.5 (8)	N22—U1—O26—C25	−56.8 (5)
N22—U1—N15—C14	−171.2 (6)	N15—U1—O26—C25	−80.4 (6)
O2—U1—N15—N16	96.7 (5)	O26—C25—C27—C28	−176.5 (7)
O3—U1—N15—N16	−83.0 (5)	C24—C25—C27—C28	−0.3 (11)
O26—U1—N15—N16	19.0 (6)	C25—C27—C28—O29	−176.7 (7)
O8—U1—N15—N16	−164.3 (6)	C25—C27—C28—C30	1.5 (12)
O4—U1—N15—N16	169.5 (4)	O29—C28—C30—C31	177.9 (8)
N22—U1—N15—N16	−6.3 (5)	C27—C28—C30—C31	−0.4 (13)
C14—N15—N16—C17	175.2 (7)	C28—C30—C31—C24	−1.8 (14)
U1—N15—N16—C17	8.5 (8)	C23—C24—C31—C30	−179.8 (8)
N15—N16—C17—N22	−5.1 (10)	C25—C24—C31—C30	2.9 (12)
N15—N16—C17—S18	179.3 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O8ⁱ	0.86	1.75	2.601 (7)	173
O29—H29···O1S	0.86	1.79	2.646 (9)	171
O1S—H1S1···O26ⁱⁱ	0.86	1.87	2.718 (8)	169
C23—H23···O2ⁱⁱⁱ	0.95	2.49	3.395 (9)	158
C27—H27···O1S	0.95	2.51	3.189 (10)	128

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

Experimental details

Crystal data
Chemical formula	[U(C₁₈H₁₅N₃O₃S)O₂(C₂H₆O)]·C₂H₆O
M_r	715.56
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	12.0152 (4), 17.6609 (4), 13.1076 (3)
β (°)	109.195 (3)
V (Å³)	2626.79 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.30
Crystal size (mm)	0.2 × 0.12 × 0.1

Data collection
Diffractometer	Agilent Xcalibur Eos
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.424, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	11844, 5467, 4148
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.120, 1.01
No. of reflections	5467
No. of parameters	309
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.48, −1.18

Computer programs: CrysAlis PRO (Agilent, 2011), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O8ⁱ	0.86	1.75	2.601 (7)	173.3
O29—H29···O1S	0.86	1.79	2.646 (9)	170.8
O1S—H1S1···O26ⁱⁱ	0.86	1.87	2.718 (8)	169.1
C23—H23···O2ⁱⁱⁱ	0.95	2.49	3.395 (9)	158.2
C27—H27···O1S	0.95	2.51	3.189 (10)	128.4

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

Acknowledgements

The authors are grateful to the Ferdowsi University of Mashhad for financial support.

References

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