Crystal structure of aqua­(nitrato-κO)dioxido{2-[3-(pyridin-2-yl-κN)-1H-1,2,4-triazol-5-yl-κN4]phenolato-κO}uranium(VI) aceto­nitrile monosolvate monohydrate

Vashchenko, O.; Raspertova, I.; Dyakonenko, V.; Shishkina, S.; Khomenko, D.; Doroschuk, R.; Lampeka, R.

doi:10.1107/S205698901502438X

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ISSN: 2056-9890

Volume 72| Part 2| February 2016| Pages 111-113

doi:10.1107/S205698901502438X

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Crystal structure of aqua(nitrato-κO)dioxido{2-[3-(pyridin-2-yl-κN)-1H-1,2,4-triazol-5-yl-κN⁴]phenolato-κO}uranium(VI) acetonitrile monosolvate monohydrate

Oleksandr Vashchenko,^a Ilona Raspertova,^a ^* Viktoriya Dyakonenko,^b Svitlana Shishkina,^b Dmytro Khomenko,^a Roman Doroschuk ^a and Rostislav Lampeka ^a

^aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, 64/13, Volodymyrska Str., Kyiv, 01601, Ukraine, and ^bSTC "Institute for Single Crystals", National Academy of Science of Ukraine, 60 Lenina Ave., Kharkiv 61001, Ukraine
^*Correspondence e-mail: lana_@univ.kiev.ua

Edited by H. Ishida, Okayama University, Japan (Received 30 November 2015; accepted 18 December 2015; online 6 January 2016)

In the title compound, [U(C₁₃H₉N₄O)(NO₃)O₂(H₂O)]·CH₃CN·H₂O, the U^VI atom is seven-coordinated in a distorted pentagonal–bipyramidal N₂O₅ manner by one tridentate triazole ligand, one monodentate nitrate anion and one water molecule in the equatorial plane and by two uranyl(VI) O atoms in the axial positions. In the crystal, the U^VI complex molecule is linked to the water and acetonitrile solvent molecules through N—H⋯N, O—H⋯O and O—H⋯N hydrogen bonds, forming a sheet structure parallel to the bc plane. The sheets are further linked by an additional O—H⋯O hydrogen bond, forming a three-dimensional network.

Keywords: crystal structure; uranyl(VI) ion; 1,2,4-triazole.

CCDC reference: 1443165

1. Chemical context

The synthesis of coordination compounds with N-donor heterocyclic ligands is one of the fastest growing areas of coordination chemistry. 1,2,4-Triazoles and their derivatives can be assigned for such types of ligands. The presence of the 1,2,4-triazole ring in the organic ligand provides an additional site for coordination (Aromí et al., 2011 ). The presence of additional donor groups in the 3- and 5-positions of the triazole moiety provides a greater number of possibilities for chelation of metal ions, involving tridentate bis-chelate functions.

It should be noted that UO₂²⁺ complexes with such types of ligands have rarely been investigated. Thus, only three uranyl complexes with 1,2,4-triazole derivatives have been characterized (Daro et al., 2001 ; Weng et al., 2012 ; Raspertova et al., 2012 ). As part of our continuing study of uranium coordination compounds with nitrogen-donor ligands (Raspertova et al., 2012), we report here the structure of the title compound.

2. Structural commentary

The coordination polyhedron of the U^VI atom in the title complex is a distorted pentagonal bipyramid. It is coordinated in a tridentate manner by the 1,2,4,-triazole ligand together with the water molecule and the monodentate nitrate anion in the equatorial plane. Two oxido ligands are placed in the axial positions (Fig. 1). The U1—O1 bond length [2.206 (3) Å] is comparable with those reported for related six-membered chelate fragments involving phenolate and N-atom donors (Sopo et al., 2008 ; Ahmadi et al., 2012 ). The U—N bond lengths [2.489 (4) and 2.658 (4) Å] are consistent with the situation in other pyridine-bonded uranium complexes (Amoroso et al., 1996 ; Gatto et al., 2004 ). The uranyl group is not exactly linear [O2=U1=O3 = 175.36 (14)°]. Non-linear O=U= groups are generally found in uranyl complexes with five non-symmetrically bonding equatorial ligands. All non-hydrogen atoms of the organic ligand are coplanar within 0.01 Å. The N1—C7 and C7—N2 bond lengths of the triazole ring are equalized [1.336 (5) Å for both]. This value is longer than a Csp² =N double bond (1.276 Å) and shorter than a Csp²—N single bond (1.347 Å) (Orpen et al., 1994 ). It can be assumed that the structure of the triazole ring is the superposition of two possible resonance structures as shown in Fig. 2.

Figure 1
The molecular structure of the title compound, shown with 50% probability displacement ellipsoids. Dashed lines indicate hydrogen bonds.

Figure 2
Scheme showing two possible resonance structures in the triazole ligand.

3. Supramolecular features

In the crystal, the complex molecule is linked to the water and acetonitrile solvent molecules through N2—H2⋯N6, O4—H4B⋯O8, O8—H8A⋯N3ⁱⁱ and O8—H8B⋯O6ⁱⁱⁱ hydrogen bonds (symmetry codes in Table 1), forming a sheet structure parallel to the bc plane. The sheets are further linked by an O4—H4A⋯O5ⁱ hydrogen bond (Table 1), forming a three-dimensional network (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O5ⁱ	0.86 (1)	1.92 (2)	2.752 (4)	162 (5)
O4—H4B⋯O8	0.86 (1)	1.73 (1)	2.581 (5)	168 (5)
N2—H2⋯N6	0.86	2.07	2.909 (5)	165
O8—H8A⋯N3ⁱⁱ	0.86 (1)	2.05 (2)	2.890 (5)	164 (6)
O8—H8B⋯O6ⁱⁱⁱ	0.86 (1)	2.22 (3)	3.001 (5)	150 (6)
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) x, y+1, z.

Figure 3
Packing diagram of the title compound, viewed along the b axis. Intermolecular hydrogen bonds are shown as dashed lines.

4. Database survey

In the Cambridge Structural Database (Version 5.36, November 2014; Groom & Allen, 2014 ), only three uranyl complexes with derivatives of 1,2,4-triazole are reported (Daro et al., 2001; Weng et al., 2012; Raspertova et al., 2012). 72 structures containing a 5-pyridin-1H-1,2,4-triazole fragment are found. A search for the 3-hydroxyphenyl-1,2,4-triazole fragment yielded 14 hits, including: 2,2′-[1-(2,4,6-trichlorophenyl)-1H-1,2,4-triazole-3,5-diyl]diphenol (Li et al., 2008 ); 2-[5-(2-pyridyl)-1,2,4-triazole-3-yl]phenol 2-[3-(2-pyridyl)-1,2,4-triazole-5-yl]phenol bis(7,7,8,8-tetracyanoquinodimethane) (Bentiss et al., 2002 ); bis[μ₂-1-phenyl-3,5-bis(2-oxyphenyl)-1,2,4-triazole]bis(pyridine)dicopper (Steinhauser et al., 2004 ). Only one compound containing both hydroxyphenyl and pyridyl, as substituents in the 3- and 5-positions of 1,2,4-triazole, was found (Bentiss et al., 2002).

5. Synthesis and crystallization

A mixture of 3-(2-hydroxyphenyl)-5-(pyridin-2-yl)-1H-1,2,4-triazole (0.5 mmol) and [UO₂(NO₃)₂]·2H₂O (0.5 mmol) in acetonitrile (20 ml) was stirred for 20 min. The solution was left to evaporate slowly at room temperature. Red single crystals suitable for X-ray analysis were obtained after 2 d.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms were located in a difference Fourier map. The positional parameters of water H atoms were refined, with the restraint O—H = 0.860 (2) Å and the constraint U_iso(H) = 1.5U_eq(O). All other H atoms were constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C, N).

Table 2
Experimental details

Crystal data
Chemical formula	[U(C₁₃H₉N₄O)(NO₃)O₂(H₂O)]·CH₃CN·H₂O
M_r	646.37
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	12.0962 (3), 7.87839 (17), 20.4041 (4)
β (°)	94.829 (2)
V (Å³)	1937.57 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	8.44
Crystal size (mm)	0.5 × 0.3 × 0.2

Data collection
Diffractometer	Agilent Xcalibur, Sapphire3
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.055, 0.185
No. of measured, independent and observed [I > 2σ(I)] reflections	9385, 4446, 3936
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.064, 1.05
No. of reflections	4446
No. of parameters	284
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.81, −0.88
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1443165

Crystal structure: contains datablocks Global, I. DOI: 10.1107/S205698901502438X/is5435sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S205698901502438X/is5435Isup2.hkl

checkCIF report

Chemical context top

The synthesis of coordination compounds with N-donor heterocyclic ligands is one of the fastest growing areas of coordination chemistry. 1,2,4-Triazoles and their derivatives can be assigned for such types of ligands. The presence of the 1,2,4-triazole ring in the organic ligand provides an additional site for coordination (Aromí et al., 2011). The presence of additional donor groups in the 3- and 5-positions of the triazole moiety provides a greater number of possibilities for chelation of metal ions, involving tridentate bis-chelate functions.

It should be note that UO₂²⁺ complexes with such types of ligands have rarely been investigated. Thus, only three uranyl complexes with 1,2,4-triazole derivatives have been characterized (Daro et al., 2001; Weng et al., 2012; Raspertova et al., 2012). As part of our continuing study of uranium coordination compounds with nitrogen-donor ligands (Raspertova et al., 2012), we report here the structure of the title compound.

Structural commentary top

The coordination polyhedron of the U^VI atom in the title complex is a distorted pentagonal bipyramid. It is coordinated in a tridentate manner by the 1,2,4,-triazole ligand together with the water molecule and the monodentate nitrate anion in the equatorial plane. Two oxo ligands are placed in the axial positions (Fig. 1). The U1—O1 bond length [2.206 (3) Å] is comparable with those reported for related six-membered chelate fragments involving phenolate and N-atom donors (Sopo et al., 2008; Ahmadi et al., 2012). The U—N bond lengths [2.489 (4) and 2.658 (4) Å] are consistent with the situation in other pyridine-bonded uranium complexes (Amoroso et al., 1996; Gatto et al., 2004). The uranyl group is not exactly linear [O2═U1═O3 = 175.36 (14)°]. Non-linear O═U═O bonds are generally found in uranyl complexes with five non-symmetrically bonding equatorial ligands. All non-hydrogen atoms of the organic ligand are coplanar within 0.01 Å. The N1—C7 and C7—N2 bond lengths of the triazole ring are equalized [1.336 (5) Å for both]. This value is longer than a Csp² ═N double bond (1.276 Å) and shorter than a Csp²—N single bond (1.347 Å) (Orpen et al., 1994). It can be assumed that the structure of the triazole ring is the superposition of two resonance structures as shown in Fig. 2.

Supramolecular features top

In the crystal, the complex molecule is linked to the water and acetonitrile solvent molecules through N2—H2···N6, O4—H4B···O8, O8—H8A···N3ⁱⁱ and O8—H8B···O6ⁱⁱⁱ hydrogen bonds (symmetry codes in Table 1), forming a sheet structure parallel to the bc plane. The sheets are further linked by an O4—H4A···O5ⁱ hydrogen bond (Table 1), forming a three-dimensional network (Fig. 3).

Database survey top

In the Cambridge Structural Database (Version 5.36, November 2014; Groom & Allen, 2014), only three uranyl complexes with derivatives of 1,2,4-triazole are reported (Daro et al., 2001; Weng et al., 2012; Raspertova et al., 2012). 72 structures containing a 5-pyridin-1H-1,2,4-triazole fragment are found. A search for the 3-hydroxyphenyl-1,2,4-triazole fragment yielded 14 hits, including: 2,2'-[1-(2,4,6-trichlorophenyl)-1H-1,2,4-triazole-3,5-diyl]diphenol (Li et al., 2008); 2-[5-(2-pyridyl)-1,2,4-triazole-3-yl]phenol 2-[3-(2-pyridyl)-1,2,4-triazole-5-yl]phenol bis(7,7,8,8-tetracyanoquinodimethane) (Bentiss et al., 2002); bis[µ₂-1-phenyl-3,5-bis(2-oxyphenyl)-1,2,4-triazole]bis(pyridine)dicopper (Steinhauser et al., 2004). Only one compound containing both hydroxyphenyl and pyridyl, as substituents in the 3- and 5-positions of 1,2,4-triazole, was found (Bentiss et al., 2002).

Synthesis and crystallization top

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. A l l hydrogen atoms were located in a difference Fourier map. The positional parameters of water H atoms were refined, with the restraint O—H = 0.860 (2) Å and the constraint U_iso(H) = 1.5U_eq(O). All other H atoms were constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C, N).

Related literature top

For related literature, see: Ahmadi et al. (2012); Amoroso et al. (1996); Aromí et al. (2011); Bentiss et al. (2002); Orpen et al. (1994); Daro et al. (2001); Gatto et al. (2004); Groom & Allen (2014); Li et al. (2008); Raspertova et al. (2012); Sopo et al. (2008); Steinhauser et al. (2004); Weng et al. (2012).

Structure description top

The synthesis of coordination compounds with N-donor heterocyclic ligands is one of the fastest growing areas of coordination chemistry. 1,2,4-Triazoles and their derivatives can be assigned for such types of ligands. The presence of the 1,2,4-triazole ring in the organic ligand provides an additional site for coordination (Aromí et al., 2011). The presence of additional donor groups in the 3- and 5-positions of the triazole moiety provides a greater number of possibilities for chelation of metal ions, involving tridentate bis-chelate functions.

The coordination polyhedron of the U^VI atom in the title complex is a distorted pentagonal bipyramid. It is coordinated in a tridentate manner by the 1,2,4,-triazole ligand together with the water molecule and the monodentate nitrate anion in the equatorial plane. Two oxo ligands are placed in the axial positions (Fig. 1). The U1—O1 bond length [2.206 (3) Å] is comparable with those reported for related six-membered chelate fragments involving phenolate and N-atom donors (Sopo et al., 2008; Ahmadi et al., 2012). The U—N bond lengths [2.489 (4) and 2.658 (4) Å] are consistent with the situation in other pyridine-bonded uranium complexes (Amoroso et al., 1996; Gatto et al., 2004). The uranyl group is not exactly linear [O2═U1═O3 = 175.36 (14)°]. Non-linear O═U═O bonds are generally found in uranyl complexes with five non-symmetrically bonding equatorial ligands. All non-hydrogen atoms of the organic ligand are coplanar within 0.01 Å. The N1—C7 and C7—N2 bond lengths of the triazole ring are equalized [1.336 (5) Å for both]. This value is longer than a Csp² ═N double bond (1.276 Å) and shorter than a Csp²—N single bond (1.347 Å) (Orpen et al., 1994). It can be assumed that the structure of the triazole ring is the superposition of two resonance structures as shown in Fig. 2.

In the Cambridge Structural Database (Version 5.36, November 2014; Groom & Allen, 2014), only three uranyl complexes with derivatives of 1,2,4-triazole are reported (Daro et al., 2001; Weng et al., 2012; Raspertova et al., 2012). 72 structures containing a 5-pyridin-1H-1,2,4-triazole fragment are found. A search for the 3-hydroxyphenyl-1,2,4-triazole fragment yielded 14 hits, including: 2,2'-[1-(2,4,6-trichlorophenyl)-1H-1,2,4-triazole-3,5-diyl]diphenol (Li et al., 2008); 2-[5-(2-pyridyl)-1,2,4-triazole-3-yl]phenol 2-[3-(2-pyridyl)-1,2,4-triazole-5-yl]phenol bis(7,7,8,8-tetracyanoquinodimethane) (Bentiss et al., 2002); bis[µ₂-1-phenyl-3,5-bis(2-oxyphenyl)-1,2,4-triazole]bis(pyridine)dicopper (Steinhauser et al., 2004). Only one compound containing both hydroxyphenyl and pyridyl, as substituents in the 3- and 5-positions of 1,2,4-triazole, was found (Bentiss et al., 2002).

Synthesis and crystallization top

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 2. A l l hydrogen atoms were located in a difference Fourier map. The positional parameters of water H atoms were refined, with the restraint O—H = 0.860 (2) Å and the constraint U_iso(H) = 1.5U_eq(O). All other H atoms were constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C, N).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, shown with 50% probability displacement ellipsoids. Dashed lines indicate hydrogen bonds.
	Fig. 2. Scheme showing the resonance structures in the triazole ligand.
	Fig. 3. Packing diagram of the title compound, viewed along the b axis. Intermolecular hydrogen bonds are shown as dashed lines.

Aqua(nitrato-κO)dioxido{2-[3-(pyridin-2-yl-κN)-1H-1,2,4-triazol-5-yl-κN⁴]phenolato-κO}uranium(VI) acetonitrile monosolvate monohydrate top

Crystal data top

[U(C₁₃H₉N₄O)(NO₃)O₂(H₂O)]·CH₃CN·H₂O	F(000) = 1216
M_r = 646.37	D_x = 2.216 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.0962 (3) Å	Cell parameters from 4414 reflections
b = 7.87839 (17) Å	θ = 3.3–31.9°
c = 20.4041 (4) Å	µ = 8.44 mm⁻¹
β = 94.829 (2)°	T = 294 K
V = 1937.57 (7) Å³	Block, red
Z = 4	0.5 × 0.3 × 0.2 mm

Data collection top

Agilent Xcalibur, Sapphire3 diffractometer	4446 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3936 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 16.1827 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −15→15
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −5→10
T_min = 0.055, T_max = 0.185	l = −26→26
9385 measured reflections

Refinement top

Refinement on F²	4 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.064	w = 1/[σ²(F_o²) + (0.0276P)²] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
4446 reflections	Δρ_max = 1.81 e Å⁻³
284 parameters	Δρ_min = −0.88 e Å⁻³

Crystal data top

[U(C₁₃H₉N₄O)(NO₃)O₂(H₂O)]·CH₃CN·H₂O	V = 1937.57 (7) Å³
M_r = 646.37	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.0962 (3) Å	µ = 8.44 mm⁻¹
b = 7.87839 (17) Å	T = 294 K
c = 20.4041 (4) Å	0.5 × 0.3 × 0.2 mm
β = 94.829 (2)°

Data collection top

Agilent Xcalibur, Sapphire3 diffractometer	4446 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	3936 reflections with I > 2σ(I)
T_min = 0.055, T_max = 0.185	R_int = 0.032
9385 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	4 restraints
wR(F²) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 1.81 e Å⁻³
4446 reflections	Δρ_min = −0.88 e Å⁻³
284 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
U1	0.81873 (2)	0.51832 (2)	0.40174 (2)	0.01286 (6)
O1	0.7272 (3)	0.2815 (4)	0.37710 (15)	0.0193 (7)
O2	0.6934 (2)	0.6205 (4)	0.41869 (15)	0.0189 (7)
O3	0.9494 (2)	0.4323 (4)	0.38551 (15)	0.0179 (6)
O4	0.9187 (2)	0.7071 (4)	0.47688 (15)	0.0164 (6)
H4A	0.9886 (8)	0.709 (7)	0.489 (2)	0.025*
H4B	0.890 (3)	0.768 (5)	0.5061 (16)	0.025*
O5	0.8563 (2)	0.3461 (4)	0.50215 (14)	0.0186 (7)
O6	0.8368 (3)	0.2773 (4)	0.60322 (15)	0.0234 (7)
O7	0.7619 (3)	0.5091 (4)	0.56334 (18)	0.0258 (8)
N1	0.7589 (3)	0.5025 (4)	0.28218 (18)	0.0128 (7)
N2	0.6933 (3)	0.4457 (5)	0.18299 (18)	0.0162 (7)
H2	0.6608	0.3920	0.1501	0.019*
N3	0.7399 (3)	0.6016 (4)	0.17900 (18)	0.0159 (8)
N4	0.8707 (3)	0.7819 (4)	0.32904 (18)	0.0134 (7)
N5	0.8162 (3)	0.3796 (5)	0.55859 (18)	0.0174 (8)
N6	0.5829 (3)	0.3255 (5)	0.0595 (2)	0.0266 (9)
C1	0.6794 (3)	0.1782 (5)	0.3324 (2)	0.0138 (8)
C2	0.6414 (3)	0.0177 (5)	0.3517 (2)	0.0184 (9)
H2A	0.6503	−0.0141	0.3957	0.022*
C3	0.5915 (3)	−0.0919 (5)	0.3057 (2)	0.0183 (9)
H3	0.5661	−0.1965	0.3194	0.022*
C4	0.5781 (3)	−0.0498 (5)	0.2396 (2)	0.0166 (9)
H4	0.5443	−0.1250	0.2090	0.020*
C5	0.6158 (3)	0.1056 (5)	0.2200 (2)	0.0155 (9)
H5	0.6081	0.1343	0.1756	0.019*
C6	0.6654 (3)	0.2206 (5)	0.2653 (2)	0.0126 (8)
C7	0.7042 (3)	0.3861 (5)	0.2445 (2)	0.0114 (8)
C8	0.7785 (3)	0.6308 (5)	0.2401 (2)	0.0142 (9)
C9	0.8385 (3)	0.7813 (5)	0.2635 (2)	0.0142 (9)
C10	0.8617 (3)	0.9142 (5)	0.2225 (2)	0.0163 (9)
H10	0.8386	0.9105	0.1778	0.020*
C11	0.9198 (3)	1.0527 (6)	0.2489 (2)	0.0184 (9)
H11	0.9361	1.1435	0.2222	0.022*
C12	0.9532 (3)	1.0555 (6)	0.3147 (2)	0.0169 (9)
H12	0.9923	1.1478	0.3331	0.020*
C13	0.9277 (3)	0.9180 (5)	0.3534 (2)	0.0176 (9)
H13	0.9510	0.9201	0.3980	0.021*
C14	0.5369 (4)	0.2758 (6)	0.0120 (2)	0.0199 (10)
C15	0.4767 (4)	0.2097 (6)	−0.0472 (2)	0.0271 (11)
H15A	0.4567	0.3017	−0.0767	0.041*
H15B	0.4107	0.1531	−0.0358	0.041*
H15C	0.5227	0.1308	−0.0682	0.041*
O8	0.8271 (3)	0.9203 (5)	0.55170 (19)	0.0344 (9)
H8A	0.811 (5)	0.899 (8)	0.5911 (11)	0.052*
H8B	0.844 (5)	1.026 (2)	0.554 (3)	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
U1	0.01190 (9)	0.01556 (9)	0.01102 (9)	0.00016 (6)	0.00039 (6)	−0.00106 (6)
O1	0.0240 (17)	0.0209 (15)	0.0128 (16)	−0.0051 (14)	0.0006 (13)	0.0014 (13)
O2	0.0149 (15)	0.0223 (16)	0.0193 (16)	0.0039 (13)	0.0005 (13)	0.0015 (14)
O3	0.0129 (14)	0.0216 (15)	0.0190 (17)	0.0029 (13)	0.0000 (13)	−0.0040 (14)
O4	0.0138 (15)	0.0233 (15)	0.0120 (16)	0.0025 (14)	−0.0002 (13)	−0.0054 (13)
O5	0.0216 (16)	0.0249 (16)	0.0089 (15)	0.0012 (13)	−0.0011 (13)	−0.0012 (13)
O6	0.0261 (18)	0.0266 (17)	0.0173 (17)	0.0002 (15)	0.0008 (14)	0.0083 (15)
O7	0.0230 (17)	0.0289 (18)	0.0260 (19)	0.0110 (14)	0.0042 (15)	0.0026 (15)
N1	0.0115 (16)	0.0133 (17)	0.0135 (18)	0.0012 (14)	0.0007 (14)	0.0015 (14)
N2	0.0154 (17)	0.0184 (17)	0.0144 (19)	−0.0051 (15)	−0.0009 (15)	−0.0043 (16)
N3	0.0167 (18)	0.0177 (18)	0.0134 (19)	−0.0033 (15)	0.0017 (15)	0.0001 (15)
N4	0.0104 (16)	0.0174 (17)	0.0120 (18)	0.0003 (14)	−0.0015 (14)	−0.0026 (15)
N5	0.0140 (18)	0.0236 (19)	0.0150 (19)	−0.0034 (16)	0.0033 (15)	0.0007 (16)
N6	0.027 (2)	0.033 (2)	0.019 (2)	−0.0034 (19)	−0.0013 (18)	−0.0018 (19)
C1	0.0110 (19)	0.0156 (19)	0.015 (2)	0.0022 (16)	0.0003 (16)	−0.0033 (18)
C2	0.012 (2)	0.023 (2)	0.020 (2)	0.0018 (18)	0.0005 (18)	0.0047 (19)
C3	0.013 (2)	0.016 (2)	0.027 (3)	−0.0022 (18)	0.0048 (19)	−0.0059 (19)
C4	0.013 (2)	0.016 (2)	0.020 (2)	−0.0016 (18)	−0.0021 (17)	−0.0070 (19)
C5	0.0103 (19)	0.020 (2)	0.017 (2)	0.0040 (17)	0.0032 (17)	−0.0005 (18)
C6	0.0065 (18)	0.017 (2)	0.015 (2)	0.0020 (16)	0.0026 (16)	0.0008 (17)
C7	0.0084 (18)	0.0141 (19)	0.012 (2)	0.0010 (16)	0.0011 (16)	−0.0027 (17)
C8	0.0112 (19)	0.018 (2)	0.014 (2)	0.0017 (17)	0.0039 (17)	0.0002 (18)
C9	0.0075 (19)	0.020 (2)	0.016 (2)	0.0015 (17)	0.0026 (17)	−0.0018 (18)
C10	0.013 (2)	0.023 (2)	0.014 (2)	−0.0004 (18)	0.0044 (17)	−0.0014 (19)
C11	0.014 (2)	0.020 (2)	0.022 (2)	−0.0016 (18)	0.0037 (18)	0.004 (2)
C12	0.013 (2)	0.0138 (19)	0.024 (2)	−0.0029 (17)	0.0018 (18)	−0.0033 (19)
C13	0.013 (2)	0.017 (2)	0.022 (2)	−0.0021 (18)	0.0002 (18)	−0.0036 (19)
C14	0.019 (2)	0.022 (2)	0.020 (2)	−0.0022 (19)	0.0042 (19)	0.001 (2)
C15	0.030 (3)	0.029 (3)	0.022 (3)	−0.007 (2)	−0.002 (2)	0.000 (2)
O8	0.049 (2)	0.0243 (18)	0.033 (2)	0.0018 (18)	0.0193 (19)	−0.0056 (18)

Geometric parameters (Å, º) top

U1—O1	2.206 (3)	C2—H2A	0.9300
U1—O2	1.776 (3)	C2—C3	1.376 (6)
U1—O3	1.777 (3)	C3—H3	0.9300
U1—O4	2.390 (3)	C3—C4	1.386 (6)
U1—O5	2.467 (3)	C4—H4	0.9300
U1—N1	2.489 (4)	C4—C5	1.378 (6)
U1—N4	2.658 (4)	C5—H5	0.9300
O1—C1	1.319 (5)	C5—C6	1.394 (6)
O4—H4A	0.860 (2)	C6—C7	1.461 (5)
O4—H4B	0.860 (2)	C8—C9	1.451 (6)
O5—N5	1.313 (4)	C9—C10	1.385 (6)
O6—N5	1.226 (5)	C10—H10	0.9300
O7—N5	1.221 (5)	C10—C11	1.383 (6)
N1—C7	1.336 (5)	C11—H11	0.9300
N1—C8	1.360 (5)	C11—C12	1.368 (6)
N2—H2	0.8600	C12—H12	0.9300
N2—N3	1.357 (5)	C12—C13	1.391 (6)
N2—C7	1.336 (5)	C13—H13	0.9300
N3—C8	1.314 (5)	C14—C15	1.453 (6)
N4—C9	1.360 (5)	C15—H15A	0.9600
N4—C13	1.347 (5)	C15—H15B	0.9600
N6—C14	1.146 (6)	C15—H15C	0.9600
C1—C2	1.413 (6)	O8—H8A	0.860 (2)
C1—C6	1.405 (6)	O8—H8B	0.860 (2)

O1—U1—O4	152.83 (11)	C3—C2—C1	120.4 (4)
O1—U1—O5	77.17 (10)	C3—C2—H2A	119.8
O1—U1—N1	68.61 (11)	C2—C3—H3	119.3
O1—U1—N4	132.17 (11)	C2—C3—C4	121.5 (4)
O2—U1—O1	90.45 (12)	C4—C3—H3	119.3
O2—U1—O3	175.36 (14)	C3—C4—H4	120.6
O2—U1—O4	89.24 (12)	C5—C4—C3	118.8 (4)
O2—U1—O5	100.84 (12)	C5—C4—H4	120.6
O2—U1—N1	91.78 (13)	C4—C5—H5	119.3
O2—U1—N4	90.02 (12)	C4—C5—C6	121.3 (4)
O3—U1—O1	94.15 (13)	C6—C5—H5	119.3
O3—U1—O4	86.96 (12)	C1—C6—C7	118.7 (4)
O3—U1—O5	80.83 (12)	C5—C6—C1	120.1 (4)
O3—U1—N1	89.32 (13)	C5—C6—C7	121.2 (4)
O3—U1—N4	86.43 (13)	N1—C7—C6	126.9 (4)
O4—U1—O5	76.21 (10)	N2—C7—N1	107.7 (4)
O4—U1—N1	138.56 (11)	N2—C7—C6	125.3 (4)
O4—U1—N4	75.00 (11)	N1—C8—C9	120.5 (4)
O5—U1—N1	143.57 (10)	N3—C8—N1	113.7 (4)
O5—U1—N4	149.01 (10)	N3—C8—C9	125.7 (4)
N1—U1—N4	63.57 (10)	N4—C9—C8	114.9 (4)
C1—O1—U1	149.5 (3)	N4—C9—C10	122.4 (4)
U1—O4—H4A	129 (4)	C10—C9—C8	122.7 (4)
U1—O4—H4B	126 (3)	C9—C10—H10	120.6
H4A—O4—H4B	104 (4)	C11—C10—C9	118.8 (4)
N5—O5—U1	124.2 (2)	C11—C10—H10	120.6
C7—N1—U1	133.5 (3)	C10—C11—H11	120.2
C7—N1—C8	104.5 (4)	C12—C11—C10	119.6 (4)
C8—N1—U1	122.0 (3)	C12—C11—H11	120.2
N3—N2—H2	124.3	C11—C12—H12	120.5
C7—N2—H2	124.3	C11—C12—C13	119.0 (4)
C7—N2—N3	111.5 (3)	C13—C12—H12	120.5
C8—N3—N2	102.6 (3)	N4—C13—C12	122.7 (4)
C9—N4—U1	118.9 (3)	N4—C13—H13	118.6
C13—N4—U1	123.6 (3)	C12—C13—H13	118.6
C13—N4—C9	117.5 (4)	N6—C14—C15	178.4 (5)
O6—N5—O5	116.9 (4)	C14—C15—H15A	109.5
O7—N5—O5	118.6 (4)	C14—C15—H15B	109.5
O7—N5—O6	124.6 (4)	C14—C15—H15C	109.5
O1—C1—C2	119.5 (4)	H15A—C15—H15B	109.5
O1—C1—C6	122.5 (4)	H15A—C15—H15C	109.5
C6—C1—C2	118.0 (4)	H15B—C15—H15C	109.5
C1—C2—H2A	119.8	H8A—O8—H8B	102 (6)

U1—O1—C1—C2	172.3 (4)	C1—C6—C7—N1	4.2 (6)
U1—O1—C1—C6	−7.1 (8)	C1—C6—C7—N2	−177.7 (4)
U1—O5—N5—O6	175.9 (2)	C2—C1—C6—C5	−0.3 (6)
U1—O5—N5—O7	−4.3 (5)	C2—C1—C6—C7	180.0 (4)
U1—N1—C7—N2	179.1 (3)	C2—C3—C4—C5	−0.1 (6)
U1—N1—C7—C6	−2.6 (6)	C3—C4—C5—C6	−0.8 (6)
U1—N1—C8—N3	−179.2 (3)	C4—C5—C6—C1	1.0 (6)
U1—N1—C8—C9	1.8 (5)	C4—C5—C6—C7	−179.3 (4)
U1—N4—C9—C8	−0.6 (4)	C5—C6—C7—N1	−175.5 (4)
U1—N4—C9—C10	179.5 (3)	C5—C6—C7—N2	2.6 (6)
U1—N4—C13—C12	−179.3 (3)	C6—C1—C2—C3	−0.6 (6)
O1—C1—C2—C3	−180.0 (4)	C7—N1—C8—N3	−0.1 (5)
O1—C1—C6—C5	179.0 (4)	C7—N1—C8—C9	−179.2 (4)
O1—C1—C6—C7	−0.7 (6)	C7—N2—N3—C8	0.1 (4)
N1—C8—C9—N4	−0.7 (5)	C8—N1—C7—N2	0.2 (4)
N1—C8—C9—C10	179.2 (4)	C8—N1—C7—C6	178.5 (4)
N2—N3—C8—N1	0.0 (4)	C8—C9—C10—C11	−179.8 (4)
N2—N3—C8—C9	179.0 (4)	C9—N4—C13—C12	0.6 (6)
N3—N2—C7—N1	−0.2 (5)	C9—C10—C11—C12	0.1 (6)
N3—N2—C7—C6	−178.6 (4)	C10—C11—C12—C13	0.0 (6)
N3—C8—C9—N4	−179.6 (4)	C11—C12—C13—N4	−0.4 (6)
N3—C8—C9—C10	0.2 (6)	C13—N4—C9—C8	179.4 (4)
N4—C9—C10—C11	0.1 (6)	C13—N4—C9—C10	−0.4 (6)
C1—C2—C3—C4	0.8 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O5ⁱ	0.86 (1)	1.92 (2)	2.752 (4)	162 (5)
O4—H4B···O8	0.86 (1)	1.73 (1)	2.581 (5)	168 (5)
N2—H2···N6	0.86	2.07	2.909 (5)	165
O8—H8A···N3ⁱⁱ	0.86 (1)	2.05 (2)	2.890 (5)	164 (6)
O8—H8B···O6ⁱⁱⁱ	0.86 (1)	2.22 (3)	3.001 (5)	150 (6)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, −y+3/2, z+1/2; (iii) x, y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O5ⁱ	0.860 (2)	1.920 (16)	2.752 (4)	162 (5)
O4—H4B···O8	0.860 (2)	1.733 (10)	2.581 (5)	168 (5)
N2—H2···N6	0.86	2.07	2.909 (5)	165
O8—H8A···N3ⁱⁱ	0.860 (2)	2.053 (18)	2.890 (5)	164 (6)
O8—H8B···O6ⁱⁱⁱ	0.860 (2)	2.22 (3)	3.001 (5)	150 (6)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, −y+3/2, z+1/2; (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	[U(C₁₃H₉N₄O)(NO₃)O₂(H₂O)]·CH₃CN·H₂O
M_r	646.37
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	12.0962 (3), 7.87839 (17), 20.4041 (4)
β (°)	94.829 (2)
V (Å³)	1937.57 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	8.44
Crystal size (mm)	0.5 × 0.3 × 0.2

Data collection
Diffractometer	Agilent Xcalibur, Sapphire3
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014)
T_min, T_max	0.055, 0.185
No. of measured, independent and observed [I > 2σ(I)] reflections	9385, 4446, 3936
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.064, 1.05
No. of reflections	4446
No. of parameters	284
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.81, −0.88

Computer programs: CrysAlis PRO (Agilent, 2014), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), OLEX2 (Dolomanov et al., 2009).

References

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Volume 72| Part 2| February 2016| Pages 111-113

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