Crystal structure of μ-peroxido-κ4O1,O2:O1′,O2′-bis­[(nitrato-κO)(2,2′:6′,2′′-terpyridine-κ3N,N′,N′′)dioxidouranium(VI)]

Kawasaki, T.; Kitazawa, T.

doi:10.1107/S2056989015007987

metal-organic compounds

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ISSN: 2056-9890

Volume 71| Part 5| May 2015| Pages m122-m123

https://doi.org/10.1107/S2056989015007987

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Crystal structure of μ-peroxido-κ⁴O¹,O²:O^1′,O^2′-bis[(nitrato-κO)(2,2′:6′,2′′-terpyridine-κ³N,N′,N′′)dioxidouranium(VI)]

Takeshi Kawasaki ^a and Takafumi Kitazawa ^a,^b ^*

^aDepartment of Chemistry, Faculty of Science, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan, and ^bResearch Center for Materials with Integrated Properties, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan
^*Correspondence e-mail: kitazawa@chem.sci.toho-u.ac.jp

Edited by A. M. Chippindale, University of Reading, England (Received 31 March 2015; accepted 22 April 2015; online 25 April 2015)

In the title dimeric complex, [{UO₂(NO₃)(C₁₅H₁₁N₃)}₂O₂], a peroxide ion bridges the two uranyl(VI) [O=U=O]²⁺ ions. The O—O bond length of the peroxide is 1.485 (6) Å and the mid-point of this bond is located at the inversion centre of the dimer. The U atom exhibits a distorted hexagonal–bipyramidal coordination geometry with two uranyl(VI) O atoms occupying the axial positions and one O atom of the monodentate nitrate ion, both O atoms of the peroxide ion and the three N atoms of the chelating tridentate 2,2′:6′,2′′-terpyridine (terpy) ligand in the equatorial positions. Two of the N atoms of the terpy ligand lie above and below the mean plane containing the equatorial ligand atoms and the U atom [deviations from the mean plane: maximum 0.500 (2), minimum −0.472 (2) and r.m.s. = 0.2910 Å]. The dihedral angle between the terpy ligand and the mean plane is 35.61 (7)°. The bond lengths around the U atom decrease in the order U—N > U—O_nitrate > U—O_peroxo > U=O. The dimeric complexes pack in a three-dimensional network held together by weak π–π interactions [centroid–centroid distance = 3.659 (3) Å] between pyridyl rings of the terpy ligands in neighbouring dimers, together with intermolecular C—H⋯O and C—H⋯π interactions. Weak intramolecular C—H⋯O interactions are also observed.

Keywords: crystal structure; uranium(VI) complex; dimer; peroxide; 2,2′:6′,2′′-terpyridine; uranyl(VI) ion.

CCDC reference: 1061056

1. Related literature

For the structures of uranyl(VI) complexes with terpy, see: Berthet et al. (2004 ). For the structures of uranyl(VI) μ-κ²:κ²-peroxide complexes, see:Charushnikova et al. (2001 ); Goff et al. (2008 ); John et al. (2004 ); Sigmon et al. (2009 ); Takao & Ikeda (2010 ). For the structures of a uranyl(VI) complex with terpy and a uranyl(VI) μ-κ²:κ²-peroxide complex, see: Charushnikova & Den Auwer (2004 ).

2. Experimental

2.1. Crystal data

[U₂(NO₃)₂(O₂)O₄(C₁₅H₁₁N₃)₂]
M_r = 1162.62
Monoclinic, P 2₁ /c
a = 13.4924 (11) Å
b = 10.2791 (8) Å
c = 12.6977 (10) Å
β = 114.691 (1)°
V = 1600.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 10.19 mm⁻¹
T = 90 K
0.28 × 0.14 × 0.06 mm

2.2. Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: analytical (XPREP; Bruker, 2007 ) T_min = 0.163, T_max = 0.580
11692 measured reflections
4695 independent reflections
3636 reflections with I > 2σ(I)
R_int = 0.063

2.3. Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.058
S = 0.89
4695 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 2.24 e Å⁻³
Δρ_min = −1.57 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

U1—O1	1.777 (3)
U1—O2	1.775 (3)
U1—O3	2.340 (3)
U1—O3ⁱ	2.325 (3)
U1—O4	2.479 (3)
U1—N1	2.574 (3)
U1—N2	2.634 (3)
U1—N3	2.593 (3)
O3—O3ⁱ	1.485 (6)
O4—N4	1.295 (5)
O5—N4	1.232 (5)
O6—N4	1.240 (4)

O1—U1—O2	177.31 (13)
O1—U1—O3	91.64 (14)
O1—U1—O3ⁱ	90.58 (14)
O1—U1—O4	85.85 (12)
O3ⁱ—U1—O3	37.12 (13)
O3—U1—O4	66.75 (10)
O1—U1—N1	89.42 (13)
O3ⁱ—U1—N1	71.44 (10)
O1—U1—N2	76.01 (12)
O1—U1—N3	100.67 (13)
O4—U1—N3	70.03 (11)
N1—U1—N2	61.29 (11)
N2—U1—N3	60.44 (11)
Symmetry code: (i) -x+1, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C6–C10/N2 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O3ⁱ	0.95	2.28	2.773 (6)	112
C1—H1⋯O4ⁱ	0.95	2.59	3.225 (5)	125
C2—H2⋯O6ⁱ	0.95	2.59	3.357 (6)	137
C3—H3⋯O1ⁱⁱ	0.95	2.58	3.176 (6)	121
C4—H4⋯O1ⁱⁱ	0.95	2.55	3.162 (6)	122
C12—H12⋯O5ⁱⁱⁱ	0.95	2.32	3.256 (6)	169
C14—H14⋯O6^iv	0.95	2.48	3.246 (7)	138
C15—H15⋯Cg2^v	0.95	2.62	3.512 (5)	157
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x, -y+1, -z+1; (v) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1061056

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989015007987/cq2015sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015007987/cq2015Isup2.hkl

checkCIF report

Related literature top

For the structures of uranyl(VI) complexes with terpy, see: Berthet et al. (2004). For the structures of uranyl(VI) µ-η²:η²-peroxide complexes, see:Charushnikova et al. (2001); Goff et al. (2008); John et al. (2004); Sigmon et al. (2009); Takao & Ikeda (2010). For the structures of a uranyl(VI) complex with terpy and a uranyl(VI) µ-η²:η²-peroxide complex, see: Charushnikova & Den Auwer (2004).

Experimental top

10 ml of a methanolic solution containing 0.5 mmol of terpy was added to 10 ml of a methanolic solution containing 0.5 mmol of UO₂(NO₃)₂·6H₂O contained in a glass sample vial. The vial w as sealed with a lid and kept in sunlight at room temperature. Yellow crystals grew after one day. The crystal structure of the yellow material has not yet been determined. After about two months, orange crystals of the title complex were obtained.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Structure of the dimer [{UO₂(NO₃)(C₁₅H₁₁N₃)}₂O₂]. Displacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity. [Symmetry code: (i) -x + 1, -y + 1, -z + 1]
	Fig. 2. Packing diagram of [{UO₂(NO₃)(C₁₅H₁₁N₃)}₂O₂]. Dashed lines and dotted lines are π–π and C—H···π interactions, respectively.

µ-Peroxido-κ⁴O¹,O²:O^1',O^2'-bis[(nitrato-κO)(2,2':6',2''-terpyridine-κ³N,N',N'')dioxidouranium(VI)] top

Crystal data top

[U₂(NO₃)₂(O₂)O₄(C₁₅H₁₁N₃)₂]	F(000) = 1076
M_r = 1162.62	D_x = 2.413 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4370 reflections
a = 13.4924 (11) Å	θ = 2.6–30.1°
b = 10.2791 (8) Å	µ = 10.19 mm⁻¹
c = 12.6977 (10) Å	T = 90 K
β = 114.691 (1)°	Plate, orange
V = 1600.0 (2) Å³	0.28 × 0.14 × 0.06 mm
Z = 2

Data collection top

Bruker APEXII CCD area-detector diffractometer	4695 independent reflections
Radiation source: fine-focus sealed tube	3636 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
Detector resolution: 8.333 pixels mm^-1	θ_max = 31.0°, θ_min = 2.6°
phi and ω scans	h = −19→17
Absorption correction: analytical (XPREP; Bruker, 2007)	k = −14→5
T_min = 0.163, T_max = 0.580	l = −18→18
11692 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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.058	H-atom parameters constrained
S = 0.89	w = 1/[σ²(F_o²) + (0.0123P)²] where P = (F_o² + 2F_c²)/3
4695 reflections	(Δ/σ)_max = 0.001
235 parameters	Δρ_max = 2.24 e Å⁻³
0 restraints	Δρ_min = −1.57 e Å⁻³

Crystal data top

[U₂(NO₃)₂(O₂)O₄(C₁₅H₁₁N₃)₂]	V = 1600.0 (2) Å³
M_r = 1162.62	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.4924 (11) Å	µ = 10.19 mm⁻¹
b = 10.2791 (8) Å	T = 90 K
c = 12.6977 (10) Å	0.28 × 0.14 × 0.06 mm
β = 114.691 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	4695 independent reflections
Absorption correction: analytical (XPREP; Bruker, 2007)	3636 reflections with I > 2σ(I)
T_min = 0.163, T_max = 0.580	R_int = 0.063
11692 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.058	H-atom parameters constrained
S = 0.89	Δρ_max = 2.24 e Å⁻³
4695 reflections	Δρ_min = −1.57 e Å⁻³
235 parameters

Special details top

Experimental. face-indexed absorption correction carried out with XPREP (Bruker, 2007)

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 (Å²) top

	x	y	z	U_iso*/U_eq
U1	0.387048 (13)	0.333645 (14)	0.466857 (14)	0.00993 (5)
O1	0.3311 (3)	0.3633 (3)	0.3151 (3)	0.0176 (7)
O2	0.4441 (3)	0.2963 (3)	0.6171 (3)	0.0168 (7)
O3	0.4596 (3)	0.5439 (3)	0.5073 (4)	0.0306 (10)
O4	0.2546 (2)	0.4979 (3)	0.4721 (3)	0.0152 (6)
O5	0.1152 (3)	0.4243 (3)	0.3199 (3)	0.0242 (8)
O6	0.1038 (3)	0.6064 (3)	0.4006 (3)	0.0283 (9)
N1	0.5298 (3)	0.1823 (3)	0.4461 (3)	0.0126 (7)
N2	0.3249 (3)	0.1020 (3)	0.3740 (3)	0.0097 (7)
N3	0.2240 (3)	0.2190 (3)	0.4857 (3)	0.0129 (7)
N4	0.1554 (3)	0.5090 (4)	0.3945 (3)	0.0165 (8)
C1	0.6361 (4)	0.2172 (4)	0.4933 (4)	0.0142 (9)
H1	0.6585	0.2851	0.5491	0.017*
C2	0.7141 (4)	0.1591 (4)	0.4644 (4)	0.0147 (9)
H2	0.7882	0.1858	0.5006	0.018*
C3	0.6820 (4)	0.0616 (4)	0.3821 (4)	0.0157 (9)
H3	0.7329	0.0226	0.3580	0.019*
C4	0.5733 (3)	0.0215 (4)	0.3351 (4)	0.0146 (9)
H4	0.5494	−0.0468	0.2797	0.018*
C5	0.5008 (3)	0.0823 (4)	0.3700 (4)	0.0109 (8)
C6	0.3841 (3)	0.0422 (4)	0.3258 (4)	0.0116 (8)
C7	0.3392 (4)	−0.0538 (4)	0.2412 (4)	0.0149 (9)
H7	0.3831	−0.0977	0.2103	0.018*
C8	0.2299 (4)	−0.0839 (4)	0.2032 (4)	0.0163 (9)
H8	0.1971	−0.1464	0.1436	0.020*
C9	0.1686 (4)	−0.0219 (4)	0.2529 (4)	0.0164 (9)
H9	0.0934	−0.0415	0.2281	0.020*
C10	0.2192 (3)	0.0695 (4)	0.3396 (4)	0.0108 (8)
C11	0.1638 (4)	0.1318 (4)	0.4050 (4)	0.0118 (8)
C12	0.0579 (4)	0.0988 (4)	0.3906 (4)	0.0173 (10)
H12	0.0148	0.0396	0.3318	0.021*
C13	0.0181 (4)	0.1539 (5)	0.4633 (5)	0.0229 (11)
H13	−0.0543	0.1352	0.4530	0.027*
C14	0.0819 (4)	0.2362 (4)	0.5515 (4)	0.0193 (10)
H14	0.0564	0.2702	0.6052	0.023*
C15	0.1850 (4)	0.2679 (4)	0.5589 (4)	0.0156 (9)
H15	0.2293	0.3261	0.6179	0.019*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
U1	0.01075 (8)	0.00727 (7)	0.01268 (8)	−0.00116 (7)	0.00578 (6)	−0.00132 (7)
O1	0.0249 (18)	0.0142 (15)	0.0175 (17)	0.0044 (14)	0.0126 (15)	0.0039 (13)
O2	0.0163 (16)	0.0199 (15)	0.0080 (16)	0.0007 (14)	−0.0011 (13)	−0.0061 (13)
O3	0.0182 (18)	0.0076 (14)	0.075 (3)	0.0007 (14)	0.028 (2)	−0.0085 (17)
O4	0.0111 (14)	0.0162 (14)	0.0164 (16)	0.0003 (14)	0.0038 (13)	0.0012 (14)
O5	0.0236 (18)	0.0189 (16)	0.023 (2)	0.0019 (15)	0.0024 (16)	−0.0031 (15)
O6	0.0224 (19)	0.0228 (17)	0.034 (2)	0.0124 (16)	0.0064 (17)	−0.0034 (17)
N1	0.0164 (18)	0.0082 (16)	0.0143 (19)	−0.0006 (15)	0.0076 (16)	−0.0001 (14)
N2	0.0126 (17)	0.0074 (15)	0.0074 (17)	−0.0017 (14)	0.0025 (15)	0.0016 (13)
N3	0.0180 (19)	0.0115 (16)	0.0102 (19)	0.0002 (16)	0.0069 (16)	0.0012 (14)
N4	0.0161 (18)	0.0158 (17)	0.017 (2)	0.0033 (18)	0.0066 (16)	0.0043 (17)
C1	0.018 (2)	0.0094 (18)	0.016 (2)	−0.0009 (18)	0.007 (2)	0.0004 (17)
C2	0.016 (2)	0.0102 (18)	0.019 (2)	0.0000 (19)	0.0094 (19)	0.0028 (18)
C3	0.022 (2)	0.016 (2)	0.014 (2)	0.0001 (19)	0.012 (2)	0.0025 (18)
C4	0.018 (2)	0.015 (2)	0.010 (2)	0.0022 (18)	0.0046 (18)	0.0002 (17)
C5	0.013 (2)	0.0101 (18)	0.008 (2)	0.0009 (17)	0.0025 (17)	0.0038 (16)
C6	0.014 (2)	0.0117 (19)	0.009 (2)	0.0030 (17)	0.0043 (18)	0.0006 (16)
C7	0.018 (2)	0.015 (2)	0.013 (2)	−0.0036 (19)	0.0064 (19)	−0.0046 (17)
C8	0.022 (2)	0.014 (2)	0.009 (2)	−0.0040 (19)	0.0031 (19)	−0.0054 (17)
C9	0.016 (2)	0.018 (2)	0.013 (2)	−0.0082 (19)	0.0035 (18)	−0.0031 (18)
C10	0.013 (2)	0.0084 (18)	0.009 (2)	−0.0002 (17)	0.0033 (17)	−0.0006 (16)
C11	0.014 (2)	0.0091 (18)	0.010 (2)	0.0002 (17)	0.0036 (17)	0.0012 (16)
C12	0.017 (2)	0.016 (2)	0.019 (3)	−0.0022 (19)	0.007 (2)	0.0003 (19)
C13	0.014 (2)	0.026 (2)	0.032 (3)	−0.004 (2)	0.013 (2)	−0.002 (2)
C14	0.024 (3)	0.017 (2)	0.023 (3)	−0.001 (2)	0.016 (2)	−0.0033 (19)
C15	0.021 (2)	0.013 (2)	0.013 (2)	−0.0002 (19)	0.0074 (19)	−0.0010 (17)

Geometric parameters (Å, º) top

U1—O1	1.777 (3)	C2—H2	0.9500
U1—O2	1.775 (3)	C3—C4	1.395 (6)
U1—O3	2.340 (3)	C3—H3	0.9500
U1—O3ⁱ	2.325 (3)	C4—C5	1.380 (6)
U1—O4	2.479 (3)	C4—H4	0.9500
U1—N1	2.574 (3)	C5—C6	1.492 (6)
U1—N2	2.634 (3)	C6—C7	1.397 (6)
U1—N3	2.593 (3)	C7—C8	1.381 (6)
O3—O3ⁱ	1.485 (6)	C7—H7	0.9500
O3—U1ⁱ	2.325 (3)	C8—C9	1.388 (6)
O4—N4	1.295 (5)	C8—H8	0.9500
O5—N4	1.232 (5)	C9—C10	1.391 (6)
O6—N4	1.240 (4)	C9—H9	0.9500
N1—C1	1.351 (6)	C10—C11	1.476 (6)
N1—C5	1.351 (5)	C11—C12	1.404 (6)
N2—C6	1.342 (5)	C12—C13	1.369 (6)
N2—C10	1.347 (5)	C12—H12	0.9500
N3—C15	1.343 (5)	C13—C14	1.380 (7)
N3—C11	1.348 (5)	C13—H13	0.9500
C1—C2	1.386 (6)	C14—C15	1.393 (6)
C1—H1	0.9500	C14—H14	0.9500
C2—C3	1.380 (6)	C15—H15	0.9500

Cg(C1–C5/N1)···Cg(C6–C10/N2)ⁱⁱ	3.659 (3)

O1—U1—O2	177.31 (13)	N1—C1—H1	118.3
O1—U1—O3	91.64 (14)	C2—C1—H1	118.3
O1—U1—O3ⁱ	90.58 (14)	C3—C2—C1	118.7 (4)
O1—U1—O4	85.85 (12)	C3—C2—H2	120.7
O2—U1—O3	90.58 (14)	C1—C2—H2	120.7
O2—U1—O3ⁱ	90.28 (15)	C2—C3—C4	118.7 (4)
O2—U1—O4	96.43 (12)	C2—C3—H3	120.7
O3ⁱ—U1—O3	37.12 (13)	C4—C3—H3	120.7
O3—U1—O4	66.75 (10)	C5—C4—C3	119.2 (4)
O3ⁱ—U1—O4	103.66 (10)	C5—C4—H4	120.4
O1—U1—N1	89.42 (13)	C3—C4—H4	120.4
O2—U1—N1	88.43 (13)	N1—C5—C4	122.8 (4)
O3—U1—N1	108.56 (10)	N1—C5—C6	115.1 (4)
O3ⁱ—U1—N1	71.44 (10)	C4—C5—C6	122.1 (4)
O4—U1—N1	173.19 (10)	N2—C6—C7	121.7 (4)
O1—U1—N2	76.01 (12)	N2—C6—C5	115.9 (4)
O2—U1—N2	101.52 (12)	C7—C6—C5	122.4 (4)
O3—U1—N2	163.57 (12)	C8—C7—C6	118.9 (4)
O3ⁱ—U1—N2	130.60 (10)	C8—C7—H7	120.5
O4—U1—N2	121.97 (10)	C6—C7—H7	120.5
O1—U1—N3	100.67 (13)	C7—C8—C9	119.4 (4)
O2—U1—N3	78.83 (13)	C7—C8—H8	120.3
O3—U1—N3	133.88 (11)	C9—C8—H8	120.3
O3ⁱ—U1—N3	166.46 (13)	C8—C9—C10	118.7 (4)
O4—U1—N3	70.03 (11)	C8—C9—H9	120.6
N1—U1—N2	61.29 (11)	C10—C9—H9	120.6
N1—U1—N3	115.77 (11)	N2—C10—C9	121.8 (4)
N2—U1—N3	60.44 (11)	N2—C10—C11	115.3 (4)
O3ⁱ—O3—U1ⁱ	72.0 (2)	C9—C10—C11	122.8 (4)
O3ⁱ—O3—U1	70.9 (2)	N3—C11—C12	121.2 (4)
U1ⁱ—O3—U1	142.88 (13)	N3—C11—C10	115.4 (4)
N4—O4—U1	124.6 (3)	C12—C11—C10	123.3 (4)
C1—N1—C5	117.1 (4)	C13—C12—C11	118.4 (4)
C1—N1—U1	119.7 (3)	C13—C12—H12	120.8
C5—N1—U1	121.8 (3)	C11—C12—H12	120.8
C6—N2—C10	119.3 (4)	C12—C13—C14	120.9 (4)
C6—N2—U1	118.7 (3)	C12—C13—H13	119.6
C10—N2—U1	117.7 (3)	C14—C13—H13	119.6
C11—N3—C15	119.2 (4)	C13—C14—C15	117.7 (4)
C11—N3—U1	119.9 (3)	C13—C14—H14	121.2
C15—N3—U1	119.1 (3)	C15—C14—H14	121.2
O4—N4—O5	120.4 (4)	N3—C15—C14	122.4 (4)
O4—N4—O6	116.9 (4)	N3—C15—H15	118.8
O5—N4—O6	122.7 (4)	C14—C15—H15	118.8
N1—C1—C2	123.4 (4)

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

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C6–C10/N2 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O3ⁱ	0.95	2.28	2.773 (6)	112
C1—H1···O4ⁱ	0.95	2.59	3.225 (5)	125
C2—H2···O6ⁱ	0.95	2.59	3.357 (6)	137
C3—H3···O1ⁱⁱⁱ	0.95	2.58	3.176 (6)	121
C4—H4···O1ⁱⁱⁱ	0.95	2.55	3.162 (6)	122
C12—H12···O5^iv	0.95	2.32	3.256 (6)	169
C14—H14···O6^v	0.95	2.48	3.246 (7)	138
C15—H15···Cg2^vi	0.95	2.62	3.512 (5)	157

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

Selected geometric parameters (Å, º) top

U1—O1	1.777 (3)	U1—N2	2.634 (3)
U1—O2	1.775 (3)	U1—N3	2.593 (3)
U1—O3	2.340 (3)	O3—O3ⁱ	1.485 (6)
U1—O3ⁱ	2.325 (3)	O4—N4	1.295 (5)
U1—O4	2.479 (3)	O5—N4	1.232 (5)
U1—N1	2.574 (3)	O6—N4	1.240 (4)

O1—U1—O2	177.31 (13)	O3ⁱ—U1—N1	71.44 (10)
O1—U1—O3	91.64 (14)	O1—U1—N2	76.01 (12)
O1—U1—O3ⁱ	90.58 (14)	O1—U1—N3	100.67 (13)
O1—U1—O4	85.85 (12)	O4—U1—N3	70.03 (11)
O3ⁱ—U1—O3	37.12 (13)	N1—U1—N2	61.29 (11)
O3—U1—O4	66.75 (10)	N2—U1—N3	60.44 (11)
O1—U1—N1	89.42 (13)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C6–C10/N2 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O3ⁱ	0.95	2.28	2.773 (6)	112
C1—H1···O4ⁱ	0.95	2.59	3.225 (5)	125
C2—H2···O6ⁱ	0.95	2.59	3.357 (6)	137
C3—H3···O1ⁱⁱ	0.95	2.58	3.176 (6)	121
C4—H4···O1ⁱⁱ	0.95	2.55	3.162 (6)	122
C12—H12···O5ⁱⁱⁱ	0.95	2.32	3.256 (6)	169
C14—H14···O6^iv	0.95	2.48	3.246 (7)	138
C15—H15···Cg2^v	0.95	2.62	3.512 (5)	157

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

Deviations from Least-squares plane (x,y,z in crystal coordinates). top

Least-square plane: 0.0823(0.0118)x - 2.3175(0.0073)y + 11.2072(0.0058)z = 4.4537(0.0040), Rms deviation of fitted atoms = 0.2910.

Atom	Deviation
U1	0.0370(0.0010)
O3	0.0090(0.0041)
O3ⁱ	0.0555(0.0042)
O4	-0.2956(0.0023)
N1	0.1666(0.0024)
N2	-0.4723(0.0024)
N3	0.4999(0.0024)

Symmetric code: (i) -x+1,-y+1,-z+1

Acknowledgements

This work was supported by the MEXT(Ministry of Education, Culture, Sports, Science and Technology, Japan)-Supported Program for the Strategic Research Foundation at Private Universities (2012–2016).

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Volume 71| Part 5| May 2015| Pages m122-m123

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