Crystal structure of μ-peroxido-κ(4) O (1),O (2):O (1'),O (2')-bis-[(nitrato-κO)(2,2':6',2''-terpyridine-κ(3) N,N',N'')dioxidouranium(VI)].

In the title dimeric complex, [{UO2(NO3)(C15H11N3)}2O2], a peroxide ion bridges the two uran-yl(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 hexa-gonal-bipyramidal coordination geometry with two uran-yl(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-Onitrate > U-Operoxo > U=O. The dimeric complexes pack in a three-dimensional network held together by weak π-π inter-actions [centroid-centroid distance = 3.659 (3) Å] between pyridyl rings of the terpy ligands in neighbouring dimers, together with inter-molecular C-H⋯O and C-H⋯π inter-actions. Weak intra-molecular C-H⋯O inter-actions are also observed.

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 ▸).

Experimental

Crystal data

[U2(NO3)2(O2)O4(C15H11N3)2]

M = 1162.62

Monoclinic,

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

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

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.058

S = 0.89

4695 reflections

235 parameters

H-atom parameters constrained

Δρmax = 2.24 e Å−3

Δρmin = −1.57 e Å−3

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 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015007987/cq2015sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015007987/cq2015Isup2.hkl

Click here for additional data file.

2 3 15 11 3 2 2 x y z . DOI: 10.1107/S2056989015007987/cq2015fig1.tif

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]

Click here for additional data file.

2 3 15 11 3 2 2 . DOI: 10.1107/S2056989015007987/cq2015fig2.tif

Packing diagram of [{UO2(NO3)(C15H11N3)}2O2]. Dashed lines and dotted lines are π–π and C—H⋯π inter­actions, respectively.

CCDC reference: 1061056

Additional supporting information: crystallographic information; 3D view; checkCIF report

[U2(NO3)2(O2)O4(C15H11N3)2]	F(000) = 1076
Mr = 1162.62	Dx = 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

Bruker APEXII CCD area-detector diffractometer	4695 independent reflections
Radiation source: fine-focus sealed tube	3636 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.063
Detector resolution: 8.333 pixels mm-1	θmax = 31.0°, θmin = 2.6°
phi and ω scans	h = −19→17
Absorption correction: analytical (XPREP; Bruker, 2007)	k = −14→5
Tmin = 0.163, Tmax = 0.580	l = −18→18
11692 measured reflections

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(Fo2) + (0.0123P)2] where P = (Fo2 + 2Fc2)/3
4695 reflections	(Δ/σ)max = 0.001
235 parameters	Δρmax = 2.24 e Å−3
0 restraints	Δρmin = −1.57 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···O5iv	0.95	2.32	3.256 (6)	169
C14—H14···O6v	0.95	2.48	3.246 (7)	138
C15—H15···Cg2vi	0.95	2.62	3.512 (5)	157

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)

U1O1	1.777(3)
U1O2	1.775(3)
U1O3	2.340(3)
U1O3i	2.325(3)
U1O4	2.479(3)
U1N1	2.574(3)
U1N2	2.634(3)
U1N3	2.593(3)
O3O3i	1.485(6)
O4N4	1.295(5)
O5N4	1.232(5)
O6N4	1.240(4)

O1U1O2	177.31(13)
O1U1O3	91.64(14)
O1U1O3i	90.58(14)
O1U1O4	85.85(12)
O3iU1O3	37.12(13)
O3U1O4	66.75(10)
O1U1N1	89.42(13)
O3iU1N1	71.44(10)
O1U1N2	76.01(12)
O1U1N3	100.67(13)
O4U1N3	70.03(11)
N1U1N2	61.29(11)
N2U1N3	60.44(11)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (, )

Cg2 is the centroid of the C6C10/N2 ring.

DHA	DH	HA	D A	DHA
C1H1O3i	0.95	2.28	2.773(6)	112
C1H1O4i	0.95	2.59	3.225(5)	125
C2H2O6i	0.95	2.59	3.357(6)	137
C3H3O1ii	0.95	2.58	3.176(6)	121
C4H4O1ii	0.95	2.55	3.162(6)	122
C12H12O5iii	0.95	2.32	3.256(6)	169
C14H14O6iv	0.95	2.48	3.246(7)	138
C15H15Cg2v	0.95	2.62	3.512(5)	157

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .