Guanidinium dioxidobis(picolinato-κ(2)N,O)(picolinato-κO)uranate(VI).

In the title compound, (CH(6)N(3))[U(C(6)H(4)NO(2))(3)O(2)], the uranyl group is coordinated by two O and two N atoms from two chelating picolinate ligands, and one O atom from a third picolinate ligand. The coordination environment of the U(VI) atom (N(2)O(5)) is distorted penta-gonal-bipyramidal. In the crystal, all amino groups are involved in the formation of N-H⋯O and N-H⋯N hydrogen bonds, which link cations and anions into layers parallel to the ac plane.

Related literature

For the disordered crystal structure of a related complex without guanidinium in which the uranyl ion is chelated by two picolinato ligands and coordinated via the O atom of a picolinic acid mol­ecule, see: Grechishnikova et al. (2007 ▶).

Experimental

Crystal data

(CH6N3)[U(C6H4NO2)3O2]

M = 696.42

Orthorhombic,

a = 16.3842 (4) Å

b = 13.1678 (3) Å

c = 21.2743 (4) Å

V = 4589.80 (18) Å3

Z = 8

Mo Kα radiation

μ = 7.13 mm−1

T = 293 K

0.18 × 0.06 × 0.04 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T min = 0.360, T max = 0.764

77357 measured reflections

6604 independent reflections

3818 reflections with I > 2σ(I)

R int = 0.093

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.075

S = 1.01

6604 reflections

307 parameters

H-atom parameters constrained

Δρmax = 1.07 e Å−3

Δρmin = −0.71 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); data reduction: SAINT-Plus; 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812035465/cv5297sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812035465/cv5297Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(CH6N3)[U(C6H4NO2)3O2]	F(000) = 2640
Mr = 696.42	Dx = 2.016 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9491 reflections
a = 16.3842 (4) Å	θ = 6.2–24.9°
b = 13.1678 (3) Å	µ = 7.13 mm−1
c = 21.2743 (4) Å	T = 293 K
V = 4589.80 (18) Å3	Fragment, light-yellow
Z = 8	0.18 × 0.06 × 0.04 mm

Bruker Kappa APEXII CCD diffractometer	6604 independent reflections
Radiation source: fine-focus sealed tube	3818 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.093
ω and φ scans	θmax = 30.0°, θmin = 4.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	h = −23→23
Tmin = 0.360, Tmax = 0.764	k = −18→18
77357 measured reflections	l = −27→29

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) = 0.075	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0317P)2] where P = (Fo2 + 2Fc2)/3
6604 reflections	(Δ/σ)max = 0.001
307 parameters	Δρmax = 1.07 e Å−3
0 restraints	Δρmin = −0.71 e Å−3

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	0.418415 (10)	0.592900 (13)	0.227356 (7)	0.03351 (6)
O1	0.4611 (2)	0.7128 (3)	0.24392 (16)	0.0495 (9)
O2	0.3762 (2)	0.4717 (3)	0.21274 (15)	0.0496 (9)
O3	0.3164 (2)	0.6513 (3)	0.15747 (14)	0.0466 (9)
O4	0.1888 (2)	0.6949 (3)	0.13249 (18)	0.0660 (12)
O5	0.4135 (2)	0.5504 (3)	0.33518 (15)	0.0560 (10)
O6	0.4548 (3)	0.4710 (4)	0.42111 (17)	0.0715 (13)
O7	0.4928 (2)	0.5876 (3)	0.13743 (17)	0.0580 (10)
O8	0.6048 (2)	0.5233 (4)	0.09453 (17)	0.0659 (12)
N1	0.2885 (2)	0.6762 (3)	0.27861 (17)	0.0365 (9)
N2	0.5468 (2)	0.5021 (3)	0.27319 (18)	0.0381 (9)
N3	0.5676 (3)	0.6053 (3)	−0.0183 (2)	0.0532 (12)
C11	0.2433 (3)	0.6807 (3)	0.1704 (2)	0.0399 (12)
C12	0.2272 (3)	0.7013 (3)	0.2395 (2)	0.0366 (11)
C13	0.1551 (3)	0.7450 (4)	0.2593 (3)	0.0471 (13)
H13A	0.1138	0.7596	0.2307	0.057*
C14	0.1456 (4)	0.7664 (4)	0.3215 (3)	0.0584 (15)
H14A	0.0976	0.7958	0.3360	0.070*
C15	0.2082 (4)	0.7438 (5)	0.3626 (3)	0.0621 (16)
H15A	0.2032	0.7585	0.4052	0.075*
C16	0.2786 (3)	0.6989 (4)	0.3393 (2)	0.0479 (13)
H16A	0.3207	0.6839	0.3672	0.057*
C21	0.4669 (3)	0.4998 (4)	0.3676 (2)	0.0474 (13)
C22	0.5445 (3)	0.4778 (4)	0.3340 (2)	0.0391 (11)
C23	0.6114 (4)	0.4354 (4)	0.3651 (3)	0.0503 (14)
H23A	0.6084	0.4192	0.4076	0.060*
C24	0.6818 (3)	0.4182 (4)	0.3318 (3)	0.0548 (15)
H24A	0.7279	0.3929	0.3519	0.066*
C25	0.6833 (3)	0.4389 (4)	0.2682 (3)	0.0493 (13)
H25A	0.7295	0.4251	0.2443	0.059*
C26	0.6142 (3)	0.4808 (4)	0.2410 (3)	0.0459 (13)
H26A	0.6151	0.4946	0.1981	0.055*
C31	0.5434 (3)	0.5758 (4)	0.0917 (2)	0.0445 (13)
C32	0.5242 (3)	0.6342 (4)	0.0327 (2)	0.0389 (11)
C33	0.4686 (4)	0.7118 (5)	0.0309 (3)	0.0601 (16)
H33A	0.4392	0.7287	0.0668	0.072*
C34	0.4562 (4)	0.7646 (5)	−0.0237 (3)	0.0735 (19)
H34A	0.4200	0.8188	−0.0250	0.088*
C35	0.4985 (4)	0.7357 (5)	−0.0765 (3)	0.0681 (18)
H35A	0.4908	0.7688	−0.1146	0.082*
C36	0.5523 (4)	0.6569 (5)	−0.0712 (2)	0.0592 (16)
H36A	0.5805	0.6376	−0.1072	0.071*
N11	0.8357 (3)	0.4011 (4)	−0.0134 (2)	0.0632 (14)
H11A	0.8357	0.3657	−0.0474	0.076*
H11B	0.8791	0.4044	0.0093	0.076*
N12	0.7021 (3)	0.4469 (4)	−0.0293 (2)	0.0658 (14)
H12A	0.7003	0.4122	−0.0635	0.079*
H12B	0.6596	0.4796	−0.0169	0.079*
N13	0.7708 (3)	0.5039 (4)	0.0568 (2)	0.0719 (16)
H13B	0.7278	0.5362	0.0688	0.086*
H13C	0.8146	0.5066	0.0790	0.086*
C1	0.7694 (3)	0.4500 (4)	0.0039 (3)	0.0514 (14)

	U11	U22	U33	U12	U13	U23
U1	0.02556 (9)	0.04300 (10)	0.03197 (8)	0.00403 (9)	0.00182 (8)	0.00058 (8)
O1	0.039 (2)	0.054 (2)	0.056 (2)	0.0013 (19)	0.0014 (16)	−0.0038 (18)
O2	0.042 (2)	0.047 (2)	0.059 (2)	0.0028 (18)	−0.0024 (17)	0.0004 (17)
O3	0.038 (2)	0.065 (2)	0.0370 (18)	0.0144 (19)	−0.0010 (15)	−0.0033 (16)
O4	0.055 (3)	0.082 (3)	0.060 (2)	0.029 (2)	−0.028 (2)	−0.015 (2)
O5	0.045 (2)	0.082 (3)	0.0405 (19)	0.016 (2)	0.0066 (17)	0.0084 (18)
O6	0.067 (3)	0.104 (4)	0.043 (2)	0.015 (3)	0.008 (2)	0.026 (2)
O7	0.053 (2)	0.077 (3)	0.0440 (19)	0.014 (2)	0.0162 (18)	0.0023 (19)
O8	0.050 (3)	0.096 (3)	0.051 (2)	0.029 (2)	0.0112 (19)	0.008 (2)
N1	0.028 (2)	0.041 (2)	0.040 (2)	0.0035 (17)	0.0023 (18)	0.0013 (18)
N2	0.029 (2)	0.044 (2)	0.042 (2)	0.0005 (18)	0.000 (2)	0.0056 (19)
N3	0.054 (3)	0.060 (3)	0.045 (2)	−0.007 (2)	0.012 (2)	−0.003 (2)
C11	0.038 (3)	0.036 (3)	0.046 (3)	0.001 (2)	−0.008 (2)	−0.005 (2)
C12	0.030 (3)	0.028 (2)	0.051 (3)	0.000 (2)	0.002 (2)	0.002 (2)
C13	0.032 (3)	0.037 (3)	0.072 (4)	0.003 (2)	−0.003 (3)	0.001 (2)
C14	0.049 (4)	0.048 (3)	0.079 (4)	0.012 (3)	0.024 (3)	0.000 (3)
C15	0.069 (4)	0.064 (4)	0.054 (3)	0.016 (3)	0.018 (3)	0.001 (3)
C16	0.048 (3)	0.058 (4)	0.038 (3)	0.008 (3)	0.004 (2)	−0.004 (2)
C21	0.048 (3)	0.056 (4)	0.038 (3)	0.003 (3)	0.001 (2)	0.002 (2)
C22	0.036 (3)	0.038 (3)	0.043 (3)	−0.001 (2)	−0.005 (2)	0.001 (2)
C23	0.055 (4)	0.045 (3)	0.051 (3)	0.006 (3)	−0.008 (3)	0.006 (2)
C24	0.038 (3)	0.047 (3)	0.079 (4)	0.009 (3)	−0.013 (3)	0.000 (3)
C25	0.033 (3)	0.045 (3)	0.070 (4)	0.006 (2)	0.005 (3)	0.001 (3)
C26	0.034 (3)	0.048 (3)	0.055 (3)	0.006 (3)	0.003 (2)	0.002 (2)
C31	0.042 (3)	0.052 (4)	0.040 (3)	−0.004 (3)	0.009 (2)	−0.002 (2)
C32	0.035 (3)	0.045 (3)	0.036 (3)	−0.005 (2)	0.005 (2)	−0.004 (2)
C33	0.062 (4)	0.069 (4)	0.049 (3)	0.015 (3)	0.011 (3)	0.001 (3)
C34	0.075 (5)	0.071 (5)	0.074 (4)	0.025 (4)	0.006 (4)	0.006 (4)
C35	0.081 (5)	0.073 (5)	0.050 (4)	0.000 (4)	−0.002 (3)	0.012 (3)
C36	0.067 (4)	0.070 (4)	0.041 (3)	−0.014 (4)	0.015 (3)	0.003 (3)
N11	0.048 (3)	0.089 (4)	0.053 (3)	0.017 (3)	0.000 (2)	−0.012 (3)
N12	0.045 (3)	0.093 (4)	0.059 (3)	0.012 (3)	−0.007 (2)	−0.030 (3)
N13	0.039 (3)	0.111 (4)	0.065 (3)	0.018 (3)	−0.004 (2)	−0.033 (3)
C1	0.045 (4)	0.062 (4)	0.048 (3)	−0.001 (3)	0.003 (3)	−0.005 (3)

U1—O1	1.762 (4)	C21—C22	1.486 (7)
U1—O2	1.766 (4)	C22—C23	1.397 (7)
U1—O3	2.366 (3)	C23—C24	1.371 (8)
U1—O5	2.362 (3)	C23—H23A	0.9300
U1—O7	2.269 (3)	C24—C25	1.381 (8)
U1—N1	2.631 (4)	C24—H24A	0.9300
U1—N2	2.609 (4)	C25—C26	1.386 (7)
O3—C11	1.288 (5)	C25—H25A	0.9300
O4—C11	1.218 (5)	C26—H26A	0.9300
O5—C21	1.298 (6)	C31—C32	1.506 (7)
O6—C21	1.217 (6)	C32—C33	1.371 (7)
O7—C31	1.287 (6)	C33—C34	1.369 (8)
O8—C31	1.221 (6)	C33—H33A	0.9300
N1—C16	1.335 (6)	C34—C35	1.372 (9)
N1—C12	1.345 (6)	C34—H34A	0.9300
N2—C26	1.330 (6)	C35—C36	1.365 (9)
N2—C22	1.334 (6)	C35—H35A	0.9300
N3—C36	1.340 (7)	C36—H36A	0.9300
N3—C32	1.351 (6)	N11—C1	1.316 (7)
C11—C12	1.518 (7)	N11—H11A	0.8600
C12—C13	1.379 (7)	N11—H11B	0.8600
C13—C14	1.360 (8)	N12—C1	1.310 (7)
C13—H13A	0.9300	N12—H12A	0.8600
C14—C15	1.381 (8)	N12—H12B	0.8600
C14—H14A	0.9300	N13—C1	1.331 (7)
C15—C16	1.389 (7)	N13—H13B	0.8600
C15—H15A	0.9300	N13—H13C	0.8600
C16—H16A	0.9300
O1—U1—O2	178.53 (16)	O6—C21—O5	123.2 (5)
O1—U1—O7	89.03 (15)	O6—C21—C22	121.9 (5)
O2—U1—O7	91.94 (15)	O5—C21—C22	114.9 (4)
O1—U1—O5	91.81 (15)	N2—C22—C23	122.1 (5)
O2—U1—O5	86.77 (15)	N2—C22—C21	116.4 (4)
O7—U1—O5	146.05 (13)	C23—C22—C21	121.5 (5)
O1—U1—O3	96.59 (15)	C24—C23—C22	118.8 (5)
O2—U1—O3	84.64 (14)	C24—C23—H23A	120.6
O7—U1—O3	81.95 (12)	C22—C23—H23A	120.6
O5—U1—O3	131.53 (12)	C23—C24—C25	119.3 (5)
O1—U1—N2	90.92 (14)	C23—C24—H24A	120.4
O2—U1—N2	88.11 (14)	C25—C24—H24A	120.4
O7—U1—N2	82.41 (13)	C24—C25—C26	118.2 (5)
O5—U1—N2	63.64 (12)	C24—C25—H25A	120.9
O3—U1—N2	162.51 (12)	C26—C25—H25A	120.9
O1—U1—N1	82.23 (14)	N2—C26—C25	123.1 (5)
O2—U1—N1	97.65 (14)	N2—C26—H26A	118.4
O7—U1—N1	142.81 (12)	C25—C26—H26A	118.4
O5—U1—N1	70.66 (12)	O8—C31—O7	124.1 (5)
O3—U1—N1	63.45 (12)	O8—C31—C32	120.1 (5)
N2—U1—N1	133.52 (12)	O7—C31—C32	115.7 (5)
C11—O3—U1	128.3 (3)	N3—C32—C33	122.6 (5)
C21—O5—U1	127.9 (3)	N3—C32—C31	114.6 (5)
C31—O7—U1	170.5 (4)	C33—C32—C31	122.9 (5)
C16—N1—C12	116.9 (4)	C34—C33—C32	120.0 (5)
C16—N1—U1	126.3 (3)	C34—C33—H33A	120.0
C12—N1—U1	116.8 (3)	C32—C33—H33A	120.0
C26—N2—C22	118.2 (4)	C33—C34—C35	118.6 (6)
C26—N2—U1	125.0 (3)	C33—C34—H34A	120.7
C22—N2—U1	116.7 (3)	C35—C34—H34A	120.7
C36—N3—C32	115.6 (5)	C36—C35—C34	117.9 (6)
O4—C11—O3	125.8 (5)	C36—C35—H35A	121.0
O4—C11—C12	119.1 (5)	C34—C35—H35A	121.0
O3—C11—C12	115.0 (4)	N3—C36—C35	125.2 (5)
N1—C12—C13	123.6 (5)	N3—C36—H36A	117.4
N1—C12—C11	115.1 (4)	C35—C36—H36A	117.4
C13—C12—C11	121.3 (5)	C1—N11—H11A	120.0
C14—C13—C12	118.8 (5)	C1—N11—H11B	120.0
C14—C13—H13A	120.6	H11A—N11—H11B	120.0
C12—C13—H13A	120.6	C1—N12—H12A	120.0
C13—C14—C15	119.1 (5)	C1—N12—H12B	120.0
C13—C14—H14A	120.4	H12A—N12—H12B	120.0
C15—C14—H14A	120.4	C1—N13—H13B	120.0
C14—C15—C16	118.8 (5)	C1—N13—H13C	120.0
C14—C15—H15A	120.6	H13B—N13—H13C	120.0
C16—C15—H15A	120.6	N12—C1—N11	121.9 (5)
N1—C16—C15	122.8 (5)	N12—C1—N13	119.1 (5)
N1—C16—H16A	118.6	N11—C1—N13	118.9 (5)
C15—C16—H16A	118.6

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11A···O4i	0.86	2.02	2.859 (6)	166
N11—H11B···O6ii	0.86	2.12	2.918 (6)	154
N12—H12A···O3i	0.86	2.18	3.033 (6)	169
N12—H12B···N3	0.86	2.24	3.042 (7)	156
N13—H13B···O8	0.86	2.10	2.847 (6)	146
N13—H13C···O6ii	0.86	2.35	3.083 (6)	144

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11A⋯O4i	0.86	2.02	2.859 (6)	166
N11—H11B⋯O6ii	0.86	2.12	2.918 (6)	154
N12—H12A⋯O3i	0.86	2.18	3.033 (6)	169
N12—H12B⋯N3	0.86	2.24	3.042 (7)	156
N13—H13B⋯O8	0.86	2.10	2.847 (6)	146
N13—H13C⋯O6ii	0.86	2.35	3.083 (6)	144

Symmetry codes: (i) ; (ii) .