Poly[di-ammonium [di-aqua-(μ7-benzene-1,2,3,4,5,6-hexa-carboxyl-ato)tetra-oxido-diuranium(VI)]].

Uranyl-carboxyl-ate hybrid materials dominate the catalog of uranyl compounds owing in part to the affinity between COO(-) functional groups and UO2 (2+). Polycarboxyl-ate organic ligands may present a degree of steric hindrance and could thus influence the resulting uranyl topology. Single crystals of the title compound, {(NH4)2[(UO2)2(C12O12)(H2O)2]} n , were synthesized hydro-thermally as a result of reacting uranyl nitrate with benzene-1,2,3,4,5,6-hexa-carb-oxy-lic acid (mellitic acid). The structure is comprised of a single unique monomeric uranyl cation adopting a penta-gonal bipyramidal geometry. The uranyl coordination sphere is composed of four O atoms originating from one half of a fully deprotonated mellitic acid ligand and a single water mol-ecule. The observed axial U-O bonds display an average distance of 1.765 (8) Å, whereas equatorial O atoms are found at an average distance of 2.40 (5) Å. All uranium-oxygen bond lengths are in good agreement with literature values. Furthermore, the coordin-ation between the uranyl penta-gonal bipyramids and the mellitic acid anion constructs a three-dimensional anionic framework which is charge-balanced with ammonium cations. Additional stabilization of the structure is provided by O-H⋯O and N-H⋯O hydrogen bonding inter-actions between the components.

Related literature

The background literature for uranyl aromatic, carboxyl­ate coordination polymers is extensive: Go et al. (2007 ▶); Andrews & Cahill (2012 ▶); Frisch & Cahill (2006 ▶); Rowland & Cahill (2010 ▶); Couston et al. (1995 ▶); Severance et al. (2011 ▶); Mihalcea et al. (2012 ▶); Thuery (2009 ▶); Leciejewicz et al. (1995 ▶). For related uranyl mellitic complexes, see: Volkringer et al. (2012 ▶). For f-block homo- and heterometallic mellitic acid compounds, see: Li et al. (2006 ▶); Tang et al. (2008 ▶); Taylor et al. (2008 ▶); Chui et al. (2001 ▶); Han et al. (2012 ▶); Mihalcea et al. (2012 ▶); Volkringer et al. (2012 ▶). For typical U=O bond lengths, see: Burns (2005 ▶).

Experimental

Crystal data

(NH4)2[(UO2)2(C12O12)(H2O)2]

M = 948.29

Monoclinic,

a = 8.0083 (4) Å

b = 10.2948 (6) Å

c = 11.7481 (6) Å

β = 99.733 (1)°

V = 954.62 (9) Å3

Z = 2

Mo Kα radiation

μ = 17.05 mm−1

T = 100 K

0.4 × 0.3 × 0.2 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1999 ▶) T min = 0.467, T max = 0.746

18160 measured reflections

2912 independent reflections

2398 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.017

wR(F 2) = 0.035

S = 1.04

2698 reflections

178 parameters

All H-atom parameters refined

Δρmax = 1.02 e Å−3

Δρmin = −0.98 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalMaker (CrystalMaker, 2009 ▶) and ORTEP-3 (Burnett & Johnson 1996 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) I, publication_text. DOI: 10.1107/S1600536814006047/gg2133sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814006047/gg2133Isup2.hkl

CCDC reference: 992448

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

(NH4)2[(UO2)2(C12O12)(H2O)2]	F(000) = 852
Mr = 948.29	Dx = 3.299 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 18686 reflections
a = 8.0083 (4) Å	θ = 7.0–60.6°
b = 10.2948 (6) Å	µ = 17.05 mm−1
c = 11.7481 (6) Å	T = 100 K
β = 99.733 (1)°	Rods, yellow
V = 954.62 (9) Å3	0.4 × 0.3 × 0.2 mm
Z = 2

Bruker APEXII CCD diffractometer	2912 independent reflections
Radiation source: fine-focus sealed tube	2398 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω scans	θmax = 30.5°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)	h = −11→8
Tmin = 0.467, Tmax = 0.746	k = −14→14
18160 measured reflections	l = −16→16

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)] = 0.017	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.035	All H-atom parameters refined
S = 1.04	w = 1/[σ2(Fo2) + (0.0125P)2 + 1.2966P] where P = (Fo2 + 2Fc2)/3
2698 reflections	(Δ/σ)max = 0.001
178 parameters	Δρmax = 1.02 e Å−3
0 restraints	Δρmin = −0.98 e Å−3

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 > 2σ(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	0.412520 (13)	0.721169 (10)	0.152007 (9)	0.00526 (4)
O1	0.5032 (3)	0.5786 (2)	0.10655 (18)	0.0103 (4)
O2	0.3232 (3)	0.8648 (2)	0.19911 (18)	0.0091 (4)
O3	0.2643 (3)	0.6031 (2)	0.28641 (18)	0.0082 (4)
O5	0.1465 (3)	0.6550 (2)	0.05335 (18)	0.0083 (4)
O4	0.3585 (3)	0.7973 (2)	−0.04722 (18)	0.0096 (4)
O8	0.6415 (3)	0.8435 (2)	0.10897 (18)	0.0112 (4)
O9	0.6149 (3)	0.7076 (2)	0.3302 (2)	0.0125 (5)
O7	0.8885 (3)	0.7764 (2)	0.21059 (19)	0.0112 (4)
O6	−0.1157 (3)	0.6646 (2)	−0.04255 (18)	0.0093 (4)
C1	0.2569 (4)	0.6268 (3)	0.3903 (2)	0.0065 (6)
C2	0.1216 (4)	0.5613 (3)	0.4453 (2)	0.0050 (5)
C3	0.0179 (4)	0.6342 (3)	0.5063 (2)	0.0054 (5)
C5	0.8015 (4)	0.8427 (3)	0.1337 (2)	0.0069 (5)
C4	0.1018 (4)	0.4272 (3)	0.4383 (2)	0.0064 (6)
C6	0.0162 (4)	0.7181 (3)	0.0055 (2)	0.0065 (5)
N1	0.8845 (4)	0.5051 (3)	0.1615 (3)	0.0107 (5)
H1	0.852 (5)	0.507 (4)	0.089 (4)	0.022 (11)*
H2	0.980 (6)	0.463 (4)	0.185 (4)	0.031 (13)*
H3	0.813 (6)	0.468 (4)	0.190 (4)	0.030 (13)*
H4	0.905 (6)	0.590 (5)	0.190 (4)	0.035 (13)*
H6	0.571 (6)	0.706 (4)	0.381 (4)	0.031 (14)*
H5	0.716 (7)	0.748 (5)	0.355 (4)	0.041 (14)*

	U11	U22	U33	U12	U13	U23
U1	0.00418 (6)	0.00674 (6)	0.00524 (5)	−0.00009 (4)	0.00189 (4)	0.00013 (4)
O1	0.0106 (11)	0.0116 (11)	0.0092 (10)	0.0035 (9)	0.0032 (8)	0.0001 (8)
O2	0.0094 (11)	0.0093 (11)	0.0096 (10)	−0.0007 (8)	0.0045 (8)	−0.0028 (8)
O3	0.0085 (11)	0.0096 (10)	0.0069 (10)	−0.0019 (8)	0.0023 (8)	−0.0015 (8)
O5	0.0059 (10)	0.0079 (10)	0.0106 (10)	0.0008 (8)	−0.0001 (8)	0.0004 (8)
O4	0.0090 (11)	0.0132 (11)	0.0073 (10)	0.0058 (8)	0.0034 (8)	0.0035 (8)
O8	0.0062 (11)	0.0136 (11)	0.0141 (11)	−0.0020 (9)	0.0027 (8)	0.0039 (9)
O9	0.0083 (12)	0.0229 (14)	0.0068 (11)	−0.0051 (10)	0.0026 (9)	0.0000 (9)
O7	0.0112 (11)	0.0108 (11)	0.0118 (11)	0.0005 (9)	0.0029 (9)	0.0057 (9)
O6	0.0091 (11)	0.0083 (10)	0.0103 (10)	0.0009 (9)	0.0011 (8)	0.0003 (9)
C1	0.0055 (14)	0.0061 (14)	0.0081 (13)	0.0026 (11)	0.0014 (11)	0.0018 (10)
C2	0.0024 (13)	0.0100 (14)	0.0027 (12)	−0.0001 (11)	0.0005 (10)	−0.0005 (10)
C3	0.0047 (13)	0.0054 (13)	0.0055 (13)	0.0001 (10)	−0.0005 (10)	−0.0001 (10)
C5	0.0099 (14)	0.0047 (13)	0.0074 (13)	−0.0004 (11)	0.0056 (11)	−0.0023 (11)
C4	0.0040 (14)	0.0094 (14)	0.0061 (13)	0.0015 (11)	0.0016 (10)	−0.0001 (11)
C6	0.0062 (14)	0.0082 (14)	0.0065 (13)	−0.0007 (11)	0.0048 (10)	0.0005 (11)
N1	0.0113 (15)	0.0110 (14)	0.0108 (14)	0.0006 (11)	0.0045 (11)	0.0019 (11)

U1—O1	1.760 (2)	O6—C6	1.240 (4)
U1—O2	1.771 (2)	C1—O4ii	1.269 (4)
U1—O5	2.348 (2)	C1—C2	1.510 (4)
U1—O8	2.349 (2)	C2—C4	1.391 (4)
U1—O9	2.425 (2)	C2—C3	1.402 (4)
U1—O4	2.437 (2)	C3—C4iii	1.397 (4)
U1—O3	2.452 (2)	C3—C6ii	1.520 (4)
O3—C1	1.256 (4)	C5—C4iv	1.514 (4)
O5—C6	1.276 (4)	C4—C3iii	1.397 (4)
O4—C1i	1.269 (3)	C4—C5v	1.514 (4)
O8—C5	1.264 (4)	C6—C3i	1.520 (4)
O7—C5	1.247 (4)
O1—U1—O2	179.34 (10)	C6—O5—U1	132.53 (19)
O1—U1—O5	89.70 (9)	C1i—O4—U1	138.25 (19)
O2—U1—O5	90.90 (9)	C5—O8—U1	138.1 (2)
O1—U1—O8	90.27 (9)	O3—C1—O4ii	123.4 (3)
O2—U1—O8	89.48 (9)	O3—C1—C2	119.0 (3)
O5—U1—O8	136.52 (7)	O4ii—C1—C2	117.6 (2)
O1—U1—O9	87.94 (9)	C4—C2—C3	119.3 (3)
O2—U1—O9	91.41 (9)	C4—C2—C1	120.1 (3)
O5—U1—O9	145.87 (8)	C3—C2—C1	120.6 (3)
O8—U1—O9	77.55 (8)	C4iii—C3—C2	120.5 (3)
O1—U1—O4	89.55 (8)	C4iii—C3—C6ii	116.7 (2)
O2—U1—O4	90.93 (8)	C2—C3—C6ii	122.5 (3)
O5—U1—O4	67.67 (7)	O7—C5—O8	126.2 (3)
O8—U1—O4	68.85 (7)	O7—C5—C4iv	116.3 (3)
O9—U1—O4	146.29 (8)	O8—C5—C4iv	117.5 (3)
O1—U1—O3	92.95 (9)	C2—C4—C3iii	120.1 (3)
O2—U1—O3	86.99 (8)	C2—C4—C5v	122.6 (3)
O5—U1—O3	71.12 (7)	C3iii—C4—C5v	117.2 (3)
O8—U1—O3	152.22 (7)	O6—C6—O5	123.0 (3)
O9—U1—O3	75.01 (8)	O6—C6—C3i	117.0 (3)
O4—U1—O3	138.70 (7)	O5—C6—C3i	120.0 (3)
C1—O3—U1	129.60 (19)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H6···O4ii	0.74 (5)	2.02 (5)	2.700 (3)	152 (5)
O9—H5···O6vi	0.91 (6)	1.88 (5)	2.744 (3)	158 (4)
O9—H5···O7	0.91 (6)	2.38 (5)	2.884 (3)	115 (4)
N1—H3···O2v	0.81 (5)	2.12 (5)	2.908 (4)	165 (5)
N1—H1···O5vii	0.85 (4)	2.36 (4)	2.990 (4)	131 (3)
N1—H1···O6viii	0.85 (4)	2.29 (4)	2.905 (4)	130 (3)
N1—H4···O7	0.94 (5)	1.94 (5)	2.851 (4)	162 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H6⋯O4i	0.74 (5)	2.02 (5)	2.700 (3)	152 (5)
O9—H5⋯O6ii	0.91 (6)	1.88 (5)	2.744 (3)	158 (4)
O9—H5⋯O7	0.91 (6)	2.38 (5)	2.884 (3)	115 (4)
N1—H3⋯O2iii	0.81 (5)	2.12 (5)	2.908 (4)	165 (5)
N1—H1⋯O5iv	0.85 (4)	2.36 (4)	2.990 (4)	131 (3)
N1—H1⋯O6v	0.85 (4)	2.29 (4)	2.905 (4)	130 (3)
N1—H4⋯O7	0.94 (5)	1.94 (5)	2.851 (4)	162 (5)

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