NdO(NO₃)

The title compound, neodymium(III) oxide nitrate, which is isostructural with LaO(NO₃), arose from a solvothermal reaction. The Nd ion (site symmetry m) is ten-coordinated by eight O atoms of NO₃ groups and two μ₂-oxide ions. A three-dimensional structure is constructed by the inter­connection of NdO₁₀ polyhedra. The oxide ion and the N atom and one of the nitrate O atoms possess site symmetry m.

Related literature

For background, see: Gobichon et al. (1997); Guillou et al. (1994). For an isostructural compound, see: Zhang et al. (2004).

Experimental

Crystal data

• NdO(NO₃)

• M_r = 222.25

• Orthorhombic, P n m a

• a = 7.5233 (15) Å

• b = 5.1618 (10) Å

• c = 8.7157 (17) Å

• V = 338.46 (11) ų

• Z = 4

• Mo Kα radiation

• μ = 15.19 mm⁻¹

• T = 293 (2) K

• 0.16 × 0.14 × 0.12 mm

Data collection

• Rigaku R-AXIS RAPID diffractometer

• Absorption correction: multi-scan (ABSCOR; Higashi, 1995) T_min = 0.107, T_max = 0.158

• 2962 measured reflections

• 410 independent reflections

• 405 reflections with I > 2σ(I)

• R_int = 0.034

Refinement

• R[F² > 2σ(F²)] = 0.024

• wR(F²) = 0.068

• S = 1.81

• 410 reflections

• 34 parameters

• 30 restraints

• Δρ_max = 1.02 e Å⁻³

• Δρ_min = −1.42 e Å⁻³

Table 1
Selected bond lengths (Å)

Nd1—O2^i	2.434 (5)
Nd1—O2	2.458 (5)
Nd1—O3^ii	2.6362 (12)
Nd1—O1	2.694 (3)
Nd1—O1^iii	2.719 (4)
Nd1—O1^ii	2.826 (4)
Symmetry codes: (i) ; (ii) ; (iii) .

Data collection: PROCESS-AUTO (Rigaku, 2002); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXL97.

Supporting information

S1. Comment

The lanthanide nitrates are not only applied for separation of the lanthanide elements but also widely utilized as the precursor of organic or inorganic synthesis. Thus, a large number of lanthanide nitrates are structurally determinated besides a few anhydrous examples (Guillou, et al., 1994; Zhang, et al., 2004; Gobichon, et al., 1997). In this work, the title compound, (I), an anhydrous neodymium oxide nitrate, was unexpectedly obtained under solvothermal conditions in a mixed solvent of H₂O and DMF.

The asymmetric unit of (I) is consisted of 0.5 N d, 0.5 O and 0.5 NO₃ (Fig. 1). All oxygen atoms of NO₃ group are coordinated to the Nd ions. Two oxygen atoms of nitrate group (O1 and O1^vi) are coordinated to three different Nd ions with Nd—O distances in the range of 2.694–2.826 A°, and the last one (O3) is coordinated to two different Nd ions with Nd—O distance of 2.636 A° (Table 1). A µ₂-O (O2) exists in the structure of (I) with Nd—O distances of 2.434 and 2.458 A° and corresponding Nd—O2—Nd bond angles of 110.72°. These two Nd—O distances are significantly shorter than the others Nd—O distances. Then, the linkages of two adjacent Nd ions are in two modes, of which one is via Nd-µ₂-O—Nd bonds with Nd—Nd distance of 4.0254 (8)A° and the other via Nd—O(NO₃)-Nd bonds. A three-dimensional framework constructed by the interconnections of NdO₁₀ polyhedra is shown in Fig. 2.

There are two different structures with the same molecular formula of LnONO₃, such as LnONO₃(Ln=Y, La) in the P₄/mmm space group and LaONO₃ in Pnma space group. In this work, NdONO₃ is the isostructural compound of the reported LaONO₃ (Zhang, et al., 2004).

Related literature

For background, see: Gobichon et al. (1997); Guillou et al. (1994). For an isostructural compound, see: Zhang et al. (2004).

S2. Experimental

Isonicotine (0.123 g, 1.0 mmol) was added to a mixed solution of 5 ml H₂O/3 ml DMF. After being stirred for 5 h, the isonicotine was partially dissovled with pH = 6.0. Then, Nd(NO₃)₃^.6H₂O (0.220 g, 0.5 mmol) was added and stirred for 7 h. The molar ratio of Nd(NO₃)₃^.6H₂O: isonicotine was 1:2. Finally, the solution with pH = 7.0 was sealed into 23 ml autoclave and heated up to 438 K for 4 days. After naturally cooling to room temperature, colourless prisms of (I) were obtained.

Computing details

Data collection: PROCESS-AUTO (Rigaku, 2002); cell refinement: PROCESS-AUTO (Rigaku, 2002); data reduction: CrystalStructure (Rigaku, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. A fragment of the structure of (I), showing the Nd coordination sphere and displacement ellipsoids at the 50% probability level. [Symmetry codes: (i) -1/2 + x, y, 1.5 - z; (ii) x, 0.5 - y, z; (iii) 1 - x, 1/2 + y, 2 - z; (iv) 1 - x, -y, 2 - z; (v) -1/2 + x, 0.5 - y, 1.5 - z; (vi) x, -0.5 - y, z; (vii) 1/2 + x, 0.5 - y, 1.5 - z.]
	Fig. 2. A packing diagram for (I), viewed along [010].

neodymium(III) oxide nitrate

Crystal data

NdO(NO3)	F(000) = 396
Mr = 222.25	Dx = 4.362 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 2000 reflections
a = 7.5233 (15) Å	θ = 3.6–27.0°
b = 5.1618 (10) Å	µ = 15.19 mm^−1
c = 8.7157 (17) Å	T = 293 K
V = 338.46 (11) Å^3	Prism, colourless
Z = 4	0.16 × 0.14 × 0.12 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	410 independent reflections
Radiation source: fine-focus sealed tube	405 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
Detector resolution: 10.00 pixels mm^-1	θmax = 27.0°, θmin = 3.6°
ω scans	h = −9→8
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −5→6
Tmin = 0.107, Tmax = 0.158	l = −11→11
2962 measured reflections

Refinement

Refinement on F^2	30 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.024	Secondary atom site location: difference Fourier map
wR(F^2) = 0.068	w = 1/[σ^2(Fo^2) + (0.0285P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.81	(Δ/σ)max = 0.002
410 reflections	Δρmax = 1.02 e Å^−3
34 parameters	Δρmin = −1.42 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Nd1	0.35352 (4)	0.2500	0.83222 (4)	0.0055 (2)
O1	0.6501 (4)	−0.0288 (7)	0.8846 (4)	0.0047 (7)
O2	0.0359 (6)	0.2500	0.8985 (6)	0.0080 (10)
O3	0.7902 (7)	−0.2500	0.6964 (6)	0.0088 (10)
N1	0.6934 (10)	−0.2500	0.8195 (7)	0.0120 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Nd1	0.0051 (3)	0.0052 (3)	0.0061 (3)	0.000	0.00018 (11)	0.000
O1	0.0054 (10)	0.0043 (10)	0.0045 (10)	0.0002 (7)	0.0004 (7)	−0.0001 (8)
O2	0.0072 (12)	0.0091 (12)	0.0076 (13)	0.000	−0.0001 (9)	0.000
O3	0.0091 (13)	0.0088 (13)	0.0086 (12)	0.000	0.0022 (9)	0.000
N1	0.0121 (15)	0.0120 (15)	0.0121 (15)	0.000	−0.0005 (9)	0.000

Geometric parameters (Å, º)

Nd1—O2^i	2.434 (5)	Nd1—Nd1^ii	4.0254 (8)
Nd1—O2	2.458 (5)	Nd1—Nd1^i	4.0254 (8)
Nd1—O3^ii	2.6362 (12)	O1—N1	1.316 (5)
Nd1—O3^iii	2.6362 (12)	O1—Nd1^vi	2.719 (4)
Nd1—O1^iv	2.694 (3)	O1—Nd1^i	2.826 (4)
Nd1—O1	2.694 (3)	O2—Nd1^ii	2.434 (5)
Nd1—O1^v	2.719 (4)	O3—N1	1.297 (8)
Nd1—O1^vi	2.719 (4)	O3—Nd1^i	2.6362 (12)
Nd1—O1^ii	2.826 (4)	O3—Nd1^viii	2.6362 (12)
Nd1—O1^vii	2.826 (4)	N1—O1^ix	1.316 (5)
O2^i—Nd1—O2	137.90 (13)	O3^ii—Nd1—O1^ii	48.73 (13)
O2^i—Nd1—O3^ii	91.36 (11)	O3^iii—Nd1—O1^ii	109.73 (13)
O2—Nd1—O3^ii	81.18 (12)	O1^iv—Nd1—O1^ii	146.51 (6)
O2^i—Nd1—O3^iii	91.36 (11)	O1—Nd1—O1^ii	106.85 (12)
O2—Nd1—O3^iii	81.18 (12)	O1^v—Nd1—O1^ii	144.63 (7)
O3^ii—Nd1—O3^iii	156.5 (2)	O1^vi—Nd1—O1^ii	112.81 (4)
O2^i—Nd1—O1^iv	70.92 (12)	O2^i—Nd1—O1^vii	75.69 (11)
O2—Nd1—O1^iv	139.92 (10)	O2—Nd1—O1^vii	68.33 (11)
O3^ii—Nd1—O1^iv	133.51 (14)	O3^ii—Nd1—O1^vii	109.73 (13)
O3^iii—Nd1—O1^iv	69.06 (14)	O3^iii—Nd1—O1^vii	48.73 (13)
O2^i—Nd1—O1	70.92 (12)	O1^iv—Nd1—O1^vii	106.85 (12)
O2—Nd1—O1	139.92 (10)	O1—Nd1—O1^vii	146.51 (6)
O3^ii—Nd1—O1	69.06 (14)	O1^v—Nd1—O1^vii	112.81 (4)
O3^iii—Nd1—O1	133.51 (14)	O1^vi—Nd1—O1^vii	144.63 (7)
O1^iv—Nd1—O1	64.57 (15)	O1^ii—Nd1—O1^vii	61.23 (15)
O2^i—Nd1—O1^v	139.04 (10)	Nd1^ii—Nd1—Nd1^i	138.29 (2)
O2—Nd1—O1^v	77.12 (12)	N1—O1—Nd1	126.5 (4)
O3^ii—Nd1—O1^v	119.67 (13)	N1—O1—Nd1^vi	91.7 (3)
O3^iii—Nd1—O1^v	70.90 (13)	Nd1—O1—Nd1^vi	111.71 (11)
O1^iv—Nd1—O1^v	68.29 (11)	N1—O1—Nd1^i	91.1 (3)
O1—Nd1—O1^v	94.51 (7)	Nd1—O1—Nd1^i	93.62 (12)
O2^i—Nd1—O1^vi	139.04 (10)	Nd1^vi—O1—Nd1^i	145.72 (12)
O2—Nd1—O1^vi	77.12 (12)	Nd1^ii—O2—Nd1	110.73 (19)
O3^ii—Nd1—O1^vi	70.90 (13)	N1—O3—Nd1^i	100.35 (11)
O3^iii—Nd1—O1^vi	119.67 (13)	N1—O3—Nd1^viii	100.35 (11)
O1^iv—Nd1—O1^vi	94.51 (7)	Nd1^i—O3—Nd1^viii	156.5 (2)
O1—Nd1—O1^vi	68.29 (11)	O3—N1—O1	119.7 (3)
O1^v—Nd1—O1^vi	49.66 (16)	O3—N1—O1^ix	119.7 (3)
O2^i—Nd1—O1^ii	75.69 (11)	O1—N1—O1^ix	120.4 (6)
O2—Nd1—O1^ii	68.33 (12)

Symmetry codes: (i) x+1/2, y, −z+3/2; (ii) x−1/2, y, −z+3/2; (iii) x−1/2, y+1, −z+3/2; (iv) x, −y+1/2, z; (v) −x+1, y+1/2, −z+2; (vi) −x+1, −y, −z+2; (vii) x−1/2, −y+1/2, −z+3/2; (viii) x+1/2, y−1, −z+3/2; (ix) x, −y−1/2, z.