Rare earth crown ether complexes: (15-crown-5)­tris­(nitrato)­praseodymium(III)

McIntosh, N.N.; Kahwa, I.A.; Mague, J.T.

doi:10.1107/S1600536800019036

Rare earth crown ether complexes: (15-crown-5)tris(nitrato)praseodymium(III)

N. N. McIntosh, I. A. Kahwa and J. T. Mague

The title compound, tris(nitrato-κ²O,O′)(1,4,7,10,13-pentaoxacyclopentadecane-κ⁵O)praseodymium(III), [Pr(NO₃)₃(C₁₀H₂₀O₅)], was obtained from a reaction designed to explore CO₂-fixation by lanthanide salts. The structure is the same as found previously for the La, Ce, Eu and Nd analogs.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800019036/na6017sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536800019036/na6017Isup2.hkl Contains datablock I

CCDC reference: 155839

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.006 Å
R factor = 0.027
wR factor = 0.075
Data-to-parameter ratio = 14.2

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No syntax errors found

ADDSYM reports no extra symmetry

General Notes



ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      1.157
          Tmax scaled      0.493 Tmin scaled      0.262

Comment top

We have earlier reported on the conversion of carbon dioxide into oxalate in the presence of Pr^III salts (Barrett et al., 1998). As part of a continuing study of this process, the action of carbon dioxide on an ethanolic solution of Pr^III nitrate and 15-crown-5 was studied. The crystals obtained at the end of the reaction proved to be [Pr(15-crown-5)(NO₃)₃], (I). The structure of the complex is the same as found for the La (Lu et al., 1983; Rogers & Rollins, 1990), Ce (Lin & Xing, 1983), Eu (Bunzli et al., 1982) and Nd (Lu et al., 1983) analogs with the metal ion 11-coordinate and all three nitrate ligands on the same side of the metal.

Experimental top

Crystals of the title compound were obtained from an ethanol solution, originally charged with 1 mmol each of Pr^III nitrate and 15-crown-5, that had been treated with carbon dioxide under reflux as part of a study of the chemical activation and reduction of carbon dioxide promoted by trivalent lanthanide ions. Analysis calculated for C₁₀H₂₀N₃O₁₄: C 21.94, H 3.88, N 7.68%; found: C 21.4, H 3.6, N 7.7%.

Computing details top

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top

Fig. 1. Perspective view of the title molecule.

Tris(nitrato)(1,4,7,10,13-pentaoxacyclopentadecane)praseodymium(III) top

Crystal data top

[Pr(NO₃)₃(C₁₀H₂₀O₅)]	F(000) = 1088
M_r = 547.20	D_x = 1.972 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.3236 (5) Å	Cell parameters from 25 reflections
b = 14.5789 (14) Å	θ = 24.3–25.8°
c = 13.6184 (6) Å	µ = 2.72 mm⁻¹
β = 95.361 (4)°	T = 293 K
V = 1843.0 (2) Å³	Plate, light green
Z = 4	0.5 × 0.5 × 0.26 mm

Data collection top

Enraf-Nonius CAD-4 diffractometer	2940 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.042
Graphite monochromator	θ_max = 26.0°, θ_min = 2.1°
θ/2θ scans	h = 0→11
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968)	k = 0→17
T_min = 0.227, T_max = 0.426	l = −16→16
3838 measured reflections	2 standard reflections every 120 min
3612 independent reflections	intensity decay: 5.1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.075	w = 1/[σ²(F_o²) + (0.0445P)² + 0.7265P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = −0.001
3611 reflections	Δρ_max = 1.23 e Å⁻³
254 parameters	Δρ_min = −0.74 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0083 (4)

Crystal data top

[Pr(NO₃)₃(C₁₀H₂₀O₅)]	V = 1843.0 (2) Å³
M_r = 547.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.3236 (5) Å	µ = 2.72 mm⁻¹
b = 14.5789 (14) Å	T = 293 K
c = 13.6184 (6) Å	0.5 × 0.5 × 0.26 mm
β = 95.361 (4)°

Data collection top

Enraf-Nonius CAD-4 diffractometer	2940 reflections with I > 2σ(I)
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968)	R_int = 0.042
T_min = 0.227, T_max = 0.426	2 standard reflections every 120 min
3838 measured reflections	intensity decay: 5.1%
3612 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.075	H-atom parameters constrained
S = 1.04	Δρ_max = 1.23 e Å⁻³
3611 reflections	Δρ_min = −0.74 e Å⁻³
254 parameters

Special details top

Experimental. A light green crystal of the complex was removed from the mother liquor, rapidly cut to size and wedged into a thin-walled glass capillary which was then flame-sealed. General procedures for crystal alignment, unit cell determination and refinement and collection of intensity data have been published [Mague, J. T. & Lloyd, C. L. (1988). Organometallics 7, 983–993].

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 on F² for ALL reflections except for 1 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion 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
Pr	0.71279 (2)	0.983235 (14)	0.270874 (12)	0.02341 (10)
O1	0.6130 (3)	1.0524 (2)	0.0928 (2)	0.0371 (6)
O2	0.4943 (3)	1.0952 (2)	0.2557 (2)	0.0341 (6)
O3	0.6330 (3)	1.0649 (2)	0.4326 (2)	0.0323 (6)
O4	0.9050 (3)	1.0828 (2)	0.3816 (2)	0.0356 (6)
O5	0.8638 (3)	1.1128 (2)	0.1852 (2)	0.0367 (6)
C1	0.4899 (5)	1.1123 (3)	0.0847 (3)	0.0442 (10)
H1A	0.4346 (5)	1.1038 (3)	0.0215 (3)	0.053*
H1B	0.5208 (5)	1.1758 (3)	0.0900 (3)	0.053*
C2	0.4002 (4)	1.0890 (3)	0.1664 (3)	0.0402 (9)
H2A	0.3208 (4)	1.1318 (3)	0.1678 (3)	0.048*
H2B	0.3614 (4)	1.0275 (3)	0.1579 (3)	0.048*
C3	0.4185 (4)	1.1131 (3)	0.3414 (3)	0.0433 (10)
H3A	0.3652 (4)	1.0592 (3)	0.3585 (3)	0.052*
H3B	0.3511 (4)	1.1634 (3)	0.3284 (3)	0.052*
C4	0.5286 (5)	1.1375 (3)	0.4234 (3)	0.0422 (10)
H4A	0.5748 (5)	1.1950 (3)	0.4092 (3)	0.051*
H4B	0.4837 (5)	1.1444 (3)	0.4844 (3)	0.051*
C5	0.7490 (4)	1.0842 (3)	0.5068 (3)	0.0380 (9)
H5A	0.7882 (4)	1.0272 (3)	0.5346 (3)	0.046*
H5B	0.7133 (4)	1.1198 (3)	0.5596 (3)	0.046*
C6	0.8641 (5)	1.1365 (3)	0.4622 (3)	0.0433 (10)
H6A	0.8281 (5)	1.1958 (3)	0.4391 (3)	0.052*
H6B	0.9460 (5)	1.1459 (3)	0.5105 (3)	0.052*
C7	1.0183 (4)	1.1243 (3)	0.3321 (3)	0.0401 (10)
H7A	1.0834 (4)	1.0773 (3)	0.3124 (3)	0.048*
H7B	1.0730 (4)	1.1662 (3)	0.3766 (3)	0.048*
C8	0.9555 (4)	1.1752 (3)	0.2435 (3)	0.0408 (10)
H8A	0.9003 (4)	1.2273 (3)	0.2631 (3)	0.049*
H8B	1.0315 (4)	1.1974 (3)	0.2056 (3)	0.049*
C9	0.8174 (5)	1.1527 (3)	0.0914 (3)	0.0436 (10)
H9A	0.9001 (5)	1.1678 (3)	0.0562 (3)	0.052*
H9B	0.7637 (5)	1.2086 (3)	0.1003 (3)	0.052*
C10	0.7241 (5)	1.0841 (3)	0.0341 (3)	0.0424 (10)
H10A	0.6805 (5)	1.1121 (3)	−0.0261 (3)	0.051*
H10B	0.7821 (5)	1.0326 (3)	0.0162 (3)	0.051*
N1	0.9535 (4)	0.9039 (3)	0.1729 (3)	0.0478 (10)
O6	0.8265 (4)	0.9077 (2)	0.1318 (2)	0.0483 (8)
O7	0.9731 (3)	0.9289 (2)	0.2625 (2)	0.0459 (7)
O8	1.0543 (5)	0.8766 (3)	0.1293 (3)	0.0866 (15)
N2	0.7816 (3)	0.8157 (2)	0.3962 (2)	0.0342 (7)
O9	0.7866 (3)	0.8967 (2)	0.4296 (2)	0.0373 (6)
O10	0.7475 (3)	0.8064 (2)	0.3048 (2)	0.0372 (6)
O11	0.8086 (4)	0.7502 (2)	0.4498 (3)	0.0626 (10)
N3	0.4549 (3)	0.8586 (2)	0.2500 (2)	0.0344 (7)
O12	0.5204 (3)	0.8806 (2)	0.1760 (2)	0.0381 (6)
O13	0.4923 (3)	0.9016 (2)	0.3295 (2)	0.0391 (7)
O14	0.3629 (3)	0.7999 (2)	0.2451 (3)	0.0598 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pr	0.02571 (13)	0.02156 (14)	0.02326 (13)	0.00014 (7)	0.00389 (7)	−0.00068 (7)
O1	0.043 (2)	0.036 (2)	0.0320 (13)	−0.0008 (13)	0.0017 (11)	0.0040 (12)
O2	0.0301 (13)	0.039 (2)	0.0329 (13)	0.0070 (11)	0.0033 (10)	0.0025 (12)
O3	0.0343 (13)	0.032 (2)	0.0308 (13)	0.0001 (11)	0.0071 (10)	−0.0064 (11)
O4	0.0334 (14)	0.042 (2)	0.0326 (14)	−0.0135 (12)	0.0089 (11)	−0.0092 (12)
O5	0.042 (2)	0.036 (2)	0.0322 (14)	−0.0114 (12)	0.0023 (11)	0.0054 (12)
C1	0.057 (3)	0.038 (3)	0.036 (2)	0.007 (2)	−0.009 (2)	0.005 (2)
C2	0.032 (2)	0.039 (2)	0.047 (2)	0.008 (2)	−0.009 (2)	0.004 (2)
C3	0.034 (2)	0.050 (3)	0.048 (2)	0.014 (2)	0.015 (2)	0.004 (2)
C4	0.050 (3)	0.041 (3)	0.039 (2)	0.013 (2)	0.017 (2)	−0.002 (2)
C5	0.041 (2)	0.045 (3)	0.028 (2)	−0.004 (2)	0.004 (2)	−0.012 (2)
C6	0.043 (2)	0.049 (3)	0.040 (2)	−0.010 (2)	0.009 (2)	−0.020 (2)
C7	0.026 (2)	0.055 (3)	0.040 (2)	−0.012 (2)	0.006 (2)	−0.003 (2)
C8	0.039 (2)	0.040 (3)	0.044 (2)	−0.014 (2)	0.007 (2)	0.000 (2)
C9	0.057 (3)	0.038 (3)	0.035 (2)	−0.009 (2)	0.006 (2)	0.011 (2)
C10	0.057 (3)	0.044 (3)	0.027 (2)	−0.003 (2)	0.005 (2)	0.011 (2)
N1	0.059 (2)	0.034 (2)	0.055 (2)	0.015 (2)	0.029 (2)	0.008 (2)
O6	0.062 (2)	0.046 (2)	0.039 (2)	0.010 (2)	0.0114 (14)	−0.0021 (14)
O7	0.041 (2)	0.044 (2)	0.055 (2)	0.0079 (13)	0.0129 (14)	−0.0013 (15)
O8	0.086 (3)	0.103 (4)	0.079 (3)	0.048 (3)	0.052 (2)	0.009 (2)
N2	0.032 (2)	0.028 (2)	0.040 (2)	−0.0017 (13)	−0.0071 (14)	0.0073 (14)
O9	0.050 (2)	0.025 (2)	0.0352 (14)	−0.0005 (12)	−0.0046 (12)	0.0005 (11)
O10	0.045 (2)	0.031 (2)	0.0340 (14)	0.0022 (12)	−0.0024 (12)	−0.0015 (12)
O11	0.088 (3)	0.034 (2)	0.060 (2)	−0.008 (2)	−0.026 (2)	0.017 (2)
N3	0.029 (2)	0.031 (2)	0.043 (2)	0.0007 (13)	0.0016 (14)	0.0048 (14)
O12	0.045 (2)	0.040 (2)	0.0285 (14)	−0.0089 (13)	−0.0013 (12)	0.0006 (12)
O13	0.039 (2)	0.043 (2)	0.0364 (15)	−0.0067 (13)	0.0087 (12)	−0.0007 (13)
O14	0.047 (2)	0.049 (2)	0.083 (2)	−0.025 (2)	0.006 (2)	−0.006 (2)

Geometric parameters (Å, º) top

Pr—O6	2.509 (3)	O4—C6	1.428 (5)
Pr—O9	2.542 (3)	O4—C7	1.439 (4)
Pr—O7	2.566 (3)	O5—C9	1.434 (5)
Pr—O13	2.567 (3)	O5—C8	1.435 (5)
Pr—O12	2.587 (3)	C1—C2	1.492 (6)
Pr—O2	2.603 (3)	C3—C4	1.487 (6)
Pr—O10	2.634 (3)	C5—C6	1.491 (6)
Pr—O4	2.663 (3)	C7—C8	1.489 (6)
Pr—O3	2.670 (2)	C9—C10	1.496 (6)
Pr—O5	2.687 (3)	N1—O8	1.224 (5)
Pr—O1	2.709 (3)	N1—O6	1.263 (5)
Pr—N1	2.952 (4)	N1—O7	1.270 (5)
O1—C1	1.438 (5)	N2—O11	1.214 (4)
O1—C10	1.443 (5)	N2—O10	1.263 (4)
O2—C2	1.434 (5)	N2—O9	1.264 (4)
O2—C3	1.444 (5)	N3—O14	1.210 (4)
O3—C4	1.436 (5)	N3—O12	1.267 (4)
O3—C5	1.437 (4)	N3—O13	1.271 (4)

O6—Pr—O9	108.92 (10)	O13—Pr—N1	128.60 (11)
O6—Pr—O7	50.42 (10)	O12—Pr—N1	93.94 (11)
O9—Pr—O7	72.69 (10)	O2—Pr—N1	146.33 (9)
O6—Pr—O13	116.01 (10)	O10—Pr—N1	67.01 (10)
O9—Pr—O13	70.52 (9)	O4—Pr—N1	88.26 (11)
O7—Pr—O13	131.24 (10)	O3—Pr—N1	146.07 (10)
O6—Pr—O12	72.03 (10)	O5—Pr—N1	68.16 (10)
O9—Pr—O12	104.93 (9)	O1—Pr—N1	87.33 (10)
O7—Pr—O12	114.44 (10)	C1—O1—C10	111.8 (3)
O13—Pr—O12	49.38 (8)	C1—O1—Pr	120.0 (2)
O6—Pr—O2	126.72 (9)	C10—O1—Pr	114.3 (2)
O9—Pr—O2	121.75 (9)	C2—O2—C3	113.0 (3)
O7—Pr—O2	157.90 (10)	C2—O2—Pr	116.1 (2)
O13—Pr—O2	70.83 (9)	C3—O2—Pr	119.2 (2)
O12—Pr—O2	79.75 (9)	C4—O3—C5	112.1 (3)
O6—Pr—O10	69.47 (10)	C4—O3—Pr	119.7 (2)
O9—Pr—O10	49.15 (8)	C5—O3—Pr	114.7 (2)
O7—Pr—O10	66.69 (10)	C6—O4—C7	113.0 (3)
O13—Pr—O10	65.20 (9)	C6—O4—Pr	121.3 (2)
O12—Pr—O10	65.77 (9)	C7—O4—Pr	116.7 (2)
O2—Pr—O10	135.23 (9)	C9—O5—C8	110.5 (3)
O6—Pr—O4	110.93 (10)	C9—O5—Pr	123.1 (2)
O9—Pr—O4	71.00 (9)	C8—O5—Pr	121.0 (2)
O7—Pr—O4	66.69 (10)	O1—C1—C2	107.7 (3)
O13—Pr—O4	126.37 (8)	O2—C2—C1	106.1 (3)
O12—Pr—O4	175.46 (8)	O2—C3—C4	107.1 (3)
O2—Pr—O4	100.56 (9)	O3—C4—C3	107.8 (3)
O10—Pr—O4	111.67 (9)	O3—C5—C6	109.7 (3)
O6—Pr—O3	171.15 (9)	O4—C6—C5	106.7 (3)
O9—Pr—O3	66.03 (9)	O4—C7—C8	109.8 (3)
O7—Pr—O3	120.80 (9)	O5—C8—C7	107.6 (3)
O13—Pr—O3	69.94 (9)	O5—C9—C10	107.8 (3)
O12—Pr—O3	115.86 (8)	O1—C10—C9	109.8 (3)
O2—Pr—O3	60.64 (8)	O8—N1—O6	122.0 (4)
O10—Pr—O3	109.31 (8)	O8—N1—O7	120.8 (4)
O4—Pr—O3	60.94 (8)	O6—N1—O7	117.2 (3)
O6—Pr—O5	72.87 (10)	O8—N1—Pr	175.7 (3)
O9—Pr—O5	127.37 (9)	O6—N1—Pr	57.4 (2)
O7—Pr—O5	70.22 (10)	O7—N1—Pr	60.0 (2)
O13—Pr—O5	158.21 (9)	N1—O6—Pr	97.5 (2)
O12—Pr—O5	123.85 (8)	N1—O7—Pr	94.6 (2)
O2—Pr—O5	87.86 (9)	O11—N2—O10	121.8 (4)
O10—Pr—O5	134.72 (9)	O11—N2—O9	121.3 (3)
O4—Pr—O5	60.67 (8)	O10—N2—O9	116.9 (3)
O3—Pr—O5	104.03 (8)	O11—N2—Pr	177.5 (3)
O6—Pr—O1	67.78 (9)	O10—N2—Pr	60.6 (2)
O9—Pr—O1	171.48 (9)	O9—N2—Pr	56.4 (2)
O7—Pr—O1	108.80 (9)	N2—O9—Pr	99.1 (2)
O13—Pr—O1	103.46 (9)	N2—O10—Pr	94.8 (2)
O12—Pr—O1	66.68 (9)	O14—N3—O12	121.8 (4)
O2—Pr—O1	59.67 (8)	O14—N3—O13	122.2 (3)
O10—Pr—O1	123.20 (9)	O12—N3—O13	116.0 (3)
O4—Pr—O1	117.43 (9)	O14—N3—Pr	171.9 (3)
O3—Pr—O1	118.27 (8)	O12—N3—Pr	58.8 (2)
O5—Pr—O1	59.99 (8)	O13—N3—Pr	57.9 (2)
O6—Pr—N1	25.11 (11)	N3—O12—Pr	96.5 (2)
O9—Pr—N1	91.89 (10)	N3—O13—Pr	97.3 (2)
O7—Pr—N1	25.39 (11)

Experimental details

Crystal data
Chemical formula	[Pr(NO₃)₃(C₁₀H₂₀O₅)]
M_r	547.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.3236 (5), 14.5789 (14), 13.6184 (6)
β (°)	95.361 (4)
V (Å³)	1843.0 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.72
Crystal size (mm)	0.5 × 0.5 × 0.26

Data collection
Diffractometer	Enraf-Nonius CAD-4 diffractometer
Absorption correction	Empirical (using intensity measurements) via ψ scan (North et al., 1968)
T_min, T_max	0.227, 0.426
No. of measured, independent and observed [I > 2σ(I)] reflections	3838, 3612, 2940
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.075, 1.04
No. of reflections	3611
No. of parameters	254
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.23, −0.74

Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, XCAD4 (Harms & Wocadlo, 1987), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

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Rare earth crown ether complexes: (15-crown-5)­tris­(nitrato)­praseodymium(III)

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Rare earth crown ether complexes: (15-crown-5)tris(nitrato)praseodymium(III)