Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199016157/qb0157sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199016157/qb0157Isup2.hkl |
CCDC reference: 140854
The title complex (I) was prepared by methods similar to those in the literature (Hart & Laming, 1965). Hot solutions of Nd(NO3)3.6H2O (0.219 g, 0.5 mmol) in ethanol (15 ml) and bipy (0.156 g, 1 mmol) in ethanol (15 ml) were mixed. Violet crystals formed overnight.
Data collection: XSCANS (Fait, 1991); cell refinement: XSCANS (Fait, 1991); data reduction: XSCANS (Fait, 1991); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Nd(NO3)3(C10H8N2)2] | F(000) = 1268 |
Mr = 642.64 | Dx = 1.852 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 47 reflections |
a = 16.935 (3) Å | θ = 5.4–30.0° |
b = 9.0806 (7) Å | µ = 2.32 mm−1 |
c = 14.987 (3) Å | T = 190 K |
V = 2304.8 (6) Å3 | Block, violet |
Z = 4 | 0.34 × 0.28 × 0.19 mm |
Siemens P4 diffractometer | 1867 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.025 |
Graphite monochromator | θmax = 27.0°, θmin = 2.6° |
ω scans | h = −1→21 |
Absorption correction: ψ scan (North et al., 1968) | k = −1→11 |
Tmin = 0.506, Tmax = 0.667 | l = −1→19 |
3149 measured reflections | 3 standard reflections every 100 reflections |
2499 independent reflections | intensity decay: <1% |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 2.23 | w = 1/[σ2(Fo2) + (0.0268P)2 + 3.6161P] where P = (Fo2 + 2Fc2)/3 |
2499 reflections | (Δ/σ)max = 0.010 |
169 parameters | Δρmax = 1.66 e Å−3 |
0 restraints | Δρmin = −2.21 e Å−3 |
[Nd(NO3)3(C10H8N2)2] | V = 2304.8 (6) Å3 |
Mr = 642.64 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 16.935 (3) Å | µ = 2.32 mm−1 |
b = 9.0806 (7) Å | T = 190 K |
c = 14.987 (3) Å | 0.34 × 0.28 × 0.19 mm |
Siemens P4 diffractometer | 1867 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.025 |
Tmin = 0.506, Tmax = 0.667 | 3 standard reflections every 100 reflections |
3149 measured reflections | intensity decay: <1% |
2499 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 2.23 | Δρmax = 1.66 e Å−3 |
2499 reflections | Δρmin = −2.21 e Å−3 |
169 parameters |
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 | ||
Nd1 | 0.0000 | 0.09597 (5) | 0.7500 | 0.01788 (16) | |
N1 | 0.0861 (3) | 0.1858 (7) | 0.9146 (4) | 0.0342 (14) | |
O1 | 0.0187 (3) | 0.1242 (6) | 0.9199 (4) | 0.0350 (12) | |
O2 | 0.1171 (2) | 0.1955 (6) | 0.8385 (3) | 0.0332 (11) | |
O3 | 0.1188 (4) | 0.2358 (9) | 0.9817 (4) | 0.071 (2) | |
N2 | 0.0000 | 0.4203 (10) | 0.7500 | 0.078 (5) | |
O4 | −0.0372 (3) | 0.3470 (6) | 0.8087 (5) | 0.0464 (14) | |
O5 | 0.0000 | 0.5529 (10) | 0.7500 | 0.133 (7) | |
N3 | −0.0720 (3) | −0.1317 (6) | 0.6847 (4) | 0.0288 (13) | |
N4 | −0.1309 (3) | 0.0139 (6) | 0.8264 (4) | 0.0268 (12) | |
C1 | −0.0379 (4) | −0.2108 (8) | 0.6210 (5) | 0.0341 (15) | |
H1A | 0.0150 | −0.1879 | 0.6048 | 0.041* | |
C2 | −0.0755 (5) | −0.3254 (8) | 0.5766 (5) | 0.0401 (18) | |
H2A | −0.0494 | −0.3789 | 0.5308 | 0.048* | |
C3 | −0.1519 (5) | −0.3593 (10) | 0.6011 (6) | 0.047 (2) | |
H3A | −0.1792 | −0.4382 | 0.5731 | 0.057* | |
C4 | −0.1882 (4) | −0.2774 (9) | 0.6666 (6) | 0.0403 (18) | |
H4A | −0.2411 | −0.2983 | 0.6835 | 0.048* | |
C5 | −0.1475 (4) | −0.1650 (7) | 0.7075 (5) | 0.0262 (13) | |
C6 | −0.1811 (4) | −0.0732 (7) | 0.7820 (5) | 0.0260 (14) | |
C7 | −0.2621 (4) | −0.0768 (8) | 0.8016 (6) | 0.0372 (18) | |
H7A | −0.2970 | −0.1367 | 0.7677 | 0.045* | |
C8 | −0.2902 (4) | 0.0085 (9) | 0.8709 (6) | 0.0407 (18) | |
H8A | −0.3448 | 0.0085 | 0.8855 | 0.049* | |
C9 | −0.2383 (4) | 0.0928 (8) | 0.9183 (6) | 0.0386 (18) | |
H9A | −0.2564 | 0.1511 | 0.9668 | 0.046* | |
C10 | −0.1593 (4) | 0.0929 (8) | 0.8953 (6) | 0.0353 (17) | |
H10A | −0.1237 | 0.1509 | 0.9293 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Nd1 | 0.0110 (2) | 0.0170 (2) | 0.0257 (3) | 0.000 | 0.00157 (18) | 0.000 |
N1 | 0.022 (3) | 0.034 (3) | 0.046 (4) | −0.009 (2) | 0.000 (3) | −0.003 (3) |
O1 | 0.021 (2) | 0.036 (3) | 0.048 (3) | −0.0103 (19) | 0.005 (2) | −0.008 (2) |
O2 | 0.017 (2) | 0.040 (3) | 0.042 (3) | −0.008 (2) | −0.001 (2) | 0.002 (2) |
O3 | 0.048 (4) | 0.104 (6) | 0.060 (4) | −0.036 (4) | −0.009 (3) | −0.025 (4) |
N2 | 0.125 (12) | 0.006 (4) | 0.102 (11) | 0.000 | −0.073 (10) | 0.000 |
O4 | 0.042 (3) | 0.030 (3) | 0.067 (4) | 0.015 (3) | −0.005 (3) | −0.015 (3) |
O5 | 0.236 (19) | 0.007 (4) | 0.154 (14) | 0.000 | −0.081 (13) | 0.000 |
N3 | 0.019 (2) | 0.018 (3) | 0.049 (3) | −0.001 (2) | −0.001 (2) | −0.002 (3) |
N4 | 0.013 (2) | 0.025 (3) | 0.042 (3) | −0.004 (2) | 0.005 (2) | 0.001 (3) |
C1 | 0.028 (3) | 0.029 (3) | 0.046 (4) | 0.002 (3) | −0.003 (3) | −0.003 (3) |
C2 | 0.048 (4) | 0.033 (4) | 0.039 (4) | −0.002 (3) | 0.006 (4) | −0.008 (3) |
C3 | 0.049 (5) | 0.038 (4) | 0.055 (5) | −0.015 (4) | −0.011 (4) | −0.014 (4) |
C4 | 0.031 (3) | 0.040 (4) | 0.050 (5) | −0.013 (3) | −0.002 (3) | −0.004 (4) |
C5 | 0.024 (3) | 0.022 (3) | 0.032 (4) | −0.001 (3) | −0.005 (3) | 0.002 (3) |
C6 | 0.020 (3) | 0.027 (3) | 0.031 (3) | −0.004 (3) | 0.004 (3) | 0.007 (3) |
C7 | 0.019 (3) | 0.036 (4) | 0.056 (5) | −0.009 (3) | 0.006 (3) | −0.001 (4) |
C8 | 0.019 (3) | 0.045 (4) | 0.058 (5) | −0.001 (3) | 0.012 (3) | 0.010 (4) |
C9 | 0.028 (4) | 0.037 (4) | 0.050 (4) | 0.002 (3) | 0.015 (3) | 0.000 (4) |
C10 | 0.022 (3) | 0.033 (4) | 0.052 (5) | −0.003 (3) | 0.011 (3) | −0.004 (3) |
Nd1—O4 | 2.524 (5) | N2—O4 | 1.271 (8) |
Nd1—O4i | 2.524 (5) | N2—O4i | 1.271 (8) |
Nd1—O2 | 2.551 (5) | N3—C1 | 1.327 (9) |
Nd1—O2i | 2.551 (5) | N3—C5 | 1.358 (8) |
Nd1—O1 | 2.578 (6) | N4—C6 | 1.339 (9) |
Nd1—O1i | 2.578 (6) | N4—C10 | 1.346 (9) |
Nd1—N3 | 2.592 (6) | C1—C2 | 1.389 (10) |
Nd1—N3i | 2.592 (5) | C2—C3 | 1.380 (11) |
Nd1—N4 | 2.604 (5) | C3—C4 | 1.377 (12) |
Nd1—N4i | 2.604 (5) | C4—C5 | 1.376 (10) |
Nd1—N2 | 2.945 (9) | C5—C6 | 1.504 (10) |
Nd1—N1 | 2.979 (6) | C6—C7 | 1.403 (9) |
N1—O3 | 1.235 (8) | C7—C8 | 1.380 (11) |
N1—O2 | 1.259 (8) | C8—C9 | 1.365 (11) |
N1—O1 | 1.272 (7) | C9—C10 | 1.382 (9) |
N2—O5 | 1.203 (12) | ||
O4—Nd1—O4i | 50.8 (3) | N3—Nd1—N2 | 142.91 (12) |
O4—Nd1—O2 | 72.12 (18) | N3i—Nd1—N2 | 142.91 (13) |
O4i—Nd1—O2 | 70.57 (18) | N4—Nd1—N2 | 106.64 (13) |
O4—Nd1—O2i | 70.57 (18) | N4i—Nd1—N2 | 106.64 (13) |
O4i—Nd1—O2i | 72.12 (17) | O4—Nd1—N1 | 65.54 (18) |
O2—Nd1—O2i | 138.5 (2) | O4i—Nd1—N1 | 85.37 (19) |
O4—Nd1—O1 | 66.20 (19) | O2—Nd1—N1 | 24.81 (15) |
O4i—Nd1—O1 | 102.93 (19) | O2i—Nd1—N1 | 135.54 (16) |
O2—Nd1—O1 | 49.90 (15) | O1—Nd1—N1 | 25.16 (15) |
O2i—Nd1—O1 | 125.01 (15) | O1i—Nd1—N1 | 148.27 (16) |
O4—Nd1—O1i | 102.93 (19) | N3—Nd1—N1 | 139.57 (18) |
O4i—Nd1—O1i | 66.20 (19) | N3i—Nd1—N1 | 71.08 (18) |
O2—Nd1—O1i | 125.01 (15) | N4—Nd1—N1 | 97.51 (17) |
O2i—Nd1—O1i | 49.90 (15) | N4i—Nd1—N1 | 91.50 (17) |
O1—Nd1—O1i | 168.6 (2) | N2—Nd1—N1 | 74.10 (12) |
O4—Nd1—N3 | 137.29 (17) | O3—N1—O2 | 121.6 (6) |
O4i—Nd1—N3 | 134.9 (2) | O3—N1—O1 | 120.9 (7) |
O2—Nd1—N3 | 147.60 (17) | O2—N1—O1 | 117.5 (6) |
O2i—Nd1—N3 | 73.77 (17) | O3—N1—Nd1 | 174.1 (6) |
O1—Nd1—N3 | 120.67 (18) | O2—N1—Nd1 | 58.2 (3) |
O1i—Nd1—N3 | 69.43 (18) | O1—N1—Nd1 | 59.5 (4) |
O4—Nd1—N3i | 134.9 (2) | N1—O1—Nd1 | 95.3 (4) |
O4i—Nd1—N3i | 137.29 (17) | N1—O2—Nd1 | 97.0 (3) |
O2—Nd1—N3i | 73.77 (17) | O5—N2—O4 | 121.6 (4) |
O2i—Nd1—N3i | 147.60 (17) | O5—N2—O4i | 121.6 (4) |
O1—Nd1—N3i | 69.43 (18) | O4—N2—O4i | 116.8 (8) |
O1i—Nd1—N3i | 120.67 (18) | O5—N2—Nd1 | 180.000 (3) |
N3—Nd1—N3i | 74.2 (2) | O4—N2—Nd1 | 58.4 (4) |
O4—Nd1—N4 | 83.84 (19) | O4i—N2—Nd1 | 58.4 (4) |
O4i—Nd1—N4 | 128.66 (19) | N2—O4—Nd1 | 96.2 (5) |
O2—Nd1—N4 | 122.32 (17) | C1—N3—C5 | 118.1 (6) |
O2i—Nd1—N4 | 70.62 (17) | C1—N3—Nd1 | 119.9 (4) |
O1—Nd1—N4 | 72.48 (16) | C5—N3—Nd1 | 121.7 (4) |
O1i—Nd1—N4 | 110.98 (16) | C6—N4—C10 | 118.0 (5) |
N3—Nd1—N4 | 62.44 (18) | C6—N4—Nd1 | 119.4 (4) |
N3i—Nd1—N4 | 90.33 (18) | C10—N4—Nd1 | 119.3 (4) |
O4—Nd1—N4i | 128.66 (19) | N3—C1—C2 | 123.4 (7) |
O4i—Nd1—N4i | 83.84 (19) | C3—C2—C1 | 118.0 (7) |
O2—Nd1—N4i | 70.62 (17) | C2—C3—C4 | 119.2 (7) |
O2i—Nd1—N4i | 122.32 (17) | C5—C4—C3 | 119.6 (7) |
O1—Nd1—N4i | 110.98 (16) | N3—C5—C4 | 121.7 (7) |
O1i—Nd1—N4i | 72.48 (16) | N3—C5—C6 | 114.8 (6) |
N3—Nd1—N4i | 90.33 (17) | C4—C5—C6 | 123.5 (6) |
N3i—Nd1—N4i | 62.44 (18) | N4—C6—C7 | 122.1 (7) |
N4—Nd1—N4i | 146.7 (3) | N4—C6—C5 | 117.1 (5) |
O4—Nd1—N2 | 25.40 (16) | C7—C6—C5 | 120.8 (6) |
O4i—Nd1—N2 | 25.40 (16) | C8—C7—C6 | 118.8 (7) |
O2—Nd1—N2 | 69.26 (12) | C9—C8—C7 | 119.0 (6) |
O2i—Nd1—N2 | 69.26 (12) | C8—C9—C10 | 119.6 (7) |
O1—Nd1—N2 | 84.29 (12) | N4—C10—C9 | 122.5 (7) |
O1i—Nd1—N2 | 84.29 (12) |
Symmetry code: (i) −x, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Nd(NO3)3(C10H8N2)2] |
Mr | 642.64 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 190 |
a, b, c (Å) | 16.935 (3), 9.0806 (7), 14.987 (3) |
V (Å3) | 2304.8 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.32 |
Crystal size (mm) | 0.34 × 0.28 × 0.19 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.506, 0.667 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3149, 2499, 1867 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.129, 2.23 |
No. of reflections | 2499 |
No. of parameters | 169 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.66, −2.21 |
Computer programs: XSCANS (Fait, 1991), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).
Compounds Ln(bipy)2(NO3)3 (Ln = La—Lu; bipy = 2,2'-bipyridyl) have been known for many years (Lobanov & Smirnova, 1963; Sinha, 1964; Hart & Laming, 1965). The structures of the La and Lu compounds have more recently been confirmed by X-ray diffraction studies (Al-Kharaghouli & Wood, 1972; Kravchenko, 1972; Kepert et al., 1996). Nd(bipy)2(NO3)3, (I), is isomorphous with those structures, with three bidentate nitrate and two bipyridyl ligands giving a ten-coordinate environment about the Nd atom. The coordination polyhedron has been described as a bicapped dodecahedron (Al-Kharaghouli & Wood, 1972) or sphenocorona (Kepert et al., 1996). The average Nd—N bond length of 2.596 Å (Table 1) is 0.07 Å shorter than in the La analogue closely corresponding to the 0.05 Å expected on ionic radius grounds (Shannon, 1976). Similarly the average Nd—O bond length of 2.549 Å is 0.05 Å less than that found for the La analogue and is similar to the average value of 2.587 Å found in the 12-coordinate Nd(NO3)3(18-crown-6) (Bombieri et al., 1980). The O5 atom of the NO3 group on the twofold axis exhibits very high anisotropic displacement parameters perpendicular to that axis. This may be due to non-planarity of the NO3 group and consequent disorder of the O5 across the axis which could not be resolved in the presence of the Nd atom.
It has generally been believed that bipy and phen (1,10-phenanthroline) will not form complexes beyond a 2:1 stoichiometry with Ln(NO3)3 (Forsberg, 1973; Fréchette, 1992), however, the complexes Ln(bipy)3(NO3)3 (Ln = Ce, Pr, Nd, Yb) have been reported (Dong et al., 1992) from the reaction of hydrated lanthanide nitrates with 2,2'-bipyridyl (3 moles). A study of the 1:3 N d:bipy complex was undertaken to clarify this point. Unfortunately all crystals obtained from this reaction were of poor quality with the best data giving R1 = 0.096 (wR2 = 1/3, all data) but the structure was Nd(bipy)2(NO3)3.(bipy). There are no unusual non-bonded contacts between the non co-ordinated bipy molecules and the Nd(bipy)2(NO3)3 molecules.