metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2414-3146

Di­aqua­(nitrato-κ2O,O′)bis­­(L-valine-κO)lead(II) nitrate at 296 K

aInstituto de Física, Universidad Autónoma de Puebla, Av. San Claudio y 18 Sur, 72570 Puebla, Pue., Mexico, and bFacultad de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, 04510 México D.F., Mexico
*Correspondence e-mail: sylvain_bernes@hotmail.com

Edited by T. J. Prior, University of Hull, England (Received 11 March 2016; accepted 30 March 2016; online 12 April 2016)

The structure of the title complex, [Pb(NO3)(C5H11NO2)2(H2O)2]NO3, had been determined previously at 173 and 193 K, and is now reported at 296 K, in the same space group. The main difference with the low-temperature structures is that a methyl group of one valine ligand is clearly disordered over two positions, for which the occupancies converged to 0.56 (3) and 0.44 (3). Bond-length variations within the coordination sphere of PbII as a function of T are difficult to assess because uncertainties on these parameters are high. On the other hand, Pb⋯O distances above 2.9 Å cannot be assigned unambiguously to formal Pb—O bonds. As a consequence, the polymeric nature of the complex previously described at 173 K is uncertain, as well as the actual coordination number of PbII, and it is thus not possible to determine if the metal environment is holo- or hemidirected.

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

The complex [Pb(H2O)2(L-valine)2(NO3)]+NO3 has been synthesized by many groups, in a context related to lead–amino­acids and lead–enzymes inter­actions studies. The X-ray structure has been published twice, using data collected at T = 173 K (Burford et al., 2004[Burford, N., Eelman, M. D., LeBlanc, W. G., Cameron, T. S. & Robertson, K. N. (2004). Chem. Commun. pp. 332-333.]) and T = 193 K (Saunders et al., 2011[Saunders, C. D. L., Longobardi, L. E., Burford, N., Lumsden, M. D., Werner-Zwanziger, U., Chen, B. & McDonald, R. (2011). Inorg. Chem. 50, 2799-2810.]). However, these structures appear with different names and connectivity diagrams in the CSD: the former, ESAPET, is considered as a polymeric compound with the coordinated nitrate ion bridging metal centers in the crystal, while the latter, ESAPET01, is deposited as a monomeric species. These representations are indeed consistent with the structure descriptions given in both articles.

We have now determined the structure of the same compound at room temperature (Fig. 1[link]). One L-valine ligand has a different conformation at room temperature, with one methyl group disordered over two positions, C14A and C14B, a feature not present at low temperature. The positions of the other ligands around PbII are unchanged at 296 K (see Fig. 2[link] for a fit between the three refinements).

[Figure 1]
Figure 1
The asymmetric unit for the title complex, with displacement ellipsoids at the 30% probability level. The chosen asymmetric unit is identical to that used in Saunders et al. (2011[Saunders, C. D. L., Longobardi, L. E., Burford, N., Lumsden, M. D., Werner-Zwanziger, U., Chen, B. & McDonald, R. (2011). Inorg. Chem. 50, 2799-2810.]), as well as the labeling scheme. H atoms bonded to C atoms are omitted for clarity. Atoms C14A and C14B are disordered sites for C14 and were refined isotropically.
[Figure 2]
Figure 2
A fit between the refinements of the title compound at T = 173 (blue), 193 (green) and 296 K (red). The fit was carried out using Pb and O atoms of cation [Pb(H2O)2(L-valine)2(NO3)]+ (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]). Labels are for the T = 296 K refinement. Sites C14A and C14B correspond to a single atom disordered over two positions.

A comparison of the Pb⋯O distances in the coordination sphere of the metal at T = 173, 193 and 296 K is given in Table 1[link]. No clear trend can be extracted from these data, because uncertainties for the 173 and 296 K refinements are four to six times higher than those of the 193 K refinement. However, these distances are informative regarding the mode of coordination of the L-valine ligands. The first one is clearly monodentate, since the Pb⋯O12 distance is greater than 3.2 Å at any temperature. The situation for the other ligand is more ambiguous. Distance Pb⋯O22 increases as T increases, to reach 2.934 (10) Å at 296 K. Taking into account the upper limit of 2.9 Å for a Pb—O bond, retained by Saunders et al. (see Fig. 5 in Saunders et al., 2011[Saunders, C. D. L., Longobardi, L. E., Burford, N., Lumsden, M. D., Werner-Zwanziger, U., Chen, B. & McDonald, R. (2011). Inorg. Chem. 50, 2799-2810.]), we could consider that the carbonyl group C21=O22 is not engaged in coordination. As a consequence, both zwitterionic valine ligands in our refinement should be considered as monodentate (Fig. 1[link]), in contrast with the low-temperature refinements, described with κO and κ2O,O′ coordination modes.

Table 1
Comparison for distances in the coordination sphere (Å) at different temperatures

Bonda T = 173 Kb T = 193 Kc T = 296 Kd
Pb⋯O1 2.510 (12) 2.512 (3) 2.504 (14)
Pb⋯O2 2.891 2.915 (2) 2.891 (13)
Pb⋯O11 2.442 (10) 2.459 (2) 2.462 (12)
Pb⋯O12 3.275 3.266 (3) 3.209 (19)
Pb⋯O21 2.362 (11) 2.356 (2) 2.363 (12)
Pb⋯O22 2.873 2.892 (2) 2.934 (10)
Pb⋯O32 2.853 2.847 (3) 2.878 (18)
Pb⋯O33 2.778 2.790 (3) 2.820 (13)
Pb⋯O31′ 2.95 (1) 2.969 (3) 2.996 (16)
Notes: (a) In the last entry, Pb⋯O31′ is the shortest inter­molecular Pb⋯Onitrate distance. (b) Burford et al. (2004[Burford, N., Eelman, M. D., LeBlanc, W. G., Cameron, T. S. & Robertson, K. N. (2004). Chem. Commun. pp. 332-333.]) [distances not found in the deposited CIF were estimated using Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.])]; (c) Saunders et al. (2011[Saunders, C. D. L., Longobardi, L. E., Burford, N., Lumsden, M. D., Werner-Zwanziger, U., Chen, B. & McDonald, R. (2011). Inorg. Chem. 50, 2799-2810.]); (d) this work.

Using the same criterion, the complex at T = 296 K is not a polymeric compound, since the shortest inter­molecular Pb⋯Onitrate distance is Pb⋯O31i = 2.996 (16) Å [symmetry code: (i) −1 + x, y, z]. This distance was 2.95 (1) Å at 173 K and 2.969 (3) Å at 193 K. As commented by Saunders et al., these distances close to the 2.9 Å threshold mean that `the assignment of the environment of lead in these compounds as hemi- or holodirected is arbitrary'.

In the here reported structure, all H atoms bonded to heteroatoms are engaged in hydrogen bonds (Table 2[link]) of variable strengths.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H11⋯O12 0.85 (3) 1.99 (10) 2.724 (19) 144 (17)
O1—H12⋯O21i 0.85 (3) 1.92 (5) 2.756 (16) 171 (20)
O2—H21⋯O32ii 0.85 (3) 2.50 (10) 3.26 (2) 150 (16)
O2—H22⋯O22iii 0.85 (3) 2.10 (6) 2.919 (17) 162 (19)
N11—H11A⋯O32ii 0.93 2.24 2.85 (2) 123
N11—H11B⋯O42iv 0.93 1.90 2.817 (16) 169
N11—H11C⋯O12v 0.93 1.93 2.80 (2) 156
N21—H21A⋯O2vi 0.93 2.24 2.947 (19) 132
N21—H21B⋯O42v 0.93 2.03 2.924 (18) 160
N21—H21C⋯O41 0.93 1.86 2.785 (18) 177
Symmetry codes: (i) x-1, y, z; (ii) [-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iii) [-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iv) x+1, y-1, z; (v) x+1, y, z; (vi) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

Synthesis and crystallization

2 mmol (0.67 g) of Pb(NO3)2 were dissolved in 20 ml of previously degassed distilled water. To this solution, 4 mmol (0.47 g) of solid valine were added in several portions and with constant stirring. The pH value was adjusted to 5.0 with NaOH 0.1 M, and the solution was left to rest. Two weeks later, suitable crystals were collected.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. The structure refinement was started using coordinates deposited for ESAPET01, since the first structure, ESAPET, was collected with permuted cell axis for the ortho­rhom­bic cell. Atom C14 is disordered over two sites, C14A and C14B, for which occupancies converged to 0.56 (3) and 0.44 (3). Both atoms C14A and C14B were refined isotropically with a common displacement parameter, which was fixed in the last cycles, in order to avoid correlation with the refined occupancy. Bond lengths C13—C15 and C13—C14(A,B) in this iso-propyl group were restrained to 1.54 (2) Å. It was also necessary to refine nitrate atom N30 isotropically, otherwise a non-positive definite ellipsoid is obtained for this atom. C- and N- bonded H atoms were placed in calculated positions, with fixed bond lengths C—H = 0.96 Å (meth­yl), 0.98 Å (methine) and N—H = 0.93 Å (ammonium, with free rotation about the C—N bonds). Water H atoms were found in a difference map and refined with restrained distances: 0.85 (2) Å for O—H bonds and 1.40 (3) Å for H⋯H separation in each water mol­ecule. Displacement parameters for H atoms were calculated as Uiso(H) = xUeq(carrier atom), with x = 1.5 (methyl, ammonium, water) or x = 1.2 (methine).

Table 3
Experimental details

Crystal data
Chemical formula [Pb(NO3)(C5H11NO2)2(H2O)2]NO3
Mr 601.54
Crystal system, space group Orthorhombic, P212121
Temperature (K) 296
a, b, c (Å) 5.4311 (5), 13.6861 (15), 27.340 (4)
V3) 2032.2 (4)
Z 4
Radiation type Mo Kα
μ (mm−1) 8.37
Crystal size (mm) 0.40 × 0.25 × 0.10
 
Data collection
Diffractometer Bruker P4
Absorption correction ψ scan (XSCANS; Bruker, 1997[Bruker (1997). XSCANS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.143, 0.437
No. of measured, independent and observed [I > 2σ(I)] reflections 5226, 3566, 2874
Rint 0.039
(sin θ/λ)max−1) 0.595
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.116, 1.02
No. of reflections 3566
No. of parameters 256
No. of restraints 9
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 1.47, −1.82
Absolute structure Flack x determined using 1007 quotients [(I+)−(I)]/[(I+)+(I)] (Parsons et al., 2013[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.])
Absolute structure parameter 0.001 (19)
Computer programs: XSCANS (Bruker, 1997[Bruker (1997). XSCANS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 and SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]).

Structural data


Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Experimental top

2 mmol (0.67 g) of Pb(NO3)2 were dissolved in 20 ml of previously degassed distilled water. To this solution, 4 mmol (0.47 g) of solid valine were added in several portions and with constant stirring. The pH value was adjusted to 5.0 with NaOH 0.1 M, and the solution was left to rest. Two weeks later, suitable crystals were collected.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 3. The structure refinement was started using coordinates deposited for ESAPET01, since the first structure, ESAPET, was collected with permuted cell axis for the orthorhombic cell. Atom C14 is disordered over two sites, C14A and C14B, for which occupancies converged to 0.56 (3) and 0.44 (3). Both atoms C14A and C14B were refined isotropically with a common displacement parameter, which was fixed in the last cycles, in order to avoid correlation with the refined occupancy. Bond lengths C13—C15 and C13—C14(A,B) in this iso-propyl group were restrained to 1.54 (2) Å. It was also necessary to refine nitrate atom N30 isotropically, otherwise a non-positive definite ellipsoid is obtained for this atom. C- and N- bonded H atoms were placed in calculated positions, with fixed bond lengths C—H = 0.96 Å (methyl), 0.98 Å (methine) and N—H = 0.93 Å (ammonium, with free rotation about the C—N bonds). Water H atoms were found in a difference map and refined with restrained distances: 0.85 (2) Å for O—H bonds and 1.40 (3) Å for H···H separation in each water molecule. Displacement parameters for H atoms were calculated as Uiso(H) = xUeq(carrier atom), with x = 1.5 (methyl, ammonium, water) or x = 1.2 (methine).

Structure description top

The complex [Pb(H2O)2(L-valine)2(NO3)]+NO3- has been synthesized by many groups, in a context related to lead–aminoacids and lead–enzymes interactions studies. The X-ray structure has been published twice, using data collected at T = 173 K (Burford et al., 2004) and T = 193 K (Saunders et al., 2011). However, these structures appear with different names and connectivity diagrams in the CSD: the former, ESAPET, is considered as a polymeric compound with the coordinated nitrate ion bridging metal centers in the crystal, while the latter, ESAPET01, is deposited as a monomeric species. These representations are indeed consistent with the structure descriptions given in both articles.

We have now determined the structure of the same compound at room temperature (Fig. 1). One L-valine ligand has a different conformation at room temperature, with one methyl group disordered over two positions, C14A and C14B, a feature not present at low temperature. The positions of the other ligands around PbII are unchanged at 296 K (see Fig. 2 for a fit between the three refinements).

A comparison of the Pb···O distances in the coordination sphere of the metal at T = 173, 193 and 296 K is given in Table 1. No clear trend can be extracted from these data, because uncertainties for the 173 and 296 K refinements are four to six times higher than those of the 193 K refinement. However, these distances are informative regarding the mode of coordination of the L-valine ligands. The first one is clearly monodentate, since the Pb···O12 distance is greater than 3.2 Å at any temperature. The situation for the other ligand is more ambiguous. Distance Pb···O22 increases as T increases, to reach 2.934 (10) Å at 296 K. Taking into account the upper limit of 2.9 Å for a Pb—O bond, retained by Saunders et al. (see Figure 5 in Saunders et al., 2011), we could consider that the carbonyl group C21O22 is not engaged in coordination. As a consequence, both zwitterionic valine ligands in our refinement should be considered as monodentate (Fig. 1), in contrast with the low-temperature refinements, described with κO and κ2O,O' coordination modes.

Using the same criterion, the complex at T = 296 K is not a polymeric compound, since the shortest intermolecular Pb···Onitrate distance is Pb···O31i = 2.996 (16) Å [symmetry code: (i) -1 + x, y, z]. This distance was 2.95 (1) Å at 173 K and 2.969 (3) Å at 193 K. As commented by Saunders et al., these distances close to the 2.9 Å threshold mean that `the assignment of the environment of lead in these compounds as hemi- or holodirected is arbitrary'.

In the here reported structure, all H atoms bonded to heteroatoms are engaged in hydrogen bonds (Table 2) of variable strengths.

Computing details top

Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS (Bruker, 1997); data reduction: XSCANS (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Figures top
[Figure 1] Fig. 1. The asymmetric unit for the title complex, with displacement ellipsoids at the 30% probability level. The chosen asymmetric unit is identical to that used in Saunders et al. (2011), as well as the labeling scheme. H atoms bonded to C atoms are omitted for clarity. Atoms C14A and C14B are disordered sites for C14 and were refined isotropically.
[Figure 2] Fig. 2. A fit between the refinements of the title compound at T = 173 (blue), 193 (green) and 296 K (red). The fit was carried out using Pb and O atoms of cation [Pb(H2O)2(L-valine)2(NO3)]+ (Macrae et al., 2008). Labels are for the T = 296 K refinement. Sites C14A and C14B correspond to a single atom disordered over two positions.
Diaqua(nitrato-κ2O,O')bis(L-valine-κO)lead(II) nitrate top
Crystal data top
[Pb(NO3)(C5H11NO2)2(H2O)2]NO3Dx = 1.966 Mg m3
Mr = 601.54Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 75 reflections
a = 5.4311 (5) Åθ = 4.7–12.5°
b = 13.6861 (15) ŵ = 8.37 mm1
c = 27.340 (4) ÅT = 296 K
V = 2032.2 (4) Å3Prism, colorless
Z = 40.40 × 0.25 × 0.10 mm
F(000) = 1168
Data collection top
Bruker P4
diffractometer
2874 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, FN4Rint = 0.039
Graphite monochromatorθmax = 25.0°, θmin = 1.7°
2θ/ω scansh = 66
Absorption correction: ψ scan
(XSCANS; Bruker, 1997)
k = 1616
Tmin = 0.143, Tmax = 0.437l = 3232
5226 measured reflections3 standard reflections every 97 reflections
3566 independent reflections intensity decay: 1.5%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.044H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.116 w = 1/[σ2(Fo2) + (0.0526P)2 + 11.4316P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
3566 reflectionsΔρmax = 1.47 e Å3
256 parametersΔρmin = 1.82 e Å3
9 restraintsAbsolute structure: Flack x determined using 1007 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 constraintsAbsolute structure parameter: 0.001 (19)
Crystal data top
[Pb(NO3)(C5H11NO2)2(H2O)2]NO3V = 2032.2 (4) Å3
Mr = 601.54Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.4311 (5) ŵ = 8.37 mm1
b = 13.6861 (15) ÅT = 296 K
c = 27.340 (4) Å0.40 × 0.25 × 0.10 mm
Data collection top
Bruker P4
diffractometer
2874 reflections with I > 2σ(I)
Absorption correction: ψ scan
(XSCANS; Bruker, 1997)
Rint = 0.039
Tmin = 0.143, Tmax = 0.4373 standard reflections every 97 reflections
5226 measured reflections intensity decay: 1.5%
3566 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.044H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.116 w = 1/[σ2(Fo2) + (0.0526P)2 + 11.4316P]
where P = (Fo2 + 2Fc2)/3
S = 1.02Δρmax = 1.47 e Å3
3566 reflectionsΔρmin = 1.82 e Å3
256 parametersAbsolute structure: Flack x determined using 1007 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
9 restraintsAbsolute structure parameter: 0.001 (19)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Pb0.24568 (16)0.10974 (4)0.28034 (2)0.0475 (2)
O10.032 (2)0.1354 (9)0.3523 (6)0.067 (4)
H110.04 (3)0.075 (4)0.359 (9)0.101*
H120.170 (16)0.162 (11)0.347 (8)0.101*
O20.185 (2)0.0767 (9)0.2321 (5)0.061 (3)
H210.29 (2)0.106 (12)0.249 (7)0.092*
H220.06 (2)0.114 (11)0.226 (8)0.092*
O110.485 (3)0.0106 (8)0.3275 (5)0.065 (3)
O120.140 (3)0.0502 (11)0.3636 (8)0.085 (6)
O210.506 (2)0.2061 (7)0.3299 (5)0.053 (3)
O220.226 (3)0.3153 (7)0.3106 (4)0.060 (3)
N300.722 (3)0.1876 (8)0.2209 (4)0.039 (3)*
O310.914 (3)0.2259 (12)0.2149 (7)0.080 (5)
O320.531 (3)0.2376 (12)0.2190 (7)0.078 (5)
O330.711 (2)0.0993 (8)0.2349 (5)0.067 (3)
N110.723 (3)0.1705 (9)0.3596 (5)0.052 (3)
H11A0.70410.16270.32600.079*
H11B0.75640.23570.36650.079*
H11C0.85330.13190.37040.079*
N210.486 (2)0.4622 (8)0.3514 (5)0.044 (3)
H21A0.50300.46490.31760.066*
H21B0.59800.50480.36590.066*
H21C0.32690.48020.36000.066*
C110.360 (4)0.0632 (14)0.3549 (9)0.048 (5)
C120.487 (3)0.1396 (11)0.3855 (6)0.044 (4)
H12A0.37920.19680.38740.053*
C130.547 (6)0.1088 (17)0.4366 (8)0.109 (10)
H13A0.38530.10900.45260.131*0.56 (3)
H13B0.68210.06380.42920.131*0.44 (3)
C14A0.638 (9)0.008 (3)0.4464 (17)0.099*0.56 (3)
H14A0.53740.03830.42940.149*0.56 (3)
H14B0.80550.00250.43530.149*0.56 (3)
H14C0.63160.00470.48090.149*0.56 (3)
C14B0.390 (10)0.040 (4)0.466 (2)0.099*0.44 (3)
H14D0.27370.00850.44470.149*0.44 (3)
H14E0.49210.00790.48130.149*0.44 (3)
H14F0.30240.07640.49060.149*0.44 (3)
C150.689 (7)0.182 (2)0.4660 (9)0.143 (15)
H15A0.62680.24640.45950.215*
H15B0.67200.16760.50010.215*
H15C0.85990.17900.45700.215*
C210.414 (3)0.2902 (12)0.3333 (6)0.044 (4)
C220.535 (3)0.3606 (10)0.3686 (6)0.045 (4)
H22A0.71340.34910.36850.054*
C230.435 (5)0.3465 (16)0.4217 (8)0.089 (8)
H23A0.25850.36100.42060.106*
C240.552 (6)0.421 (2)0.4562 (9)0.123 (11)
H24A0.54940.48460.44110.184*
H24B0.71850.40280.46300.184*
H24C0.45970.42350.48620.184*
C250.458 (7)0.2498 (19)0.4397 (10)0.136 (13)
H25A0.43330.24960.47440.204*
H25B0.61990.22550.43240.204*
H25C0.33720.20890.42440.204*
N400.025 (2)0.5992 (10)0.3857 (6)0.058 (4)
O410.002 (2)0.5112 (9)0.3745 (8)0.095 (6)
O420.239 (3)0.6316 (7)0.3869 (6)0.088 (4)
O430.150 (3)0.6499 (10)0.3947 (6)0.086 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pb0.0392 (3)0.0462 (3)0.0572 (3)0.0063 (4)0.0086 (5)0.0039 (2)
O10.038 (6)0.060 (8)0.104 (11)0.003 (5)0.015 (7)0.007 (8)
O20.067 (10)0.054 (6)0.063 (8)0.010 (6)0.017 (6)0.000 (5)
O110.079 (9)0.046 (7)0.071 (9)0.007 (7)0.011 (8)0.008 (6)
O120.043 (8)0.054 (9)0.157 (19)0.001 (7)0.021 (10)0.011 (10)
O210.045 (6)0.035 (6)0.080 (9)0.010 (5)0.002 (6)0.008 (6)
O220.067 (8)0.050 (6)0.063 (7)0.015 (8)0.038 (9)0.007 (5)
O310.082 (10)0.087 (11)0.072 (11)0.022 (9)0.026 (9)0.029 (10)
O320.059 (8)0.093 (11)0.083 (12)0.034 (7)0.011 (9)0.024 (10)
O330.054 (8)0.062 (7)0.086 (8)0.003 (7)0.010 (7)0.003 (6)
N110.049 (8)0.049 (6)0.060 (7)0.002 (8)0.016 (9)0.004 (6)
N210.034 (6)0.032 (6)0.067 (9)0.005 (5)0.001 (7)0.001 (6)
C110.050 (11)0.034 (9)0.060 (12)0.003 (8)0.005 (9)0.006 (9)
C120.042 (8)0.043 (8)0.048 (10)0.006 (6)0.002 (8)0.001 (7)
C130.16 (3)0.113 (19)0.051 (12)0.086 (19)0.022 (15)0.007 (13)
C150.19 (4)0.17 (3)0.064 (14)0.08 (3)0.03 (2)0.028 (16)
C210.036 (8)0.049 (9)0.047 (10)0.003 (7)0.008 (7)0.007 (8)
C220.049 (9)0.036 (8)0.050 (10)0.003 (7)0.003 (8)0.003 (7)
C230.14 (2)0.066 (13)0.058 (13)0.005 (14)0.021 (14)0.004 (10)
C240.19 (3)0.12 (2)0.066 (16)0.04 (2)0.007 (19)0.026 (15)
C250.23 (4)0.10 (2)0.077 (18)0.06 (2)0.00 (2)0.015 (17)
N400.041 (7)0.042 (8)0.092 (12)0.009 (7)0.008 (8)0.003 (8)
O410.052 (8)0.033 (7)0.199 (19)0.005 (6)0.015 (10)0.009 (9)
O420.052 (7)0.050 (6)0.161 (14)0.017 (8)0.001 (13)0.014 (7)
O430.070 (9)0.071 (8)0.117 (13)0.026 (7)0.014 (8)0.017 (9)
Geometric parameters (Å, º) top
Pb—O212.363 (12)C12—H12A0.9800
Pb—O112.462 (12)C13—C14A1.49 (2)
Pb—O12.504 (14)C13—C151.50 (2)
Pb—O332.820 (13)C13—C14B1.50 (3)
Pb—O322.878 (18)C13—H13A0.9800
Pb—O22.891 (13)C13—H13B0.9800
Pb—O222.934 (10)C14A—H14A0.9600
Pb—O31i2.996 (16)C14A—H14B0.9600
Pb—O123.209 (19)C14A—H14C0.9600
O1—H110.85 (3)C14B—H14D0.9600
O1—H120.85 (3)C14B—H14E0.9600
O2—H210.85 (3)C14B—H14F0.9600
O2—H220.85 (3)C15—H15A0.9600
O11—C111.24 (2)C15—H15B0.9600
O12—C111.23 (2)C15—H15C0.9600
O21—C211.260 (19)C21—C221.52 (2)
O22—C211.24 (2)C22—C231.56 (3)
N30—O311.18 (2)C22—H22A0.9800
N30—O321.241 (19)C23—C251.42 (3)
N30—O331.269 (16)C23—C241.53 (3)
N11—C121.52 (2)C23—H23A0.9800
N11—H11A0.9301C24—H24A0.9600
N11—H11B0.9301C24—H24B0.9600
N11—H11C0.9301C24—H24C0.9600
N21—C221.492 (19)C25—H25A0.9600
N21—H21A0.9301C25—H25B0.9600
N21—H21B0.9301C25—H25C0.9600
N21—H21C0.9301N40—O431.201 (17)
C11—C121.51 (3)N40—O421.25 (2)
C12—C131.49 (3)N40—O411.251 (18)
O21—Pb—O1175.9 (4)C13—C12—C11115.0 (14)
O21—Pb—O180.3 (4)C13—C12—N11109.4 (16)
O11—Pb—O190.0 (5)C11—C12—N11108.6 (14)
O21—Pb—O3375.2 (4)C13—C12—H12A107.9
O11—Pb—O3374.0 (4)C11—C12—H12A107.9
O1—Pb—O33153.3 (4)N11—C12—H12A107.9
O21—Pb—O3270.9 (5)C14A—C13—C12120 (3)
O11—Pb—O32115.3 (4)C14A—C13—C15110 (3)
O1—Pb—O32134.2 (4)C12—C13—C15115.0 (18)
O33—Pb—O3244.8 (4)C12—C13—C14B124 (3)
O21—Pb—O2145.4 (3)C15—C13—C14B115 (3)
O11—Pb—O273.1 (4)C14A—C13—H13A102.8
O1—Pb—O2114.4 (4)C12—C13—H13A102.8
O33—Pb—O281.7 (4)C15—C13—H13A102.8
O32—Pb—O2109.4 (5)C12—C13—H13B98.3
O21—Pb—O2247.6 (4)C15—C13—H13B98.3
O11—Pb—O22120.9 (4)C14B—C13—H13B98.3
O1—Pb—O2267.8 (4)C13—C14A—H14A109.5
O33—Pb—O22101.9 (4)C13—C14A—H14B109.5
O32—Pb—O2266.5 (5)H14A—C14A—H14B109.5
O2—Pb—O22166.0 (3)C13—C14A—H14C109.5
O21—Pb—O31i114.0 (4)H14A—C14A—H14C109.5
O11—Pb—O31i170.1 (4)H14B—C14A—H14C109.5
O1—Pb—O31i91.9 (5)C13—C14B—H14D109.5
O33—Pb—O31i107.6 (5)C13—C14B—H14E109.5
O32—Pb—O31i69.7 (4)H14D—C14B—H14E109.5
O2—Pb—O31i97.3 (4)C13—C14B—H14F109.5
O22—Pb—O31i68.7 (4)H14D—C14B—H14F109.5
O21—Pb—O1294.6 (4)H14E—C14B—H14F109.5
O11—Pb—O1242.9 (4)C13—C15—H15A109.5
O1—Pb—O1255.3 (4)C13—C15—H15B109.5
O33—Pb—O12116.0 (4)H15A—C15—H15B109.5
O32—Pb—O12157.6 (4)C13—C15—H15C109.5
O2—Pb—O1272.6 (4)H15A—C15—H15C109.5
O22—Pb—O12116.6 (4)H15B—C15—H15C109.5
O31i—Pb—O12132.7 (4)O22—C21—O21122.9 (16)
Pb—O1—H1194 (10)O22—C21—C22120.1 (14)
Pb—O1—H12118 (10)O21—C21—C22117.0 (14)
H11—O1—H12112 (6)N21—C22—C21108.3 (13)
Pb—O2—H2196 (10)N21—C22—C23110.3 (14)
Pb—O2—H22135 (10)C21—C22—C23111.2 (15)
H21—O2—H22111 (6)N21—C22—H22A109.0
C11—O11—Pb114.5 (13)C21—C22—H22A109.0
C11—O12—Pb77.8 (16)C23—C22—H22A109.0
C21—O21—Pb108.2 (10)C25—C23—C24112 (2)
C21—O22—Pb81.1 (9)C25—C23—C22114 (2)
O31—N30—O32119.1 (13)C24—C23—C22110 (2)
O31—N30—O33120.4 (14)C25—C23—H23A106.7
O32—N30—O33119.9 (15)C24—C23—H23A106.7
N30—O32—Pb95.1 (10)C22—C23—H23A106.7
N30—O33—Pb97.2 (9)C23—C24—H24A109.5
C12—N11—H11A109.5C23—C24—H24B109.5
C12—N11—H11B109.5H24A—C24—H24B109.5
H11A—N11—H11B109.5C23—C24—H24C109.5
C12—N11—H11C109.5H24A—C24—H24C109.5
H11A—N11—H11C109.5H24B—C24—H24C109.5
H11B—N11—H11C109.5C23—C25—H25A109.5
C22—N21—H21A109.5C23—C25—H25B109.5
C22—N21—H21B109.5H25A—C25—H25B109.5
H21A—N21—H21B109.5C23—C25—H25C109.5
C22—N21—H21C109.5H25A—C25—H25C109.5
H21A—N21—H21C109.5H25B—C25—H25C109.5
H21B—N21—H21C109.5O43—N40—O42121.9 (15)
O12—C11—O11124 (2)O43—N40—O41120.9 (15)
O12—C11—C12116 (2)O42—N40—O41117.3 (14)
O11—C11—C12119.1 (17)
O31—N30—O32—Pb154.4 (14)N11—C12—C13—C1553 (3)
O33—N30—O32—Pb17.3 (15)C11—C12—C13—C14B33 (4)
O31—N30—O33—Pb153.9 (15)N11—C12—C13—C14B156 (4)
O32—N30—O33—Pb17.7 (16)Pb—O22—C21—O213.5 (16)
Pb—O12—C11—O117 (2)Pb—O22—C21—C22173.8 (15)
Pb—O12—C11—C12177.6 (18)Pb—O21—C21—O225 (2)
Pb—O11—C11—O129 (3)Pb—O21—C21—C22172.8 (11)
Pb—O11—C11—C12180.0 (12)O22—C21—C22—N2129 (2)
O12—C11—C12—C1376 (3)O21—C21—C22—N21153.5 (15)
O11—C11—C12—C1396 (3)O22—C21—C22—C2392 (2)
O12—C11—C12—N11161 (2)O21—C21—C22—C2385 (2)
O11—C11—C12—N1127 (2)N21—C22—C23—C25176 (2)
C11—C12—C13—C14A40 (4)C21—C22—C23—C2556 (3)
N11—C12—C13—C14A82 (3)N21—C22—C23—C2457 (3)
C11—C12—C13—C15176 (2)C21—C22—C23—C24177 (2)
Symmetry code: (i) x1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H11···O120.85 (3)1.99 (10)2.724 (19)144 (17)
O1—H12···O21i0.85 (3)1.92 (5)2.756 (16)171 (20)
O2—H21···O32ii0.85 (3)2.50 (10)3.26 (2)150 (16)
O2—H22···O22iii0.85 (3)2.10 (6)2.919 (17)162 (19)
N11—H11A···O32ii0.932.242.85 (2)123
N11—H11B···O42iv0.931.902.817 (16)169
N11—H11B···N40iv0.932.613.510 (19)164
N11—H11C···O12v0.931.932.80 (2)156
N21—H21A···O2vi0.932.242.947 (19)132
N21—H21A···O33vi0.932.613.198 (18)122
N21—H21B···O41v0.932.212.951 (18)136
N21—H21B···O42v0.932.032.924 (18)160
N21—H21B···N40v0.932.483.384 (18)163
N21—H21C···O410.931.862.785 (18)177
N21—H21C···N400.932.613.477 (19)156
Symmetry codes: (i) x1, y, z; (ii) x+1, y1/2, z+1/2; (iii) x, y1/2, z+1/2; (iv) x+1, y1, z; (v) x+1, y, z; (vi) x+1, y+1/2, z+1/2.
Comparison for distances in the coordination sphere (Å) at different temperatures top
BondaT = 173 KbT = 193 KcT = 296 Kd
Pb···O12.510 (12)2.512 (3)2.504 (14)
Pb···O22.8912.915 (2)2.891 (13)
Pb···O112.442 (10)2.459 (2)2.462 (12)
Pb···O123.2753.266 (3)3.209 (19)
Pb···O212.362 (11)2.356 (2)2.363 (12)
Pb···O222.8732.892 (2)2.934 (10)
Pb···O322.8532.847 (3)2.878 (18)
Pb···O332.7782.790 (3)2.820 (13)
Pb···O31'2.95 (1)2.969 (3)2.996 (16)
Notes: (a) In the last entry, Pb···O31' is the shortest intermolecular Pb···Onitrate distance. (b) Burford et al. (2004) [distances not found in the deposited CIF were estimated using Mercury (Macrae et al., 2008)]; (c) Saunders et al. (2011); (d) this work.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H11···O120.85 (3)1.99 (10)2.724 (19)144 (17)
O1—H12···O21i0.85 (3)1.92 (5)2.756 (16)171 (20)
O2—H21···O32ii0.85 (3)2.50 (10)3.26 (2)150 (16)
O2—H22···O22iii0.85 (3)2.10 (6)2.919 (17)162 (19)
N11—H11A···O32ii0.932.242.85 (2)122.5
N11—H11B···O42iv0.931.902.817 (16)168.5
N11—H11C···O12v0.931.932.80 (2)155.9
N21—H21A···O2vi0.932.242.947 (19)131.7
N21—H21B···O42v0.932.032.924 (18)160.1
N21—H21C···O410.931.862.785 (18)176.7
Symmetry codes: (i) x1, y, z; (ii) x+1, y1/2, z+1/2; (iii) x, y1/2, z+1/2; (iv) x+1, y1, z; (v) x+1, y, z; (vi) x+1, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Pb(NO3)(C5H11NO2)2(H2O)2]NO3
Mr601.54
Crystal system, space groupOrthorhombic, P212121
Temperature (K)296
a, b, c (Å)5.4311 (5), 13.6861 (15), 27.340 (4)
V3)2032.2 (4)
Z4
Radiation typeMo Kα
µ (mm1)8.37
Crystal size (mm)0.40 × 0.25 × 0.10
Data collection
DiffractometerBruker P4
Absorption correctionψ scan
(XSCANS; Bruker, 1997)
Tmin, Tmax0.143, 0.437
No. of measured, independent and
observed [I > 2σ(I)] reflections
5226, 3566, 2874
Rint0.039
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.116, 1.02
No. of reflections3566
No. of parameters256
No. of restraints9
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(Fo2) + (0.0526P)2 + 11.4316P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)1.47, 1.82
Absolute structureFlack x determined using 1007 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Absolute structure parameter0.001 (19)

Computer programs: XSCANS (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), SHELXTL (Sheldrick, 2008).

 

Acknowledgements

SB acknowledges support by the Instituto de Física Luis Rivera Terrazas (Puebla, Mexico).

References

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First citationBurford, N., Eelman, M. D., LeBlanc, W. G., Cameron, T. S. & Robertson, K. N. (2004). Chem. Commun. pp. 332–333.  Web of Science CSD CrossRef Google Scholar
First citationMacrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
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First citationSaunders, C. D. L., Longobardi, L. E., Burford, N., Lumsden, M. D., Werner-Zwanziger, U., Chen, B. & McDonald, R. (2011). Inorg. Chem. 50, 2799–2810.  Web of Science CSD CrossRef CAS PubMed Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar

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