Diaqua­(nitrato-κ2O,O′)bis­(l-phenyl­alaninato-κ2O,O′)lead(II) nitrate

Bernès, S.; Gasque, L.

doi:10.1107/S1600536808006995

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Pages m566-m567

doi:10.1107/S1600536808006995

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Diaqua(nitrato-κ²O,O′)bis(L-phenylalaninato-κ²O,O′)lead(II) nitrate

Sylvain Bernès ^a ^* and Laura Gasque ^b

^aDEP Facultad de Ciencias Químicas, UANL, Guerrero y Progreso S/N, Col. Treviño, 64570 Monterrey, NL, Mexico, and ^bDepartamento de Química Inorgánica y Nuclear, Facultad de Química, UNAM, 04510 México, DF, Mexico
^*Correspondence e-mail: sylvain_bernes@hotmail.com

(Received 21 February 2008; accepted 12 March 2008; online 20 March 2008)

In the title complex, [Pb(C₉H₁₁NO₂)₂(NO₃)(H₂O)₂]NO₃, the cation is a monomeric species including zwitterionic aminoacids. In both zwitterions, rotation of the NH₃⁺ groups about their C—N bonds is blocked by intermolecular N—H⋯O hydrogen bonds. Assuming a limit for Pb—O bond lengths of 3 Å, the Pb^II ion is coordinated by eight O atoms. Each phenylalaninate ligand coordinates asymmetrically, with one short and one long Pb—O bond. Coordinated water molecules are also found at significantly different distances, while the bidentate nitrate ion coordinates symmetrically. The resulting [Pb^IIO₈] core is hemi-directed, with a void placed almost trans to a carboxylate group. However, the 6s² lone pair of the metal center can not be considered as stereochemically active, as a non-coordinating O atom of a nitrate belonging to a symmetry-related cation is placed in the empty hemisphere, with a short Pb⋯O separation of 3.035 (10) Å.

Related literature

A useful classification of Pb complexes into holo- and hemi-directed arrangements of ligands has been proposed by Shimoni-Livny et al. (1998 ), which allows the prediction of the character of the Pb lone pair. A complex containing zwitterionic phenylalaninate has been reported (Apfelbaum-Tibika & Bino, 1984 ). Recently, a polymeric Pb^II complex of neutral phenylalanine has been described (Marandi & Shahbakhsh, 2007 ).

Experimental

Crystal data

[Pb(C₉H₁₁NO₂)₂(NO₃)(H₂O)₂]NO₃
M_r = 697.62
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.3851 (9) Å
b = 13.5599 (17) Å
c = 34.235 (4) Å
V = 2499.9 (6) Å³
Z = 4
Mo Kα radiation
μ = 6.82 mm⁻¹
T = 298 (1) K
0.60 × 0.20 × 0.18 mm

Data collection

Bruker P4 diffractometer
Absorption correction: ψ scan (XSCANS; Siemens, 1996 ) T_min = 0.160, T_max = 0.294
5243 measured reflections
4948 independent reflections
4026 reflections with I > 2σ(I)
R_int = 0.027
3 standard reflections every 97 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.110
S = 1.06
4948 reflections
319 parameters
18 restraints
H-atom parameters constrained
Δρ_max = 1.61 e Å⁻³
Δρ_min = −2.35 e Å⁻³
Absolute structure: Flack (1983 ), 1153 Friedel pairs
Flack parameter: −0.024 (14)

Table 1
Selected bond lengths (Å)

Pb1—O1	2.354 (7)
Pb1—O2	2.979 (6)
Pb1—O11	2.453 (7)
Pb1—O12	2.791 (7)
Pb1—O3	2.628 (8)
Pb1—O4	2.886 (6)
Pb1—O21	2.927 (12)
Pb1—O22	2.994 (11)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4ⁱ	0.92	2.25	2.956 (11)	134
N1—H1B⋯O33	0.92	2.07	2.932 (11)	155
N1—H1C⋯O32ⁱⁱ	0.92	1.87	2.786 (11)	173
N11—H11A⋯O22ⁱⁱⁱ	0.92	1.95	2.800 (12)	152
N11—H11B⋯O33^iv	0.92	1.95	2.749 (9)	145
N11—H11C⋯O12^v	0.92	1.96	2.833 (11)	158
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x+1, y, z; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) x, y+1, z; (v) x-1, y, z.

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL-Plus; molecular graphics: SHELXTL-Plus and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL-Plus.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808006995/ez2121sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808006995/ez2121Isup2.hkl

checkCIF report

Comment top

A particular feature characterizing Pb^II is the role of the 6s² lone pair, which determines the arrangement of ligands coordinating to this metal ion. A stereochemically active lone pair is reflected in a hemidirected disposition of ligands around Pb^II, i.e. with all coordination bonds directed throughout only one hemisphere of an encompassing globe. In such a case, the lone pair is assumed to be localized in the empty hemisphere. The opposite situation is found in holodirected Pb^II complexes, in which the bonds to ligand atoms are distributed isotropically around the metal center (Shimoni-Livny et al., 1998). For coordination number 8, examples of either type of stereochemistry have been found. The complex reported here, (I), may be considered as a borderline case: although the coordination geometry seems to be hemidirected, the lone pair is probably not stereochemically active.

Complex (I) was prepared and crystallized from water (see Experimental) and is a part of our general research dealing with interactions between aminoacids and Pb^II. The naturally occurring aminoacid L-phenlyalanine is found in its zwitterionic form, and coordinates through O atoms of the carboxylate group. The coordination is asymmetric, however, all carboxylic O atoms may be considered as bonded to the metal ion, assuming a limit for Pb—O bond lengths of 3 Å. To date, only one complex that includes zwitterionic phenylalaninate has been characterized by X-ray diffraction (Apfelbaum-Tibika & Bino, 1984). This aminoacid, in its neutral form, was recently coordinated to Pb^II, forming a polymeric structure (Marandi & Shahbakhsh, 2007). In (I), rotation of NH₃⁺ groups about their C—N bonds is blocked by intermolecular N—H···O hydrogen bonds, involving nitrate and water O atoms. The cation is completed by two water molecules, found at significantly different distances, and a bidentate nitrate ion, which coordinates in a symmetric manner. The asymmetric unit contains one cation and one nitrate counter-ion (Fig. 1).

The [Pb^IIO₈] core structure in the cation is best described as hemidirected. The equatorial plane defining the encompassing globe contains atoms Pb1/O1/O3/O4/O21 (Fig. 2, top molecule). Although atoms O2 and O22 are placed in the anti-hemisphere, they are close to the equatorial plane, since they belong to carboxylate groups forming bite angles [O1—Pb1—O2: 47.3 (2)°; O21—Pb1—O22: 42.6 (2)]. Deviations of these atoms from the mean plane Pb1/O1/O3/O4/O21 are 1.81 (O2) and 1.84 Å (O22). This arrangement for O atoms around Pb^II is thus consistent with the presence of a stereochemically active lone pair 6s², placed roughly trans to the carboxylate group O11/O12. However, a careful examination of the packing structure reveals a short Pb···O intermolecular contact, involving a nitrate group of a neighboring cation (Fig. 2, bottom molecule). The contact distance is sufficiently short, 3.035 (10) Å, to impede activity for the lone pair, which is thus expected to have little p character.

Related literature top

A useful classification of Pb complexes into holo- and hemi-directed arrangements of ligands has been proposed by Shimoni-Livny et al. (1998), which allows the prediction of the character of the Pb lone pair. A complex containing zwitterionic phenylalaninate has been reported (Apfelbaum-Tibika & Bino, 1984). Recently, a polymeric Pb^II complex of neutral phenylalanine has been described (Marandi & Shahbakhsh, 2007).

Experimental top

An amount of Pb(NO₃)₂ (1 mmol, 0.331 g) was dissolved in 80 ml of previously degassed and distilled water. Solid L-phenylalanine (2 mmol, 0.330 g, Sigma) was added in small fractions with magnetic stirring, dissolving upon coordination to the metal ion. After the complete addition with continuous stirring, pH was adjusted to 5.3 by dropwise addition of 0.01 M NaOH. The solution was left to rest, and colourless needles were collected after one week.

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 2008); program(s) used to refine structure: SHELXTL-Plus (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL-Plus (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of (I) showing the atom numbering scheme, with displacement ellipsoids at the 30% probability level.
	Fig. 2. Two symmetry-related molecules in the crystal structure, omitting H atoms and non-coordinated nitrate ions. The blue plane is calculated using atoms Pb1/O1/O3/O4/O21 (spheres of arbitrary radii) and corresponds to the equatorial plane defining the hemidirected ligand arrangement. The short inter-cation contact is shown as a dashed line. Symmetry code: (i) 1 + x, y, z.

Diaqua(nitrato-κ²O,O')bis(L-phenylalaninato- κ²O,O')lead(II) nitrate top

Crystal data top

[Pb(C₉H₁₁NO₂)₂(NO₃)(H₂O)₂]NO₃	F(000) = 1360
M_r = 697.62	D_x = 1.854 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 83 reflections
a = 5.3851 (9) Å	θ = 4.7–14.1°
b = 13.5599 (17) Å	µ = 6.82 mm⁻¹
c = 34.235 (4) Å	T = 298 K
V = 2499.9 (6) Å³	Needle, colourless
Z = 4	0.60 × 0.20 × 0.18 mm

Data collection top

Bruker P4 diffractometer	4026 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.027
Graphite monochromator	θ_max = 29.0°, θ_min = 1.6°
ω scans	h = −7→2
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −1→18
T_min = 0.160, T_max = 0.294	l = −1→46
5243 measured reflections	3 standard reflections every 97 reflections
4948 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.047	w = 1/[σ²(F_o²) + (0.044P)² + 6.7647P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.110	(Δ/σ)_max = 0.001
S = 1.06	Δρ_max = 1.61 e Å⁻³
4948 reflections	Δρ_min = −2.35 e Å⁻³
319 parameters	Extinction correction: SHELXTL-Plus (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
18 restraints	Extinction coefficient: 0.0034 (3)
0 constraints	Absolute structure: Flack (1983), 1153 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.024 (14)
Secondary atom site location: difference Fourier map

Crystal data top

[Pb(C₉H₁₁NO₂)₂(NO₃)(H₂O)₂]NO₃	V = 2499.9 (6) Å³
M_r = 697.62	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.3851 (9) Å	µ = 6.82 mm⁻¹
b = 13.5599 (17) Å	T = 298 K
c = 34.235 (4) Å	0.60 × 0.20 × 0.18 mm

Data collection top

Bruker P4 diffractometer	4026 reflections with I > 2σ(I)
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	R_int = 0.027
T_min = 0.160, T_max = 0.294	3 standard reflections every 97 reflections
5243 measured reflections	intensity decay: 1%
4948 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.110	Δρ_max = 1.61 e Å⁻³
S = 1.06	Δρ_min = −2.35 e Å⁻³
4948 reflections	Absolute structure: Flack (1983), 1153 Friedel pairs
319 parameters	Absolute structure parameter: −0.024 (14)
18 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Pb1	0.77229 (7)	0.50814 (2)	0.280652 (9)	0.04579 (14)
C1	0.586 (2)	0.3234 (7)	0.3200 (3)	0.044 (2)
N1	0.4874 (15)	0.1511 (5)	0.3341 (2)	0.0444 (18)
H1A	0.4767	0.1481	0.3074	0.067*
H1B	0.3683	0.1109	0.3450	0.067*
H1C	0.6423	0.1303	0.3420	0.067*
O1	0.5070 (14)	0.4129 (4)	0.3202 (2)	0.0543 (19)
C2	0.4473 (19)	0.2538 (6)	0.3472 (3)	0.040 (2)
H2A	0.2695	0.2689	0.3460	0.047*
O2	0.7618 (16)	0.2944 (4)	0.3007 (2)	0.063 (2)
C3	0.542 (2)	0.2689 (7)	0.3900 (3)	0.049 (2)
H3A	0.7103	0.2441	0.3920	0.059*
H3B	0.5457	0.3389	0.3957	0.059*
C4	0.383 (2)	0.2178 (8)	0.4199 (3)	0.052 (3)
C5	0.424 (3)	0.1204 (9)	0.4308 (3)	0.072 (3)
H5A	0.5568	0.0861	0.4199	0.086*
C6	0.274 (3)	0.0743 (11)	0.4570 (4)	0.092 (4)
H6A	0.3058	0.0091	0.4638	0.110*
C7	0.081 (4)	0.1218 (18)	0.4732 (4)	0.113 (8)
H7A	−0.0191	0.0892	0.4912	0.135*
C8	0.030 (3)	0.2169 (18)	0.4634 (4)	0.105 (7)
H8A	−0.1051	0.2494	0.4746	0.127*
C9	0.182 (2)	0.2651 (10)	0.4365 (3)	0.067 (3)
H9A	0.1476	0.3300	0.4296	0.080*
C11	0.5983 (19)	0.6746 (6)	0.3283 (3)	0.037 (2)
N11	0.2477 (15)	0.7919 (4)	0.3286 (2)	0.0433 (16)
H11A	0.2942	0.8134	0.3042	0.065*
H11B	0.1714	0.8425	0.3419	0.065*
H11C	0.1392	0.7399	0.3262	0.065*
O11	0.4650 (14)	0.6227 (4)	0.3079 (2)	0.0532 (18)
C12	0.4715 (18)	0.7594 (6)	0.3506 (2)	0.035 (2)
H12A	0.5875	0.8148	0.3527	0.042*
O12	0.8305 (13)	0.6650 (5)	0.3327 (2)	0.0514 (18)
C13	0.390 (2)	0.7277 (8)	0.3918 (2)	0.049 (2)
H13A	0.3070	0.7829	0.4043	0.059*
H13B	0.2697	0.6747	0.3895	0.059*
C14	0.597 (2)	0.6940 (8)	0.4175 (3)	0.055 (3)
C15	0.644 (3)	0.5949 (10)	0.4225 (4)	0.085 (4)
H15A	0.5448	0.5489	0.4099	0.102*
C16	0.837 (4)	0.5621 (15)	0.4461 (5)	0.119 (6)
H16A	0.8706	0.4951	0.4484	0.143*
C17	0.979 (4)	0.631 (2)	0.4661 (4)	0.117 (8)
H17A	1.1048	0.6092	0.4826	0.140*
C18	0.936 (3)	0.7289 (17)	0.4620 (4)	0.096 (6)
H18A	1.0341	0.7749	0.4750	0.115*
C19	0.742 (3)	0.7592 (10)	0.4377 (3)	0.075 (3)
H19A	0.7103	0.8264	0.4352	0.090*
O3	1.0478 (14)	0.4723 (5)	0.3424 (3)	0.076 (2)
H31	1.0178	0.5014	0.3639	0.114*
H32	1.1827	0.4402	0.3402	0.114*
O4	0.8220 (16)	0.6871 (5)	0.23573 (17)	0.0556 (18)
H41	0.7685	0.6839	0.2124	0.083*
H42	0.9634	0.7148	0.2371	0.083*
N21	0.290 (2)	0.4320 (7)	0.2286 (3)	0.069 (2)
O21	0.314 (2)	0.5177 (6)	0.2350 (3)	0.095 (2)
O22	0.465 (2)	0.3712 (8)	0.2319 (3)	0.097 (3)
O23	0.0891 (19)	0.3971 (8)	0.2220 (3)	0.094 (3)
N31	−0.0031 (15)	0.0127 (6)	0.3617 (3)	0.057 (2)
O31	−0.1845 (18)	−0.0373 (6)	0.3673 (3)	0.089 (3)
O32	−0.0270 (14)	0.1025 (5)	0.3546 (3)	0.075 (3)
O33	0.2098 (14)	−0.0227 (5)	0.3605 (3)	0.074 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pb1	0.0489 (2)	0.03533 (16)	0.05312 (19)	0.00897 (17)	0.01081 (17)	−0.00091 (13)
C1	0.035 (6)	0.038 (4)	0.057 (6)	0.001 (4)	0.009 (5)	0.000 (4)
N1	0.044 (5)	0.030 (3)	0.059 (5)	0.000 (3)	−0.003 (4)	−0.001 (3)
O1	0.047 (4)	0.033 (3)	0.082 (5)	0.011 (3)	0.017 (4)	0.012 (3)
C2	0.038 (6)	0.030 (4)	0.051 (5)	−0.004 (4)	0.004 (5)	0.000 (4)
O2	0.065 (5)	0.043 (3)	0.080 (4)	0.001 (4)	0.029 (5)	0.006 (3)
C3	0.043 (6)	0.055 (5)	0.047 (5)	0.001 (5)	−0.004 (5)	−0.006 (4)
C4	0.049 (6)	0.066 (6)	0.041 (5)	−0.007 (5)	−0.005 (5)	−0.009 (4)
C5	0.080 (9)	0.072 (7)	0.064 (7)	0.004 (7)	0.009 (7)	0.006 (6)
C6	0.107 (13)	0.100 (9)	0.068 (7)	−0.026 (12)	0.000 (9)	0.022 (7)
C7	0.089 (14)	0.18 (2)	0.073 (10)	−0.043 (16)	0.007 (9)	0.033 (12)
C8	0.069 (11)	0.21 (2)	0.042 (7)	0.006 (14)	0.005 (7)	−0.022 (10)
C9	0.048 (7)	0.096 (8)	0.057 (6)	0.019 (7)	0.002 (6)	−0.013 (5)
C11	0.028 (5)	0.031 (4)	0.051 (5)	0.001 (4)	0.006 (4)	0.008 (4)
N11	0.036 (4)	0.034 (3)	0.060 (4)	0.007 (4)	0.001 (4)	0.001 (3)
O11	0.049 (5)	0.036 (3)	0.075 (5)	0.001 (3)	−0.002 (4)	−0.016 (3)
C12	0.035 (5)	0.028 (3)	0.043 (5)	0.005 (4)	0.001 (4)	−0.003 (3)
O12	0.041 (4)	0.051 (4)	0.062 (4)	0.020 (3)	0.009 (3)	−0.001 (3)
C13	0.049 (6)	0.061 (6)	0.037 (4)	0.006 (5)	0.013 (5)	0.002 (4)
C14	0.054 (7)	0.071 (7)	0.039 (5)	0.005 (6)	0.011 (5)	0.007 (5)
C15	0.089 (11)	0.088 (9)	0.078 (8)	0.022 (9)	0.005 (8)	0.021 (7)
C16	0.125 (16)	0.128 (14)	0.103 (12)	0.057 (14)	0.013 (12)	0.032 (11)
C17	0.088 (13)	0.21 (3)	0.049 (8)	0.052 (16)	0.009 (7)	0.029 (11)
C18	0.068 (11)	0.167 (18)	0.052 (8)	−0.016 (12)	0.004 (7)	0.009 (9)
C19	0.069 (9)	0.104 (8)	0.052 (6)	−0.019 (9)	0.014 (7)	0.000 (5)
O3	0.053 (4)	0.051 (4)	0.124 (7)	0.006 (4)	−0.001 (5)	−0.004 (5)
O4	0.064 (5)	0.057 (4)	0.046 (3)	−0.009 (4)	0.014 (4)	0.007 (3)
N21	0.077 (5)	0.058 (4)	0.071 (4)	−0.001 (4)	0.004 (5)	−0.015 (3)
O21	0.109 (6)	0.062 (4)	0.113 (5)	−0.016 (5)	0.013 (5)	−0.018 (4)
O22	0.097 (7)	0.108 (6)	0.086 (5)	0.035 (6)	0.003 (5)	−0.019 (5)
O23	0.076 (5)	0.108 (6)	0.099 (6)	−0.032 (5)	0.009 (5)	−0.021 (5)
N31	0.046 (5)	0.042 (4)	0.083 (6)	−0.002 (4)	0.004 (4)	−0.017 (4)
O31	0.069 (5)	0.059 (4)	0.137 (7)	−0.024 (5)	0.011 (6)	0.003 (5)
O32	0.041 (4)	0.033 (3)	0.151 (8)	0.007 (3)	−0.002 (5)	0.002 (4)
O33	0.042 (4)	0.041 (3)	0.138 (7)	0.011 (4)	−0.006 (4)	−0.015 (4)

Geometric parameters (Å, º) top

Pb1—O1	2.354 (7)	C11—O12	1.266 (12)
Pb1—O2	2.979 (6)	C11—C12	1.540 (12)
Pb1—O11	2.453 (7)	N11—C12	1.488 (11)
Pb1—O12	2.791 (7)	N11—H11A	0.9200
Pb1—O3	2.628 (8)	N11—H11B	0.9200
Pb1—O4	2.886 (6)	N11—H11C	0.9200
Pb1—O21	2.927 (12)	C12—C13	1.541 (12)
Pb1—O22	2.994 (11)	C12—H12A	0.9800
C1—O2	1.217 (12)	C13—C14	1.490 (15)
C1—O1	1.287 (11)	C13—H13A	0.9700
C1—C2	1.522 (13)	C13—H13B	0.9700
N1—C2	1.479 (10)	C14—C19	1.370 (16)
N1—H1A	0.9200	C14—C15	1.380 (16)
N1—H1B	0.9200	C15—C16	1.39 (2)
N1—H1C	0.9200	C15—H15A	0.9300
C2—C3	1.566 (13)	C16—C17	1.38 (3)
C2—H2A	0.9800	C16—H16A	0.9300
C3—C4	1.503 (15)	C17—C18	1.36 (3)
C3—H3A	0.9700	C17—H17A	0.9300
C3—H3B	0.9700	C18—C19	1.40 (2)
C4—C9	1.379 (15)	C18—H18A	0.9300
C4—C5	1.390 (16)	C19—H19A	0.9300
C5—C6	1.359 (18)	O3—H31	0.8500
C5—H5A	0.9300	O3—H32	0.8500
C6—C7	1.34 (3)	O4—H41	0.8501
C6—H6A	0.9300	O4—H42	0.8500
C7—C8	1.36 (3)	N21—O21	1.189 (11)
C7—H7A	0.9300	N21—O23	1.203 (14)
C8—C9	1.40 (2)	N21—O22	1.257 (13)
C8—H8A	0.9300	N31—O31	1.204 (11)
C9—H9A	0.9300	N31—O33	1.243 (11)
C11—O11	1.225 (12)	N31—O32	1.249 (11)

O1—Pb1—O11	73.7 (2)	C8—C7—H7A	119.7
O1—Pb1—O3	77.2 (3)	C7—C8—C9	119.1 (18)
O11—Pb1—O3	101.1 (2)	C7—C8—H8A	120.5
O1—Pb1—O12	96.8 (2)	C9—C8—H8A	120.5
O11—Pb1—O12	49.5 (2)	C4—C9—C8	121.0 (14)
O3—Pb1—O12	64.2 (2)	C4—C9—H9A	119.5
O1—Pb1—O4	145.5 (2)	C8—C9—H9A	119.5
O11—Pb1—O4	74.5 (2)	O11—C11—O12	126.0 (10)
O3—Pb1—O4	122.1 (2)	O11—C11—C12	116.9 (9)
O12—Pb1—O4	71.87 (19)	O12—C11—C12	117.2 (10)
O1—Pb1—O21	79.6 (3)	C12—N11—H11A	109.5
O11—Pb1—O21	66.8 (2)	C12—N11—H11B	109.5
O3—Pb1—O21	156.2 (3)	H11A—N11—H11B	109.5
O12—Pb1—O21	113.7 (2)	C12—N11—H11C	109.5
O4—Pb1—O21	75.9 (2)	H11A—N11—H11C	109.5
O1—Pb1—O2	47.3 (2)	H11B—N11—H11C	109.5
O11—Pb1—O2	121.0 (2)	C11—O11—Pb1	100.7 (6)
O3—Pb1—O2	69.2 (2)	N11—C12—C13	108.4 (8)
O12—Pb1—O2	126.6 (2)	N11—C12—C11	109.3 (7)
O4—Pb1—O2	160.55 (19)	C13—C12—C11	111.9 (7)
O21—Pb1—O2	98.6 (2)	N11—C12—H12A	109.1
O1—Pb1—O22	69.2 (3)	C13—C12—H12A	109.1
O11—Pb1—O22	103.4 (3)	C11—C12—H12A	109.1
O3—Pb1—O22	130.2 (3)	C11—O12—Pb1	83.8 (7)
O12—Pb1—O22	152.9 (2)	C14—C13—C12	114.3 (9)
O4—Pb1—O22	106.0 (3)	C14—C13—H13A	108.7
O21—Pb1—O22	42.6 (2)	C12—C13—H13A	108.7
O2—Pb1—O22	61.0 (3)	C14—C13—H13B	108.7
O2—C1—O1	124.4 (9)	C12—C13—H13B	108.7
O2—C1—C2	120.9 (8)	H13A—C13—H13B	107.6
O1—C1—C2	114.7 (9)	C19—C14—C15	117.3 (12)
C2—N1—H1A	109.5	C19—C14—C13	121.9 (11)
C2—N1—H1B	109.5	C15—C14—C13	120.8 (12)
H1A—N1—H1B	109.5	C14—C15—C16	121.6 (17)
C2—N1—H1C	109.5	C14—C15—H15A	119.2
H1A—N1—H1C	109.5	C16—C15—H15A	119.2
H1B—N1—H1C	109.5	C17—C16—C15	119.1 (18)
C1—O1—Pb1	108.2 (6)	C17—C16—H16A	120.5
N1—C2—C1	109.1 (7)	C15—C16—H16A	120.5
N1—C2—C3	111.0 (8)	C18—C17—C16	120.9 (19)
C1—C2—C3	109.3 (8)	C18—C17—H17A	119.6
N1—C2—H2A	109.1	C16—C17—H17A	119.6
C1—C2—H2A	109.1	C17—C18—C19	118.5 (18)
C3—C2—H2A	109.1	C17—C18—H18A	120.8
C1—O2—Pb1	80.0 (5)	C19—C18—H18A	120.8
C4—C3—C2	113.2 (9)	C14—C19—C18	122.6 (14)
C4—C3—H3A	108.9	C14—C19—H19A	118.7
C2—C3—H3A	108.9	C18—C19—H19A	118.7
C4—C3—H3B	108.9	Pb1—O3—H31	120.1
C2—C3—H3B	108.9	Pb1—O3—H32	120.5
H3A—C3—H3B	107.8	H31—O3—H32	118.4
C9—C4—C5	117.2 (12)	Pb1—O4—H41	115.2
C9—C4—C3	120.8 (11)	Pb1—O4—H42	115.0
C5—C4—C3	121.9 (11)	H41—O4—H42	112.3
C6—C5—C4	121.3 (13)	O21—N21—O23	120.9 (13)
C6—C5—H5A	119.4	O21—N21—O22	123.0 (14)
C4—C5—H5A	119.4	O23—N21—O22	115.8 (10)
C7—C6—C5	120.8 (16)	N21—O21—Pb1	98.3 (9)
C7—C6—H6A	119.6	N21—O22—Pb1	93.3 (7)
C5—C6—H6A	119.6	O31—N31—O33	122.4 (9)
C6—C7—C8	120.7 (17)	O31—N31—O32	119.8 (9)
C6—C7—H7A	119.7	O33—N31—O32	117.7 (9)

O2—C1—O1—Pb1	−3.4 (14)	O11—C11—C12—N11	−28.1 (11)
C2—C1—O1—Pb1	174.9 (7)	O12—C11—C12—N11	151.7 (9)
O11—Pb1—O1—C1	−177.6 (8)	O11—C11—C12—C13	91.9 (11)
O3—Pb1—O1—C1	−71.9 (7)	O12—C11—C12—C13	−88.3 (11)
O12—Pb1—O1—C1	−133.3 (7)	O11—C11—O12—Pb1	0.7 (11)
O4—Pb1—O1—C1	158.9 (6)	C12—C11—O12—Pb1	−179.1 (7)
O21—Pb1—O1—C1	113.7 (7)	O1—Pb1—O12—C11	−62.1 (6)
O2—Pb1—O1—C1	1.6 (6)	O11—Pb1—O12—C11	−0.4 (6)
O22—Pb1—O1—C1	70.7 (7)	O3—Pb1—O12—C11	−134.3 (7)
O2—C1—C2—N1	−22.5 (14)	O4—Pb1—O12—C11	84.4 (6)
O1—C1—C2—N1	159.1 (9)	O21—Pb1—O12—C11	19.5 (7)
O2—C1—C2—C3	99.1 (11)	O2—Pb1—O12—C11	−102.5 (6)
O1—C1—C2—C3	−79.4 (12)	O22—Pb1—O12—C11	−5.4 (9)
O1—C1—O2—Pb1	2.6 (11)	N11—C12—C13—C14	−179.4 (8)
C2—C1—O2—Pb1	−175.7 (10)	C11—C12—C13—C14	60.0 (11)
O1—Pb1—O2—C1	−1.6 (7)	C12—C13—C14—C19	82.9 (12)
O11—Pb1—O2—C1	−0.7 (7)	C12—C13—C14—C15	−99.1 (12)
O3—Pb1—O2—C1	90.0 (7)	C19—C14—C15—C16	−2.2 (19)
O12—Pb1—O2—C1	59.6 (7)	C13—C14—C15—C16	179.6 (12)
O4—Pb1—O2—C1	−140.7 (8)	C14—C15—C16—C17	2 (2)
O21—Pb1—O2—C1	−68.7 (7)	C15—C16—C17—C18	−2 (3)
O22—Pb1—O2—C1	−89.3 (7)	C16—C17—C18—C19	1 (3)
N1—C2—C3—C4	−70.6 (11)	C15—C14—C19—C18	1.6 (18)
C1—C2—C3—C4	169.0 (9)	C13—C14—C19—C18	179.8 (11)
C2—C3—C4—C9	−89.2 (11)	C17—C18—C19—C14	−1 (2)
C2—C3—C4—C5	87.8 (13)	O23—N21—O21—Pb1	155.0 (10)
C9—C4—C5—C6	−0.8 (18)	O22—N21—O21—Pb1	−18.1 (12)
C3—C4—C5—C6	−177.9 (11)	O1—Pb1—O21—N21	−61.2 (8)
C4—C5—C6—C7	0 (2)	O11—Pb1—O21—N21	−137.8 (8)
C5—C6—C7—C8	1 (2)	O3—Pb1—O21—N21	−74.7 (9)
C6—C7—C8—C9	0 (2)	O12—Pb1—O21—N21	−154.2 (7)
C5—C4—C9—C8	0.9 (17)	O4—Pb1—O21—N21	143.3 (8)
C3—C4—C9—C8	178.1 (11)	O2—Pb1—O21—N21	−17.7 (8)
C7—C8—C9—C4	0 (2)	O22—Pb1—O21—N21	9.3 (7)
O12—C11—O11—Pb1	−0.8 (12)	O21—N21—O22—Pb1	17.6 (12)
C12—C11—O11—Pb1	179.0 (6)	O23—N21—O22—Pb1	−155.9 (9)
O1—Pb1—O11—C11	114.7 (6)	O1—Pb1—O22—N21	88.6 (7)
O3—Pb1—O11—C11	41.7 (6)	O11—Pb1—O22—N21	22.1 (7)
O12—Pb1—O11—C11	0.4 (6)	O3—Pb1—O22—N21	139.5 (7)
O4—Pb1—O11—C11	−78.8 (6)	O12—Pb1—O22—N21	26.0 (11)
O21—Pb1—O11—C11	−159.8 (7)	O4—Pb1—O22—N21	−55.3 (7)
O2—Pb1—O11—C11	114.0 (6)	O21—Pb1—O22—N21	−8.7 (6)
O22—Pb1—O11—C11	178.0 (6)	O2—Pb1—O22—N21	140.4 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.92	2.25	2.956 (11)	134
N1—H1B···O33	0.92	2.07	2.932 (11)	155
N1—H1C···O32ⁱⁱ	0.92	1.87	2.786 (11)	173
N11—H11A···O22ⁱⁱⁱ	0.92	1.95	2.800 (12)	152
N11—H11B···O33^iv	0.92	1.95	2.749 (9)	145
N11—H11C···O12^v	0.92	1.96	2.833 (11)	158
O3—H32···O1ⁱⁱ	0.85	1.91	2.710 (11)	156
O4—H42···O2^vi	0.85	2.24	2.949 (10)	140

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

Experimental details

Crystal data
Chemical formula	[Pb(C₉H₁₁NO₂)₂(NO₃)(H₂O)₂]NO₃
M_r	697.62
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	5.3851 (9), 13.5599 (17), 34.235 (4)
V (Å³)	2499.9 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.82
Crystal size (mm)	0.60 × 0.20 × 0.18

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	ψ scan (XSCANS; Siemens, 1996)
T_min, T_max	0.160, 0.294
No. of measured, independent and observed [I > 2σ(I)] reflections	5243, 4948, 4026
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.110, 1.06
No. of reflections	4948
No. of parameters	319
No. of restraints	18
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.61, −2.35
Absolute structure	Flack (1983), 1153 Friedel pairs
Absolute structure parameter	−0.024 (14)

Computer programs: XSCANS (Siemens, 1996), SHELXTL-Plus (Sheldrick, 2008) and Mercury (Macrae et al., 2006).

Selected bond lengths (Å) top

Pb1—O1	2.354 (7)	Pb1—O3	2.628 (8)
Pb1—O2	2.979 (6)	Pb1—O4	2.886 (6)
Pb1—O11	2.453 (7)	Pb1—O21	2.927 (12)
Pb1—O12	2.791 (7)	Pb1—O22	2.994 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.92	2.25	2.956 (11)	133.6
N1—H1B···O33	0.92	2.07	2.932 (11)	155.2
N1—H1C···O32ⁱⁱ	0.92	1.87	2.786 (11)	172.6
N11—H11A···O22ⁱⁱⁱ	0.92	1.95	2.800 (12)	151.9
N11—H11B···O33^iv	0.92	1.95	2.749 (9)	144.6
N11—H11C···O12^v	0.92	1.96	2.833 (11)	157.7

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

Acknowledgements

SB is grateful to Universidad Autónoma de Puebla (Mexico) for diffractometer time.

References

Apfelbaum-Tibika, F. & Bino, A. (1984). Inorg. Chem. 23, 2902–2905. CSD CrossRef CAS Web of Science Google Scholar
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