metal-organic papers
Acta Cryst.(2004). E60, m1501±m1503 doi: 10.1107/S1600536804023189 Xiao and Yuan [Pb(C8H4NO6)2(C12H8N2)]H2O
m1501
Acta Crystallographica Section EStructure Reports Online
ISSN 1600-5368
Bis(hydrogen
5-nitroisophthalato)(1,10-phenanthroline)lead(II) monohydrate
Hong-Ping Xiao* and Ji-Xin Yuan
School of Chemistry and Materials Science, Wenzhou Normal College, Zhejiang, Wenzhou 325027, People's Republic of China
Correspondence e-mail: hp_xiao@wznc.zj.cn
Key indicators
Single-crystal X-ray study
T= 293 K
Mean(C±C) = 0.005 AÊ
Rfactor = 0.021
wRfactor = 0.054
Data-to-parameter ratio = 11.9
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved
In the title compound, [Pb(C8H4NO6)2(C12H8N2)]H2O, the
lead(II) ion lies on a twofold axis and exhibits an approximately tetrahedral con®guration. The water molecule also lies on a twofold rotation axis. OÐH O hydrogen bonds and CÐH interactions are involved in the formation of two-dimensional network structures which are interlinked by CÐH O hydrogen bonds.
Comment
Bi- or multidentate ligands containing carboxyl groups are often used to coordinate to metal centers to generate inter-esting coordination polymers (Huet al., 2004; Sunet al., 2003; Yaghiet al., 1998). The lead(II) ion usually shows a different coordination chemistry, due to the presence of the lone-pair electrons (Foreman, 2000; Yuan et al., 2004). Hence, it is of interest to study the crystal structures of lead(II) carboxylates. We report here the hydrothermal synthesis and crystal struc-ture of a mononuclear compound, namely bis(hydrogen 5-nitroisophthalato)(1,10-phenanthroline)lead(II) mono-hydrate, (I).
In (I), the coordination geometry of the PbIIatom is best
described as highly distorted tetrahedral, made up of two N atoms of a phenanthroline ligand and two O atoms from two hydrogen 5-nitroisophthalate anions (Fig. 1). The crystal structure analysis shows that a crystallographic twofold symmetry axis passes through the lead(II) ion and bisects the C13ÐC13i and C14ÐC14i bonds [symmetry code: (i) 1
2ÿx, 3
2ÿy, z]. The 1,10-phenanthroline system is almost
perpen-dicular to the benzene ring of the 5-nitroisophthalate anion, the dihedral angle between the planes being 83.80 (2). The
water molecule also lies on a twofold rotation axis.
O3ÐH3 O2iiand O7ÐH7A O4ii[symmetry code: (ii)
1ÿx, 1ÿy, 2ÿz] intermolecular hydrogen bonds (Table 2) link the molecules into a two-dimensional network structure. This network structure is further stabilized by ± stacking interactions between the N1-pyridine rings of the 1,10-phenanthroline moieties at (x, y, z) and (1
2ÿx, 12ÿy, z)
[centroid±centroid distance = 3.490 (2) AÊ]. The two-dimen-sional networks are interlinked by CÐH O interactions, as shown in Fig. 2.
Experimental
The title compound was synthesized by a hydrothermal method from a mixture of 5-nitroisophthalic acid (0.5 mmol), Pb(NO3)24H2O
(0.5 mmol), 1,10-phenanthroline (1.0 mol) and water (10.0 ml) in a 15 ml Te¯on-lined stainless steel reactor. The solution was heated at 403 K for 5 d and then cooled slowly to room temperature; colorless crystals of (I) were collected for X-ray analysis.
Crystal data
[Pb(C8H4NO6)2(C12H8N2)]H2O
Mr= 825.65
Orthorhombic,Pccn a= 22.6083 (17) AÊ
b= 6.2232 (5) AÊ
c= 20.0394 (15) AÊ
V= 2819.5 (4) AÊ3
Z= 4
Dx= 1.945 Mg mÿ3
MoKradiation Cell parameters from 853
re¯ections
= 2.3±23.2
= 6.06 mmÿ1
T= 293 (2) K Prism, colorless 0.260.130.12 mm
Data collection
Bruker SMART CCD area-detector diffractometer
'and!scans
Absorption correction: multi-scan (SADABS; Bruker, 2000)
Tmin= 0.302,Tmax= 0.530
13880 measured re¯ections
2543 independent re¯ections 2003 re¯ections withI> 2(I)
Rint= 0.030
max= 25.2
h=ÿ20!27
k=ÿ7!7
l=ÿ23!24 Refinement
Re®nement onF2
R[F2> 2(F2)] = 0.021
wR(F2) = 0.054
S= 1.04 2543 re¯ections 213 parameters
H atoms treated by a mixture of independent and constrained re®nement
w= 1/[2(F
o2) + (0.0253P)2
+ 1.2381P]
whereP= (Fo2+ 2Fc2)/3
(/)max= 0.002
max= 0.64 e AÊÿ3
min=ÿ0.42 e AÊÿ3
Table 1
Selected geometric parameters (AÊ,).
Pb1ÐN1 2.434 (2) Pb1ÐO1 2.554 (2)
N1ÐPb1ÐN1i 68.27 (11)
N1ÐPb1ÐO1i 77.21 (8) N1ÐPb1ÐO1O1iÐPb1ÐO1 146.23 (11)74.96 (8)
Symmetry code: (i)1
2ÿx;32ÿy;z.
Table 2
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
O7ÐH7A O4ii 0.81 (2) 2.09 (2) 2.860 (3) 157 (4)
O3ÐH3 O2ii 0.82 1.73 2.506 (3) 156
C3ÐH3A O3 0.93 2.34 2.676 (4) 101
C3ÐH3A O3ii 0.93 2.27 3.158 (4) 160
C9ÐH9 O1iii 0.93 2.45 3.099 (4) 127
C10ÐH10 O5iv 0.93 2.53 3.292 (4) 140
C11ÐH11 O4v 0.93 2.55 3.390 (4) 150
Symmetry codes: (ii) 1ÿx;1ÿy;2ÿz; (iii) x;yÿ1;z; (iv) 1ÿx;yÿ3 2;32ÿz; (v)
1ÿx;yÿ1 2;32ÿz.
The water H atom was located and re®ned with an OÐH distance restraint [OÐH = 0.82 (2) AÊ] and withUiso(H) = 1.5Ueq(O). The
other H atoms were placed in calculated positions (CÐH = 0.93 AÊ) and included in the re®nement in the riding-model approximation, withUiso(H) values set at 1.2Ueq(parent atom).
Data collection:SMART(Bruker, 2000); cell re®nement:SAINT
(Bruker, 2000); data reduction:SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to re®ne structure:SHELXTL; molecular graphics:SHELXTL; software used to prepare material for publication:SHELXTL.
The authors acknowledge ®nancial support from the Wenzhou Science and Technology project of China (No. S2003A008).
References
Bruker (2000).SMART(Version 5.618),SAINT(Version 6.02a),SADABS
(Version 2.03) andSHELXTL(Version 5.03). Bruker AXS Inc., Madison, Wisconsin, USA.
metal-organic papers
m1502
Xiao and Yuan [Pb(C8H4NO6)2(C12H8N2)]H2O Acta Cryst.(2004). E60, m1501±m1503 Figure 2The three-dimensional network in (I), formed by hydrogen bonds and± stacking interactions.
Figure 1
The coordination environment of the Pb atom in (I), with the atom numbering, showing displacement ellipsoids at the 50% probability level. Unlabelled atoms are related to labelled atoms by1
Foreman, M. R. St J., Gelbrich, T., Hursthouse, M. B. & Plater, M. J. (2000).
Inorg. Chem. Commun.3, 234±238.
Hu, M. L., Xiao, H. P. & Yuan, J. X. (2004).Acta Cryst. C60, m112±m113. Sun, D. F., Cao, R., Sun, Y. Q., Bi, W. H., Yuan, D. Q., Shi, Q. & Li, X. (2003).
Chem. Commun.pp. 1528±1529.
Yaghi, O. M., Li, H., Davis, C., Richardson, D. & Groy, T. (1998).Acc. Chem. Res.31, 474±484.
Yuan, Y. P., Mao, J. G. & Song, J. L. (2004).J. Solid State Chem.177, 922± 927.
metal-organic papers
supporting information
sup-1 Acta Cryst. (2004). E60, m1501–m1503
supporting information
Acta Cryst. (2004). E60, m1501–m1503 [https://doi.org/10.1107/S1600536804023189]
Bis(hydrogen 5-nitroisophthalato)(1,10-phenanthroline)lead(II) monohydrate
Hong-Ping Xiao and Ji-Xin Yuan
Bis(hydrogen 5-nitroisophthalato)(1,10-phenanthroline)lead(II) monohydrate
Crystal data
[Pb(C8H4NO6)2(C12H8N2)]·H2O
Mr = 825.65
Orthorhombic, Pccn Hall symbol: -P 2ab 2ac a = 22.6083 (17) Å b = 6.2232 (5) Å c = 20.0394 (15) Å V = 2819.5 (4) Å3
Z = 4
F(000) = 1600 Dx = 1.945 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 853 reflections θ = 2.3–23.2°
µ = 6.06 mm−1
T = 293 K Prism, colourless 0.26 × 0.13 × 0.12 mm
Data collection
Bruker SMART CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
Absorption correction: multi-scan (SADABS; Bruker, 2000) Tmin = 0.302, Tmax = 0.530
13880 measured reflections 2543 independent reflections 2003 reflections with I > 2σ(I) Rint = 0.030
θmax = 25.2°, θmin = 1.8°
h = −20→27 k = −7→7 l = −23→24
Refinement
Refinement on F2
Least-squares matrix: full R[F2 > 2σ(F2)] = 0.021
wR(F2) = 0.054
S = 1.04 2543 reflections 213 parameters 1 restraint
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(F
o2) + (0.0253P)2 + 1.2381P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.002
Δρmax = 0.64 e Å−3
Δρmin = −0.42 e Å−3
Special details
supporting information
sup-2 Acta Cryst. (2004). E60, m1501–m1503
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 (Å2)
x y z Uiso*/Ueq
Pb1 0.2500 0.7500 0.904950 (8) 0.03181 (8) O1 0.34422 (10) 0.9424 (4) 0.86794 (13) 0.0423 (6) O2 0.36931 (10) 0.6618 (4) 0.92858 (14) 0.0471 (6) O3 0.57389 (11) 0.5822 (5) 0.99528 (18) 0.0786 (11)
H3 0.5985 0.5322 1.0210 0.118*
O4 0.64384 (10) 0.8229 (4) 0.97585 (13) 0.0484 (6) O5 0.58348 (16) 1.4197 (6) 0.8245 (2) 0.1108 (15) O6 0.49290 (15) 1.4638 (5) 0.79860 (17) 0.0787 (10)
O7 0.2500 0.2500 0.9500 (2) 0.105 (2)
N1 0.28146 (11) 0.5626 (4) 0.80440 (12) 0.0272 (6) N2 0.53229 (17) 1.3657 (6) 0.82561 (19) 0.0614 (10) C1 0.38201 (15) 0.8328 (6) 0.89767 (17) 0.0348 (8) C2 0.44522 (14) 0.9112 (5) 0.89687 (16) 0.0334 (8) C3 0.48973 (15) 0.8019 (5) 0.93080 (19) 0.0358 (8)
H3A 0.4806 0.6756 0.9534 0.043*
C4 0.54736 (13) 0.8772 (5) 0.93168 (17) 0.0338 (8) C5 0.56154 (15) 1.0644 (6) 0.89802 (16) 0.0390 (8)
H5 0.5999 1.1186 0.8988 0.047*
C6 0.51765 (16) 1.1684 (6) 0.86338 (19) 0.0395 (8) C7 0.45961 (15) 1.0970 (5) 0.86251 (17) 0.0379 (8)
H7 0.4308 1.1728 0.8392 0.045*
C8 0.59368 (14) 0.7597 (5) 0.97018 (18) 0.0383 (8) C9 0.31253 (14) 0.3823 (5) 0.80486 (17) 0.0357 (8)
H9 0.3224 0.3210 0.8457 0.043*
C10 0.33097 (16) 0.2810 (5) 0.7468 (2) 0.0399 (9)
H10 0.3529 0.1548 0.7490 0.048*
C11 0.31675 (15) 0.3676 (5) 0.68679 (18) 0.0384 (8)
H11 0.3289 0.3007 0.6476 0.046*
C12 0.28363 (14) 0.5583 (5) 0.68380 (16) 0.0324 (7) C13 0.26705 (13) 0.6529 (5) 0.74480 (17) 0.0289 (7) C14 0.26590 (17) 0.6597 (6) 0.62321 (18) 0.0430 (9)
H14 0.2768 0.5984 0.5827 0.052*
H7A 0.2781 (15) 0.265 (6) 0.9750 (18) 0.065*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
supporting information
sup-3 Acta Cryst. (2004). E60, m1501–m1503
O3 0.0313 (14) 0.077 (2) 0.128 (3) −0.0167 (14) −0.0275 (16) 0.069 (2) O4 0.0268 (13) 0.0628 (15) 0.0556 (17) −0.0085 (11) −0.0058 (12) 0.0191 (14) O5 0.062 (2) 0.098 (3) 0.172 (4) −0.021 (2) 0.010 (2) 0.085 (3) O6 0.076 (2) 0.0595 (19) 0.101 (3) 0.0011 (16) −0.0095 (18) 0.0459 (19) O7 0.033 (3) 0.240 (8) 0.041 (3) 0.030 (3) 0.000 0.000 N1 0.0242 (14) 0.0261 (13) 0.0311 (15) 0.0066 (11) 0.0003 (11) 0.0035 (12) N2 0.058 (2) 0.048 (2) 0.078 (3) −0.0034 (19) 0.010 (2) 0.031 (2) C1 0.0279 (18) 0.0378 (18) 0.039 (2) 0.0009 (16) −0.0022 (14) 0.0058 (16) C2 0.0258 (17) 0.0352 (19) 0.039 (2) −0.0011 (14) −0.0031 (14) 0.0087 (15) C3 0.0292 (18) 0.0342 (19) 0.044 (2) −0.0014 (13) 0.0012 (16) 0.0142 (15) C4 0.0269 (17) 0.036 (2) 0.0380 (19) 0.0006 (14) 0.0022 (15) 0.0096 (16) C5 0.0279 (18) 0.043 (2) 0.046 (2) −0.0059 (15) 0.0049 (15) 0.0082 (17) C6 0.042 (2) 0.0322 (17) 0.044 (2) −0.0032 (17) 0.0046 (17) 0.0141 (17) C7 0.0330 (19) 0.037 (2) 0.044 (2) 0.0051 (15) −0.0017 (15) 0.0117 (16) C8 0.0272 (18) 0.047 (2) 0.041 (2) −0.0021 (15) −0.0014 (15) 0.0129 (18) C9 0.0338 (19) 0.0318 (19) 0.041 (2) 0.0084 (14) 0.0016 (15) 0.0051 (15) C10 0.038 (2) 0.0299 (19) 0.052 (2) 0.0137 (14) 0.0071 (17) −0.0030 (16) C11 0.041 (2) 0.038 (2) 0.036 (2) 0.0093 (16) 0.0069 (16) −0.0053 (16) C12 0.0333 (19) 0.0355 (18) 0.0283 (18) 0.0032 (15) 0.0060 (14) −0.0037 (15) C13 0.0238 (16) 0.0282 (15) 0.0349 (19) −0.0007 (13) −0.0040 (13) 0.0053 (15) C14 0.055 (2) 0.051 (2) 0.0237 (18) 0.0092 (17) 0.0027 (16) −0.0030 (17)
Geometric parameters (Å, º)
Pb1—N1 2.434 (2) C3—H3A 0.93
Pb1—N1i 2.434 (2) C4—C5 1.384 (4)
Pb1—O1i 2.554 (2) C4—C8 1.492 (4)
Pb1—O1 2.554 (2) C5—C6 1.373 (5)
O1—C1 1.245 (4) C5—H5 0.93
O2—C1 1.264 (5) C6—C7 1.385 (5)
O3—C8 1.294 (4) C7—H7 0.93
O3—H3 0.82 C9—C10 1.388 (5)
O4—C8 1.206 (4) C9—H9 0.93
O5—N2 1.205 (4) C10—C11 1.356 (5)
O6—N2 1.208 (4) C10—H10 0.93
O7—H7A 0.81 (2) C11—C12 1.405 (4)
N1—C9 1.324 (4) C11—H11 0.93
N1—C13 1.359 (4) C12—C13 1.407 (4)
N2—C6 1.480 (5) C12—C14 1.426 (5)
C1—C2 1.510 (5) C13—C13i 1.434 (6)
C2—C7 1.385 (4) C14—C14i 1.334 (7)
C2—C3 1.392 (4) C14—H14 0.93
C3—C4 1.385 (4)
N1—Pb1—N1i 68.27 (11) C4—C5—H5 120.8
N1—Pb1—O1i 77.21 (8) C5—C6—C7 122.7 (3)
N1i—Pb1—O1i 74.96 (8) C5—C6—N2 119.2 (3)
supporting information
sup-4 Acta Cryst. (2004). E60, m1501–m1503
N1i—Pb1—O1 77.21 (8) C2—C7—C6 119.0 (3)
O1i—Pb1—O1 146.23 (11) C2—C7—H7 120.5
C1—O1—Pb1 100.2 (2) C6—C7—H7 120.5
C8—O3—H3 109.5 O4—C8—O3 124.5 (3)
C9—N1—C13 118.9 (3) O4—C8—C4 123.3 (3)
C9—N1—Pb1 123.7 (2) O3—C8—C4 112.1 (3)
C13—N1—Pb1 117.3 (2) N1—C9—C10 122.6 (3)
O5—N2—O6 124.0 (4) N1—C9—H9 118.7
O5—N2—C6 117.1 (3) C10—C9—H9 118.7
O6—N2—C6 118.9 (3) C11—C10—C9 119.5 (3)
O1—C1—O2 122.7 (3) C11—C10—H10 120.3
O1—C1—C2 117.8 (3) C9—C10—H10 120.3
O2—C1—C2 119.5 (3) C10—C11—C12 120.0 (3)
C7—C2—C3 118.8 (3) C10—C11—H11 120.0
C7—C2—C1 119.9 (3) C12—C11—H11 120.0
C3—C2—C1 121.4 (3) C11—C12—C13 117.3 (3)
C4—C3—C2 121.4 (3) C11—C12—C14 124.1 (3)
C4—C3—H3A 119.3 C13—C12—C14 118.7 (3)
C2—C3—H3A 119.3 N1—C13—C12 121.8 (3)
C5—C4—C3 119.8 (3) N1—C13—C13i 118.50 (17)
C5—C4—C8 120.1 (3) C12—C13—C13i 119.72 (19)
C3—C4—C8 120.1 (3) C14i—C14—C12 121.6 (2)
C6—C5—C4 118.4 (3) C14i—C14—H14 119.2
C6—C5—H5 120.8 C12—C14—H14 119.2
Symmetry code: (i) −x+1/2, −y+3/2, z.
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
O7—H7A···O4ii 0.81 (2) 2.09 (2) 2.860 (3) 157 (4)
O3—H3···O2ii 0.82 1.73 2.506 (3) 156
C3—H3A···O3 0.93 2.34 2.676 (4) 101
C3—H3A···O3ii 0.93 2.27 3.158 (4) 160
C9—H9···O1iii 0.93 2.45 3.099 (4) 127
C10—H10···O5iv 0.93 2.53 3.292 (4) 140
C11—H11···O4v 0.93 2.55 3.390 (4) 150