catena-Poly[[(2,9-dimethyl-1,10-phenanthroline-κ²N,N′)lead(II)]-di-μ-2-hydroxy­benzoato-κ³O¹,O^1′:O²;κ³O²:O¹,O^1′]

In the title polymeric comound, [Pb(C₇H₅O₃)₂(C₁₄H₁₂N₂)]_n, the Pb^II atom is located on a twofold rotation axis and is coordinated by two N atoms from one 2,9-dimethyl-1,10-phenanthroline (dmphen) ligand and six O atoms from four 2-hydroxy­benzoate anions. The compound forms a zigzag polymeric chain along the c axis through bridging hydr­oxy groups of two 2-hydroxy­benzoate ligands. The crystal packing is stabilized by the intra­molecular hydrogen bonding and π–π inter­actions between dmphen rings of neighboring mol­ecules, with a distance between the ring planes of 3.385 (3) Å.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.018
• wR factor = 0.044
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O2
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.11 Ratio

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Pb1         (2)       2.10

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Comment

The coordination chemistry of lead(II) with N and O donor ligands has been investigated in the past decade and frequently discussed as lead is an environmental pollutant with severe toxic effects (Kovalevsky et al.2003). Recently, we obtained the title lead(II) complex, (I), by reaction of lead acetate, sodium salicylate and dmphen in ethanol/water mixtures, and its crystal structure is reported here.

A segment of the polymeric structure of (I) is illustrated in Fig.1. The Pb^II atom, which lies on a twofold axis, is coordinated by two N atoms from dmphen, two O atoms from hydroxy groups of the two 2-hydroxy-benzoate ligands, and four O atoms of carboxylate groups from another two 2-hydroxy-benzoate ligands (Figure 1). The dmphen ligand lies about the twofold axis and chelates to the Pb^II atom with Pb—N distances of 2.516 (3) Å. The six Pb—O bonds are divided into three groups with the different bond distances of 2.656 (3), 2.695 (3) and 2.887 (4) Å, respectively. The molecular structure forms a one-dimensional chain linked through two bridging 2-hydroxy-benzoate groups. An intra-molecular hydrogen bond between the coordinated hydroxy group and carboxyl O atom (Figure 1 and Table 1) stabilizes the conformation of the hydroxybenzoate ligands. Adjacent chains are connected by π-π interactions with a distance of 3.385 (3)Å between dmphen rings of neighboring molecules, forming a three-dimensional framework structure (Figure 2).

Related literature

For information on the coordination chemistry of lead, see: Kovalevsky et al.(2003).

S2. Experimental

To a solution of 2,9-dimethyl-1,10-phenanthroline (C₁₄H₁₂N₂^.0.5H₂O, 0.1088 g, 0.5 mmol), 2-hydrooxy-benzoate (0.0696 g, 0.5 mmol) and sodium hydroxide (0.0185 g,0.5 mmol) in ethanol/water (v:v=1:10, 11 ml) was added a solution of Pb(CH₃COO)₂ (0.1902 g, 0.5 mmol) in distilled water (5 ml). The resulting solution was stirred for 4 h at 323 K and filtered. Colorless single crystals of (I) were obtained by slow evaporation of the filtrate over 4 days.

S3. Refinement

The carbon-bound H atoms were placed in calculated positions (C—H = 0.93 Å), and were included in the refinement in the riding model approximation, with U_iso(H) = 1.2 U_eq(C). The hydroxyl H atoms were placed in calculated positions (O—H =0.82 Å) and refined with free torsion angles to fit the electron density, with U_iso(H) = 1.5 U_eq(O).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures

	Fig. 1. A segment of the polymeric structure of (I). hydrogen bonds are shown as dashed lines. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) -x + 1, y, -z + 5/2; (ii) x, -y + 1, z + 1/2; (iii) -x + 1, -y + 1, -z + 2]
	Fig. 2. Crystal packing of (I) showing the π-π interactions between the dmphen rings.

catena-Poly[(2,9-dimethyl-1,10-phenanthroline-κ²N,N')lead(II)]- di-µ-2-hydroxybenzoato-κ³O¹,O^1':O²;κ³O²:O¹,O^1']

Crystal data

[Pb(C7H5O3)2(C14H12N2)]	F(000) = 1336
Mr = 689.67	Dx = 1.831 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 5195 reflections
a = 19.6407 (19) Å	θ = 2.8–26.9°
b = 12.9690 (12) Å	µ = 6.79 mm^−1
c = 9.8195 (9) Å	T = 293 K
V = 2501.2 (4) Å^3	Block, yellow
Z = 4	0.24 × 0.15 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2323 independent reflections
Radiation source: fine-focus sealed tube	1682 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
φ and ω scans	θmax = 25.5°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −23→23
Tmin = 0.241, Tmax = 0.443	k = −15→15
17366 measured reflections	l = −11→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.018	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.044	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0159P)^2 + 3.2022P] where P = (Fo^2 + 2Fc^2)/3
2323 reflections	(Δ/σ)max = 0.002
169 parameters	Δρmax = 0.44 e Å^−3
0 restraints	Δρmin = −0.68 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Pb1	0.5000	0.681947 (12)	1.2500	0.02840 (7)
O1	0.39415 (14)	0.73146 (19)	1.0950 (3)	0.0421 (7)
O2	0.46065 (14)	0.6121 (2)	1.0038 (3)	0.0509 (7)
O3	0.41486 (16)	0.4894 (2)	0.8289 (3)	0.0676 (10)
H3	0.4414	0.5131	0.8854	0.101*
N1	0.54686 (15)	0.8440 (2)	1.1448 (3)	0.0283 (7)
C1	0.59274 (19)	0.8427 (3)	1.0457 (4)	0.0330 (8)
C2	0.61983 (19)	0.9346 (3)	0.9934 (4)	0.0410 (9)
H2	0.6525	0.9320	0.9249	0.049*
C3	0.5986 (2)	1.0276 (3)	1.0422 (4)	0.0412 (10)
H3A	0.6164	1.0884	1.0069	0.049*
C4	0.54957 (19)	1.0310 (3)	1.1463 (4)	0.0325 (8)
C5	0.52573 (17)	0.9357 (3)	1.1951 (3)	0.0271 (7)
C6	0.5238 (2)	1.1256 (3)	1.2008 (4)	0.0408 (10)
H6	0.5401	1.1880	1.1675	0.049*
C7	0.6143 (2)	0.7411 (3)	0.9886 (4)	0.0452 (10)
H7A	0.6383	0.7027	1.0571	0.068*
H7B	0.6437	0.7521	0.9118	0.068*
H7C	0.5749	0.7030	0.9601	0.068*
C8	0.3607 (2)	0.5531 (3)	0.8161 (4)	0.0420 (9)
C9	0.35326 (18)	0.6393 (3)	0.9001 (4)	0.0309 (8)
C10	0.29722 (19)	0.7031 (3)	0.8802 (4)	0.0418 (10)
H10	0.2917	0.7608	0.9353	0.050*
C11	0.2497 (2)	0.6826 (3)	0.7808 (4)	0.0505 (12)
H11	0.2128	0.7264	0.7677	0.061*
C12	0.2578 (2)	0.5956 (4)	0.7005 (5)	0.0552 (12)
H12	0.2257	0.5810	0.6336	0.066*
C13	0.3120 (2)	0.5310 (3)	0.7180 (4)	0.0555 (12)
H13	0.3163	0.4723	0.6642	0.067*
C14	0.40548 (19)	0.6634 (3)	1.0067 (4)	0.0326 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pb1	0.03391 (11)	0.02267 (9)	0.02861 (10)	0.000	−0.00428 (10)	0.000
O1	0.0499 (17)	0.0371 (15)	0.0393 (16)	0.0065 (13)	−0.0091 (13)	−0.0094 (13)
O2	0.0411 (17)	0.0631 (18)	0.0486 (17)	0.0182 (15)	−0.0138 (14)	−0.0164 (15)
O3	0.076 (2)	0.0532 (19)	0.073 (2)	0.0292 (17)	−0.0294 (19)	−0.0326 (17)
N1	0.0315 (17)	0.0251 (15)	0.0284 (16)	0.0009 (13)	0.0007 (13)	−0.0006 (12)
C1	0.033 (2)	0.032 (2)	0.034 (2)	0.0013 (17)	0.0004 (17)	−0.0017 (16)
C2	0.039 (2)	0.044 (2)	0.040 (2)	−0.0061 (19)	0.0102 (18)	0.0028 (19)
C3	0.047 (2)	0.036 (2)	0.041 (2)	−0.0098 (19)	0.0067 (19)	0.0072 (17)
C4	0.040 (2)	0.0274 (19)	0.0303 (19)	−0.0050 (17)	−0.0022 (16)	0.0037 (16)
C5	0.0288 (17)	0.0301 (19)	0.0225 (16)	0.0018 (15)	0.0007 (14)	−0.0014 (15)
C6	0.055 (3)	0.0255 (19)	0.041 (2)	−0.0057 (17)	−0.0036 (17)	0.0023 (16)
C7	0.043 (3)	0.043 (2)	0.050 (3)	0.004 (2)	0.015 (2)	−0.003 (2)
C8	0.047 (2)	0.038 (2)	0.041 (2)	0.0015 (19)	−0.009 (2)	−0.0066 (19)
C9	0.030 (2)	0.0321 (19)	0.0305 (19)	−0.0013 (16)	−0.0011 (16)	0.0034 (16)
C10	0.035 (2)	0.046 (2)	0.044 (2)	0.0038 (19)	0.0001 (19)	−0.0031 (19)
C11	0.032 (2)	0.067 (3)	0.053 (3)	0.002 (2)	−0.0090 (19)	0.008 (2)
C12	0.049 (3)	0.067 (3)	0.049 (3)	−0.015 (2)	−0.017 (2)	−0.002 (2)
C13	0.063 (3)	0.051 (3)	0.052 (3)	−0.006 (2)	−0.015 (2)	−0.013 (2)
C14	0.037 (2)	0.0318 (19)	0.0295 (19)	−0.0016 (17)	−0.0012 (17)	0.0040 (16)

Geometric parameters (Å, º)

Pb1—N1	2.516 (3)	C3—C4	1.405 (5)
Pb1—N1^i	2.516 (3)	C3—H3A	0.9300
Pb1—O1	2.656 (3)	C4—C5	1.405 (5)
Pb1—O1^i	2.656 (3)	C4—C6	1.432 (5)
Pb1—O2	2.695 (3)	C5—C5^i	1.478 (7)
Pb1—O2^i	2.695 (3)	C6—C6^i	1.344 (8)
Pb1—O3^ii	2.887 (3)	C6—H6	0.9300
Pb1—O3^iii	2.887 (3)	C7—H7A	0.9600
Pb1—C14	3.035 (4)	C7—H7B	0.9600
Pb1—C14^i	3.035 (4)	C7—H7C	0.9600
O1—C14	1.257 (4)	C8—C13	1.387 (5)
O2—C14	1.272 (4)	C8—C9	1.397 (5)
O3—C8	1.353 (4)	C9—C10	1.390 (5)
O3—Pb1^iii	2.887 (3)	C9—C14	1.499 (5)
O3—H3	0.8200	C10—C11	1.377 (5)
N1—C1	1.326 (4)	C10—H10	0.9300
N1—C5	1.353 (4)	C11—C12	1.385 (6)
C1—C2	1.402 (5)	C11—H11	0.9300
C1—C7	1.495 (5)	C12—C13	1.366 (6)
C2—C3	1.364 (5)	C12—H12	0.9300
C2—H2	0.9300	C13—H13	0.9300
N1—Pb1—N1^i	66.71 (13)	C1—N1—Pb1	122.6 (2)
N1—Pb1—O1	81.32 (9)	C5—N1—Pb1	118.2 (2)
N1^i—Pb1—O1	75.34 (8)	N1—C1—C2	121.1 (3)
N1—Pb1—O1^i	75.34 (8)	N1—C1—C7	118.6 (3)
N1^i—Pb1—O1^i	81.32 (9)	C2—C1—C7	120.3 (3)
O1—Pb1—O1^i	152.01 (11)	C3—C2—C1	120.4 (4)
N1—Pb1—O2	91.01 (9)	C3—C2—H2	119.8
N1^i—Pb1—O2	122.98 (9)	C1—C2—H2	119.8
O1—Pb1—O2	48.90 (8)	C2—C3—C4	119.5 (4)
O1^i—Pb1—O2	145.09 (8)	C2—C3—H3A	120.2
N1—Pb1—O2^i	122.97 (9)	C4—C3—H3A	120.2
N1^i—Pb1—O2^i	91.01 (9)	C5—C4—C3	116.7 (3)
O1—Pb1—O2^i	145.09 (8)	C5—C4—C6	120.6 (3)
O1^i—Pb1—O2^i	48.90 (8)	C3—C4—C6	122.7 (3)
O2—Pb1—O2^i	140.70 (12)	N1—C5—C4	123.1 (3)
N1—Pb1—O3^ii	164.79 (9)	N1—C5—C5^i	118.42 (19)
N1^i—Pb1—O3^ii	108.72 (10)	C4—C5—C5^i	118.5 (2)
O1—Pb1—O3^ii	83.49 (8)	C6^i—C6—C4	121.0 (2)
O1^i—Pb1—O3^ii	119.06 (8)	C6^i—C6—H6	119.5
O2—Pb1—O3^ii	79.39 (9)	C4—C6—H6	119.5
O2^i—Pb1—O3^ii	70.51 (8)	C1—C7—H7A	109.5
N1—Pb1—O3^iii	108.72 (10)	C1—C7—H7B	109.5
N1^i—Pb1—O3^iii	164.79 (9)	H7A—C7—H7B	109.5
O1—Pb1—O3^iii	119.06 (8)	C1—C7—H7C	109.5
O1^i—Pb1—O3^iii	83.49 (8)	H7A—C7—H7C	109.5
O2—Pb1—O3^iii	70.51 (8)	H7B—C7—H7C	109.5
O2^i—Pb1—O3^iii	79.39 (9)	O3—C8—C13	118.7 (4)
O3^ii—Pb1—O3^iii	79.34 (14)	O3—C8—C9	121.1 (3)
N1—Pb1—C14	88.10 (9)	C13—C8—C9	120.2 (4)
N1^i—Pb1—C14	99.53 (10)	C10—C9—C8	118.4 (3)
O1—Pb1—C14	24.37 (8)	C10—C9—C14	121.0 (3)
O1^i—Pb1—C14	161.67 (9)	C8—C9—C14	120.5 (3)
O2—Pb1—C14	24.75 (8)	C11—C10—C9	121.4 (4)
O2^i—Pb1—C14	148.74 (9)	C11—C10—H10	119.3
O3^ii—Pb1—C14	78.23 (9)	C9—C10—H10	119.3
O3^iii—Pb1—C14	94.70 (9)	C10—C11—C12	118.9 (4)
N1—Pb1—C14^i	99.53 (10)	C10—C11—H11	120.6
N1^i—Pb1—C14^i	88.10 (9)	C12—C11—H11	120.6
O1—Pb1—C14^i	161.67 (9)	C13—C12—C11	121.2 (4)
O1^i—Pb1—C14^i	24.37 (8)	C13—C12—H12	119.4
O2—Pb1—C14^i	148.74 (9)	C11—C12—H12	119.4
O2^i—Pb1—C14^i	24.75 (8)	C12—C13—C8	119.8 (4)
O3^ii—Pb1—C14^i	94.70 (9)	C12—C13—H13	120.1
O3^iii—Pb1—C14^i	78.23 (9)	C8—C13—H13	120.1
C14—Pb1—C14^i	170.91 (13)	O1—C14—O2	122.3 (3)
C14—O1—Pb1	95.0 (2)	O1—C14—C9	120.5 (3)
C14—O2—Pb1	92.7 (2)	O2—C14—C9	117.3 (3)
C8—O3—Pb1^iii	154.2 (2)	O1—C14—Pb1	60.66 (19)
C8—O3—H3	109.5	O2—C14—Pb1	62.50 (19)
Pb1^iii—O3—H3	95.9	C9—C14—Pb1	170.1 (2)
C1—N1—C5	119.1 (3)
N1—Pb1—O1—C14	104.8 (2)	Pb1—N1—C5—C4	178.6 (3)
N1^i—Pb1—O1—C14	172.9 (2)	C1—N1—C5—C5^i	179.6 (4)
O1^i—Pb1—O1—C14	138.4 (2)	Pb1—N1—C5—C5^i	−2.5 (5)
O2—Pb1—O1—C14	5.8 (2)	C3—C4—C5—N1	−1.3 (5)
O2^i—Pb1—O1—C14	−117.2 (2)	C6—C4—C5—N1	178.1 (4)
O3^ii—Pb1—O1—C14	−75.8 (2)	C3—C4—C5—C5^i	179.8 (4)
O3^iii—Pb1—O1—C14	−1.8 (2)	C6—C4—C5—C5^i	−0.8 (6)
C14^i—Pb1—O1—C14	−161.1 (3)	C5—C4—C6—C6^i	−0.1 (7)
N1—Pb1—O2—C14	−83.3 (2)	C3—C4—C6—C6^i	179.2 (5)
N1^i—Pb1—O2—C14	−20.6 (3)	Pb1^iii—O3—C8—C13	6.3 (9)
O1—Pb1—O2—C14	−5.7 (2)	Pb1^iii—O3—C8—C9	−174.0 (4)
O1^i—Pb1—O2—C14	−148.6 (2)	O3—C8—C9—C10	178.7 (4)
O2^i—Pb1—O2—C14	125.0 (2)	C13—C8—C9—C10	−1.6 (6)
O3^ii—Pb1—O2—C14	84.9 (2)	O3—C8—C9—C14	0.0 (6)
O3^iii—Pb1—O2—C14	167.2 (2)	C13—C8—C9—C14	179.7 (4)
C14^i—Pb1—O2—C14	166.4 (2)	C8—C9—C10—C11	0.1 (6)
N1^i—Pb1—N1—C1	178.7 (3)	C14—C9—C10—C11	178.7 (3)
O1—Pb1—N1—C1	−103.6 (3)	C9—C10—C11—C12	0.9 (6)
O1^i—Pb1—N1—C1	92.0 (3)	C10—C11—C12—C13	−0.4 (7)
O2—Pb1—N1—C1	−55.5 (3)	C11—C12—C13—C8	−1.1 (7)
O2^i—Pb1—N1—C1	103.5 (3)	O3—C8—C13—C12	−178.2 (4)
O3^ii—Pb1—N1—C1	−105.9 (4)	C9—C8—C13—C12	2.1 (7)
O3^iii—Pb1—N1—C1	14.2 (3)	Pb1—O1—C14—O2	−11.0 (4)
C14—Pb1—N1—C1	−80.1 (3)	Pb1—O1—C14—C9	168.7 (3)
C14^i—Pb1—N1—C1	94.9 (3)	Pb1—O2—C14—O1	10.8 (4)
N1^i—Pb1—N1—C5	0.90 (19)	Pb1—O2—C14—C9	−168.9 (3)
O1—Pb1—N1—C5	78.6 (2)	C10—C9—C14—O1	11.9 (5)
O1^i—Pb1—N1—C5	−85.8 (2)	C8—C9—C14—O1	−169.5 (4)
O2—Pb1—N1—C5	126.7 (2)	C10—C9—C14—O2	−168.5 (4)
O2^i—Pb1—N1—C5	−74.2 (3)	C8—C9—C14—O2	10.2 (5)
O3^ii—Pb1—N1—C5	76.3 (4)	N1—Pb1—C14—O1	−73.0 (2)
O3^iii—Pb1—N1—C5	−163.5 (2)	N1^i—Pb1—C14—O1	−7.0 (2)
C14—Pb1—N1—C5	102.1 (3)	O1^i—Pb1—C14—O1	−98.1 (4)
C14^i—Pb1—N1—C5	−82.8 (3)	O2—Pb1—C14—O1	−169.5 (4)
C5—N1—C1—C2	0.4 (5)	O2^i—Pb1—C14—O1	101.1 (3)
Pb1—N1—C1—C2	−177.3 (3)	O3^ii—Pb1—C14—O1	100.3 (2)
C5—N1—C1—C7	−178.5 (3)	O3^iii—Pb1—C14—O1	178.4 (2)
Pb1—N1—C1—C7	3.8 (5)	N1—Pb1—C14—O2	96.5 (2)
N1—C1—C2—C3	−1.0 (6)	N1^i—Pb1—C14—O2	162.5 (2)
C7—C1—C2—C3	177.8 (4)	O1—Pb1—C14—O2	169.5 (4)
C1—C2—C3—C4	0.4 (6)	O1^i—Pb1—C14—O2	71.4 (4)
C2—C3—C4—C5	0.7 (5)	O2^i—Pb1—C14—O2	−89.3 (3)
C2—C3—C4—C6	−178.7 (4)	O3^ii—Pb1—C14—O2	−90.2 (2)
C1—N1—C5—C4	0.7 (5)	O3^iii—Pb1—C14—O2	−12.1 (2)

Symmetry codes: (i) −x+1, y, −z+5/2; (ii) x, −y+1, z+1/2; (iii) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.82	1.77	2.507 (4)	148