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Bis[N-(1-naphth­yl)ethyl­enedi­ammonium] hexa­bromidoplumbate(II)

aState Key Laboratory of Silicon Materials, Zhejiang University, Key Laboratory of Macromolecule Synthesis and Functionalization (Zhejiang University), Ministry of Education, Department of Material Science and Engineering, Zhejiang University, Hangzhou 310027, People's Republic of China
*Correspondence e-mail: wmang@zju.edu.cn

(Received 8 January 2010; accepted 9 March 2010; online 17 March 2010)

The title compound, (C12H16N2)2[PbBr6], is an organic–inorganic salt, with two doubly protonated N-(1-naphth­yl)ethyl­enediammonium cations and one octa­hedral hexa­bromidoplumbate(II) anion. The PbII atom is located on a centre of inversion. The crystal structure consists of alternating inorganic and organic layers parallel to the bc plane. Face-to-face aromatic stacking inter­actions [centroid–centroid distance = 3.505 (5) Å] occur between parallel naphthalene systems in the organic layers, and N—H⋯Br hydrogen bonds between the cations and anions stabilize the crystal structure.

Related literature

For the related structure bis­[N-(1-naphth­yl)ethyl­enedi­ammonium] hexa­iodido­plumbate(II), see: Zheng et al. (2007[Zheng, Y.-Y., Wu, G., Chen, H.-Z. & Wang, M. (2007). Acta Cryst. E63, m504-m506.]).

[Scheme 1]

Experimental

Crystal data
  • (C12H16N2)2[PbBr6]

  • Mr = 1063.19

  • Triclinic, [P \overline 1]

  • a = 8.1193 (4) Å

  • b = 8.5598 (4) Å

  • c = 12.4328 (6) Å

  • α = 80.4601 (13)°

  • β = 79.4756 (14)°

  • γ = 62.8592 (10)°

  • V = 752.63 (6) Å3

  • Z = 1

  • Mo Kα radiation

  • μ = 13.59 mm−1

  • T = 296 K

  • 0.39 × 0.33 × 0.20 mm

Data collection
  • Rigaku R-AXIS RAPID diffractometer

  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.008, Tmax = 0.066

  • 6484 measured reflections

  • 2938 independent reflections

  • 2444 reflections with I > 2σ(I)

  • Rint = 0.092

Refinement
  • R[F2 > 2σ(F2)] = 0.067

  • wR(F2) = 0.174

  • S = 1.00

  • 2938 reflections

  • 162 parameters

  • H-atom parameters constrained

  • Δρmax = 3.73 e Å−3

  • Δρmin = −3.27 e Å−3

Table 1
Selected bond lengths (Å)

Pb1—Br1 3.0749 (8)
Pb1—Br2 2.9944 (10)
Pb1—Br3 3.0118 (10)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1A⋯Br1 0.90 2.48 3.364 (8) 168
N1—H1B⋯Br3i 0.90 2.89 3.618 (7) 139
N2—H2B⋯Br2ii 0.89 2.59 3.339 (9) 143
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x+2, -y+1, -z+1.

Data collection: PROCESS-AUTO (Rigaku, 2006[Rigaku (2006). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2007[Rigaku (2007). CrystalStructure. Rigaku Americas, The Woodlands, Texas, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information


Comment top

The title compound is a organic-inorganic compound, its structure is similar to bis(N-(1-naphthyl)ethylenediammonium) hexaiodoplumbate(II) (Zheng et al., 2007). The crystal structure is composed of alternating organic and inorganic sheets nearly parallel to the bc plane (Fig. 1). The PbII cation is located on an inversion center and coordinated by six Br- anions with a distorted octahedral geometry (Fig. 2). The Pb—Br bond lengths (Table 1) are in the range form 2.9944 (10) to 3.0749 (8) Å. The face-to-face distance between adjacent parallel naphthalene ring systems is 3.505 Å, indicating aromatic π-π interaction. The N—H···Br hydrogen bonding is present in the crystal structure (Table 2).

Related literature top

For the related structure bis[N-(1-naphthyl)ethylenediammonium] hexaiodoplumbate(II), see: Zheng et al. (2007).

Experimental top

The N-(1-naphthyl)ethylenediamine hydrobromide and PbBr2 are used as recieved. Concentrated hydrobromide and acetonitrile were degassed before using. All reactions were carried out under a nitrogen atmosphere. The title compound is prepared by a reaction of 0.1016 g N-(1-naphthyl)ethylenediamine hydrobromide with 0.0719 g PbBr2 in the mixture solution of 14.6 ml hydrobromide and 1.8 ml acetonitrile at 353 K. The resulting solution was kept at 353 K for 1 h and then slowly cooled down to room temperature. The single crystals were filtered off from the solution.

Refinement top

H atoms were placed in calculated positions with C—H = 0.93 (methylene), 0.97 (aromatic) and N—H = 0.89 or 0.90 Å, and included in the final cycles of the refinement in the riding-model approximation with Uiso(H) = 1.2Ueq(C,N) or 1.5Ueq(N).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 2006); data reduction: CrystalStructure (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular packing of the title compound viewed along the b axis.
[Figure 2] Fig. 2. The structure of the title compound [symmetry code: (i) 1-x,1-y,1-z].
Bis[N-(1-naphthyl)ethylenediammonium] hexabromidoplumbate(II) top
Crystal data top
(C12H16N2)2[PbBr6]Z = 1
Mr = 1063.19F(000) = 496
Triclinic, P1Dx = 2.346 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.1193 (4) ÅCell parameters from 6259 reflections
b = 8.5598 (4) Åθ = 3.0–27.4°
c = 12.4328 (6) ŵ = 13.59 mm1
α = 80.4601 (13)°T = 296 K
β = 79.4756 (14)°Chunk, colourless
γ = 62.8592 (10)°0.39 × 0.33 × 0.20 mm
V = 752.63 (6) Å3
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2938 independent reflections
Radiation source: rolling anode2444 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.092
Detector resolution: 10.00 pixels mm-1θmax = 26.0°, θmin = 3.0°
ω scansh = 910
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 1010
Tmin = 0.008, Tmax = 0.066l = 1515
6484 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.067H-atom parameters constrained
wR(F2) = 0.174 w = 1/[σ2(Fo2) + (0.073P)2 + 3P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.002
2938 reflectionsΔρmax = 3.73 e Å3
162 parametersΔρmin = 3.27 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0104 (12)
Crystal data top
(C12H16N2)2[PbBr6]γ = 62.8592 (10)°
Mr = 1063.19V = 752.63 (6) Å3
Triclinic, P1Z = 1
a = 8.1193 (4) ÅMo Kα radiation
b = 8.5598 (4) ŵ = 13.59 mm1
c = 12.4328 (6) ÅT = 296 K
α = 80.4601 (13)°0.39 × 0.33 × 0.20 mm
β = 79.4756 (14)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2938 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
2444 reflections with I > 2σ(I)
Tmin = 0.008, Tmax = 0.066Rint = 0.092
6484 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0670 restraints
wR(F2) = 0.174H-atom parameters constrained
S = 1.00Δρmax = 3.73 e Å3
2938 reflectionsΔρmin = 3.27 e Å3
162 parameters
Special details top

Experimental. Spectroscopic analysis: IR (KBr, cm-1): 3008 (N—H asymmatric stretching), 2906 (N—H asymmatric stretching), 1573 (NH2 bending), 1142 (CH2 non-planar oscillating). Chemical analysis (calculated): C 27.09%, H 3.01%, N 5.27%; (found): C 27.12%, H 3.04%, N 5.23%.

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 > 2sigma(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) top
xyzUiso*/Ueq
Pb10.50000.50000.50000.03697 (12)
Br30.69148 (13)0.55171 (12)0.66759 (8)0.0503 (2)
Br20.85539 (12)0.36179 (13)0.34710 (8)0.0533 (3)
Br10.44025 (12)0.86889 (11)0.39152 (8)0.0482 (2)
N20.8772 (11)0.7533 (10)0.4518 (7)0.054 (2)
H2A0.76950.79730.49510.081*
H2B0.96590.67410.49120.081*
H2C0.86580.70180.39880.081*
N10.7162 (9)1.0520 (8)0.2540 (6)0.0418 (17)
H1A0.64640.99440.28160.050*
H1B0.66731.15300.28630.050*
C10.7317 (10)0.9604 (10)0.0702 (7)0.0371 (19)
C60.7273 (11)1.0045 (10)0.0447 (8)0.043 (2)
C100.7082 (12)1.0940 (10)0.1348 (8)0.042 (2)
C20.7567 (12)0.7896 (10)0.1148 (8)0.042 (2)
H20.75280.75960.19030.051*
C110.9145 (12)0.9392 (12)0.2815 (8)0.047 (2)
H11A0.96680.83060.24650.056*
H11B0.98951.00140.25130.056*
C90.6906 (13)1.2553 (10)0.0898 (9)0.050 (2)
H90.68221.33660.13430.059*
C50.7545 (13)0.8761 (12)0.1131 (9)0.051 (2)
H50.75190.90450.18850.061*
C120.9269 (12)0.8946 (12)0.4031 (8)0.051 (2)
H12A1.05340.86160.41590.061*
H12B0.84540.99950.44020.061*
C80.6851 (12)1.2998 (10)0.0233 (8)0.049 (2)
H80.67031.41150.05400.058*
C40.7839 (13)0.7129 (12)0.0684 (9)0.056 (3)
H40.80250.62910.11410.067*
C70.7014 (12)1.1792 (12)0.0885 (8)0.046 (2)
H70.69571.21090.16350.055*
C30.7876 (13)0.6654 (11)0.0432 (9)0.052 (3)
H30.81060.55060.07110.063*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pb10.03482 (19)0.03828 (18)0.0450 (3)0.02084 (16)0.00683 (18)0.00605 (16)
Br30.0562 (4)0.0602 (4)0.0498 (5)0.0361 (4)0.0112 (4)0.0079 (4)
Br20.0390 (4)0.0651 (5)0.0514 (6)0.0190 (4)0.0035 (4)0.0078 (4)
Br10.0429 (4)0.0463 (4)0.0596 (6)0.0249 (3)0.0068 (4)0.0014 (4)
N20.051 (4)0.055 (4)0.062 (5)0.028 (3)0.020 (4)0.007 (4)
N10.040 (3)0.039 (3)0.054 (4)0.022 (3)0.003 (3)0.014 (3)
C10.029 (3)0.042 (3)0.046 (5)0.018 (3)0.001 (3)0.011 (3)
C60.029 (3)0.040 (3)0.063 (6)0.015 (3)0.012 (4)0.008 (4)
C100.041 (4)0.045 (4)0.045 (5)0.024 (3)0.006 (4)0.003 (3)
C20.049 (4)0.042 (3)0.048 (5)0.029 (3)0.009 (4)0.001 (3)
C110.039 (4)0.052 (4)0.057 (6)0.026 (4)0.001 (4)0.008 (4)
C90.055 (5)0.037 (3)0.066 (6)0.028 (3)0.006 (5)0.009 (4)
C50.046 (4)0.063 (5)0.053 (6)0.030 (4)0.009 (4)0.008 (4)
C120.051 (4)0.054 (4)0.063 (6)0.032 (4)0.022 (4)0.000 (4)
C80.047 (4)0.038 (4)0.063 (6)0.025 (3)0.002 (4)0.002 (4)
C40.053 (5)0.055 (4)0.070 (7)0.025 (4)0.008 (5)0.025 (4)
C70.038 (4)0.058 (4)0.038 (5)0.022 (4)0.000 (4)0.004 (4)
C30.045 (4)0.045 (4)0.071 (7)0.020 (4)0.009 (5)0.011 (4)
Geometric parameters (Å, º) top
Pb1—Br13.0749 (8)C10—C91.354 (12)
Pb1—Br1i3.0749 (8)C2—C31.405 (13)
Pb1—Br22.9944 (10)C2—H20.9300
Pb1—Br2i2.9944 (10)C11—C121.506 (13)
Pb1—Br3i3.0118 (10)C11—H11A0.9700
Pb1—Br33.0118 (10)C11—H11B0.9700
N2—C121.451 (12)C9—C81.399 (14)
N2—H2A0.8900C9—H90.9300
N2—H2B0.8900C5—C41.343 (14)
N2—H2C0.8900C5—H50.9300
N1—C101.472 (12)C12—H12A0.9700
N1—C111.522 (10)C12—H12B0.9700
N1—H1A0.9000C8—C71.361 (14)
N1—H1B0.9000C8—H80.9300
C1—C21.410 (11)C4—C31.382 (15)
C1—C61.419 (13)C4—H40.9300
C1—C101.428 (12)C7—H70.9300
C6—C51.414 (13)C3—H30.9300
C6—C71.436 (13)
Br2—Pb1—Br2i180.0C1—C10—N1119.1 (7)
Br2—Pb1—Br3i88.45 (3)C3—C2—C1118.9 (9)
Br2i—Pb1—Br3i91.55 (3)C3—C2—H2120.6
Br2—Pb1—Br391.55 (3)C1—C2—H2120.6
Br2i—Pb1—Br388.45 (3)C12—C11—N1113.4 (7)
Br3i—Pb1—Br3180.0C12—C11—H11A108.9
Br2—Pb1—Br186.43 (3)N1—C11—H11A108.9
Br2i—Pb1—Br193.57 (3)C12—C11—H11B108.9
Br3i—Pb1—Br192.47 (3)N1—C11—H11B108.9
Br3—Pb1—Br187.53 (3)H11A—C11—H11B107.7
Br2—Pb1—Br1i93.57 (3)C10—C9—C8120.1 (9)
Br2i—Pb1—Br1i86.43 (3)C10—C9—H9119.9
Br3i—Pb1—Br1i87.53 (3)C8—C9—H9119.9
Br3—Pb1—Br1i92.47 (3)C4—C5—C6119.6 (10)
Br1—Pb1—Br1i180.0C4—C5—H5120.2
C12—N2—H2A109.5C6—C5—H5120.2
C12—N2—H2B109.5N2—C12—C11114.6 (8)
H2A—N2—H2B109.5N2—C12—H12A108.6
C12—N2—H2C109.5C11—C12—H12A108.6
H2A—N2—H2C109.5N2—C12—H12B108.6
H2B—N2—H2C109.5C11—C12—H12B108.6
C10—N1—C11112.3 (7)H12A—C12—H12B107.6
C10—N1—H1A109.2C7—C8—C9119.8 (8)
C11—N1—H1A109.2C7—C8—H8120.1
C10—N1—H1B109.2C9—C8—H8120.1
C11—N1—H1B109.2C5—C4—C3122.1 (10)
H1A—N1—H1B107.9C5—C4—H4118.9
C2—C1—C6119.0 (8)C3—C4—H4118.9
C2—C1—C10123.5 (8)C8—C7—C6121.8 (9)
C6—C1—C10117.5 (7)C8—C7—H7119.1
C5—C6—C1120.0 (8)C6—C7—H7119.1
C5—C6—C7121.9 (9)C4—C3—C2120.4 (9)
C1—C6—C7118.1 (8)C4—C3—H3119.8
C9—C10—C1122.5 (9)C2—C3—H3119.8
C9—C10—N1118.2 (8)
C2—C1—C6—C52.2 (12)C1—C10—C9—C83.4 (14)
C10—C1—C6—C5178.4 (8)N1—C10—C9—C8179.1 (8)
C2—C1—C6—C7179.9 (8)C1—C6—C5—C40.1 (13)
C10—C1—C6—C70.5 (11)C7—C6—C5—C4177.9 (9)
C2—C1—C10—C9177.7 (8)N1—C11—C12—N278.7 (10)
C6—C1—C10—C92.9 (12)C10—C9—C8—C71.4 (14)
C2—C1—C10—N12.1 (12)C6—C5—C4—C30.4 (15)
C6—C1—C10—N1178.6 (7)C9—C8—C7—C61.0 (13)
C11—N1—C10—C9100.8 (9)C5—C6—C7—C8176.5 (8)
C11—N1—C10—C175.0 (10)C1—C6—C7—C81.3 (12)
C6—C1—C2—C33.7 (12)C5—C4—C3—C21.2 (15)
C10—C1—C2—C3177.0 (8)C1—C2—C3—C43.2 (13)
C10—N1—C11—C12179.9 (7)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Br10.902.483.364 (8)168
N1—H1B···Br3ii0.902.893.618 (7)139
N2—H2B···Br2iii0.892.593.339 (9)143
Symmetry codes: (ii) x+1, y+2, z+1; (iii) x+2, y+1, z+1.

Experimental details

Crystal data
Chemical formula(C12H16N2)2[PbBr6]
Mr1063.19
Crystal system, space groupTriclinic, P1
Temperature (K)296
a, b, c (Å)8.1193 (4), 8.5598 (4), 12.4328 (6)
α, β, γ (°)80.4601 (13), 79.4756 (14), 62.8592 (10)
V3)752.63 (6)
Z1
Radiation typeMo Kα
µ (mm1)13.59
Crystal size (mm)0.39 × 0.33 × 0.20
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.008, 0.066
No. of measured, independent and
observed [I > 2σ(I)] reflections
6484, 2938, 2444
Rint0.092
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.067, 0.174, 1.00
No. of reflections2938
No. of parameters162
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)3.73, 3.27

Computer programs: PROCESS-AUTO (Rigaku, 2006), CrystalStructure (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top
Pb1—Br13.0749 (8)Pb1—Br33.0118 (10)
Pb1—Br22.9944 (10)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Br10.902.483.364 (8)168
N1—H1B···Br3i0.902.893.618 (7)139
N2—H2B···Br2ii0.892.593.339 (9)143
Symmetry codes: (i) x+1, y+2, z+1; (ii) x+2, y+1, z+1.
 

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 50990063, 50773067 and 50503021). The authors are grateful to Professor J.-M. Gu for assistance with the crystal structure analysis.

References

First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
First citationHigashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku (2006). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku (2007). CrystalStructure. Rigaku Americas, The Woodlands, Texas, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationZheng, Y.-Y., Wu, G., Chen, H.-Z. & Wang, M. (2007). Acta Cryst. E63, m504–m506.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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