catena-Poly[benzyldecyldimethylammonium [plumbate(II)-tri-μ-bromido]], {(C
19H
34N)[PbBr
3]}
n, crystallizes as an inorganic–organic hybrid following monoclinic space-group symmetry
P2
1/
c. The structure consists of extended chains running along the [001] direction and built of [PbBr
3]
− units. These inorganic chains are separated by interdigitated ammonium cations which form hydrophilic layers through weak C—H
Br interactions. The architecture is essentialy the same as found for
n-alkylbenzyldimethylammonium bromides.
Supporting information
CCDC reference: 893478
All chemicals were of reagent grade quality obtained from commercial sources
and used without further purification. The crystalline phase was obtained
using a mixture of aqueous solutions of Pb(NO3)2 and the ammonium bromide
in a 1:2 molar ratio. Well shaped crystals were obtained by slow evaporation
at room temperature.
Suitable single crystals of the title compound were carefully selected using a
polarizing microscope. The anisotropic atomic displacement parameters of all
non-H atoms were restrained using rigid-bond and pseudo-isotropic restraints
(DELU 0.01 0.01 and ISOR 0.1 0.2 instructions of SHELXL97; Sheldrick,
2008). This was deemed necessary because of the strong absorption of the
material and the unmodelled disorder in the organic side chain. H atoms were
included from geometrical constraints in a riding model assuming C—H = 0.97 Å for CH2 groups, 0.96 Å for CH3 groups and 0.93 Å for CH groups of
benzene rings.
Data collection: COLLECT (Nonius, 1997); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and BS (Ozawa & Kang, 2004); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
catena-poly[benzyldecyldimethylammonium
[plumbate(II)-tri-µ-bromido]]
top
Crystal data top
(C19H34N)[PbBr3] | F(000) = 1368 |
Mr = 723.39 | Dx = 1.910 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4354 (1) Å | Cell parameters from 5124 reflections |
b = 34.7040 (5) Å | θ = 1.0–28.7° |
c = 7.6873 (1) Å | µ = 11.47 mm−1 |
β = 92.062 (1)° | T = 293 K |
V = 2515.55 (6) Å3 | Needle, colourless |
Z = 4 | 0.19 × 0.06 × 0.05 mm |
Data collection top
Nonius KappaCCD diffractometer | 6250 independent reflections |
Radiation source: fine-focus sealed tube | 3604 reflections with I > 2σ(I) |
Horizontally mounted graphite crystal monochromator | Rint = 0.030 |
Detector resolution: 9 pixels mm-1 | θmax = 28.5°, θmin = 2.8° |
ϕ and ο scans to fill Ewald sphere | h = −12→12 |
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997) | k = −46→32 |
Tmin = 0.219, Tmax = 0.598 | l = −10→0 |
9624 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.076 | w = 1/[σ2(Fo2) + (0.0106P)2 + 3.275P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.003 |
6250 reflections | Δρmax = 0.67 e Å−3 |
221 parameters | Δρmin = −0.52 e Å−3 |
194 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00081 (6) |
Crystal data top
(C19H34N)[PbBr3] | V = 2515.55 (6) Å3 |
Mr = 723.39 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.4354 (1) Å | µ = 11.47 mm−1 |
b = 34.7040 (5) Å | T = 293 K |
c = 7.6873 (1) Å | 0.19 × 0.06 × 0.05 mm |
β = 92.062 (1)° | |
Data collection top
Nonius KappaCCD diffractometer | 6250 independent reflections |
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997) | 3604 reflections with I > 2σ(I) |
Tmin = 0.219, Tmax = 0.598 | Rint = 0.030 |
9624 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.039 | 194 restraints |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.67 e Å−3 |
6250 reflections | Δρmin = −0.52 e Å−3 |
221 parameters | |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.3711 (4) | 0.82919 (14) | 0.7120 (6) | 0.0620 (12) | |
C1 | 0.2369 (5) | 0.84799 (17) | 0.6444 (7) | 0.0634 (15) | |
H1A | 0.2107 | 0.8678 | 0.7262 | 0.076* | |
H1B | 0.1620 | 0.8288 | 0.6413 | 0.076* | |
C2 | 0.4148 (7) | 0.7976 (2) | 0.5922 (9) | 0.097 (2) | |
H2A | 0.4537 | 0.8086 | 0.4898 | 0.145* | |
H2B | 0.3336 | 0.7822 | 0.5596 | 0.145* | |
H2C | 0.4851 | 0.7817 | 0.6505 | 0.145* | |
C3 | 0.3404 (7) | 0.8118 (2) | 0.8855 (8) | 0.088 (2) | |
H3A | 0.3131 | 0.8318 | 0.9640 | 0.132* | |
H3B | 0.4237 | 0.7991 | 0.9320 | 0.132* | |
H3C | 0.2646 | 0.7935 | 0.8715 | 0.132* | |
C4 | 0.4947 (5) | 0.8571 (2) | 0.7350 (9) | 0.0779 (18) | |
H4A | 0.5796 | 0.8424 | 0.7644 | 0.093* | |
H4B | 0.5091 | 0.8697 | 0.6243 | 0.093* | |
C11 | 0.2440 (6) | 0.8660 (2) | 0.4655 (8) | 0.0800 (18) | |
H11A | 0.3135 | 0.8866 | 0.4691 | 0.096* | |
H11B | 0.2746 | 0.8467 | 0.3835 | 0.096* | |
C12 | 0.1025 (7) | 0.8819 (2) | 0.4041 (9) | 0.093 (2) | |
H12A | 0.0752 | 0.9023 | 0.4823 | 0.111* | |
H12B | 0.0318 | 0.8617 | 0.4090 | 0.111* | |
C13 | 0.1037 (8) | 0.8977 (3) | 0.2203 (10) | 0.121 (3) | |
H13A | 0.1714 | 0.9187 | 0.2195 | 0.145* | |
H13B | 0.1394 | 0.8776 | 0.1459 | 0.145* | |
C14 | −0.0268 (9) | 0.9114 (3) | 0.1419 (11) | 0.125 (3) | |
H14A | −0.0658 | 0.9303 | 0.2201 | 0.151* | |
H14B | −0.0925 | 0.8899 | 0.1356 | 0.151* | |
C15 | −0.0240 (9) | 0.9293 (3) | −0.0362 (11) | 0.130 (3) | |
H15A | 0.0428 | 0.9505 | −0.0278 | 0.156* | |
H15B | 0.0170 | 0.9103 | −0.1120 | 0.156* | |
C16 | −0.1439 (10) | 0.9433 (3) | −0.1232 (14) | 0.159 (4) | |
H16A | −0.1873 | 0.9612 | −0.0443 | 0.191* | |
H16B | −0.2085 | 0.9216 | −0.1361 | 0.191* | |
C17 | −0.1441 (10) | 0.9621 (3) | −0.2901 (12) | 0.142 (4) | |
H17A | −0.0874 | 0.9852 | −0.2735 | 0.171* | |
H17B | −0.0911 | 0.9454 | −0.3652 | 0.171* | |
C18 | −0.2660 (13) | 0.9735 (4) | −0.3891 (16) | 0.210 (6) | |
H18A | −0.3154 | 0.9500 | −0.4227 | 0.252* | |
H18B | −0.3266 | 0.9869 | −0.3097 | 0.252* | |
C19 | −0.2620 (12) | 0.9956 (4) | −0.5349 (14) | 0.191 (5) | |
H19A | −0.3567 | 1.0031 | −0.5703 | 0.287* | |
H19B | −0.2205 | 0.9811 | −0.6265 | 0.287* | |
H19C | −0.2061 | 1.0182 | −0.5108 | 0.287* | |
C41 | 0.4784 (6) | 0.8874 (2) | 0.8697 (9) | 0.0746 (16) | |
C42 | 0.5422 (8) | 0.8821 (2) | 1.0338 (10) | 0.098 (2) | |
H42 | 0.5899 | 0.8592 | 1.0591 | 0.118* | |
C43 | 0.5358 (11) | 0.9102 (3) | 1.1587 (13) | 0.131 (3) | |
H43 | 0.5791 | 0.9061 | 1.2677 | 0.157* | |
C44 | 0.4673 (11) | 0.9438 (4) | 1.1258 (15) | 0.141 (4) | |
H44 | 0.4625 | 0.9624 | 1.2124 | 0.169* | |
C45 | 0.4053 (9) | 0.9503 (3) | 0.9651 (14) | 0.126 (3) | |
H45 | 0.3592 | 0.9735 | 0.9416 | 0.151* | |
C46 | 0.4113 (7) | 0.9221 (2) | 0.8365 (11) | 0.095 (2) | |
H46 | 0.3696 | 0.9268 | 0.7271 | 0.114* | |
Pb1 | 0.87732 (2) | 0.750252 (7) | 0.98516 (2) | 0.05543 (10) | |
Br2 | 0.66563 (6) | 0.78536 (2) | 1.22246 (8) | 0.0746 (2) | |
Br3 | 1.10409 (6) | 0.77713 (2) | 1.23811 (7) | 0.06660 (19) | |
Br4 | 0.86569 (6) | 0.81763 (2) | 0.75282 (8) | 0.07328 (19) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.045 (2) | 0.064 (3) | 0.077 (3) | −0.002 (2) | 0.007 (2) | −0.001 (2) |
C1 | 0.049 (3) | 0.067 (4) | 0.074 (4) | −0.001 (3) | 0.009 (3) | −0.007 (3) |
C2 | 0.088 (5) | 0.077 (5) | 0.126 (6) | 0.021 (4) | 0.013 (4) | −0.025 (4) |
C3 | 0.088 (5) | 0.087 (6) | 0.087 (4) | −0.018 (4) | −0.004 (4) | 0.020 (4) |
C4 | 0.041 (3) | 0.091 (5) | 0.103 (5) | −0.008 (3) | 0.010 (3) | −0.002 (4) |
C11 | 0.079 (4) | 0.086 (5) | 0.075 (4) | −0.006 (4) | −0.003 (3) | 0.001 (3) |
C12 | 0.094 (5) | 0.081 (6) | 0.102 (5) | 0.012 (4) | −0.008 (4) | 0.006 (4) |
C13 | 0.115 (6) | 0.120 (8) | 0.125 (6) | −0.016 (5) | −0.029 (5) | 0.042 (5) |
C14 | 0.121 (6) | 0.132 (8) | 0.122 (6) | 0.013 (6) | −0.010 (5) | 0.021 (6) |
C15 | 0.119 (7) | 0.138 (9) | 0.132 (7) | 0.009 (6) | −0.021 (5) | 0.034 (6) |
C16 | 0.133 (7) | 0.168 (11) | 0.176 (9) | 0.039 (7) | 0.002 (6) | 0.060 (8) |
C17 | 0.158 (8) | 0.140 (9) | 0.128 (7) | 0.025 (7) | −0.007 (6) | 0.031 (6) |
C18 | 0.176 (10) | 0.246 (16) | 0.208 (13) | 0.052 (11) | −0.003 (9) | 0.101 (11) |
C19 | 0.213 (12) | 0.196 (14) | 0.163 (10) | 0.010 (10) | −0.024 (9) | 0.056 (8) |
C41 | 0.060 (4) | 0.069 (4) | 0.094 (4) | −0.016 (3) | 0.002 (3) | 0.006 (3) |
C42 | 0.095 (5) | 0.097 (6) | 0.102 (5) | −0.029 (4) | −0.013 (4) | 0.016 (4) |
C43 | 0.135 (8) | 0.153 (9) | 0.105 (6) | −0.051 (7) | −0.006 (6) | −0.010 (6) |
C44 | 0.137 (9) | 0.134 (8) | 0.152 (8) | −0.044 (7) | 0.023 (7) | −0.053 (8) |
C45 | 0.117 (7) | 0.075 (6) | 0.186 (9) | −0.016 (5) | 0.016 (6) | −0.017 (6) |
C46 | 0.085 (5) | 0.071 (5) | 0.128 (6) | −0.013 (4) | −0.006 (4) | 0.007 (4) |
Pb1 | 0.05189 (14) | 0.07954 (18) | 0.03502 (12) | −0.00273 (11) | 0.00378 (8) | −0.00064 (11) |
Br2 | 0.0637 (4) | 0.1004 (5) | 0.0600 (4) | 0.0208 (3) | 0.0060 (3) | 0.0061 (4) |
Br3 | 0.0586 (3) | 0.0865 (5) | 0.0546 (3) | −0.0130 (3) | 0.0007 (3) | −0.0009 (3) |
Br4 | 0.0624 (4) | 0.0738 (5) | 0.0846 (4) | 0.0005 (3) | 0.0154 (3) | 0.0032 (4) |
Geometric parameters (Å, º) top
N1—C2 | 1.499 (7) | C16—H16A | 0.9700 |
N1—C1 | 1.501 (6) | C16—H16B | 0.9700 |
N1—C3 | 1.502 (7) | C17—C18 | 1.412 (11) |
N1—C4 | 1.522 (7) | C17—H17A | 0.9700 |
C1—C11 | 1.514 (8) | C17—H17B | 0.9700 |
C1—H1A | 0.9700 | C18—C19 | 1.360 (12) |
C1—H1B | 0.9700 | C18—H18A | 0.9700 |
C2—H2A | 0.9600 | C18—H18B | 0.9700 |
C2—H2B | 0.9600 | C19—H19A | 0.9600 |
C2—H2C | 0.9600 | C19—H19B | 0.9600 |
C3—H3A | 0.9600 | C19—H19C | 0.9600 |
C3—H3B | 0.9600 | C41—C46 | 1.381 (9) |
C3—H3C | 0.9600 | C41—C42 | 1.390 (9) |
C4—C41 | 1.487 (9) | C42—C43 | 1.371 (12) |
C4—H4A | 0.9700 | C42—H42 | 0.9300 |
C4—H4B | 0.9700 | C43—C44 | 1.352 (13) |
C11—C12 | 1.505 (8) | C43—H43 | 0.9300 |
C11—H11A | 0.9700 | C44—C45 | 1.367 (12) |
C11—H11B | 0.9700 | C44—H44 | 0.9300 |
C12—C13 | 1.516 (9) | C45—C46 | 1.393 (11) |
C12—H12A | 0.9700 | C45—H45 | 0.9300 |
C12—H12B | 0.9700 | C46—H46 | 0.9300 |
C13—C14 | 1.432 (9) | Pb1—Br4 | 2.9420 (7) |
C13—H13A | 0.9700 | Pb1—Br3 | 2.9883 (6) |
C13—H13B | 0.9700 | Pb1—Br2 | 3.0106 (6) |
C14—C15 | 1.505 (10) | Pb1—Br2i | 3.0504 (6) |
C14—H14A | 0.9700 | Pb1—Br3i | 3.0627 (6) |
C14—H14B | 0.9700 | Pb1—Br4ii | 3.1323 (7) |
C15—C16 | 1.381 (10) | Br2—Pb1ii | 3.0504 (6) |
C15—H15A | 0.9700 | Br3—Pb1ii | 3.0627 (6) |
C15—H15B | 0.9700 | Br4—Pb1i | 3.1323 (7) |
C16—C17 | 1.440 (11) | | |
| | | |
C2—N1—C1 | 110.7 (4) | C15—C16—C17 | 124.5 (9) |
C2—N1—C3 | 108.6 (5) | C15—C16—H16A | 106.2 |
C1—N1—C3 | 107.1 (4) | C17—C16—H16A | 106.2 |
C2—N1—C4 | 108.1 (4) | C15—C16—H16B | 106.2 |
C1—N1—C4 | 113.4 (5) | C17—C16—H16B | 106.2 |
C3—N1—C4 | 108.9 (5) | H16A—C16—H16B | 106.4 |
N1—C1—C11 | 115.4 (4) | C18—C17—C16 | 125.6 (10) |
N1—C1—H1A | 108.4 | C18—C17—H17A | 105.9 |
C11—C1—H1A | 108.4 | C16—C17—H17A | 105.9 |
N1—C1—H1B | 108.4 | C18—C17—H17B | 105.9 |
C11—C1—H1B | 108.4 | C16—C17—H17B | 105.9 |
H1A—C1—H1B | 107.5 | H17A—C17—H17B | 106.2 |
N1—C2—H2A | 109.5 | C19—C18—C17 | 123.8 (12) |
N1—C2—H2B | 109.5 | C19—C18—H18A | 106.4 |
H2A—C2—H2B | 109.5 | C17—C18—H18A | 106.4 |
N1—C2—H2C | 109.5 | C19—C18—H18B | 106.4 |
H2A—C2—H2C | 109.5 | C17—C18—H18B | 106.4 |
H2B—C2—H2C | 109.5 | H18A—C18—H18B | 106.5 |
N1—C3—H3A | 109.5 | C18—C19—H19A | 109.5 |
N1—C3—H3B | 109.5 | C18—C19—H19B | 109.5 |
H3A—C3—H3B | 109.5 | H19A—C19—H19B | 109.5 |
N1—C3—H3C | 109.5 | C18—C19—H19C | 109.5 |
H3A—C3—H3C | 109.5 | H19A—C19—H19C | 109.5 |
H3B—C3—H3C | 109.5 | H19B—C19—H19C | 109.5 |
C41—C4—N1 | 115.7 (5) | C46—C41—C42 | 117.6 (8) |
C41—C4—H4A | 108.4 | C46—C41—C4 | 123.1 (7) |
N1—C4—H4A | 108.4 | C42—C41—C4 | 119.1 (7) |
C41—C4—H4B | 108.4 | C43—C42—C41 | 120.9 (9) |
N1—C4—H4B | 108.4 | C43—C42—H42 | 119.6 |
H4A—C4—H4B | 107.4 | C41—C42—H42 | 119.6 |
C12—C11—C1 | 111.6 (5) | C44—C43—C42 | 121.0 (11) |
C12—C11—H11A | 109.3 | C44—C43—H43 | 119.5 |
C1—C11—H11A | 109.3 | C42—C43—H43 | 119.5 |
C12—C11—H11B | 109.3 | C43—C44—C45 | 119.9 (11) |
C1—C11—H11B | 109.3 | C43—C44—H44 | 120.1 |
H11A—C11—H11B | 108.0 | C45—C44—H44 | 120.1 |
C11—C12—C13 | 112.9 (6) | C44—C45—C46 | 119.9 (10) |
C11—C12—H12A | 109.0 | C44—C45—H45 | 120.1 |
C13—C12—H12A | 109.0 | C46—C45—H45 | 120.1 |
C11—C12—H12B | 109.0 | C41—C46—C45 | 120.8 (8) |
C13—C12—H12B | 109.0 | C41—C46—H46 | 119.6 |
H12A—C12—H12B | 107.8 | C45—C46—H46 | 119.6 |
C14—C13—C12 | 118.5 (7) | Br4—Pb1—Br3 | 99.039 (19) |
C14—C13—H13A | 107.7 | Br4—Pb1—Br2 | 92.014 (19) |
C12—C13—H13A | 107.7 | Br3—Pb1—Br2 | 87.391 (17) |
C14—C13—H13B | 107.7 | Br4—Pb1—Br2i | 84.885 (19) |
C12—C13—H13B | 107.7 | Br3—Pb1—Br2i | 173.57 (2) |
H13A—C13—H13B | 107.1 | Br2—Pb1—Br2i | 97.60 (2) |
C13—C14—C15 | 118.5 (8) | Br4—Pb1—Br3i | 83.211 (18) |
C13—C14—H14A | 107.7 | Br3—Pb1—Br3i | 90.030 (18) |
C15—C14—H14A | 107.7 | Br2—Pb1—Br3i | 174.16 (2) |
C13—C14—H14B | 107.7 | Br2i—Pb1—Br3i | 85.365 (17) |
C15—C14—H14B | 107.7 | Br4—Pb1—Br4ii | 174.33 (2) |
H14A—C14—H14B | 107.1 | Br3—Pb1—Br4ii | 81.286 (18) |
C16—C15—C14 | 123.0 (9) | Br2—Pb1—Br4ii | 82.336 (18) |
C16—C15—H15A | 106.6 | Br2i—Pb1—Br4ii | 95.316 (19) |
C14—C15—H15A | 106.6 | Br3i—Pb1—Br4ii | 102.460 (18) |
C16—C15—H15B | 106.6 | Pb1—Br2—Pb1ii | 78.714 (14) |
C14—C15—H15B | 106.6 | Pb1—Br3—Pb1ii | 78.860 (14) |
H15A—C15—H15B | 106.5 | Pb1—Br4—Pb1i | 78.443 (17) |
| | | |
C2—N1—C1—C11 | −59.4 (7) | C43—C44—C45—C46 | 0.8 (16) |
C3—N1—C1—C11 | −177.6 (5) | C42—C41—C46—C45 | −1.5 (10) |
C4—N1—C1—C11 | 62.3 (7) | C4—C41—C46—C45 | −176.7 (7) |
C2—N1—C4—C41 | −171.6 (6) | C44—C45—C46—C41 | 0.5 (13) |
C1—N1—C4—C41 | 65.3 (7) | Br4—Pb1—Br2—Pb1ii | −139.032 (18) |
C3—N1—C4—C41 | −53.8 (7) | Br3—Pb1—Br2—Pb1ii | −40.071 (17) |
N1—C1—C11—C12 | 176.4 (5) | Br2i—Pb1—Br2—Pb1ii | 135.86 (2) |
C1—C11—C12—C13 | −176.1 (6) | Br3i—Pb1—Br2—Pb1ii | −103.96 (15) |
C11—C12—C13—C14 | 176.0 (8) | Br4ii—Pb1—Br2—Pb1ii | 41.482 (17) |
C12—C13—C14—C15 | 176.3 (8) | Br4—Pb1—Br3—Pb1ii | 131.479 (17) |
C13—C14—C15—C16 | 179.7 (10) | Br2—Pb1—Br3—Pb1ii | 39.853 (18) |
C14—C15—C16—C17 | 177.1 (10) | Br2i—Pb1—Br3—Pb1ii | −101.23 (15) |
C15—C16—C17—C18 | 173.9 (12) | Br3i—Pb1—Br3—Pb1ii | −145.39 (2) |
C16—C17—C18—C19 | 171.1 (13) | Br4ii—Pb1—Br3—Pb1ii | −42.789 (16) |
N1—C4—C41—C46 | −86.4 (8) | Br3—Pb1—Br4—Pb1i | 132.408 (14) |
N1—C4—C41—C42 | 98.4 (7) | Br2—Pb1—Br4—Pb1i | −139.914 (15) |
C46—C41—C42—C43 | 1.3 (11) | Br2i—Pb1—Br4—Pb1i | −42.463 (16) |
C4—C41—C42—C43 | 176.7 (7) | Br3i—Pb1—Br4—Pb1i | 43.463 (15) |
C41—C42—C43—C44 | 0.0 (14) | Br4ii—Pb1—Br4—Pb1i | −134.8 (2) |
C42—C43—C44—C45 | −1.0 (17) | | |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, −y+3/2, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11B···Br3iii | 0.97 | 3.09 | 3.761 (7) | 128 |
C3—H3C···Br3iv | 0.96 | 3.04 | 3.950 (7) | 159 |
C2—H2B···Br3iii | 0.96 | 3.23 | 3.992 (7) | 137 |
C4—H4A···Br4 | 0.97 | 2.84 | 3.757 (6) | 159 |
C1—H1B···Br4v | 0.97 | 2.98 | 3.779 (5) | 141 |
C42—H42···Br2 | 0.93 | 2.93 | 3.823 (8) | 161 |
C2—H2C···Br2i | 0.96 | 2.93 | 3.837 (7) | 159 |
C2—H2A···Br2vi | 0.96 | 3.03 | 3.788 (7) | 137 |
C3—H3B···Br2 | 0.96 | 3.17 | 4.049 (6) | 153 |
C13—H13A···Cg1vi | 0.97 | 3.37 | 3.989 | 123 |
C16—H16B···Cg1iii | 0.97 | 3.22 | 3.880 | 127 |
Symmetry codes: (i) x, −y+3/2, z−1/2; (iii) x−1, y, z−1; (iv) x−1, −y+3/2, z−1/2; (v) x−1, y, z; (vi) x, y, z−1. |
Experimental details
Crystal data |
Chemical formula | (C19H34N)[PbBr3] |
Mr | 723.39 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 9.4354 (1), 34.7040 (5), 7.6873 (1) |
β (°) | 92.062 (1) |
V (Å3) | 2515.55 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 11.47 |
Crystal size (mm) | 0.19 × 0.06 × 0.05 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.219, 0.598 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9624, 6250, 3604 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.672 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.076, 1.01 |
No. of reflections | 6250 |
No. of parameters | 221 |
No. of restraints | 194 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −0.52 |
Selected geometric parameters (Å, º) topN1—C2 | 1.499 (7) | C15—C16 | 1.381 (10) |
N1—C1 | 1.501 (6) | C16—C17 | 1.440 (11) |
N1—C3 | 1.502 (7) | C17—C18 | 1.412 (11) |
N1—C4 | 1.522 (7) | C18—C19 | 1.360 (12) |
C1—C11 | 1.514 (8) | Pb1—Br4 | 2.9420 (7) |
C4—C41 | 1.487 (9) | Pb1—Br3 | 2.9883 (6) |
C11—C12 | 1.505 (8) | Pb1—Br2 | 3.0106 (6) |
C12—C13 | 1.516 (9) | Pb1—Br2i | 3.0504 (6) |
C13—C14 | 1.432 (9) | Pb1—Br3i | 3.0627 (6) |
C14—C15 | 1.505 (10) | Pb1—Br4ii | 3.1323 (7) |
| | | |
Br4—Pb1—Br3 | 99.039 (19) | Br2i—Pb1—Br3i | 85.365 (17) |
Br4—Pb1—Br2 | 92.014 (19) | Br4—Pb1—Br4ii | 174.33 (2) |
Br3—Pb1—Br2 | 87.391 (17) | Br3—Pb1—Br4ii | 81.286 (18) |
Br4—Pb1—Br2i | 84.885 (19) | Br2—Pb1—Br4ii | 82.336 (18) |
Br3—Pb1—Br2i | 173.57 (2) | Br2i—Pb1—Br4ii | 95.316 (19) |
Br2—Pb1—Br2i | 97.60 (2) | Br3i—Pb1—Br4ii | 102.460 (18) |
Br4—Pb1—Br3i | 83.211 (18) | Pb1—Br2—Pb1ii | 78.714 (14) |
Br3—Pb1—Br3i | 90.030 (18) | Pb1—Br3—Pb1ii | 78.860 (14) |
Br2—Pb1—Br3i | 174.16 (2) | Pb1—Br4—Pb1i | 78.443 (17) |
| | | |
C2—N1—C1—C11 | −59.4 (7) | C11—C12—C13—C14 | 176.0 (8) |
C3—N1—C1—C11 | −177.6 (5) | C12—C13—C14—C15 | 176.3 (8) |
C4—N1—C1—C11 | 62.3 (7) | C13—C14—C15—C16 | 179.7 (10) |
C2—N1—C4—C41 | −171.6 (6) | C14—C15—C16—C17 | 177.1 (10) |
C1—N1—C4—C41 | 65.3 (7) | C15—C16—C17—C18 | 173.9 (12) |
C3—N1—C4—C41 | −53.8 (7) | C16—C17—C18—C19 | 171.1 (13) |
N1—C1—C11—C12 | 176.4 (5) | N1—C4—C41—C46 | −86.4 (8) |
C1—C11—C12—C13 | −176.1 (6) | N1—C4—C41—C42 | 98.4 (7) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, −y+3/2, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11B···Br3iii | 0.97 | 3.09 | 3.761 (7) | 127.6 |
C3—H3C···Br3iv | 0.96 | 3.04 | 3.950 (7) | 158.8 |
C2—H2B···Br3iii | 0.96 | 3.23 | 3.992 (7) | 137.4 |
C4—H4A···Br4 | 0.97 | 2.84 | 3.757 (6) | 158.6 |
C1—H1B···Br4v | 0.97 | 2.98 | 3.779 (5) | 140.6 |
C42—H42···Br2 | 0.93 | 2.93 | 3.823 (8) | 160.9 |
C2—H2C···Br2i | 0.96 | 2.93 | 3.837 (7) | 158.8 |
C2—H2A···Br2vi | 0.96 | 3.03 | 3.788 (7) | 137.0 |
C3—H3B···Br2 | 0.96 | 3.17 | 4.049 (6) | 153.0 |
C13—H13A···Cg1vi | 0.97 | 3.37 | 3.989 | 123.4 |
C16—H16B···Cg1iii | 0.97 | 3.22 | 3.880 | 127.3 |
Symmetry codes: (i) x, −y+3/2, z−1/2; (iii) x−1, y, z−1; (iv) x−1, −y+3/2, z−1/2; (v) x−1, y, z; (vi) x, y, z−1. |
A persistent problem in solid-state inorganic chemistry is the correlation of structural features, characteristic for a particular type of materials, with their physical properties. In this connection, low-dimensional compounds play an important role, because the interactions between atoms and molecules, when confined to one or two dimensions, make theoretical models much simpler (Day, 1983). Many useful physical and chemical properties could only be found and defined in terms of low-dimensional structural models. For example, the architecture of alternate hydrophobic and hydrophilic layers, as observed in the crystals of alkylbenzylammonium bromides (Hodorowicz et al., 2005), provided an explanation of the structure of ammonium cation layers formed at the surface or intercalated between the silicate units, such as those observed in Na–montmorillonite (Kwolek et al., 2003). This knowledge could be utilized in the crystal engineering of organoclays for specific applications. On the other hand, halometalates(II) represent particularly suitable systems for designing the construction of low-dimensional structural archetypes from which modifications with enhanced properties could be derived. The synthesis of inorganic–organic hybrids based on n-alkylbenzyldimethylammonium cations and inorganic [{PbBr3}-]n chains represents an attempt to combine the properties of organic and inorganic domains to modify the macroscopic properties of the crystalline phase (Mitzi et al., 2001; Portier et al., 2001). Some of the low-dimensional polymeric halometalates of copper(II), manganese(II) and cadmium(II) have been studied previously (Ravindran et al., 1990, and references therein; Bonamartini-Corradi et al., 1993, 1994). Also, tin derivatives have been exploited due to their nonmagnetic semiconducting properties (Willett, 1991). Concerning haloplumbates, much work has been carried out on iodoplumbates(II) of the AMzX2z+1 type due to their potential semiconducting properties (quantum-wire systems) (Papavassiliou, 1997). Among these systems containing MX6 face-sharing octahedra, there are compounds like [Et4NPbI3]n and [Bu4NPbI3]n with short-chain quaternary ammonium cations (Papavassiliou, 1997). A few years ago, the structures of the inorganic–organic hybrids {Bu2[PbI3]I.2H2O}n (Billing & Lemmerer, 2006) and {[(CH3)2C═ NHCH2CH2CH3][PbI3]} (Elleuch et al., 2007) were reported. The composition and structure of iodoplumbate anions (chains, ribbons or rods) are determined by the size, shape and charge of the counter-ions used for crystallization (Krautscheid et al., 2001). Much less is known about bromoplumbate(II) systems with long-chain organic ammonium molecules. In the present paper, we report the investigation of the structure of the inorganic–organic hybrid complex salt, (I), containing one-dimensional polymeric bromoplumbate(II) anions built of face-sharing {PbBr6) (distorted) octahedra and quaternary benzyldecyldimethylammonium cations. The aim of this work was to increase our knowledge of the factors controlling the stereochemistry of bromoplumbates(II) and the mutual packing properties of long-chain quaternary ammonium cations in different environments, particularly in relation to their behaviour in crystalline bromides (Hodorowicz et al., 2005).
The title compound belongs to a family of one-dimensional inorganic–organic hybrid solids with the general formula AMX3, in which A is an organic ammonium cation, M is a divalent metal, in our case PbII, and X is Cl, Br, or I (Cheetham et al., 2006). The structure consists of the long hydrocarbon chain benzyldecyldimethylammonium cations and [{PbBr3}-]n polymeric chains as counter-ions. The assymmetric part of the unit cell contains the ammonium cation and a [PbBr3- unit (Fig. 1). The displacement parameters of the atoms in the decyl chain clearly increase along the chain and the highest displacements were observed for the terminal C atoms, which have additional degrees of freedom. This and some unusually short C—C bonds in some parts of the chain (Table 1) are a consequence of complex unmodelled disorder in the chain. The curvature of hydrocarbon chain is not as severe as observed in analogous bromides (Hodorowicz et al., 2005). Each PbII atom is surrounded in a one-dimensional polymeric chain by six bridging Br atoms, three of which are crystallographically independent. The polymeric chain runs along the a axis. The Pb—Br bond lengths [2.942 (1)–3.050 (1) Å; Table 1], agree well with those observed for other haloplumbates(II), for example, [PbBr3]- and [PbI3]- (Nagapetyan et al., 1988). All the Pb—Br bond lengths are shorter than the sum of the ionic radii (Pb2+ = 1.20 Å and Br- = 1.96 Å), probably due to partially covalent interactions. The Pb—Br bond lengths and Br—Pb—Br angles differ significantly from regular octahedral values. As a consequence, the {PbBr6} unit has barely C1 symmetry, with the triangular bromide faces (Br2, Br3 and Br4) shared by two adjacent polyhedra (Fig. 2). The nonbonding intramolecular Pb···Pb distances are 3.8437 (2) Å. The angle of Pb1i—Pb1—Pb1ii angle of 179.48 (1)° [symmetry codes: (i) x, -y+3/2, z-1/2; (ii) x, -y+3/2, z+1/2] indicates a linear development of the one-dimensional polymeric chains. Figs. 3 and 4 show the alternating hydrophilic and hydrophobic layers viewed along [100] and [001], respectively. In Fig. 3, the mode of mutual packing of the polymeric [{PbBr3}-]n chains and the benzyldecyldimethylammonium cations is presented. The polymeric [{PbBr3}-]n chains parallel to [100] and the >N+(CH3)2 moieties of the quaternary ammonium cations form hydrophilic layers through weak C—H···Br interactions (geometry given in Table 2). The hydrophobic layers are built of the benzyl and decyl groups of the ammonium cations, the mutual arrangement of which are defined by the three torsion angles N1—C4—C41—C46, C1—N1—C4—C41 and C11—C1—N1—C4 (Table 1), indicating synclinal/+synclinal/+synclinal conformations, respectively. The conformation of the decyl group is of zigzag type (all trans conformations). In the layers, the decyl chains are antiparallel to one another and are joined via weak C—H···π interactions belonging to category I of the Malone weak-hydrogen-bond classification (Malone et al., 1997). The C—H···π interactions (Fig. 5) are responsible for the self-assembly of ammonium cations in the hydrophobic layers (Table 2).
In conclusion, an organic–inorganic layered hybrid material based on benzyldecyldimethylammonium cations, which interact with adjacent [{PbBr3}-]n inorganic chains, has been obtained and structurally characterized. Due to a hydrophobic effect, the architecture of the bilayers, built of interdigitated ammonium cations interacting via weak C—H···π bridges, is preserved in the crystalline state irrespective of the counter-ion type. These properties predispose the ammonium cations to be utilized in the crystal engineering of layered materials as structure-directing agents (Rey et al., 2004; Shen et al., 2003). On the other hand, the incorporation of organic ions into inorganic frameworks opens the way for the engineering of a new class of layered multifunctional materials.