metal-organic compounds
Bis[4-(dimethylamino)pyridinium] octaaquachloridolanthanum(III) tetrachloride trihydrate
aUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, Faculté des Sciences Exactes, Département de Chimie, Université Mentouri de Constantine, 25000 Constantine, Algeria, and bLaboratoire de Chimie de Coordination, UPR-CNRS 8241, 205 route de Narbonne, 31077 Toulouse Cedex 4, France
*Correspondence e-mail: b_meriem80@yahoo.fr
The title organic–inorganic salt, (C7H11N2)2[LaCl(H2O)8]Cl4·3H2O, consists of two 4-(dimethylamino)pyridinium and one [La(H2O)8Cl]2+ cations, four chloride anions and three solvent water molecules. In the crystal, the various units are connected by N—H⋯Cl, O—H⋯Cl, O—H⋯O and N—H⋯O hydrogen bonds, forming a network of alternating organic and inorganic layers. The 4-(dimethylamino)pyridinium cations stack along the c axis, while the inorganic layers lie parallel to the ac plane. The chloride anions are located between these entities, forming hydrogen bonds with the NH atom of the pyridinium ions and the water molecules. There are also C—H⋯Cl hydrogen bonds present involving one of the 4-(dimethylamino)pyridinium cations, resulting in the formation of a three-dimensional supramolecular architecture.
Related literature
For common applications of organic–inorganic hybrid materials, see: Cui et al. (2000); Lacroix et al. (1994); Chakravarthy & Guloy (1997). For the crystal structures of compounds involving 4-(dimethylamino)pyridinium, see: Chao et al. (1977); Mayr-Stein & Bolte (2000); Lo & Ng (2008, 2009); Koon et al. (2009). For hydrogen-bond motifs, see: Bernstein et al. (1995).
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Agilent, 2011); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812040901/su2504sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812040901/su2504Isup2.hkl
4-(Dimethylamino)pyridine (1 mmol, 0.08g) and hydrochloric acid (1M) were added slowly to a solution of LaCl3.6H2O (1mmol, 0.08g). The mixture was refluxed at 353 K for about 1 h and then cooled to room temperature. Slow evaporation of the solvent at room temperature lead to the formation of colourless plate-like crystals of the title compound.
The H atoms of the coordinated water molecules were located in difference Fourier syntheses and were initially refined using distance restraints: O—H = 0.85 (2) Å, and H···H = 1.40 (2) Å, with Uiso(H) = 1.5Ueq(O). In the final cycles of
they were constrained to ride on their parent O atoms. The N-bound H atoms were located in a difference Fourier map but like the C-bound H atoms they were included in calculated positions and treated as riding atoms: N—H = 0.86 Å, C—H = 0.93 and 0.96 Å for CH and CH3 H atoms, respectively, with Uiso(H) = 1.5Ueq(C) for the methyl groups and = 1.2Ueq(N,C) for the other H atoms.Data collection: CrysAlis PRO (Agilent, 2011); cell
CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound, showing the atom-numbering. Displacement ellipsoids are drawn at the 50% probability level. The O—H···Cl hydrogen bonds are shown as double dashed lines. | |
Fig. 2. A view along the a axis of the three-dimensional hydrogen-bonded network of the title compound, showing the aggregation of the hydrogen-bonding motifs, R22(4), R22(8) and R62(12). Hydrogen bonds are drawn as dashed lines. [symmetry codes: (i) -x + 2, -y + 1, -z + 1; (ii) -x + 2, -y + 1, -z + 2; (iii) x - 1, y + 1, z]. |
(C7H11N2)2[LaCl(H2O)8]Cl4·3H2O | Z = 2 |
Mr = 760.69 | F(000) = 772 |
Triclinic, P1 | Dx = 1.597 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.6741 (4) Å | Cell parameters from 22004 reflections |
b = 12.6695 (7) Å | θ = 3.0–28.3° |
c = 14.3601 (7) Å | µ = 1.82 mm−1 |
α = 68.354 (5)° | T = 180 K |
β = 75.273 (4)° | Plate, colourless |
γ = 84.264 (4)° | 0.43 × 0.28 × 0.08 mm |
V = 1582.16 (15) Å3 |
Oxford Xcalibur Sapphire1 diffractometer | 7144 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 6518 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
Detector resolution: 8.2632 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ω scans | h = −12→12 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −16→16 |
Tmin = 0.548, Tmax = 0.864 | l = −18→18 |
33782 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.056 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0257P)2 + 0.4439P] where P = (Fo2 + 2Fc2)/3 |
7144 reflections | (Δ/σ)max = 0.003 |
320 parameters | Δρmax = 0.76 e Å−3 |
0 restraints | Δρmin = −1.03 e Å−3 |
(C7H11N2)2[LaCl(H2O)8]Cl4·3H2O | γ = 84.264 (4)° |
Mr = 760.69 | V = 1582.16 (15) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.6741 (4) Å | Mo Kα radiation |
b = 12.6695 (7) Å | µ = 1.82 mm−1 |
c = 14.3601 (7) Å | T = 180 K |
α = 68.354 (5)° | 0.43 × 0.28 × 0.08 mm |
β = 75.273 (4)° |
Oxford Xcalibur Sapphire1 diffractometer | 7144 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | 6518 reflections with I > 2σ(I) |
Tmin = 0.548, Tmax = 0.864 | Rint = 0.038 |
33782 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.056 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.76 e Å−3 |
7144 reflections | Δρmin = −1.03 e Å−3 |
320 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles |
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. |
x | y | z | Uiso*/Ueq | ||
La1 | 0.98356 (1) | 0.46700 (1) | 0.74019 (1) | 0.0192 (1) | |
Cl5 | 1.19118 (6) | 0.36620 (5) | 0.61364 (4) | 0.0342 (2) | |
O1 | 1.12672 (17) | 0.62452 (14) | 0.58572 (13) | 0.0428 (6) | |
O2 | 0.95865 (16) | 0.45114 (13) | 0.92689 (11) | 0.0297 (5) | |
O3 | 1.21742 (15) | 0.45676 (15) | 0.78883 (12) | 0.0346 (5) | |
O4 | 0.97883 (18) | 0.26017 (13) | 0.86085 (12) | 0.0361 (5) | |
O5 | 0.85068 (17) | 0.34195 (15) | 0.68566 (14) | 0.0436 (6) | |
O6 | 0.71719 (15) | 0.46052 (14) | 0.83325 (11) | 0.0343 (5) | |
O7 | 0.83661 (17) | 0.59127 (14) | 0.61058 (12) | 0.0374 (5) | |
O8 | 0.93133 (19) | 0.65745 (14) | 0.76941 (12) | 0.0383 (6) | |
N1 | 0.4241 (2) | 0.81063 (18) | 0.68388 (17) | 0.0442 (7) | |
N2 | 0.4146 (3) | 1.15628 (18) | 0.59093 (18) | 0.0461 (8) | |
C1 | 0.4218 (2) | 0.9227 (2) | 0.65305 (18) | 0.0322 (7) | |
C2 | 0.5477 (3) | 0.9873 (2) | 0.62318 (19) | 0.0370 (8) | |
C3 | 0.5401 (3) | 1.1014 (2) | 0.5933 (2) | 0.0416 (8) | |
C4 | 0.2929 (3) | 1.0995 (2) | 0.6179 (2) | 0.0479 (9) | |
C5 | 0.2927 (3) | 0.9862 (2) | 0.6480 (2) | 0.0436 (9) | |
C6 | 0.2940 (4) | 0.7466 (3) | 0.7103 (3) | 0.0670 (11) | |
C7 | 0.5568 (4) | 0.7456 (2) | 0.6892 (3) | 0.0618 (11) | |
N3 | 0.4436 (2) | 0.07909 (18) | 0.85825 (17) | 0.0432 (7) | |
N4 | 0.4840 (2) | −0.26628 (19) | 0.94889 (18) | 0.0473 (8) | |
C8 | 0.4561 (2) | −0.0328 (2) | 0.88707 (17) | 0.0334 (7) | |
C9 | 0.3378 (2) | −0.1043 (2) | 0.9155 (2) | 0.0395 (8) | |
C10 | 0.3548 (3) | −0.2174 (2) | 0.9445 (2) | 0.0465 (9) | |
C11 | 0.5998 (3) | −0.2022 (2) | 0.9229 (2) | 0.0444 (8) | |
C12 | 0.5908 (2) | −0.0884 (2) | 0.89126 (19) | 0.0378 (8) | |
C13 | 0.3050 (3) | 0.1370 (3) | 0.8590 (3) | 0.0613 (11) | |
C14 | 0.5691 (4) | 0.1508 (3) | 0.8259 (3) | 0.0609 (11) | |
Cl1 | 0.54269 (5) | 0.45268 (5) | 0.68027 (4) | 0.0344 (2) | |
Cl2 | 0.91549 (7) | 0.13843 (5) | 0.59452 (5) | 0.0433 (2) | |
Cl3 | 0.97602 (7) | 0.78867 (5) | 0.91759 (4) | 0.0388 (2) | |
Cl4 | 0.65967 (6) | 0.50633 (5) | 1.04257 (4) | 0.0340 (2) | |
O1W | 0.42022 (18) | 0.63535 (14) | 0.50183 (13) | 0.0391 (5) | |
O2W | 0.9449 (3) | 0.06121 (17) | 0.82838 (17) | 0.0733 (9) | |
O3W | 0.9016 (3) | 0.86973 (17) | 0.62175 (16) | 0.0676 (8) | |
H11 | 1.09960 | 0.68050 | 0.54710 | 0.0640* | |
H12 | 1.20950 | 0.61670 | 0.56780 | 0.0640* | |
H21 | 0.99110 | 0.39140 | 0.96650 | 0.0450* | |
H22 | 0.88380 | 0.47160 | 0.96220 | 0.0450* | |
H31 | 1.22900 | 0.46190 | 0.84310 | 0.0520* | |
H32 | 1.29400 | 0.44680 | 0.74990 | 0.0520* | |
H41 | 0.99590 | 0.24250 | 0.91960 | 0.0540* | |
H42 | 0.96630 | 0.19990 | 0.85180 | 0.0540* | |
H51 | 0.76890 | 0.35990 | 0.67430 | 0.0650* | |
H52 | 0.88930 | 0.29500 | 0.65740 | 0.0650* | |
H61 | 0.68810 | 0.48120 | 0.88450 | 0.0510* | |
H62 | 0.65100 | 0.46360 | 0.80330 | 0.0510* | |
H71 | 0.87490 | 0.61120 | 0.54710 | 0.0560* | |
H72 | 0.75130 | 0.57010 | 0.62470 | 0.0560* | |
H81 | 0.92450 | 0.71900 | 0.72020 | 0.0570* | |
H82 | 0.95110 | 0.67060 | 0.81790 | 0.0570* | |
H2 | 0.63590 | 0.95080 | 0.62430 | 0.0440* | |
H2A | 0.41240 | 1.22910 | 0.57180 | 0.0550* | |
H3 | 0.62340 | 1.14270 | 0.57390 | 0.0500* | |
H4 | 0.20700 | 1.13940 | 0.61560 | 0.0570* | |
H5 | 0.20670 | 0.94860 | 0.66590 | 0.0520* | |
H6A | 0.22750 | 0.76040 | 0.76690 | 0.1010* | |
H6B | 0.31660 | 0.66700 | 0.72960 | 0.1010* | |
H6C | 0.25220 | 0.77020 | 0.65180 | 0.1010* | |
H7A | 0.61200 | 0.75610 | 0.62060 | 0.0920* | |
H7B | 0.53530 | 0.66650 | 0.72600 | 0.0920* | |
H7C | 0.61060 | 0.77130 | 0.72440 | 0.0920* | |
H4A | 0.49240 | −0.33900 | 0.96850 | 0.0570* | |
H9 | 0.24700 | −0.07270 | 0.91420 | 0.0470* | |
H10 | 0.27570 | −0.26280 | 0.96190 | 0.0560* | |
H11A | 0.68830 | −0.23740 | 0.92680 | 0.0530* | |
H12A | 0.67300 | −0.04580 | 0.87200 | 0.0450* | |
H13A | 0.25120 | 0.10850 | 0.82580 | 0.0920* | |
H13B | 0.31940 | 0.21710 | 0.82290 | 0.0920* | |
H13C | 0.25350 | 0.12350 | 0.92890 | 0.0920* | |
H14A | 0.61670 | 0.13040 | 0.88130 | 0.0920* | |
H14B | 0.53970 | 0.22900 | 0.80830 | 0.0920* | |
H14C | 0.63330 | 0.14010 | 0.76690 | 0.0920* | |
H11W | 0.43610 | 0.61070 | 0.45270 | 0.0590* | |
H21W | 0.45310 | 0.59110 | 0.55210 | 0.0590* | |
H12W | 0.96180 | −0.00920 | 0.85550 | 0.1100* | |
H22W | 0.94090 | 0.07510 | 0.76670 | 0.1100* | |
H13W | 0.92930 | 0.93010 | 0.62480 | 0.1010* | |
H23W | 0.94670 | 0.86620 | 0.56370 | 0.1010* |
U11 | U22 | U33 | U12 | U13 | U23 | |
La1 | 0.0199 (1) | 0.0190 (1) | 0.0202 (1) | 0.0010 (1) | −0.0061 (1) | −0.0082 (1) |
Cl5 | 0.0366 (3) | 0.0363 (3) | 0.0326 (3) | 0.0084 (2) | −0.0054 (2) | −0.0195 (3) |
O1 | 0.0333 (9) | 0.0315 (10) | 0.0442 (10) | 0.0023 (7) | 0.0006 (7) | 0.0014 (8) |
O2 | 0.0320 (8) | 0.0342 (9) | 0.0248 (7) | 0.0070 (7) | −0.0090 (6) | −0.0129 (7) |
O3 | 0.0220 (7) | 0.0563 (11) | 0.0345 (8) | 0.0010 (7) | −0.0080 (6) | −0.0258 (8) |
O4 | 0.0578 (11) | 0.0232 (9) | 0.0292 (8) | −0.0007 (7) | −0.0161 (7) | −0.0077 (7) |
O5 | 0.0318 (8) | 0.0492 (11) | 0.0738 (13) | 0.0131 (8) | −0.0257 (8) | −0.0438 (10) |
O6 | 0.0251 (7) | 0.0533 (11) | 0.0307 (8) | 0.0001 (7) | −0.0078 (6) | −0.0214 (8) |
O7 | 0.0343 (8) | 0.0452 (11) | 0.0312 (8) | 0.0027 (7) | −0.0141 (7) | −0.0083 (8) |
O8 | 0.0621 (11) | 0.0244 (9) | 0.0325 (9) | 0.0036 (8) | −0.0162 (8) | −0.0124 (7) |
N1 | 0.0510 (13) | 0.0267 (12) | 0.0516 (13) | −0.0011 (10) | −0.0022 (10) | −0.0167 (10) |
N2 | 0.0626 (15) | 0.0242 (11) | 0.0532 (14) | 0.0006 (10) | −0.0205 (11) | −0.0114 (10) |
C1 | 0.0363 (12) | 0.0279 (12) | 0.0336 (12) | 0.0008 (10) | −0.0043 (9) | −0.0153 (10) |
C2 | 0.0324 (12) | 0.0374 (14) | 0.0396 (13) | 0.0019 (10) | −0.0075 (10) | −0.0130 (11) |
C3 | 0.0449 (14) | 0.0366 (15) | 0.0413 (14) | −0.0113 (12) | −0.0094 (11) | −0.0093 (12) |
C4 | 0.0444 (15) | 0.0405 (16) | 0.0643 (18) | 0.0127 (12) | −0.0178 (13) | −0.0249 (14) |
C5 | 0.0326 (12) | 0.0411 (16) | 0.0624 (17) | −0.0019 (11) | −0.0070 (12) | −0.0267 (14) |
C6 | 0.078 (2) | 0.0392 (18) | 0.082 (2) | −0.0244 (16) | −0.0016 (18) | −0.0250 (17) |
C7 | 0.080 (2) | 0.0334 (16) | 0.068 (2) | 0.0189 (15) | −0.0171 (17) | −0.0187 (15) |
N3 | 0.0473 (12) | 0.0294 (12) | 0.0466 (12) | 0.0040 (10) | −0.0076 (10) | −0.0096 (10) |
N4 | 0.0484 (13) | 0.0284 (12) | 0.0572 (14) | 0.0009 (10) | −0.0025 (11) | −0.0133 (11) |
C8 | 0.0348 (12) | 0.0335 (13) | 0.0300 (11) | 0.0025 (10) | −0.0070 (9) | −0.0102 (10) |
C9 | 0.0262 (11) | 0.0425 (15) | 0.0491 (15) | 0.0028 (10) | −0.0077 (10) | −0.0170 (12) |
C10 | 0.0385 (14) | 0.0438 (17) | 0.0563 (17) | −0.0104 (12) | −0.0038 (12) | −0.0193 (14) |
C11 | 0.0366 (13) | 0.0414 (16) | 0.0491 (15) | 0.0077 (11) | −0.0074 (11) | −0.0130 (13) |
C12 | 0.0267 (11) | 0.0382 (15) | 0.0451 (14) | −0.0026 (10) | −0.0058 (10) | −0.0123 (12) |
C13 | 0.072 (2) | 0.0458 (18) | 0.067 (2) | 0.0261 (16) | −0.0248 (17) | −0.0222 (16) |
C14 | 0.076 (2) | 0.0347 (17) | 0.0626 (19) | −0.0163 (15) | −0.0038 (16) | −0.0109 (15) |
Cl1 | 0.0247 (2) | 0.0445 (3) | 0.0366 (3) | 0.0009 (2) | −0.0099 (2) | −0.0158 (3) |
Cl2 | 0.0529 (4) | 0.0348 (3) | 0.0459 (3) | 0.0063 (3) | −0.0157 (3) | −0.0177 (3) |
Cl3 | 0.0485 (3) | 0.0358 (3) | 0.0342 (3) | 0.0040 (3) | −0.0174 (3) | −0.0110 (3) |
Cl4 | 0.0317 (3) | 0.0403 (3) | 0.0372 (3) | 0.0066 (2) | −0.0128 (2) | −0.0208 (3) |
O1W | 0.0455 (10) | 0.0304 (9) | 0.0404 (9) | 0.0044 (7) | −0.0106 (8) | −0.0125 (8) |
O2W | 0.138 (2) | 0.0342 (12) | 0.0592 (13) | 0.0006 (13) | −0.0433 (14) | −0.0167 (10) |
O3W | 0.1061 (18) | 0.0352 (12) | 0.0511 (12) | 0.0020 (11) | −0.0040 (12) | −0.0139 (10) |
La1—Cl5 | 2.8829 (6) | O1W—H11W | 0.8500 |
La1—O1 | 2.5585 (17) | O1W—H21W | 0.8500 |
La1—O2 | 2.5632 (15) | N4—H4A | 0.8600 |
La1—O3 | 2.5101 (15) | O2W—H22W | 0.8500 |
La1—O4 | 2.5505 (17) | O2W—H12W | 0.8500 |
La1—O5 | 2.5710 (19) | O3W—H13W | 0.8500 |
La1—O6 | 2.5775 (15) | O3W—H23W | 0.8500 |
La1—O7 | 2.5885 (17) | C1—C2 | 1.418 (4) |
La1—O8 | 2.5786 (19) | C1—C5 | 1.419 (4) |
O1—H11 | 0.7900 | C2—C3 | 1.348 (4) |
O1—H12 | 0.7800 | C4—C5 | 1.338 (4) |
O2—H21 | 0.8500 | C2—H2 | 0.9300 |
O2—H22 | 0.8500 | C3—H3 | 0.9300 |
O3—H31 | 0.8400 | C4—H4 | 0.9300 |
O3—H32 | 0.8400 | C5—H5 | 0.9300 |
O4—H41 | 0.8400 | C6—H6B | 0.9600 |
O4—H42 | 0.8500 | C6—H6C | 0.9600 |
O5—H51 | 0.8400 | C6—H6A | 0.9600 |
O5—H52 | 0.8500 | C7—H7C | 0.9600 |
O6—H61 | 0.8400 | C7—H7A | 0.9600 |
O6—H62 | 0.8500 | C7—H7B | 0.9600 |
O7—H71 | 0.8400 | C8—C9 | 1.412 (3) |
O7—H72 | 0.8400 | C8—C12 | 1.422 (3) |
O8—H81 | 0.8500 | C9—C10 | 1.342 (4) |
O8—H82 | 0.8400 | C11—C12 | 1.343 (4) |
N1—C1 | 1.322 (4) | C9—H9 | 0.9300 |
N1—C6 | 1.456 (5) | C10—H10 | 0.9300 |
N1—C7 | 1.458 (4) | C11—H11A | 0.9300 |
N2—C3 | 1.339 (4) | C12—H12A | 0.9300 |
N2—C4 | 1.336 (4) | C13—H13B | 0.9600 |
N2—H2A | 0.8600 | C13—H13A | 0.9600 |
N3—C8 | 1.324 (4) | C13—H13C | 0.9600 |
N3—C14 | 1.462 (5) | C14—H14C | 0.9600 |
N3—C13 | 1.462 (4) | C14—H14A | 0.9600 |
N4—C10 | 1.344 (4) | C14—H14B | 0.9600 |
N4—C11 | 1.341 (4) | ||
Cl5—La1—O1 | 70.83 (4) | C4—N2—H2A | 120.00 |
Cl5—La1—O2 | 130.08 (4) | C8—N3—C14 | 121.1 (2) |
Cl5—La1—O3 | 72.34 (4) | C13—N3—C14 | 116.7 (3) |
Cl5—La1—O4 | 78.77 (4) | C8—N3—C13 | 122.3 (2) |
Cl5—La1—O5 | 71.63 (4) | C10—N4—C11 | 120.3 (3) |
Cl5—La1—O6 | 142.42 (4) | H11W—O1W—H21W | 112.00 |
Cl5—La1—O7 | 101.27 (4) | C11—N4—H4A | 120.00 |
Cl5—La1—O8 | 139.80 (4) | C10—N4—H4A | 120.00 |
O1—La1—O2 | 122.67 (5) | H12W—O2W—H22W | 108.00 |
O1—La1—O3 | 77.88 (5) | H13W—O3W—H23W | 107.00 |
O1—La1—O4 | 146.68 (6) | C2—C1—C5 | 115.6 (2) |
O1—La1—O5 | 112.45 (6) | N1—C1—C2 | 122.3 (2) |
O1—La1—O6 | 130.10 (5) | N1—C1—C5 | 122.0 (2) |
O1—La1—O7 | 65.71 (5) | C1—C2—C3 | 120.3 (3) |
O1—La1—O8 | 70.66 (6) | N2—C3—C2 | 121.1 (3) |
O2—La1—O3 | 65.87 (5) | N2—C4—C5 | 121.1 (3) |
O2—La1—O4 | 68.56 (5) | C1—C5—C4 | 120.9 (3) |
O2—La1—O5 | 124.62 (6) | C3—C2—H2 | 120.00 |
O2—La1—O6 | 70.04 (5) | C1—C2—H2 | 120.00 |
O2—La1—O7 | 128.53 (5) | C2—C3—H3 | 119.00 |
O2—La1—O8 | 65.90 (5) | N2—C3—H3 | 119.00 |
O3—La1—O4 | 80.24 (6) | N2—C4—H4 | 119.00 |
O3—La1—O5 | 135.98 (6) | C5—C4—H4 | 119.00 |
O3—La1—O6 | 135.89 (5) | C4—C5—H5 | 119.00 |
O3—La1—O7 | 142.78 (6) | C1—C5—H5 | 120.00 |
O3—La1—O8 | 88.74 (6) | H6A—C6—H6C | 109.00 |
O4—La1—O5 | 68.67 (6) | N1—C6—H6B | 109.00 |
O4—La1—O6 | 82.76 (6) | N1—C6—H6A | 109.00 |
O4—La1—O7 | 135.63 (6) | H6A—C6—H6B | 109.00 |
O4—La1—O8 | 133.68 (5) | N1—C6—H6C | 109.00 |
O5—La1—O6 | 71.22 (6) | H6B—C6—H6C | 109.00 |
O5—La1—O7 | 69.44 (6) | H7B—C7—H7C | 109.00 |
O5—La1—O8 | 135.28 (6) | N1—C7—H7A | 109.00 |
O6—La1—O7 | 70.55 (5) | N1—C7—H7B | 109.00 |
O6—La1—O8 | 74.49 (6) | H7A—C7—H7B | 109.00 |
O7—La1—O8 | 72.67 (6) | H7A—C7—H7C | 109.00 |
La1—O1—H11 | 130.00 | N1—C7—H7C | 110.00 |
La1—O1—H12 | 119.00 | N3—C8—C9 | 122.6 (2) |
H11—O1—H12 | 111.00 | N3—C8—C12 | 121.6 (2) |
La1—O2—H21 | 117.00 | C9—C8—C12 | 115.8 (2) |
La1—O2—H22 | 123.00 | C8—C9—C10 | 120.8 (2) |
H21—O2—H22 | 108.00 | N4—C10—C9 | 121.3 (3) |
La1—O3—H31 | 126.00 | N4—C11—C12 | 121.5 (3) |
La1—O3—H32 | 121.00 | C8—C12—C11 | 120.3 (2) |
H31—O3—H32 | 113.00 | C10—C9—H9 | 120.00 |
La1—O4—H41 | 121.00 | C8—C9—H9 | 120.00 |
La1—O4—H42 | 131.00 | N4—C10—H10 | 119.00 |
H41—O4—H42 | 109.00 | C9—C10—H10 | 119.00 |
La1—O5—H51 | 121.00 | N4—C11—H11A | 119.00 |
La1—O5—H52 | 126.00 | C12—C11—H11A | 119.00 |
H51—O5—H52 | 110.00 | C11—C12—H12A | 120.00 |
La1—O6—H61 | 122.00 | C8—C12—H12A | 120.00 |
La1—O6—H62 | 122.00 | N3—C13—H13B | 109.00 |
H61—O6—H62 | 112.00 | H13A—C13—H13C | 109.00 |
La1—O7—H71 | 119.00 | N3—C13—H13C | 109.00 |
La1—O7—H72 | 114.00 | H13A—C13—H13B | 110.00 |
H71—O7—H72 | 112.00 | N3—C13—H13A | 110.00 |
La1—O8—H81 | 121.00 | H13B—C13—H13C | 109.00 |
La1—O8—H82 | 124.00 | N3—C14—H14C | 110.00 |
H81—O8—H82 | 111.00 | H14A—C14—H14C | 109.00 |
C1—N1—C6 | 121.2 (2) | H14B—C14—H14C | 109.00 |
C1—N1—C7 | 121.9 (2) | H14A—C14—H14B | 109.00 |
C6—N1—C7 | 116.8 (3) | N3—C14—H14A | 109.00 |
C3—N2—C4 | 121.0 (2) | N3—C14—H14B | 109.00 |
C3—N2—H2A | 119.00 | ||
C6—N1—C1—C2 | −177.6 (3) | C5—C1—C2—C3 | 0.5 (4) |
C7—N1—C1—C2 | −0.1 (4) | N1—C1—C2—C3 | −179.3 (2) |
C6—N1—C1—C5 | 2.6 (4) | C2—C1—C5—C4 | −0.8 (4) |
C7—N1—C1—C5 | −179.9 (3) | N1—C1—C5—C4 | 179.1 (2) |
C3—N2—C4—C5 | 0.0 (4) | C1—C2—C3—N2 | −0.1 (4) |
C4—N2—C3—C2 | −0.2 (4) | N2—C4—C5—C1 | 0.5 (4) |
C13—N3—C8—C9 | 3.4 (4) | C12—C8—C9—C10 | 0.1 (4) |
C13—N3—C8—C12 | −176.6 (3) | N3—C8—C9—C10 | −179.9 (2) |
C14—N3—C8—C12 | 2.2 (4) | N3—C8—C12—C11 | 178.6 (2) |
C14—N3—C8—C9 | −177.9 (3) | C9—C8—C12—C11 | −1.4 (3) |
C11—N4—C10—C9 | −0.8 (4) | C8—C9—C10—N4 | 1.0 (4) |
C10—N4—C11—C12 | −0.5 (4) | N4—C11—C12—C8 | 1.6 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···Cl5i | 0.86 | 2.71 | 3.314 (3) | 129 |
N2—H2A···O1Wii | 0.86 | 2.24 | 2.909 (3) | 134 |
N4—H4A···Cl4iii | 0.86 | 2.51 | 3.213 (2) | 140 |
N4—H4A···Cl4iv | 0.86 | 2.77 | 3.418 (3) | 133 |
O1—H11···Cl2v | 0.79 | 2.46 | 3.2316 (19) | 165 |
O1—H12···O1Wvi | 0.78 | 2.01 | 2.784 (2) | 167 |
O2W—H12W···Cl3iii | 0.85 | 2.38 | 3.222 (2) | 169 |
O3W—H13W···Cl2vii | 0.85 | 2.51 | 3.293 (2) | 153 |
O2—H21···Cl3viii | 0.85 | 2.32 | 3.1537 (17) | 166 |
O1W—H21W···Cl1 | 0.85 | 2.31 | 3.1538 (19) | 173 |
O2—H22···Cl4 | 0.85 | 2.27 | 3.1023 (17) | 168 |
O2W—H22W···Cl2 | 0.85 | 2.37 | 3.213 (2) | 172 |
O3W—H23W···Cl2v | 0.85 | 2.34 | 3.193 (2) | 176 |
O3—H31···Cl4viii | 0.84 | 2.34 | 3.1471 (17) | 160 |
O3—H32···Cl1vi | 0.84 | 2.36 | 3.1413 (16) | 157 |
O4—H41···Cl3viii | 0.84 | 2.31 | 3.1459 (17) | 173 |
O4—H42···O2W | 0.85 | 1.95 | 2.791 (3) | 178 |
O5—H51···Cl1 | 0.84 | 2.38 | 3.1707 (19) | 158 |
O5—H52···Cl2 | 0.85 | 2.43 | 3.241 (2) | 160 |
O6—H61···Cl4 | 0.84 | 2.35 | 3.1708 (17) | 164 |
O6—H62···Cl1 | 0.85 | 2.32 | 3.1250 (16) | 158 |
O7—H71···Cl5v | 0.84 | 2.46 | 3.1402 (17) | 139 |
O7—H72···Cl1 | 0.84 | 2.41 | 3.2287 (18) | 162 |
O8—H81···O3W | 0.85 | 1.94 | 2.786 (3) | 172 |
O8—H82···Cl3 | 0.84 | 2.48 | 3.2711 (19) | 156 |
C11—H11A···Cl3iii | 0.93 | 2.80 | 3.612 (3) | 147 |
C14—H14B···Cl1 | 0.96 | 2.75 | 3.639 (4) | 154 |
Symmetry codes: (i) x−1, y+1, z; (ii) −x+1, −y+2, −z+1; (iii) x, y−1, z; (iv) −x+1, −y, −z+2; (v) −x+2, −y+1, −z+1; (vi) x+1, y, z; (vii) x, y+1, z; (viii) −x+2, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | (C7H11N2)2[LaCl(H2O)8]Cl4·3H2O |
Mr | 760.69 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 180 |
a, b, c (Å) | 9.6741 (4), 12.6695 (7), 14.3601 (7) |
α, β, γ (°) | 68.354 (5), 75.273 (4), 84.264 (4) |
V (Å3) | 1582.16 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.82 |
Crystal size (mm) | 0.43 × 0.28 × 0.08 |
Data collection | |
Diffractometer | Oxford Xcalibur Sapphire1 diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2011) |
Tmin, Tmax | 0.548, 0.864 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 33782, 7144, 6518 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.056, 1.11 |
No. of reflections | 7144 |
No. of parameters | 320 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.76, −1.03 |
Computer programs: CrysAlis PRO (Agilent, 2011), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···Cl5i | 0.8600 | 2.7100 | 3.314 (3) | 129.00 |
N2—H2A···O1Wii | 0.8600 | 2.2400 | 2.909 (3) | 134.00 |
N4—H4A···Cl4iii | 0.8600 | 2.5100 | 3.213 (2) | 140.00 |
N4—H4A···Cl4iv | 0.8600 | 2.7700 | 3.418 (3) | 133.00 |
O1—H11···Cl2v | 0.7900 | 2.4600 | 3.2316 (19) | 165.00 |
O1—H12···O1Wvi | 0.7800 | 2.0100 | 2.784 (2) | 167.00 |
O2W—H12W···Cl3iii | 0.8500 | 2.3800 | 3.222 (2) | 169.00 |
O3W—H13W···Cl2vii | 0.8500 | 2.5100 | 3.293 (2) | 153.00 |
O2—H21···Cl3viii | 0.8500 | 2.3200 | 3.1537 (17) | 166.00 |
O1W—H21W···Cl1 | 0.8500 | 2.3100 | 3.1538 (19) | 173.00 |
O2—H22···Cl4 | 0.8500 | 2.2700 | 3.1023 (17) | 168.00 |
O2W—H22W···Cl2 | 0.8500 | 2.3700 | 3.213 (2) | 172.00 |
O3W—H23W···Cl2v | 0.8500 | 2.3400 | 3.193 (2) | 176.00 |
O3—H31···Cl4viii | 0.8400 | 2.3400 | 3.1471 (17) | 160.00 |
O3—H32···Cl1vi | 0.8400 | 2.3600 | 3.1413 (16) | 157.00 |
O4—H41···Cl3viii | 0.8400 | 2.3100 | 3.1459 (17) | 173.00 |
O4—H42···O2W | 0.8500 | 1.9500 | 2.791 (3) | 178.00 |
O5—H51···Cl1 | 0.8400 | 2.3800 | 3.1707 (19) | 158.00 |
O5—H52···Cl2 | 0.8500 | 2.4300 | 3.241 (2) | 160.00 |
O6—H61···Cl4 | 0.8400 | 2.3500 | 3.1708 (17) | 164.00 |
O6—H62···Cl1 | 0.8500 | 2.3200 | 3.1250 (16) | 158.00 |
O7—H71···Cl5v | 0.8400 | 2.4600 | 3.1402 (17) | 139.00 |
O7—H72···Cl1 | 0.8400 | 2.4100 | 3.2287 (18) | 162.00 |
O8—H81···O3W | 0.8500 | 1.9400 | 2.786 (3) | 172.00 |
O8—H82···Cl3 | 0.8400 | 2.4800 | 3.2711 (19) | 156.00 |
C11—H11A···Cl3iii | 0.9300 | 2.8000 | 3.612 (3) | 147.00 |
C14—H14B···Cl1 | 0.9600 | 2.7500 | 3.639 (4) | 154.00 |
Symmetry codes: (i) x−1, y+1, z; (ii) −x+1, −y+2, −z+1; (iii) x, y−1, z; (iv) −x+1, −y, −z+2; (v) −x+2, −y+1, −z+1; (vi) x+1, y, z; (vii) x, y+1, z; (viii) −x+2, −y+1, −z+2. |
Acknowledgements
Technical support (X-ray measurements) from the Laboratory of Coordination Chemistry, UPR-CNRS 8241, Toulouse, is gratefully acknowledged.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Organic–inorganic hybrid compounds are of great interest because of their special magnetic (Cui et al., 2000), electronic (Lacroix et al., 1994) and optoelectronic properties (Chakravarthy & Guloy, 1997). It is expected that the packing interactions that govern the crystal organization will be influenced by the features of the cations and anions, which in turn will affect specific properties of the solids. The supramolecular networks become especially interesting when the cation and anion can participate in hydrogen-bonding. As part of a study of the effect of cations and anions on the crystal structures of organic–inorganic compounds, we report herein on the crystal structure of the title compound. This type of hybrid material generally exhibits a structure consisting of alternating organic–inorganic layers, characterized by isolated anions as found with other compounds involving 4-(dimethylamino)pyridinium (Chao et al., 1977; Mayr-Stein & Bolte, 2000; Lo and Ng, 2008, 2009; Koon et al., 2009).
The title structure contains three cations, one inorganic [La(H2O)8Cl]2+ cation and two independent monoprotonated 4-(dimethylamino)pyridinium cations, four chloride anions and three water molecules (Fig. 1). Atom La1 is coordinated by eight water molecules with distances ranging from 2.510 (1) to 2.588 (2) Å, and by one chloride ion with La1—Cl5 = 2.8829 (6) Å. The overall structure consists of layers stacked along the c axis. The chloride anions are located between the organic entities forming hydrogen bonds with the NH atoms of the pyridinium ions and the water molecules (Table 1).
Each Cl- anion accepts hydrogen bonds which can be divided into two groups. The first group involves hydrogen bonds linking Cl4- with two organic cations via the pyridinium N4—H4A H atom (Table 1), generating centrosymmetric R22(4) motifs (Bernstein et al., 1995) along the c axis at y = 1/2. The second 4-(dimethylamino)pyridinium molecule is linked to one [La(H2O)8Cl]2+ cation through an intermolecular N2—H2A···Cl5i hydrogen bond [symmetry code: (i) x - 1, y + 1, z] which can be described by the graph-set motif D(3). The second type of hydrogen bond, in which the Cl- anion is the acceptor, is a linkage between the water molecules (free and coordinated) and the Cl- anion. The inorganic [La(H2O)8Cl]2+ cations are indirectly linked via Cl- anions through intermolecular O—H···Cl and O—H···O hydrogen bonds generating cycles R22(8) and R62(12), which connect cationic and anionic entities (Fig. 2 and Table 1).
In the 4-(dimethylamino)pyridinium cations the N—C bond linking the dimethylamino substituent to the pyridinium ring is characteristically short [1.321 (3) and 1.324 (3)Å]. The dimethylamino group lies close to the plane of the pyridinium ring with a dihedral angle, between the pyridinium and the dimethylamine plane (C/N/C atoms), of 3.5 (3) and 2.0 (3)°.
On the structural level, the atomic arrangement of this material consists of a network of alternating organic–inorganic layers. The chloride anions are located between these entities forming hydrogen bonds with the NH atoms of the pyridinium ions and the water molecules. There are also C—H···Cl interactions present (Table 1) involving one of the 4-(dimethylamino)pyridinium cations, which results in the formation of a three-dimensional supramolecular architecture.