metal-organic compounds
Tris[4-(dimethylamino)pyridinium][(bis-μ-dichlorido)-decaaquadichloridodineodymium(III)] pentachloride dihydrate
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 compound, (C7H11N2)3[Nd2Cl4(H2O)10]Cl5·2H2O, consists of three 4-(dimethylamino)pyridinium cations, one of which is disordered about an inversion center, one [Nd2Cl4(H2O)10]2+ dication possessing inversion symmetry, five chloride anions, one of which is disordered over two inversion centers, and two lattice water molecules. The 4-(dimethylamino)pyridinium cations are protonated at the pyridine N atoms and form N—H⋯Cl hydrogen bonds with Cl− counter-ions. The dimethylamino groups (C/N/C) lie close to the plane of the pyridinium rings, making dihedral angles of 1.6 (6)° and 6.5 (3)°. In the crystal, the [Nd2Cl4(H2O)10]2+ dications are linked via O—H⋯O and O—H⋯Cl hydrogen bonds, forming sheets lying parallel to the bc plane. These sheets are linked via O—H⋯Cl hydrogen bonds, forming a three-dimensional network. The 4-(dimethylamino)pyridinium cations are located in the cavities and linked to the framework by C—H⋯Cl interactions.
Related literature
For the crystal structures of complexes involving 4-(dimethylamino)pyridinium, see: Chao et al. (1977); Mayr-Stein & Bolte (2000); Lo & Ng (2008, 2009); Koon et al. (2009); Benslimane et al. (2012). 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/S1600536812041724/su2506sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812041724/su2506Isup2.hkl
4-(Dimethylamino)pyridine (1 mmol, 0.08g for) and hydrochloric acid (1M) was added slowly to an aqueous solution of NdCl3.6H2O (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 4-(dimethylamino)pyridinium cation (B) was found to be disordered about an inversion center. The disorder was treated using the PART -1 instruction in SHELXL97 (Sheldrick, 2008.) Restraints using the SAME instruction were applied to maintain a reasonable geometry. The ADP's were also restrained to have similar values. The occupancy factors were fixed at 0.5. 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 last cycles of
they were constrained to ride on their parent O atoms. The N-bound and C-bound H atoms were included in calculated positions and refined using a riding model: N-H = 0.88 Å, C-H = 0.95 (aromatic), 0.98 (methyl) Å, with Uiso(H) = 1.5Ueq(C) for the methyl groups and 1.2Ueq(C) for 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 scheme. Displacement ellipsoids are drawn at the 50% probability level. O-H···Cl and N-H···Cl hydrogen bonds are shown as double dashed lines [symmetry code: (i) -x+1, -y+1, -z]. The 4-(dimethylamino)pyridinium cations consists of ordered (A) and disordered (B) entities. The organic entity (B) is disordered about an inversion center. | |
Fig. 2. A view along the b axis of the hydrogen-bonded network of the title compound, showing the formation of ring motifs via O-H···Cl and N-H···Cl hydrogen-bonds (dashed lines) [symmetry codes: (i) -x+1, -y+1, 1-z); (ii) -x, -y+1, -z+1; (iii) -x+2,-y+1, -z]. | |
Fig. 3. A view along the a axis of the hydrogen-bonded network of the title compound, showing the formation of ring motifs via O-H···Cl hydrogen-bonds (dashed lines) [symmetry codes: (i) x, y+1, z); (ii) -x+1, -y+1, -z+1]. |
(C7H11N2)3[Nd2Cl4(H2O)10]Cl5·2H2O | Z = 1 |
Mr = 1193.26 | F(000) = 594 |
Triclinic, P1 | Dx = 1.778 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.5172 (4) Å | Cell parameters from 15563 reflections |
b = 10.7739 (5) Å | θ = 3.0–28.5° |
c = 11.9976 (5) Å | µ = 2.90 mm−1 |
α = 74.855 (4)° | T = 180 K |
β = 69.780 (4)° | Platelet, colourless |
γ = 85.075 (4)° | 0.36 × 0.22 × 0.16 mm |
V = 1114.28 (8) Å3 |
Agilent Xcalibur Sapphire1 diffractometer | 4551 independent reflections |
Radiation source: fine-focus sealed tube | 4088 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
Detector resolution: 8.2632 pixels mm-1 | θmax = 26.4°, θmin = 3.0° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −13→13 |
Tmin = 0.475, Tmax = 0.633 | l = −14→14 |
23060 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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.068 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0222P)2 + 2.5244P] where P = (Fo2 + 2Fc2)/3 |
4551 reflections | (Δ/σ)max < 0.001 |
210 parameters | Δρmax = 0.95 e Å−3 |
0 restraints | Δρmin = −1.76 e Å−3 |
(C7H11N2)3[Nd2Cl4(H2O)10]Cl5·2H2O | γ = 85.075 (4)° |
Mr = 1193.26 | V = 1114.28 (8) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.5172 (4) Å | Mo Kα radiation |
b = 10.7739 (5) Å | µ = 2.90 mm−1 |
c = 11.9976 (5) Å | T = 180 K |
α = 74.855 (4)° | 0.36 × 0.22 × 0.16 mm |
β = 69.780 (4)° |
Agilent Xcalibur Sapphire1 diffractometer | 4551 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | 4088 reflections with I > 2σ(I) |
Tmin = 0.475, Tmax = 0.633 | Rint = 0.034 |
23060 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.068 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.95 e Å−3 |
4551 reflections | Δρmin = −1.76 e Å−3 |
210 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 | Occ. (<1) | |
Nd1 | 0.48488 (2) | 0.51184 (2) | 0.18894 (2) | 0.0276 (1) | |
Cl1 | 0.49345 (10) | 0.66402 (8) | −0.04455 (7) | 0.0285 (3) | |
Cl11 | 0.79337 (11) | 0.51474 (10) | 0.06963 (10) | 0.0421 (3) | |
O11 | 0.2356 (3) | 0.4935 (3) | 0.1820 (3) | 0.0523 (10) | |
O12 | 0.4711 (4) | 0.7381 (3) | 0.1875 (3) | 0.0550 (12) | |
O13 | 0.2865 (6) | 0.5264 (5) | 0.3836 (3) | 0.111 (2) | |
O14 | 0.5955 (5) | 0.5337 (3) | 0.3421 (3) | 0.0655 (13) | |
O15 | 0.4930 (4) | 0.2980 (3) | 0.3127 (2) | 0.0432 (9) | |
N31 | −0.00665 (19) | −0.11195 (8) | 1.07329 (14) | 0.0521 (19) | 0.500 |
N32 | 0.0280 (4) | 0.25416 (14) | 0.8530 (3) | 0.0521 (19) | 0.500 |
C31 | 0.00000 | 0.00000 | 1.00000 | 0.0413 (12) | |
C32 | 0.14423 (11) | 0.0583 (2) | 0.9163 (3) | 0.0413 (12) | 0.500 |
C33 | 0.1501 (3) | 0.1728 (2) | 0.8432 (3) | 0.0413 (12) | 0.500 |
C34 | −0.1136 (3) | 0.20203 (19) | 0.9333 (4) | 0.0413 (12) | 0.500 |
C35 | −0.12188 (16) | 0.08640 (17) | 1.0072 (3) | 0.0413 (12) | 0.500 |
C36 | −0.1501 (3) | −0.1736 (2) | 1.1571 (3) | 0.098 (5) | 0.500 |
C37 | 0.1136 (3) | −0.20276 (19) | 1.0670 (4) | 0.098 (5) | 0.500 |
N11 | 0.9754 (4) | −0.0990 (4) | 0.3994 (4) | 0.0544 (14) | |
N12 | 1.0009 (6) | 0.2582 (4) | 0.1682 (4) | 0.0614 (18) | |
C11 | 0.9844 (4) | 0.0171 (4) | 0.3236 (4) | 0.0362 (12) | |
C12 | 1.1192 (5) | 0.0674 (5) | 0.2318 (4) | 0.0488 (16) | |
C13 | 1.1231 (6) | 0.1873 (5) | 0.1574 (4) | 0.0572 (17) | |
C14 | 0.8722 (7) | 0.2147 (5) | 0.2527 (6) | 0.068 (2) | |
C15 | 0.8601 (5) | 0.0985 (5) | 0.3294 (5) | 0.0567 (17) | |
C16 | 0.8358 (7) | −0.1516 (6) | 0.4911 (6) | 0.083 (2) | |
C17 | 1.1055 (7) | −0.1817 (6) | 0.3913 (7) | 0.088 (3) | |
Cl3 | 0.51832 (13) | 0.21187 (10) | 0.57337 (9) | 0.0429 (3) | |
Cl4 | 0.07818 (14) | 0.49945 (15) | 0.64240 (11) | 0.0727 (5) | |
Cl6 | 0.50000 | 0.00000 | 0.00000 | 0.0420 (5) | |
O1W | 0.5008 (5) | 0.0727 (3) | 0.2546 (3) | 0.0672 (13) | |
H111 | 0.14610 | 0.49370 | 0.23020 | 0.0790* | |
H112 | 0.23500 | 0.49450 | 0.11120 | 0.0790* | |
H121 | 0.48380 | 0.80390 | 0.12760 | 0.0820* | |
H122 | 0.46940 | 0.76020 | 0.25090 | 0.0820* | |
H131 | 0.23040 | 0.55930 | 0.34170 | 0.1670* | |
H132 | 0.23300 | 0.51220 | 0.45890 | 0.1670* | |
H141 | 0.55620 | 0.47610 | 0.40730 | 0.0980* | |
H142 | 0.68760 | 0.51610 | 0.31140 | 0.0980* | |
H151 | 0.50200 | 0.22980 | 0.28800 | 0.0650* | |
H152 | 0.50060 | 0.28000 | 0.38360 | 0.0650* | |
H32 | 0.23430 | 0.01240 | 0.91520 | 0.0490* | 0.500 |
H32A | 0.03790 | 0.33510 | 0.81110 | 0.0620* | 0.500 |
H33 | 0.24240 | 0.20160 | 0.78040 | 0.0490* | 0.500 |
H34 | −0.20210 | 0.25030 | 0.93380 | 0.0490* | 0.500 |
H35 | −0.21530 | 0.05930 | 1.06910 | 0.0490* | 0.500 |
H36A | −0.13100 | −0.25800 | 1.20490 | 0.1460* | 0.500 |
H36B | −0.21150 | −0.18420 | 1.10930 | 0.1460* | 0.500 |
H36C | −0.20330 | −0.11950 | 1.21270 | 0.1460* | 0.500 |
H37A | 0.07940 | −0.28050 | 1.13340 | 0.1460* | 0.500 |
H37B | 0.19810 | −0.16470 | 1.07540 | 0.1460* | 0.500 |
H37C | 0.14530 | −0.22520 | 0.98780 | 0.1460* | 0.500 |
H12 | 1.00550 | 0.33520 | 0.11860 | 0.0740* | |
H12A | 1.20780 | 0.01730 | 0.22180 | 0.0590* | |
H13 | 1.21510 | 0.22070 | 0.09680 | 0.0690* | |
H14 | 0.78600 | 0.26750 | 0.25900 | 0.0820* | |
H15 | 0.76560 | 0.07030 | 0.38910 | 0.0680* | |
H16A | 0.78800 | −0.08910 | 0.53910 | 0.1240* | |
H16B | 0.85550 | −0.23100 | 0.54560 | 0.1240* | |
H16C | 0.76920 | −0.17030 | 0.45080 | 0.1240* | |
H17A | 1.14130 | −0.20270 | 0.31140 | 0.1320* | |
H17B | 1.07790 | −0.26110 | 0.45660 | 0.1320* | |
H17C | 1.18490 | −0.13720 | 0.40040 | 0.1320* | |
H11W | 0.49450 | −0.00300 | 0.30050 | 0.1000* | |
H12W | 0.50320 | 0.06830 | 0.18430 | 0.1000* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Nd1 | 0.0410 (1) | 0.0217 (1) | 0.0170 (1) | 0.0017 (1) | −0.0077 (1) | −0.0030 (1) |
Cl1 | 0.0433 (5) | 0.0198 (4) | 0.0207 (4) | 0.0021 (3) | −0.0107 (3) | −0.0029 (3) |
Cl11 | 0.0362 (5) | 0.0397 (5) | 0.0472 (6) | −0.0027 (4) | −0.0187 (4) | 0.0017 (4) |
O11 | 0.0269 (15) | 0.070 (2) | 0.0489 (18) | 0.0026 (14) | 0.0025 (13) | −0.0175 (16) |
O12 | 0.114 (3) | 0.0252 (14) | 0.0345 (16) | 0.0054 (16) | −0.0362 (18) | −0.0082 (12) |
O13 | 0.150 (5) | 0.107 (4) | 0.0282 (19) | 0.053 (3) | 0.013 (2) | −0.011 (2) |
O14 | 0.118 (3) | 0.0475 (19) | 0.0464 (19) | 0.008 (2) | −0.049 (2) | −0.0110 (15) |
O15 | 0.075 (2) | 0.0263 (14) | 0.0281 (14) | −0.0017 (14) | −0.0222 (14) | 0.0009 (11) |
N31 | 0.061 (4) | 0.033 (3) | 0.056 (3) | −0.002 (3) | −0.021 (3) | 0.002 (2) |
N32 | 0.061 (4) | 0.033 (3) | 0.056 (3) | −0.002 (3) | −0.021 (3) | 0.002 (2) |
C31 | 0.031 (2) | 0.041 (2) | 0.047 (2) | 0.0040 (17) | −0.0102 (17) | −0.0080 (18) |
C32 | 0.031 (2) | 0.041 (2) | 0.047 (2) | 0.0040 (17) | −0.0102 (17) | −0.0080 (18) |
C33 | 0.031 (2) | 0.041 (2) | 0.047 (2) | 0.0040 (17) | −0.0102 (17) | −0.0080 (18) |
C34 | 0.031 (2) | 0.041 (2) | 0.047 (2) | 0.0040 (17) | −0.0102 (17) | −0.0080 (18) |
C35 | 0.031 (2) | 0.041 (2) | 0.047 (2) | 0.0040 (17) | −0.0102 (17) | −0.0080 (18) |
C36 | 0.091 (8) | 0.081 (8) | 0.096 (9) | 0.004 (6) | −0.028 (7) | 0.014 (7) |
C37 | 0.091 (8) | 0.081 (8) | 0.096 (9) | 0.004 (6) | −0.028 (7) | 0.014 (7) |
N11 | 0.050 (2) | 0.044 (2) | 0.060 (3) | −0.0031 (18) | −0.0208 (19) | 0.0069 (19) |
N12 | 0.093 (4) | 0.035 (2) | 0.064 (3) | −0.006 (2) | −0.042 (3) | −0.0022 (19) |
C11 | 0.035 (2) | 0.033 (2) | 0.037 (2) | −0.0004 (16) | −0.0106 (17) | −0.0046 (17) |
C12 | 0.034 (2) | 0.054 (3) | 0.051 (3) | −0.001 (2) | −0.008 (2) | −0.009 (2) |
C13 | 0.061 (3) | 0.060 (3) | 0.043 (3) | −0.027 (3) | −0.009 (2) | −0.003 (2) |
C14 | 0.073 (4) | 0.048 (3) | 0.080 (4) | 0.024 (3) | −0.030 (3) | −0.013 (3) |
C15 | 0.041 (3) | 0.056 (3) | 0.060 (3) | 0.012 (2) | −0.009 (2) | −0.007 (2) |
C16 | 0.074 (4) | 0.084 (4) | 0.066 (4) | −0.033 (3) | −0.018 (3) | 0.024 (3) |
C17 | 0.081 (4) | 0.056 (4) | 0.117 (6) | 0.021 (3) | −0.047 (4) | 0.008 (4) |
Cl3 | 0.0650 (7) | 0.0375 (5) | 0.0298 (5) | 0.0030 (5) | −0.0210 (5) | −0.0083 (4) |
Cl4 | 0.0507 (7) | 0.0898 (10) | 0.0383 (6) | 0.0214 (7) | 0.0100 (5) | 0.0094 (6) |
Cl6 | 0.0588 (9) | 0.0270 (7) | 0.0404 (8) | −0.0014 (6) | −0.0198 (7) | −0.0040 (6) |
O1W | 0.128 (3) | 0.0297 (16) | 0.050 (2) | 0.0021 (19) | −0.042 (2) | −0.0041 (14) |
Nd1—Cl1 | 2.8298 (8) | N12—H12 | 0.8800 |
Nd1—Cl11 | 2.7852 (11) | C31—C35ii | 1.417 (2) |
Nd1—O11 | 2.429 (3) | C31—C32ii | 1.467 (2) |
Nd1—O12 | 2.426 (3) | C31—C35 | 1.417 (2) |
Nd1—O13 | 2.477 (4) | C31—C32 | 1.467 (2) |
Nd1—O14 | 2.479 (4) | C32—C33 | 1.306 (4) |
Nd1—O15 | 2.404 (3) | C34—C35 | 1.318 (4) |
Nd1—Cl1i | 2.8345 (9) | C32—H32 | 0.9500 |
O11—H111 | 0.8500 | C33—H33 | 0.9500 |
O11—H112 | 0.8500 | C34—H34 | 0.9500 |
O12—H121 | 0.8500 | C35—H35 | 0.9500 |
O12—H122 | 0.8500 | C36—H36B | 0.9800 |
O13—H131 | 0.8500 | C36—H36C | 0.9800 |
O13—H132 | 0.8500 | C36—H36A | 0.9800 |
O14—H141 | 0.8500 | C37—H37A | 0.9800 |
O14—H142 | 0.8500 | C37—H37B | 0.9800 |
O15—H151 | 0.8500 | C37—H37C | 0.9800 |
O15—H152 | 0.8500 | C11—C15 | 1.404 (7) |
N31—C31 | 1.2855 (12) | C11—C12 | 1.408 (6) |
N31—C36 | 1.474 (4) | C12—C13 | 1.360 (7) |
N31—C37 | 1.435 (3) | C14—C15 | 1.333 (8) |
N32—C33 | 1.385 (4) | C12—H12A | 0.9500 |
N32—C34 | 1.418 (5) | C13—H13 | 0.9500 |
O1W—H12W | 0.8500 | C14—H14 | 0.9500 |
O1W—H11W | 0.8500 | C15—H15 | 0.9500 |
N32—H32A | 0.8800 | C16—H16B | 0.9800 |
N11—C11 | 1.330 (6) | C16—H16C | 0.9800 |
N11—C17 | 1.452 (8) | C16—H16A | 0.9800 |
N11—C16 | 1.446 (8) | C17—H17C | 0.9800 |
N12—C13 | 1.322 (8) | C17—H17A | 0.9800 |
N12—C14 | 1.319 (9) | C17—H17B | 0.9800 |
Cl1—Nd1—Cl11 | 81.28 (3) | C32—C31—C35ii | 66.36 (14) |
Cl1—Nd1—O11 | 74.96 (8) | C32—C31—C32ii | 180.00 |
Cl1—Nd1—O12 | 69.82 (8) | C35—C31—C35ii | 180.00 |
Cl1—Nd1—O13 | 124.05 (12) | C32ii—C31—C35ii | 113.64 (14) |
Cl1—Nd1—O14 | 134.06 (8) | N31ii—C31—C32 | 58.94 (12) |
Cl1—Nd1—O15 | 146.10 (7) | N31—C31—C35ii | 55.70 (14) |
Cl1—Nd1—Cl1i | 74.27 (2) | C32ii—C31—C35 | 66.36 (14) |
Cl11—Nd1—O11 | 148.14 (8) | C32—C31—C35 | 113.64 (14) |
Cl11—Nd1—O12 | 94.54 (9) | N31ii—C31—C35ii | 124.30 (14) |
Cl11—Nd1—O13 | 144.01 (13) | N31ii—C31—C32ii | 121.06 (12) |
Cl11—Nd1—O14 | 74.88 (10) | C31—C32—C33 | 120.66 (19) |
Cl11—Nd1—O15 | 91.79 (9) | N32—C33—C32 | 123.0 (3) |
Cl1i—Nd1—Cl11 | 79.91 (3) | N32—C34—C35 | 119.7 (3) |
O11—Nd1—O12 | 96.80 (12) | C31—C35—C34 | 124.0 (3) |
O11—Nd1—O13 | 67.84 (15) | C33—C32—H32 | 120.00 |
O11—Nd1—O14 | 136.94 (12) | C31—C32—H32 | 120.00 |
O11—Nd1—O15 | 96.19 (12) | C32—C33—H33 | 119.00 |
Cl1i—Nd1—O11 | 73.49 (8) | N32—C33—H33 | 118.00 |
O12—Nd1—O13 | 74.71 (15) | N32—C34—H34 | 120.00 |
O12—Nd1—O14 | 73.57 (12) | C35—C34—H34 | 120.00 |
O12—Nd1—O15 | 144.06 (10) | C31—C35—H35 | 118.00 |
Cl1i—Nd1—O12 | 144.08 (8) | C34—C35—H35 | 118.00 |
O13—Nd1—O14 | 69.15 (16) | H36A—C36—H36B | 109.00 |
O13—Nd1—O15 | 79.52 (14) | H36A—C36—H36C | 109.00 |
Cl1i—Nd1—O13 | 128.31 (13) | N31—C36—H36C | 109.00 |
O14—Nd1—O15 | 74.08 (11) | N31—C36—H36A | 110.00 |
Cl1i—Nd1—O14 | 136.47 (9) | H36B—C36—H36C | 109.00 |
Cl1i—Nd1—O15 | 71.85 (7) | N31—C36—H36B | 109.00 |
Nd1—Cl1—Nd1i | 105.74 (3) | H37B—C37—H37C | 109.00 |
Nd1—O11—H111 | 137.00 | H37A—C37—H37C | 109.00 |
Nd1—O11—H112 | 113.00 | N31—C37—H37B | 110.00 |
H111—O11—H112 | 109.00 | N31—C37—H37A | 109.00 |
Nd1—O12—H121 | 130.00 | H37A—C37—H37B | 110.00 |
Nd1—O12—H122 | 119.00 | N31—C37—H37C | 109.00 |
H121—O12—H122 | 110.00 | C12—C11—C15 | 115.1 (4) |
Nd1—O13—H131 | 88.00 | N11—C11—C15 | 122.4 (4) |
Nd1—O13—H132 | 163.00 | N11—C11—C12 | 122.5 (4) |
H131—O13—H132 | 108.00 | C11—C12—C13 | 120.3 (5) |
Nd1—O14—H141 | 107.00 | N12—C13—C12 | 121.1 (5) |
Nd1—O14—H142 | 104.00 | N12—C14—C15 | 121.7 (6) |
H141—O14—H142 | 109.00 | C11—C15—C14 | 121.2 (5) |
Nd1—O15—H151 | 125.00 | C11—C12—H12A | 120.00 |
Nd1—O15—H152 | 125.00 | C13—C12—H12A | 120.00 |
H151—O15—H152 | 109.00 | C12—C13—H13 | 119.00 |
C31—N31—C36 | 122.21 (17) | N12—C13—H13 | 119.00 |
C31—N31—C37 | 125.7 (2) | N12—C14—H14 | 119.00 |
C36—N31—C37 | 110.75 (19) | C15—C14—H14 | 119.00 |
C33—N32—C34 | 117.4 (2) | C14—C15—H15 | 119.00 |
H11W—O1W—H12W | 109.00 | C11—C15—H15 | 119.00 |
C34—N32—H32A | 121.00 | N11—C16—H16A | 109.00 |
C33—N32—H32A | 121.00 | N11—C16—H16B | 109.00 |
C11—N11—C16 | 122.2 (4) | H16A—C16—H16B | 109.00 |
C11—N11—C17 | 121.4 (5) | H16A—C16—H16C | 109.00 |
C16—N11—C17 | 116.4 (5) | N11—C16—H16C | 109.00 |
C13—N12—C14 | 120.6 (5) | H16B—C16—H16C | 109.00 |
C13—N12—H12 | 120.00 | N11—C17—H17B | 109.00 |
C14—N12—H12 | 120.00 | N11—C17—H17C | 109.00 |
N31—C31—C35 | 124.30 (14) | N11—C17—H17A | 109.00 |
N31—C31—C32 | 121.06 (12) | H17A—C17—H17C | 109.00 |
N31—C31—N31ii | 180.00 | H17B—C17—H17C | 110.00 |
N31ii—C31—C35 | 55.70 (14) | H17A—C17—H17B | 109.00 |
N31—C31—C32ii | 58.94 (12) | ||
Cl11—Nd1—Cl1—Nd1i | 81.90 (4) | C33—N32—C34—C35 | 9.3 (5) |
O11—Nd1—Cl1—Nd1i | −76.70 (9) | C16—N11—C11—C12 | −178.2 (5) |
O12—Nd1—Cl1—Nd1i | −179.96 (10) | C16—N11—C11—C15 | 1.9 (7) |
O13—Nd1—Cl1—Nd1i | −125.94 (16) | C17—N11—C11—C12 | −0.3 (7) |
O14—Nd1—Cl1—Nd1i | 140.86 (13) | C17—N11—C11—C15 | 179.8 (5) |
O15—Nd1—Cl1—Nd1i | 1.78 (17) | C14—N12—C13—C12 | 0.8 (8) |
Cl1i—Nd1—Cl1—Nd1i | 0.00 (4) | C13—N12—C14—C15 | −0.3 (9) |
Cl1—Nd1—Cl1i—Nd1i | 0.00 (3) | N31ii—C31—C32—C33 | 0.9 (2) |
Cl11—Nd1—Cl1i—Nd1i | −83.69 (4) | C35—C31—C32—C33 | −10.1 (3) |
O11—Nd1—Cl1i—Nd1i | 78.59 (9) | N31—C31—C32—C33 | −179.1 (2) |
O12—Nd1—Cl1i—Nd1i | 0.06 (16) | C32—C31—C35—C34 | 10.0 (3) |
O13—Nd1—Cl1i—Nd1i | 121.24 (15) | C35ii—C31—C32—C33 | 169.9 (3) |
O14—Nd1—Cl1i—Nd1i | −138.80 (13) | N31—C31—C35—C34 | 178.6 (2) |
O15—Nd1—Cl1i—Nd1i | −178.95 (10) | N31ii—C31—C35—C34 | −1.4 (2) |
C36—N31—C31—C32 | −179.1 (2) | C32ii—C31—C35—C34 | −170.0 (3) |
C36—N31—C31—C35 | 13.0 (2) | C31—C32—C33—N32 | 11.0 (4) |
C36—N31—C31—C32ii | 0.88 (19) | N32—C34—C35—C31 | −10.1 (5) |
C36—N31—C31—C35ii | −167.0 (2) | N11—C11—C12—C13 | −179.2 (5) |
C37—N31—C31—C32 | −13.5 (3) | C15—C11—C12—C13 | 0.7 (7) |
C37—N31—C31—C35 | 178.6 (2) | N11—C11—C15—C14 | 179.7 (5) |
C37—N31—C31—C32ii | 166.5 (3) | C12—C11—C15—C14 | −0.3 (8) |
C37—N31—C31—C35ii | −1.4 (2) | C11—C12—C13—N12 | −1.0 (8) |
C34—N32—C33—C32 | −10.2 (5) | N12—C14—C15—C11 | 0.1 (9) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H111···Cl4iii | 0.85 | 2.16 | 3.010 (3) | 177 |
O11—H112···Cl11i | 0.85 | 2.30 | 3.149 (4) | 173 |
O12—H121···Cl6iv | 0.85 | 2.24 | 3.080 (3) | 168 |
O12—H122···Cl3v | 0.85 | 2.25 | 3.089 (3) | 171 |
O13—H131···O11 | 0.85 | 2.19 | 2.738 (6) | 122 |
O13—H131···Cl4iii | 0.85 | 2.99 | 3.631 (6) | 134 |
O13—H132···Cl4 | 0.85 | 2.16 | 3.005 (4) | 172 |
O14—H142···Cl4v | 0.85 | 2.46 | 3.159 (4) | 140 |
O14—H142···Cl11 | 0.85 | 2.73 | 3.210 (4) | 118 |
O15—H151···O1W | 0.85 | 1.84 | 2.683 (4) | 172 |
O15—H152···Cl3 | 0.85 | 2.26 | 3.109 (3) | 175 |
N12—H12···Cl11vi | 0.88 | 2.65 | 3.358 (5) | 138 |
N12—H12···Cl11 | 0.88 | 2.78 | 3.451 (5) | 134 |
O1W—H11W···Cl3vii | 0.85 | 2.35 | 3.197 (3) | 179 |
O1W—H12W···Cl6 | 0.85 | 2.52 | 3.349 (3) | 167 |
N32—H32A···Cl4 | 0.88 | 2.26 | 3.0808 (16) | 156 |
C34—H34···Cl1iii | 0.95 | 2.82 | 3.703 (3) | 155 |
Symmetry codes: (i) −x+1, −y+1, −z; (iii) −x, −y+1, −z+1; (iv) x, y+1, z; (v) −x+1, −y+1, −z+1; (vi) −x+2, −y+1, −z; (vii) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C7H11N2)3[Nd2Cl4(H2O)10]Cl5·2H2O |
Mr | 1193.26 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 180 |
a, b, c (Å) | 9.5172 (4), 10.7739 (5), 11.9976 (5) |
α, β, γ (°) | 74.855 (4), 69.780 (4), 85.075 (4) |
V (Å3) | 1114.28 (8) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 2.90 |
Crystal size (mm) | 0.36 × 0.22 × 0.16 |
Data collection | |
Diffractometer | Agilent Xcalibur Sapphire1 diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2011) |
Tmin, Tmax | 0.475, 0.633 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23060, 4551, 4088 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.068, 1.11 |
No. of reflections | 4551 |
No. of parameters | 210 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.95, −1.76 |
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 |
O11—H111···Cl4i | 0.85 | 2.16 | 3.010 (3) | 177 |
O11—H112···Cl11ii | 0.85 | 2.30 | 3.149 (4) | 173 |
O12—H121···Cl6iii | 0.85 | 2.24 | 3.080 (3) | 168 |
O12—H122···Cl3iv | 0.85 | 2.25 | 3.089 (3) | 171 |
O13—H131···O11 | 0.85 | 2.19 | 2.738 (6) | 122 |
O13—H131···Cl4i | 0.85 | 2.99 | 3.631 (6) | 134 |
O13—H132···Cl4 | 0.85 | 2.16 | 3.005 (4) | 172 |
O14—H142···Cl4iv | 0.85 | 2.46 | 3.159 (4) | 140 |
O14—H142···Cl11 | 0.85 | 2.73 | 3.210 (4) | 118 |
O15—H151···O1W | 0.85 | 1.84 | 2.683 (4) | 172 |
O15—H152···Cl3 | 0.85 | 2.26 | 3.109 (3) | 175 |
N12—H12···Cl11v | 0.88 | 2.65 | 3.358 (5) | 138 |
N12—H12···Cl11 | 0.88 | 2.78 | 3.451 (5) | 134 |
O1W—H11W···Cl3vi | 0.85 | 2.35 | 3.197 (3) | 179 |
O1W—H12W···Cl6 | 0.85 | 2.52 | 3.349 (3) | 167 |
N32—H32A···Cl4 | 0.88 | 2.26 | 3.0808 (16) | 156 |
C34—H34···Cl1i | 0.95 | 2.82 | 3.703 (3) | 155 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z; (iii) x, y+1, z; (iv) −x+1, −y+1, −z+1; (v) −x+2, −y+1, −z; (vi) −x+1, −y, −z+1. |
Acknowledgements
The authors acknowledge technical support (X-ray measurements) by the Laboratory of Coordination Chemistry, UPR-CNRS 8241,Toulouse.
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.
We report herein on the synthesis and crystal structure of a new hybrid organic-inorganic compound. It consists 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 asymmetric unit of the title compound contains one half of a centrosymmetric [Nd2Cl4(H2O)10]2+ dication, and one and one half 4-(dimethylamino)pyridinium cations, two and one half chloride anions, and one water molecule (Fig. 1). The organic cations consist of ordered (A) and disordered (B) entities (Fig. 1). They are protonated on the nitrogen atoms N12 and N32 of the pyridine rings. The organic entity (B) is disordered about an inversion center.
The two Nd atoms of the dication are linked by two bridging chloride atoms with an Nd1···Nd1i separation of 4.5158 (4)Å and an Nd1-Cl1-Nd1i angle of 105.74 (3)° (symmetry code: (i) -x+1, -y+1, -z) . Each NdIII atom is coordinated by the O atoms of five water molecules with the Nd-O distances ranging from 2.404 (3) to 2.479 (4) Å, and by three chloride ions with bond Nd1-Cl11 being 2.7851 (10) while the bridging Nd1-Cl1 and Nd1-Cl1i distances are 2.8298 (8) and 2.8345 (9) Å, respectively.
In the 4-(dimethylamino)pyridinium cations, the N-C bonds linking the dimethylamino substituent to the pyridinium ring are short [1.330 (5) and 1.2855 (12) Å], suggesting some delocalization in the cation. The dimethylamino groups (C16/N11/C17 and C36/N32/C37) lie close to the plane of their respective pyridinium rings, with dihedral angles of 1.6 (6) ° and 6.5 (3) °, respectively.
In the crystal, each Cl- anion accepts hydrogen bonds which can be divided into two groups. The first group involves hydrogen bonds linking atom Cl11 with two organic cations via the pyridinium N12-H12 H atom (Table 1), generating centrosymmetric R22(4) motifs (Bernstein et al., 1995) at y = 1/2, and this arrangement is analogous to that seen in (C7H10N2)2[LaCl(H2O)8]Cl4.3H2O (Benslimane et al., 2012). The second type of hydrogen bond, in which the Cl- anion is the acceptor, is a linkage between the (free and coordinated) water molecules and the Cl- anion which enlcose R24(12) ring motifs along direction [001] (Fig. 2 and Table. 1). The [Nd2Cl4(H2O)10]2+ dications are linked via O-H···O and O-H···Cl hydrogen bonds to form sheets lying parallel to the bc plane (Fig. 3). These sheets are linked via O-H···Cl hydrogen bonds to form a three dimentional framework. The 4-(dimethylamino)pyridinium cations are located in the cavities. The dimeric cations are linked via hydrogen bonds between Cl- anions and water molecules resulting in the formation of centrosymmetric R24(8) and R46(12) rings along direction [001] (Fig. 3 and Table. 1).