metal-organic compounds
Bis[(2S,4S)-4-(2-hydroxyethyl)-2-methylpiperazine-1,4-diium] di-μ-chlorido-bis[trichloridocadmium(II)]
aOrdered Matter Science Research Center, Southeast University, Nanjing 210096, People's Republic of China
*Correspondence e-mail: rongtao198806@163.com
The 7H18N2O)2[Cd2Cl8], comprises one 4-(2-hydroxyethyl)-2-methylpiperazine-1,4-diium dication and a half [Cd2Cl8]4− anion. The two Cd atoms are each coordinated by two bridging Cl atoms and three terminal Cl atoms and the [Cd2Cl8]4− anion is located on an inversion centre. The consists of N—H⋯Cl hydrogen-bonded sheets, which are further linked by C—H⋯Cl contacts, yielding a three-dimensional network.
of the title compound, (CRelated literature
For general background to ferroelectric metal-organic frameworks, see: Fu et al. (2009, 2010); Ye et al. (2006); Zhang et al. (2008, 2010).
Experimental
Crystal data
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Refinement
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Data collection: CrystalClear (Rigaku, 2005); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536811006945/rn2080sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811006945/rn2080Isup2.hkl
Ethylene oxide (25 mmol) was added by bubbling of this gas into a solution of rac-2-methyl piperazine (10 mmol) in toluene at 318–323 K. The toluene solvent was then removed under reduced pressure, the rac-2-methyl-4-ethoxyl piperazine was obtained at 376–381 K by reduced pressure distillation of the mixture. A solution of chlorhydric acid (10 mmol) was added to a solution of half equimolar amount of rac-2-methyl-4-ethoxyl piperazine inethanol (20 mL), then cadmium chloride(5 mmol) in water (10 mL) was added. Crystals suitable for
were grown by slow evaporation of the mixture at room temperaturePositional parameters of all the H atoms bonded to C atoms were calculated geometrically and were allowed to ride on the C atoms to which they are bonded, with Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.5Ueq(C) for the methyl group. The other H bonded to O/N atoms were calculated geometrically and were allowed to ride on the O/N atoms with Uiso(H) = 1.2Ueq(N) and Uiso(H) = 1.5Ueq(O).
Data collection: CrystalClear (Rigaku, 2005); cell
CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).(C7H18N2O)2[Cd2Cl8] | Z = 2 |
Mr = 800.86 | F(000) = 792 |
Monoclinic, P21/n | Dx = 1.896 Mg m−3 |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0318 (16) Å | θ = 3.0–27.5° |
b = 11.144 (2) Å | µ = 2.30 mm−1 |
c = 15.816 (3) Å | T = 293 K |
β = 97.81 (3)° | Prism, colourless |
V = 1402.6 (5) Å3 | 0.20 × 0.20 × 0.20 mm |
Rigaku SCXmini diffractometer | 3217 independent reflections |
Radiation source: fine-focus sealed tube | 3008 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
CCD_Profile_fitting scans | h = −10→10 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −14→14 |
Tmin = 0.632, Tmax = 0.638 | l = −20→20 |
14193 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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.060 | H-atom parameters constrained |
S = 1.19 | w = 1/[σ2(Fo2) + (0.022P)2 + 0.433P] where P = (Fo2 + 2Fc2)/3 |
3217 reflections | (Δ/σ)max = 0.001 |
136 parameters | Δρmax = 0.35 e Å−3 |
2 restraints | Δρmin = −0.88 e Å−3 |
(C7H18N2O)2[Cd2Cl8] | V = 1402.6 (5) Å3 |
Mr = 800.86 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.0318 (16) Å | µ = 2.30 mm−1 |
b = 11.144 (2) Å | T = 293 K |
c = 15.816 (3) Å | 0.20 × 0.20 × 0.20 mm |
β = 97.81 (3)° |
Rigaku SCXmini diffractometer | 3217 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 3008 reflections with I > 2σ(I) |
Tmin = 0.632, Tmax = 0.638 | Rint = 0.037 |
14193 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 2 restraints |
wR(F2) = 0.060 | H-atom parameters constrained |
S = 1.19 | Δρmax = 0.35 e Å−3 |
3217 reflections | Δρmin = −0.88 e Å−3 |
136 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.07749 (3) | 0.14056 (2) | 0.435513 (16) | 0.02832 (11) | |
Cl4 | 0.13747 (12) | 0.02958 (8) | 0.59105 (5) | 0.0299 (2) | |
Cl2 | 0.34061 (12) | 0.04831 (9) | 0.39588 (6) | 0.0364 (2) | |
Cl3 | 0.13624 (14) | 0.33698 (9) | 0.51000 (6) | 0.0363 (2) | |
Cl1 | −0.02934 (12) | 0.23097 (9) | 0.28873 (6) | 0.0369 (2) | |
N2 | 1.0951 (4) | 0.3458 (3) | 0.78336 (19) | 0.0267 (6) | |
H2A | 1.0310 | 0.3654 | 0.8237 | 0.032* | |
H2D | 1.2013 | 0.3360 | 0.8091 | 0.032* | |
N1 | 0.8525 (4) | 0.3466 (3) | 0.63036 (19) | 0.0262 (6) | |
H1D | 0.9222 | 0.3270 | 0.5917 | 0.031* | |
C6 | 0.8591 (5) | 0.2469 (3) | 0.6942 (2) | 0.0266 (7) | |
H6A | 0.8235 | 0.1729 | 0.6649 | 0.032* | |
H6B | 0.7812 | 0.2642 | 0.7344 | 0.032* | |
C4 | 1.0905 (5) | 0.4452 (3) | 0.7205 (2) | 0.0332 (8) | |
H4A | 1.1679 | 0.4280 | 0.6800 | 0.040* | |
H4B | 1.1262 | 0.5191 | 0.7499 | 0.040* | |
C5 | 1.0336 (5) | 0.2302 (3) | 0.7425 (2) | 0.0261 (7) | |
H5A | 1.1095 | 0.2063 | 0.7019 | 0.031* | |
C3 | 0.9163 (5) | 0.4608 (3) | 0.6735 (2) | 0.0328 (8) | |
H3A | 0.8411 | 0.4854 | 0.7134 | 0.039* | |
H3B | 0.9173 | 0.5236 | 0.6311 | 0.039* | |
O1 | 0.7146 (4) | 0.2021 (3) | 0.49063 (18) | 0.0422 (7) | |
H1A | 0.6727 | 0.1408 | 0.4683 | 0.063* | |
C1 | 0.6018 (5) | 0.2547 (4) | 0.5418 (3) | 0.0375 (9) | |
H1B | 0.5787 | 0.1985 | 0.5857 | 0.045* | |
H1C | 0.4965 | 0.2739 | 0.5068 | 0.045* | |
C7 | 1.0337 (6) | 0.1329 (4) | 0.8089 (3) | 0.0410 (10) | |
H7A | 1.1452 | 0.1236 | 0.8388 | 0.061* | |
H7B | 0.9976 | 0.0587 | 0.7815 | 0.061* | |
H7C | 0.9584 | 0.1546 | 0.8486 | 0.061* | |
C2 | 0.6798 (5) | 0.3669 (4) | 0.5825 (3) | 0.0372 (9) | |
H2B | 0.6075 | 0.3986 | 0.6215 | 0.045* | |
H2C | 0.6868 | 0.4265 | 0.5384 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.03076 (17) | 0.02561 (17) | 0.02899 (17) | −0.00180 (10) | 0.00547 (12) | 0.00126 (10) |
Cl4 | 0.0366 (5) | 0.0285 (5) | 0.0240 (4) | −0.0056 (4) | 0.0020 (3) | 0.0008 (3) |
Cl2 | 0.0334 (5) | 0.0380 (5) | 0.0409 (5) | 0.0029 (4) | 0.0160 (4) | 0.0066 (4) |
Cl3 | 0.0476 (6) | 0.0283 (5) | 0.0354 (5) | −0.0012 (4) | 0.0140 (4) | −0.0020 (4) |
Cl1 | 0.0296 (5) | 0.0426 (6) | 0.0379 (5) | −0.0037 (4) | 0.0026 (4) | 0.0134 (4) |
N2 | 0.0242 (15) | 0.0290 (16) | 0.0268 (15) | 0.0015 (12) | 0.0028 (12) | −0.0039 (12) |
N1 | 0.0293 (16) | 0.0260 (16) | 0.0234 (15) | 0.0015 (12) | 0.0037 (12) | −0.0019 (12) |
C6 | 0.0281 (18) | 0.0222 (18) | 0.0298 (18) | −0.0016 (14) | 0.0056 (14) | 0.0004 (14) |
C4 | 0.038 (2) | 0.0281 (19) | 0.0325 (19) | −0.0086 (16) | 0.0027 (16) | 0.0004 (16) |
C5 | 0.0274 (18) | 0.0234 (18) | 0.0279 (17) | 0.0014 (14) | 0.0049 (14) | −0.0028 (14) |
C3 | 0.043 (2) | 0.0246 (19) | 0.0294 (19) | −0.0022 (16) | −0.0009 (16) | 0.0004 (15) |
O1 | 0.0465 (17) | 0.0395 (17) | 0.0403 (16) | −0.0039 (13) | 0.0052 (13) | −0.0102 (13) |
C1 | 0.031 (2) | 0.040 (2) | 0.039 (2) | 0.0002 (17) | −0.0041 (17) | −0.0033 (18) |
C7 | 0.049 (3) | 0.031 (2) | 0.042 (2) | 0.0033 (18) | 0.003 (2) | 0.0055 (18) |
C2 | 0.038 (2) | 0.034 (2) | 0.037 (2) | 0.0083 (17) | −0.0064 (18) | −0.0045 (17) |
Cd1—Cl3 | 2.5003 (11) | C4—C3 | 1.502 (6) |
Cd1—Cl2 | 2.5052 (11) | C4—H4A | 0.9700 |
Cd1—Cl4i | 2.5603 (10) | C4—H4B | 0.9700 |
Cd1—Cl1 | 2.5690 (11) | C5—C7 | 1.509 (5) |
Cd1—Cl4 | 2.7371 (10) | C5—H5A | 0.9800 |
Cl4—Cd1i | 2.5603 (10) | C3—H3A | 0.9700 |
N2—C4 | 1.486 (5) | C3—H3B | 0.9700 |
N2—C5 | 1.495 (4) | O1—C1 | 1.421 (5) |
N2—H2A | 0.9000 | O1—H1A | 0.8200 |
N2—H2D | 0.9000 | C1—C2 | 1.503 (5) |
N1—C6 | 1.497 (4) | C1—H1B | 0.9700 |
N1—C3 | 1.501 (5) | C1—H1C | 0.9700 |
N1—C2 | 1.505 (5) | C7—H7A | 0.9600 |
N1—H1D | 0.9100 | C7—H7B | 0.9600 |
C6—C5 | 1.514 (5) | C7—H7C | 0.9600 |
C6—H6A | 0.9700 | C2—H2B | 0.9700 |
C6—H6B | 0.9700 | C2—H2C | 0.9700 |
Cl3—Cd1—Cl2 | 111.44 (4) | C3—C4—H4B | 109.5 |
Cl3—Cd1—Cl4i | 143.67 (4) | H4A—C4—H4B | 108.1 |
Cl2—Cd1—Cl4i | 103.18 (4) | N2—C5—C7 | 110.4 (3) |
Cl3—Cd1—Cl1 | 95.79 (4) | N2—C5—C6 | 109.9 (3) |
Cl2—Cd1—Cl1 | 97.14 (4) | C7—C5—C6 | 110.7 (3) |
Cl4i—Cd1—Cl1 | 90.41 (4) | N2—C5—H5A | 108.6 |
Cl3—Cd1—Cl4 | 88.47 (3) | C7—C5—H5A | 108.6 |
Cl2—Cd1—Cl4 | 89.31 (4) | C6—C5—H5A | 108.6 |
Cl4i—Cd1—Cl4 | 81.10 (4) | N1—C3—C4 | 111.4 (3) |
Cl1—Cd1—Cl4 | 170.34 (3) | N1—C3—H3A | 109.4 |
Cd1i—Cl4—Cd1 | 98.90 (4) | C4—C3—H3A | 109.4 |
C4—N2—C5 | 112.1 (3) | N1—C3—H3B | 109.4 |
C4—N2—H2A | 109.2 | C4—C3—H3B | 109.4 |
C5—N2—H2A | 109.2 | H3A—C3—H3B | 108.0 |
C4—N2—H2D | 109.2 | C1—O1—H1A | 109.5 |
C5—N2—H2D | 109.2 | O1—C1—C2 | 109.0 (3) |
H2A—N2—H2D | 107.9 | O1—C1—H1B | 109.9 |
C6—N1—C3 | 110.1 (3) | C2—C1—H1B | 109.9 |
C6—N1—C2 | 113.4 (3) | O1—C1—H1C | 109.9 |
C3—N1—C2 | 109.6 (3) | C2—C1—H1C | 109.9 |
C6—N1—H1D | 107.9 | H1B—C1—H1C | 108.3 |
C3—N1—H1D | 107.9 | C5—C7—H7A | 109.5 |
C2—N1—H1D | 107.9 | C5—C7—H7B | 109.5 |
N1—C6—C5 | 112.2 (3) | H7A—C7—H7B | 109.5 |
N1—C6—H6A | 109.2 | C5—C7—H7C | 109.5 |
C5—C6—H6A | 109.2 | H7A—C7—H7C | 109.5 |
N1—C6—H6B | 109.2 | H7B—C7—H7C | 109.5 |
C5—C6—H6B | 109.2 | C1—C2—N1 | 113.1 (3) |
H6A—C6—H6B | 107.9 | C1—C2—H2B | 109.0 |
N2—C4—C3 | 110.8 (3) | N1—C2—H2B | 109.0 |
N2—C4—H4A | 109.5 | C1—C2—H2C | 109.0 |
C3—C4—H4A | 109.5 | N1—C2—H2C | 109.0 |
N2—C4—H4B | 109.5 | H2B—C2—H2C | 107.8 |
Cl3—Cd1—Cl4—Cd1i | 145.07 (4) | N1—C6—C5—N2 | 55.2 (4) |
Cl2—Cd1—Cl4—Cd1i | −103.46 (4) | N1—C6—C5—C7 | 177.4 (3) |
Cl4i—Cd1—Cl4—Cd1i | 0.0 | C6—N1—C3—C4 | 55.9 (4) |
Cl1—Cd1—Cl4—Cd1i | 28.7 (2) | C2—N1—C3—C4 | −178.7 (3) |
C3—N1—C6—C5 | −55.7 (4) | N2—C4—C3—N1 | −56.5 (4) |
C2—N1—C6—C5 | −178.9 (3) | O1—C1—C2—N1 | −53.4 (5) |
C5—N2—C4—C3 | 56.5 (4) | C6—N1—C2—C1 | −52.8 (5) |
C4—N2—C5—C7 | −177.7 (3) | C3—N1—C2—C1 | −176.3 (3) |
C4—N2—C5—C6 | −55.3 (4) |
Symmetry code: (i) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···Cl4ii | 0.82 | 2.68 | 3.188 (3) | 121 |
N1—H1D···Cl3iii | 0.91 | 2.29 | 3.163 (3) | 161 |
N2—H2D···Cl4iv | 0.90 | 2.88 | 3.405 (3) | 119 |
N2—H2D···Cl1v | 0.90 | 2.35 | 3.125 (3) | 144 |
N2—H2A···Cl2vi | 0.90 | 2.25 | 3.119 (3) | 164 |
Symmetry codes: (ii) −x+1, −y, −z+1; (iii) x+1, y, z; (iv) −x+3/2, y+1/2, −z+3/2; (v) x+3/2, −y+1/2, z+1/2; (vi) x+1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | (C7H18N2O)2[Cd2Cl8] |
Mr | 800.86 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.0318 (16), 11.144 (2), 15.816 (3) |
β (°) | 97.81 (3) |
V (Å3) | 1402.6 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.30 |
Crystal size (mm) | 0.20 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Rigaku SCXmini diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.632, 0.638 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14193, 3217, 3008 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.060, 1.19 |
No. of reflections | 3217 |
No. of parameters | 136 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.88 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···Cl4i | 0.82 | 2.68 | 3.188 (3) | 121 |
N1—H1D···Cl3ii | 0.91 | 2.29 | 3.163 (3) | 161 |
N2—H2D···Cl4iii | 0.90 | 2.88 | 3.405 (3) | 119 |
N2—H2D···Cl1iv | 0.90 | 2.35 | 3.125 (3) | 144 |
N2—H2A···Cl2v | 0.90 | 2.25 | 3.119 (3) | 164 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1, y, z; (iii) −x+3/2, y+1/2, −z+3/2; (iv) x+3/2, −y+1/2, z+1/2; (v) x+1/2, −y+1/2, z+1/2. |
Acknowledgements
The authors are grateful to the starter fund of Southeast University for financial support to purchase the X-ray diffractometer.
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.
The study of ferroelectric materials has received much attention. Some materials have predominantly dielectric-ferroelectric performance.The title compound was studied as part of our work to obtain potential ferroelectric phase-change materials [Fu et al.(2009); Ye et al. (2006); Zhang et al. (2008; 2010)] .
As one part of our continuing studies on dielectric-ferroelectric materials, we synthesized the title compound (C7H18N2O).CdCl4 (Fig 1).Unfortunately, the study carried out on the title compound indicated that the permittivity is temperature-independent, suggesting that there may be no dielectric disuniformity between 80 K to 350 K [Fu et al. (2010)].
The asymmetric unit of the title compound contains one [C7H17N2O] 2+ basic ion and half of the [Cd2Cl8]4- complex ion which is situated on an inversion centre. The intermolecular hydrogen bonds (O1—H1A···Cl4, N1—H1D···Cl3, N2—H2D···Cl4, N2—H2D···Cl1 and N2—H2A···Cl2) link the molecules into sheets and stabilize the structure (Fig 2).