Acta Cryst. (2007). E63, m2884 [ doi:10.1107/S1600536807052774 ]
![[mu]](/logos/entities/mu_rmgif.gif)
3-chlorido-2-chlorido-dichloridodicopper(I)]]The title compound, {(C5H14N2)[Cu2Cl4]}n, was synthesized by the hydrothermal reaction of CuCl2 with homochiral (R)-2-methylpiperazine. One Cu atom has a slightly distorted tetrahedral geometry defined by one terminal and three bridging Cl- anions, while the other displays a trigonal planar geometry composed of one terminal and two bridging Cl- anions. The crystal structure contains a polymeric anion forming a chain running along the a axis and (R)-2-methylpiperazinediium cations filling the space between these chains. Cations and anions are connected by hydrogen bonds.
A mixture of (R)-2-methylpiperazine (20 mg, 0.2 mmol), CuCl2 (27 mg, 0.2 mmol), water (1 ml) and methanol (1 ml) sealed in a glass tube were maintained at 110–115 °C. Crystals suitable for X-ray analysis were obtained after 5 days.
Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on the C and N atoms to which they are bonded, with Uiso(H) = 1.2Ueq(C or N).
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 1999).
![[Figure 1]](./bt2555fig1thm.gif)
| Fig. 1. A view of the title compoud with atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level. Atoms with suffix A and B are generated by the symmetry operator 1/2 + x, −1/2 − y, −1 − z and −1/2 + x, −1/2 − y, −1 − z, respectively. The dashed open lines show the Cu—Cu interaction. |
![[Figure 2]](./bt2555fig2thm.gif)
| Fig. 2. The chain structure of the title compound. Methyl C atoms and H atoms bonded to C atoms were omitted for clarity. The dashed lines show the N—H···Cl hydrogen bonds presented in Table 2. |
![[Figure 3]](./bt2555fig3thm.gif)
| Fig. 3. The crystal packing of the title compound viewed along the a axis. H atoms bonded to C atoms were omitted for clarity. The dashed lines show hydrogen bonds. |
| (C5H14N2)[Cu2Cl4] | F000 = 736 |
| Mr = 371.06 | Dx = 2.038 Mg m−3 |
| Orthorhombic, P212121 | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: P 2ac 2ab | Cell parameters from 3251 reflections |
| a = 6.1943 (16) Å | θ = 3.1–27.5º |
| b = 12.544 (4) Å | µ = 4.36 mm−1 |
| c = 15.561 (5) Å | T = 293 (2) K |
| V = 1209.1 (6) Å3 | Block, colourless |
| Z = 4 | 0.25 × 0.06 × 0.05 mm |
| Rigaku Mercury2 (2x2 bin mode) diffractometer | 2756 independent reflections |
| Radiation source: fine-focus sealed tube | 2439 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.058 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5º |
| T = 293(2) K | θmin = 3.1º |
| ω scans | h = −8→8 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −16→16 |
| Tmin = 0.721, Tmax = 1.000 | l = −20→20 |
| 12245 measured reflections |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.040 | w = 1/[σ2(Fo2) + (0.0374P)2] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.091 | (Δ/σ)max < 0.001 |
| S = 1.06 | Δρmax = 0.75 e Å−3 |
| 2756 reflections | Δρmin = −0.52 e Å−3 |
| 119 parameters | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), with 1149 Friedel pairs |
| Secondary atom site location: difference Fourier map | Flack parameter: −0.04 (2) |
| (C5H14N2)[Cu2Cl4] | V = 1209.1 (6) Å3 |
| Mr = 371.06 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα |
| a = 6.1943 (16) Å | µ = 4.36 mm−1 |
| b = 12.544 (4) Å | T = 293 (2) K |
| c = 15.561 (5) Å | 0.25 × 0.06 × 0.05 mm |
| Rigaku Mercury2 (2x2 bin mode) diffractometer | 2756 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 2439 reflections with I > 2σ(I) |
| Tmin = 0.721, Tmax = 1.000 | Rint = 0.058 |
| 12245 measured reflections |
| R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
| wR(F2) = 0.091 | Δρmax = 0.75 e Å−3 |
| S = 1.06 | Δρmin = −0.52 e Å−3 |
| 2756 reflections | Absolute structure: Flack (1983), with 1149 Friedel pairs |
| 119 parameters | Flack parameter: −0.04 (2) |
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. |
| x | y | z | Uiso*/Ueq | ||
| Cu1 | 0.34591 (11) | −0.14923 (6) | −0.54943 (4) | 0.0524 (2) | |
| Cu2 | −0.07136 (10) | −0.04816 (6) | −0.53360 (4) | 0.04967 (19) | |
| Cl1 | 0.2405 (2) | 0.00613 (11) | −0.47681 (8) | 0.0450 (3) | |
| Cl2 | −0.18532 (19) | 0.05572 (11) | −0.64711 (9) | 0.0495 (3) | |
| Cl3 | 0.20460 (19) | −0.32180 (10) | −0.50581 (8) | 0.0427 (3) | |
| Cl4 | 0.30984 (18) | −0.14203 (9) | −0.69686 (7) | 0.0361 (2) | |
| N1 | −0.1874 (6) | −0.1985 (3) | −0.7303 (2) | 0.0357 (8) | |
| H1A | −0.0828 | −0.1566 | −0.7087 | 0.043* | |
| H1B | −0.3155 | −0.1712 | −0.7142 | 0.043* | |
| N2 | −0.3208 (6) | −0.3814 (3) | −0.8259 (2) | 0.0377 (9) | |
| H2A | −0.1932 | −0.4097 | −0.8415 | 0.045* | |
| H2B | −0.4262 | −0.4232 | −0.8470 | 0.045* | |
| C1 | −0.2082 (11) | −0.0895 (5) | −0.8625 (4) | 0.0707 (18) | |
| H8A | −0.2054 | −0.0927 | −0.9242 | 0.106* | |
| H8B | −0.0961 | −0.0427 | −0.8427 | 0.106* | |
| H8C | −0.3458 | −0.0630 | −0.8439 | 0.106* | |
| C2 | −0.1730 (8) | −0.1982 (4) | −0.8266 (3) | 0.0387 (11) | |
| H4A | −0.0294 | −0.2233 | −0.8437 | 0.046* | |
| C3 | −0.3411 (8) | −0.2726 (4) | −0.8632 (3) | 0.0430 (11) | |
| H5A | −0.4839 | −0.2447 | −0.8511 | 0.052* | |
| H5B | −0.3243 | −0.2766 | −0.9251 | 0.052* | |
| C4 | −0.3356 (8) | −0.3795 (4) | −0.7302 (3) | 0.0383 (10) | |
| H6A | −0.3169 | −0.4511 | −0.7077 | 0.046* | |
| H6B | −0.4769 | −0.3541 | −0.7129 | 0.046* | |
| C5 | −0.1646 (8) | −0.3078 (4) | −0.6943 (3) | 0.0384 (10) | |
| H3A | −0.1772 | −0.3051 | −0.6322 | 0.046* | |
| H3B | −0.0231 | −0.3359 | −0.7084 | 0.046* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0531 (4) | 0.0554 (4) | 0.0486 (4) | 0.0069 (3) | −0.0020 (3) | 0.0041 (3) |
| Cu2 | 0.0480 (4) | 0.0455 (4) | 0.0555 (4) | −0.0046 (3) | 0.0058 (3) | −0.0045 (3) |
| Cl1 | 0.0429 (6) | 0.0455 (6) | 0.0467 (7) | 0.0023 (5) | −0.0051 (5) | −0.0029 (5) |
| Cl2 | 0.0329 (6) | 0.0514 (7) | 0.0642 (8) | −0.0014 (6) | −0.0048 (6) | 0.0195 (7) |
| Cl3 | 0.0311 (5) | 0.0369 (6) | 0.0600 (7) | −0.0024 (5) | 0.0010 (5) | 0.0114 (5) |
| Cl4 | 0.0311 (5) | 0.0378 (5) | 0.0395 (6) | 0.0010 (5) | −0.0001 (4) | 0.0033 (5) |
| N1 | 0.0295 (19) | 0.0309 (18) | 0.047 (2) | −0.0047 (17) | −0.0019 (18) | −0.0051 (17) |
| N2 | 0.034 (2) | 0.040 (2) | 0.039 (2) | −0.0001 (18) | −0.0053 (18) | −0.0113 (17) |
| C1 | 0.076 (4) | 0.058 (4) | 0.078 (4) | 0.008 (3) | 0.013 (4) | 0.016 (3) |
| C2 | 0.033 (2) | 0.041 (3) | 0.042 (3) | 0.003 (2) | 0.007 (2) | 0.003 (2) |
| C3 | 0.037 (3) | 0.057 (3) | 0.035 (2) | 0.003 (2) | −0.002 (2) | −0.002 (2) |
| C4 | 0.042 (3) | 0.033 (2) | 0.040 (2) | 0.000 (2) | −0.002 (2) | 0.003 (2) |
| C5 | 0.046 (3) | 0.036 (2) | 0.034 (2) | 0.002 (2) | −0.005 (2) | −0.0025 (19) |
| Cu1—Cl4 | 2.3068 (15) | N2—H2A | 0.9000 |
| Cu1—Cl1 | 2.3453 (16) | N2—H2B | 0.9000 |
| Cu1—Cl3i | 2.4099 (14) | C1—C2 | 1.490 (7) |
| Cu1—Cl3 | 2.4317 (15) | C1—H8A | 0.9600 |
| Cu1—Cu2 | 2.8893 (12) | C1—H8B | 0.9600 |
| Cu2—Cl3ii | 2.2278 (14) | C1—H8C | 0.9600 |
| Cu2—Cl1 | 2.2308 (15) | C2—C3 | 1.510 (7) |
| Cu2—Cl2 | 2.3057 (15) | C2—H4A | 0.9800 |
| Cl3—Cu2i | 2.2277 (14) | C3—H5A | 0.9700 |
| Cl3—Cu1ii | 2.4099 (14) | C3—H5B | 0.9700 |
| N1—C5 | 1.488 (6) | C4—C5 | 1.498 (6) |
| N1—C2 | 1.501 (6) | C4—H6A | 0.9700 |
| N1—H1A | 0.9000 | C4—H6B | 0.9700 |
| N1—H1B | 0.9000 | C5—H3A | 0.9700 |
| N2—C3 | 1.488 (6) | C5—H3B | 0.9700 |
| N2—C4 | 1.492 (6) | ||
| Cl4—Cu1—Cl1 | 114.81 (5) | H2A—N2—H2B | 107.9 |
| Cl4—Cu1—Cl3i | 116.74 (5) | C2—C1—H8A | 109.5 |
| Cl1—Cu1—Cl3i | 102.13 (5) | C2—C1—H8B | 109.5 |
| Cl4—Cu1—Cl3 | 106.12 (5) | H8A—C1—H8B | 109.5 |
| Cl1—Cu1—Cl3 | 120.33 (5) | C2—C1—H8C | 109.5 |
| Cl3i—Cu1—Cl3 | 95.63 (4) | H8A—C1—H8C | 109.5 |
| Cl4—Cu1—Cu2 | 88.91 (4) | H8B—C1—H8C | 109.5 |
| Cl1—Cu1—Cu2 | 49.11 (4) | C1—C2—N1 | 111.6 (4) |
| Cl3i—Cu1—Cu2 | 149.37 (5) | C1—C2—C3 | 108.9 (4) |
| Cl3—Cu1—Cu2 | 92.57 (4) | N1—C2—C3 | 109.5 (4) |
| Cl3ii—Cu2—Cl1 | 130.84 (6) | C1—C2—H4A | 108.9 |
| Cl3ii—Cu2—Cl2 | 115.72 (6) | N1—C2—H4A | 108.9 |
| Cl1—Cu2—Cl2 | 113.33 (6) | C3—C2—H4A | 108.9 |
| Cl3ii—Cu2—Cu1 | 105.04 (5) | N2—C3—C2 | 111.2 (4) |
| Cl1—Cu2—Cu1 | 52.63 (4) | N2—C3—H5A | 109.4 |
| Cl2—Cu2—Cu1 | 117.17 (4) | C2—C3—H5A | 109.4 |
| Cu2—Cl1—Cu1 | 78.26 (5) | N2—C3—H5B | 109.4 |
| Cu2i—Cl3—Cu1ii | 111.45 (5) | C2—C3—H5B | 109.4 |
| Cu2i—Cl3—Cu1 | 120.29 (6) | H5A—C3—H5B | 108.0 |
| Cu1ii—Cl3—Cu1 | 124.45 (5) | N2—C4—C5 | 109.8 (4) |
| C5—N1—C2 | 111.9 (4) | N2—C4—H6A | 109.7 |
| C5—N1—H1A | 109.2 | C5—C4—H6A | 109.7 |
| C2—N1—H1A | 109.2 | N2—C4—H6B | 109.7 |
| C5—N1—H1B | 109.2 | C5—C4—H6B | 109.7 |
| C2—N1—H1B | 109.2 | H6A—C4—H6B | 108.2 |
| H1A—N1—H1B | 107.9 | N1—C5—C4 | 110.2 (4) |
| C3—N2—C4 | 111.7 (3) | N1—C5—H3A | 109.6 |
| C3—N2—H2A | 109.3 | C4—C5—H3A | 109.6 |
| C4—N2—H2A | 109.3 | N1—C5—H3B | 109.6 |
| C3—N2—H2B | 109.3 | C4—C5—H3B | 109.6 |
| C4—N2—H2B | 109.3 | H3A—C5—H3B | 108.1 |
| Symmetry codes: (i) x+1/2, −y−1/2, −z−1; (ii) x−1/2, −y−1/2, −z−1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···Cl4 | 0.90 | 2.45 | 3.203 (4) | 142 |
| N1—H1A···Cl2 | 0.90 | 2.90 | 3.442 (4) | 120 |
| N1—H1B···Cl4iii | 0.90 | 2.36 | 3.236 (4) | 163 |
| N2—H2A···Cl2iv | 0.90 | 2.39 | 3.260 (4) | 162 |
| N2—H2B···Cl2v | 0.90 | 2.42 | 3.187 (4) | 143 |
| Symmetry codes: (iii) x−1, y, z; (iv) −x, y−1/2, −z−3/2; (v) −x−1, y−1/2, −z−3/2. |
| Cu1—Cl4 | 2.3068 (15) | Cu2—Cl3ii | 2.2278 (14) |
| Cu1—Cl1 | 2.3453 (16) | Cu2—Cl1 | 2.2308 (15) |
| Cu1—Cl3i | 2.4099 (14) | Cu2—Cl2 | 2.3057 (15) |
| Cu1—Cl3 | 2.4317 (15) | Cl3—Cu2i | 2.2277 (14) |
| Cu1—Cu2 | 2.8893 (12) | Cl3—Cu1ii | 2.4099 (14) |
| Symmetry codes: (i) x+1/2, −y−1/2, −z−1; (ii) x−1/2, −y−1/2, −z−1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···Cl4 | 0.90 | 2.45 | 3.203 (4) | 142 |
| N1—H1A···Cl2 | 0.90 | 2.90 | 3.442 (4) | 120 |
| N1—H1B···Cl4iii | 0.90 | 2.36 | 3.236 (4) | 163 |
| N2—H2A···Cl2iv | 0.90 | 2.39 | 3.260 (4) | 162 |
| N2—H2B···Cl2v | 0.90 | 2.42 | 3.187 (4) | 143 |
| Symmetry codes: (iii) x−1, y, z; (iv) −x, y−1/2, −z−3/2; (v) −x−1, y−1/2, −z−3/2. |
This work was supported by a Start-up Grant from SEU XRG. [Does the name of this body need to be given in full?]
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Newnham, R. E. (1975). Structure–Property Relations. New York: Springer.
Qu, Z.-R., Zhao, H., Wang, Y.-P., Wang, X.-S., Ye, Q., Li, Y.-H., Xiong, R.-G., Abrahams, B. H., Liu, Z.-G., Xue, Z.-L. & You, X.-Z. (2004). Chem. Eur. J. 10, 54–60.
Rigaku (2005). CrystalClear. Version 1.4.0. Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Sheldrick, G. M. (1999). SHELXTL/PC. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.
Macro-physical properties, such as ferroelectricity and second harmonic generation, are only found in noncentrosymmetric bulk material (Newnham, 1975). We have focused on the synthesis and design of noncentrosymmetric coordination compounds constructed by chiral organic ligand as building block with inorganic metal ions through hydrothermal synthesis (Qu et al., 2004). We report here the crystal structure of the title compound, cantena Poly [(R)-2-methylpiperazine-dium (µ2-chloro)-(µ3-chloro)-dichloro-di-copper(I)].
In I, there are two chemically and crystallographically independent Cu atoms with a distance of Cu1—Cu2 2.8893 (12) Å. As shown in Fig.1, Cu1 has a slightly distorted tetrahedral geometry defined by one terminal and three bridging Cl anions; Cu2 displays a trigonal geometry composed of one terminal and two bridging Cl anions. The distance from Cu2 to the plane of Cl1 Cl2 Cl3B is of 0.0426 (10) Å. The six atoms Cu1 Cl1 Cu2 Cl3B Cu1B Cl3 form a six-membered ring. Besides the terminal Cl atoms, the adjacent six-membered rings share edges to form the Cl-bridged Cu chain. The diprotonated piperidine molecules and the chains are connected by hydrogen bonds.