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.
Supporting information
CCDC reference: 672578
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- R factor = 0.040
- wR factor = 0.091
- Data-to-parameter ratio = 23.2
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.80
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 7
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1A .. CL2 .. 2.90 Ang.
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.21 Ratio
Alert level G
ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be
replaced by the scaled T values. Since the ratio of scaled T's
is identical to the ratio of reported T values, the scaling
does not imply a change to the absorption corrections used in
the study.
Ratio of Tmax expected/reported 0.804
Tmax scaled 0.804 Tmin scaled 0.580
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 27.48
From the CIF: _reflns_number_total 2756
Count of symmetry unique reflns 1618
Completeness (_total/calc) 170.33%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1138
Fraction of Friedel pairs measured 0.703
Are heavy atom types Z>Si present yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2 = . R
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (1) 1.00
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu2 (1) 1.03
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
4 ALERT level C = Check and explain
7 ALERT level G = General alerts; check
3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
4 ALERT type 4 Improvement, methodology, query or suggestion
2 ALERT type 5 Informative message, check
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).
Poly[(
R)-2-methylpiperazinediium
[µ
3-chlorido-µ
2-chlorido-dichloridodicopper(I)]]
top
Crystal data top
(C5H14N2)[Cu2Cl4] | F(000) = 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 = 3.1–27.5° |
b = 12.544 (4) Å | µ = 4.36 mm−1 |
c = 15.561 (5) Å | T = 293 K |
V = 1209.1 (6) Å3 | Block, colourless |
Z = 4 | 0.25 × 0.06 × 0.05 mm |
Data collection top
Rigaku Mercury2 (2x2 bin mode) diffractometer | 2756 independent reflections |
Radiation source: fine-focus sealed tube | 2439 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.058 |
Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
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 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)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.091 | w = 1/[σ2(Fo2) + (0.0374P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
2756 reflections | Δρmax = 0.75 e Å−3 |
119 parameters | Δρmin = −0.53 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with 1149 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.04 (2) |
Crystal data top
(C5H14N2)[Cu2Cl4] | V = 1209.1 (6) Å3 |
Mr = 371.06 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.1943 (16) Å | µ = 4.36 mm−1 |
b = 12.544 (4) Å | T = 293 K |
c = 15.561 (5) Å | 0.25 × 0.06 × 0.05 mm |
Data collection top
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 | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.091 | Δρmax = 0.75 e Å−3 |
S = 1.06 | Δρmin = −0.53 e Å−3 |
2756 reflections | Absolute structure: Flack (1983), with 1149 Friedel pairs |
119 parameters | Absolute structure parameter: −0.04 (2) |
0 restraints | |
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 | |
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* | |
Atomic displacement parameters (Å2) top | 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) |
Geometric parameters (Å, º) top
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. |
Hydrogen-bond geometry (Å, º) top
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. |
Experimental details
Crystal data |
Chemical formula | (C5H14N2)[Cu2Cl4] |
Mr | 371.06 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 6.1943 (16), 12.544 (4), 15.561 (5) |
V (Å3) | 1209.1 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.36 |
Crystal size (mm) | 0.25 × 0.06 × 0.05 |
|
Data collection |
Diffractometer | Rigaku Mercury2 (2x2 bin mode) diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.721, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12245, 2756, 2439 |
Rint | 0.058 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.091, 1.06 |
No. of reflections | 2756 |
No. of parameters | 119 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.75, −0.53 |
Absolute structure | Flack (1983), with 1149 Friedel pairs |
Absolute structure parameter | −0.04 (2) |
Selected bond lengths (Å) topCu1—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. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl4 | 0.90 | 2.45 | 3.203 (4) | 141.9 |
N1—H1A···Cl2 | 0.90 | 2.90 | 3.442 (4) | 120.2 |
N1—H1B···Cl4iii | 0.90 | 2.36 | 3.236 (4) | 163.0 |
N2—H2A···Cl2iv | 0.90 | 2.39 | 3.260 (4) | 162.3 |
N2—H2B···Cl2v | 0.90 | 2.42 | 3.187 (4) | 142.9 |
Symmetry codes: (iii) x−1, y, z; (iv) −x, y−1/2, −z−3/2; (v) −x−1, y−1/2, −z−3/2. |
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.