The crystal structure of the title compound {(C
5H
14N
2)
2[Cd
2Cl
8]}
n, (I), consists of hydrogen-bonded 2-methylpiperazinediium (H
2MPPA
2+) cations in the presence of one-dimensional polymeric {[CdCl
3(μ
3-Cl)]
2−}
n anions. The Cd
II centres are hexacoordinated by three terminal chlorides and three bridging chlorides and have a slightly distorted octahedral CdCl
3(μ
3-Cl)
3 arrangement. The alternating CdCl
6 octahedra form four-membered Cd
2Cl
2 rings by the sharing of neighbouring Cd–Cl edges to give rise to extended one-dimensional ladder-like chains parallel to the
b axis, with a Cd
Cd distance of 4.094 (2) Å and a Cd
Cd
Cd angle of 91.264 (8)°. The H
2MPPA
2+ cations crosslink the [CdCl
3(μ
3-Cl)]
n chains by the formation of two N—H
Cl hydrogen bonds to each chain, giving rise to one-dimensional ladder-like H
2MPPA
2+–Cl
2 hydrogen-bonded chains [graph set
R42(14)]. The [CdCl
3(μ
3-Cl)]
n chains are interwoven with the H
2MPPA
2+–Cl
2 hydrogen-bonded chains, giving rise to a three-dimensional supramolecular network.
Supporting information
CCDC reference: 993495
Data collection: CrystalClear (Rigaku, 2005); cell refinement: 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
catena-Poly[bis[(
S)-2-methylpiperazine-1,4-diium]
[bis[trichloridocadmium(II)]-di-µ
3-chlorido]]
top
Crystal data top
(C5H14N2)[CdCl4] | F(000) = 696 |
Mr = 356.38 | Dx = 1.968 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 4003 reflections |
a = 13.342 (7) Å | θ = 2.6–27.5° |
b = 5.853 (3) Å | µ = 2.66 mm−1 |
c = 15.404 (8) Å | T = 291 K |
V = 1202.9 (11) Å3 | Block, colourless |
Z = 4 | 0.36 × 0.32 × 0.30 mm |
Data collection top
Rigaku Mercury2 diffractometer | 2758 independent reflections |
Radiation source: fine-focus sealed tube | 2654 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 2.6° |
CCD profile fitting scans | h = −17→17 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −7→7 |
Tmin = 0.35, Tmax = 0.40 | l = −19→19 |
12240 measured reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.023 | w = 1/[σ2(Fo2) + (0.022P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.048 | (Δ/σ)max = 0.001 |
S = 1.01 | Δρmax = 0.82 e Å−3 |
2758 reflections | Δρmin = −0.57 e Å−3 |
114 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0058 (4) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), with how many Friedel pairs? |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.06 (2) |
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 | |
C1 | 0.6439 (2) | 0.5947 (5) | 0.57259 (18) | 0.0335 (6) | |
H1 | 0.6716 | 0.7441 | 0.5884 | 0.040* | |
C2 | 0.7118 (2) | 0.4106 (6) | 0.60808 (17) | 0.0354 (6) | |
H2A | 0.7167 | 0.4264 | 0.6706 | 0.042* | |
H2B | 0.6830 | 0.2620 | 0.5956 | 0.042* | |
C3 | 0.8107 (2) | 0.4090 (5) | 0.47352 (17) | 0.0354 (6) | |
H3A | 0.7861 | 0.2598 | 0.4561 | 0.043* | |
H3B | 0.8779 | 0.4273 | 0.4506 | 0.043* | |
C4 | 0.74363 (19) | 0.5910 (6) | 0.43714 (17) | 0.0337 (6) | |
H4A | 0.7720 | 0.7400 | 0.4495 | 0.040* | |
H4B | 0.7393 | 0.5741 | 0.3746 | 0.040* | |
C5 | 0.5386 (2) | 0.5758 (9) | 0.6091 (2) | 0.0599 (9) | |
H5A | 0.5113 | 0.4285 | 0.5952 | 0.090* | |
H5B | 0.4972 | 0.6928 | 0.5842 | 0.090* | |
H5C | 0.5407 | 0.5942 | 0.6710 | 0.090* | |
Cd1 | 0.893832 (13) | 0.92676 (4) | 0.763339 (12) | 0.03140 (7) | |
Cl1 | 0.88902 (5) | 0.92559 (11) | 0.59419 (4) | 0.02782 (12) | |
Cl2 | 0.71085 (5) | 0.90735 (16) | 0.77661 (5) | 0.04507 (18) | |
Cl3 | 0.92925 (5) | 0.92619 (13) | 0.93032 (4) | 0.02815 (13) | |
Cl4 | 1.08727 (4) | 0.91555 (12) | 0.74166 (4) | 0.02624 (12) | |
N1 | 0.64182 (16) | 0.5756 (5) | 0.47552 (14) | 0.0314 (5) | |
H1A | 0.6134 | 0.4444 | 0.4617 | 0.041 (8)* | |
H1B | 0.6119 | 0.6750 | 0.4575 | 0.037 (9)* | |
N2 | 0.81308 (16) | 0.4241 (4) | 0.56966 (13) | 0.0306 (4) | |
H2C | 0.8414 | 0.3201 | 0.5872 | 0.042 (10)* | |
H2D | 0.8433 | 0.5511 | 0.5842 | 0.025 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0380 (14) | 0.0306 (14) | 0.0319 (14) | 0.0026 (13) | −0.0092 (11) | −0.0045 (13) |
C2 | 0.0413 (15) | 0.0330 (14) | 0.0319 (14) | −0.0041 (14) | −0.0100 (11) | 0.0027 (14) |
C3 | 0.0392 (14) | 0.0359 (15) | 0.0311 (13) | 0.0062 (15) | −0.0089 (11) | −0.0057 (13) |
C4 | 0.0375 (14) | 0.0330 (14) | 0.0306 (13) | −0.0028 (14) | −0.0101 (11) | 0.0063 (13) |
C5 | 0.0441 (18) | 0.085 (3) | 0.050 (2) | 0.004 (2) | −0.0037 (15) | −0.003 (2) |
Cd1 | 0.02546 (10) | 0.04512 (12) | 0.02363 (10) | −0.00011 (10) | 0.00011 (7) | 0.00010 (9) |
Cl1 | 0.0366 (3) | 0.0220 (3) | 0.0249 (3) | −0.0008 (4) | −0.0043 (2) | −0.0001 (3) |
Cl2 | 0.0273 (3) | 0.0614 (4) | 0.0466 (4) | −0.0015 (4) | 0.0026 (3) | 0.0016 (4) |
Cl3 | 0.0358 (3) | 0.0225 (3) | 0.0262 (3) | −0.0006 (3) | 0.0023 (2) | 0.0002 (3) |
Cl4 | 0.0236 (3) | 0.0309 (3) | 0.0242 (3) | −0.0006 (2) | 0.0001 (2) | 0.0002 (3) |
N1 | 0.0361 (11) | 0.0233 (10) | 0.0347 (12) | 0.0038 (11) | −0.0153 (9) | 0.0016 (11) |
N2 | 0.0357 (11) | 0.0240 (10) | 0.0321 (11) | 0.0017 (12) | −0.0149 (9) | 0.0026 (11) |
Geometric parameters (Å, º) top
C1—N1 | 1.500 (3) | C5—H5A | 0.9600 |
C1—C2 | 1.510 (4) | C5—H5B | 0.9600 |
C1—C5 | 1.517 (4) | C5—H5C | 0.9600 |
C1—H1 | 0.9800 | Cd1—Cl2 | 2.4525 (15) |
C2—N2 | 1.477 (4) | Cd1—Cl4 | 2.6032 (14) |
C2—H2A | 0.9700 | Cd1—Cl1 | 2.6064 (15) |
C2—H2B | 0.9700 | Cd1—Cl3 | 2.6152 (15) |
C3—N2 | 1.484 (3) | Cd1—Cl4i | 2.8730 (16) |
C3—C4 | 1.500 (4) | Cl4—Cd1ii | 2.8730 (16) |
C3—H3A | 0.9700 | N1—H1A | 0.8825 |
C3—H3B | 0.9700 | N1—H1B | 0.7586 |
C4—N1 | 1.484 (3) | N2—H2C | 0.7656 |
C4—H4A | 0.9700 | N2—H2D | 0.8743 |
C4—H4B | 0.9700 | | |
| | | |
N1—C1—C2 | 108.6 (2) | C1—C5—H5C | 109.5 |
N1—C1—C5 | 110.3 (2) | H5A—C5—H5C | 109.5 |
C2—C1—C5 | 111.7 (3) | H5B—C5—H5C | 109.5 |
N1—C1—H1 | 108.8 | Cl2—Cd1—Cl4 | 175.15 (3) |
C2—C1—H1 | 108.7 | Cl2—Cd1—Cl1 | 93.36 (2) |
C5—C1—H1 | 108.8 | Cl4—Cd1—Cl1 | 84.04 (2) |
N2—C2—C1 | 111.4 (2) | Cl2—Cd1—Cl3 | 95.61 (3) |
N2—C2—H2A | 109.4 | Cl4—Cd1—Cl3 | 86.96 (2) |
C1—C2—H2A | 109.4 | Cl1—Cd1—Cl3 | 171.00 (2) |
N2—C2—H2B | 109.4 | Cl2—Cd1—Cl4i | 97.80 (3) |
C1—C2—H2B | 109.3 | Cl4—Cd1—Cl4i | 86.253 (18) |
H2A—C2—H2B | 108.0 | Cl1—Cd1—Cl4i | 88.740 (19) |
N2—C3—C4 | 110.1 (2) | Cl3—Cd1—Cl4i | 90.67 (2) |
N2—C3—H3A | 109.7 | Cd1—Cl4—Cd1ii | 96.63 (2) |
C4—C3—H3A | 109.6 | C4—N1—C1 | 112.1 (2) |
N2—C3—H3B | 109.7 | C4—N1—H1A | 110.5 |
C4—C3—H3B | 109.7 | C1—N1—H1A | 108.3 |
H3A—C3—H3B | 108.1 | C4—N1—H1B | 106.8 |
N1—C4—C3 | 110.7 (2) | C1—N1—H1B | 108.5 |
N1—C4—H4A | 109.5 | H1A—N1—H1B | 110.6 |
C3—C4—H4A | 109.4 | C2—N2—C3 | 112.1 (2) |
N1—C4—H4B | 109.6 | C2—N2—H2C | 105.5 |
C3—C4—H4B | 109.5 | C3—N2—H2C | 108.3 |
H4A—C4—H4B | 108.1 | C2—N2—H2D | 111.4 |
C1—C5—H5A | 109.5 | C3—N2—H2D | 108.4 |
C1—C5—H5B | 109.5 | H2C—N2—H2D | 111.0 |
H5A—C5—H5B | 109.5 | | |
Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+2, y−1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl3iii | 0.88 | 2.29 | 3.164 (3) | 169 |
N1—H1B···Cl3iv | 0.76 | 2.43 | 3.145 (3) | 157 |
N2—H2C···Cl1v | 0.77 | 2.40 | 3.112 (3) | 156 |
N2—H2D···Cl1 | 0.87 | 2.28 | 3.128 (3) | 163 |
Symmetry codes: (iii) −x+3/2, −y+1, z−1/2; (iv) −x+3/2, −y+2, z−1/2; (v) x, y−1, z. |