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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): m895.
Published online 2010 July 7. doi:  10.1107/S1600536810026073
PMCID: PMC3007331

Bis(1-benzyl­piperazine-1,4-diium) hexa­chloridocadmate(II) dihydrate

Abstract

The asymmetric unit of the title compound, (C11H18N2)2[CdCl6]·2H2O, consists of one 1-benzyl­piperazine-1,4-diium dication, one water mol­ecule and one-half of a [CdCl6]4− anion, located on an inversion centre. The crystal packing is governed by an extensive three-dimensional network of inter­molecular O—H(...)Cl, C—H(...)Cl, N—H(...)O and N—H(...)Cl hydrogen bonds, two of them bifurcated.

Related literature

For meta-chlorido complexes, see: El Glaoui, Jeanneau, et al. (2009 [triangle]); El Glaoui, Kefi et al. (2009 [triangle]). For the role of C—H(...)Cl hydrogen bonds, see: Janiak & Scharmann (2003 [triangle]. For a discussion of Cd—Cl distances and Cl—Cd—Cl bond angles, see: Bala et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m895-scheme1.jpg

Experimental

Crystal data

  • (C11H18N2)2[CdCl6]·2H2O
  • M r = 717.68
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m895-efi1.jpg
  • a = 12.734 (2) Å
  • b = 9.1686 (14) Å
  • c = 13.216 (2) Å
  • β = 103.249 (3)°
  • V = 1502.0 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.29 mm−1
  • T = 100 K
  • 0.55 × 0.45 × 0.25 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.622, T max = 0.746
  • 11244 measured reflections
  • 4446 independent reflections
  • 4123 reflections with I > 2σ(I)
  • R int = 0.016

Refinement

  • R[F 2 > 2σ(F 2)] = 0.022
  • wR(F 2) = 0.057
  • S = 1.07
  • 4446 reflections
  • 172 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.51 e Å−3
  • Δρmin = −0.83 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 1998 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810026073/hb5541sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810026073/hb5541Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We would like to acknowledge the support provided by the Secretary of State for Scientific Research and Technology of Tunisia. The diffractometer was funded by NSF grant 0087210, by Ohio Board of Regents grant CAP-491, and by YSU.

supplementary crystallographic information

Comment

As a part of our ongoing investigations in molecular salts containing meta-chlorido complexes (El Glaoui, Jeanneau, et al., 2009; El Glaoui, Kefi et al., 2009), we present here the crystal structure of one such compound, (C11H18N2)2CdCl6.2H2O, (Fig. 1). The asymmetric unit of its structure consists of one 1-benzylpiperazine-1,4-diium dication doubly protonated at the N1 and N2 nitrogen atoms, one water molecule and one-half of a CdCl64- anion (located on a crystallographic inversion centre) (Fig. 1). The atomic arrangement of (C11H18N2)2CdCl6.2H2O can be described as built up by inorganic chains of CdCl6 octahedra and water molecules extending along the b direction held together by O—H···Cl hydrogen bonds (Fig. 2, Table 1). Two such chains cross the unit cell at z = 0, z = 1/2 and x = 1/2 (Fig. 3). The organic groups are located between these chains and connect to them through N—H···Cl, C—H···Cl and N—H···O hydrogen bonds to form a three dimensional infinite network (Fig. 3, Table 1). All the chloride ions are involved in hydrogen bonding. It should be pointed out at this point that the C—H···Cl hydrogen bonds do usually not play a large role in stabilizing a structure (Janiak & Scharmann, 2003), but due to the large number of these interactions in the title compound they seem to substantially contribute to the choice of packing observed in the structure of the title compound. Among all the hydrogen bonds, two are bifurcated: N2—H2A···(Cl1, Cl2) and N2—H2B···(Cl2, Cl3). The H1 hydrogen atom attached to the N1 nitrogen atom is bonded only to the water molecule, via the N1—H1···O1 hydrogen bond, and not to the CdCl64- anion.

The Cd II ion is in an octahedral coordination environment composed of six chloride anions as to form an hexachlorocadmate (II) ion. In this kind of anion, the Cd—Cl bond lengths and Cl—Cd—Cl bond angles are generally not equal to one another but vary with the environment around the Cl atoms (Bala et al., 2006). In the title compound, the values of the Cd—Cl bond lengths vary between 2.5528 (5) and 2.7055 (4) Å. The Cl—Cd—Cl angles range from 87.354 (11) to 92.646 (11)°. These geometrical parameters agree with those found in [Co(NH3)6]4 [CdCl6] [CdCl4(SCN)(H2O)]2Cl2.2H2O where the Cd—Cl distances are between 2.5937 (9) and 2.691 (1) Å and the Cl—Cd—Cl angles ranging from 89.23 (3) to 95.50 (3)° (Bala et al., 2006). Owing to the obvious differences of Cd—Cl distances and Cl—Cd—Cl angles in (C11H18N2)2CdCl6.2H2O, the coordination geometry of the Cd atom could be regarded as a slightly distorted octahedron which is in full agreement with the literature data (Bala, et al., 2006).

Experimental

1-Benzypyperazine (2 mmol, 0.352 g) and CdCl2 (1 mmol, 0.183 g), were dissolved in dilute HCl (10 ml, 1 M) and the resultant solution was slowly evaporated at room temperature. A crystal of the title compound, which remained stable under normal conditions of temperature and humidity, was isolated after several days and subjected to X-ray diffraction analysis (yield 55%).

Refinement

C—H and NH2+ hydrogen atoms were placed in calculated positions with C—H in the range 0.93–0.97 and N—H equal to 0.92 Å. The N—H+ and the water hydrogen atom postitions were refined with N—H and O—H distance restraints of 0.91 (2) and 0.84 (2) Å. The Uiso(H) values of all H atoms were constrained to 1.2 or 1.5 times Ueq of the respective parent atom.

Figures

Fig. 1.
A view of the title compound, showing 50% probability displacement ellipsoids, arbitrary spheres for the H atoms, and the atom numbering scheme.
Fig. 2.
Projection along the a axis of the inorganic chains in (C11H18N2)2CdCl6.2H2O. Hydrogen bonds are denoted by dotted lines.
Fig. 3.
The packing of (C11H18N2)2CdCl6.2H2O, viewed down the b axis. Hydrogen bonds are denoted by dotted lines.

Crystal data

(C11H18N2)2[CdCl6]·2H2OF(000) = 732
Mr = 717.68Dx = 1.587 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2788 reflections
a = 12.734 (2) Åθ = 2.7–31.0°
b = 9.1686 (14) ŵ = 1.29 mm1
c = 13.216 (2) ÅT = 100 K
β = 103.249 (3)°Plate, colourless
V = 1502.0 (4) Å30.55 × 0.45 × 0.25 mm
Z = 2

Data collection

Bruker SMART APEX CCD diffractometer4446 independent reflections
Radiation source: fine-focus sealed tube4123 reflections with I > 2σ(I)
graphiteRint = 0.016
ω scansθmax = 31.3°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −17→18
Tmin = 0.622, Tmax = 0.746k = −12→13
11244 measured reflectionsl = −18→19

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.022Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.057H atoms treated by a mixture of independent and constrained refinement
S = 1.07w = 1/[σ2(Fo2) + (0.0269P)2 + 0.6306P] where P = (Fo2 + 2Fc2)/3
4446 reflections(Δ/σ)max = 0.001
172 parametersΔρmax = 0.51 e Å3
3 restraintsΔρmin = −0.83 e Å3

Special details

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)

xyzUiso*/Ueq
C10.03492 (12)0.81561 (17)0.11848 (12)0.0242 (3)
H1C0.07590.77940.07220.029*
C2−0.07139 (13)0.85867 (19)0.08024 (14)0.0312 (3)
H2−0.10320.85030.00810.037*
C3−0.13120 (12)0.91374 (16)0.14687 (15)0.0292 (3)
H3−0.20320.94570.12020.035*
C4−0.08597 (12)0.92209 (16)0.25191 (14)0.0269 (3)
H4−0.12720.95880.29780.032*
C50.01972 (11)0.87702 (15)0.29110 (12)0.0213 (3)
H50.05000.88140.36370.026*
C60.08142 (10)0.82535 (13)0.22417 (11)0.0164 (2)
C70.19878 (10)0.78999 (13)0.26364 (11)0.0156 (2)
H7A0.22670.74310.20760.019*
H7B0.20740.72030.32220.019*
C80.23911 (10)1.04936 (12)0.22283 (10)0.0125 (2)
H8A0.16091.07120.20670.015*
H8B0.25911.02050.15750.015*
C90.30187 (10)1.18282 (12)0.26720 (10)0.0122 (2)
H9A0.28581.26350.21620.015*
H9B0.27951.21380.33090.015*
C100.44650 (10)1.02741 (13)0.36618 (10)0.0120 (2)
H10A0.43071.05400.43370.014*
H10B0.52441.00510.37820.014*
C110.38168 (9)0.89435 (12)0.32287 (10)0.0116 (2)
H11A0.40220.86270.25840.014*
H11B0.39810.81370.37380.014*
Cd10.50000.50000.50000.01071 (4)
Cl10.36321 (2)0.69672 (3)0.55240 (2)0.01362 (6)
Cl20.59831 (3)0.49308 (3)0.69137 (2)0.01174 (6)
Cl30.37573 (2)0.28368 (3)0.54229 (2)0.01263 (6)
N10.26320 (8)0.92695 (11)0.29971 (8)0.01118 (18)
N20.41977 (8)1.15258 (10)0.29270 (8)0.01172 (19)
H2A0.45651.23420.32210.014*
H2B0.44161.13170.23260.014*
O10.23289 (9)0.99157 (10)0.49769 (9)0.0180 (2)
H10.2483 (14)0.9558 (19)0.3591 (12)0.018 (4)*
H1A0.2690 (17)0.924 (2)0.5315 (17)0.044 (6)*
H1B0.2655 (18)1.066 (2)0.5229 (18)0.047 (7)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0181 (7)0.0284 (7)0.0253 (7)−0.0036 (5)0.0031 (6)−0.0025 (6)
C20.0203 (7)0.0358 (8)0.0323 (9)−0.0051 (6)−0.0049 (6)0.0040 (7)
C30.0131 (6)0.0210 (6)0.0504 (10)−0.0028 (5)0.0008 (6)0.0050 (6)
C40.0169 (7)0.0201 (6)0.0458 (10)−0.0028 (5)0.0117 (6)−0.0048 (6)
C50.0166 (6)0.0208 (6)0.0274 (7)−0.0038 (5)0.0068 (5)−0.0034 (5)
C60.0113 (6)0.0134 (5)0.0241 (7)−0.0034 (4)0.0033 (5)−0.0013 (5)
C70.0132 (6)0.0106 (5)0.0223 (6)−0.0020 (4)0.0027 (5)−0.0012 (4)
C80.0126 (5)0.0112 (5)0.0129 (6)0.0007 (4)0.0013 (4)0.0025 (4)
C90.0122 (5)0.0106 (5)0.0144 (5)0.0007 (4)0.0042 (4)0.0005 (4)
C100.0114 (5)0.0129 (5)0.0111 (6)0.0004 (4)0.0014 (4)0.0004 (4)
C110.0096 (5)0.0116 (5)0.0136 (5)0.0017 (4)0.0028 (4)0.0007 (4)
Cd10.01320 (7)0.00972 (6)0.00955 (7)−0.00012 (4)0.00332 (5)0.00002 (4)
Cl10.01548 (14)0.01289 (12)0.01327 (13)0.00202 (10)0.00489 (11)0.00058 (10)
Cl20.01277 (14)0.01112 (12)0.01138 (14)−0.00071 (8)0.00289 (11)0.00010 (9)
Cl30.01428 (13)0.01192 (12)0.01209 (13)−0.00170 (9)0.00382 (10)−0.00078 (9)
N10.0112 (5)0.0100 (4)0.0127 (5)−0.0004 (3)0.0032 (4)0.0003 (4)
N20.0119 (5)0.0110 (4)0.0131 (5)−0.0008 (3)0.0046 (4)−0.0005 (4)
O10.0185 (5)0.0165 (4)0.0190 (5)0.0001 (3)0.0046 (4)−0.0001 (3)

Geometric parameters (Å, °)

C1—C21.389 (2)C9—H9A0.9900
C1—C61.390 (2)C9—H9B0.9900
C1—H1C0.9500C10—N21.4915 (16)
C2—C31.385 (3)C10—C111.5102 (17)
C2—H20.9500C10—H10A0.9900
C3—C41.378 (3)C10—H10B0.9900
C3—H30.9500C11—N11.4992 (15)
C4—C51.390 (2)C11—H11A0.9900
C4—H40.9500C11—H11B0.9900
C5—C61.3938 (19)Cd1—Cl2i2.5528 (5)
C5—H50.9500Cd1—Cl22.5528 (5)
C6—C71.5012 (18)Cd1—Cl32.6751 (4)
C7—N11.5158 (15)Cd1—Cl3i2.6751 (4)
C7—H7A0.9900Cd1—Cl1i2.7055 (4)
C7—H7B0.9900Cd1—Cl12.7055 (4)
C8—N11.4978 (15)N1—H10.889 (14)
C8—C91.5051 (16)N2—H2A0.9200
C8—H8A0.9900N2—H2B0.9200
C8—H8B0.9900O1—H1A0.837 (16)
C9—N21.4875 (15)O1—H1B0.830 (16)
C2—C1—C6120.17 (15)C11—C10—H10A109.5
C2—C1—H1C119.9N2—C10—H10B109.5
C6—C1—H1C119.9C11—C10—H10B109.5
C3—C2—C1120.28 (16)H10A—C10—H10B108.1
C3—C2—H2119.9N1—C11—C10110.70 (9)
C1—C2—H2119.9N1—C11—H11A109.5
C4—C3—C2119.81 (14)C10—C11—H11A109.5
C4—C3—H3120.1N1—C11—H11B109.5
C2—C3—H3120.1C10—C11—H11B109.5
C3—C4—C5120.30 (15)H11A—C11—H11B108.1
C3—C4—H4119.8Cl2i—Cd1—Cl2180.0
C5—C4—H4119.8Cl2i—Cd1—Cl392.646 (11)
C4—C5—C6120.22 (14)Cl2—Cd1—Cl387.354 (11)
C4—C5—H5119.9Cl2i—Cd1—Cl3i87.354 (11)
C6—C5—H5119.9Cl2—Cd1—Cl3i92.646 (11)
C1—C6—C5119.18 (13)Cl3—Cd1—Cl3i180.0
C1—C6—C7119.76 (12)Cl2i—Cd1—Cl1i87.784 (12)
C5—C6—C7120.93 (13)Cl2—Cd1—Cl1i92.218 (12)
C6—C7—N1110.75 (10)Cl3—Cd1—Cl1i90.322 (15)
C6—C7—H7A109.5Cl3i—Cd1—Cl1i89.680 (15)
N1—C7—H7A109.5Cl2i—Cd1—Cl192.215 (12)
C6—C7—H7B109.5Cl2—Cd1—Cl187.783 (11)
N1—C7—H7B109.5Cl3—Cd1—Cl189.678 (14)
H7A—C7—H7B108.1Cl3i—Cd1—Cl190.321 (14)
N1—C8—C9109.69 (10)Cl1i—Cd1—Cl1180.0
N1—C8—H8A109.7C8—N1—C11109.14 (9)
C9—C8—H8A109.7C8—N1—C7113.30 (10)
N1—C8—H8B109.7C11—N1—C7110.23 (9)
C9—C8—H8B109.7C8—N1—H1108.9 (11)
H8A—C8—H8B108.2C11—N1—H1106.7 (11)
N2—C9—C8110.79 (9)C7—N1—H1108.3 (12)
N2—C9—H9A109.5C9—N2—C10111.02 (9)
C8—C9—H9A109.5C9—N2—H2A109.4
N2—C9—H9B109.5C10—N2—H2A109.4
C8—C9—H9B109.5C9—N2—H2B109.4
H9A—C9—H9B108.1C10—N2—H2B109.4
N2—C10—C11110.58 (10)H2A—N2—H2B108.0
N2—C10—H10A109.5H1A—O1—H1B103 (3)
C6—C1—C2—C31.0 (2)N1—C8—C9—N259.09 (13)
C1—C2—C3—C4−1.8 (2)N2—C10—C11—N1−56.82 (13)
C2—C3—C4—C50.7 (2)C9—C8—N1—C11−59.78 (12)
C3—C4—C5—C61.1 (2)C9—C8—N1—C7176.99 (10)
C2—C1—C6—C50.8 (2)C10—C11—N1—C859.02 (13)
C2—C1—C6—C7−175.11 (13)C10—C11—N1—C7−175.95 (10)
C4—C5—C6—C1−1.8 (2)C6—C7—N1—C8−48.38 (14)
C4—C5—C6—C7173.99 (12)C6—C7—N1—C11−171.01 (10)
C1—C6—C7—N1109.33 (14)C8—C9—N2—C10−56.81 (13)
C5—C6—C7—N1−66.48 (15)C11—C10—N2—C955.34 (12)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···Cl1ii0.922.583.3383 (11)140
N2—H2A···Cl2ii0.922.593.2672 (11)131
N2—H2B···Cl2iii0.922.473.1846 (11)135
N2—H2B···Cl3iii0.922.583.2799 (12)133
N1—H1···O10.89 (1)1.92 (1)2.7945 (16)170 (2)
O1—H1A···Cl10.84 (2)2.39 (2)3.1678 (11)155 (2)
O1—H1B···Cl3iv0.83 (2)2.42 (2)3.2152 (11)161 (2)
C9—H9A···Cl3iii0.992.833.331 (2)112
C9—H9B···Cl3iv0.992.853.659 (3)139
C10—H10A···Cl3iv0.992.733.565 (2)143
C10—H10B···Cl2iii0.992.843.340 (4)112
C11—H11A···Cl1iii0.992.713.626 (1)154
C11—H11B···Cl10.992.723.587 (1)146

Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) x, −y+3/2, z−1/2; (iv) x, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5541).

References

  • Bala, R., Sharma, R. P., Sharma, U. & Ferretti, V. (2006). Acta Cryst. C62, m628–m631. [PubMed]
  • Brandenburg, K. (1998). DIAMOND Impact GbR, Bonn, Germany.
  • Bruker (2009). APEX2, SAINT and SADABS Bruker AXS Inc., Madison Wisconsin, USA.
  • El Glaoui, M., Jeanneau, E., Lefebvre, F. & Ben Nasr, C. (2009). Can. J. Anal. Sci. Spectr.54, 70–81.
  • El Glaoui, M., Kefi, R., Jeanneau, E., Lefebvre, F. & Ben Nasr, C. (2009). Can. J. Anal. Sci. Spectr.54, 281–291.
  • Janiak, C. & Scharmann, T. G. (2003). Polyhedron, 22, 1123–1133.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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