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Acta Crystallogr Sect E Struct Rep Online. 2008 November 1; 64(Pt 11): m1412.
Published online 2008 October 15. doi:  10.1107/S1600536808033011
PMCID: PMC2959686

Bis(4,4′-methyl­enedicyclo­hexyl­aminium) μ-benzene-1,4-dicarboxyl­ato-bis­[tri­chlorido­zinc(II)] tetra­hydrate

Abstract

The title compound, (C13H28N2)2[Zn2(C8H4O4)Cl6]·4H2O, was prepared by the reaction of ZnCl2·6H2O, benzene-1,4-dicarboxylic acid and 4,4′-diamino­dicyclo­hexyl­methane in methanol. The [Zn2Cl6(C8H4O4)]4− anions lie on centres of inversion and comprise two ZnCl3 groups bridged by benzene-1,4-dicarboxyl­ate. In addition to N—H(...)Cl and N—H(...)O hydrogen bonds between the cations and anions, solvent water mol­ecules form O—H(...)O and O—H(...)Cl hydrogen bonds to give a three-dimensional network.

Related literature

For related structures, see: Clausen et al. (2005 [triangle]); Thirumurugan & Rao (2005 [triangle]); Li et al. (1998 [triangle], 1999 [triangle]).

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Object name is e-64-m1412-scheme1.jpg

Experimental

Crystal data

  • (C13H28N2)2[Zn2(C8H4O4)Cl6]·4H2O
  • M r = 1004.36
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1412-efi1.jpg
  • a = 14.264 (3) Å
  • b = 14.202 (2) Å
  • c = 11.712 (2) Å
  • β = 100.498 (16)°
  • V = 2333.0 (7) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.42 mm−1
  • T = 295 (2) K
  • 0.70 × 0.40 × 0.10 mm

Data collection

  • Bruker P4 diffractometer
  • Absorption correction: ψ scan (XSCANS; Siemens, 1995 [triangle]) T min = 0.694, T max = 0.868
  • 5093 measured reflections
  • 4071 independent reflections
  • 3405 reflections with I > 2σ(I)
  • R int = 0.027
  • 3 standard reflections every 97 reflections intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.057
  • wR(F 2) = 0.132
  • S = 1.05
  • 4071 reflections
  • 244 parameters
  • 2 restraints
  • H-atom parameters constrained
  • Δρmax = 1.10 e Å−3
  • Δρmin = −0.83 e Å−3

Data collection: XSCANS (Siemens, 1995 [triangle]); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808033011/bi2304sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808033011/bi2304Isup2.hkl

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

Acknowledgments

The authors are grateful to the National Science Council of Taiwan for support. This research was also supported by the Project of the Specific Research Fields in Chung Yuan Christian University, Taiwan, under grant No. CYCU-97-CR-CH.

supplementary crystallographic information

Comment

The dianion of benzene-1,4-dicarboxylic acid is an important linker to bridge metal atoms which show significant chemical and physical properties (Clausen et al., 2005; Thirumurugan & Rao, 2005; Li et al., 1998, 1999). Since the anions contain four O atoms which are good hydrogen-bond acceptors, co-crystallization with organic cations would be expected to result in extensive hydrogen-bond networks. The title compound (Fig. 1) contains N—H···Cl and N—H···O hydrogen bonds between the cations and the anions, as well as O—H···O and O—H···Cl interactions formed by the lattice water molecules.

Experimental

ZnCl2.6H2O (0.49 g, 2.00 mmol) was added to a solution of 4,4'-diaminodicyclohexylmethane (0.21 g,1.00 mmol) and benzene-1,4-dicarboxylic acid (0.17 g, 1.00 mmol) in 30 ml MeOH. The mixture was refluxed for 24 h to yield a colorless solution with some white solid. The solution was filtered and then diethyl ether was added to induce precipitation. The precipitate was filtered and washed by ether (3 × 10 ml), then dried under reduced pressure to give a white powder. Colourless crystals were obtained by slow diffusion of ether into a methanol solution of the white powder over several weeks.

Refinement

H atoms bound to C and N atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H = 0.93–0.98 Å and N—H = 0.89 Å, and with Uiso(H) = 1.2 or 1.5Ueq(C/N). The H atoms of the water molecules were located in difference Fourier maps, then constrained to ride on their parent O atom with Uiso(H) = 1.5Ueq(O). The C8—C11 and C11—C12 bond distances were restrained to be identical with a standard uncertainty of 0.02 Å.

Figures

Fig. 1.
Molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level for non-H atoms. The [Zn2Cl6(C8H4O4)]4- anion lies on a centre of inversion. Symmetry code: -x, 1 - y, -z.

Crystal data

(C13H28N2)2[Zn2(C8H4O4)Cl6]·4H2OF(000) = 1052
Mr = 1004.36Dx = 1.430 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 33 reflections
a = 14.264 (3) Åθ = 5.7–12.5°
b = 14.202 (2) ŵ = 1.42 mm1
c = 11.712 (2) ÅT = 295 K
β = 100.498 (16)°Plate, colourless
V = 2333.0 (7) Å30.70 × 0.40 × 0.10 mm
Z = 2

Data collection

Bruker P4 diffractometer3405 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.027
graphiteθmax = 25.0°, θmin = 2.0°
ω scansh = −16→16
Absorption correction: ψ scan (XSCANS; Siemens, 1995)k = −1→16
Tmin = 0.694, Tmax = 0.868l = −1→13
5093 measured reflections3 standard reflections every 97 reflections
4071 independent reflections intensity decay: none

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)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0344P)2 + 8.1458P] where P = (Fo2 + 2Fc2)/3
4071 reflections(Δ/σ)max < 0.001
244 parametersΔρmax = 1.10 e Å3
2 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
Zn0.37495 (3)0.50908 (4)0.23918 (5)0.04083 (17)
Cl10.48147 (11)0.41661 (13)0.17455 (16)0.0807 (5)
Cl20.41895 (9)0.66231 (9)0.22022 (11)0.0522 (3)
Cl30.37246 (11)0.48512 (10)0.42863 (12)0.0611 (4)
O10.2401 (2)0.4944 (3)0.1703 (3)0.0528 (9)
O20.2553 (2)0.4968 (3)−0.0161 (3)0.0515 (8)
O30.3060 (3)0.6499 (3)−0.1424 (4)0.0829 (14)
H3B0.28300.5919−0.10770.124*
H3C0.37350.6415−0.16680.124*
O40.4724 (3)0.2921 (3)0.5161 (3)0.0663 (11)
H4B0.45310.35550.48710.099*
H4C0.49170.28940.59720.099*
N10.3214 (3)0.6947 (3)0.5109 (4)0.0624 (12)
H1A0.34700.64580.48020.094*
H1B0.35750.70970.57870.094*
H1C0.31790.74370.46290.094*
N2−0.3906 (3)0.6298 (3)0.0987 (4)0.0495 (10)
H2A−0.43990.60000.11930.074*
H2B−0.35770.58970.06290.074*
H2C−0.41190.67690.05080.074*
C10.2069 (3)0.4959 (3)0.0619 (4)0.0392 (10)
C20.0992 (3)0.4974 (3)0.0298 (4)0.0365 (9)
C30.0434 (3)0.4915 (4)0.1146 (4)0.0447 (11)
H3A0.07240.48570.19220.054*
C4−0.0549 (3)0.4940 (3)0.0853 (4)0.0425 (11)
H4A−0.09150.49000.14320.051*
C50.2238 (3)0.6694 (4)0.5292 (5)0.0494 (12)
H5A0.22860.61610.58310.059*
C60.1788 (4)0.7515 (4)0.5812 (5)0.0599 (14)
H6A0.21710.76770.65580.072*
H6B0.17660.80580.53060.072*
C70.0792 (4)0.7268 (6)0.5970 (6)0.087 (2)
H7A0.05040.77960.63010.104*
H7B0.08060.67330.64870.104*
C80.0217 (4)0.7026 (8)0.4758 (9)0.153 (5)
H8A0.03230.75440.42440.183*
C90.0658 (4)0.6144 (7)0.4308 (9)0.144 (5)
H9A0.06800.56330.48620.173*
H9B0.02780.59430.35760.173*
C100.1653 (4)0.6397 (5)0.4146 (6)0.084 (2)
H10A0.19490.58580.38450.101*
H10B0.16260.69070.35900.101*
C11−0.0777 (4)0.6972 (7)0.4707 (7)0.129 (4)
H11A−0.09850.75840.49320.154*
H11B−0.08860.65290.52990.154*
C12−0.1428 (5)0.6698 (5)0.3598 (5)0.082 (2)
H12A−0.11060.62240.32000.099*
C13−0.2310 (6)0.6253 (5)0.3937 (6)0.086 (2)
H13A−0.21190.57360.44700.104*
H13B−0.26370.67160.43310.104*
C14−0.2979 (5)0.5892 (4)0.2885 (5)0.0648 (16)
H14A−0.26650.54050.25120.078*
H14B−0.35380.56190.31190.078*
C15−0.3274 (3)0.6681 (3)0.2049 (4)0.0448 (11)
H15A−0.36400.71380.24160.054*
C16−0.2440 (4)0.7187 (4)0.1693 (5)0.0568 (14)
H16A−0.26690.77260.12140.068*
H16B−0.21180.67670.12370.068*
C17−0.1739 (4)0.7515 (4)0.2759 (5)0.0657 (16)
H17A−0.20350.80010.31550.079*
H17B−0.11820.77860.25160.079*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn0.0279 (3)0.0487 (3)0.0448 (3)0.0002 (2)0.0038 (2)−0.0039 (2)
Cl10.0513 (8)0.0921 (12)0.0964 (12)0.0202 (8)0.0077 (8)−0.0412 (10)
Cl20.0443 (6)0.0524 (7)0.0572 (7)−0.0055 (5)0.0023 (5)0.0085 (6)
Cl30.0727 (9)0.0612 (8)0.0493 (7)0.0159 (7)0.0108 (6)0.0109 (6)
O10.0318 (16)0.074 (2)0.050 (2)−0.0063 (17)−0.0002 (14)−0.0007 (18)
O20.0348 (17)0.063 (2)0.060 (2)0.0050 (16)0.0154 (15)0.0004 (17)
O30.086 (3)0.063 (3)0.112 (4)0.007 (2)0.051 (3)0.012 (2)
O40.074 (3)0.052 (2)0.065 (2)0.0020 (19)−0.010 (2)0.0026 (18)
N10.059 (3)0.057 (3)0.074 (3)−0.014 (2)0.020 (2)−0.018 (2)
N20.034 (2)0.059 (3)0.056 (2)−0.0009 (19)0.0076 (18)−0.004 (2)
C10.032 (2)0.030 (2)0.055 (3)0.0004 (18)0.006 (2)−0.005 (2)
C20.028 (2)0.035 (2)0.046 (2)−0.0022 (18)0.0072 (18)−0.0064 (19)
C30.036 (2)0.059 (3)0.038 (2)−0.001 (2)0.0023 (19)−0.002 (2)
C40.035 (2)0.054 (3)0.040 (2)0.000 (2)0.0110 (19)−0.003 (2)
C50.041 (3)0.044 (3)0.060 (3)−0.001 (2)0.001 (2)−0.006 (2)
C60.057 (3)0.064 (3)0.056 (3)0.001 (3)0.003 (3)−0.022 (3)
C70.042 (3)0.116 (6)0.097 (5)0.002 (3)−0.001 (3)−0.063 (5)
C80.044 (4)0.219 (11)0.181 (9)0.025 (5)−0.015 (5)−0.162 (9)
C90.038 (3)0.181 (9)0.198 (10)0.017 (5)−0.018 (5)−0.149 (8)
C100.065 (4)0.097 (5)0.081 (4)0.030 (4)−0.013 (3)−0.049 (4)
C110.084 (5)0.167 (9)0.113 (6)0.057 (6)−0.042 (5)−0.090 (6)
C120.077 (4)0.090 (5)0.066 (4)0.044 (4)−0.024 (3)−0.038 (4)
C130.120 (6)0.074 (4)0.054 (4)−0.001 (4)−0.013 (4)−0.001 (3)
C140.089 (4)0.052 (3)0.049 (3)−0.010 (3)0.003 (3)−0.001 (3)
C150.040 (2)0.048 (3)0.047 (3)0.000 (2)0.011 (2)−0.004 (2)
C160.046 (3)0.063 (3)0.059 (3)−0.011 (3)0.005 (2)0.012 (3)
C170.046 (3)0.071 (4)0.079 (4)−0.011 (3)0.009 (3)−0.011 (3)

Geometric parameters (Å, °)

Zn—O11.956 (3)C7—C81.543 (9)
Zn—Cl12.2418 (15)C7—H7A0.97
Zn—Cl32.2514 (15)C7—H7B0.97
Zn—Cl22.2869 (14)C8—C111.410 (7)
O1—C11.272 (6)C8—C91.537 (10)
O2—C11.243 (6)C8—H8A0.98
O3—H3B1.00C9—C101.510 (11)
O3—H3C1.06C9—H9A0.97
O4—H4B0.98C9—H9B0.97
O4—H4C0.94C10—H10A0.97
N1—C51.491 (6)C10—H10B0.97
N1—H1A0.89C11—C121.503 (6)
N1—H1B0.89C11—H11A0.97
N1—H1C0.89C11—H11B0.97
N2—C151.500 (6)C12—C131.524 (11)
N2—H2A0.89C12—C171.534 (9)
N2—H2B0.89C12—H12A0.98
N2—H2C0.89C13—C141.503 (8)
C1—C21.513 (6)C13—H13A0.97
C2—C31.385 (6)C13—H13B0.97
C2—C4i1.386 (6)C14—C151.497 (7)
C3—C41.382 (6)C14—H14A0.97
C3—H3A0.93C14—H14B0.97
C4—C2i1.386 (6)C15—C161.512 (7)
C4—H4A0.93C15—H15A0.98
C5—C101.505 (7)C16—C171.523 (8)
C5—C61.512 (7)C16—H16A0.97
C5—H5A0.98C16—H16B0.97
C6—C71.506 (8)C17—H17A0.97
C6—H6A0.97C17—H17B0.97
C6—H6B0.97
O1—Zn—Cl1118.31 (12)C7—C8—H8A106.4
O1—Zn—Cl3101.50 (11)C10—C9—C8107.6 (7)
Cl1—Zn—Cl3112.19 (7)C10—C9—H9A110.2
O1—Zn—Cl2109.14 (12)C8—C9—H9A110.2
Cl1—Zn—Cl2108.05 (7)C10—C9—H9B110.2
Cl3—Zn—Cl2107.06 (6)C8—C9—H9B110.2
C1—O1—Zn124.7 (3)H9A—C9—H9B108.5
H3B—O3—H3C113.5C5—C10—C9109.6 (6)
H4B—O4—H4C113.5C5—C10—H10A109.8
C5—N1—H1A109.5C9—C10—H10A109.8
C5—N1—H1B109.5C5—C10—H10B109.8
H1A—N1—H1B109.5C9—C10—H10B109.8
C5—N1—H1C109.5H10A—C10—H10B108.2
H1A—N1—H1C109.5C8—C11—C12120.6 (7)
H1B—N1—H1C109.5C8—C11—H11A107.2
C15—N2—H2A109.5C12—C11—H11A107.2
C15—N2—H2B109.5C8—C11—H11B107.2
H2A—N2—H2B109.5C12—C11—H11B107.2
C15—N2—H2C109.5H11A—C11—H11B106.8
H2A—N2—H2C109.5C11—C12—C13107.0 (6)
H2B—N2—H2C109.5C11—C12—C17114.7 (7)
O2—C1—O1125.4 (4)C13—C12—C17109.0 (5)
O2—C1—C2119.5 (4)C11—C12—H12A108.6
O1—C1—C2115.2 (4)C13—C12—H12A108.6
C3—C2—C4i118.9 (4)C17—C12—H12A108.6
C3—C2—C1120.7 (4)C14—C13—C12111.0 (6)
C4i—C2—C1120.4 (4)C14—C13—H13A109.4
C4—C3—C2120.7 (4)C12—C13—H13A109.4
C4—C3—H3A119.7C14—C13—H13B109.4
C2—C3—H3A119.7C12—C13—H13B109.4
C3—C4—C2i120.4 (4)H13A—C13—H13B108.0
C3—C4—H4A119.8C15—C14—C13110.0 (5)
C2i—C4—H4A119.8C15—C14—H14A109.7
N1—C5—C10108.6 (5)C13—C14—H14A109.7
N1—C5—C6110.4 (4)C15—C14—H14B109.7
C10—C5—C6111.6 (4)C13—C14—H14B109.7
N1—C5—H5A108.7H14A—C14—H14B108.2
C10—C5—H5A108.7C14—C15—N2109.0 (4)
C6—C5—H5A108.7C14—C15—C16113.2 (4)
C7—C6—C5110.4 (5)N2—C15—C16109.2 (4)
C7—C6—H6A109.6C14—C15—H15A108.4
C5—C6—H6A109.6N2—C15—H15A108.4
C7—C6—H6B109.6C16—C15—H15A108.4
C5—C6—H6B109.6C15—C16—C17110.6 (5)
H6A—C6—H6B108.1C15—C16—H16A109.5
C6—C7—C8107.2 (6)C17—C16—H16A109.5
C6—C7—H7A110.3C15—C16—H16B109.5
C8—C7—H7A110.3C17—C16—H16B109.5
C6—C7—H7B110.3H16A—C16—H16B108.1
C8—C7—H7B110.3C16—C17—C12111.3 (5)
H7A—C7—H7B108.5C16—C17—H17A109.4
C11—C8—C9114.4 (7)C12—C17—H17A109.4
C11—C8—C7114.4 (7)C16—C17—H17B109.4
C9—C8—C7108.3 (7)C12—C17—H17B109.4
C11—C8—H8A106.4H17A—C17—H17B108.0
C9—C8—H8A106.4

Symmetry codes: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl30.892.413.252 (4)159
N1—H1B···Cl2ii0.892.513.290 (4)147
N1—H1C···O3ii0.891.942.828 (5)178
N2—H2A···Cl1iii0.892.953.725 (5)146
N2—H2A···Cl2iii0.892.673.321 (4)131
N2—H2B···O2i0.892.062.928 (4)166
N2—H2C···O4iv0.891.952.813 (4)164
O3—H3B···O21.001.812.798 (4)167.8
O3—H3C···Cl1v1.062.243.262 (4)160.3
O4—H4B···Cl30.982.213.172 (4)164.9
O4—H4C···Cl2vi0.942.383.258 (3)154.9

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BI2304).

References

  • Clausen, H. F., Poulsen, R. D., Bond, A. D., Chevallier, M.-A. S. & Iversen, B. B. (2005). J. Solid State Chem.178, 3342–3351.
  • Li, H., Eddaoudi, M., Groy, T. L. & Yaghi, O. M. (1998). J. Am. Chem. Soc.120, 8571–8572.
  • Li, H., Eddaoudi, M., O’Keeffe, M. & Yaghi, O. M. (1999). Nature (London), 402, 276–279.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Siemens (1995). XSCANS Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
  • Thirumurugan, A. & Rao, C. N. R. (2005). J. Mater. Chem.15, 3852–3858.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography