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Acta Cryst. (2009). E65, m1469    [ doi:10.1107/S1600536809043736 ]

Bis(hexamethylenetetramine)bis(trichloroacetato)copper(II)

L.-M. Li, F.-F. Jian and Y.-F. Li

Abstract top

In the title compound, [Cu(C2Cl3O2)2(C6H12N4)2], the CuII ion (site symmetry 2) is coordinated by two trichloroacetate anions and two hexamethylenetetramine molecules, resulting in a distorted CuN2O2 geometry that is intermediate between tetrahedral and square planar. The Cl atoms are disordered over two sets of sites, with relative occupancies of 0.749 (7) and 0.251 (7). In the crystal, the packing is consolidated by intermolecular C-H...O interactions.

Comment top

Metal-organic framework coordination polymers have attracted tremendous attention because of their molecular topologies and their potentially useful ionexchange,adsorption,catalytic and magnetic properties. Much of this work has been concerned (e.g. Chen et al., 2001). In order to search for new complexes of this type, we synthesized the title compound, (I), and report its crystal structure here.

The title structure contains one copper(II), two N atoms of the hexamethylenetetramine ligands and two O atoms of trichloroacetate anions. The coordination sphere of the copper(II) ion is best described as a seriously distorted tetrahedral. The Cu—O and Cu—N bond lengths are in agreement with those reported recently (Moncol et al., 2007). The Cl atoms are disordered over two sites, with relatives occupancies 0.749 (7) and 0.251 (7).The crystal packing is stabilized by intra- and intermolecular C—H···O hydrogen interaction (Table 1).

Related literature top

For background to coordination networks, see: Chen et al. (2001). For a related structure, see: Moncol et al. (2007).

Experimental top

The title compound was obtained by adding hexamethylenetetramine (2 mmol) dropwise to a solution of trichloroacetatocopper(II) (1 mmol) in ethanol (30 ml) under stirred for 1 h at room temperature. A green solution was formed and after a few days block crystals precipitated.

Refinement top

H atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H and N—H distances of 0.93–0.96 and 0.86 Å, and with Uiso = 1.2Ueq.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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).

Figures top
[Figure 1] Fig. 1. The structure of (I) showing 30% probability displacement ellipsoids. Atoms with suffix A are generated by the symmetry operation (–x, y, 1/2–z).
Bis(hexamethylenetetramine)bis(trichloroacetato)copper(II) top
Crystal data top
[Cu(C2Cl3O2)2(C6H12N4)2]F(000) = 1356
Mr = 668.67Dx = 1.666 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 23.291 (5) ÅCell parameters from 2740 reflections
b = 6.4759 (13) Åθ = 3.3–27.5°
c = 20.702 (4) ŵ = 1.46 mm−1
β = 121.36 (3)°T = 293 K
V = 2666.3 (9) Å3Block, green
Z = 40.30 × 0.20 × 0.15 mm
Data collection top
Bruker SMART CCD
diffractometer		2740 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.023
graphiteθmax = 27.5°, θmin = 3.3°
Detector resolution: 3 pixels mm-1h = −30→30
ω scansk = −7→8
12444 measured reflectionsl = −26→26
3048 independent reflections
Refinement top
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) = 0.184H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.1275P)2 + 3.9764P]
where P = (Fo2 + 2Fc2)/3
3048 reflections(Δ/σ)max = 0.042
187 parametersΔρmax = 1.52 e Å−3
78 restraintsΔρmin = −0.98 e Å−3
Crystal data top
[Cu(C2Cl3O2)2(C6H12N4)2]V = 2666.3 (9) Å3
Mr = 668.67Z = 4
Monoclinic, C2/cMo Kα radiation
a = 23.291 (5) ŵ = 1.46 mm−1
b = 6.4759 (13) ÅT = 293 K
c = 20.702 (4) Å0.30 × 0.20 × 0.15 mm
β = 121.36 (3)°
Data collection top
Bruker SMART CCD
diffractometer		2740 reflections with I > 2σ(I)
12444 measured reflectionsRint = 0.023
3048 independent reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.057H-atom parameters constrained
wR(F2) = 0.184Δρmax = 1.52 e Å−3
S = 1.09Δρmin = −0.98 e Å−3
3048 reflectionsAbsolute structure: ?
187 parametersFlack parameter: ?
78 restraintsRogers parameter: ?
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
xyzUiso*/UeqOcc. (<1)
Cu10.00000.79415 (8)0.25000.0315 (2)
O10.06660 (12)0.7420 (4)0.35558 (14)0.0428 (6)
O20.01619 (16)0.4397 (5)0.33908 (17)0.0669 (9)
N10.07476 (12)0.8907 (4)0.23307 (14)0.0303 (5)
N20.15738 (18)1.1697 (5)0.2701 (2)0.0483 (7)
N30.10588 (16)1.0194 (5)0.14402 (17)0.0445 (7)
N40.18698 (16)0.8189 (5)0.2547 (2)0.0477 (8)
C10.10233 (18)1.0882 (5)0.27694 (19)0.0396 (7)
H1A0.06671.19000.25840.047*
H1B0.11831.06290.32990.047*
C20.1318 (2)1.2073 (6)0.1894 (3)0.0499 (9)
H2A0.09621.30960.17040.060*
H2B0.16781.26290.18400.060*
C30.1605 (2)0.8664 (7)0.1743 (2)0.0519 (9)
H3A0.19670.91860.16870.062*
H3B0.14390.74020.14490.062*
C40.13189 (18)0.7387 (5)0.2620 (2)0.0406 (7)
H4A0.14850.70850.31470.049*
H4B0.11560.61080.23370.049*
C50.21037 (19)1.0132 (7)0.2968 (2)0.0547 (10)
H5A0.22770.98610.35000.066*
H5B0.24701.06700.29240.066*
C60.05198 (17)0.9380 (6)0.15232 (18)0.0410 (7)
H6A0.03460.81290.12250.049*
H6B0.01571.03790.13280.049*
C70.1155 (2)0.5072 (6)0.45812 (19)0.0579 (10)
C80.05989 (16)0.5630 (6)0.37587 (17)0.0378 (7)
Cl10.1084 (2)0.6786 (5)0.51998 (15)0.0872 (9)0.749 (7)
Cl20.1139 (3)0.2478 (4)0.48019 (19)0.1149 (15)0.749 (7)
Cl30.19694 (13)0.5452 (9)0.47005 (18)0.1191 (16)0.749 (7)
Cl1'0.1398 (7)0.7198 (12)0.5194 (5)0.102 (2)0.251 (7)
Cl2'0.0839 (6)0.2990 (15)0.4873 (5)0.106 (2)0.251 (7)
Cl3'0.1851 (4)0.430 (2)0.4518 (6)0.133 (3)0.251 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0256 (3)0.0403 (4)0.0277 (3)0.0000.0133 (2)0.000
O10.0349 (12)0.0555 (14)0.0316 (12)−0.0009 (10)0.0129 (10)0.0104 (10)
O20.0620 (18)0.0575 (17)0.0507 (16)−0.0134 (14)0.0079 (14)0.0011 (14)
N10.0288 (11)0.0309 (12)0.0326 (12)0.0013 (9)0.0170 (10)0.0000 (10)
N20.0535 (19)0.0428 (15)0.0538 (18)−0.0155 (14)0.0316 (16)−0.0081 (14)
N30.0491 (17)0.0516 (17)0.0424 (15)−0.0001 (13)0.0304 (13)0.0039 (13)
N40.0360 (15)0.0541 (18)0.061 (2)0.0086 (12)0.0305 (15)0.0094 (15)
C10.0476 (18)0.0345 (15)0.0432 (17)−0.0034 (13)0.0282 (15)−0.0068 (14)
C20.059 (2)0.0409 (19)0.058 (2)−0.0043 (15)0.037 (2)0.0067 (16)
C30.059 (2)0.056 (2)0.061 (2)0.0055 (19)0.046 (2)0.0001 (19)
C40.0395 (17)0.0361 (15)0.054 (2)0.0087 (13)0.0295 (16)0.0081 (15)
C50.0361 (18)0.071 (3)0.053 (2)−0.0117 (17)0.0208 (16)0.0022 (19)
C60.0376 (16)0.0516 (19)0.0336 (15)−0.0027 (14)0.0185 (13)−0.0008 (14)
C70.064 (2)0.058 (2)0.0289 (16)0.0017 (19)0.0086 (16)0.0075 (16)
C80.0346 (15)0.0496 (18)0.0253 (13)0.0018 (13)0.0129 (12)0.0010 (13)
Cl10.115 (2)0.0970 (16)0.0377 (8)0.0104 (14)0.0319 (13)−0.0064 (9)
Cl20.147 (3)0.0608 (12)0.0681 (13)0.0104 (14)0.0082 (17)0.0246 (11)
Cl30.0462 (11)0.208 (5)0.0721 (16)0.0175 (17)0.0089 (11)0.030 (2)
Cl1'0.131 (5)0.090 (3)0.036 (2)0.008 (3)0.010 (3)−0.011 (2)
Cl2'0.148 (5)0.064 (3)0.063 (3)−0.009 (3)0.024 (3)0.026 (3)
Cl3'0.053 (3)0.196 (6)0.092 (4)0.044 (4)−0.001 (3)0.005 (4)
Geometric parameters (Å, °) top
Cu1—O11.941 (3)C1—H1B0.9700
Cu1—O1i1.941 (3)C2—H2A0.9700
Cu1—N1i2.045 (2)C2—H2B0.9700
Cu1—N12.045 (2)C3—H3A0.9700
O1—C81.270 (4)C3—H3B0.9700
O2—C81.203 (5)C4—H4A0.9700
N1—C61.499 (4)C4—H4B0.9700
N1—C41.506 (4)C5—H5A0.9700
N1—C11.505 (4)C5—H5B0.9700
N2—C11.460 (5)C6—H6A0.9700
N2—C51.465 (6)C6—H6B0.9700
N2—C21.473 (6)C7—C81.553 (5)
N3—C61.452 (4)C7—Cl21.747 (5)
N3—C21.462 (5)C7—Cl1'1.754 (7)
N3—C31.470 (5)C7—Cl3'1.764 (7)
N4—C41.463 (5)C7—Cl11.766 (5)
N4—C51.465 (6)C7—Cl2'1.786 (7)
N4—C31.477 (5)C7—Cl31.797 (5)
C1—H1A0.9700
O1—Cu1—O1i159.95 (17)N4—C4—H4A109.3
O1—Cu1—N1i96.49 (11)N1—C4—H4A109.3
O1i—Cu1—N1i89.63 (10)N4—C4—H4B109.3
O1—Cu1—N189.63 (10)N1—C4—H4B109.3
O1i—Cu1—N196.49 (11)H4A—C4—H4B108.0
N1i—Cu1—N1144.38 (14)N2—C5—N4112.9 (3)
C8—O1—Cu1111.6 (2)N2—C5—H5A109.0
C6—N1—C4107.7 (2)N4—C5—H5A109.0
C6—N1—C1107.0 (3)N2—C5—H5B109.0
C4—N1—C1107.7 (3)N4—C5—H5B109.0
C6—N1—Cu1114.51 (19)H5A—C5—H5B107.8
C4—N1—Cu1112.75 (19)N3—C6—N1112.3 (3)
C1—N1—Cu1106.88 (18)N3—C6—H6A109.1
C1—N2—C5108.8 (3)N1—C6—H6A109.1
C1—N2—C2108.3 (3)N3—C6—H6B109.1
C5—N2—C2107.9 (3)N1—C6—H6B109.1
C6—N3—C2108.7 (3)H6A—C6—H6B107.9
C6—N3—C3108.3 (3)C8—C7—Cl2113.0 (3)
C2—N3—C3108.1 (3)C8—C7—Cl1'112.4 (4)
C4—N4—C5108.6 (3)Cl2—C7—Cl1'127.5 (4)
C4—N4—C3108.4 (3)C8—C7—Cl3'105.0 (4)
C5—N4—C3107.5 (3)Cl2—C7—Cl3'83.9 (5)
N2—C1—N1111.6 (3)Cl1'—C7—Cl3'108.3 (5)
N2—C1—H1A109.3C8—C7—Cl1108.0 (3)
N1—C1—H1A109.3Cl2—C7—Cl1113.0 (3)
N2—C1—H1B109.3Cl1'—C7—Cl125.7 (4)
N1—C1—H1B109.3Cl3'—C7—Cl1131.9 (4)
H1A—C1—H1B108.0C8—C7—Cl2'106.9 (4)
N3—C2—N2112.3 (3)Cl2—C7—Cl2'27.9 (4)
N3—C2—H2A109.2Cl1'—C7—Cl2'112.5 (5)
N2—C2—H2A109.2Cl3'—C7—Cl2'111.6 (5)
N3—C2—H2B109.2Cl1—C7—Cl2'91.0 (4)
N2—C2—H2B109.2C8—C7—Cl3109.7 (3)
H2A—C2—H2B107.9Cl2—C7—Cl3105.1 (3)
N3—C3—N4112.4 (3)Cl1'—C7—Cl382.7 (5)
N3—C3—H3A109.1Cl3'—C7—Cl326.5 (4)
N4—C3—H3A109.1Cl1—C7—Cl3107.8 (3)
N3—C3—H3B109.1Cl2'—C7—Cl3130.4 (5)
N4—C3—H3B109.1O2—C8—O1127.3 (3)
H3A—C3—H3B107.8O2—C8—C7119.2 (3)
N4—C4—N1111.6 (3)O1—C8—C7113.5 (3)
Symmetry codes: (i) −x, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···O2ii0.972.523.416 (5)153
Symmetry codes: (ii) −x, y+1, −z+1/2.
Table 1
Selected geometric parameters (Å, °) top
Cu1—O11.941 (3)Cu1—N12.045 (2)
O1—Cu1—O1i159.95 (17)O1i—Cu1—N196.49 (11)
O1—Cu1—N189.63 (10)N1i—Cu1—N1144.38 (14)
Symmetry codes: (i) −x, y, −z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···O2ii0.972.523.416 (5)153
Symmetry codes: (ii) −x, y+1, −z+1/2.
Acknowledgements top

The authors would like to thank the Natural Science Foundation of Shandong Province (No. Y2008B30).

references
References top

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Chen, B., Eddaoudi, M., Hyde, S. T., OKeeffe, M. & Yaghi, O. M. (2001). Science, 291, 1021–1023.

Moncol, J., Maroszova, J., Peter, L., Mark, H., Marian, V., Morris, H., Svorec, J., Melnik, M., Mazur, M. & Koman, M. (2007). Inorg. Chim. Acta, 360, 3213–3225.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.