inorganic compounds
Poly[diamminedi-μ3-dicyanamido-copper(II)]
aFaculty Chemistry Engineering, Michoacán University, Morelia, Michoacán, Mexico, bCOFEPRIS, Michoacán University, Morelia, Michoacán, Mexico, cInstitute of Analytical Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, SK-812 37 Bratislava, Slovak Republic 81237, and dInstitute of Physical Chemistry and Chemical Physics, Slovak University of Technology, Radlinského 9, SK-812 37 Bratislava, Slovak Republic
*Correspondence e-mail: viktor.vrabel@stuba.sk
The II complex, [Cu(C2N3)2(NH3)2]n, contains one half-molecule, the complex being completed through inversion symmetry, with the CuII atom situated on the centre of symmetry. The around CuII is a Jahn–Teller-distorted [CuN6] octahedron. The terminal N atoms of two dicyanamide ligands and two ammine ligands form an approximate square plane, with N—Cu—N bite angles of 89.72 (5) and 90.28 (5)°. The is completed in the axial positions by the central amide-type N atoms of two additional dicyanamide ligands, with an elongated Cu—N distance of 2.548 (1) Å. In turn, each of the four dicyanamide ligands, acting as bidentate, link the CuII ions into a two-dimensional polymeric structure parallel to (100). The ammine H atoms are involved in intermolecular hydrogen bonding with the free terminal N atoms of neighbouring dicyanamide ligands, yielding a three-dimensional network.
of the title polymeric mononuclear CuRelated literature
For bonding modes of the dicyanamide ligand, see: Burčák et al. (2004); Yang et al. (2004); van Albada et al. (2001); Potočňák et al. (2002); Zhang et al. (2004); Mohamadou et al. (2003); Batten et al. (2000); Kožíšek et al. (2007). For magnetic properties of [M(dicyanamide)2] compounds, see: Batten & Murray (2003); Kurmoo & Kepert (1998).
Experimental
Crystal data
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Data collection
Refinement
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Data collection: CrysAlis CCD (Oxford Diffraction, 2010); cell CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: enCIFer (Allen et al., 2004).
Supporting information
10.1107/S1600536812045382/lr2087sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812045382/lr2087Isup2.hkl
A solution of Cu(SO4)2.5H2O (2.0 mmol) in water (3 ml) was added to a solution of K[N(CN)2] (4.0 mmol) in water (10 ml)and mixed with a solution of ammine (4.0 mmol) in water (10 ml). After standing for a few days, blue crystals of (I) were isolated (yield: ca 10%).
The ammine H atoms were located in a difference Fourier map and refined with a fixed isotropic displacement parameter.
Data collection: CrysAlis CCD (Oxford Diffraction, 2010); cell
CrysAlis CCD (Oxford Diffraction, 2010); data reduction: CrysAlis RED (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: enCIFer (Allen et al., 2004).[Cu(C2N3)2(NH3)2] | F(000) = 230 |
Mr = 229.72 | Dx = 1.682 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 15460 reflections |
a = 7.1310 (2) Å | θ = 3.7–29.3° |
b = 9.6301 (2) Å | µ = 2.38 mm−1 |
c = 7.2162 (2) Å | T = 298 K |
β = 113.782 (3)° | Block, dark blue |
V = 453.47 (2) Å3 | 0.52 × 0.32 × 0.17 mm |
Z = 2 |
Oxford Diffraction Gemini R CCD diffractometer | 1126 independent reflections |
Radiation source: fine-focus sealed tube | 1019 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
Detector resolution: 10.4340 pixels mm-1 | θmax = 28.3°, θmin = 3.7° |
ω and ϕ scans | h = −9→9 |
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2010), based on expressions derived by Clark & Reid (1995)] | k = −12→12 |
Tmin = 0.410, Tmax = 0.682 | l = −9→9 |
19836 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.017 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.052 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0314P)2 + 0.113P] where P = (Fo2 + 2Fc2)/3 |
1126 reflections | (Δ/σ)max < 0.001 |
74 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
[Cu(C2N3)2(NH3)2] | V = 453.47 (2) Å3 |
Mr = 229.72 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.1310 (2) Å | µ = 2.38 mm−1 |
b = 9.6301 (2) Å | T = 298 K |
c = 7.2162 (2) Å | 0.52 × 0.32 × 0.17 mm |
β = 113.782 (3)° |
Oxford Diffraction Gemini R CCD diffractometer | 1126 independent reflections |
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2010), based on expressions derived by Clark & Reid (1995)] | 1019 reflections with I > 2σ(I) |
Tmin = 0.410, Tmax = 0.682 | Rint = 0.016 |
19836 measured reflections |
R[F2 > 2σ(F2)] = 0.017 | 0 restraints |
wR(F2) = 0.052 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.21 e Å−3 |
1126 reflections | Δρmin = −0.25 e Å−3 |
74 parameters |
Experimental. face-indexed (CrysAlis RED; Oxford Diffraction, 2010) Absorption correction: CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.8 (release 30-07-2007 CrysAlis171 .NET) (compiled Jul 30 2007,18:35:48) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.12500 (18) | 0.20615 (12) | 0.40737 (17) | 0.0314 (2) | |
C2 | 0.2567 (2) | −0.00704 (11) | 0.5168 (2) | 0.0313 (3) | |
N1 | −0.26849 (18) | 0.41648 (13) | 0.45514 (19) | 0.0362 (2) | |
H1 | −0.351 (3) | 0.472 (2) | 0.371 (4) | 0.054 (6)* | |
H2 | −0.283 (3) | 0.417 (2) | 0.572 (3) | 0.053 (5)* | |
H3 | −0.281 (3) | 0.338 (3) | 0.410 (3) | 0.062 (6)* | |
N2 | 0.09027 (19) | 0.32110 (12) | 0.42058 (18) | 0.0416 (3) | |
N3 | 0.15107 (18) | 0.07772 (11) | 0.36879 (16) | 0.0389 (3) | |
N4 | 0.3460 (2) | −0.09051 (13) | 0.63406 (19) | 0.0462 (3) | |
Cu1 | 0.0000 | 0.5000 | 0.5000 | 0.02839 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0349 (5) | 0.0285 (6) | 0.0293 (5) | 0.0008 (4) | 0.0114 (4) | −0.0034 (4) |
C2 | 0.0340 (6) | 0.0271 (6) | 0.0332 (6) | −0.0019 (4) | 0.0140 (5) | −0.0056 (4) |
N1 | 0.0405 (6) | 0.0299 (5) | 0.0365 (6) | −0.0005 (4) | 0.0138 (5) | −0.0001 (5) |
N2 | 0.0518 (7) | 0.0276 (5) | 0.0431 (6) | 0.0054 (5) | 0.0168 (5) | −0.0042 (4) |
N3 | 0.0520 (6) | 0.0267 (5) | 0.0313 (5) | 0.0077 (4) | 0.0097 (5) | −0.0046 (4) |
N4 | 0.0520 (7) | 0.0353 (6) | 0.0459 (6) | 0.0033 (5) | 0.0140 (5) | 0.0045 (5) |
Cu1 | 0.03572 (14) | 0.01832 (13) | 0.03050 (14) | 0.00135 (6) | 0.01271 (10) | −0.00132 (6) |
C1—N2 | 1.1466 (17) | N1—H2 | 0.89 (2) |
C1—N3 | 1.2975 (16) | N1—H3 | 0.81 (2) |
C2—N4 | 1.1546 (18) | N2—Cu1 | 2.0021 (11) |
C2—N3 | 1.3135 (17) | Cu1—N1i | 1.9793 (12) |
N1—Cu1 | 1.9793 (12) | Cu1—N2i | 2.0021 (11) |
N1—H1 | 0.84 (2) | ||
N2—C1—N3 | 172.98 (14) | C1—N2—Cu1 | 163.67 (11) |
N4—C2—N3 | 173.97 (14) | C1—N3—C2 | 120.18 (11) |
Cu1—N1—H1 | 102.1 (15) | N1i—Cu1—N1 | 180.00 (7) |
Cu1—N1—H2 | 108.6 (12) | N1i—Cu1—N2 | 89.72 (5) |
H1—N1—H2 | 111 (2) | N1—Cu1—N2 | 90.28 (5) |
Cu1—N1—H3 | 112.9 (15) | N1i—Cu1—N2i | 90.28 (5) |
H1—N1—H3 | 112 (2) | N1—Cu1—N2i | 89.72 (5) |
H2—N1—H3 | 110.2 (19) | N2—Cu1—N2i | 180.0 |
N3—C1—N2—Cu1 | 124.8 (10) | C1—N2—Cu1—N1i | 130.8 (4) |
N2—C1—N3—C2 | −178.5 (11) | C1—N2—Cu1—N1 | −49.2 (4) |
N4—C2—N3—C1 | 179 (100) | C1—N2—Cu1—N2i | 24 (100) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N4ii | 0.84 (2) | 2.43 (2) | 3.2555 (18) | 165.4 (19) |
N1—H2···N4iii | 0.89 (2) | 2.34 (2) | 3.2278 (18) | 175.7 (17) |
N1—H3···N4iv | 0.81 (2) | 2.43 (2) | 3.2073 (18) | 162.1 (19) |
Symmetry codes: (ii) x−1, −y+1/2, z−1/2; (iii) −x, y+1/2, −z+3/2; (iv) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C2N3)2(NH3)2] |
Mr | 229.72 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 7.1310 (2), 9.6301 (2), 7.2162 (2) |
β (°) | 113.782 (3) |
V (Å3) | 453.47 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.38 |
Crystal size (mm) | 0.52 × 0.32 × 0.17 |
Data collection | |
Diffractometer | Oxford Diffraction Gemini R CCD diffractometer |
Absorption correction | Analytical [CrysAlis RED (Oxford Diffraction, 2010), based on expressions derived by Clark & Reid (1995)] |
Tmin, Tmax | 0.410, 0.682 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19836, 1126, 1019 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.017, 0.052, 1.07 |
No. of reflections | 1126 |
No. of parameters | 74 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.21, −0.25 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1998), enCIFer (Allen et al., 2004).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N4i | 0.84 (2) | 2.43 (2) | 3.2555 (18) | 165.4 (19) |
N1—H2···N4ii | 0.89 (2) | 2.34 (2) | 3.2278 (18) | 175.7 (17) |
N1—H3···N4iii | 0.81 (2) | 2.43 (2) | 3.2073 (18) | 162.1 (19) |
Symmetry codes: (i) x−1, −y+1/2, z−1/2; (ii) −x, y+1/2, −z+3/2; (iii) −x, −y, −z+1. |
Acknowledgements
The authors thank the Grant Agency of Slovak Republic (grant No. 1/0679/11 and CONACYT No. SNI20438) as well as the Structural Funds, Interreg IIIA, for financial support in purchasing the diffractometer.
References
Albada, G. A. van, Mutikainen, I., Turpeinen, U. & Reedijk, J. (2001). Acta Cryst. E57, m421–m423. CSD CrossRef IUCr Journals Google Scholar
Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335–338. Web of Science CrossRef CAS IUCr Journals Google Scholar
Batten, S. R., Harris, A. R., Jensen, P., Murray, K. S. & Ziebell, A. (2000). J. Chem. Soc. Dalton Trans. pp. 3829–3836. Web of Science CSD CrossRef Google Scholar
Batten, S. R. & Murray, K. S. (2003). Coord. Chem. Rev. 246, 103–130. Web of Science CrossRef CAS Google Scholar
Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Burčák, M., Potočňák, I., Baran, P. & Jäger, L. (2004). Acta Cryst. C60, m601–m604. Web of Science CSD CrossRef IUCr Journals Google Scholar
Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897. CrossRef CAS Web of Science IUCr Journals Google Scholar
Kožíšek, J., Díaz, J. G. & Albor, A. G. (2007). Acta Cryst. E63, i125–i126. Web of Science CrossRef IUCr Journals Google Scholar
Kurmoo, M. & Kepert, C. J. (1998). New J. Chem. 22, 1515–1524. Web of Science CSD CrossRef CAS Google Scholar
Mohamadou, A., van Albada, G. A., Kooijman, H., Wieczorek, B., Spek, A. L. & Reedijk, J. (2003). New J. Chem. pp. 983–988. Web of Science CSD CrossRef Google Scholar
Oxford Diffraction (2010). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Potočňák, I., Burčák, M., Massa, W. & Jäger, L. (2002). Acta Cryst. C58, m523–m528. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, H.-J., Kou, H.-Z., Gao, F., Cui, A.-L. & Wang, R.-J. (2004). Acta Cryst. E60, m611–m613. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhang, B., Kou, H.-Z., He, Y., Wang, H.-G. & Cui, A.-L. (2004). Acta Cryst. C60, m341–m342. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
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Among the various classes of ligands currently employed for the generation of coordination compounds, dicyanamide (dca) has been attracting a lot of attention, partly due to the discovery of interesting magnetic properties in the M(dca)2 compounds (Batten & Murray, 2003; Kurmoo & Kepert, 1998). A particular feature of this ligand is the variability in coordination modes it can display and thus it is able to generate one- to three-dimensional networks, as well as molecular and ionic compounds, depending on its metallic centers and its organic coligands. In coordination compounds of copper, the dca anion, (N(CN)2), exhibits a rich variety of bonding modes. It can coordinate either in a monodentate manner (Burčák et al., 2004; Yang et al., 2004;) or, more typically, in a bidentate manner [two types of binding: mainly through two nitrile N atoms (Albada et al., 2001; Potočňák et al., 2002; Zhang et al., 2004), but also through one amide and one nitrile N atom (Mohamadou et al., 2003), or even in a tridentate manner (Batten et al., 2000; Kožíšek et al., 2007). The asymmetric unit of the title compound, (I), [Cu(N(CN)2)2(NH3)2]n, contains one-half of the molecule with the CuII atom situated at the centre of symmetry and is octahedrally coordinated by two ammino and two bidentate dca ligands, forming a CuN6 coordination environment (Fig.1). Two terminal N atoms of two dca units and two ammino ligands forming an approximate square plane with N—Cu—N bite angles of 89.72 (5) and 90.28 (5)°. Coordinaton polyhedron is completed in axial position by the central amide N atoms of two additional dca ligands with the Cu–N elongated distance of 2.548 (1) Å as a result of the Jahn–Teller effect. The amino H atoms are involved in intermolecular hydrogen bonding with the free terminal N atoms of neighbouring dicyanamide ligands, yielding a three-dimensional network (Fig.2).