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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 7| July 2014| Pages m267-m268
https://doi.org/10.1107/S1600536814013695

catena-Poly[[(pyrazine-2-carboxamide-κN4)copper(I)]-μ3-iodido]

Lukáš Krivosudskýa* and Erik Rakovskýa

aComenius University, Faculty of Natural Sciences, Department of Inorganic Chemistry, Mlynská dolina CH2, 842 15 Bratislava, Slovak Republic
*Correspondence e-mail: krivosudskyl@fns.uniba.sk

(Received 3 June 2014; accepted 11 June 2014; online 18 June 2014)

In the title metal–organic polymeric complex, [CuI(C5H5N3O)]n, the asymmetric unit is composed of one monomer unit of the polymer and one CuI atom linked to one iodide anion and one pyrazine-2-carboxamide mol­ecule. The CuI atom is in a distorted tetra­hedral coordination completed by one pyrazine N atom of the pyrazine-2-carboxamide ligand and three iodide anions. The polymeric structure adopts a well-known ladder-like motif of {CuNI3} tetra­hedra running in the b-axis direction. The mol­ecules of the organic ligand are connected via medium-to-strong N—H⋯O and N—H⋯N hydrogen bonds and weak π–π inter­actions [the distance between two parallel planes of the rings is 3.5476 (14) Å and the centroid–centroid contact is 4.080 (2) Å]. The title compound has a relatively high decomposition temperature (564 K) as a result of relatively strong covalent and non-covalent inter­actions inside and between the chains.

CCDC reference: 885829

Related literature

For other CuI coordination polymers, see: Peng et al. (2006[Peng, R., Li, D., Wu, T., Zhou, X.-P. & Ng, S. W. (2006). Inorg. Chem. 45, 4035-4046.], 2010[Peng, R., Li, M. & Li, D. (2010). Coord. Chem. Rev. 254, 1-18.]); Feng et al. (2006[Feng, H., Zhou, X.-P., Wu, T., Li, D., Yin, Y.-G. & Ng, S. W. (2006). Inorg. Chim. Acta, 359, 4027-4035.]); Wu et al. (2005[Wu, T., Li, D. & Ng, S. W. (2005). CrystEngComm, 7, 514-518.]); Rath & Holt (1985[Rath, N. P. & Holt, E. M. (1985). J. Chem. Soc. Chem. Commun. pp. 665-667.]); Rath et al. (1986[Rath, N. P., Holt, E. M. & Tanimura, K. (1986). J. Chem. Soc. Dalton Trans. pp. 2303-2310.]). For complexes of pyrazine-2-carboxamide with other transition metals and studies of their biological activity, see: Somoskovi et al. (2004[Somoskovi, A., Wade, M. M., Sun, Z. H. & Zhang, Y. (2004). J. Antimicrob. Chemother. 53, 192-196.]); Singh & Seth (1975[Singh, P. P. & Seth, J. N. (1975). J. Inorg. Nucl. Chem. 37, 593-597.]); Azizov et al. (1978[Azizov, T. A., Khdzhaev, O. F. & Parpiev, N. A. (1978). Koord. Khim. 4, 1234-1237.]). For other CuI complexes of pyrazine-2-carboxamide, see: Munakata et al. (1997[Munakata, M., Wu, L. P., Kuroda-Sowa, T., Maekawa, M., Moriwaki, K. & Kitagawa, S. (1997). Inorg. Chem. 36, 5416-5418.]); Goher & Mautner (1999[Goher, M. A. & Mautner, F. A. (1999). J. Chem. Soc. Dalton Trans. pp. 1535-1536.], 2000[Goher, M. A. & Mautner, F. A. (2000). Polyhedron, 19, 601-606.], 2001[Goher, M. A. & Mautner, F. A. (2001). J. Coord. Chem. 53, 79-90.]). For a description of the Cambridge Structural Database, see: Allen (2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]). For non-covalent inter­actions, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N. L. (1995). Angew. Chem. Int. Ed. 34, 1555-1573.]); Bondi (1964[Bondi, A. (1964). J. Phys. Chem. 68, 441-452.]); Janiak (2000[Janiak, C. (2000). J. Chem. Soc. Dalton Trans. pp. 3885-3896.]); Jia et al. (2009[Jia, X. L., Zhou, J., Zheng, S. T. & Yang, G. Y. (2009). J. Cluster Sci. 20, 555-563.]); Wells (1975[Wells, A. F. (1975). In Structural Inorganic Chemistry. Oxford University Press.]). For the riding constraints used in the refinement, see: Cooper et al. (2010[Cooper, R. I., Thompson, A. L. & Watkin, D. J. (2010). J. Appl. Cryst. 43, 1100-1107.]).

[Scheme 1]

Experimental

Crystal data

  • [CuI(C5H5N3O)]

  • Mr = 313.56

  • Monoclinic, C 2/c

  • a = 29.5408 (7) Å

  • b = 4.0795 (1) Å

  • c = 14.3164 (3) Å

  • β = 111.712 (3)°

  • V = 1602.89 (7) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 6.52 mm−1

  • T = 100 K

  • 0.22 × 0.06 × 0.03 mm
Data collection

  • Agilent SuperNova diffractometer

  • Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012[Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England.]) Tmin = 0.562, Tmax = 1.000

  • 11538 measured reflections

  • 2135 independent reflections

  • 1339 reflections with I > 2σ(I)

  • Rint = 0.024
Refinement

  • R[F2 > 2σ(F2)] = 0.021

  • wR(F2) = 0.042

  • S = 1.00

  • 1556 reflections

  • 100 parameters

  • H-atom parameters constrained

  • Δρmax = 0.96 e Å−3

  • Δρmin = −0.87 e Å−3

Table 1
Selected bond lengths (Å)

I1—Cu1i 2.6437 (5)
I1—Cu1ii 2.6310 (5)
I1—Cu1 2.6016 (5)
Cu1—N1 2.059 (3)
Cu1—Cu1ii 2.7974 (6)
Symmetry codes: (i) x, y-1, z; (ii) [-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}].

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N3—H311⋯O1iii 0.84 2.05 2.883 (5) 170 (1)
N3—H312⋯N2iv 0.87 2.32 3.124 (5) 154 (1)
Symmetry codes: (iii) -x+1, -y+3, -z+1; (iv) [-x+1, y, -z+{\script{1\over 2}}].

Data collection: CrysAlis PRO (Agilent, 2012[Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007[Palatinus, L. & Chapuis, G. (2007). J. Appl. Cryst. 40, 786-790.]); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003[Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487.]); molecular graphics: DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]), Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]) and ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]); software used to prepare material for publication: CRYSTALS, PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information

CCDC reference: 885829

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S1600536814013695/vn2084sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536814013695/vn2084Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536814013695/vn2084Isup3.mol

checkCIF report


Comment top

Copper(I) coordination polymers are well known for their photochemical and photophysical properties. There are several methods for the synthesis of such metal-organic frameworks (Peng et al., 2010). One possible strategy is the use of copper(I) halide, especially iodide, which dissolves in concentrated aqueous solutions of iodides. After addition of an organic ligand polynuclear copper(I) complexes can be crystallized (Peng et al., 2006; Feng et al., 2006; Wu et al., 2005; Rath & Holt, 1985; Rath et al., 1986).

Pyrazine-2-carboxamide (usually pyrazinamide, in medical literature abbreviated as PZA) is a drug used for tuberculosis treatment in the last 60 years. Nowadays the possibility of increasing the activity of the drug by forming transition metal complexes is examinated widely (Somoskovi et al., 2004). In addition to complexes with transition metals with potential biological effects, e.g. Mn(II), Ni(II), Fe(II), Zn(II), Cu(II) (Singh & Seth 1975; Azizov et al., 1978; Goher & Mautner, 2000) the complexes with Cu(I) have also been prepared. They have been found to be water-insoluble stable compounds with and expected polymeric structure, as has been confirmed by X–ray structure analysis of six compounds with simplified formulas [Cu2(µ-PZA)3]n(ClO4)2.C3H6O, [Cu2(µ-PZA)2(µ-C3H6O)]n(BF4)2 (Munakata et al., 1997); [Cu(µ-N3)PZA2]n (Goher & Mautner, 1999); [Cu(µ-I)PZA2]n (Goher & Mautner, 2000); [Cu(µ-CN)PZA2]n and [Cu(µ-SCN)PZA2]n (Goher & Mautner, 2001).

Goher & Mautner (2000) have succesfully prepared eleven new pyrazine-2-carboxamide complexes of Cu(I) including [CuI(pyrazine-2-carboxamide)]n, (I), but which was only obtained as a powder sample. We have successfully optimised the preparation process of (I) as well as other copper(I) complexes to obtain crystalline samples suitable for single crystal X-ray structure determination and the crystal structure of (I) is reported here.

As shown in Fig. 1, the asymmetric unit of (I) consists of one copper(I) cation bonded to one iodide anion and one pyrazine-2-carboxamide ligand. This unit is an elementary building block of catenary polymer as depicted in Fig. 2. The CuI is coordinated by one N atom from pyrazine-2-carboxamide ligand and three I– anions to form a distorted tetrahedral coordination environment, where the Cu—N bond length is 2.059 (3) Å and the Cu—I bond lengths are 2.6016 (5), 2.6437 (5) and 2.6310 (5) Å. The Cu—N bond length is similar to the mean value of Cu—N bond lengths in above mentioned complexes (2.048 Å). There is a number of structures containing a similar ladder–like linkage of {CuNI3} tetrahedrons. In most cases one of the Cu—I bond lengths tends to be shorter then the other two, e.g. in the realated compound [Cu2(µ3-I)2(4-(4-carboxyphenyl)pyridine-N)2]n the Cu—I bond lengths are 2.631 (1), 2.662 (1), 2.667 (1) and 2.604 (1), 2.658 (1), 2.662 (1) Å (Jia et al., 2009). The I—Cu—N bond angles are 105.07 (8), 114.64 (8) and 103.54 (8)°. The distance between two CuI centres 2.7974 (6) Å indicates that there there could be a weak metal—metal interaction as the sum of van der Waals radii of two copper atoms is 2.8 Å (Bondi, 1964).

The polymeric chains running in the b axis direction are connected via hydrogen bonds between the pyrazinamide ligands (Fig. 3). The amide groups of the ligands form typical dimers consisting of eight-membered rings with the graph set R22(8) linked by a strong N–H···O hydrogen bond. The second hydrogen atom of the –NH2 group forms medium N–H···N hydrogen bond to the non-coordinating N atom of the pyrazine ring, thus forming a ten-membered ring with the graph set R22(10) (Table 2.) (Bernstein et al. 1995).

Moreover, there is a weak π–π interaction between adjacent pyrazine rings in the polymer chain. The distance between two parallel planes of the rings is 3.5476 (14) Å and the centroid-centroid contact is 4.080 (2) Å (Fig. 4). The angle α between the ring normal and the centroid-centroid vector is 29.6 ° and the horizontal displacement of the rings d is 2.014 Å. It is well–known that often the ring planes are offset so that a ring atom lies almost over the center of the other ring and its hydrogen atom almost on the top of a carbon atom (Janiak, 2000). In the compound (I) this is not the case.

There are 9 compounds with the same ladder–like polymeric structure and pyrazine derivatives as the ligands in the CSD (Allen, 2002). The relevant parameters of the π–π interaction of these compounds compared to compound (I) are listed in Table 3. The entries DINQOG, GABHOH and ODOFOC correspond to the compounds with general formula [CuI(2-sub-pyrazine)]n, where sub is cyano–, iodo– and chloro– functional group respectively. More complicated substituents on the pyrazine ring obviously lead to an increasing α angle and displacement d. Interestingly, in the case of non–substituted pyrazine the two parameters are similar to those of compound (I).

Compound (I) is stable in air and insoluble in water and most solvents, it is only sparingly soluble in dimethylsulfoxide forming a pale orange solution. We performed a thermal decompostion analysis and we found that, surprisingly, the decomposition takes place at a quite high temperature (291 °C) starting with the release of pyrazine-2-carboxamide. The crystal structure analysis of (I) clearly elucidates that the organic molecule is well–anchored not only via covalent bonding to the copper(I) center but also via non-covalent interactions between pyrazine-2-carboxamide molecules. Thanks to the thermal stability and the photoluminiscence properties of (I) described in (Goher & Mautner, 2000) the compound is a possible candidate for the use as a photoactive material.

Related literature top

For other CuI coordination polymers, see: Peng et al. (2006, 2010); Feng et al. (2006); Wu et al. (2005); Rath & Holt (1985); Rath et al. (1986). For complexes of pyrazine-2-carboxamide with other transition metals and studies of their biological activity, see: Somoskovi et al. (2004); Singh & Seth (1975); Azizov et al. (1978). For other CuI complexes of pyrazine-2-carboxamide, see: Munakata et al. (1997); Goher & Mautner (1999, 2000, 2001). For a description of the Cambridge Structural Database, see: Allen (2002). For non-covalent interactions , see: Bernstein et al. (1995); Bondi (1964); Janiak (2000); Jia et al. (2009); Wells (1975). For the riding constraints used in the refinement, see: Cooper et al. (2010).

Experimental top

All reactants except copper(I) iodide were obtained commercially and used without further purification. Copper(I) iodide was prepared as follows: Cu(NO3)2.3H2O (12.7 g, 52.5 mmol) was dissolved in 270 ml of distilled water and the solution was cooled until below room temperature. Na2S2O3.5H2O (13.03 g, 52.5 mmol) and KI (9.6 g, 57.8 mmol, 10% excess) were dissolved in 20 ml of distilled water and added slowly into the solution of copper(II) nitrate. The resulting mixture was heated for 20 minutes, cooled to room temperature and filtered. The product was washed with 50 ml of distilled water, 20 ml of ethanol and 20 ml of acetone. Yield: 9.4 g, 94%.

Synthesis of the [Cu(µ3-I)(C5H5N3O)]n (I): CuI (1 g, 5.25 mmol) was dissolved in 50 ml of 3.5 M solution of KI. Pyrazine-2-carboxamide (0.6464 g, 5.25 mmol) was added and the solution was boiled. The almost clear solution was filtered quickly and boiled again. The solution was slowly cooled to room temperature and placed in a refrigerator for 20 minutes. Fine red needle crystals of (I) were filtered, washed with distilled water (50 ml), ethanol (10 ml) and diethylether (10 ml). Yield 1.33 g, 80.8%.

Copper was determined gravimetrically as CuO. C, H and N were estimated on a CHN analyser Vario MICRO cube. Analysis calculated for C5H5N3O1I1Cu1 (found): C 19.15 (19.52), H 1.61 (1.43), N 13.40 (13.68), Cu 20.27 (19.91).

FT—IR spectra were obtained using an FT—IR Nicolet Magna 750 spectrophotometer. The IR spectrum of prepared compound exhibits characteristic bands of pyrazine-2-carboxamide: 3374(s) - νas(NH2), 3161(s) - νs(NH2), 1612(s) - ν(NH2), 1101(w) - δ(NH2), 1376(s) - amide, 1706(s) - ν(C=O), 529(m) - δ(OCN) (Goher & Mautner, 2000).

The thermal decomposition of the substance has been studied under controlled heating at a rate of 5°C.min–1 to 800°C in air using a derivatograph Q-1500 D device. In the first step of thermal decomposition pyrazine-2-carboxamide is released (291 °C, exothermal process) and copper(I) iodide is formed. At 381°C γ-CuI with the sphalerite structure is exothermically transformed to β-CuI adopting wurtzite structure (Wells, 1975). Finally copper(I) iodide is oxidized to copper(II) oxide and molecular iodine is released at 487°C.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. All non-H atoms were refined anisotropically as free atoms. The H atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H in the range 0.93–0.98, N—H in the range 0.86–0.89) and Uiso(H) (in the range 1.2–1.5 times Ueq of the parent atom), after which the positions were refined with riding constraints (Cooper et al., 2010).

Structure description top

Copper(I) coordination polymers are well known for their photochemical and photophysical properties. There are several methods for the synthesis of such metal-organic frameworks (Peng et al., 2010). One possible strategy is the use of copper(I) halide, especially iodide, which dissolves in concentrated aqueous solutions of iodides. After addition of an organic ligand polynuclear copper(I) complexes can be crystallized (Peng et al., 2006; Feng et al., 2006; Wu et al., 2005; Rath & Holt, 1985; Rath et al., 1986).

Pyrazine-2-carboxamide (usually pyrazinamide, in medical literature abbreviated as PZA) is a drug used for tuberculosis treatment in the last 60 years. Nowadays the possibility of increasing the activity of the drug by forming transition metal complexes is examinated widely (Somoskovi et al., 2004). In addition to complexes with transition metals with potential biological effects, e.g. Mn(II), Ni(II), Fe(II), Zn(II), Cu(II) (Singh & Seth 1975; Azizov et al., 1978; Goher & Mautner, 2000) the complexes with Cu(I) have also been prepared. They have been found to be water-insoluble stable compounds with and expected polymeric structure, as has been confirmed by X–ray structure analysis of six compounds with simplified formulas [Cu2(µ-PZA)3]n(ClO4)2.C3H6O, [Cu2(µ-PZA)2(µ-C3H6O)]n(BF4)2 (Munakata et al., 1997); [Cu(µ-N3)PZA2]n (Goher & Mautner, 1999); [Cu(µ-I)PZA2]n (Goher & Mautner, 2000); [Cu(µ-CN)PZA2]n and [Cu(µ-SCN)PZA2]n (Goher & Mautner, 2001).

Goher & Mautner (2000) have succesfully prepared eleven new pyrazine-2-carboxamide complexes of Cu(I) including [CuI(pyrazine-2-carboxamide)]n, (I), but which was only obtained as a powder sample. We have successfully optimised the preparation process of (I) as well as other copper(I) complexes to obtain crystalline samples suitable for single crystal X-ray structure determination and the crystal structure of (I) is reported here.

As shown in Fig. 1, the asymmetric unit of (I) consists of one copper(I) cation bonded to one iodide anion and one pyrazine-2-carboxamide ligand. This unit is an elementary building block of catenary polymer as depicted in Fig. 2. The CuI is coordinated by one N atom from pyrazine-2-carboxamide ligand and three I– anions to form a distorted tetrahedral coordination environment, where the Cu—N bond length is 2.059 (3) Å and the Cu—I bond lengths are 2.6016 (5), 2.6437 (5) and 2.6310 (5) Å. The Cu—N bond length is similar to the mean value of Cu—N bond lengths in above mentioned complexes (2.048 Å). There is a number of structures containing a similar ladder–like linkage of {CuNI3} tetrahedrons. In most cases one of the Cu—I bond lengths tends to be shorter then the other two, e.g. in the realated compound [Cu2(µ3-I)2(4-(4-carboxyphenyl)pyridine-N)2]n the Cu—I bond lengths are 2.631 (1), 2.662 (1), 2.667 (1) and 2.604 (1), 2.658 (1), 2.662 (1) Å (Jia et al., 2009). The I—Cu—N bond angles are 105.07 (8), 114.64 (8) and 103.54 (8)°. The distance between two CuI centres 2.7974 (6) Å indicates that there there could be a weak metal—metal interaction as the sum of van der Waals radii of two copper atoms is 2.8 Å (Bondi, 1964).

The polymeric chains running in the b axis direction are connected via hydrogen bonds between the pyrazinamide ligands (Fig. 3). The amide groups of the ligands form typical dimers consisting of eight-membered rings with the graph set R22(8) linked by a strong N–H···O hydrogen bond. The second hydrogen atom of the –NH2 group forms medium N–H···N hydrogen bond to the non-coordinating N atom of the pyrazine ring, thus forming a ten-membered ring with the graph set R22(10) (Table 2.) (Bernstein et al. 1995).

Moreover, there is a weak π–π interaction between adjacent pyrazine rings in the polymer chain. The distance between two parallel planes of the rings is 3.5476 (14) Å and the centroid-centroid contact is 4.080 (2) Å (Fig. 4). The angle α between the ring normal and the centroid-centroid vector is 29.6 ° and the horizontal displacement of the rings d is 2.014 Å. It is well–known that often the ring planes are offset so that a ring atom lies almost over the center of the other ring and its hydrogen atom almost on the top of a carbon atom (Janiak, 2000). In the compound (I) this is not the case.

There are 9 compounds with the same ladder–like polymeric structure and pyrazine derivatives as the ligands in the CSD (Allen, 2002). The relevant parameters of the π–π interaction of these compounds compared to compound (I) are listed in Table 3. The entries DINQOG, GABHOH and ODOFOC correspond to the compounds with general formula [CuI(2-sub-pyrazine)]n, where sub is cyano–, iodo– and chloro– functional group respectively. More complicated substituents on the pyrazine ring obviously lead to an increasing α angle and displacement d. Interestingly, in the case of non–substituted pyrazine the two parameters are similar to those of compound (I).

Compound (I) is stable in air and insoluble in water and most solvents, it is only sparingly soluble in dimethylsulfoxide forming a pale orange solution. We performed a thermal decompostion analysis and we found that, surprisingly, the decomposition takes place at a quite high temperature (291 °C) starting with the release of pyrazine-2-carboxamide. The crystal structure analysis of (I) clearly elucidates that the organic molecule is well–anchored not only via covalent bonding to the copper(I) center but also via non-covalent interactions between pyrazine-2-carboxamide molecules. Thanks to the thermal stability and the photoluminiscence properties of (I) described in (Goher & Mautner, 2000) the compound is a possible candidate for the use as a photoactive material.

For other CuI coordination polymers, see: Peng et al. (2006, 2010); Feng et al. (2006); Wu et al. (2005); Rath & Holt (1985); Rath et al. (1986). For complexes of pyrazine-2-carboxamide with other transition metals and studies of their biological activity, see: Somoskovi et al. (2004); Singh & Seth (1975); Azizov et al. (1978). For other CuI complexes of pyrazine-2-carboxamide, see: Munakata et al. (1997); Goher & Mautner (1999, 2000, 2001). For a description of the Cambridge Structural Database, see: Allen (2002). For non-covalent interactions , see: Bernstein et al. (1995); Bondi (1964); Janiak (2000); Jia et al. (2009); Wells (1975). For the riding constraints used in the refinement, see: Cooper et al. (2010).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: DIAMOND (Brandenburg, 1999), Mercury (Macrae et al., 2006) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. ADP representation of (I) with atom labeling scheme. The displacement ellipsoids are drawn at the 50% probability level, H atoms are drawn as spheres with arbitrary radii.
[Figure 2] Fig. 2. Polymeric structure of the title compound demonstrating the ladder–like motif of the {CuNI3} tetrahedrons. Displacement ellipsoids are drawn at the 80% probability level.
[Figure 3] Fig. 3. Eight- and ten-membered rings formed by hydrogen bonds in the crystal structure. Each polymer chain is attached to other two polymer chains.
[Figure 4] Fig. 4. π–π stacking interaction in the crystal structure of (I). The angle α is the angle between the ring normal and centroid-centroid vector and d is the displacement between two rings (or centroids).
catena-Poly[[(pyrazine-2-carboxamide-κN4)copper(I)]-µ3-iodido] top
Crystal data top
[CuI(C5H5N3O)]F(000) = 1168
Mr = 313.56Dx = 2.599 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 6637 reflections
a = 29.5408 (7) Åθ = 2–30°
b = 4.0795 (1) ŵ = 6.52 mm−1
c = 14.3164 (3) ÅT = 100 K
β = 111.712 (3)°Needle, red
V = 1602.89 (7) Å30.22 × 0.06 × 0.03 mm
Z = 8
Data collection top
Agilent SuperNova
diffractometer		2135 independent reflections
Radiation source: SuperNova (Mo) X-ray Source1339 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.024
Detector resolution: 10.3801 pixels mm-1θmax = 29.2°, θmin = 2.9°
ω scansh = −40→37
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)		k = −5→5
Tmin = 0.562, Tmax = 1.000l = −19→14
11538 measured reflections
Refinement top
Refinement on F2Primary atom site location: iterative
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.021Hydrogen site location: difference Fourier map
wR(F2) = 0.042H-atom parameters constrained
S = 1.00 Method = Modified Sheldrick w = 1/[σ2(F2) + 6.36P]
where P = (max(Fo2,0) + 2Fc2)/3
1556 reflections(Δ/σ)max = 0.001
100 parametersΔρmax = 0.96 e Å−3
0 restraintsΔρmin = −0.87 e Å−3
Crystal data top
[CuI(C5H5N3O)]V = 1602.89 (7) Å3
Mr = 313.56Z = 8
Monoclinic, C2/cMo Kα radiation
a = 29.5408 (7) ŵ = 6.52 mm−1
b = 4.0795 (1) ÅT = 100 K
c = 14.3164 (3) Å0.22 × 0.06 × 0.03 mm
β = 111.712 (3)°
Data collection top
Agilent SuperNova
diffractometer		2135 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)		1339 reflections with I > 2σ(I)
Tmin = 0.562, Tmax = 1.000Rint = 0.024
11538 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0210 restraints
wR(F2) = 0.042H-atom parameters constrained
S = 1.00Δρmax = 0.96 e Å−3
1556 reflectionsΔρmin = −0.87 e Å−3
100 parameters
Special details top

Experimental. Absorption correction: CrysAlis PRO (Agilent, 2012) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I10.220190 (8)0.31394 (6)0.101635 (17)0.0111
Cu10.268365 (16)0.80730 (12)0.20718 (3)0.0128
N10.33830 (11)0.8564 (7)0.2104 (2)0.0107
C20.37134 (13)1.0182 (9)0.2869 (3)0.0127
C10.41814 (13)1.0748 (9)0.2896 (3)0.0111
N20.43237 (11)0.9779 (7)0.2156 (2)0.0142
C40.39912 (14)0.8216 (10)0.1390 (3)0.0156
C30.35231 (13)0.7580 (8)0.1366 (3)0.0117
C50.45324 (13)1.2545 (8)0.3789 (3)0.0123
O10.43762 (9)1.3879 (7)0.4387 (2)0.0187
N30.49934 (11)1.2586 (7)0.3874 (2)0.0171
H210.36251.09510.33970.0157*
H410.40760.75450.08530.0177*
H310.33050.64490.08250.0152*
H3110.52041.35470.43650.0212*
H3120.50941.15270.34640.0198*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.01335 (12)0.00921 (12)0.00965 (12)−0.00022 (11)0.00295 (9)−0.00083 (11)
Cu10.0102 (2)0.0136 (2)0.0134 (2)−0.0017 (2)0.00299 (18)−0.0011 (2)
N10.0123 (16)0.0075 (16)0.0123 (16)−0.0001 (13)0.0044 (13)0.0031 (13)
C20.0143 (19)0.012 (2)0.0126 (19)0.0009 (16)0.0056 (16)0.0001 (16)
C10.0106 (18)0.0130 (18)0.0091 (18)0.0028 (15)0.0029 (15)0.0056 (15)
N20.0131 (16)0.0161 (18)0.0129 (16)−0.0003 (14)0.0042 (14)−0.0014 (14)
C40.018 (2)0.0193 (19)0.0108 (18)0.0037 (18)0.0071 (16)0.0004 (18)
C30.0113 (18)0.009 (2)0.0102 (18)−0.0003 (14)−0.0013 (15)0.0010 (14)
C50.0119 (19)0.011 (2)0.0125 (19)−0.0009 (14)0.0023 (15)0.0004 (15)
O10.0128 (14)0.0252 (17)0.0194 (15)−0.0049 (12)0.0074 (12)−0.0105 (12)
N30.0142 (17)0.021 (2)0.0162 (17)−0.0036 (14)0.0056 (14)−0.0092 (14)
Geometric parameters (Å, º) top
I1—Cu1i2.6437 (5)C1—N21.336 (5)
I1—Cu1ii2.6310 (5)C1—C51.505 (5)
I1—Cu12.6016 (5)N2—C41.333 (5)
Cu1—N12.059 (3)C4—C31.394 (5)
Cu1—Cu1ii2.7974 (6)C4—H410.933
Cu1—Cu1iii2.7974 (6)C3—H310.927
N1—C21.341 (5)C5—O11.240 (4)
N1—C31.331 (5)C5—N31.321 (5)
C2—C11.388 (5)N3—H3110.843
C2—H210.939N3—H3120.866
Cu1i—I1—Cu1ii64.057 (14)C2—N1—C3116.8 (3)
Cu1i—I1—Cu1102.106 (17)N1—C2—C1121.4 (3)
Cu1ii—I1—Cu164.633 (14)N1—C2—H21119.2
Cu1ii—Cu1—Cu1iii93.63 (3)C1—C2—H21119.4
Cu1ii—Cu1—I1iv127.34 (3)C2—C1—N2122.1 (3)
Cu1iii—Cu1—I1iv57.750 (12)C2—C1—C5118.1 (3)
Cu1ii—Cu1—I1iii58.193 (19)N2—C1—C5119.8 (3)
Cu1iii—Cu1—I1iii57.174 (19)C1—N2—C4116.2 (3)
I1iv—Cu1—I1iii114.921 (19)N2—C4—C3122.1 (3)
Cu1ii—Cu1—I158.193 (12)N2—C4—H41118.5
Cu1iii—Cu1—I1126.95 (3)C3—C4—H41119.3
I1iv—Cu1—I1102.106 (17)C4—C3—N1121.4 (3)
I1iii—Cu1—I1116.38 (2)C4—C3—H31119.5
Cu1ii—Cu1—N1127.58 (8)N1—C3—H31119.2
Cu1iii—Cu1—N1117.90 (8)C1—C5—O1119.0 (3)
I1iv—Cu1—N1105.07 (8)C1—C5—N3116.6 (3)
I1iii—Cu1—N1103.54 (8)O1—C5—N3124.4 (3)
I1—Cu1—N1114.64 (8)C5—N3—H311120.0
Cu1—N1—C2119.1 (2)C5—N3—H312122.1
Cu1—N1—C3123.9 (2)H311—N3—H312117.7
Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H311···O1v0.842.052.883 (5)170 (1)
N3—H312···N2vi0.872.323.124 (5)154 (1)
Symmetry codes: (v) −x+1, −y+3, −z+1; (vi) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula[CuI(C5H5N3O)]
Mr313.56
Crystal system, space groupMonoclinic, C2/c
Temperature (K)100
a, b, c (Å)29.5408 (7), 4.0795 (1), 14.3164 (3)
β (°) 111.712 (3)
V (Å3)1602.89 (7)
Z8
Radiation typeMo Kα
µ (mm−1)6.52
Crystal size (mm)0.22 × 0.06 × 0.03
Data collection
DiffractometerAgilent SuperNova
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2012)
Tmin, Tmax0.562, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections		11538, 2135, 1339
Rint0.024
(sin θ/λ)max (Å−1)0.685
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.021, 0.042, 1.00
No. of reflections1556
No. of parameters100
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.96, −0.87

Computer programs: CrysAlis PRO (Agilent, 2012), SUPERFLIP (Palatinus & Chapuis, 2007), DIAMOND (Brandenburg, 1999), Mercury (Macrae et al., 2006) and ORTEP-3 for Windows (Farrugia, 2012), CRYSTALS (Betteridge et al., 2003), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Selected bond lengths (Å) top
I1—Cu1i2.6437 (5)Cu1—N12.059 (3)
I1—Cu1ii2.6310 (5)Cu1—Cu1ii2.7974 (6)
I1—Cu12.6016 (5)
Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y−1/2, −z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H311···O1iii0.8432.0472.883 (5)170 (1)
N3—H312···N2iv0.8662.3203.124 (5)154 (1)
Symmetry codes: (iii) −x+1, −y+3, −z+1; (iv) −x+1, y, −z+1/2.
Comparison of the angle between the ring normal and centroid vector α and the horizontal displacement of the rings d. top
CSD IdentifierSubstitution on pyrazine ringPlane–plane distance (Å)Centroid-centroid distance (Å)Angle α [°]Displacement d (Å)
AGIYEU02none *3.614.1830.32.11
DINQOG2-cyano4.104.1000
EMEMAK012-ethyl *3.544.2734.02.39
GABHOH2-iodo3.764.1826.11.84
LIDYAZ2,3-dimethyl *3.514.3235.62.52
MUHQOV2,5-dimethyl *3.514.2935.32.48
ODOFOC2-chloro3.854.1120.71.46
RIPTOA2-phenoxy3.394.2537.12.57
XEBMUM2-methyl *3.594.2331.92.23
Compound (I)2-carboxamide3.554.0829.62.01
* pyrazine ring coordinated to copper via both N atoms
 

Acknowledgements

This work was supported by the Ministry of Education of the Slovak Republic (grant VEGA 1/0336/13). The authors are also grateful to Dr Bernd Schweizer, PhD (Laboratory of Organic Chemistry, ETH Zürich, Switzerland) for the X-ray diffraction measurements and thank Nadácia SPP (Scholarship Hlavička) for financial assistance.

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ISSN: 2056-9890
Volume 70| Part 7| July 2014| Pages m267-m268
https://doi.org/10.1107/S1600536814013695
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