research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 6| June 2015| Pages 624-627

Crystal structure of catena-poly[[chlorido­(4,4′-di­methyl-2,2′-bi­pyridine-κ2N,N′)copper(II)]-μ-chlorido]

aChemistry Department, Florida Institute of Technology, 150 West University Boulevard, Melbourne, FL 32901, USA, and bNaval Research Laboratory, 4555 Overlook Ave, Washington, DC 20375, USA
*Correspondence e-mail: aknight@fit.edu

Edited by M. Zeller, Youngstown State University, USA (Received 26 March 2015; accepted 7 May 2015; online 13 May 2015)

The title compound, [CuCl2(C12H12N2)]n, was obtained via a DMSO-mediated dehydration of Cu(4,4′-dimethyl-2,2′-bi­pyridine)­copper(II)·0.25H2O. The central CuII atom is coordinated in a distorted trigonal–bipyramidal geometry by two N atoms of a chelating 4,4′-dimethyl-2,2′-bi­pyridine ligand [average Cu—N = 2.03 (3) Å] and three Cl atoms, one terminal with a short Cu—Cl bond of 2.2506 (10) Å, and two symmetry-equivalent and bridging bonds. The bridging Cl atom links the CuII ions into chains parallel to [001] via one medium and one long Cu—Cl bond [2.3320 (10) and 2.5623 (9) Å]. The structure displays both inter- and intra­molecular C—H⋯Cl hydrogen bonding.

1. Chemical context

Bi­pyridine complexes of copper(II), [(2,2′-bipy)CuX2] (X = Cl, Br) have been used in a number of important applications in recent years, most notably in the areas of catalysis for organic synthesis (Ricardo et al., 2008[Ricardo, C., Matosziuk, L. M., Evanseck, J. D. & Pintauer, T. (2008). Inorg. Chem. 48, 16-18.]; Csonka et al., 2008[Csonka, R., Kaizer, J., Giorgi, M., Réglier, M., Hajba, L., Mink, J. & Speier, G. (2008). Inorg. Chem. 47, 6121-6123.]; Thorpe et al., 2012[Thorpe, S. B., Calderone, J. A. & Santos, W. L. (2012). Org. Lett. 14, 1918-1921.]), DNA cleavage (Jaividhya et al., 2012[Jaividhya, P., Dhivya, R., Akbarsha, M. A. & Palaniandavar, M. (2012). J. Inorg. Biochem. 114, 94-105.]), degradation of pesticides (Knight et al., 2014[Knight, D. A., Nita, R., Moore, M., Zabetakis, D., Khandelwal, M., Martin, B. D., Fontana, J., Goldberg, E., Funk, A. R., Chang, E. L. & Trammell, S. A. (2014). J. Nanopart. Res. 16, 1-12.]) and water oxidation (Barnett et al., 2012[Barnett, S. M., Goldberg, K. I. & Mayer, J. M. (2012). Nat. Chem. 4, 498-502.]). Such complexes are characterized by an extensive number of metal coordination geometries including square-planar/tetra­hedral, square-pyramidal/trigonal–bipyramidal and distorted octa­hedral. The associated halide ligands (chloride, bromide) can adopt terminal or bridging bonding modes leading to monomeric, dimeric or polymeric chain structures which can influence complex solubility in organic solvents and consequently their possible application in homogeneous catalysis. A third factor which influences the structural forms of these complexes is the nature of the solvent, with strongly coordinating ligands forming solvent adducts. For example, the reaction of dimethyl-2,2′-bi­pyridine with CuI and/or CuII in DMSO or water led to the isolation of 10 different crystalline materials, suggesting that a large number of structural motifs are possible including five-coordinate monomers, distorted tetra­hedral monomers, stacked planar monomers, stacked planar bibridged dimers and and five-coordinate bibridged dimers (Willett et al., 2001[Willett, R. D., Pon, G. & Nagy, C. (2001). Inorg. Chem. 40, 4342-4352.]). A large number of ring-substituted 2,2′-bi­pyridine complexes have also been prepared and characterized including di­chlorido­(4,4′-dimethyl-2,2′-bi­pyridine) copper(II) hemihydate. In this paper we describe the synthesis and structural characterization of a previously unknown form of di­chlorido­(4,4′-dimethyl-2,2′-bi­pyridine)­copper(II) via a DMSO-mediated dehydration of Cu(4,4′-dimethyl-2,2′-bi­pyri­dine)Cl2·0.25H2O. The crystal structure reveals single chlorido-bridged copper(II) chains with a distorted trigonal–bipyramidal geometry of the metal cations. We conclude that the presence of the 4,4′-dimethyl substituents does not prevent the formation of a catenated structure, which was previously suggested as an explanation for the dimeric arrangement in Cu(4,4′-dimethyl-2,2′-bi­pyridine)Cl2·0.5H2O (González et al., 1993[Gonzalez Q. O., Atria, A. M., Spodine, E., Manzur, J. & Garland, M. T. (1993). Acta Cryst. C49, 1589-1591.]).

[Scheme 1]

2. Structural commentary

In the title complex (1), Fig. 1[link], the central CuII atom is coord­inated by the two nitro­gen atoms, N1 and N12 of the chelating 2,2′-bi­pyridine subunit and three chlorine atoms, one terminal (Cl1) with a short Cu—Cl bond, and two bridging chlorine atoms (Cl2), which are symmetry equivalent. The bridging chlorine ligand links Cu atoms into chains via one medium and one long Cu—Cl bond [2.3320 (10) and 2.5623 (9) Å]. The geometry around the Cu ion is best described as a distorted trigonal bipyramid with the coordin­ation polyhedron defined by the two N atoms and three Cl atoms, one of which links the monomeric subunits into a chain, which contrasts with the four-coordinate square-planar geometry found in Cu(2,2′-bi­pyridine)Cl2 (Wang et al., 2004[Wang, Y.-Q., Bi, W.-H., Li, X. & Cao, R. (2004). Acta Cryst. E60, m876-m877.]; Garland et al., 1988[Garland, M. T., Grandjean, D., Spodine, E., Atria, A. M. & Manzur, J. (1988). Acta Cryst. C44, 1209-1212.]). The two axial sites are occupied by N1 and Cl1 [N1—Cu1—Cl1 = 172.93 (10)°] and the basal plane contains the N12 atom, the Cl2 atom and the bridging Cl2 atom. The terminal Cu1—Cl1 and medium-length bridging Cu1—Cl2 bond lengths in (1) are 2.2506 (10) and 2.3320 (10) Å which are comparable to those found in the related structure Cu(2,2′-bi­pyridine)Cl2 [2.254 (4) Å; Wang et al., 2004[Wang, Y.-Q., Bi, W.-H., Li, X. & Cao, R. (2004). Acta Cryst. E60, m876-m877.]] and its polymorph [2.291 (3) Å; Hernández-Molina et al., 1999[Hernández-Molina, M., González-Platas, J., Ruiz-Pérez, C., Lloret, F. & Julve, M. (1999). Inorg. Chim. Acta, 284, 258-265.]], and in di­chlorido­(4,4′-dimeth­yl)-2,2′-bi­pyridine)­copper(II) hemihydrate [2.255 (2) and 2.274 (2) Å, respectively; González et al., 1993[Gonzalez Q. O., Atria, A. M., Spodine, E., Manzur, J. & Garland, M. T. (1993). Acta Cryst. C49, 1589-1591.]]. However, the longer bridging Cu—Cl bond has a length of 2.5623 (9) Å which is shorter than those found in the above comparison structures [3.047 (3), 2.674 (3) and 2.754 (2) Å]. The Cu—N1 and Cu—N12 bond lengths in (1) are 2.009 (3) and 2.047 (3) Å, similar to those found in the above structures [2.024 (6), 2.037 (8), and 2.001 (3) and 2.035 (4) Å, respectively]. These comparisons indicate that neither hydration nor 4,4′-dialkyl substitution significantly affects either the terminal Cu—Cl or Cu—N bond lengths. The bi­pyridine ring presents a bite angle of 79.25 (12)° to Cu, similar to that found in the above-mentioned structures, 80.5 (3), 79.6 (3) and 80.2 (1)° respectively, and forming a virtually planar five-membered ring. The C—C and C—N bond lengths and angles are within expected limits.

[Figure 1]
Figure 1
ORTEP-style view of compound (1), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) x − 1, −y + 2, z − [{1\over 2}].]

3. Supra­molecular features

The crystal structure of (1) can best be described as a linear polymer consisting of monomeric units with chains extending parallel to [001]. The chains are connected via weak C—H⋯Cl hydrogen bonds (Table 1[link] and Fig. 2[link]). Adjacent copper atoms are bridged via single chlorine atoms [Cu1—Cl2i = 2.5623 (9) Å; (i) = x, −y + 2, z − [{1\over 2}]). This contrasts with the structure found in Cu(2,2′-bi­pyridine)Cl2 in which two chlorine atoms link the monomeric substructures into a catenated complex. In (1) an intra­molecular C—H⋯Cl hydrogen bond is also observed (Table 1[link]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C11—H11A⋯Cl1 0.95 2.61 3.211 (4) 122
C8—H8A⋯Cl2i 0.95 2.88 3.666 (4) 140
C10—H10A⋯Cl1ii 0.95 2.88 3.733 (4) 149
Symmetry codes: (i) [x-1, -y+2, z-{\script{1\over 2}}]; (ii) [x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}].
[Figure 2]
Figure 2
Selected portion of the crystal packing diagram of compound (1), showing inter­chain C—H⋯Cl hydrogen bonding (see Table 1[link] for details).

4. Database survey

A large number of unsubstituted and substituted bi­pyridine copper complexes with halide ligands can be found in the Cambridge Structural Database (CSD, Version 5.35; Groom & Allen, 2015[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]). These structures have four-, five, and six-coord­ination. The related structure di­chlorido­(4,4′-dimeth­yl)-2,2′-bi­pyridine)­copper(II) hemihydrate (González et al., 1993[Gonzalez Q. O., Atria, A. M., Spodine, E., Manzur, J. & Garland, M. T. (1993). Acta Cryst. C49, 1589-1591.]) crystallizes with a dimeric arrangement of subunits. The unsubstituted complex Cu(2,2′-bi­pyridine)Cl2 has been found to form both simple monomeric (Kostakis et al., 2006[Kostakis, G. E., Nordlander, E., Haukka, M. & Plakatouras, J. C. (2006). Acta Cryst. E62, m77-m79.]) and chain structures (Hernández-Molina et al., 1999[Hernández-Molina, M., González-Platas, J., Ruiz-Pérez, C., Lloret, F. & Julve, M. (1999). Inorg. Chim. Acta, 284, 258-265.]; Wang et al., 2004[Wang, Y.-Q., Bi, W.-H., Li, X. & Cao, R. (2004). Acta Cryst. E60, m876-m877.]), the latter bearing similarities to the structure of (1).

5. Synthesis and crystallization

Solvents and reagents were obtained and purified as follows: DMSO (Aldrich), dried over 4 Å mol­ecular sieves, CuCl2·2H2O, 4,4′-dimethyl-2,2′-bi­pyridine (Sigma–Aldrich) used as received. Cu(4,4′-dimethyl-2,2′-bi­pyridine)Cl2·0.25 H2O was prepared according to the literature procedure (Moore et al., 2012[Moore, M., Knight, D. A., Zabetakis, D., Deschamps, J. R., Dressick, W. J., Chang, E. L., Lascano, B., Nita, R. & Trammell, S. A. (2012). Inorg. Chim. Acta, 388, 168-174.]). Cu(4,4′-dimethyl-2,2′-bi­pyridine)Cl2·0.25 H2O (0.4091 g, 1.266 mmol) was dissolved in anhydrous DMSO (500 ml) and stored at 277 K for 30 months (shorter periods of time, e.g. 7 days, did not result in dehydration). The DMSO was then removed under a stream of N2 and the resulting solid was further dried in vacuo at 313 K to give (1) as a green powder (0.386 g, 1.21 mmol, 96% yield). A portion of (1) was dissolved in DMSO and concentrated under a stream of N2 (flow rate = 12 l/min) over 7 days in an open vial to give green plates. Analysis calculated for CuC12H12N2Cl2: C, 45.23; H, 3.80; N, 8.79. Found: C, 44.69; H, 3.66; N, 8.20.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. The H atoms were included in calculated positions and refined as riding: C—H = 0.95–0.98 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula [CuCl2(C12H12N2)]
Mr 318.68
Crystal system, space group Monoclinic, Cc
Temperature (K) 150
a, b, c (Å) 9.1101 (6), 20.0087 (12), 7.1231 (4)
β (°) 110.491 (2)
V3) 1216.25 (13)
Z 4
Radiation type Mo Kα
μ (mm−1) 2.21
Crystal size (mm) 0.27 × 0.12 × 0.07
 
Data collection
Diffractometer Bruker APEXII CCD
Absorption correction Multi-scan (SADABS; Bruker, 2002[Bruker (2002). SMART, SAINT, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.646, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections 7099, 2945, 2829
Rint 0.049
(sin θ/λ)max−1) 0.685
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.072, 1.05
No. of reflections 2945
No. of parameters 156
No. of restraints 2
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.56, −0.48
Absolute structure Classical Flack method preferred over Parsons because s.u. lower (Flack, 1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.])
Absolute structure parameter 0.011 (15)
Computer programs: SMART, SAINT and XPREP (Bruker, 2002[Bruker (2002). SMART, SAINT, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 and SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]).

Supporting information


Chemical context top

Bi­pyridine complexes of copper(II), [(2,2'-bipy)CuX2] (X = Cl, Br) have been used in a number of important applications in recent years, most notably in the areas of catalysis for organic synthesis (Ricardo et al., 2008; Csonka et al., 2008; Thorpe et al., 2012), DNA cleavage (Jaividhya et al., 2012), degradation of pesticides (Knight et al., 2014) and water oxidation (Barnett et al. 2012). Such complexes are characterized by an extensive number of metal coordination geometries including square-planar/tetra­hedral, square-pyramidal/trigonal–bipyramidal and distorted o­cta­hedral. The associated halide ligands (chloride, bromide) can adopt terminal or bridging bonding modes leading to monomeric, dimeric or polymeric chain structures which can influence complex solubility in organic solvents and consequently their possible application in homogeneous catalysis. A third factor which influences the structural forms of these complexes is the nature of the solvent, with strongly coordinating ligands forming solvent adducts. For example, the reaction of di­methyl-2,2'-bi­pyridine with CuI and/or CuII in DMSO or water led to the isolation of 10 different crystalline materials, suggesting that a large number of structural motifs are possible including five-coordinate monomers, distorted tetra­hedral monomers, stacked planar monomers, stacked planar bibridged dimers and and five-coordinate bibridged dimers (Willett et al., 2001). A large number of ring-substituted 2,2'-bi­pyridine complexes have also been prepared and characterized including di­chloro­(4,4'-di­methyl-2,2'-bi­pyridine) copper(II) hemihydate. In this paper we describe the synthesis and structural characterization of a previously unknown form of di­chloro­(4,4'-di­methyl-2,2'-bi­pyridine)­copper(II) via a DMSO-mediated dehydration of Cu(4,4'-di­methyl-2,2'-bi­pyridine)Cl2·0.25 H2O. The crystal structure reveals single chloro-bridged copper(II) chains with a distorted trigonal–bipyramidal geometry. We conclude that the presence of the 4,4'-di­methyl substituents does not prevent the formation of a catenated structure, which was previously suggested as an explanation for the dimeric arrangement in Cu(4,4'-di­methyl-2,2'-bi­pyridine)Cl2·0.5H2O (González et al., 1993).

Structural commentary top

In the title complex (1), Fig.1, the central CuII atom is coordinated by the two nitro­gen atoms, N1 and N12 of the chelating 2,2'-bi­pyridine subunit and three chlorine atoms, one terminal (Cl1) with a short Cu—Cl bond, and two bridging chlorine atoms (Cl2), which are symmetry equivalent. The bridging chlorine ligand links Cu atoms into chains via one medium and one long Cu—Cl bond [2.3320 (10) and 2.5623 (9) Å]. The geometry around the Cu ion is best described as a distorted trigonal bipyramid with the coordination polyhedron defined by the two N atoms and three Cl atoms, one of which links the monomeric subunits into a chain, which contrasts with the four-coordinate square-planar geometry found in Cu(2,2'-bi­pyridine)Cl2 (Wang et al., 2004; Garland et al., 1988). The two axial sites are occupied by N1 and Cl1 [N1—Cu1—Cl1 = 172.93 (10)°] and the basal plane contains the N12 atom, the Cl2 atom and the bridging Cl2 atom. The terminal Cu1—Cl1 and medium-length bridging Cu1—Cl2 bond lengths in (1) are 2.2506 (10) and 2.3320 (10) Å which are comparable to those found in the related structure Cu(2,2'-bi­pyridine)Cl2 [2.254 (4) Å; Wang et al., 2004] and its polymorph [2.291 (3) Å; Hernández-Molina et al., 1999], and in di­chloro­(4,4'-di­methyl)-2,2'-bi­pyridine)­copper(II) hemihydrate [2.255 (2) and 2.274 (2) Å, respectively; González et al., 1993]. However, the longer bridging Cu—Cl bond has a length of 2.5623 (9) Å which is shorter than those found in the above comparison structures [3.047 (3), 2.674 (3) and 2.754 (2) Å]. The Cu—N1 and Cu—N12 bond lengths in (1) are 2.009 (3) and 2.047 (3) Å, similar to those found in the above structures [2.024 (6), 2.037 (8), and 2.001 (3) and 2.035 (4) Å, respectively]. These comparisons indicate that neither hydration nor 4,4'-di­alkyl substitution significantly affects either the terminal Cu—Cl or Cu—N bond lengths. The bi­pyridine ring presents a bite angle of 79.25 (12)° to Cu, similar to that found in the above-mentioned structures, 80.5 (3), 79.6 (3) and 80.2 (1)° respectively, and forming a virtually planar five-membered ring. The C—C and C—N bond lengths and angles are within expected limits.

Supra­molecular features top

The crystal structure of (1) can best be described as a linear polymer consisting of monomeric units with chains connected via weak C—H···Cl hydrogen bonds (Table 1 and Fig. 2). Adjacent copper atoms are bridged via single chlorine atoms [Cu1—Cl2i = 2.5623 (9) Å; (i) = x, -y + 2, z -1/2). This contrasts with the structure found in Cu(2,2'-bi­pyridine)Cl2 in which two chlorine atoms link the monomeric substructures into a catenated complex. In (1) an intra­molecular C—H···Cl hydrogen bond is also observed (Table 1).

Database survey top

A large number of unsubstituted and substituted bi­pyridine copper complexes with halide ligands can be found in the Cambridge Structural Database (CSD, Version 5.35; Groom & Allen, 2015). These structures have four-, five, and six-coordination. The related structure di­chloro­(4,4'-di­methyl)-2,2'-bi­pyridine)­copper(II) hemihydrate (González et al., 1993) crystallizes with a dimeric arrangement of subunits. The unsubstituted complex Cu(2,2'-bi­pyridine)Cl2 has been found to form both simple monomeric (Kostakis et al., 2006) and chain structures (Hernández-Molina et al., 1999; Wang et al., 2004), the latter bearing similarities to the structure of (1).

Synthesis and crystallization top

Solvents and reagents were obtained and purified as follows: DMSO (Aldrich), dried over 4 Å molecular sieves, CuCl2·2H2O, 4,4'-di­methyl-2,2'-bi­pyridine (Sigma–Aldrich) used as received. Cu(4,4'-di­methyl-2,2'-bi­pyridine)Cl2·0.25 H2O was prepared according to the literature procedure (Moore et al., 2012). Cu(4,4'-di­methyl-2,2'-bi­pyridine)Cl2·0.25 H2O (0.4091 g, 1.266 mmol) was dissolved in anhydrous DMSO (500 mL) and stored at 277 K for 30 months (shorter periods of time, e.g. 7 days, did not result in dehydration). The DMSO was then removed under a stream of N2 and the resulting solid was further dried in vacuo at 313 K to give (1) as a green powder (0.386 g, 1.21 mmol, 96% yield). A portion of (1) was dissolved in DMSO and concentrated under a stream of N2 (flow rate = 12 L/min) over 7 days in an open vial to give green plates. Analysis calculated for CuC12H12N2Cl2: C, 45.23; H, 3.80; N, 8.79. Found: C, 44.69; H, 3.66; N, 8.20.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. The H atoms were included in calculated positions and refined as riding: C—H = 0.95–0.98 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.

Related literature top

For related literature, see: Barnett et al. (2012); Csonka et al. (2008); González et al. (1993); Hernández-Molina, González-Platas, Ruiz-Pérez, Lloret & Julve (1999); Jaividhya et al. (2012); Kostakis et al. (2006); Moore et al. (2012); Ricardo et al. (2008); Thorpe et al. (2012); Wang et al. (2004).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT and XPREP (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. ORTEP style view of compound (1), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) x - 1, -y + 2, z - 1/2.]
[Figure 2] Fig. 2. Selected portion of the crystal packing diagram of compound (1), showing interchain C—H···Cl hydrogen bonding (see Table 1 for details).
catena-Poly[[chlorido(4,4'-dimethyl-2,2'-bipyridine-κ2N,N')copper(II)]-µ-chlorido] top
Crystal data top
[CuCl2(C12H12N2)]F(000) = 644
Mr = 318.68Dx = 1.740 Mg m3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
a = 9.1101 (6) ÅCell parameters from 4788 reflections
b = 20.0087 (12) Åθ = 2.6–29.1°
c = 7.1231 (4) ŵ = 2.21 mm1
β = 110.491 (2)°T = 150 K
V = 1216.25 (13) Å3Plate, green
Z = 40.27 × 0.12 × 0.07 mm
Data collection top
Bruker APEXII CCD
diffractometer
2945 independent reflections
Radiation source: sealed tube2829 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.049
ω scansθmax = 29.1°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 1212
Tmin = 0.646, Tmax = 0.746k = 2727
7099 measured reflectionsl = 99
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.072 w = 1/[σ2(Fo2) + (0.0425P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
2945 reflectionsΔρmax = 0.56 e Å3
156 parametersΔρmin = 0.48 e Å3
2 restraintsAbsolute structure: Classical Flack method preferred over Parsons because s.u. lower (Flack, 1983).
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.011 (15)
Crystal data top
[CuCl2(C12H12N2)]V = 1216.25 (13) Å3
Mr = 318.68Z = 4
Monoclinic, CcMo Kα radiation
a = 9.1101 (6) ŵ = 2.21 mm1
b = 20.0087 (12) ÅT = 150 K
c = 7.1231 (4) Å0.27 × 0.12 × 0.07 mm
β = 110.491 (2)°
Data collection top
Bruker APEXII CCD
diffractometer
2945 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
2829 reflections with I > 2σ(I)
Tmin = 0.646, Tmax = 0.746Rint = 0.049
7099 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.072Δρmax = 0.56 e Å3
S = 1.05Δρmin = 0.48 e Å3
2945 reflectionsAbsolute structure: Classical Flack method preferred over Parsons because s.u. lower (Flack, 1983).
156 parametersAbsolute structure parameter: 0.011 (15)
2 restraints
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.99673 (5)0.95231 (2)0.74601 (5)0.01585 (12)
Cl11.12820 (11)0.85482 (5)0.80882 (16)0.0243 (2)
Cl21.15771 (10)1.00184 (5)1.04309 (13)0.01687 (18)
N10.8565 (4)1.03282 (16)0.6685 (5)0.0166 (6)
C20.9078 (5)1.0962 (2)0.6952 (6)0.0217 (8)
H2A1.01701.10440.75670.026*
C30.8073 (5)1.14974 (19)0.6364 (6)0.0213 (8)
H3A0.84791.19400.65760.026*
C40.6467 (5)1.13963 (18)0.5460 (6)0.0164 (7)
C4A0.5357 (5)1.19727 (19)0.4831 (7)0.0219 (8)
H4AA0.42871.18170.45920.033*
H4AB0.54141.21680.35970.033*
H4AC0.56421.23110.58920.033*
C50.5941 (5)1.07339 (18)0.5156 (6)0.0155 (6)
H5A0.48561.06410.45300.019*
C60.7009 (4)1.02135 (18)0.5771 (5)0.0136 (6)
C70.6593 (4)0.94980 (17)0.5520 (5)0.0137 (7)
C80.5058 (4)0.9266 (2)0.4740 (6)0.0167 (7)
H8A0.42080.95730.43440.020*
C90.4773 (5)0.85789 (19)0.4542 (6)0.0162 (7)
C9A0.3132 (5)0.8319 (2)0.3748 (7)0.0225 (8)
H9AA0.25820.85140.24250.034*
H9AB0.25880.84410.46660.034*
H9AC0.31510.78320.36300.034*
C100.6064 (5)0.81541 (19)0.5120 (6)0.0192 (7)
H10A0.59190.76840.49820.023*
C110.7558 (5)0.84178 (19)0.5896 (6)0.0191 (7)
H11A0.84250.81200.62900.023*
N120.7834 (3)0.90766 (15)0.6114 (5)0.0153 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01070 (19)0.0139 (2)0.0205 (2)0.00155 (17)0.00239 (16)0.00001 (18)
Cl10.0162 (4)0.0162 (4)0.0347 (5)0.0053 (3)0.0016 (4)0.0024 (4)
Cl20.0135 (4)0.0235 (4)0.0134 (4)0.0012 (3)0.0044 (3)0.0025 (3)
N10.0131 (15)0.0153 (14)0.0203 (15)0.0005 (12)0.0046 (13)0.0014 (12)
C20.0144 (18)0.0188 (18)0.029 (2)0.0023 (14)0.0042 (16)0.0002 (15)
C30.0200 (19)0.0150 (17)0.026 (2)0.0012 (14)0.0050 (17)0.0016 (15)
C40.0171 (17)0.0148 (17)0.0170 (17)0.0004 (13)0.0057 (14)0.0009 (13)
C4A0.0179 (18)0.0161 (18)0.030 (2)0.0021 (15)0.0061 (16)0.0006 (16)
C50.0107 (15)0.0151 (16)0.0198 (18)0.0020 (14)0.0043 (14)0.0005 (14)
C60.0143 (16)0.0144 (16)0.0133 (16)0.0018 (13)0.0063 (13)0.0007 (13)
C70.0149 (17)0.0130 (16)0.0140 (17)0.0000 (13)0.0062 (15)0.0001 (12)
C80.0148 (19)0.0168 (18)0.0184 (17)0.0005 (13)0.0057 (15)0.0008 (14)
C90.0154 (17)0.0172 (17)0.0161 (17)0.0030 (13)0.0057 (14)0.0018 (14)
C9A0.017 (2)0.0190 (19)0.029 (2)0.0051 (15)0.0047 (17)0.0032 (16)
C100.0202 (18)0.0128 (16)0.0239 (19)0.0004 (14)0.0069 (16)0.0013 (14)
C110.0161 (18)0.0154 (17)0.025 (2)0.0028 (13)0.0062 (16)0.0002 (14)
N120.0123 (14)0.0136 (14)0.0191 (15)0.0022 (12)0.0044 (12)0.0000 (12)
Geometric parameters (Å, º) top
Cu1—N12.009 (3)C5—C61.387 (5)
Cu1—N122.047 (3)C5—H5A0.9500
Cu1—Cl12.2506 (10)C6—C71.476 (5)
Cu1—Cl22.3320 (10)C7—N121.354 (4)
Cu1—Cl2i2.5623 (9)C7—C81.391 (5)
Cl2—Cu1ii2.5623 (9)C8—C91.398 (5)
N1—C21.343 (5)C8—H8A0.9500
N1—C61.357 (5)C9—C101.391 (5)
C2—C31.375 (6)C9—C9A1.494 (5)
C2—H2A0.9500C9A—H9AA0.9800
C3—C41.392 (5)C9A—H9AB0.9800
C3—H3A0.9500C9A—H9AC0.9800
C4—C51.400 (5)C10—C111.382 (6)
C4—C4A1.495 (5)C10—H10A0.9500
C4A—H4AA0.9800C11—N121.341 (5)
C4A—H4AB0.9800C11—H11A0.9500
C4A—H4AC0.9800
N1—Cu1—N1279.25 (12)C6—C5—H5A120.1
N1—Cu1—Cl1172.93 (10)C4—C5—H5A120.1
N12—Cu1—Cl193.82 (9)N1—C6—C5121.6 (4)
N1—Cu1—Cl292.64 (10)N1—C6—C7113.8 (3)
N12—Cu1—Cl2143.41 (9)C5—C6—C7124.6 (4)
Cl1—Cu1—Cl293.79 (4)N12—C7—C8122.0 (3)
N1—Cu1—Cl2i89.55 (9)N12—C7—C6114.5 (3)
N12—Cu1—Cl2i121.94 (9)C8—C7—C6123.4 (3)
Cl1—Cu1—Cl2i93.01 (4)C7—C8—C9119.5 (4)
Cl2—Cu1—Cl2i93.29 (3)C7—C8—H8A120.2
Cu1—Cl2—Cu1ii111.20 (4)C9—C8—H8A120.2
C2—N1—C6118.8 (3)C10—C9—C8117.6 (4)
C2—N1—Cu1124.2 (3)C10—C9—C9A122.0 (4)
C6—N1—Cu1117.0 (2)C8—C9—C9A120.4 (4)
N1—C2—C3122.1 (4)C9—C9A—H9AA109.5
N1—C2—H2A119.0C9—C9A—H9AB109.5
C3—C2—H2A119.0H9AA—C9A—H9AB109.5
C2—C3—C4120.5 (3)C9—C9A—H9AC109.5
C2—C3—H3A119.7H9AA—C9A—H9AC109.5
C4—C3—H3A119.7H9AB—C9A—H9AC109.5
C3—C4—C5117.2 (3)C11—C10—C9119.8 (3)
C3—C4—C4A121.2 (3)C11—C10—H10A120.1
C5—C4—C4A121.7 (4)C9—C10—H10A120.1
C4—C4A—H4AA109.5N12—C11—C10122.7 (3)
C4—C4A—H4AB109.5N12—C11—H11A118.6
H4AA—C4A—H4AB109.5C10—C11—H11A118.6
C4—C4A—H4AC109.5C11—N12—C7118.3 (3)
H4AA—C4A—H4AC109.5C11—N12—Cu1126.3 (3)
H4AB—C4A—H4AC109.5C7—N12—Cu1115.3 (2)
C6—C5—C4119.9 (4)
C6—N1—C2—C31.2 (6)N1—C6—C7—C8175.7 (3)
Cu1—N1—C2—C3178.8 (3)C5—C6—C7—C84.1 (6)
N1—C2—C3—C40.1 (6)N12—C7—C8—C90.5 (6)
C2—C3—C4—C51.0 (6)C6—C7—C8—C9179.5 (3)
C2—C3—C4—C4A179.3 (4)C7—C8—C9—C100.9 (6)
C3—C4—C5—C60.7 (5)C7—C8—C9—C9A178.7 (3)
C4A—C4—C5—C6179.7 (4)C8—C9—C10—C111.3 (6)
C2—N1—C6—C51.6 (5)C9A—C9—C10—C11178.3 (4)
Cu1—N1—C6—C5179.3 (3)C9—C10—C11—N120.4 (6)
C2—N1—C6—C7178.6 (3)C10—C11—N12—C71.0 (6)
Cu1—N1—C6—C70.9 (4)C10—C11—N12—Cu1174.3 (3)
C4—C5—C6—N10.6 (6)C8—C7—N12—C111.4 (6)
C4—C5—C6—C7179.7 (3)C6—C7—N12—C11178.6 (3)
N1—C6—C7—N124.3 (4)C8—C7—N12—Cu1174.4 (3)
C5—C6—C7—N12176.0 (4)C6—C7—N12—Cu15.6 (4)
Symmetry codes: (i) x, y+2, z1/2; (ii) x, y+2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11A···Cl10.952.613.211 (4)122
C8—H8A···Cl2iii0.952.883.666 (4)140
C10—H10A···Cl1iv0.952.883.733 (4)149
Symmetry codes: (iii) x1, y+2, z1/2; (iv) x1/2, y+3/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11A···Cl10.952.613.211 (4)122
C8—H8A···Cl2i0.952.883.666 (4)140
C10—H10A···Cl1ii0.952.883.733 (4)149
Symmetry codes: (i) x1, y+2, z1/2; (ii) x1/2, y+3/2, z1/2.

Experimental details

Crystal data
Chemical formula[CuCl2(C12H12N2)]
Mr318.68
Crystal system, space groupMonoclinic, Cc
Temperature (K)150
a, b, c (Å)9.1101 (6), 20.0087 (12), 7.1231 (4)
β (°) 110.491 (2)
V3)1216.25 (13)
Z4
Radiation typeMo Kα
µ (mm1)2.21
Crystal size (mm)0.27 × 0.12 × 0.07
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2002)
Tmin, Tmax0.646, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
7099, 2945, 2829
Rint0.049
(sin θ/λ)max1)0.685
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.072, 1.05
No. of reflections2945
No. of parameters156
No. of restraints2
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.56, 0.48
Absolute structureClassical Flack method preferred over Parsons because s.u. lower (Flack, 1983).
Absolute structure parameter0.011 (15)

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT and XPREP (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), SHELXTL (Sheldrick, 2008).

 

Acknowledgements

This work received support from the Defense Threat Reduction Agency–Joint Science and Technology Office for Chemical and Biological Defense (MIPR #B102405M, B112542M and HDTRA136555). DAK is grateful to the American Society of Engineering Education and Office of Naval Research for a Distinguished Faculty Fellowship.

References

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Volume 71| Part 6| June 2015| Pages 624-627
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