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

Nita, R.; Deschamps, J.R.; Trammell, S.A.; Knight, D.A.

doi:10.1107/S2056989015008944

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

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

doi:10.1107/S2056989015008944

Open

access

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

Rafaela Nita,^a Jeffrey R. Deschamps,^b Scott A. Trammell ^b and D. Andrew Knight ^a ^*

^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 Cu^II 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 Cu^II 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.

Keywords: crystal structure; copper bipyridine complex; dehydration; hydrogen bonding.

CCDC reference: 1063931

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 ; 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 Cu^I and/or Cu^II 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 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 ).

2. Structural commentary

In the title complex (1), Fig. 1, the central Cu^II 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 dichlorido(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.

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 and Fig. 2). 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).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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
Selected portion of the crystal packing diagram of compound (1), showing interchain C—H⋯Cl hydrogen bonding (see Table 1

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 ). 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) 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).

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 ). 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. The H atoms were included in calculated positions and refined as riding: C—H = 0.95–0.98 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	[CuCl₂(C₁₂H₁₂N₂)]
M_r	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)
V (Å³)	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 )
T_min, T_max	0.646, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	7099, 2945, 2829
R_int	0.049
(sin θ/λ)_max (Å⁻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
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.48
Absolute structure	Classical Flack method preferred over Parsons because s.u. lower (Flack, 1983 )
Absolute structure parameter	0.011 (15)
Computer programs: SMART, SAINT and XPREP (Bruker, 2002), SHELXS97 and SHELXTL (Sheldrick, 2008 ) and SHELXL2014 (Sheldrick, 2015 ).

Supporting information

CCDC reference: 1063931

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015008944/zl2617sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015008944/zl2617Isup2.hkl

checkCIF report

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 Cu^I and/or Cu^II 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 Cu^II 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

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

	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.]
	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
M_r = 318.68	D_x = 1.740 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 9.1101 (6) Å	Cell parameters from 4788 reflections
b = 20.0087 (12) Å	θ = 2.6–29.1°
c = 7.1231 (4) Å	µ = 2.21 mm⁻¹
β = 110.491 (2)°	T = 150 K
V = 1216.25 (13) Å³	Plate, green
Z = 4	0.27 × 0.12 × 0.07 mm

Data collection top

Bruker APEXII CCD diffractometer	2945 independent reflections
Radiation source: sealed tube	2829 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ω scans	θ_max = 29.1°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −12→12
T_min = 0.646, T_max = 0.746	k = −27→27
7099 measured reflections	l = −9→9

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.072	w = 1/[σ²(F_o²) + (0.0425P)²] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
2945 reflections	Δρ_max = 0.56 e Å⁻³
156 parameters	Δρ_min = −0.48 e Å⁻³
2 restraints	Absolute structure: Classical Flack method preferred over Parsons because s.u. lower (Flack, 1983).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.011 (15)

Crystal data top

[CuCl₂(C₁₂H₁₂N₂)]	V = 1216.25 (13) Å³
M_r = 318.68	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 9.1101 (6) Å	µ = 2.21 mm⁻¹
b = 20.0087 (12) Å	T = 150 K
c = 7.1231 (4) Å	0.27 × 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)
T_min = 0.646, T_max = 0.746	R_int = 0.049
7099 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.072	Δρ_max = 0.56 e Å⁻³
S = 1.05	Δρ_min = −0.48 e Å⁻³
2945 reflections	Absolute structure: Classical Flack method preferred over Parsons because s.u. lower (Flack, 1983).
156 parameters	Absolute 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

	x	y	z	U_iso*/U_eq
Cu1	0.99673 (5)	0.95231 (2)	0.74601 (5)	0.01585 (12)
Cl1	1.12820 (11)	0.85482 (5)	0.80882 (16)	0.0243 (2)
Cl2	1.15771 (10)	1.00184 (5)	1.04309 (13)	0.01687 (18)
N1	0.8565 (4)	1.03282 (16)	0.6685 (5)	0.0166 (6)
C2	0.9078 (5)	1.0962 (2)	0.6952 (6)	0.0217 (8)
H2A	1.0170	1.1044	0.7567	0.026*
C3	0.8073 (5)	1.14974 (19)	0.6364 (6)	0.0213 (8)
H3A	0.8479	1.1940	0.6576	0.026*
C4	0.6467 (5)	1.13963 (18)	0.5460 (6)	0.0164 (7)
C4A	0.5357 (5)	1.19727 (19)	0.4831 (7)	0.0219 (8)
H4AA	0.4287	1.1817	0.4592	0.033*
H4AB	0.5414	1.2168	0.3597	0.033*
H4AC	0.5642	1.2311	0.5892	0.033*
C5	0.5941 (5)	1.07339 (18)	0.5156 (6)	0.0155 (6)
H5A	0.4856	1.0641	0.4530	0.019*
C6	0.7009 (4)	1.02135 (18)	0.5771 (5)	0.0136 (6)
C7	0.6593 (4)	0.94980 (17)	0.5520 (5)	0.0137 (7)
C8	0.5058 (4)	0.9266 (2)	0.4740 (6)	0.0167 (7)
H8A	0.4208	0.9573	0.4344	0.020*
C9	0.4773 (5)	0.85789 (19)	0.4542 (6)	0.0162 (7)
C9A	0.3132 (5)	0.8319 (2)	0.3748 (7)	0.0225 (8)
H9AA	0.2582	0.8514	0.2425	0.034*
H9AB	0.2588	0.8441	0.4666	0.034*
H9AC	0.3151	0.7832	0.3630	0.034*
C10	0.6064 (5)	0.81541 (19)	0.5120 (6)	0.0192 (7)
H10A	0.5919	0.7684	0.4982	0.023*
C11	0.7558 (5)	0.84178 (19)	0.5896 (6)	0.0191 (7)
H11A	0.8425	0.8120	0.6290	0.023*
N12	0.7834 (3)	0.90766 (15)	0.6114 (5)	0.0153 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01070 (19)	0.0139 (2)	0.0205 (2)	0.00155 (17)	0.00239 (16)	0.00001 (18)
Cl1	0.0162 (4)	0.0162 (4)	0.0347 (5)	0.0053 (3)	0.0016 (4)	0.0024 (4)
Cl2	0.0135 (4)	0.0235 (4)	0.0134 (4)	−0.0012 (3)	0.0044 (3)	−0.0025 (3)
N1	0.0131 (15)	0.0153 (14)	0.0203 (15)	0.0005 (12)	0.0046 (13)	−0.0014 (12)
C2	0.0144 (18)	0.0188 (18)	0.029 (2)	−0.0023 (14)	0.0042 (16)	−0.0002 (15)
C3	0.0200 (19)	0.0150 (17)	0.026 (2)	−0.0012 (14)	0.0050 (17)	−0.0016 (15)
C4	0.0171 (17)	0.0148 (17)	0.0170 (17)	0.0004 (13)	0.0057 (14)	−0.0009 (13)
C4A	0.0179 (18)	0.0161 (18)	0.030 (2)	0.0021 (15)	0.0061 (16)	−0.0006 (16)
C5	0.0107 (15)	0.0151 (16)	0.0198 (18)	0.0020 (14)	0.0043 (14)	−0.0005 (14)
C6	0.0143 (16)	0.0144 (16)	0.0133 (16)	0.0018 (13)	0.0063 (13)	0.0007 (13)
C7	0.0149 (17)	0.0130 (16)	0.0140 (17)	0.0000 (13)	0.0062 (15)	−0.0001 (12)
C8	0.0148 (19)	0.0168 (18)	0.0184 (17)	0.0005 (13)	0.0057 (15)	−0.0008 (14)
C9	0.0154 (17)	0.0172 (17)	0.0161 (17)	−0.0030 (13)	0.0057 (14)	−0.0018 (14)
C9A	0.017 (2)	0.0190 (19)	0.029 (2)	−0.0051 (15)	0.0047 (17)	−0.0032 (16)
C10	0.0202 (18)	0.0128 (16)	0.0239 (19)	0.0004 (14)	0.0069 (16)	0.0013 (14)
C11	0.0161 (18)	0.0154 (17)	0.025 (2)	0.0028 (13)	0.0062 (16)	−0.0002 (14)
N12	0.0123 (14)	0.0136 (14)	0.0191 (15)	0.0022 (12)	0.0044 (12)	0.0000 (12)

Geometric parameters (Å, º) top

Cu1—N1	2.009 (3)	C5—C6	1.387 (5)
Cu1—N12	2.047 (3)	C5—H5A	0.9500
Cu1—Cl1	2.2506 (10)	C6—C7	1.476 (5)
Cu1—Cl2	2.3320 (10)	C7—N12	1.354 (4)
Cu1—Cl2ⁱ	2.5623 (9)	C7—C8	1.391 (5)
Cl2—Cu1ⁱⁱ	2.5623 (9)	C8—C9	1.398 (5)
N1—C2	1.343 (5)	C8—H8A	0.9500
N1—C6	1.357 (5)	C9—C10	1.391 (5)
C2—C3	1.375 (6)	C9—C9A	1.494 (5)
C2—H2A	0.9500	C9A—H9AA	0.9800
C3—C4	1.392 (5)	C9A—H9AB	0.9800
C3—H3A	0.9500	C9A—H9AC	0.9800
C4—C5	1.400 (5)	C10—C11	1.382 (6)
C4—C4A	1.495 (5)	C10—H10A	0.9500
C4A—H4AA	0.9800	C11—N12	1.341 (5)
C4A—H4AB	0.9800	C11—H11A	0.9500
C4A—H4AC	0.9800

N1—Cu1—N12	79.25 (12)	C6—C5—H5A	120.1
N1—Cu1—Cl1	172.93 (10)	C4—C5—H5A	120.1
N12—Cu1—Cl1	93.82 (9)	N1—C6—C5	121.6 (4)
N1—Cu1—Cl2	92.64 (10)	N1—C6—C7	113.8 (3)
N12—Cu1—Cl2	143.41 (9)	C5—C6—C7	124.6 (4)
Cl1—Cu1—Cl2	93.79 (4)	N12—C7—C8	122.0 (3)
N1—Cu1—Cl2ⁱ	89.55 (9)	N12—C7—C6	114.5 (3)
N12—Cu1—Cl2ⁱ	121.94 (9)	C8—C7—C6	123.4 (3)
Cl1—Cu1—Cl2ⁱ	93.01 (4)	C7—C8—C9	119.5 (4)
Cl2—Cu1—Cl2ⁱ	93.29 (3)	C7—C8—H8A	120.2
Cu1—Cl2—Cu1ⁱⁱ	111.20 (4)	C9—C8—H8A	120.2
C2—N1—C6	118.8 (3)	C10—C9—C8	117.6 (4)
C2—N1—Cu1	124.2 (3)	C10—C9—C9A	122.0 (4)
C6—N1—Cu1	117.0 (2)	C8—C9—C9A	120.4 (4)
N1—C2—C3	122.1 (4)	C9—C9A—H9AA	109.5
N1—C2—H2A	119.0	C9—C9A—H9AB	109.5
C3—C2—H2A	119.0	H9AA—C9A—H9AB	109.5
C2—C3—C4	120.5 (3)	C9—C9A—H9AC	109.5
C2—C3—H3A	119.7	H9AA—C9A—H9AC	109.5
C4—C3—H3A	119.7	H9AB—C9A—H9AC	109.5
C3—C4—C5	117.2 (3)	C11—C10—C9	119.8 (3)
C3—C4—C4A	121.2 (3)	C11—C10—H10A	120.1
C5—C4—C4A	121.7 (4)	C9—C10—H10A	120.1
C4—C4A—H4AA	109.5	N12—C11—C10	122.7 (3)
C4—C4A—H4AB	109.5	N12—C11—H11A	118.6
H4AA—C4A—H4AB	109.5	C10—C11—H11A	118.6
C4—C4A—H4AC	109.5	C11—N12—C7	118.3 (3)
H4AA—C4A—H4AC	109.5	C11—N12—Cu1	126.3 (3)
H4AB—C4A—H4AC	109.5	C7—N12—Cu1	115.3 (2)
C6—C5—C4	119.9 (4)

C6—N1—C2—C3	1.2 (6)	N1—C6—C7—C8	175.7 (3)
Cu1—N1—C2—C3	178.8 (3)	C5—C6—C7—C8	−4.1 (6)
N1—C2—C3—C4	0.1 (6)	N12—C7—C8—C9	−0.5 (6)
C2—C3—C4—C5	−1.0 (6)	C6—C7—C8—C9	179.5 (3)
C2—C3—C4—C4A	179.3 (4)	C7—C8—C9—C10	−0.9 (6)
C3—C4—C5—C6	0.7 (5)	C7—C8—C9—C9A	178.7 (3)
C4A—C4—C5—C6	−179.7 (4)	C8—C9—C10—C11	1.3 (6)
C2—N1—C6—C5	−1.6 (5)	C9A—C9—C10—C11	−178.3 (4)
Cu1—N1—C6—C5	−179.3 (3)	C9—C10—C11—N12	−0.4 (6)
C2—N1—C6—C7	178.6 (3)	C10—C11—N12—C7	−1.0 (6)
Cu1—N1—C6—C7	0.9 (4)	C10—C11—N12—Cu1	174.3 (3)
C4—C5—C6—N1	0.6 (6)	C8—C7—N12—C11	1.4 (6)
C4—C5—C6—C7	−179.7 (3)	C6—C7—N12—C11	−178.6 (3)
N1—C6—C7—N12	−4.3 (4)	C8—C7—N12—Cu1	−174.4 (3)
C5—C6—C7—N12	176.0 (4)	C6—C7—N12—Cu1	5.6 (4)

Symmetry codes: (i) x, −y+2, z−1/2; (ii) x, −y+2, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···Cl1	0.95	2.61	3.211 (4)	122
C8—H8A···Cl2ⁱⁱⁱ	0.95	2.88	3.666 (4)	140
C10—H10A···Cl1^iv	0.95	2.88	3.733 (4)	149

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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−1/2; (ii) x−1/2, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[CuCl₂(C₁₂H₁₂N₂)]
M_r	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)
V (Å³)	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 diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.646, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	7099, 2945, 2829
R_int	0.049
(sin θ/λ)_max (Å⁻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
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.48
Absolute structure	Classical Flack method preferred over Parsons because s.u. lower (Flack, 1983).
Absolute structure parameter	0.011 (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

Barnett, S. M., Goldberg, K. I. & Mayer, J. M. (2012). Nat. Chem. 4, 498–502. Web of Science CrossRef CAS PubMed Google Scholar
Bruker (2002). SMART, SAINT, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Csonka, R., Kaizer, J., Giorgi, M., Réglier, M., Hajba, L., Mink, J. & Speier, G. (2008). Inorg. Chem. 47, 6121–6123. Web of Science CSD CrossRef PubMed CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Garland, M. T., Grandjean, D., Spodine, E., Atria, A. M. & Manzur, J. (1988). Acta Cryst. C44, 1209–1212. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Gonzalez Q. O., Atria, A. M., Spodine, E., Manzur, J. & Garland, M. T. (1993). Acta Cryst. C49, 1589–1591. Google Scholar
Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. Web of Science CrossRef CAS Google Scholar
Hernández-Molina, M., González-Platas, J., Ruiz-Pérez, C., Lloret, F. & Julve, M. (1999). Inorg. Chim. Acta, 284, 258–265. Google Scholar
Jaividhya, P., Dhivya, R., Akbarsha, M. A. & Palaniandavar, M. (2012). J. Inorg. Biochem. 114, 94–105. Web of Science CrossRef CAS PubMed Google Scholar
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. Web of Science CrossRef CAS Google Scholar
Kostakis, G. E., Nordlander, E., Haukka, M. & Plakatouras, J. C. (2006). Acta Cryst. E62, m77–m79. Web of Science CSD CrossRef IUCr Journals Google Scholar
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. Web of Science CSD CrossRef CAS Google Scholar
Ricardo, C., Matosziuk, L. M., Evanseck, J. D. & Pintauer, T. (2008). Inorg. Chem. 48, 16–18. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Thorpe, S. B., Calderone, J. A. & Santos, W. L. (2012). Org. Lett. 14, 1918–1921. Web of Science CrossRef CAS PubMed Google Scholar
Wang, Y.-Q., Bi, W.-H., Li, X. & Cao, R. (2004). Acta Cryst. E60, m876–m877. Web of Science CSD CrossRef IUCr Journals Google Scholar
Willett, R. D., Pon, G. & Nagy, C. (2001). Inorg. Chem. 40, 4342–4352. Web of Science CSD CrossRef PubMed CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

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

doi:10.1107/S2056989015008944

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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