Di-μ-chlorido-bis­[(2,2′-bipyridine-5,5′-dicarb­oxy­lic acid-κ2N,N′)chloridocopper(II)] dimethyl­formamide tetra­solvate

Øien, S.; Wragg, D.S.; Lillerud, K.P.; Tilset, M.

doi:10.1107/S1600536812051422

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Pages m73-m74

doi:10.1107/S1600536812051422

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Di-μ-chlorido-bis[(2,2′-bipyridine-5,5′-dicarboxylic acid-κ²N,N′)chloridocopper(II)] dimethylformamide tetrasolvate

Sigurd Øien,^a ^* David Stephen Wragg,^a Karl Petter Lillerud ^a and Mats Tilset ^a

^ainGAP Centre for Research Based Innovation, Department of Chemistry, University of Oslo, 0315 Oslo, Norway
^*Correspondence e-mail: sigurdoi@kjemi.uio.no

(Received 15 November 2012; accepted 20 December 2012; online 4 January 2013)

In the title compound, [Cu₂Cl₄(C₁₂H₈N₂O₄)₂]·4C₃H₇NO, which contains a chloride-bridged centrosymmetric Cu^II dimer, the Cu^II atom is in a distorted square-pyramidal 4 + 1 coordination geometry defined by the N atoms of the chelating 2,2′-bipyridine ligand, a terminal chloride and two bridging chloride ligands. Of the two independent dimethylformamide molecules, one is hydrogen bonded to a single –COOH group, while one links two adjacent –COOH groups via a strong accepted O—H⋯O and a weak donated C(O)—H⋯O hydrogen bond. Two of these last molecules and the two –COOH groups form a centrosymmetric hydrogen-bonded ring in which the CH=O and the –COOH groups by disorder adopt two alternate orientations in a 0.44:0.56 ratio. These hydrogen bonds link the Cu^II complex molecules and the dimethylformamide solvent molecules into infinite chains along [-111]. Slipped π–π stacking interactions between two centrosymmetric pyridine rings (centroid–centroid distance = 3.63 Å) contribute to the coherence of the structure along [0-11].

Related literature

For related structures with similar coordination geometry around the copper atoms, see: Goddard et al. (1990 ); Tynan et al. (2005 ); Han et al. (2008 ); Liu et al. (2009 ); Qi et al. (2009 ). For other related structures of chloro bipyridine copper complexes, see: Wang et al. (2004 ); Zhao et al. (2010 ).

Experimental

Crystal data

[Cu₂Cl₄(C₁₂H₈N₂O₄)₂]·4C₃H₇NO
M_r = 1049.66
Triclinic, $[P \overline 1]$
a = 8.917 (5) Å
b = 11.030 (6) Å
c = 12.179 (7) Å
α = 83.171 (6)°
β = 73.903 (6)°
γ = 68.332 (6)°
V = 1069.4 (11) Å³
Z = 1
Mo Kα radiation
μ = 1.32 mm⁻¹
T = 100 K
0.20 × 0.15 × 0.02 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.789, T_max = 0.974
9231 measured reflections
4824 independent reflections
3969 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.068
S = 1.02
4824 reflections
295 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Selected bond lengths (Å)

N1—Cu1	2.0337 (18)
N2—Cu1	2.0361 (17)
Cl1—Cu1	2.2525 (10)
Cl2—Cu1ⁱ	2.2804 (10)
Cl2—Cu1	2.7183 (12)
Symmetry code: (i) -x+2, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O6Bⁱⁱ	0.82	1.72	2.515 (3)	161
O1—H1⋯O6Aⁱⁱⁱ	0.82	1.75	2.536 (4)	161
O3—H3⋯O5	0.82	1.72	2.541 (2)	177
C21A—H21A⋯O2^iv	0.93	2.71	3.591 (3)	158
C21B—H21B⋯O1ⁱⁱⁱ	0.93	2.72	3.603 (3)	159
Symmetry codes: (ii) x+1, y-1, z-1; (iii) -x+1, -y+1, -z+1; (iv) x-1, y+1, z+1.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006 ) and Materials Studio (Accelrys, 2010 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812051422/qk2049sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812051422/qk2049Isup2.hkl

checkCIF report

Comment top

In recent years, linear dicarboxylic acids have attracted much attention for their usage as linkers in metal-organic frameworks. This diverse class of porous materials can be utilized as heterogeneous catalysts or selective adsorbents, by incorporating active species onto the linkers. The reported compound (Fig. 1) consists of centrosymmetric dinuclear Cu complexes hydrogen bonded to four DMF molecules via O—H···O and C—H···O links. These Cu dimers and the DMF molecules create hydrogen bonded chains parallell to [111] (Fig. 2). The copper atoms have a slightly distorted square-pyramidal coordination by two N and three Cl atoms (two short and one long Cu—Cl bonds;Table 1), as observed in similar copper dimer complexes reported for instance by Goddard et al. (1990),Tynan et al. (2005), Han et al. (2008), Liu et al. (2009) and Qi et al. (2009). Fig. 1 and Fig. 2 show that the COOH group of O1–C7–O2 and the second DMF molecule (C21, O6A/O6B, N21, C15, C16) form a centrosymmetric hydrogen bond ring with alternating strong O—H···O(DMF) and weak C(DMF)—H···O hydrogen bonds. Due to a synchronous orientation disorder of the COOH groups and the DMF molecules the hydrogen bonds in these rings can adopt a clock or an anticlockwise sense in 0.44/0.56 ratio. Consequently, the observed bond distances C7—O1 = 1.261 (3) Å and C7—O2 = 1.264 (3) Å are approximately an average of the single and double bond distances of an ordered COOH group (e.g. C11═O4 = 1.209 (3) and C11—O3 = 1.311 (3) Å in the title compound). Apart from hydrogen bonding the structure of the title compound is held together by slipped π-π stacking interactions between centrosymmetric pairs of pyridine ring 1 (N1–C1–C8–C9–C10–C12). They show stacking distances of ca. 3.33 Å which are effective along [011] (Fig. 3). A polymeric copper(II) complex with the same organoligand as in (I) but with a Cu/Cl ratio of 1:1 has been reported by Zhao et al. (2010).

Related literature top

For related structures with similar coordination geometry around the copper atoms, see: Goddard et al. (1990); Tynan et al. (2005); Han et al. (2008); Liu et al. (2009); Qi et al. (2009). For other related structures of chloro bipyridine copper complexes, see: Wang et al. (2004); Zhao et al. (2010).

Experimental top

5,5'-dimethyl-2,2'-bipyridine was purchased from Sigma-Aldrich and oxidized with K₂Cr₂O₇ to 2,2'-bipyridine-5,5'-dicarboxylic acid according to literature methods. CuCl₂.2H₂O (>99%, Sigma-Aldrich) and dimethylformamide (DMF) (>99.5%, Merck) were used as received. 100 mg (0.41 mmol) H₂bpydc was dissolved in 10 ml of water, using a minimal amount of KOH. 70 mg (0.41 mmol) CuCl₂.2H₂O was dissolved in water. When the two solutions were combined, a blue precipitate was immediately formed. Dilute HCl was added until pH was 4. The blue microcrystalline precipitate (96 mg) was recovered, dried and dissolved in 5 ml of DMF along with 50 µL conc. HCl, giving a green solution. 1 ml of the solution was transferred to a small vial. The crystals were precipitated by vapor diffusion, using water as antisolvent.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006) and Materials Studio (Accelrys, 2010); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms showing also the disorder of one COOH group (C7 etc.) and one DMF molecule (C21A etc).
	Fig. 2. The packing of (I), showing the hydrogen bonded chains. Hydrogen atoms (except amide and carboxylic) are omitted and hydrogen bonds are shown as dashed lines.
	Fig. 3. Slipped π-π stacking interaction between the pyridine rings 1 (N1–C1–C8–C9–C10–C12) of two neighboring Cu complexes related by inversion (I).

Di-µ-chlorido-bis[(2,2'-bipyridine-5,5'-dicarboxylic acid-κ²N,N')chloridocopper(II)] dimethylformamide tetrasolvate top

Crystal data top

[Cu₂Cl₄(C₁₂H₈N₂O₄)₂]·4C₃H₇NO	Z = 1
M_r = 1049.66	F(000) = 538
Triclinic, P1	D_x = 1.627 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.917 (5) Å	Cell parameters from 3373 reflections
b = 11.030 (6) Å	θ = 2.5–27.4°
c = 12.179 (7) Å	µ = 1.32 mm⁻¹
α = 83.171 (6)°	T = 100 K
β = 73.903 (6)°	Prism, green
γ = 68.332 (6)°	0.20 × 0.15 × 0.02 mm
V = 1069.4 (11) Å³

Data collection top

Bruker APEXII CCD diffractometer	4824 independent reflections
Radiation source: fine-focus sealed tube	3969 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 27.9°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −11→11
T_min = 0.789, T_max = 0.974	k = −14→14
9231 measured reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.068	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0259P)² + 0.590P] where P = (F_o² + 2F_c²)/3
4824 reflections	(Δ/σ)_max = 0.001
295 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

[Cu₂Cl₄(C₁₂H₈N₂O₄)₂]·4C₃H₇NO	γ = 68.332 (6)°
M_r = 1049.66	V = 1069.4 (11) Å³
Triclinic, P1	Z = 1
a = 8.917 (5) Å	Mo Kα radiation
b = 11.030 (6) Å	µ = 1.32 mm⁻¹
c = 12.179 (7) Å	T = 100 K
α = 83.171 (6)°	0.20 × 0.15 × 0.02 mm
β = 73.903 (6)°

Data collection top

Bruker APEXII CCD diffractometer	4824 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3969 reflections with I > 2σ(I)
T_min = 0.789, T_max = 0.974	R_int = 0.021
9231 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.068	H-atom parameters constrained
S = 1.02	Δρ_max = 0.43 e Å⁻³
4824 reflections	Δρ_min = −0.37 e Å⁻³
295 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.5061 (2)	0.75714 (18)	0.49804 (17)	0.0142 (4)
C2	0.5665 (2)	0.64520 (18)	0.42163 (16)	0.0141 (4)
C3	0.7981 (2)	0.47716 (18)	0.32901 (16)	0.0150 (4)
H3A	0.9128	0.4329	0.3112	0.018*
C4	0.6997 (3)	0.43285 (18)	0.28504 (17)	0.0157 (4)
C5	0.5292 (2)	0.49803 (19)	0.31204 (17)	0.0168 (4)
H5	0.4611	0.4698	0.2838	0.020*
C6	0.4604 (3)	0.60601 (19)	0.38163 (17)	0.0170 (4)
H6	0.3459	0.6511	0.4010	0.020*
C7	0.7786 (3)	0.31742 (19)	0.20877 (17)	0.0174 (4)
C8	0.3416 (3)	0.84090 (19)	0.52720 (17)	0.0175 (4)
H8	0.2620	0.8292	0.4980	0.021*
C9	0.2973 (3)	0.94225 (19)	0.60049 (18)	0.0178 (4)
H9	0.1884	1.0014	0.6192	0.021*
C10	0.4173 (3)	0.95414 (18)	0.64538 (17)	0.0161 (4)
C11	0.3799 (3)	1.0583 (2)	0.72813 (18)	0.0202 (4)
C12	0.5801 (3)	0.86824 (19)	0.61159 (17)	0.0164 (4)
H12	0.6608	0.8774	0.6412	0.020*
C15	0.3041 (4)	0.7442 (2)	1.1227 (2)	0.0452 (7)
H15A	0.3318	0.7211	1.0441	0.068*
H15B	0.2396	0.6952	1.1693	0.068*
H15C	0.4047	0.7248	1.1465	0.068*
C16	0.1570 (3)	0.9324 (3)	1.2499 (2)	0.0327 (6)
H16A	0.0844	1.0220	1.2507	0.049*
H16B	0.2539	0.9263	1.2734	0.049*
H16C	0.0992	0.8818	1.3016	0.049*
C18	0.2042 (5)	1.4697 (3)	1.0417 (2)	0.0590 (10)
H18A	0.1608	1.5052	0.9764	0.088*
H18B	0.2955	1.4971	1.0395	0.088*
H18C	0.1180	1.5003	1.1103	0.088*
C19	0.2560 (3)	1.2678 (2)	0.95630 (19)	0.0272 (5)
H19	0.2955	1.1771	0.9602	0.033*
C20	0.3184 (3)	1.2590 (3)	1.1386 (2)	0.0434 (7)
H20A	0.3579	1.1668	1.1265	0.065*
H20B	0.2275	1.2811	1.2059	0.065*
H20C	0.4073	1.2827	1.1483	0.065*
C21A	0.1675 (3)	0.9574 (2)	1.04753 (19)	0.0242 (5)	0.437 (4)
H21A	0.1017	1.0445	1.0620	0.029*	0.437 (4)
O6A	0.2100 (5)	0.9214 (3)	0.9473 (3)	0.0255 (11)	0.437 (4)
C21B	0.1675 (3)	0.9574 (2)	1.04753 (19)	0.0242 (5)	0.563 (4)
H21B	0.1983	0.9165	0.9781	0.029*	0.563 (4)
O6B	0.0912 (4)	1.0793 (3)	1.0485 (2)	0.0304 (9)	0.563 (4)
N1	0.6254 (2)	0.77252 (15)	0.53787 (14)	0.0139 (3)
N2	0.7337 (2)	0.58081 (15)	0.39584 (14)	0.0140 (3)
N4	0.2618 (3)	1.32944 (19)	1.04017 (16)	0.0293 (4)
N21	0.2077 (2)	0.88264 (17)	1.13500 (15)	0.0227 (4)
O1	0.6831 (2)	0.27950 (15)	0.17378 (14)	0.0278 (4)
H1	0.7387	0.2161	0.1329	0.042*	0.437 (4)
O2	0.93592 (19)	0.26688 (15)	0.18333 (14)	0.0293 (4)
H2	0.9662	0.2047	0.1415	0.044*	0.563 (4)
O3	0.23516 (19)	1.15187 (14)	0.73405 (13)	0.0233 (3)
H3	0.2215	1.2066	0.7795	0.035*
O4	0.4777 (2)	1.05397 (17)	0.78151 (15)	0.0347 (4)
O5	0.2021 (2)	1.32076 (15)	0.87227 (13)	0.0337 (4)
Cl1	0.97529 (6)	0.78040 (5)	0.52466 (4)	0.01868 (11)
Cl2	0.88428 (6)	0.47339 (5)	0.63849 (4)	0.01680 (11)
Cu1	0.86273 (3)	0.65512 (2)	0.46635 (2)	0.01421 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0145 (10)	0.0134 (9)	0.0158 (10)	−0.0059 (8)	−0.0049 (8)	0.0017 (7)
C2	0.0139 (10)	0.0138 (9)	0.0148 (10)	−0.0054 (8)	−0.0038 (8)	0.0010 (7)
C3	0.0136 (10)	0.0149 (9)	0.0153 (10)	−0.0035 (8)	−0.0042 (8)	0.0005 (8)
C4	0.0191 (10)	0.0127 (9)	0.0153 (10)	−0.0062 (8)	−0.0034 (8)	−0.0001 (7)
C5	0.0177 (10)	0.0170 (10)	0.0187 (10)	−0.0082 (8)	−0.0067 (8)	−0.0007 (8)
C6	0.0137 (10)	0.0173 (10)	0.0199 (11)	−0.0050 (8)	−0.0050 (8)	0.0000 (8)
C7	0.0195 (11)	0.0152 (9)	0.0159 (10)	−0.0055 (8)	−0.0030 (8)	−0.0006 (8)
C8	0.0151 (10)	0.0181 (10)	0.0209 (11)	−0.0062 (8)	−0.0064 (8)	−0.0013 (8)
C9	0.0139 (10)	0.0158 (10)	0.0207 (11)	−0.0031 (8)	−0.0027 (8)	−0.0011 (8)
C10	0.0180 (10)	0.0138 (9)	0.0151 (10)	−0.0054 (8)	−0.0023 (8)	0.0000 (8)
C11	0.0207 (11)	0.0207 (10)	0.0176 (11)	−0.0079 (9)	0.0002 (9)	−0.0046 (8)
C12	0.0167 (10)	0.0174 (10)	0.0164 (10)	−0.0071 (8)	−0.0042 (8)	−0.0018 (8)
C15	0.0600 (19)	0.0260 (13)	0.0336 (15)	−0.0043 (13)	−0.0032 (14)	0.0031 (11)
C16	0.0285 (13)	0.0451 (15)	0.0223 (12)	−0.0123 (11)	−0.0022 (10)	−0.0053 (11)
C18	0.116 (3)	0.0361 (16)	0.0334 (16)	−0.0372 (18)	−0.0143 (18)	−0.0073 (13)
C19	0.0318 (13)	0.0209 (11)	0.0236 (12)	−0.0049 (10)	−0.0021 (10)	−0.0068 (9)
C20	0.0328 (15)	0.0567 (18)	0.0327 (15)	0.0025 (13)	−0.0144 (12)	−0.0170 (13)
C21A	0.0257 (12)	0.0203 (11)	0.0270 (12)	−0.0070 (9)	−0.0061 (10)	−0.0068 (9)
O6A	0.035 (2)	0.0194 (19)	0.020 (2)	−0.0058 (16)	−0.0081 (16)	−0.0050 (14)
C21B	0.0257 (12)	0.0203 (11)	0.0270 (12)	−0.0070 (9)	−0.0061 (10)	−0.0068 (9)
O6B	0.0358 (18)	0.0216 (15)	0.0283 (17)	−0.0037 (13)	−0.0062 (13)	−0.0056 (12)
N1	0.0125 (8)	0.0136 (8)	0.0165 (8)	−0.0046 (6)	−0.0047 (7)	−0.0003 (6)
N2	0.0132 (8)	0.0138 (8)	0.0152 (8)	−0.0047 (7)	−0.0040 (7)	−0.0001 (6)
N4	0.0333 (12)	0.0327 (11)	0.0208 (10)	−0.0114 (9)	−0.0017 (9)	−0.0097 (8)
N21	0.0223 (10)	0.0221 (9)	0.0213 (10)	−0.0068 (8)	−0.0020 (8)	−0.0032 (7)
O1	0.0317 (9)	0.0262 (8)	0.0302 (9)	−0.0137 (7)	−0.0056 (7)	−0.0114 (7)
O2	0.0210 (9)	0.0259 (8)	0.0344 (9)	0.0000 (7)	−0.0033 (7)	−0.0114 (7)
O3	0.0269 (9)	0.0170 (7)	0.0219 (8)	−0.0014 (6)	−0.0053 (7)	−0.0074 (6)
O4	0.0239 (9)	0.0420 (10)	0.0379 (10)	−0.0025 (8)	−0.0100 (8)	−0.0239 (8)
O5	0.0581 (12)	0.0210 (8)	0.0189 (8)	−0.0089 (8)	−0.0109 (8)	−0.0028 (7)
Cl1	0.0153 (2)	0.0184 (2)	0.0249 (3)	−0.00683 (19)	−0.0069 (2)	−0.00293 (19)
Cl2	0.0120 (2)	0.0202 (2)	0.0173 (2)	−0.00488 (19)	−0.00233 (18)	−0.00277 (19)
Cu1	0.01079 (13)	0.01549 (12)	0.01676 (13)	−0.00388 (9)	−0.00401 (9)	−0.00304 (9)

Geometric parameters (Å, º) top

C1—N1	1.355 (3)	C15—H15C	0.9600
C1—C8	1.386 (3)	C16—N21	1.453 (3)
C1—C2	1.478 (3)	C16—H16A	0.9600
C2—N2	1.355 (3)	C16—H16B	0.9600
C2—C6	1.388 (3)	C16—H16C	0.9600
C3—N2	1.333 (3)	C18—N4	1.439 (3)
C3—C4	1.391 (3)	C18—H18A	0.9600
C3—H3A	0.9300	C18—H18B	0.9600
C4—C5	1.382 (3)	C18—H18C	0.9600
C4—C7	1.495 (3)	C19—O5	1.242 (3)
C5—C6	1.388 (3)	C19—N4	1.315 (3)
C5—H5	0.9300	C19—H19	0.9300
C6—H6	0.9300	C20—N4	1.456 (3)
C7—O1	1.261 (3)	C20—H20A	0.9600
C7—O2	1.264 (3)	C20—H20B	0.9600
C8—C9	1.385 (3)	C20—H20C	0.9600
C8—H8	0.9300	C21A—O6A	1.241 (4)
C9—C10	1.381 (3)	C21A—N21	1.315 (3)
C9—H9	0.9300	C21A—H21A	0.9300
C10—C12	1.386 (3)	N1—Cu1	2.0337 (18)
C10—C11	1.501 (3)	N2—Cu1	2.0361 (17)
C11—O4	1.209 (3)	O1—H1	0.8200
C11—O3	1.311 (3)	O2—H2	0.8200
C12—N1	1.339 (3)	O3—H3	0.8200
C12—H12	0.9300	Cl1—Cu1	2.2525 (10)
C15—N21	1.451 (3)	Cl2—Cu1ⁱ	2.2804 (10)
C15—H15A	0.9600	Cl2—Cu1	2.7183 (12)
C15—H15B	0.9600

N1—C1—C8	121.94 (18)	H16A—C16—H16C	109.5
N1—C1—C2	114.49 (17)	H16B—C16—H16C	109.5
C8—C1—C2	123.57 (18)	N4—C18—H18A	109.5
N2—C2—C6	122.18 (18)	N4—C18—H18B	109.5
N2—C2—C1	114.96 (16)	H18A—C18—H18B	109.5
C6—C2—C1	122.83 (18)	N4—C18—H18C	109.5
N2—C3—C4	122.29 (19)	H18A—C18—H18C	109.5
N2—C3—H3A	118.9	H18B—C18—H18C	109.5
C4—C3—H3A	118.9	O5—C19—N4	125.3 (2)
C5—C4—C3	118.91 (18)	O5—C19—H19	117.3
C5—C4—C7	120.96 (18)	N4—C19—H19	117.3
C3—C4—C7	120.13 (18)	N4—C20—H20A	109.5
C4—C5—C6	119.42 (18)	N4—C20—H20B	109.5
C4—C5—H5	120.3	H20A—C20—H20B	109.5
C6—C5—H5	120.3	N4—C20—H20C	109.5
C5—C6—C2	118.45 (19)	H20A—C20—H20C	109.5
C5—C6—H6	120.8	H20B—C20—H20C	109.5
C2—C6—H6	120.8	O6A—C21A—N21	125.4 (3)
O1—C7—O2	125.27 (19)	O6A—C21A—H21A	117.3
O1—C7—C4	117.40 (18)	N21—C21A—H21A	117.3
O2—C7—C4	117.32 (18)	C12—N1—C1	118.42 (17)
C9—C8—C1	119.05 (19)	C12—N1—Cu1	126.23 (14)
C9—C8—H8	120.5	C1—N1—Cu1	115.10 (13)
C1—C8—H8	120.5	C3—N2—C2	118.75 (17)
C10—C9—C8	118.98 (19)	C3—N2—Cu1	126.29 (14)
C10—C9—H9	120.5	C2—N2—Cu1	114.96 (13)
C8—C9—H9	120.5	C19—N4—C18	121.5 (2)
C9—C10—C12	119.08 (18)	C19—N4—C20	121.4 (2)
C9—C10—C11	122.74 (18)	C18—N4—C20	117.0 (2)
C12—C10—C11	118.17 (18)	C21A—N21—C15	121.8 (2)
O4—C11—O3	124.97 (19)	C21A—N21—C16	122.4 (2)
O4—C11—C10	121.63 (19)	C15—N21—C16	115.8 (2)
O3—C11—C10	113.39 (18)	C7—O1—H1	109.5
N1—C12—C10	122.42 (18)	C7—O2—H2	109.5
N1—C12—H12	118.8	C11—O3—H3	109.5
C10—C12—H12	118.8	Cu1ⁱ—Cl2—Cu1	90.20 (4)
N21—C15—H15A	109.5	N1—Cu1—N2	79.91 (8)
N21—C15—H15B	109.5	N1—Cu1—Cl1	92.97 (6)
H15A—C15—H15B	109.5	N2—Cu1—Cl1	166.75 (5)
N21—C15—H15C	109.5	N1—Cu1—Cl2ⁱ	171.33 (5)
H15A—C15—H15C	109.5	N2—Cu1—Cl2ⁱ	93.45 (7)
H15B—C15—H15C	109.5	Cl1—Cu1—Cl2ⁱ	92.41 (5)
N21—C16—H16A	109.5	N1—Cu1—Cl2	96.09 (5)
N21—C16—H16B	109.5	N2—Cu1—Cl2	93.10 (6)
H16A—C16—H16B	109.5	Cl1—Cu1—Cl2	98.80 (4)
N21—C16—H16C	109.5	Cl2ⁱ—Cu1—Cl2	89.80 (4)

N1—C1—C2—N2	−4.8 (2)	C8—C1—N1—Cu1	−171.55 (15)
C8—C1—C2—N2	174.95 (18)	C2—C1—N1—Cu1	8.2 (2)
N1—C1—C2—C6	173.40 (18)	C4—C3—N2—C2	−0.1 (3)
C8—C1—C2—C6	−6.9 (3)	C4—C3—N2—Cu1	179.64 (14)
N2—C3—C4—C5	−0.4 (3)	C6—C2—N2—C3	0.6 (3)
N2—C3—C4—C7	178.92 (17)	C1—C2—N2—C3	178.81 (16)
C3—C4—C5—C6	0.3 (3)	C6—C2—N2—Cu1	−179.13 (15)
C7—C4—C5—C6	−179.00 (18)	C1—C2—N2—Cu1	−0.9 (2)
C4—C5—C6—C2	0.2 (3)	O5—C19—N4—C18	−0.3 (4)
N2—C2—C6—C5	−0.7 (3)	O5—C19—N4—C20	176.4 (2)
C1—C2—C6—C5	−178.74 (18)	O6A—C21A—N21—C15	−2.5 (4)
C5—C4—C7—O1	−2.5 (3)	O6A—C21A—N21—C16	178.3 (3)
C3—C4—C7—O1	178.22 (18)	C12—N1—Cu1—N2	179.08 (17)
C5—C4—C7—O2	176.55 (19)	C1—N1—Cu1—N2	−6.78 (13)
C3—C4—C7—O2	−2.7 (3)	C12—N1—Cu1—Cl1	−12.18 (16)
N1—C1—C8—C9	−0.9 (3)	C1—N1—Cu1—Cl1	161.96 (13)
C2—C1—C8—C9	179.35 (18)	C12—N1—Cu1—Cl2	87.00 (16)
C1—C8—C9—C10	−2.2 (3)	C1—N1—Cu1—Cl2	−98.86 (14)
C8—C9—C10—C12	3.1 (3)	C3—N2—Cu1—N1	−175.67 (17)
C8—C9—C10—C11	−178.12 (19)	C2—N2—Cu1—N1	4.05 (13)
C9—C10—C11—O4	166.9 (2)	C3—N2—Cu1—Cl1	126.0 (2)
C12—C10—C11—O4	−14.3 (3)	C2—N2—Cu1—Cl1	−54.2 (3)
C9—C10—C11—O3	−14.0 (3)	C3—N2—Cu1—Cl2ⁱ	9.96 (16)
C12—C10—C11—O3	164.78 (18)	C2—N2—Cu1—Cl2ⁱ	−170.32 (13)
C9—C10—C12—N1	−0.9 (3)	C3—N2—Cu1—Cl2	−80.03 (16)
C11—C10—C12—N1	−179.79 (18)	C2—N2—Cu1—Cl2	99.69 (13)
C10—C12—N1—C1	−2.2 (3)	Cu1ⁱ—Cl2—Cu1—N1	173.62 (5)
C10—C12—N1—Cu1	171.82 (14)	Cu1ⁱ—Cl2—Cu1—N2	93.44 (6)
C8—C1—N1—C12	3.1 (3)	Cu1ⁱ—Cl2—Cu1—Cl1	−92.40 (5)
C2—C1—N1—C12	−177.18 (16)	Cu1ⁱ—Cl2—Cu1—Cl2ⁱ	0.0

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O6Bⁱⁱ	0.82	1.72	2.515 (3)	161
O1—H1···O6Aⁱⁱⁱ	0.82	1.75	2.536 (4)	161
O3—H3···O5	0.82	1.72	2.541 (2)	177
C21A—H21A···O2^iv	0.93	2.71	3.591 (3)	158
C21B—H21B···O1ⁱⁱⁱ	0.93	2.72	3.603 (3)	159

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

Experimental details

Crystal data
Chemical formula	[Cu₂Cl₄(C₁₂H₈N₂O₄)₂]·4C₃H₇NO
M_r	1049.66
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.917 (5), 11.030 (6), 12.179 (7)
α, β, γ (°)	83.171 (6), 73.903 (6), 68.332 (6)
V (Å³)	1069.4 (11)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.32
Crystal size (mm)	0.20 × 0.15 × 0.02

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.789, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	9231, 4824, 3969
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.068, 1.02
No. of reflections	4824
No. of parameters	295
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.37

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006) and Materials Studio (Accelrys, 2010), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

N1—Cu1	2.0337 (18)	Cl2—Cu1ⁱ	2.2804 (10)
N2—Cu1	2.0361 (17)	Cl2—Cu1	2.7183 (12)
Cl1—Cu1	2.2525 (10)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O6Bⁱⁱ	0.82	1.72	2.515 (3)	161.4
O1—H1···O6Aⁱⁱⁱ	0.82	1.75	2.536 (4)	160.5
O3—H3···O5	0.82	1.72	2.541 (2)	177.4
C21A—H21A···O2^iv	0.93	2.71	3.591 (3)	157.8
C21B—H21B···O1ⁱⁱⁱ	0.93	2.72	3.603 (3)	159.1

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

Acknowledgements

This work is part of the inGAP and CLIMIT, which receive financial support from the Norwegian Research Council under contract Nos. 174893 and 215735, respectively.

References

Accelrys (2010). Materials Studio. Accelrys Inc., San Diego, California, USA. Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Goddard, R., Hemalatha, B. & Rajasekharan, M. V. (1990). Acta Cryst. C46, 33–35. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Han, K.-F., Wu, H.-Y., Wang, Z.-M. & Guo, H.-Y. (2008). Acta Cryst. E64, m1607–m1608. Web of Science CrossRef IUCr Journals Google Scholar
Liu, Y.-F., Rong, D.-F., Xia, H.-T. & Wang, D.-Q. (2009). Acta Cryst. E65, m1492. Web of Science CrossRef IUCr Journals Google Scholar
Qi, Z.-P., Wang, A.-D., Zhang, H. & Wang, X.-X. (2009). Acta Cryst. E65, m1507–m1508. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tynan, E., Jensen, P., Lees, A. C., Moubaraki, B., Murray, K. S. & Kruger, P. E. (2005). CrystEngComm, 7, 90–95. Web of Science CSD CrossRef CAS 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
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhao, J., Shi, D., Cheng, H., Chen, L., Ma, P. & Niu, J. (2010). Inorg. Chem. Commun. 13, 822–827. Web of Science CSD CrossRef CAS Google Scholar

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