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

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].

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in solvent or counterion
• R factor = 0.029
• wR factor = 0.068
• Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H21A   ..  O2      ..       2.71 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H21B   ..  O1      ..       2.72 Ang.
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         66

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............          3
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.00600 Deg.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1    --  Cl2     ..       11.0 su
PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ...................         20 Perc.
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          3
              C3 H7 N O
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        201

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

---

S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

All H atoms were placed in geometrically idealized positions, with C_sp2—H = 0.93 Å, C_sp3—H = 0.96 Å, O—H = 0.82 Å and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C_sp2) or 1.5U_eq(C_sp3,O). The atoms O6 A/B, C21 A/B and H21 A/B of one DMF molecule and H1/2 of a COOH group are disordered over 2 sites with refined occupancies of 0.437 (4) (part A and H1) and 0.563 (4) (part B and H2).

Computing details

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

	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

Crystal data

[Cu2Cl4(C12H8N2O4)2]·4C3H7NO	Z = 1
Mr = 1049.66	F(000) = 538
Triclinic, P1	Dx = 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) Å^3

Data collection

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

Refinement

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

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—Cu1^i	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	Cu1^i—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—Cl2^i	171.33 (5)
H15A—C15—H15C	109.5	N2—Cu1—Cl2^i	93.45 (7)
H15B—C15—H15C	109.5	Cl1—Cu1—Cl2^i	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	Cl2^i—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—Cl2^i	9.96 (16)
C12—C10—C11—O3	164.78 (18)	C2—N2—Cu1—Cl2^i	−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)	Cu1^i—Cl2—Cu1—N1	173.62 (5)
C10—C12—N1—Cu1	171.82 (14)	Cu1^i—Cl2—Cu1—N2	93.44 (6)
C8—C1—N1—C12	3.1 (3)	Cu1^i—Cl2—Cu1—Cl1	−92.40 (5)
C2—C1—N1—C12	−177.18 (16)	Cu1^i—Cl2—Cu1—Cl2^i	0.0

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O6B^ii	0.82	1.72	2.515 (3)	161
O1—H1···O6A^iii	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···O1^iii	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.