(2,2′-Bipyridine)(2-{1-[2-(dimethyl­amino)ethyl­imino]eth­yl}-4-methoxy­phenolato)copper(II) perchlorate

Abstract

The Cu atom of the title complex, [Cu(C₁₃H₁₉N₂O₂)(C₁₀H₈N₂)]ClO₄, has a distorted square-pyramidal geometry with all three of the donor atoms from the N,N′,O-tridentate Schiff base ligand in the equatorial positions and the bipyridine N atoms in an equatorial–axial binding mode. The Cu atom is 0.1801 (11) Å above the N₃O mean basal plane.

Related literature

For the development of efficient catalytic systems for the coupling of CO₂ with heterocycles into polycarbonates, see: Inoue et al. (1969 ▶). For the synthesis and catalytic studies of a series of bis­–(salicylaldiminato)zinc complexes, see: Darensbourg et al. (2001 ▶). For similar complexes, see: Dhar et al. (2006 ▶); Shen et al. (2003 ▶). For the synthesis, see: Hung & Lin (2009 ▶); Hung et al. (2008 ▶); For the chemical activity of complexes, see: Noh et al. (2007 ▶).

Experimental

Crystal data

• [Cu(C₁₃H₁₉N₂O₂)(C₁₀H₈N₂)]ClO₄

• M _r = 554.49

• Monoclinic,

• a = 10.1588 (10) Å

• b = 18.2163 (17) Å

• c = 13.3764 (13) Å

• β = 92.610 (2)°

• V = 2472.8 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 1.04 mm⁻¹

• T = 293 K

• 0.34 × 0.26 × 0.15 mm

Data collection

• Bruker SMART 1000 CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.719, T _max = 0.860

• 13946 measured reflections

• 4859 independent reflections

• 3488 reflections with I > 2σ(I)

• R _int = 0.037

Refinement

• R[F ² > 2σ(F ²)] = 0.038

• wR(F ²) = 0.105

• S = 0.98

• 4859 reflections

• 319 parameters

• H-atom parameters constrained

• Δρ_max = 0.33 e Å⁻³

• Δρ_min = −0.30 e Å⁻³

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

Though many bacteria convert CO₂ into organic compounds by photosynthesis, utilization of CO₂ as a chemical feedstock in industrial and laboratory is rare. Recently, reuse of CO₂ has received great attention because of environmental concern. Polycarbonates (PC) have been wildly used in the modern chemical industry. Co–polymerization of CO₂ with olefins may benefit from reducing the release of CO₂ and generating potential industrial useful PCs. Therefore, there has been increasing interest in the development of efficient catalytic systems for the coupling of CO₂ with heterocycles into polycarbonates (Inoue et al., 1969). One of the major successes is the utilization of epoxides and CO₂ as starting materials to prepare PCs and/or cyclic carbonates in the presence of a transition metal catalyst. Recently, Darensbourg et al., (2001) disclosed the synthesis, characterization and catalytic studies of a series of bis–(salicylaldiminato)zinc complexes, in which the most active catalyst for co–polymerization of cyclohexene oxide and CO₂ giving poly(cyclohexene carbonate) (>99% carbonate linkages, Mn = 41000 g^.mol^-1, Mw/Mn = 10.3) with a turnover frequency of 6.9 h^-1. In addition, Shen et al. (2003) reported that binaphthyldiaminosalen–type Zn, Cu, and Co complexes efficiently catalyzed reactions of epoxides with CO₂ to achieve five–membered ring cyclic carbonates in the presence of various catalytic amounts of organic bases. Noh et al., (2007) disclosed catalytic studies of the binary system of [(salen)Co(III)complex] / (quaternary ammonium salt) for co–polymerization of propylene oxide and CO₂. Most recently, a series of N,N,O–tridentate Schiff base zinc– and magnesium–complexes have been reported to be effective initiators / catalyst for ROP of lactide (Hung et al., 2008; Hung & Lin, 2009). We report herein the synthesis and crystal structure of [LCu(bipy)]ClO₄, where L is title tridentate ligand and bipy is 2,2'–bipyridine, a potential catalyst for CO₂ / epoxide coupling co–polymerization.

The solid structure of [LCu(bipy)]⁺ ion reveals a monomeric Cu^II complex containing a six–member and a five–member ring coordinated from the tridentate salicylideneiminate ligand and a five–member ring coordinated from the bipyridine ligand. The geometry around Cu atom is penta–coordinated with a slight distorted square pyramidal environment in which all three of the N,N,O–tridentate donor atoms and one of the N atoms of the bipyridine lignad sitting on the equatorial plane, and another N atom of the bipyridine ligand at the axial position. The distances between the Cu atom and O1, N1, N2, N3 and N4 are 1.903 (2), 1.964 (2), 2.076 (2), 2.208 (2) and 2.044 (2) Å, respectively which are all within a normal distance for a Cu—O and Cu—N distance. These bond distances are similar to those found in other Schiff base Cu^II complexes (Dhar et al., 2006).

Experimental

The ligand, 2–{1–[2–(dimethylamino)ethylimino]ethyl}–4–methoxyphenol was prepared according to the method reported previously (Hung et al., 2008). The title complex was synthesized by the following procedures: Cu(OAc)₂^.H₂O (0.197 g, 1.00 mmol) and 2,2'–bipyridine (0.199 g, 1.28 mmol) was stirred in EtOH (15 ml) at room temperature for 0.5 h. The 2–{1–[2–(dimethylamino)ethylimino]ethyl}–4–methoxyphenol (0.298 g, 1.0 mmol) in EtOH (10 ml) was added. The reaction mixture was then stirred for another 1 h, and an 10 ml ethanolic solution of NaClO₄ (0.122 g, 1.0 mmol) was added producing green precipitate. The product was isolated by filtration and the resulting precipitate was crystallized from EtOH to yield green crystals.

Refinement

The methyl H atoms were located and then constrained to an ideal geometry with C—H distances of 0.96 Å and U_iso(H) = 1.5U_eq(C), but each group was allowed to rotate freely about its C—C bond. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances in the range 0.93 Å and 0.97 Å and U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

A view of the molecular structure with the atom numbering scheme. The displacement ellipsoids are shown at the 20% probability level. H atoms are presented as a small spheres of arbitrary radius.

Crystal data

[Cu(C13H19N2O2)(C10H8N2)]ClO4	F(000) = 1148
Mr = 554.49	Dx = 1.489 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4710 reflections
a = 10.1588 (10) Å	θ = 2.3–25.6°
b = 18.2163 (17) Å	µ = 1.04 mm−1
c = 13.3764 (13) Å	T = 293 K
β = 92.610 (2)°	Parallelpiped, green
V = 2472.8 (4) Å3	0.34 × 0.26 × 0.15 mm
Z = 4

Data collection

Bruker SMART 1000 CCD diffractometer	4859 independent reflections
Radiation source: fine–focus sealed tube	3488 reflections with I > 2σ(I)
graphite	Rint = 0.037
φ and ω scans	θmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.719, Tmax = 0.860	k = −22→16
13946 measured reflections	l = −16→15

Refinement

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105	H-atom parameters constrained
S = 0.98	w = 1/[σ2(Fo2) + (0.06P)2] where P = (Fo2 + 2Fc2)/3
4859 reflections	(Δ/σ)max = 0.001
319 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
Cu	0.62390 (3)	0.172001 (16)	0.82971 (2)	0.04095 (12)
O1	0.6832 (2)	0.15346 (10)	0.96441 (14)	0.0532 (5)
O2	0.9049 (3)	−0.10697 (14)	1.0997 (2)	0.1017 (10)
N1	0.5494 (2)	0.07290 (12)	0.81586 (16)	0.0457 (5)
N2	0.4979 (2)	0.19843 (13)	0.70841 (18)	0.0528 (6)
N3	0.8094 (2)	0.16361 (12)	0.75071 (17)	0.0469 (6)
N4	0.6989 (2)	0.27569 (11)	0.84447 (15)	0.0412 (5)
C1	0.7293 (3)	0.08881 (15)	0.9916 (2)	0.0455 (6)
C2	0.8227 (3)	0.08568 (17)	1.0724 (2)	0.0583 (8)
H2A	0.8483	0.1293	1.1039	0.070*
C3	0.8779 (4)	0.02114 (19)	1.1069 (2)	0.0681 (9)
H3A	0.9395	0.0215	1.1605	0.082*
C4	0.8411 (4)	−0.04469 (18)	1.0612 (2)	0.0665 (9)
C5	0.7497 (3)	−0.04455 (16)	0.9842 (2)	0.0576 (8)
H5A	0.7257	−0.0890	0.9544	0.069*
C6	0.6895 (3)	0.02080 (15)	0.94751 (19)	0.0439 (6)
C7	0.5849 (3)	0.01591 (15)	0.8687 (2)	0.0447 (7)
C8	0.5192 (3)	−0.05759 (16)	0.8497 (2)	0.0605 (8)
H8A	0.5193	−0.0850	0.9111	0.079 (10)*
H8B	0.5666	−0.0844	0.8011	0.102 (13)*
H8C	0.4300	−0.0500	0.8250	0.098 (13)*
C9	0.4456 (3)	0.06785 (18)	0.7363 (2)	0.0629 (8)
H9A	0.3599	0.0752	0.7639	0.075*
H9B	0.4469	0.0197	0.7054	0.075*
C10	0.4709 (3)	0.12658 (16)	0.6597 (2)	0.0603 (8)
H10A	0.5457	0.1125	0.6214	0.072*
H10B	0.3947	0.1309	0.6137	0.072*
C11	0.3779 (4)	0.2319 (2)	0.7440 (3)	0.0901 (13)
H11A	0.3197	0.2441	0.6879	0.135*
H11B	0.4002	0.2758	0.7809	0.135*
H11C	0.3349	0.1980	0.7867	0.135*
C12	0.5537 (4)	0.24885 (18)	0.6336 (2)	0.0728 (10)
H12A	0.4889	0.2579	0.5805	0.109*
H12B	0.6301	0.2267	0.6066	0.109*
H12C	0.5781	0.2944	0.6654	0.109*
C13	0.8909 (5)	−0.1720 (2)	1.0445 (3)	0.1034 (15)
H13A	0.9394	−0.2106	1.0783	0.155*
H13B	0.9244	−0.1648	0.9792	0.155*
H13C	0.7994	−0.1852	1.0380	0.155*
C14	0.8536 (3)	0.10711 (16)	0.6971 (2)	0.0578 (8)
H14A	0.8076	0.0630	0.6976	0.069*
C15	0.9634 (3)	0.11167 (19)	0.6418 (2)	0.0630 (9)
H15A	0.9903	0.0718	0.6045	0.076*
C16	1.0329 (3)	0.1763 (2)	0.6427 (3)	0.0689 (9)
H16A	1.1076	0.1809	0.6055	0.083*
C17	0.9908 (3)	0.23447 (17)	0.6995 (2)	0.0572 (8)
H17A	1.0379	0.2783	0.7021	0.069*
C18	0.8784 (3)	0.22671 (14)	0.75206 (19)	0.0415 (6)
C19	0.8210 (3)	0.28739 (14)	0.81221 (18)	0.0402 (6)
C20	0.8879 (3)	0.35225 (16)	0.8336 (2)	0.0531 (7)
H20A	0.9728	0.3592	0.8123	0.064*
C21	0.8265 (3)	0.40656 (17)	0.8872 (2)	0.0611 (8)
H21A	0.8702	0.4503	0.9025	0.073*
C22	0.7019 (3)	0.39554 (15)	0.9173 (2)	0.0546 (8)
H22A	0.6587	0.4319	0.9520	0.066*
C23	0.6409 (3)	0.32963 (14)	0.8954 (2)	0.0480 (7)
H23A	0.5561	0.3220	0.9166	0.058*
Cl	0.25347 (7)	0.09143 (4)	0.40216 (5)	0.05096 (19)
O3	0.2755 (3)	0.16261 (12)	0.4419 (2)	0.0957 (9)
O4	0.2085 (3)	0.09639 (16)	0.30025 (18)	0.0956 (9)
O5	0.1576 (3)	0.05517 (15)	0.4574 (2)	0.0958 (8)
O6	0.3729 (2)	0.05090 (16)	0.4085 (2)	0.0970 (9)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cu	0.0450 (2)	0.03477 (19)	0.04338 (19)	−0.00436 (14)	0.00530 (14)	−0.00633 (13)
O1	0.0719 (14)	0.0383 (11)	0.0488 (11)	−0.0068 (9)	−0.0037 (10)	−0.0082 (8)
O2	0.157 (3)	0.0660 (17)	0.0788 (17)	0.0307 (17)	−0.0360 (18)	0.0011 (13)
N1	0.0480 (14)	0.0429 (13)	0.0461 (12)	−0.0095 (11)	0.0028 (10)	−0.0070 (11)
N2	0.0570 (15)	0.0454 (14)	0.0554 (14)	0.0058 (12)	−0.0036 (12)	−0.0100 (11)
N3	0.0431 (13)	0.0430 (14)	0.0552 (14)	0.0014 (10)	0.0088 (11)	−0.0067 (10)
N4	0.0466 (13)	0.0356 (12)	0.0416 (12)	−0.0007 (10)	0.0033 (10)	−0.0018 (9)
C1	0.0533 (17)	0.0415 (16)	0.0424 (14)	−0.0072 (13)	0.0103 (12)	−0.0023 (12)
C2	0.071 (2)	0.0517 (19)	0.0519 (17)	−0.0082 (16)	−0.0031 (15)	−0.0078 (14)
C3	0.082 (2)	0.070 (2)	0.0515 (18)	−0.0007 (19)	−0.0059 (17)	−0.0052 (16)
C4	0.089 (3)	0.057 (2)	0.0532 (18)	0.0107 (18)	0.0023 (18)	−0.0003 (15)
C5	0.080 (2)	0.0413 (17)	0.0515 (17)	−0.0015 (15)	0.0065 (16)	−0.0040 (13)
C6	0.0526 (16)	0.0415 (15)	0.0383 (14)	−0.0049 (13)	0.0089 (12)	−0.0015 (11)
C7	0.0517 (16)	0.0389 (15)	0.0451 (15)	−0.0108 (13)	0.0191 (13)	−0.0092 (12)
C8	0.074 (2)	0.0480 (18)	0.0608 (19)	−0.0214 (16)	0.0146 (17)	−0.0062 (15)
C9	0.061 (2)	0.060 (2)	0.066 (2)	−0.0155 (16)	−0.0089 (16)	−0.0077 (16)
C10	0.070 (2)	0.0530 (19)	0.0569 (18)	0.0031 (16)	−0.0116 (16)	−0.0116 (14)
C11	0.063 (2)	0.103 (3)	0.103 (3)	0.028 (2)	−0.010 (2)	−0.035 (2)
C12	0.099 (3)	0.055 (2)	0.063 (2)	0.0052 (19)	−0.0126 (19)	0.0072 (16)
C13	0.149 (4)	0.068 (3)	0.092 (3)	0.037 (3)	−0.011 (3)	0.005 (2)
C14	0.0549 (18)	0.0486 (18)	0.070 (2)	0.0049 (14)	0.0082 (15)	−0.0145 (15)
C15	0.060 (2)	0.066 (2)	0.063 (2)	0.0147 (17)	0.0092 (16)	−0.0190 (16)
C16	0.0503 (19)	0.091 (3)	0.067 (2)	0.0089 (18)	0.0195 (16)	−0.0087 (18)
C17	0.0470 (17)	0.059 (2)	0.0658 (19)	−0.0041 (14)	0.0093 (15)	0.0006 (15)
C18	0.0399 (14)	0.0445 (15)	0.0398 (14)	0.0019 (12)	−0.0011 (11)	0.0024 (11)
C19	0.0429 (15)	0.0402 (15)	0.0371 (13)	−0.0018 (12)	−0.0026 (11)	0.0038 (11)
C20	0.0515 (18)	0.0513 (18)	0.0566 (17)	−0.0134 (14)	0.0023 (14)	−0.0014 (14)
C21	0.076 (2)	0.0430 (17)	0.0639 (19)	−0.0151 (16)	−0.0035 (17)	−0.0052 (14)
C22	0.077 (2)	0.0381 (16)	0.0488 (17)	0.0009 (15)	0.0025 (15)	−0.0054 (12)
C23	0.0541 (17)	0.0423 (16)	0.0480 (16)	0.0021 (13)	0.0060 (13)	−0.0046 (12)
Cl	0.0475 (4)	0.0508 (4)	0.0552 (4)	0.0010 (3)	0.0103 (3)	0.0000 (3)
O3	0.138 (3)	0.0527 (15)	0.097 (2)	−0.0073 (15)	0.0050 (18)	−0.0065 (13)
O4	0.0810 (17)	0.146 (3)	0.0593 (15)	0.0118 (17)	−0.0038 (13)	−0.0072 (15)
O5	0.0868 (18)	0.0864 (19)	0.118 (2)	−0.0077 (15)	0.0486 (16)	0.0223 (15)
O6	0.0599 (15)	0.113 (2)	0.118 (2)	0.0323 (15)	0.0115 (14)	0.0019 (17)

Geometric parameters (Å, °)

Cu—O1	1.9037 (19)	C9—H9B	0.9700
Cu—N1	1.963 (2)	C10—H10A	0.9700
Cu—N4	2.043 (2)	C10—H10B	0.9700
Cu—N2	2.077 (2)	C11—H11A	0.9600
Cu—N3	2.207 (2)	C11—H11B	0.9600
O1—C1	1.313 (3)	C11—H11C	0.9600
O2—C4	1.393 (4)	C12—H12A	0.9600
O2—C13	1.400 (4)	C12—H12B	0.9600
N1—C7	1.298 (3)	C12—H12C	0.9600
N1—C9	1.466 (3)	C13—H13A	0.9600
N2—C11	1.462 (4)	C13—H13B	0.9600
N2—C10	1.482 (4)	C13—H13C	0.9600
N2—C12	1.490 (4)	C14—C15	1.369 (4)
N3—C14	1.343 (3)	C14—H14A	0.9300
N3—C18	1.346 (3)	C15—C16	1.372 (4)
N4—C19	1.348 (3)	C15—H15A	0.9300
N4—C23	1.347 (3)	C16—C17	1.383 (4)
C1—C2	1.407 (4)	C16—H16A	0.9300
C1—C6	1.423 (4)	C17—C18	1.375 (4)
C2—C3	1.373 (4)	C17—H17A	0.9300
C2—H2A	0.9300	C18—C19	1.501 (4)
C3—C4	1.389 (4)	C19—C20	1.386 (4)
C3—H3A	0.9300	C20—C21	1.387 (4)
C4—C5	1.355 (4)	C20—H20A	0.9300
C5—C6	1.416 (4)	C21—C22	1.360 (4)
C5—H5A	0.9300	C21—H21A	0.9300
C6—C7	1.465 (4)	C22—C23	1.376 (4)
C7—C8	1.512 (4)	C22—H22A	0.9300
C8—H8A	0.9600	C23—H23A	0.9300
C8—H8B	0.9600	Cl—O5	1.413 (2)
C8—H8C	0.9600	Cl—O3	1.416 (2)
C9—C10	1.512 (4)	Cl—O6	1.419 (2)
C9—H9A	0.9700	Cl—O4	1.421 (2)
O1—Cu—N1	91.73 (9)	N2—C10—C9	111.1 (3)
O1—Cu—N4	88.40 (8)	N2—C10—H10A	109.4
N1—Cu—N4	179.21 (9)	C9—C10—H10A	109.4
O1—Cu—N2	159.65 (9)	N2—C10—H10B	109.4
N1—Cu—N2	85.30 (9)	C9—C10—H10B	109.4
N4—Cu—N2	94.31 (9)	H10A—C10—H10B	108.0
O1—Cu—N3	101.58 (9)	N2—C11—H11A	109.5
N1—Cu—N3	103.01 (9)	N2—C11—H11B	109.5
N4—Cu—N3	77.72 (8)	H11A—C11—H11B	109.5
N2—Cu—N3	98.71 (9)	N2—C11—H11C	109.5
C1—O1—Cu	121.01 (16)	H11A—C11—H11C	109.5
C4—O2—C13	117.4 (3)	H11B—C11—H11C	109.5
C7—N1—C9	121.2 (2)	N2—C12—H12A	109.5
C7—N1—Cu	125.99 (18)	N2—C12—H12B	109.5
C9—N1—Cu	112.81 (18)	H12A—C12—H12B	109.5
C11—N2—C10	111.8 (3)	N2—C12—H12C	109.5
C11—N2—C12	108.1 (3)	H12A—C12—H12C	109.5
C10—N2—C12	108.5 (2)	H12B—C12—H12C	109.5
C11—N2—Cu	109.6 (2)	O2—C13—H13A	109.5
C10—N2—Cu	103.51 (18)	O2—C13—H13B	109.5
C12—N2—Cu	115.31 (19)	H13A—C13—H13B	109.5
C14—N3—C18	118.4 (2)	O2—C13—H13C	109.5
C14—N3—Cu	128.5 (2)	H13A—C13—H13C	109.5
C18—N3—Cu	112.95 (17)	H13B—C13—H13C	109.5
C19—N4—C23	118.5 (2)	N3—C14—C15	122.8 (3)
C19—N4—Cu	117.37 (17)	N3—C14—H14A	118.6
C23—N4—Cu	123.61 (19)	C15—C14—H14A	118.6
O1—C1—C2	118.0 (2)	C14—C15—C16	118.6 (3)
O1—C1—C6	125.1 (3)	C14—C15—H15A	120.7
C2—C1—C6	116.9 (3)	C16—C15—H15A	120.7
C3—C2—C1	122.9 (3)	C15—C16—C17	119.3 (3)
C3—C2—H2A	118.5	C15—C16—H16A	120.3
C1—C2—H2A	118.5	C17—C16—H16A	120.3
C2—C3—C4	119.6 (3)	C18—C17—C16	119.1 (3)
C2—C3—H3A	120.2	C18—C17—H17A	120.4
C4—C3—H3A	120.2	C16—C17—H17A	120.4
C5—C4—C3	119.6 (3)	N3—C18—C17	121.7 (2)
C5—C4—O2	125.0 (3)	N3—C18—C19	114.9 (2)
C3—C4—O2	115.4 (3)	C17—C18—C19	123.4 (3)
C4—C5—C6	122.4 (3)	N4—C19—C20	121.2 (2)
C4—C5—H5A	118.8	N4—C19—C18	116.2 (2)
C6—C5—H5A	118.8	C20—C19—C18	122.6 (2)
C5—C6—C1	118.5 (3)	C21—C20—C19	119.1 (3)
C5—C6—C7	119.1 (2)	C21—C20—H20A	120.4
C1—C6—C7	122.3 (2)	C19—C20—H20A	120.4
N1—C7—C6	121.2 (2)	C22—C21—C20	119.6 (3)
N1—C7—C8	120.5 (3)	C22—C21—H21A	120.2
C6—C7—C8	118.3 (3)	C20—C21—H21A	120.2
C7—C8—H8A	109.5	C21—C22—C23	118.8 (3)
C7—C8—H8B	109.5	C21—C22—H22A	120.6
H8A—C8—H8B	109.5	C23—C22—H22A	120.6
C7—C8—H8C	109.5	N4—C23—C22	122.8 (3)
H8A—C8—H8C	109.5	N4—C23—H23A	118.6
H8B—C8—H8C	109.5	C22—C23—H23A	118.6
N1—C9—C10	108.0 (2)	O5—Cl—O3	109.42 (18)
N1—C9—H9A	110.1	O5—Cl—O6	109.47 (17)
C10—C9—H9A	110.1	O3—Cl—O6	109.50 (18)
N1—C9—H9B	110.1	O5—Cl—O4	109.41 (17)
C10—C9—H9B	110.1	O3—Cl—O4	109.93 (18)
H9A—C9—H9B	108.4	O6—Cl—O4	109.10 (17)