Crystal structure of {(but-3-en-1-yl)bis­[(pyridin-2-yl)meth­yl]amine-κ³N,N′,N′′}di­chlorido­copper(II) diethyl ether hemisolvate

The hemi-diethyl etherate of the square pyramidal copper complex, 1-butene-bis­(pyridin-2-ylmeth­yl)amine copper(II) chloride is reported. The basal plane consists of the three nitro­gen atoms from the ligand and one chlorine. The second chlorine occupies the apical position of the square pyramid.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.028
• wR factor = 0.072
• Data-to-parameter ratio = 30.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Reported SumFormula    Strings  Differ     Please Check
PLAT220_ALERT_2_C Large Non-Solvent  C     Ueq(max)/Ueq(min) Range        4.2 Ratio

Alert level G
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT045_ALERT_1_G Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1    --  Cl1     ..        5.7 su
PLAT794_ALERT_5_G Tentative Bond Valency for Cu1     (II)    .....       2.19 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        426 Note

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

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


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Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

Author Response: The first four authors (Bussey, Connell, McGlone & Mraz) are undergraduate researchers who all contributed to the synthesis and crystallization of the reported complex. Dr.'s Oliver and Pintaur are the crystallographers at their respective Universities who collected data and aided with structure finalization and manuscript preparation/discussion. Prof. Oshin is the principal investigator for the research.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

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S1. Chemical context

Transition-metal-catalyzed Atom Transfer Radical Addition (ATRA) reactions of haloalkanes and α-halo­carbonyls to α-olefins have emerged as some of the most atom economical methods for simultaneously forming C—C and C—X bonds, leading to the production of more attractive molecules with well-defined compositions, architectures, and functionalities (Pintauer & Matyjaszewski, 2005). Copper(I) complexes with tridentate and tetra­dentate nitro­gen-based ligands are currently some of the most active multidentate ligand structures developed for use in ATRA reactions (Matyjaszewski et al., 2001). In view of the importance of these types of complexes, we report the synthesis and structural characterization of the title compound {(but-3-en-1-yl)bis­[(pyridin-2-yl)methyl]­amine-κN,N',N''} dichloridocopper(II) di­ethyl ether monosolvate, (I).

S2. Structural commentary

The title complex, (I) (Fig. 1), adopts a typical-for-this-class of compounds (vide infra), slightly distorted square-pyramidal geometry, as shown in the bond angles about the Cu center. A τ-5 analysis of the distortions about the Cu center yields a value of 0.01, close to an ideal value of zero for a perfect square-pyramidal geometry [Addison et al., 1984; τ-5 = (β - α)/60 where β and α are the angles formed by atoms trans across the metal center that do not include the apical atom]. In the complex, the Cu center lies 0.2761 (5) Å out of the mean basal plane formed by the three coordinating N atoms and atom Cl1, reflecting the slight distortion from a true square plane. The Cu—N bond distances are all similar [1.9980 (11)–2.0700 (10) Å] and the apical Cu—Cl2 distance is considerably longer [2.5134 (4) Å] than that of Cu—Cl1 [2.2508 (4) Å] in the basal plane. The di­ethyl ether molecule of crystallization is located in the unit cell with the O atom on the crystallographic twofold axis at [1/2, y, 3/4].

S3. Supra­molecular features

Despite an open coordination site on the copper center, the complex does not dimerize through a chloride bridge, that is often observed in similar complexes (vide infra). There are weak electrostatic C—H···Cl inter­actions between pyridine rings and the basal chlorine of adjacent molecules (Table 1 and Fig. 2). Close contacts about the butenyl chain are typical van der Waals contacts. The orientation of the butenyl chain is such that it is anti to the apical Cl ligand, effectively proximal to the vacant sixth coordination site of the Cu center. Instead, the di­ethyl ether molecule of crystallization is located in the pocket formed by the butenyl chain and the basal coordination plane of the Cu center. Perhaps surprisingly, the ether O atom is not oriented towards, or spatially close to, the Cu atom [Cu···O1ⁱⁱ = 4.9130 (9) Å; symmetry code (ii) -x+1/2, -y+3/2, -z+1] and merely serves to occupy a void space that would otherwise be formed by molecular packing.

S4. Database survey

Although there are 80 copper chloride structures that incorporate the bis­(pyridin-2-yl­methyl)­amine ligand (Allen, 2002; CSD Version 5.36 +1 update), only 20 have a sole bis­(pyridin-2-yl­methyl)­amine ligand chelating a five-coordinate copper chloride center. The remaining sixty structures either have a tethered pair or tethered tiplet of ligands, or have the bridging chlorines between two complexes and are thus the more common geometry adopted by copper coordinated by a bis­(pyridin-2-yl­methyl)­amine based ligand. The geometry of the ligand and pendant group observed herein, is also a common feature of these structures, vis-a-vis, the pendant chain is oriented anti to the apical chlorine.

S5. Synthesis and crystallization

For the preparation of (but-3-en-1-yl)bis­[(pyridin-2-yl)methyl]­amine, the bis­(pyridin-2-yl­methyl)­amine (BPMA) precursor was synthesized and purified following literature procedures (Carvalho et al., 2006). BPMA (8.064 g, 40.5 mmol) was dissolved in aceto­nitrile (15 ml) followed by the addition of tri­ethyl­amine (4.098 g, 40.5 mmol) and 4-bromo­butene (5.468 g, 40.5 mmol). The reaction was sealed and allowed to mix for 4 d to ensure complete deprotonation and coupling occurred. Generation of the tri­ethyl­amine hydrogen bromide salt, [Et₃NH]⁺.Br^-, was observed as white crystals in the brown-colored solution. The mixture was filtered and desired product extracted from the filtrate using a hexane/water mixture. The hexane layer was separated and solvent removed to yield the ligand as a yellow colored oil (yield 8.516 g, 83%). The ligand was stored in a septum-sealed round-bottomed flask under argon gas in a refrigerator.

For the synthesis of the title compound, (I), 1-butene-BPMA (2.000 g, 7.900 mmol) was dissolved in aceto­nitrile (20 ml) in a 50 ml round-bottomed flask. CuCl₂ (1.062 g, 7.900 mmol) was added to the flask to give a green-colored solution. The reaction was allowed to mix for 6 h, then pentane (20 ml) was added slowly to the solution to generate a bright-green precipitate. The solvent was removed from the round-bottomed flask by connecting it to a rotary evaporator. The precipitate obtained was washed twice by transferring two 15 ml aliquots of pentane into the flask and stirring vigorously for 30 min. The solvent was removed and the precipitate dried under vacuum for 2 h to yield a green solid (yield 2.909 g, 95%). Slow diffusion of di­ethyl ether into an aceto­nitrile solution of the complex at room temperature produced crystals of (I) suitable for X-ray analysis.

S6. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2. All non-H atoms were refined with anisotropic displacement parameters. H atoms were included in idealized positions, with C—H = 0.95 (aromatic), 0.98 (methyl), and 0.99 Å (ethyl­inic/methyl­ene). Methyl H atoms were allowed to rotate to minimize their electron-density contribution. The U_iso(H) values were set at 1.5U_eq(C) for methyl H atoms and at 1.2U_eq(C) otherwise.

Related literature

For related literature, see: Addison et al. (1984); Allen (2002); Carvalho et al. (2006); Matyjaszewski et al. (2001); Pintauer & Matyjaszewski (2005).

Computing details

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2006) and POV-RAY (Cason, 2013); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The structure and atom-labeling scheme for (I). Displacement parameters are depicted at the 50% probability level. [Symmetry code: (i) -x+1, y, -z+3/2.]
	Fig. 2. Packing diagram viewed along the a direction demonstrating the linear C—H···Cl electrostatic interactions (blue dashed lines).

{(But-3-en-1-yl)bis[(pyridin-2-yl)methyl]amine-κ³N,N',N''} dichloridocopper(II) diethyl ether hemisolvate

Crystal data

[CuCl2(C16H19N3)]·0.5C4H10O	F(000) = 1760
Mr = 424.84	Dx = 1.412 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 22.1614 (13) Å	Cell parameters from 8841 reflections
b = 11.5738 (5) Å	θ = 2.2–32.2°
c = 16.4530 (7) Å	µ = 1.37 mm^−1
β = 108.771 (1)°	T = 150 K
V = 3995.6 (3) Å^3	Rhomboid, blue
Z = 8	0.50 × 0.28 × 0.10 mm

Data collection

Bruker APEXII diffractometer	6872 independent reflections
Radiation source: fine-focus sealed tube	5660 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 8.33 pixels mm^-1	θmax = 32.6°, θmin = 1.9°
ϕ and ω scans	h = −32→33
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −17→17
Tmin = 0.471, Tmax = 0.840	l = −23→24
24823 measured reflections

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.072	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0348P)^2 + 2.0749P] where P = (Fo^2 + 2Fc^2)/3
6872 reflections	(Δ/σ)max = 0.002
223 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.43 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.15616 (2)	0.59899 (2)	0.13662 (2)	0.01989 (5)
Cl1	0.09795 (2)	0.43892 (3)	0.13435 (2)	0.03418 (8)
Cl2	0.25976 (2)	0.52731 (3)	0.12375 (2)	0.02394 (7)
N1	0.18137 (5)	0.77181 (9)	0.14348 (6)	0.01978 (19)
N2	0.11788 (5)	0.64014 (9)	0.01190 (7)	0.0215 (2)
N3	0.19179 (5)	0.61566 (9)	0.26406 (7)	0.0223 (2)
C1	0.19332 (6)	0.79568 (11)	0.06162 (8)	0.0219 (2)
H1A	0.2363	0.7679	0.0650	0.026*
H1B	0.1915	0.8800	0.0508	0.026*
C2	0.14371 (6)	0.73526 (11)	−0.01065 (8)	0.0205 (2)
C3	0.12747 (6)	0.77160 (12)	−0.09536 (8)	0.0240 (2)
H3	0.1460	0.8393	−0.1099	0.029*
C4	0.08364 (6)	0.70725 (13)	−0.15849 (8)	0.0275 (3)
H4	0.0728	0.7289	−0.2171	0.033*
C5	0.05600 (7)	0.61125 (13)	−0.13490 (9)	0.0287 (3)
H5	0.0251	0.5674	−0.1770	0.034*
C6	0.07399 (6)	0.57991 (12)	−0.04920 (9)	0.0263 (3)
H6	0.0549	0.5141	−0.0331	0.032*
C7	0.23897 (6)	0.78269 (11)	0.22018 (8)	0.0223 (2)
H7A	0.2440	0.8638	0.2403	0.027*
H7B	0.2773	0.7607	0.2053	0.027*
C8	0.23224 (6)	0.70480 (11)	0.29021 (8)	0.0219 (2)
C9	0.26692 (7)	0.72191 (12)	0.37617 (9)	0.0284 (3)
H9	0.2956	0.7850	0.3935	0.034*
C10	0.25854 (8)	0.64431 (13)	0.43618 (9)	0.0315 (3)
H10	0.2825	0.6525	0.4952	0.038*
C11	0.21516 (7)	0.55514 (13)	0.40935 (9)	0.0298 (3)
H11	0.2076	0.5034	0.4499	0.036*
C12	0.18308 (7)	0.54244 (12)	0.32283 (9)	0.0263 (3)
H12	0.1540	0.4802	0.3042	0.032*
C13	0.12613 (6)	0.83899 (11)	0.15197 (9)	0.0250 (2)
H13A	0.1182	0.8139	0.2052	0.030*
H13B	0.0879	0.8187	0.1031	0.030*
C14	0.13334 (8)	0.97031 (13)	0.15463 (11)	0.0370 (3)
H14A	0.1719	0.9922	0.2024	0.044*
H14B	0.1387	0.9976	0.1003	0.044*
C15	0.07651 (10)	1.02672 (16)	0.16678 (14)	0.0517 (5)
H15	0.0648	1.0031	0.2150	0.062*
C16	0.04196 (14)	1.1043 (2)	0.1180 (2)	0.0866 (9)
H16A	0.0519	1.1306	0.0691	0.104*
H16B	0.0064	1.1356	0.1308	0.104*
O1	0.5000	0.71720 (17)	0.7500	0.0552 (5)
C17	0.46509 (12)	0.7851 (2)	0.6791 (2)	0.0809 (9)
H17A	0.4948	0.8292	0.6570	0.097*
H17B	0.4381	0.8409	0.6973	0.097*
C18	0.42468 (16)	0.7095 (4)	0.6110 (2)	0.1069 (12)
H18A	0.4016	0.7564	0.5610	0.160*
H18B	0.3941	0.6687	0.6323	0.160*
H18C	0.4515	0.6531	0.5942	0.160*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02130 (8)	0.01992 (8)	0.01888 (8)	−0.00387 (5)	0.00706 (6)	0.00069 (5)
Cl1	0.03288 (17)	0.03282 (17)	0.03443 (18)	−0.01494 (14)	0.00746 (14)	0.00510 (13)
Cl2	0.02487 (14)	0.02391 (14)	0.02458 (14)	−0.00119 (11)	0.01009 (11)	−0.00181 (11)
N1	0.0212 (5)	0.0208 (5)	0.0182 (5)	−0.0017 (4)	0.0076 (4)	−0.0003 (4)
N2	0.0209 (5)	0.0229 (5)	0.0205 (5)	−0.0029 (4)	0.0064 (4)	−0.0002 (4)
N3	0.0255 (5)	0.0233 (5)	0.0203 (5)	0.0010 (4)	0.0106 (4)	0.0013 (4)
C1	0.0241 (6)	0.0234 (6)	0.0193 (5)	−0.0051 (4)	0.0083 (5)	−0.0001 (4)
C2	0.0202 (5)	0.0217 (6)	0.0207 (5)	−0.0004 (4)	0.0081 (4)	−0.0004 (4)
C3	0.0223 (6)	0.0292 (6)	0.0214 (6)	0.0015 (5)	0.0082 (5)	0.0034 (5)
C4	0.0254 (6)	0.0367 (7)	0.0195 (6)	0.0040 (5)	0.0058 (5)	0.0017 (5)
C5	0.0243 (6)	0.0344 (7)	0.0237 (6)	−0.0024 (5)	0.0024 (5)	−0.0041 (5)
C6	0.0228 (6)	0.0290 (7)	0.0250 (6)	−0.0049 (5)	0.0048 (5)	−0.0016 (5)
C7	0.0247 (6)	0.0214 (6)	0.0199 (5)	−0.0034 (4)	0.0061 (5)	−0.0011 (4)
C8	0.0251 (6)	0.0212 (6)	0.0202 (5)	0.0029 (4)	0.0081 (5)	−0.0011 (4)
C9	0.0364 (7)	0.0254 (6)	0.0211 (6)	0.0046 (5)	0.0060 (5)	−0.0027 (5)
C10	0.0433 (8)	0.0305 (7)	0.0196 (6)	0.0122 (6)	0.0089 (6)	0.0005 (5)
C11	0.0383 (7)	0.0302 (7)	0.0251 (6)	0.0110 (6)	0.0161 (6)	0.0078 (5)
C12	0.0303 (6)	0.0267 (6)	0.0257 (6)	0.0031 (5)	0.0142 (5)	0.0056 (5)
C13	0.0271 (6)	0.0240 (6)	0.0255 (6)	0.0033 (5)	0.0107 (5)	0.0002 (5)
C14	0.0349 (8)	0.0245 (7)	0.0458 (9)	0.0048 (6)	0.0048 (7)	−0.0025 (6)
C15	0.0609 (12)	0.0382 (9)	0.0612 (12)	0.0139 (8)	0.0269 (10)	−0.0075 (8)
C16	0.0783 (18)	0.0776 (18)	0.095 (2)	0.0474 (15)	0.0156 (16)	−0.0047 (15)
O1	0.0521 (11)	0.0461 (11)	0.0708 (13)	0.000	0.0244 (10)	0.000
C17	0.0600 (14)	0.0728 (17)	0.124 (2)	0.0280 (13)	0.0496 (16)	0.0421 (16)
C18	0.0760 (19)	0.158 (4)	0.078 (2)	0.036 (2)	0.0130 (16)	0.035 (2)

Geometric parameters (Å, º)

Cu1—N3	1.9980 (11)	C8—C9	1.3895 (18)
Cu1—N2	2.0093 (11)	C9—C10	1.391 (2)
Cu1—N1	2.0700 (10)	C9—H9	0.9500
Cu1—Cl1	2.2508 (4)	C10—C11	1.383 (2)
Cu1—Cl2	2.5134 (4)	C10—H10	0.9500
N1—C1	1.4800 (15)	C11—C12	1.379 (2)
N1—C7	1.4837 (16)	C11—H11	0.9500
N1—C13	1.4942 (16)	C12—H12	0.9500
N2—C6	1.3466 (16)	C13—C14	1.527 (2)
N2—C2	1.3469 (16)	C13—H13A	0.9900
N3—C8	1.3434 (17)	C13—H13B	0.9900
N3—C12	1.3455 (16)	C14—C15	1.488 (2)
C1—C2	1.5067 (17)	C14—H14A	0.9900
C1—H1A	0.9900	C14—H14B	0.9900
C1—H1B	0.9900	C15—C16	1.281 (3)
C2—C3	1.3878 (17)	C15—H15	0.9500
C3—C4	1.3883 (19)	C16—H16A	0.9500
C3—H3	0.9500	C16—H16B	0.9500
C4—C5	1.383 (2)	O1—C17^i	1.413 (3)
C4—H4	0.9500	O1—C17	1.413 (3)
C5—C6	1.3845 (19)	C17—C18	1.476 (4)
C5—H5	0.9500	C17—H17A	0.9900
C6—H6	0.9500	C17—H17B	0.9900
C7—C8	1.5077 (17)	C18—H18A	0.9800
C7—H7A	0.9900	C18—H18B	0.9800
C7—H7B	0.9900	C18—H18C	0.9800
N3—Cu1—N2	160.62 (5)	H7A—C7—H7B	108.3
N3—Cu1—N1	80.84 (4)	N3—C8—C9	121.93 (12)
N2—Cu1—N1	81.05 (4)	N3—C8—C7	115.75 (11)
N3—Cu1—Cl1	97.34 (3)	C9—C8—C7	122.30 (12)
N2—Cu1—Cl1	97.28 (3)	C8—C9—C10	118.31 (13)
N1—Cu1—Cl1	159.94 (3)	C8—C9—H9	120.8
N3—Cu1—Cl2	93.27 (3)	C10—C9—H9	120.8
N2—Cu1—Cl2	95.11 (3)	C11—C10—C9	119.57 (13)
N1—Cu1—Cl2	94.92 (3)	C11—C10—H10	120.2
Cl1—Cu1—Cl2	105.136 (14)	C9—C10—H10	120.2
C1—N1—C7	113.65 (9)	C12—C11—C10	118.92 (13)
C1—N1—C13	112.33 (10)	C12—C11—H11	120.5
C7—N1—C13	112.52 (10)	C10—C11—H11	120.5
C1—N1—Cu1	104.77 (7)	N3—C12—C11	121.94 (13)
C7—N1—Cu1	105.76 (7)	N3—C12—H12	119.0
C13—N1—Cu1	107.05 (8)	C11—C12—H12	119.0
C6—N2—C2	119.11 (11)	N1—C13—C14	116.05 (11)
C6—N2—Cu1	127.29 (9)	N1—C13—H13A	108.3
C2—N2—Cu1	113.44 (8)	C14—C13—H13A	108.3
C8—N3—C12	119.27 (11)	N1—C13—H13B	108.3
C8—N3—Cu1	114.07 (8)	C14—C13—H13B	108.3
C12—N3—Cu1	126.42 (9)	H13A—C13—H13B	107.4
N1—C1—C2	109.43 (10)	C15—C14—C13	110.80 (14)
N1—C1—H1A	109.8	C15—C14—H14A	109.5
C2—C1—H1A	109.8	C13—C14—H14A	109.5
N1—C1—H1B	109.8	C15—C14—H14B	109.5
C2—C1—H1B	109.8	C13—C14—H14B	109.5
H1A—C1—H1B	108.2	H14A—C14—H14B	108.1
N2—C2—C3	121.90 (12)	C16—C15—C14	125.8 (2)
N2—C2—C1	115.39 (10)	C16—C15—H15	117.1
C3—C2—C1	122.65 (11)	C14—C15—H15	117.1
C2—C3—C4	118.80 (12)	C15—C16—H16A	120.0
C2—C3—H3	120.6	C15—C16—H16B	120.0
C4—C3—H3	120.6	H16A—C16—H16B	120.0
C5—C4—C3	119.17 (12)	C17^i—O1—C17	112.4 (3)
C5—C4—H4	120.4	O1—C17—C18	109.5 (2)
C3—C4—H4	120.4	O1—C17—H17A	109.8
C4—C5—C6	119.20 (13)	C18—C17—H17A	109.8
C4—C5—H5	120.4	O1—C17—H17B	109.8
C6—C5—H5	120.4	C18—C17—H17B	109.8
N2—C6—C5	121.79 (13)	H17A—C17—H17B	108.2
N2—C6—H6	119.1	C17—C18—H18A	109.5
C5—C6—H6	119.1	C17—C18—H18B	109.5
N1—C7—C8	109.24 (10)	H18A—C18—H18B	109.5
N1—C7—H7A	109.8	C17—C18—H18C	109.5
C8—C7—H7A	109.8	H18A—C18—H18C	109.5
N1—C7—H7B	109.8	H18B—C18—H18C	109.5
C8—C7—H7B	109.8
C7—N1—C1—C2	155.62 (10)	C12—N3—C8—C9	1.93 (19)
C13—N1—C1—C2	−75.20 (13)	Cu1—N3—C8—C9	−172.73 (10)
Cu1—N1—C1—C2	40.65 (11)	C12—N3—C8—C7	−179.82 (11)
C6—N2—C2—C3	−1.47 (18)	Cu1—N3—C8—C7	5.52 (14)
Cu1—N2—C2—C3	174.32 (10)	N1—C7—C8—N3	22.88 (15)
C6—N2—C2—C1	−178.80 (11)	N1—C7—C8—C9	−158.88 (12)
Cu1—N2—C2—C1	−3.00 (13)	N3—C8—C9—C10	−0.6 (2)
N1—C1—C2—N2	−26.50 (15)	C7—C8—C9—C10	−178.72 (12)
N1—C1—C2—C3	156.20 (11)	C8—C9—C10—C11	−1.8 (2)
N2—C2—C3—C4	−0.47 (19)	C9—C10—C11—C12	2.7 (2)
C1—C2—C3—C4	176.66 (12)	C8—N3—C12—C11	−0.91 (19)
C2—C3—C4—C5	2.0 (2)	Cu1—N3—C12—C11	173.03 (10)
C3—C4—C5—C6	−1.7 (2)	C10—C11—C12—N3	−1.4 (2)
C2—N2—C6—C5	1.8 (2)	C1—N1—C13—C14	−63.24 (15)
Cu1—N2—C6—C5	−173.32 (10)	C7—N1—C13—C14	66.53 (14)
C4—C5—C6—N2	−0.2 (2)	Cu1—N1—C13—C14	−177.71 (10)
C1—N1—C7—C8	−152.29 (10)	N1—C13—C14—C15	−177.66 (13)
C13—N1—C7—C8	78.63 (12)	C13—C14—C15—C16	−125.1 (3)
Cu1—N1—C7—C8	−37.91 (11)	C17^i—O1—C17—C18	−174.1 (3)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cl2^ii	0.95	2.67	3.5541 (15)	156
C11—H11···Cl2^iii	0.95	2.74	3.4767 (15)	135
C14—H14A···Cl2^iv	0.99	2.80	3.7127 (18)	153

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