Tris(2,2′-bioxazoline-κ²N,N′)copper(II) diperchlorate and tris(2,2′-bioxazoline-κ²N,N′)­nickel(II) diperchlorate

In the two isomorphous title compounds, viz. tris­[2,2′-bi(4,5-di­hydro-1,3-oxazole)-κ²N,N′]copper(II) diperchlorate, [Cu(C₆H₈N₂O₂)₃](ClO₄)₂, (I), and tris­[2,2′-bi(4,5-di­hydro-1,3-oxazole)-κ²N,N′]­nickel(II) diperchlorate, [Ni(C₆H₈N₂O₂)₃](ClO₄)₂, (II), the M^II ions each have a distorted octahedral coordination geometry formed via six N atoms from three 2,2′-bioxazoline ligands. For each ligand, the two five-membered rings are nearly coplanar. It is noteworthy that the Jahn–Teller effect is stronger in (I) than in (II). The three-dimensional supramolecular structures of (I) and (II) are formed via weak hydrogen-bonding interactions between O atoms from per­chlorate anions and H atoms from 2,2′-bioxazoline ligands.

S1. Comment

Recently, studies of transition metal coordination compounds and supramolecules as new hybrid materials based on multifunctional organic ligands have attracted considerable interest, due to their potential use in catalysis, magnetism, electrical conductivity and molecular recognition (Hagrman et al., 1999; Inoue et al., 1996; Zaworotko, 1997). At present, the rational design of new compounds and the modification of their structures is still a challenge. A current synthetic strategy widely used in this area is to select organic building blocks that are attractive for assembling functional compounds and supramolecules. 2,2'-Bithiazoline has been used for assembling coordination compounds showing interesting magnetic properties (Liu et al., 2003). As the analogue of 2,2'-bithiazoline, 2,2'-bisoxazoline is also a good ligand, used for fabricating novel topologies (Patra et al., 2001; Walther et al., 1999; Ozarowski et al., 1988). It may act as a bidentate terminal ligand or as a bridging ligand (Haddleton et al., 1998; Patra et al., 2003). In our laboratory, chiral or achiral bisoxazolines have been used to construct novel coordination compounds. We obtained the two title novel mononuclear transition metal compounds, [Cu(C₆H₈N₂O₂)₃](ClO₄)₂, (I), and [Ni(C₆H₈N₂O₂)₃](ClO₄)₂, (II). The syntheses and structures of these two compounds are reported here. \sch

Selected geometric parameters for (I) are listed in Table 1. As shown in Fig. 1, the asymmetric unit of (I) consists of two counterions: two perchlorate anions, and a discrete [Cu(C₆H₈N₂O₂)₃]²⁺ cation built from one Cu atom and three 2,2'-bisoxazoline molecules. The local coordination geometry around the Cu centre can be described as a distorted octahedron, formed by six N atoms from three 2,2'-bisoxazoline molecules. The Cu atom and the four N atoms (N1, N2, N3 and N6) in the equatorial plane are nearly coplanar, and the Cu—N bond distances are similar. The average Cu—N bond distance for atoms N1, N2, N3 and N6 is 2.018 Å, compared with the value of 2.020 Å in [CuBrL¹]_n {L¹ is 2,2'-bis[(4S)-4-benzyl-2-oxazoline]; Haddleton et al., 1998}, but slightly longer than the value of 1.972 Å in the compound [(Cu₂L₃)(ClO₄)₂] {L is 2,2'-bis[(4R)-benzyl-1,3-oxazoline]; Patra et al., 2001}, in which the Cu atom is tri-coordinated. However, the Cu–N bond distances for atoms N4 and N5 in the axial positions are 2.597 (3) and 2.410 (3) Å, respectively, much longer than the other Cu—N distances in (I), which results in a distorted octahedral coordination environment around the Cu^II centre. It is noted that there is a much more pronounced Jahn-Teller distortion in (I) than in the related [(CuL₃)(ClO₄)₂] [Cu—N bond distances in the range 2.028 (6)–2.364 (6) Å, L is 2,2'-bis[(4R)-benzyl-1,3-oxazoline]; Patra et al., 2003]. This is in agreement with the smaller chelating angles of 73.35 (12) (N3—Cu—N4) and 75.57 (12)° (N5—Cu—N6), compared with 79.97 (13)° for N1—Cu—N2. For three bisoxazoline molecules, the double-bond distances between C and N atoms in 2,2'-bisoxazoline ligands are in the range 1.255 (5)–1.273 (5) Å, which is similar to those reported previously (Walther et al., 1999). The two five-membered rings of each bisoxazoline molecule are approximately coplanar, with the dihedral angles varying from 4.45 (2) to 5.97 (3)°.

The structure of compound (II) is depicted in Fig. 2. Similar to (I), (II) is also an ionic complex. Each Ni atom of the cation in (II) lies approximately on a threefold axis and is coordinated by six N atoms from three 2,2'-bisoxazoline molecules, which form a slightly distorted octahedral geometry. Selected geometric parameters for (II) are listed in Table 3. The Ni—N bond distances, in the range 2.089 (3)–2.127 (3) Å, are comparable with the range of 2.070 (3)–2.085 (5) Å in the related 2,2'-bpy nickel(II) hexafluorophosphate, in which two hexafluorophosphate ions act as counter-ions (2,2'-bpy is 2,2'-bipyridine; Breu et al., 2000), and with similar corresponding Cu—N chelating angles of 77.95 (12) (N1—Ni—N2), 78.53 (12) (N3—Ni—N4) and 78.53 (12)° (N5—Ni—N6). All 2,2'-bisoxazoline molecules in (II) act as bidentate terminal ligands.

There are extensive hydrogen-bonding interactions between the perchlorate anions and the discrete cations in the structures of (I) and (II). The crystal packing of (I) and (II) is stabilized by intermolecular C—H···O(perchlorate) hydrogen bonds, leading to three-dimensional supramolecular structures (Figs. 3 and 4). The hydrogen-bonding geometries in (I) and (II) are listed in Tables 2 and 4, respectively.

S2. Experimental

All organic solvents and common materials used for synthesis were of reagent grade and used without further purification. 2,2'-Bisoxazoline was prepared according to the literature method of Evans et al. (1998). Compound (I) was synthesized by adding an acetonitrile solution (20 ml) containing copper(II) perchlorate hexahydrate (0.181 g, 0.5 mmol) dropwise with continuous stirring to a dichloromethane solution (10 ml) of 2,2'-bisoxazoline (1.5 mmol, 0.21 g) over a period of 20 min. Slow evaporation of the resulting blue solution at room temperature yielded blue crystals of (I) within 4 d. Compound (II) was prepared in the same way as (I), using nickel(II) perchlorate hexahydrate. Slow evaporation of the resulting green solution at room temperature yielded green crystals of (II) within 7 d. Elemental analysis: compound (I), calculated: C 31.65, H 3.52, N 12.31, Cl 10.40%; found: C 31.45, H 3.54, N 12.36, Cl 10.44%; compound (II), calculated: C 31.86, H 3.54, N 12.39, Cl 10.47%; found: C 31.82, H 3.55, N 12.43, Cl 10.50%.

S3. Refinement

In compound (I), there is positional disorder of the perchlorate atoms O7 and O8 over two sites, O7 and O7' and O8 and O8'; the site-occupancy factors were assigned as 50% and 50%, respectively. For both compounds, all H atoms were located in difference Fourier maps and were then regenerated in ideal positions and refined using a riding model, with C—H distances of 0.95–0.97 Å and with U_iso(H) = 1.2U_eq(C).

Computing details

For both compounds, data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids drawn at the 30% probability level. All H atoms have been omitted for clarity.
	Fig. 2. The molecular structure of (II), showing the atom-numbering scheme. Displacement ellipsoids drawn at the 30% probability level. All H atoms have been omitted for clarity.
	Fig. 3. The crystal packing of (I), viewed along the a axis, with hydrogen bonds shown as dashed lines.
	Fig. 4. The crystal packing of (II), viewed along the a axis, with hydrogen bonds shown as dashed lines.

(I) tris[2,2'-bi(4,5-dihydrooxazole)-k²N,N']copper(II) diperchlorate

Crystal data

[Cu(C6H8N2O2)3](ClO4)2	F(000) = 1396
Mr = 682.87	Dx = 1.687 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 350 reflections
a = 9.3766 (19) Å	θ = 1.7–27.5°
b = 17.734 (4) Å	µ = 1.09 mm^−1
c = 16.350 (3) Å	T = 293 K
β = 98.54 (3)°	Block, blue
V = 2688.7 (10) Å^3	0.23 × 0.15 × 0.14 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID IP diffractometer	6132 independent reflections
Radiation source: rotating anode	2689 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
oscillation scans	θmax = 27.5°, θmin = 1.7°
Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995)	h = −12→12
Tmin = 0.732, Tmax = 0.862	k = 0→22
6132 measured reflections	l = −21→20

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.112	H-atom parameters constrained
S = 0.83	w = 1/[σ^2(Fo^2) + (0.0339P)^2] where P = (Fo^2 + 2Fc^2)/3
6132 reflections	(Δ/σ)max < 0.001
370 parameters	Δρmax = 0.45 e Å^−3
0 restraints	Δρmin = −0.29 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
Cu	0.34984 (5)	0.11920 (3)	0.24188 (3)	0.04296 (16)
O1	0.0648 (3)	0.16522 (19)	0.39957 (19)	0.0746 (10)
O2	−0.0468 (3)	0.21241 (17)	0.23332 (19)	0.0605 (8)
O3	0.5435 (3)	0.21256 (19)	0.05641 (19)	0.0636 (9)
O4	0.6565 (3)	0.29840 (18)	0.1906 (2)	0.0649 (9)
O5	0.4107 (3)	−0.12169 (18)	0.2177 (2)	0.0668 (9)
O6	0.6396 (3)	−0.04954 (17)	0.31838 (19)	0.0607 (9)
N1	0.2623 (4)	0.1275 (2)	0.3489 (2)	0.0480 (9)
N2	0.1576 (3)	0.1674 (2)	0.1977 (2)	0.0477 (9)
N3	0.4229 (3)	0.14216 (19)	0.13609 (18)	0.0408 (8)
N4	0.5201 (3)	0.23477 (19)	0.2704 (2)	0.0471 (9)
N5	0.2936 (4)	−0.01005 (19)	0.2046 (2)	0.0491 (9)
N6	0.5239 (3)	0.0611 (2)	0.29325 (19)	0.0444 (9)
C1	0.1381 (5)	0.1558 (2)	0.3373 (3)	0.0480 (11)
C2	0.2970 (5)	0.1109 (3)	0.4374 (2)	0.0622 (13)
H2A	0.3746	0.1427	0.4636	0.075*
H2B	0.3240	0.0584	0.4467	0.075*
C3	0.1548 (5)	0.1285 (3)	0.4697 (3)	0.0808 (16)
H3A	0.1096	0.0827	0.4855	0.097*
H3B	0.1712	0.1620	0.5170	0.097*
C4	0.0787 (4)	0.1799 (2)	0.2531 (3)	0.0461 (11)
C5	0.0748 (4)	0.1926 (3)	0.1179 (3)	0.0618 (13)
H5A	0.0445	0.1501	0.0822	0.074*
H5B	0.1308	0.2270	0.0893	0.074*
C6	−0.0539 (5)	0.2321 (3)	0.1457 (3)	0.0665 (14)
H6A	−0.0473	0.2863	0.1389	0.080*
H6B	−0.1435	0.2145	0.1141	0.080*
C7	0.5053 (4)	0.1977 (2)	0.1299 (3)	0.0443 (10)
C8	0.3910 (4)	0.1070 (3)	0.0549 (2)	0.0602 (13)
H8A	0.2878	0.1042	0.0367	0.072*
H8B	0.4316	0.0567	0.0552	0.072*
C9	0.4637 (5)	0.1604 (3)	−0.0001 (3)	0.0830 (17)
H9A	0.5277	0.1328	−0.0308	0.100*
H9B	0.3923	0.1866	−0.0389	0.100*
C10	0.5596 (4)	0.2452 (2)	0.2012 (3)	0.0455 (11)
C11	0.6050 (5)	0.2886 (3)	0.3261 (3)	0.0622 (13)
H11A	0.6732	0.2624	0.3668	0.075*
H11B	0.5426	0.3194	0.3547	0.075*
C12	0.6829 (5)	0.3365 (3)	0.2700 (3)	0.0827 (17)
H12A	0.6445	0.3873	0.2658	0.099*
H12B	0.7854	0.3388	0.2905	0.099*
C13	0.4040 (5)	−0.0477 (2)	0.2336 (3)	0.0496 (11)
C14	0.1938 (5)	−0.0632 (3)	0.1599 (3)	0.0668 (14)
H14A	0.1711	−0.0489	0.1021	0.080*
H14B	0.1050	−0.0655	0.1836	0.080*
C15	0.2727 (5)	−0.1394 (3)	0.1687 (3)	0.0665 (14)
H15A	0.2199	−0.1759	0.1968	0.080*
H15B	0.2855	−0.1594	0.1150	0.080*
C16	0.5262 (4)	−0.0102 (3)	0.2842 (2)	0.0449 (11)
C17	0.6641 (5)	0.0818 (3)	0.3412 (3)	0.0633 (13)
H17A	0.6515	0.1098	0.3906	0.076*
H17B	0.7209	0.1118	0.3083	0.076*
C18	0.7348 (5)	0.0056 (3)	0.3631 (3)	0.0752 (16)
H18A	0.8297	0.0035	0.3463	0.090*
H18B	0.7446	−0.0033	0.4222	0.090*
Cl1	0.22425 (15)	−0.11517 (9)	0.42087 (8)	0.0770 (4)
O7	0.2245 (7)	−0.1710 (3)	0.4804 (3)	0.174 (2)
O8	0.1318 (5)	−0.0601 (3)	0.4402 (4)	0.182 (3)
O9	0.1850 (5)	−0.1498 (3)	0.3460 (2)	0.1315 (18)
O10	0.3622 (4)	−0.0838 (2)	0.4265 (2)	0.1041 (13)
Cl2	0.21048 (14)	−0.02020 (8)	−0.11150 (8)	0.0697 (4)
O11	0.2340 (5)	−0.0774 (3)	−0.0527 (3)	0.1433 (18)
O12	0.1253 (5)	−0.0420 (2)	−0.1853 (2)	0.1221 (16)
O13	0.1366 (4)	0.0390 (3)	−0.0782 (3)	0.1281 (17)
O14	0.3418 (4)	0.0115 (3)	−0.1246 (2)	0.1238 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0413 (3)	0.0455 (3)	0.0436 (3)	0.0061 (3)	0.0112 (2)	0.0068 (3)
O1	0.082 (2)	0.084 (3)	0.067 (2)	0.032 (2)	0.0426 (18)	0.011 (2)
O2	0.0498 (18)	0.061 (2)	0.073 (2)	0.0176 (16)	0.0159 (15)	0.0046 (18)
O3	0.066 (2)	0.078 (2)	0.049 (2)	−0.0056 (18)	0.0184 (16)	0.0170 (19)
O4	0.0563 (19)	0.052 (2)	0.091 (2)	−0.0177 (17)	0.0254 (17)	−0.0034 (19)
O5	0.0557 (18)	0.046 (2)	0.102 (2)	0.0009 (18)	0.0210 (17)	−0.005 (2)
O6	0.0502 (18)	0.054 (2)	0.077 (2)	0.0177 (17)	0.0036 (16)	0.0147 (18)
N1	0.056 (2)	0.044 (2)	0.048 (2)	0.0069 (19)	0.0169 (16)	0.0055 (18)
N2	0.0428 (19)	0.048 (2)	0.054 (2)	0.0075 (17)	0.0113 (17)	0.0050 (19)
N3	0.0386 (18)	0.047 (2)	0.036 (2)	−0.0035 (17)	0.0044 (14)	0.0035 (17)
N4	0.046 (2)	0.040 (2)	0.055 (2)	−0.0031 (17)	0.0057 (18)	0.0045 (19)
N5	0.044 (2)	0.040 (2)	0.064 (2)	0.0000 (19)	0.0088 (17)	0.0064 (19)
N6	0.048 (2)	0.045 (2)	0.041 (2)	−0.0009 (18)	0.0078 (16)	0.0005 (18)
C1	0.062 (3)	0.036 (3)	0.050 (3)	0.007 (2)	0.018 (2)	0.004 (2)
C2	0.082 (3)	0.060 (3)	0.047 (3)	0.011 (3)	0.014 (2)	0.000 (3)
C3	0.100 (4)	0.093 (4)	0.055 (3)	0.034 (4)	0.031 (3)	0.012 (3)
C4	0.039 (2)	0.036 (2)	0.066 (3)	0.007 (2)	0.016 (2)	−0.001 (2)
C5	0.047 (2)	0.078 (4)	0.061 (3)	0.008 (3)	0.009 (2)	0.011 (3)
C6	0.055 (3)	0.068 (4)	0.074 (4)	0.017 (3)	−0.001 (2)	0.001 (3)
C7	0.037 (2)	0.047 (3)	0.050 (3)	0.006 (2)	0.011 (2)	0.009 (2)
C8	0.052 (3)	0.082 (4)	0.046 (3)	0.004 (3)	0.004 (2)	−0.004 (3)
C9	0.089 (4)	0.117 (5)	0.045 (3)	0.003 (4)	0.017 (3)	0.015 (3)
C10	0.039 (2)	0.038 (3)	0.059 (3)	0.001 (2)	0.008 (2)	0.012 (2)
C11	0.064 (3)	0.046 (3)	0.075 (3)	−0.006 (3)	0.005 (3)	−0.004 (3)
C12	0.077 (4)	0.066 (4)	0.111 (5)	−0.025 (3)	0.033 (3)	−0.025 (4)
C13	0.053 (3)	0.037 (3)	0.063 (3)	0.004 (2)	0.022 (2)	0.007 (2)
C14	0.055 (3)	0.061 (3)	0.086 (4)	−0.010 (3)	0.013 (3)	0.001 (3)
C15	0.068 (3)	0.049 (3)	0.087 (4)	−0.009 (3)	0.026 (3)	−0.010 (3)
C16	0.044 (3)	0.048 (3)	0.046 (3)	0.003 (2)	0.016 (2)	0.008 (2)
C17	0.059 (3)	0.066 (3)	0.059 (3)	0.008 (3)	−0.011 (2)	0.001 (3)
C18	0.061 (3)	0.086 (4)	0.071 (3)	0.018 (3)	−0.013 (3)	0.006 (3)
Cl1	0.0924 (10)	0.0773 (10)	0.0661 (9)	−0.0303 (9)	0.0271 (7)	−0.0259 (8)
O7	0.299 (7)	0.133 (5)	0.104 (4)	−0.074 (5)	0.072 (4)	−0.001 (4)
O8	0.120 (4)	0.133 (5)	0.309 (8)	−0.009 (3)	0.082 (4)	−0.107 (5)
O9	0.136 (3)	0.167 (5)	0.092 (3)	−0.062 (3)	0.018 (3)	−0.051 (3)
O10	0.070 (2)	0.117 (3)	0.124 (3)	−0.026 (2)	0.009 (2)	−0.025 (3)
Cl2	0.0722 (9)	0.0699 (9)	0.0668 (9)	0.0064 (8)	0.0089 (7)	0.0050 (8)
O11	0.180 (5)	0.115 (4)	0.129 (4)	−0.013 (4)	0.004 (3)	0.055 (3)
O12	0.169 (4)	0.107 (4)	0.084 (3)	−0.030 (3)	0.000 (3)	−0.027 (3)
O13	0.088 (3)	0.153 (4)	0.135 (4)	0.043 (3)	−0.011 (3)	−0.051 (3)
O14	0.080 (3)	0.180 (5)	0.116 (3)	−0.002 (3)	0.032 (2)	0.031 (3)

Geometric parameters (Å, º)

Cu—N1	2.045 (3)	C5—C6	1.522 (6)
Cu—N2	2.028 (3)	C5—H5A	0.9700
Cu—N3	1.995 (3)	C5—H5B	0.9700
Cu—N4	2.597 (3)	C6—H6A	0.9700
Cu—N5	2.410 (4)	C6—H6B	0.9700
Cu—N6	2.006 (3)	C7—C10	1.466 (6)
O1—C1	1.321 (5)	C8—C9	1.534 (6)
O1—C3	1.470 (5)	C8—H8A	0.9700
O2—C4	1.308 (4)	C8—H8B	0.9700
O2—C6	1.467 (5)	C9—H9A	0.9700
O3—C7	1.330 (4)	C9—H9B	0.9700
O3—C9	1.436 (6)	C11—C12	1.515 (6)
O4—C10	1.339 (4)	C11—H11A	0.9700
O4—C12	1.451 (5)	C11—H11B	0.9700
O5—C13	1.342 (5)	C12—H12A	0.9700
O5—C15	1.452 (5)	C12—H12B	0.9700
O6—C16	1.324 (5)	C13—C16	1.469 (6)
O6—C18	1.448 (5)	C14—C15	1.537 (6)
N1—C1	1.256 (5)	C14—H14A	0.9700
N1—C2	1.465 (5)	C14—H14B	0.9700
N2—C4	1.270 (5)	C15—H15A	0.9700
N2—C5	1.485 (5)	C15—H15B	0.9700
N3—C7	1.265 (5)	C17—C18	1.525 (6)
N3—C8	1.457 (5)	C17—H17A	0.9700
N4—C10	1.255 (5)	C17—H17B	0.9700
N4—C11	1.469 (5)	C18—H18A	0.9700
N5—C13	1.262 (5)	C18—H18B	0.9700
N5—C14	1.448 (5)	Cl1—O9	1.370 (4)
N6—C16	1.273 (5)	Cl1—O8	1.374 (5)
N6—C17	1.474 (5)	Cl1—O7	1.389 (5)
C1—C4	1.470 (6)	Cl1—O10	1.398 (4)
C2—C3	1.537 (6)	Cl2—O11	1.393 (4)
C2—H2A	0.9700	Cl2—O12	1.399 (4)
C2—H2B	0.9700	Cl2—O14	1.399 (4)
C3—H3A	0.9700	Cl2—O13	1.410 (4)
C3—H3B	0.9700
N1—Cu—N2	79.97 (14)	O3—C7—C10	119.7 (4)
N1—Cu—N3	163.80 (14)	N3—C8—C9	102.7 (4)
N1—Cu—N4	95.96 (13)	N3—C8—H8A	111.2
N1—Cu—N5	100.61 (13)	C9—C8—H8A	111.2
N1—Cu—N6	94.79 (13)	N3—C8—H8B	111.2
N2—Cu—N3	90.40 (13)	C9—C8—H8B	111.2
N2—Cu—N4	102.82 (12)	H8A—C8—H8B	109.1
N2—Cu—N5	99.28 (13)	O3—C9—C8	104.8 (4)
N2—Cu—N6	171.97 (14)	O3—C9—H9A	110.8
N3—Cu—N4	73.35 (12)	C8—C9—H9A	110.8
N3—Cu—N5	93.74 (13)	O3—C9—H9B	110.8
N3—Cu—N6	96.04 (13)	C8—C9—H9B	110.8
N4—Cu—N5	154.34 (11)	H9A—C9—H9B	108.9
N4—Cu—N6	83.69 (12)	N4—C10—O4	121.1 (4)
N5—Cu—N6	75.57 (13)	N4—C10—C7	121.2 (4)
C1—O1—C3	103.9 (3)	O4—C10—C7	117.7 (4)
C4—O2—C6	104.8 (3)	N4—C11—C12	104.7 (4)
C7—O3—C9	105.6 (3)	N4—C11—H11A	110.8
C10—O4—C12	104.0 (3)	C12—C11—H11A	110.8
C13—O5—C15	104.8 (3)	N4—C11—H11B	110.8
C16—O6—C18	104.7 (3)	C12—C11—H11B	110.8
C1—N1—C2	107.1 (3)	H11A—C11—H11B	108.9
C1—N1—Cu	112.4 (3)	O4—C12—C11	104.3 (4)
C2—N1—Cu	140.6 (3)	O4—C12—H12A	110.9
C4—N2—C5	106.9 (3)	C11—C12—H12A	110.9
C4—N2—Cu	113.6 (3)	O4—C12—H12B	110.9
C5—N2—Cu	139.5 (3)	C11—C12—H12B	110.9
C7—N3—C8	107.8 (3)	H12A—C12—H12B	108.9
C7—N3—Cu	121.4 (3)	N5—C13—O5	120.3 (4)
C8—N3—Cu	130.7 (3)	N5—C13—C16	120.0 (4)
C10—N4—C11	105.0 (4)	O5—C13—C16	119.7 (4)
C10—N4—Cu	102.1 (3)	N5—C14—C15	105.0 (3)
C11—N4—Cu	152.3 (3)	N5—C14—H14A	110.7
C13—N5—C14	106.1 (4)	C15—C14—H14A	110.7
C13—N5—Cu	105.8 (3)	N5—C14—H14B	110.7
C14—N5—Cu	147.9 (3)	C15—C14—H14B	110.7
C16—N6—C17	106.3 (4)	H14A—C14—H14B	108.8
C16—N6—Cu	119.2 (3)	O5—C15—C14	103.8 (3)
C17—N6—Cu	134.5 (3)	O5—C15—H15A	111.0
N1—C1—O1	120.8 (4)	C14—C15—H15A	111.0
N1—C1—C4	118.1 (4)	O5—C15—H15B	111.0
O1—C1—C4	121.1 (4)	C14—C15—H15B	111.0
N1—C2—C3	102.8 (3)	H15A—C15—H15B	109.0
N1—C2—H2A	111.2	N6—C16—O6	120.0 (4)
C3—C2—H2A	111.2	N6—C16—C13	119.3 (4)
N1—C2—H2B	111.2	O6—C16—C13	120.7 (4)
C3—C2—H2B	111.2	N6—C17—C18	103.1 (4)
H2A—C2—H2B	109.1	N6—C17—H17A	111.2
O1—C3—C2	104.4 (3)	C18—C17—H17A	111.1
O1—C3—H3A	110.9	N6—C17—H17B	111.1
C2—C3—H3A	110.9	C18—C17—H17B	111.1
O1—C3—H3B	110.9	H17A—C17—H17B	109.1
C2—C3—H3B	110.9	O6—C18—C17	105.4 (3)
H3A—C3—H3B	108.9	O6—C18—H18A	110.7
N2—C4—O2	119.9 (4)	C17—C18—H18A	110.7
N2—C4—C1	115.9 (4)	O6—C18—H18B	110.7
O2—C4—C1	124.2 (4)	C17—C18—H18B	110.7
N2—C5—C6	102.2 (3)	H18A—C18—H18B	108.8
N2—C5—H5A	111.3	O9—Cl1—O8	115.4 (3)
C6—C5—H5A	111.3	O9—Cl1—O7	106.2 (3)
N2—C5—H5B	111.3	O8—Cl1—O7	106.4 (4)
C6—C5—H5B	111.3	O9—Cl1—O10	111.1 (3)
H5A—C5—H5B	109.2	O8—Cl1—O10	108.1 (3)
O2—C6—C5	105.0 (3)	O7—Cl1—O10	109.4 (3)
O2—C6—H6A	110.8	O11—Cl2—O12	113.9 (3)
C5—C6—H6A	110.8	O11—Cl2—O14	110.2 (3)
O2—C6—H6B	110.8	O12—Cl2—O14	112.5 (3)
C5—C6—H6B	110.8	O11—Cl2—O13	108.2 (3)
H6A—C6—H6B	108.8	O12—Cl2—O13	106.7 (3)
N3—C7—O3	118.4 (4)	O14—Cl2—O13	104.7 (3)
N3—C7—C10	121.9 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17A···O7^i	0.97	2.49	3.346 (3)	145
C15—H15A···O9	0.97	2.55	3.134 (6)	119
C2—H2B···O10	0.97	2.57	3.516 (6)	163
C8—H8A···O13	0.97	2.47	3.215 (5)	133
C8—H8B···O14^ii	0.97	2.56	3.338 (4)	137

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

(II) tris[2,2'-bi(4,5-dihydrooxazole)-k²N,N']nickel(II) diperchlorate

Crystal data

[Ni(C6H8N2O2)3](ClO4)2	F(000) = 1392
Mr = 678.04	Dx = 1.651 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 345 reflections
a = 9.3911 (19) Å	θ = 1.7–27.5°
b = 17.683 (4) Å	µ = 0.99 mm^−1
c = 16.743 (3) Å	T = 293 K
β = 101.14 (3)°	Block, green
V = 2728.0 (9) Å^3	0.21 × 0.17 × 0.11 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	5940 independent reflections
Radiation source: rolating anode	2979 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
oscillation scans	θmax = 27.5°, θmin = 1.7°
Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995)	h = 0→12
Tmin = 0.804, Tmax = 0.896	k = 0→22
21381 measured reflections	l = −21→21

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.104	H-atom parameters constrained
S = 0.93	w = 1/[σ^2(Fo^2) + (0.0298P)^2] where P = (Fo^2 + 2Fc^2)/3
5940 reflections	(Δ/σ)max < 0.001
370 parameters	Δρmax = 0.62 e Å^−3
0 restraints	Δρmin = −0.34 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
Ni	0.39912 (5)	0.12931 (3)	0.24517 (3)	0.04193 (14)
N1	0.3211 (3)	0.13468 (17)	0.35590 (17)	0.0497 (8)
N2	0.1888 (3)	0.17470 (17)	0.20645 (19)	0.0487 (8)
N3	0.4455 (3)	0.14860 (18)	0.12980 (17)	0.0494 (8)
N4	0.5180 (3)	0.23227 (17)	0.26417 (19)	0.0478 (8)
N5	0.3385 (3)	0.01582 (17)	0.21778 (18)	0.0506 (8)
N6	0.5924 (3)	0.07173 (18)	0.29429 (18)	0.0487 (8)
O1	0.1250 (4)	0.16979 (19)	0.4076 (2)	0.0876 (10)
O2	−0.0121 (3)	0.21525 (16)	0.24855 (19)	0.0672 (8)
O3	0.5574 (3)	0.22775 (18)	0.05702 (18)	0.0772 (9)
O4	0.6680 (3)	0.30441 (16)	0.20577 (18)	0.0734 (9)
O5	0.4294 (4)	−0.10238 (16)	0.2196 (2)	0.0797 (9)
O6	0.6930 (3)	−0.04385 (16)	0.31415 (18)	0.0738 (9)
O7	0.2469 (6)	−0.1671 (3)	0.4718 (3)	0.1495 (17)
O8	0.1607 (7)	−0.0499 (3)	0.4468 (4)	0.203 (3)
O9	0.1506 (5)	−0.1349 (3)	0.3428 (2)	0.175 (2)
O10	0.3661 (5)	−0.0845 (3)	0.4022 (3)	0.1426 (17)
O11	0.2292 (5)	−0.0735 (2)	−0.0370 (2)	0.1295 (15)
O12	0.1200 (4)	−0.0515 (2)	−0.17209 (19)	0.1083 (12)
O13	0.1204 (4)	0.0414 (2)	−0.0752 (2)	0.1062 (12)
O14	0.3384 (3)	0.0115 (2)	−0.1142 (2)	0.0938 (10)
C1	0.1921 (5)	0.1620 (2)	0.3455 (2)	0.0549 (10)
C2	0.3653 (5)	0.1185 (3)	0.4434 (2)	0.0772 (14)
H2A	0.4469	0.1498	0.4681	0.093*
H2B	0.3912	0.0657	0.4528	0.093*
C3	0.2289 (7)	0.1383 (3)	0.4769 (3)	0.112 (2)
H3A	0.1893	0.0935	0.4979	0.135*
H3B	0.2514	0.1753	0.5203	0.135*
C4	0.1212 (4)	0.1844 (2)	0.2635 (3)	0.0493 (10)
C5	0.0900 (4)	0.1989 (2)	0.1305 (2)	0.0658 (12)
H5A	0.0596	0.1561	0.0951	0.079*
H5B	0.1363	0.2360	0.1013	0.079*
C6	−0.0388 (5)	0.2335 (3)	0.1614 (3)	0.0747 (13)
H6A	−0.0424	0.2878	0.1531	0.090*
H6B	−0.1295	0.2116	0.1336	0.090*
C7	0.5219 (4)	0.2066 (2)	0.1266 (2)	0.0534 (10)
C8	0.4076 (4)	0.1185 (3)	0.0471 (2)	0.0699 (13)
H8A	0.3032	0.1166	0.0286	0.084*
H8B	0.4473	0.0682	0.0438	0.084*
C9	0.4771 (6)	0.1751 (3)	−0.0026 (3)	0.0891 (16)
H9A	0.5421	0.1496	−0.0324	0.107*
H9B	0.4034	0.2016	−0.0411	0.107*
C10	0.5699 (4)	0.2499 (2)	0.2028 (3)	0.0529 (10)
C11	0.5915 (5)	0.2824 (2)	0.3301 (3)	0.0671 (12)
H11A	0.6516	0.2534	0.3730	0.081*
H11B	0.5214	0.3112	0.3532	0.081*
C12	0.6844 (6)	0.3346 (3)	0.2881 (3)	0.0979 (17)
H12A	0.6497	0.3864	0.2871	0.117*
H12B	0.7852	0.3333	0.3156	0.117*
C13	0.4440 (5)	−0.0292 (2)	0.2395 (2)	0.0544 (10)
C14	0.2159 (5)	−0.0295 (3)	0.1720 (3)	0.0773 (14)
H14A	0.1885	−0.0122	0.1162	0.093*
H14B	0.1320	−0.0270	0.1978	0.093*
C15	0.2775 (6)	−0.1091 (3)	0.1758 (3)	0.0865 (15)
H15A	0.2232	−0.1425	0.2048	0.104*
H15B	0.2737	−0.1290	0.1214	0.104*
C16	0.5804 (4)	0.0008 (2)	0.2837 (2)	0.0537 (10)
C17	0.7428 (4)	0.0871 (2)	0.3380 (2)	0.0645 (12)
H17A	0.7430	0.1117	0.3899	0.077*
H17B	0.7944	0.1187	0.3057	0.077*
C18	0.8099 (5)	0.0087 (3)	0.3501 (3)	0.0833 (15)
H18A	0.8916	0.0045	0.3227	0.100*
H18B	0.8431	−0.0019	0.4075	0.100*
Cl2	0.20326 (13)	−0.01923 (7)	−0.09911 (7)	0.0716 (3)
Cl1	0.22549 (15)	−0.10577 (8)	0.41391 (8)	0.0829 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.0385 (2)	0.0434 (3)	0.0434 (3)	0.0009 (2)	0.00666 (19)	0.0025 (2)
N1	0.057 (2)	0.0462 (18)	0.0453 (18)	0.0039 (16)	0.0089 (15)	0.0022 (16)
N2	0.0425 (17)	0.050 (2)	0.0522 (19)	0.0022 (15)	0.0060 (16)	0.0095 (16)
N3	0.0448 (18)	0.064 (2)	0.0380 (18)	−0.0047 (16)	0.0048 (14)	0.0005 (16)
N4	0.0448 (18)	0.0459 (19)	0.0511 (19)	−0.0049 (15)	0.0052 (16)	0.0027 (16)
N5	0.0438 (18)	0.051 (2)	0.058 (2)	−0.0068 (16)	0.0129 (16)	−0.0007 (17)
N6	0.0490 (19)	0.051 (2)	0.0480 (18)	0.0066 (15)	0.0130 (15)	0.0020 (16)
O1	0.095 (2)	0.106 (3)	0.071 (2)	0.031 (2)	0.0390 (19)	0.0025 (19)
O2	0.0499 (17)	0.0685 (19)	0.086 (2)	0.0191 (14)	0.0193 (15)	0.0055 (17)
O3	0.080 (2)	0.098 (2)	0.0570 (18)	−0.0074 (18)	0.0221 (17)	0.0180 (19)
O4	0.072 (2)	0.063 (2)	0.090 (2)	−0.0213 (16)	0.0253 (18)	−0.0048 (18)
O5	0.090 (2)	0.0484 (18)	0.106 (2)	−0.0021 (16)	0.0325 (19)	−0.0121 (17)
O6	0.068 (2)	0.0633 (19)	0.089 (2)	0.0291 (16)	0.0107 (18)	0.0122 (17)
O7	0.217 (5)	0.133 (4)	0.114 (3)	0.006 (4)	0.070 (3)	0.005 (3)
O8	0.233 (6)	0.160 (5)	0.213 (6)	0.077 (4)	0.034 (5)	−0.067 (4)
O9	0.178 (5)	0.244 (5)	0.092 (3)	−0.096 (4)	−0.002 (3)	−0.047 (3)
O10	0.107 (3)	0.161 (4)	0.147 (4)	−0.021 (3)	−0.008 (3)	0.041 (3)
O11	0.134 (3)	0.145 (4)	0.103 (3)	0.003 (3)	0.007 (2)	0.058 (3)
O12	0.131 (3)	0.114 (3)	0.074 (2)	−0.026 (2)	0.005 (2)	−0.030 (2)
O13	0.076 (2)	0.118 (3)	0.125 (3)	0.003 (2)	0.020 (2)	−0.041 (2)
O14	0.071 (2)	0.119 (3)	0.095 (2)	−0.004 (2)	0.0246 (19)	−0.004 (2)
C1	0.065 (3)	0.048 (2)	0.056 (3)	−0.003 (2)	0.022 (2)	−0.005 (2)
C2	0.100 (4)	0.074 (3)	0.053 (3)	0.011 (3)	0.003 (3)	0.000 (2)
C3	0.156 (6)	0.133 (5)	0.054 (3)	0.050 (4)	0.036 (3)	0.003 (3)
C4	0.046 (2)	0.042 (2)	0.063 (3)	−0.0005 (17)	0.016 (2)	0.001 (2)
C5	0.051 (2)	0.075 (3)	0.068 (3)	0.001 (2)	0.002 (2)	0.018 (2)
C6	0.056 (3)	0.068 (3)	0.096 (4)	0.014 (2)	0.004 (3)	0.015 (3)
C7	0.046 (2)	0.065 (3)	0.049 (2)	0.000 (2)	0.0102 (19)	0.007 (2)
C8	0.062 (3)	0.097 (4)	0.048 (2)	−0.002 (3)	0.005 (2)	−0.010 (3)
C9	0.093 (4)	0.121 (4)	0.052 (3)	0.006 (3)	0.011 (3)	0.006 (3)
C10	0.040 (2)	0.050 (3)	0.068 (3)	−0.0032 (18)	0.008 (2)	0.006 (2)
C11	0.065 (3)	0.059 (3)	0.075 (3)	−0.005 (2)	0.008 (2)	−0.011 (2)
C12	0.117 (4)	0.084 (4)	0.097 (4)	−0.046 (3)	0.033 (3)	−0.027 (3)
C13	0.067 (3)	0.041 (2)	0.060 (3)	−0.002 (2)	0.025 (2)	−0.004 (2)
C14	0.073 (3)	0.077 (4)	0.079 (3)	−0.027 (3)	0.008 (3)	−0.011 (3)
C15	0.100 (4)	0.063 (3)	0.103 (4)	−0.019 (3)	0.038 (3)	−0.020 (3)
C16	0.063 (3)	0.052 (3)	0.052 (2)	0.016 (2)	0.023 (2)	0.010 (2)
C17	0.041 (2)	0.087 (3)	0.060 (3)	0.005 (2)	−0.004 (2)	0.005 (2)
C18	0.063 (3)	0.104 (4)	0.077 (3)	0.031 (3)	−0.003 (3)	0.013 (3)
Cl2	0.0709 (8)	0.0790 (8)	0.0622 (7)	−0.0005 (6)	0.0066 (6)	−0.0051 (7)
Cl1	0.0852 (9)	0.0838 (9)	0.0748 (8)	−0.0043 (7)	0.0034 (7)	−0.0258 (7)

Geometric parameters (Å, º)

Ni—N1	2.123 (3)	O13—Cl2	1.426 (4)
Ni—N2	2.114 (3)	O14—Cl2	1.447 (3)
Ni—N3	2.089 (3)	C1—C4	1.461 (5)
Ni—N4	2.127 (3)	C2—C3	1.535 (6)
Ni—N5	2.112 (3)	C2—H2A	0.9700
Ni—N6	2.105 (3)	C2—H2B	0.9700
N1—C1	1.284 (5)	C3—H3A	0.9700
N1—C2	1.471 (5)	C3—H3B	0.9700
N2—C4	1.256 (4)	C5—C6	1.532 (5)
N2—C5	1.484 (4)	C5—H5A	0.9700
N3—C7	1.259 (5)	C5—H5B	0.9700
N3—C8	1.462 (4)	C6—H6A	0.9700
N4—C10	1.258 (5)	C6—H6B	0.9700
N4—C11	1.479 (5)	C7—C10	1.482 (5)
N5—C13	1.267 (5)	C8—C9	1.527 (6)
N5—C14	1.488 (5)	C8—H8A	0.9700
N6—C16	1.269 (4)	C8—H8B	0.9700
N6—C17	1.485 (4)	C9—H9A	0.9700
O1—C1	1.323 (5)	C9—H9B	0.9700
O1—C3	1.474 (5)	C11—C12	1.532 (6)
O2—C4	1.343 (4)	C11—H11A	0.9700
O2—C6	1.468 (5)	C11—H11B	0.9700
O3—C7	1.326 (4)	C12—H12A	0.9700
O3—C9	1.463 (5)	C12—H12B	0.9700
O4—C10	1.328 (4)	C13—C16	1.450 (6)
O4—C12	1.458 (5)	C14—C15	1.518 (6)
O5—C13	1.337 (4)	C14—H14A	0.9700
O5—C15	1.477 (5)	C14—H14B	0.9700
O6—C16	1.339 (4)	C15—H15A	0.9700
O6—C18	1.475 (5)	C15—H15B	0.9700
O7—Cl1	1.443 (4)	C17—C18	1.521 (5)
O8—Cl1	1.333 (5)	C17—H17A	0.9700
O9—Cl1	1.361 (4)	C17—H17B	0.9700
O10—Cl1	1.422 (4)	C18—H18A	0.9700
O11—Cl2	1.402 (4)	C18—H18B	0.9700
O12—Cl2	1.435 (3)
N1—Ni—N2	77.95 (12)	O3—C7—C10	121.7 (4)
N1—Ni—N3	165.71 (12)	N3—C8—C9	103.0 (4)
N1—Ni—N4	95.22 (12)	N3—C8—H8A	111.2
N1—Ni—N5	96.21 (12)	C9—C8—H8A	111.2
N1—Ni—N6	95.60 (12)	N3—C8—H8B	111.2
N2—Ni—N3	90.22 (12)	C9—C8—H8B	111.2
N2—Ni—N4	98.81 (11)	H8A—C8—H8B	109.1
N2—Ni—N5	95.60 (12)	O3—C9—C8	105.3 (3)
N2—Ni—N6	170.86 (12)	O3—C9—H9A	110.7
N3—Ni—N4	78.53 (12)	C8—C9—H9A	110.7
N3—Ni—N5	92.86 (12)	O3—C9—H9B	110.7
N3—Ni—N6	97.01 (12)	C8—C9—H9B	110.7
N4—Ni—N5	163.19 (12)	H9A—C9—H9B	108.8
N4—Ni—N6	88.14 (12)	N4—C10—O4	121.6 (4)
N5—Ni—N6	78.53 (12)	N4—C10—C7	118.3 (3)
C1—N1—C2	106.6 (3)	O4—C10—C7	120.0 (4)
C1—N1—Ni	111.9 (3)	N4—C11—C12	104.1 (3)
C2—N1—Ni	141.4 (3)	N4—C11—H11A	110.9
C4—N2—C5	106.7 (3)	C12—C11—H11A	110.9
C4—N2—Ni	113.5 (2)	N4—C11—H11B	110.9
C5—N2—Ni	139.8 (3)	C12—C11—H11B	110.9
C7—N3—C8	107.0 (3)	H11A—C11—H11B	109.0
C7—N3—Ni	113.3 (3)	O4—C12—C11	104.3 (3)
C8—N3—Ni	139.5 (3)	O4—C12—H12A	110.9
C10—N4—C11	105.2 (3)	C11—C12—H12A	110.9
C10—N4—Ni	111.4 (3)	O4—C12—H12B	110.9
C11—N4—Ni	141.3 (3)	C11—C12—H12B	110.9
C13—N5—C14	107.0 (3)	H12A—C12—H12B	108.9
C13—N5—Ni	111.8 (3)	N5—C13—O5	120.0 (4)
C14—N5—Ni	140.6 (3)	N5—C13—C16	118.8 (4)
C16—N6—C17	107.5 (3)	O5—C13—C16	121.2 (4)
C16—N6—Ni	112.2 (3)	N5—C14—C15	103.1 (4)
C17—N6—Ni	140.4 (3)	N5—C14—H14A	111.1
C1—O1—C3	103.6 (3)	C15—C14—H14A	111.1
C4—O2—C6	104.4 (3)	N5—C14—H14B	111.1
C7—O3—C9	103.6 (3)	C15—C14—H14B	111.1
C10—O4—C12	104.3 (3)	H14A—C14—H14B	109.1
C13—O5—C15	104.1 (3)	O5—C15—C14	105.6 (3)
C16—O6—C18	104.8 (3)	O5—C15—H15A	110.6
N1—C1—O1	120.8 (4)	C14—C15—H15A	110.6
N1—C1—C4	118.5 (4)	O5—C15—H15B	110.6
O1—C1—C4	120.7 (4)	C14—C15—H15B	110.6
N1—C2—C3	103.0 (4)	H15A—C15—H15B	108.7
N1—C2—H2A	111.2	N6—C16—O6	119.2 (4)
C3—C2—H2A	111.2	N6—C16—C13	118.5 (4)
N1—C2—H2B	111.2	O6—C16—C13	122.3 (4)
C3—C2—H2B	111.2	N6—C17—C18	103.2 (3)
H2A—C2—H2B	109.1	N6—C17—H17A	111.1
O1—C3—C2	105.7 (4)	C18—C17—H17A	111.1
O1—C3—H3A	110.6	N6—C17—H17B	111.1
C2—C3—H3A	110.6	C18—C17—H17B	111.1
O1—C3—H3B	110.6	H17A—C17—H17B	109.1
C2—C3—H3B	110.6	O6—C18—C17	105.3 (3)
H3A—C3—H3B	108.7	O6—C18—H18A	110.7
N2—C4—O2	120.3 (4)	C17—C18—H18A	110.7
N2—C4—C1	118.1 (4)	O6—C18—H18B	110.7
O2—C4—C1	121.6 (4)	C17—C18—H18B	110.7
N2—C5—C6	103.3 (3)	H18A—C18—H18B	108.8
N2—C5—H5A	111.1	O11—Cl2—O13	109.4 (3)
C6—C5—H5A	111.1	O11—Cl2—O12	110.4 (2)
N2—C5—H5B	111.1	O13—Cl2—O12	107.5 (2)
C6—C5—H5B	111.1	O11—Cl2—O14	110.7 (2)
H5A—C5—H5B	109.1	O13—Cl2—O14	108.1 (2)
O2—C6—C5	104.7 (3)	O12—Cl2—O14	110.7 (2)
O2—C6—H6A	110.8	O8—Cl1—O9	116.2 (4)
C5—C6—H6A	110.8	O8—Cl1—O10	111.8 (4)
O2—C6—H6B	110.8	O9—Cl1—O10	108.4 (3)
C5—C6—H6B	110.8	O8—Cl1—O7	107.1 (3)
H6A—C6—H6B	108.9	O9—Cl1—O7	106.5 (3)
N3—C7—O3	120.7 (4)	O10—Cl1—O7	106.2 (3)
N3—C7—C10	117.7 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5B···O7^i	0.97	2.48	3.451 (6)	179
C17—H17A···O7^ii	0.97	2.50	3.468 (6)	176
C15—H15A···O9	0.97	2.54	3.277 (7)	133
C8—H8A···O13	0.97	2.57	3.345 (5)	137
C8—H8B···O14^iii	0.97	2.55	3.347 (6)	139

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