catena-Poly[[[pyridine­copper(II)]bis­[μ₃-4-(2-oxidobenzyl­ideneamino)­benzoato]] dimethyl­formamide disolvate], a polymer composed of dimeric dicopper building units

The title compound, {[Cu(C₁₄H₉NO₃)(C₅H₅N)]·C₃H₇NO}_n or {[Cu₂L₂(py)₂]·2DMF}_n [py is pyridine, L is 4-(salicylidene­amino)benzoate and DMF is dimethyl­formamide], is composed of dimeric dicopper [CuL(py)]₂ building units, which are inter­linked into a one-dimensional chain through the formation of Cu—O_COO bonds. The dimeric unit is centrosymmetric, containing two Cu^II atoms linked by bridging phenolate O atoms into a Cu₂O₂ plane with a chelating Cu—O bond length of 1.927 (2) Å and a bridging Cu—O bond length of 2.440 (2) Å. Inter­chain C—H...O and π–π stacking inter­actions are responsible for an extensive three-dimensional structure in which the resulting channels are filled by DMF solvent mol­ecules.

S1. Comment

The design and construction of metal-organic frameworks is of great interest owing to their potential as new functional materials, as well as their fascinating variety of topologies (Kitagawa et al., 2004; Steel, 2005; Takaoka et al., 2005). By rational choice of organic ligand and transition metal ion, one aims to modify the structure and the physical properties of complex architectures. Recently, use of a second building block has been demonstrated to be fruitful in constructing and analyzing structures of complex architecture (Kim et al., 2001). Schiff bases are excellent as ligands and are employed for preparing complexes with special functions such as biological activities, catalysis or magnetism. A salen-type Schiff base is one of the most appealing candidates for the formation of dimeric dinuclear complexes through the bridging phenol O atoms (Bai et al., 2006; Iskander et al., 2000). Numerous dimeric copper complexes with these ligands exhibit antiferromagnetic exchange (Bai et al., 2006; Shyu et al., 1996). Considering that these dimers as `magnetic brick' building blocks introduced into the framework would exhibit unusual magnetic behavior, we focused our preparative efforts on exploiting these `magnetic bricks' to create new architectures. In this paper, the bridging ligand 4-(salicylideneamino)benzoic acid (H₂L) (see scheme), which was derived from the condensation of salicylaldehyde and 4-aminobenzoic acid, was exploited to bridge the bricks of a dimeric dicopper complex into polymeric {[CuL(py)]₂}_n, (I), through a self-assembly process.

Single-crystal structural analysis reveals that the title compound, crystallized in the triclinic P1 group, is composed of dimeric [CuL(py)]₂ building units which are interlinked through the formation of Cu—O_carboxylate into a one-dimensional polymer along the crystallographic c axis. The asymmetric unit of complex (I) consists of half of the dimer along with one solvent dimethylformamide (DMF) molecule (Fig. 1). The dimeric unit is centrosymmetric, with the Cu₂O₂ plane bridged by two phenol O atoms. The Cu···Cu separation is 3.300 (5) Å and the Cu1—O1—Cu1ⁱ angle is 97.50 (9)° in the Cu₂O₂ plane [symmetry code: (i) 1 - x, -y, 1 - z]. This dimerization via the bridging phenol O atoms has previously been noted in the generation of simple binuclear complexes.

In the dimeric unit, each copper(II) center is in a square-pyramidal geometric environment, with the basal plane consisting of a chelating phenol O atom and an imine N atom from one ligand, a carboxylate O atom from a neighboring dimer and a pyridyl N atom, and the apical site occupied by a bridging phenol O atom from another ligand in the dimer. The coordination polyhedron around each copper center is best described as (4 + 1) distorted square pyramidal, with the value of tetragonality parameter τ equal to 0.158 [τ = (b - α)/60, where α and β are the N1—Cu1—N2 and O1—Cu1—O3ⁱⁱ angles, respectively (Addison et al., 1984); symmetry code as in Table 1]. The Cu—O bond lengths (average 1.928 Å) are shorter than the Cu—N bonds (average 2.029 Å) in the basal plane. The chelating Cu—O length of 1.927 (2) Å is shorter than the bridging length of 2.440 (2) Å, as is the situation in [Cu(LBPh₃)]₂ [LBPh₃ is N-(salicylidene)-N'- (1-triphenylborylimidazol-2-ylmethylene)-1,3-propanediamine; Shyu et al., 1996]. However, the Cu···Cu separation in the Cu₂O₂ plane is longer than that [3.085 (4) Å] in [Cu(LBPh₃)]₂, possibly because of the steric hindrance of pyridyl rings and phenyl rings around the Cu₂O₂ plane. The pyridyl ring is almost perpendicular to the plane of Cu₂O₂ with a dihedral angle of 91.6°. In further comparison to the most closely related phenol-O-bridging dinuclear copper compounds, it was found that the bridging bond lengths of Cu—O_phenol are similar to the chelating ones if the chelating and bridged phenol O atoms are in the same equatorial plane (Paschke et al., 2003). The long bridging bond length and the long separation of Cu···Cu in the Cu₂O₂ plane reveal that the dimerization of the title compound is a little loose. In the polymer, there is one subunit of binuclear macrocycle Cu₂L₂, which is stabilized by π–π stacking interactions between the rings of the benzoate groups, with a centroid–centroid distance of 3.677 Å, an interplanar distance of 3.154 Å and the shift between the centroid of 1.890 Å. The Cu···Cu distance in this macrocycle is 8.953 Å, an intermediate between those observed for other Cu^II₂ complexes containing similar aromatic spacers (Paital et al., 2007). Adjacent macrocycles are linked by two bridging phenol O atoms. Therefore, this polymer can also be described as being composed of binuclear macrocycles interlinked through the formation of bridging Cu—O_phenol bonds (Fig. 2), based on the long bridging Cu—O_phenol distances.

It is worth noting that unusual supramolecular interactions in the solid state, including C—H···O hydrogen bonds and π–π stacking, generate a unique supramolecular architecture. The interchain contacts of C3—H3···O2ⁱⁱⁱ [C3···O2ⁱⁱⁱ = 3.300 (5) Å, H3···O2ⁱⁱⁱ = 2.45 Å and C3—H3···O2ⁱⁱⁱ = 152°; symmetry code: (iii) x, y - 1, z + 1] together with π–π stacking interactions between pyridyl rings (the centroid-centroid distance is 3.718 Å, the interplanar distance 2.738 Å, and the shift between the centroids 2.517 Å) drive polymers to arrange along the crystallographic b axis, while the polymers also extend along the a axis through the interchain π–π stacking interactions between aromatic rings of salicylaldimine groups (the centroid–centroid distance is 3.638 Å, the interplanar distance 2.742 Å and the shift between the centroids 2.391 Å) (Müller-Dethlefs & Hobza, 2000). These weak interactions are responsible for an extensive three-dimensional structure in which the resulting channels are filled by solvent DMF molecules (Fig. 3).

Related literature

For related literature, see: Addison et al. (1984); Bai et al. (2006); Iskander et al. (2000); Kim et al. (2001); Kitagawa et al. (2004); Müller-Dethlefs & Hobza (2000); Paital et al. (2007); Paschke et al. (2003); Shyu et al. (1996); Steel (2005); Takaoka et al. (2005).

S2. Experimental

For the synthesis of 4-(salicylideneamino)benzoic acid (H₂L), a solution of salicylaldehyde (0.9780 g, 8 mmol) in CH₃OH (10 ml) was added to a solution of 4-aminobenzoic acid (1.096 g, 8 mmol) in CH₃OH (50 ml) with stirring, and a large amount of yellow precipitate was formed immediately. The slurry mixture was further vigorously stirred for 4 h and filtered. The yellow powder product was recrystallized in CH₃CH₂OH (80 ml) for purification. For the synthesis of the title complex, a solution of Cu(ClO₄)₂·6H₂O (0.0373 g, 0.1 mmol) in DMF (5 ml) was added to a solution of H₂L (0.0482 g, 0.2 mmol) and Et₃N (0.0552 ml, 0.4 mmol) in DMF (5 ml) with stirring. The resulting precipitate was filtered off and then dissolved in pyridine (2 ml). Ethyl ether was diffused into the pyridine solution. Two weeks later, crystals were selected for X-ray diffraction.

S3. Refinement

Anisotropic displacement parameters were applied to all non-hydrogen atoms, except for solvent molecules. All H atoms were positioned geometrically with C—H distances of 0.93 or 0.96 Å and refined using a riding model.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A displacement ellipsoid representation (at the 30% probability level) of the coordination enviroment of the Cu^II atom in the title compound. Unlabeled atoms are related by an inversion center to the labeled atoms. [Symmetry codes: (i) -x + 1, -y, -z + 1; (ii) -x + 1, -y, -z.]
	Fig. 2. A view of the chain along the crystallographic c axis.
	Fig. 3. The packing of the title compound, projected along the a axis. The three-dimensional network with channels is obtained by interchain interactions of C—H···O and π-π- stacking. Solvent DMF molecules are encapsulated in the channels.

catena-Poly[[[pyridinecopper(II)]bis(µ₃-4-(2-oxidobenzylideneamino)benzoato)] dimethylformamide disolvate]

Crystal data

[Cu(C14H9NO3)(C5H5N)]·C3H7NO	V = 1051.7 (3) Å^3
Mr = 454.96	Z = 2
Triclinic, P1	F(000) = 470
Hall symbol: -P 1	Dx = 1.437 Mg m^−3
a = 8.9547 (13) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.6215 (15) Å	θ = 2.5–28.3°
c = 11.3899 (16) Å	µ = 1.07 mm^−1
α = 80.393 (5)°	T = 298 K
β = 86.408 (3)°	Prism, black
γ = 80.138 (2)°	0.23 × 0.20 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer	4757 independent reflections
Radiation source: fine-focus sealed tube	3900 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.093
ω scans	θmax = 28.3°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −10→11
Tmin = 0.752, Tmax = 0.842	k = −13→14
7282 measured reflections	l = −14→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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.184	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.1101P)^2] where P = (Fo^2 + 2Fc^2)/3
4757 reflections	(Δ/σ)max < 0.001
246 parameters	Δρmax = 1.07 e Å^−3
0 restraints	Δρmin = −0.64 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
Cu1	0.44343 (4)	−0.07274 (4)	0.39760 (3)	0.02736 (18)
O1	0.3492 (3)	−0.0224 (2)	0.54311 (19)	0.0312 (5)
O2	0.6357 (3)	0.2253 (3)	−0.2139 (2)	0.0481 (7)
O3	0.4509 (3)	0.1227 (2)	−0.2554 (2)	0.0337 (5)
O4	−0.1534 (10)	0.3646 (9)	0.1886 (7)	0.185 (3)*
N1	0.5252 (3)	−0.2498 (3)	0.4904 (2)	0.0326 (6)
N2	0.3216 (3)	0.0842 (3)	0.3017 (2)	0.0286 (6)
N3	−0.1575 (6)	0.4098 (6)	−0.0063 (5)	0.0835 (14)*
C1	0.4470 (5)	−0.3025 (4)	0.5862 (3)	0.0417 (9)
H1	0.3554	−0.2563	0.6097	0.050*
C2	0.4982 (6)	−0.4213 (4)	0.6493 (4)	0.0585 (13)
H2	0.4411	−0.4556	0.7141	0.070*
C3	0.6347 (7)	−0.4902 (4)	0.6169 (4)	0.0629 (14)
H3	0.6718	−0.5706	0.6602	0.075*
C4	0.7147 (6)	−0.4386 (4)	0.5201 (4)	0.0613 (13)
H4	0.8067	−0.4837	0.4958	0.074*
C5	0.6567 (5)	−0.3180 (4)	0.4589 (3)	0.0399 (8)
H5	0.7116	−0.2831	0.3930	0.048*
C6	0.2127 (4)	0.0440 (3)	0.5565 (3)	0.0283 (7)
C7	0.1424 (4)	0.0393 (4)	0.6711 (3)	0.0360 (8)
H7	0.1922	−0.0119	0.7361	0.043*
C8	0.0004 (4)	0.1100 (4)	0.6879 (3)	0.0410 (9)
H8	−0.0434	0.1052	0.7644	0.049*
C9	−0.0780 (4)	0.1868 (4)	0.5956 (4)	0.0445 (9)
H9	−0.1743	0.2322	0.6086	0.053*
C10	−0.0110 (4)	0.1953 (4)	0.4828 (3)	0.0385 (8)
H10	−0.0620	0.2492	0.4199	0.046*
C11	0.1329 (4)	0.1242 (3)	0.4608 (3)	0.0299 (7)
C12	0.1946 (4)	0.1429 (3)	0.3404 (3)	0.0325 (7)
H12	0.1371	0.2032	0.2851	0.039*
C13	0.3612 (4)	0.1199 (3)	0.1776 (3)	0.0280 (7)
C14	0.4978 (4)	0.1656 (3)	0.1470 (3)	0.0321 (7)
H14	0.5584	0.1783	0.2060	0.039*
C15	0.5421 (4)	0.1916 (3)	0.0288 (3)	0.0349 (8)
H15	0.6314	0.2249	0.0082	0.042*
C16	0.4554 (4)	0.1690 (3)	−0.0602 (3)	0.0262 (6)
C17	0.3184 (4)	0.1262 (3)	−0.0285 (3)	0.0304 (7)
H17	0.2578	0.1129	−0.0872	0.037*
C18	0.2712 (4)	0.1032 (3)	0.0902 (3)	0.0316 (7)
H18	0.1782	0.0762	0.1106	0.038*
C19	0.5200 (4)	0.1763 (3)	−0.1867 (3)	0.0305 (7)
C20	−0.0747 (14)	0.3537 (14)	−0.1090 (10)	0.207 (6)*
H20A	−0.1114	0.4045	−0.1825	0.310*
H20B	−0.0917	0.2663	−0.1053	0.310*
H20C	0.0319	0.3544	−0.1051	0.310*
C21	−0.2667 (13)	0.5097 (11)	−0.0481 (8)	0.165 (4)*
H21A	−0.3199	0.5456	0.0177	0.248*
H21B	−0.3367	0.4790	−0.0926	0.248*
H21C	−0.2208	0.5752	−0.0988	0.248*
C22	−0.1006 (17)	0.3341 (15)	0.1051 (13)	0.201 (6)*
H22	−0.0234	0.2633	0.1062	0.241*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0310 (3)	0.0299 (3)	0.0180 (2)	0.00142 (17)	0.00179 (15)	−0.00217 (16)
O1	0.0297 (12)	0.0403 (13)	0.0204 (11)	0.0010 (10)	0.0016 (9)	−0.0037 (10)
O2	0.0538 (18)	0.0603 (18)	0.0320 (14)	−0.0221 (14)	0.0136 (12)	−0.0048 (12)
O3	0.0374 (13)	0.0377 (13)	0.0223 (11)	0.0036 (10)	0.0027 (9)	−0.0060 (10)
N1	0.0432 (17)	0.0289 (14)	0.0250 (14)	−0.0035 (12)	−0.0048 (12)	−0.0031 (11)
N2	0.0322 (14)	0.0318 (14)	0.0188 (12)	0.0002 (11)	0.0024 (10)	−0.0026 (10)
C1	0.055 (2)	0.039 (2)	0.0312 (19)	−0.0096 (17)	−0.0007 (16)	−0.0034 (15)
C2	0.097 (4)	0.045 (2)	0.033 (2)	−0.021 (3)	−0.011 (2)	0.0077 (18)
C3	0.096 (4)	0.033 (2)	0.054 (3)	0.002 (2)	−0.027 (3)	0.0055 (19)
C4	0.065 (3)	0.040 (2)	0.075 (3)	0.013 (2)	−0.020 (3)	−0.012 (2)
C5	0.045 (2)	0.0327 (19)	0.039 (2)	−0.0009 (16)	−0.0060 (16)	−0.0024 (15)
C6	0.0316 (17)	0.0295 (16)	0.0239 (15)	−0.0058 (13)	0.0055 (12)	−0.0065 (12)
C7	0.042 (2)	0.042 (2)	0.0257 (17)	−0.0108 (16)	0.0069 (14)	−0.0077 (15)
C8	0.045 (2)	0.052 (2)	0.0286 (18)	−0.0147 (18)	0.0157 (15)	−0.0133 (16)
C9	0.0331 (19)	0.045 (2)	0.054 (2)	0.0005 (16)	0.0113 (17)	−0.0166 (18)
C10	0.0333 (18)	0.041 (2)	0.0376 (19)	0.0032 (15)	0.0020 (15)	−0.0079 (16)
C11	0.0284 (16)	0.0342 (17)	0.0274 (16)	−0.0047 (13)	0.0036 (13)	−0.0077 (13)
C12	0.0330 (17)	0.0340 (18)	0.0287 (17)	−0.0013 (14)	−0.0028 (13)	−0.0035 (14)
C13	0.0333 (17)	0.0258 (15)	0.0193 (15)	0.0048 (13)	0.0008 (12)	0.0018 (12)
C14	0.0367 (18)	0.0377 (18)	0.0230 (16)	−0.0066 (14)	−0.0019 (13)	−0.0069 (13)
C15	0.0373 (19)	0.0343 (18)	0.0335 (18)	−0.0090 (15)	0.0060 (14)	−0.0061 (14)
C16	0.0328 (16)	0.0217 (14)	0.0205 (15)	0.0021 (12)	0.0024 (12)	−0.0011 (11)
C17	0.0324 (17)	0.0359 (18)	0.0206 (15)	0.0012 (14)	−0.0037 (12)	−0.0038 (13)
C18	0.0269 (16)	0.0388 (18)	0.0269 (17)	−0.0038 (13)	0.0010 (12)	−0.0013 (13)
C19	0.0395 (18)	0.0251 (16)	0.0214 (15)	0.0045 (13)	0.0028 (13)	0.0011 (12)

Geometric parameters (Å, º)

Cu1—O1	1.927 (2)	C7—C8	1.381 (5)
Cu1—O1^i	2.440 (2)	C7—H7	0.9300
Cu1—O3^ii	1.930 (2)	C8—C9	1.369 (6)
Cu1—N2	2.020 (3)	C8—H8	0.9300
Cu1—N1	2.038 (3)	C9—C10	1.378 (5)
O1—C6	1.316 (4)	C9—H9	0.9300
O1—Cu1^i	2.440 (2)	C10—C11	1.408 (5)
O2—C19	1.238 (4)	C10—H10	0.9300
O3—C19	1.284 (4)	C11—C12	1.442 (4)
O3—Cu1^ii	1.930 (2)	C12—H12	0.9300
O4—C22	1.107 (14)	C13—C18	1.372 (4)
N1—C5	1.335 (5)	C13—C14	1.395 (5)
N1—C1	1.352 (4)	C14—C15	1.376 (4)
N2—C12	1.289 (4)	C14—H14	0.9300
N2—C13	1.439 (4)	C15—C16	1.390 (5)
N3—C21	1.358 (11)	C15—H15	0.9300
N3—C22	1.455 (13)	C16—C17	1.387 (5)
N3—C20	1.498 (12)	C16—C19	1.513 (4)
C1—C2	1.364 (6)	C17—C18	1.385 (4)
C1—H1	0.9300	C17—H17	0.9300
C2—C3	1.376 (7)	C18—H18	0.9300
C2—H2	0.9300	C20—H20A	0.9600
C3—C4	1.365 (7)	C20—H20B	0.9600
C3—H3	0.9300	C20—H20C	0.9600
C4—C5	1.384 (6)	C21—H21A	0.9599
C4—H4	0.9300	C21—H21B	0.9599
C5—H5	0.9300	C21—H21C	0.9601
C6—C7	1.411 (4)	C22—H22	0.9300
C6—C11	1.415 (5)
O1—Cu1—O3^ii	176.68 (9)	C8—C9—H9	120.7
O1—Cu1—N2	90.46 (10)	C10—C9—H9	120.7
O3^ii—Cu1—N2	91.26 (10)	C9—C10—C11	121.5 (3)
O1—Cu1—N1	89.10 (11)	C9—C10—H10	119.3
O3^ii—Cu1—N1	89.86 (11)	C11—C10—H10	119.3
N2—Cu1—N1	167.16 (12)	C10—C11—C6	119.6 (3)
O1—Cu1—O1^i	82.50 (9)	C10—C11—C12	117.1 (3)
O3^ii—Cu1—O1^i	94.38 (10)	C6—C11—C12	123.2 (3)
N2—Cu1—O1^i	100.60 (10)	N2—C12—C11	126.5 (3)
N1—Cu1—O1^i	92.06 (10)	N2—C12—H12	116.8
C6—O1—Cu1	126.9 (2)	C11—C12—H12	116.8
C6—O1—Cu1^i	115.3 (2)	C18—C13—C14	120.0 (3)
Cu1—O1—Cu1^i	97.50 (9)	C18—C13—N2	121.1 (3)
C19—O3—Cu1^ii	118.6 (2)	C14—C13—N2	118.8 (3)
C5—N1—C1	117.7 (3)	C15—C14—C13	119.4 (3)
C5—N1—Cu1	121.5 (2)	C15—C14—H14	120.3
C1—N1—Cu1	120.8 (3)	C13—C14—H14	120.3
C12—N2—C13	116.7 (3)	C14—C15—C16	121.0 (3)
C12—N2—Cu1	122.9 (2)	C14—C15—H15	119.5
C13—N2—Cu1	119.5 (2)	C16—C15—H15	119.5
C21—N3—C22	140.8 (9)	C17—C16—C15	118.8 (3)
C21—N3—C20	109.4 (7)	C17—C16—C19	121.2 (3)
C22—N3—C20	109.6 (9)	C15—C16—C19	119.5 (3)
N1—C1—C2	122.1 (4)	C18—C17—C16	120.4 (3)
N1—C1—H1	118.9	C18—C17—H17	119.8
C2—C1—H1	118.9	C16—C17—H17	119.8
C1—C2—C3	119.7 (4)	C13—C18—C17	120.2 (3)
C1—C2—H2	120.1	C13—C18—H18	119.9
C3—C2—H2	120.1	C17—C18—H18	119.9
C4—C3—C2	118.9 (4)	O2—C19—O3	125.7 (3)
C4—C3—H3	120.6	O2—C19—C16	119.3 (3)
C2—C3—H3	120.6	O3—C19—C16	114.8 (3)
C3—C4—C5	118.9 (4)	N3—C20—H20A	109.5
C3—C4—H4	120.6	N3—C20—H20B	109.5
C5—C4—H4	120.6	H20A—C20—H20B	109.5
N1—C5—C4	122.7 (4)	N3—C20—H20C	109.5
N1—C5—H5	118.6	H20A—C20—H20C	109.5
C4—C5—H5	118.6	H20B—C20—H20C	109.5
O1—C6—C7	119.5 (3)	N3—C21—H21A	109.5
O1—C6—C11	123.0 (3)	N3—C21—H21B	109.5
C7—C6—C11	117.5 (3)	H21A—C21—H21B	109.5
C8—C7—C6	120.6 (3)	N3—C21—H21C	109.5
C8—C7—H7	119.7	H21A—C21—H21C	109.5
C6—C7—H7	119.7	H21B—C21—H21C	109.5
C9—C8—C7	122.1 (3)	O4—C22—N3	117.1 (14)
C9—C8—H8	118.9	O4—C22—H22	121.5
C7—C8—H8	118.9	N3—C22—H22	121.5
C8—C9—C10	118.6 (3)

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