Two new polymorphs of di­phenyl(4-pyridyl)­methyl methacryl­ate

The title compound (D4PyMA), C₂₂H₁₉NO₂, exhibits polymorphism after crystallization by slow evaporation from a binary mixture of chloro­form and hexane. Long needle-like crystals have an orthorhombic structure (space group Fdd2), with one mol­ecule in the asymmetric unit, while small tablet-like crystals exhibit a monoclinic crystal structure (space group P2₁/n), in which two independent but chemically identical mol­ecules comprise the asymmetric unit. The bond lengths and angles are normal, while the torsion angles around the -C-O- bond linking the di­phenyl(4-pyridyl)methyl and methacryl­ate groups show the flexibility of the mol­ecule by way of packing effects. The two polymorphs both contain weak C-H...[pi] and C-H...O/N contacts but have different conformations.

S1. Comment

Methacrylate monomers with large bulky ester groups were synthesized to study the stereo-specific and asymmetric polymerization in which the ester group plays an important role. Okamoto et al. (1983, 1994) reported on a series of bulky methacrylates and found that many of these types of monomer yield highly isotactic optically active polymers with one-handed helical conformation by asymmetric anionic polymerization. The bulky side groups of the monomers containing pyridyl groups are especially interesting, because of their ability to form complexes with acidic low-molecular-weight molecules. Poly(4-vinylpyridine) complexed with, for example, nona- or pentadecylphenol self-assembles in lamellar structures with a periodicity in the order of 30–50 Å. (Ruokolainen et al., 1996). Block copolymers containing 4-vinylpyridine blocks complexed with nona- or pentadecylphenol resulted in supramolecular polymeric materials with hierarchical structure-within-structure morphologies (Ruokalainen et al., 1998, 1999). Based on its helical conformation, the title complex (D4PyMA), complexed with similar amphiphiles, may give rise to self-assembled structures that are even more interesting. After thorough purification of the synthesized monomer, two types of crystals were found and two polymorphs, (I) (orthorhombic) and (II) (monoclinic), were detected, as described below. An extensive literature search revealed no reports on the crystal structure of D4PyMA. The crystal and molecular structure of diphenyl-2-pyridylmethyl methacrylate (D2PyMA) has, however, been reported (Kageyama et al., 1986). The crystal structures of related methacrylates with a large bulky ester substituent, such as 1,1-diphenylethyl methacrylate and triphenylmethyl methacrylate (Kageyama et al., 1985) and diphenyl methyl methacrylate (Kageyama et al., 1982), all have a monoclinic space group (P2₁/a, P2₁/a and C2/c, respectively)

The molecular geometries of (I) and (II), with the atomic numbering, are shown in Figs. 1 and 2. The structure of D2PyMA, which differs only in the position of the N atom in the pyridyl ring, is reported (Kageyama et al., 1986) to be monoclinic, with the same space group (P2₁/n) as (II). In the case of the former, there is only one molecule in the asymmetric unit, whereas (II) contains two. Furthermore, the structure of D2PyMA was determined at ambient temperature, whilst that of (II) was determined at 100 K.

The distance between two adjacent double bonds is of importance to allow polymerization in the crystalline state (below the melting temperature). It was found that a distance of 3.76 Å is short enough to form linear polymers using γ-radiation (Enkelmann et al., 1978). However, it is not only the distance that is important; the crystal geometry has also to be taken into account, since methyl acrylate does not react under γ-radiation, although the distance between the double bonds is 3.711 Å (Brown et al., 1971).

The possibility of polymerization in the crystalline phase is very unlikely for either polymorph, since the shortest intermolecular distance between the mid-points of the double bonds is 5.455 (5) Å in (I) [C1=C3; the two closest equivalent mid-points are at (1/4 + x, 1/4 − y, 1/4 + z) and (−1/4 + x, 1/4 − y, −1/4 + z)], and 4.117 (6) Å (C11=C13; symmetry code of closest midpoint: −x, 1 − y, 1 − z) and 4.914 (6) Å (C21=C23; symmetry code of closest midpoint: −x, 1 − y, −z) in the two residues of (II). In (I), the observed C—H···π contacts shorter than 3.0 Å are C13—H13···Cg1 (2.71 Å; Cg1 is the centroid of the N/C6–C10 ring; symmetry code: 1/2 − x, −y, 1/2 + z), C8—H8···Cg2 (2.85 Å; Cg2 is the centroid of the C11–C16 ring; symmetry code: x, y, −1 + z) and C10—H10···Cg3 (2.94 Å; Cg3 is the centroid of the C17–C22 ring; symmetry code: −x, −y, z). In (II), the contacts are C29—H29···Cg4 (2.94 Å; Cg4 is the centroid of the N11/C16–C110 ring; symmetry code: −x, 1 − y, 1 − z) and C114—H114···Cg5 (2.60 Å; Cg5 is the centroid of the N21/C26–C210 ring; 1/2 + x, 1/2 − y, 1/2 + z). [For a general discussions of C—H···π contacts see Malone et al. (1997), Nisho et al. (1998) and Desiraju & Steiner (1999).]

Two very weak hydrogen-bond-like contacts were also observed, viz. a C19—H19···N(-x, −y, 1 + z) contact (2.54 Å) in (I) and a C110—H110···O11(1/2 − x, 1/2 + y, 3/2 − z) contact (2.44 Å) in II.

The density of the orthorhombic structure is higher than that for the monoclinic structure (1.279 versus 1.266 Mg m⁻³). This result suggests that the orthorhombic form may be thermodynamically more stable (Burger & Ramberger, 1979).

The main differences in the conformations appear around the Cn5—On2 bond; the C4—O2—C5—C11 torsion angle in (I) is 55.9 (3)°, and the corresponding angles in (II) are 50.3 (4) and −52.4 (4)°. The C4—O2—C5—C6 torsion angle in (I) is −72.2 (2)°, and the corresponding angles in (II) are −77.7 (4) and 75.5 (4)° in (II). The C4—O2—C5—C17 angle in (I) is 173.0 (2)°, and the corresponding angles in (II) are 166.5 (3) and −169.5 (3)°.

Several examples of concomitant polymorphism have been reported previously, for example, benzanilide from ethanol in a triclinic form (Bowes, et al., 2003) and a monoclinic form (Kashino et al., 1979). Yet another example is the crystallization of 2-iodo-4-nitroaniline from ethanol, which yields a mixture of triclinic and orthorhombic crystals (McWilliams et al., 2001). Fig. 3 shows the two crystal types, viz. the monoclinic crystal, (II), grown on top of an orthorhombic needle-like crystal of (I).

S2. Experimental

D4PyMA was synthesized according to the following procedure. To a suspension (60 wt% in mineral oil from Fluka) of NaH (13.9 g, 0.35 mol) in a 1000 ml three-necked flask, flushed with dry N₂ gas and equipped with a reflux condenser, was added hexane (35 ml), and the mixture was stirred for 1 h. The supernatant mixture of hexane/mineral oil was removed with a syringe. To the remaining NaH (30.5 g, 0.117 mol), α-(4-pyridyl)benzhydrol suspended in tetrahydrofuran (THF, 300 ml) was added stepwise (H₂) under stirring. After adding all the α-(4-pyridyl)benzhydrol suspension, the reaction mixture was refluxed for 20 h. The mixture was then cooled to 273 K, and freshly distilled methacryloylchloride (12.2 g, 0.117 mol) was added dropwise under stirring. After the addition was complete, the mixture was stirred for an additional 20 h at room temperature. Subsequently, THF was removed by evaporation. The reaction product was added stepwise to a solution Na₂CO₃ (5.5 g, 51.9 mmol) in a 350 ml water/ice mixture. Extraction was executed with diethyl ether (300 ml). The diethyl ether layer contained the product and the water layer, the excess of methacryloylchloride and NaCl. The remaining undissolved products were filtered off if necessary and the layers were separated. The remaining water layer was extracted another two times. The diethyl ether fractions were combined and the solvent was removed by evaporation. The crude product (dark-red oil) was purified by column chromatography over neutral Al₂O₃ activity type 1 using a chloroform–hexane mixture (2:1, v/v) and was recrystallized twice, firstly from a hexane–diethyl ether mixture(1:1, v/v) and secondly from chloroform. Yield 12.1 g (36.7 mmol, 35.5%) of pure monomer. ¹H NMR (Varian VXR, 300 MHz, CDCl3): δ 1.93 (s, 3H, CH3), 5.60 (s, 1H, vinyl H), 6.19 (s, 1H, vinyl H), 7.1–7.4 (m, 12H, aromatic), 8.48–8.51 (d, 2H, aromatic next to N). Mass (Jeol JMS 600H 70 eV eI): m/z = 329 (calcualted: 329.4). Single crystals of (I) and (II) suitable for analysis were grown by slow evaporation from a chloroform–hexane (5:95, v/v) solution at room temperature in air.

S3. Refinement

Crystals of the monoclinic phase, (II), were grown together; consequently a single-crystal had to be cleaved from an aggreagate, resulting in plate-shaped fragments. Most crystals of (II) showed broad profiles with anisotropic mosaicity. At ambient temperature, only very weak low-order reflections of (II) were observed, from which the unit cell was determinated [a = 16.974 (5) Å, b = 11.967 (4) Å, c = 17.968 (6) Å, β = 100.795 (6)° and V = 3585 (2) ų]. The volume of (II) is comparable to two times the reported value of the unit cell of D2PyMA (3589 ų; Kageyama et al., 1986), the latter with Z=4. The absolute configuration of the orthorhombic phase, (I), could not be determined reliably; therefore the Friedel pairs were merged. The N-atom positions were discriminated from the other possible positions by comparing the geometric and displacement parameters after isotropic refinement. All H atoms in (I) and (II) were placed in idealized positions and constrained to ride on their parent atom. The final difference Fourier map for (II) contained a relatively large residual electron density [0.98 (13) e/ų]. No satisfactory discrete disorder model could be fitted to this density.

Computing details

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT? and XPREP (Bruker, 2000); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLUTO (Meetsma, 2004) and PLATON (Spek, 2003); software used to prepare material for publication: PLATON.

Figures

	Fig. 1. A perspective drawing of (I), with the atomic labelling of non-H atoms. All non-H atoms are represented by displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A perspective drawing of the two unique molecules of (II), with the atomic labelling. All non-H atoms are represented by displacement ellipsoids drawn at the 50% probability level. H-atoms have been omitted for clarity.
	Fig. 3. A light microscopic picture of a crystal of the monoclinic compound, (II), on top of a crystal of the orthorhombic compound, (I).

(I) diphenyl(4-pyridyl)methyl methacrylate

Crystal data

C22H19NO2	The final unit cell was obtained from the xyz centroids of 4817 reflections after integration using the SAINT software package (Bruker, 2000).
Mr = 329.40	Dx = 1.279 Mg m^−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 4817 reflections
a = 19.170 (1) Å	θ = 2.3–27.4°
b = 42.244 (3) Å	µ = 0.08 mm^−1
c = 8.4475 (6) Å	T = 100 K
V = 6840.9 (8) Å^3	Needle, colorless
Z = 16	0.38 × 0.10 × 0.06 mm
F(000) = 2784

Data collection

Bruker SMART Apex; area detector diffractometer	1944 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	1750 reflections with I > 2σ(I)
Parallel mounted graphite monochromator	Rint = 0.052
Detector resolution: 4096x4096 / 62x62 (binned 512) pixels mm^-1	θmax = 26.7°, θmin = 2.3°
π and ω scans	h = −24→24
Absorption correction: multi-scan (SADABS, Bruker, 2000)	k = −53→53
Tmin = 0.910, Tmax = 0.994	l = −10→10
13883 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)] = 0.037	Hydrogen site location: difference Fourier map
wR(F^2) = 0.085	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0124P)^2 + 8.7015P] where P = (Fo^2 + 2Fc^2)/3
1944 reflections	(Δ/σ)max < 0.001
291 parameters	Δρmax = 0.24 e Å^−3
1 restraint	Δρmin = −0.20 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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)
O1	0.22564 (9)	0.07996 (4)	0.1146 (2)	0.0307 (6)
O2	0.11558 (9)	0.09228 (4)	0.1832 (2)	0.0227 (5)
N	0.08673 (11)	−0.00934 (5)	−0.1274 (3)	0.0262 (7)
C1	0.13339 (17)	0.15317 (6)	0.1032 (3)	0.0328 (9)
C2	0.25401 (15)	0.14140 (7)	0.0114 (4)	0.0416 (10)
C3	0.18642 (14)	0.13299 (6)	0.0806 (3)	0.0281 (8)
C4	0.18008 (13)	0.09882 (6)	0.1271 (3)	0.0238 (7)
C5	0.10218 (12)	0.06076 (5)	0.2484 (3)	0.0185 (7)
C6	0.09934 (11)	0.03615 (5)	0.1156 (3)	0.0180 (7)
C7	0.10586 (14)	0.04425 (6)	−0.0422 (3)	0.0243 (8)
C8	0.09946 (14)	0.02110 (7)	−0.1570 (3)	0.0281 (8)
C9	0.07974 (13)	−0.01689 (6)	0.0260 (3)	0.0235 (8)
C10	0.08500 (12)	0.00469 (6)	0.1489 (3)	0.0206 (7)
C11	0.15524 (12)	0.05446 (5)	0.3804 (3)	0.0207 (7)
C12	0.19774 (13)	0.02824 (6)	0.3885 (3)	0.0258 (7)
C13	0.24400 (13)	0.02423 (7)	0.5139 (3)	0.0302 (8)
C14	0.24952 (14)	0.04720 (7)	0.6293 (4)	0.0322 (8)
C15	0.20825 (15)	0.07387 (7)	0.6207 (4)	0.0332 (9)
C16	0.16070 (14)	0.07727 (6)	0.4990 (3)	0.0267 (8)
C17	0.02824 (12)	0.06362 (5)	0.3183 (3)	0.0186 (7)
C18	0.00821 (13)	0.04424 (6)	0.4450 (3)	0.0209 (7)
C19	−0.05867 (14)	0.04557 (6)	0.5059 (3)	0.0252 (7)
C20	−0.10703 (14)	0.06604 (6)	0.4408 (3)	0.0272 (8)
C21	−0.08803 (14)	0.08511 (7)	0.3150 (4)	0.0296 (8)
C22	−0.02094 (14)	0.08392 (6)	0.2535 (3)	0.0258 (8)
H1	0.13766	0.17425	0.07195	0.0410 (17)*	1.00 (6)
H1'	0.09108	0.14712	0.15421	0.0457 (18)*	1.00 (6)
H2	0.25777	0.13215	−0.09468	0.0624*
H2'	0.29158	0.13317	0.07846	0.0624*
H2"	0.25789	0.16448	0.00409	0.0624*
H7	0.11598	0.06521	−0.07221	0.0244 (14)*	1.00 (5)
H8	0.10490	0.02656	−0.27134	0.0594 (19)*	1.00 (7)
H9	0.06983	−0.03931	0.04542	0.0261 (14)*	1.00 (5)
H10	0.07996	−0.00245	0.25598	0.0246 (14)*	1.00 (5)
H12	0.19696	0.01191	0.31011	0.0409 (16)*	1.00 (6)
H13	0.27250	0.00533	0.51681	0.0523 (18)*	1.00 (6)
H14	0.27649	0.04558	0.71442	0.0431 (17)*	1.00 (6)
H15	0.21296	0.09142	0.70478	0.0375 (15)*	1.00 (6)
H16	0.13416	0.09491	0.49635	0.0176 (14)*	1.00 (5)
H18	0.03959	0.03092	0.48312	0.0137 (13)*	1.00 (4)
H19	−0.07126	0.03241	0.59752	0.0169 (13)*	1.00 (4)
H20	−0.15363	0.06671	0.48514	0.0273 (15)*	1.00 (5)
H21	−0.12134	0.09948	0.26717	0.0245 (14)*	1.00 (5)
H22	−0.00873	0.09536	0.16244	0.0254 (14)*	1.00 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0268 (9)	0.0310 (10)	0.0342 (11)	−0.0016 (8)	0.0059 (9)	0.0015 (9)
O2	0.0259 (9)	0.0172 (8)	0.0251 (9)	−0.0008 (7)	0.0018 (8)	0.0035 (8)
N	0.0241 (11)	0.0281 (12)	0.0265 (11)	−0.0032 (9)	−0.0003 (10)	−0.0054 (10)
C1	0.0515 (19)	0.0175 (12)	0.0293 (16)	−0.0060 (12)	0.0016 (14)	0.0017 (12)
C2	0.0402 (17)	0.0421 (17)	0.0425 (18)	−0.0141 (14)	−0.0064 (15)	0.0146 (15)
C3	0.0363 (14)	0.0289 (13)	0.0192 (13)	−0.0083 (12)	−0.0064 (11)	0.0027 (10)
C4	0.0282 (12)	0.0241 (12)	0.0191 (12)	−0.0048 (11)	−0.0001 (11)	−0.0004 (11)
C5	0.0213 (12)	0.0149 (11)	0.0192 (12)	0.0001 (9)	0.0014 (10)	0.0014 (10)
C6	0.0119 (10)	0.0203 (12)	0.0219 (12)	0.0019 (9)	0.0005 (9)	0.0000 (10)
C7	0.0287 (13)	0.0224 (13)	0.0217 (13)	−0.0030 (10)	0.0001 (11)	0.0030 (11)
C8	0.0305 (14)	0.0337 (14)	0.0200 (14)	−0.0022 (11)	−0.0030 (11)	0.0002 (11)
C9	0.0210 (12)	0.0191 (12)	0.0304 (15)	−0.0010 (10)	0.0047 (11)	0.0001 (11)
C10	0.0173 (11)	0.0218 (12)	0.0227 (13)	0.0011 (9)	0.0029 (10)	0.0030 (10)
C11	0.0183 (11)	0.0207 (11)	0.0231 (13)	−0.0045 (9)	0.0037 (10)	0.0048 (10)
C12	0.0218 (12)	0.0295 (13)	0.0260 (13)	0.0015 (11)	0.0011 (11)	0.0003 (12)
C13	0.0212 (13)	0.0379 (15)	0.0315 (15)	0.0048 (12)	−0.0042 (12)	0.0050 (13)
C14	0.0257 (13)	0.0420 (16)	0.0289 (15)	−0.0037 (12)	−0.0049 (13)	0.0076 (14)
C15	0.0353 (15)	0.0343 (15)	0.0301 (15)	−0.0101 (12)	−0.0020 (13)	−0.0048 (13)
C16	0.0282 (13)	0.0236 (13)	0.0284 (14)	−0.0048 (11)	−0.0044 (12)	0.0016 (12)
C17	0.0199 (11)	0.0175 (11)	0.0185 (12)	0.0006 (9)	−0.0030 (10)	−0.0052 (10)
C18	0.0235 (12)	0.0206 (12)	0.0186 (12)	−0.0016 (10)	−0.0010 (10)	−0.0050 (10)
C19	0.0303 (13)	0.0248 (13)	0.0205 (12)	−0.0066 (10)	0.0033 (12)	−0.0056 (11)
C20	0.0253 (13)	0.0253 (13)	0.0311 (14)	0.0000 (10)	0.0079 (12)	−0.0101 (12)
C21	0.0240 (14)	0.0268 (13)	0.0379 (16)	0.0055 (11)	−0.0015 (12)	−0.0008 (12)
C22	0.0290 (14)	0.0216 (12)	0.0267 (13)	−0.0007 (10)	0.0033 (12)	0.0033 (12)

Geometric parameters (Å, º)

O1—C4	1.187 (3)	C18—C19	1.383 (4)
O2—C4	1.353 (3)	C19—C20	1.382 (4)
O2—C5	1.464 (3)	C20—C21	1.382 (4)
N—C8	1.333 (4)	C21—C22	1.388 (4)
N—C9	1.341 (4)	C1—H1	0.9300
C1—C3	1.340 (4)	C1—H1'	0.9500
C2—C3	1.465 (4)	C2—H2	0.9800
C3—C4	1.501 (4)	C2—H2'	0.9800
C5—C6	1.531 (3)	C2—H2"	0.9800
C5—C11	1.533 (3)	C7—H7	0.9400
C5—C17	1.540 (3)	C8—H8	1.0000
C6—C7	1.382 (4)	C9—H9	0.9800
C6—C10	1.386 (3)	C10—H10	0.9600
C7—C8	1.383 (4)	C12—H12	0.9600
C9—C10	1.385 (4)	C13—H13	0.9700
C11—C12	1.377 (3)	C14—H14	0.8900
C11—C16	1.394 (3)	C15—H15	1.0300
C12—C13	1.392 (4)	C16—H16	0.9000
C13—C14	1.380 (4)	C18—H18	0.8800
C14—C15	1.379 (4)	C19—H19	0.9800
C15—C16	1.382 (4)	C20—H20	0.9700
C17—C18	1.401 (3)	C21—H21	0.9700
C17—C22	1.387 (3)	C22—H22	0.9400
O1···C6	3.048 (3)	C18···H10^v	2.9200
O1···C7	3.050 (3)	C19···H10^v	2.8200
O1···C11	2.833 (3)	C19···H2"^xi	2.9800
O1···C12	3.227 (3)	C20···H14^xii	3.0600
O1···H2	2.8900	C21···H9^v	3.0100
O1···H2'	2.6000	C21···H16^x	3.0600
O1···H7	2.7000	C22···H9^v	2.7400
O1···H20^i	2.6200	H1···H2"	2.4100
O2···H1'	2.3800	H1···N^ix	2.8800
O2···H7	2.4400	H1···C9^ix	3.0900
O2···H16	2.6700	H1···H9^ix	2.5700
O2···H22	2.3900	H1'···O2	2.3800
N···H19^ii	2.5400	H2···O1	2.8900
N···H1^iii	2.8800	H2···H15^iv	2.5600
C4···C7	3.063 (4)	H2'···O1	2.6000
C4···C16	3.292 (4)	H2"···H1	2.4100
C6···O1	3.048 (3)	H2"···C7^xiii	3.0900
C7···C4	3.063 (4)	H2"···C19^xiv	2.9800
C7···O1	3.050 (3)	H7···O1	2.7000
C8···C15^iv	3.584 (4)	H7···O2	2.4400
C8···C14^iv	3.571 (4)	H7···C4	2.5200
C9···C9^v	3.374 (4)	H8···C14^iv	3.0300
C9···C13^vi	3.395 (4)	H8···C15^iv	2.9600
C9···C10^v	3.364 (3)	H8···C16^iv	3.0800
C10···C10^v	3.283 (3)	H8···H18^iv	2.4300
C10···C12	3.124 (4)	H9···C21^v	3.0100
C10···C9^v	3.364 (3)	H9···C22^v	2.7400
C10···C18	3.349 (4)	H9···C1^iii	3.0600
C11···O1	2.833 (3)	H9···H1^iii	2.5700
C12···O1	3.227 (3)	H10···C11	2.9900
C12···C10	3.124 (4)	H10···C12	2.8300
C13···C9^vii	3.395 (4)	H10···C17	3.0100
C14···C8^viii	3.571 (4)	H10···C18	2.8900
C15···C8^viii	3.584 (4)	H10···H12	2.3700
C16···C4	3.292 (4)	H10···H18	2.5000
C16···C18	3.271 (4)	H10···C18^v	2.9200
C18···C16	3.271 (4)	H10···C19^v	2.8200
C18···C10	3.349 (4)	H12···C6	2.6900
C1···H9^ix	3.0600	H12···C10	2.5600
C4···H7	2.5200	H12···H10	2.3700
C6···H12	2.6900	H13···C8^vii	3.0700
C7···H2"^x	3.0900	H13···C9^vii	2.8800
C8···H13^vi	3.0700	H13···C10^vii	2.9800
C9···H13^vi	2.8800	H14···C20^xv	3.0600
C9···H1^iii	3.0900	H15···H2^viii	2.5600
C10···H13^vi	2.9800	H16···O2	2.6700
C10···H12	2.5600	H16···C17	2.8500
C11···H10	2.9900	H16···C21^xiii	3.0600
C11···H18	2.5800	H16···H21^xiii	2.3600
C12···H10	2.8300	H18···C11	2.5800
C14···H8^viii	3.0300	H18···C16	3.0400
C15···H8^viii	2.9600	H18···H8^viii	2.4300
C16···H8^viii	3.0800	H18···H10	2.5000
C16···H18	3.0400	H19···N^xvi	2.5400
C17···H16	2.8500	H20···O1^xvii	2.6200
C17···H10	3.0100	H21···H16^x	2.3600
C18···H10	2.8900	H22···O2	2.3900
C4—O2—C5	118.56 (18)	C3—C1—H1	120.00
C8—N—C9	115.4 (2)	C3—C1—H1'	123.00
C1—C3—C2	125.0 (2)	H1—C1—H1'	117.00
C1—C3—C4	120.9 (2)	C3—C2—H2	109.00
C2—C3—C4	114.2 (2)	C3—C2—H2'	109.00
O1—C4—O2	124.5 (2)	C3—C2—H2"	109.00
O1—C4—C3	124.2 (2)	H2—C2—H2'	109.00
O2—C4—C3	111.2 (2)	H2—C2—H2"	109.00
O2—C5—C6	110.39 (19)	H2'—C2—H2"	109.00
O2—C5—C11	108.38 (17)	C6—C7—H7	121.00
O2—C5—C17	103.56 (17)	C8—C7—H7	120.00
C6—C5—C11	116.04 (18)	N—C8—H8	115.00
C6—C5—C17	107.55 (18)	C7—C8—H8	120.00
C11—C5—C17	110.2 (2)	N—C9—H9	114.00
C5—C6—C7	122.4 (2)	C10—C9—H9	122.00
C5—C6—C10	120.6 (2)	C6—C10—H10	121.00
C7—C6—C10	116.8 (2)	C9—C10—H10	120.00
C6—C7—C8	119.6 (2)	C11—C12—H12	122.00
N—C8—C7	124.6 (2)	C13—C12—H12	117.00
N—C9—C10	124.1 (2)	C12—C13—H13	119.00
C6—C10—C9	119.6 (2)	C14—C13—H13	121.00
C5—C11—C12	124.7 (2)	C13—C14—H14	124.00
C5—C11—C16	116.9 (2)	C15—C14—H14	116.00
C12—C11—C16	118.4 (2)	C14—C15—H15	120.00
C11—C12—C13	120.9 (2)	C16—C15—H15	120.00
C12—C13—C14	120.1 (3)	C11—C16—H16	121.00
C13—C14—C15	119.6 (3)	C15—C16—H16	118.00
C14—C15—C16	120.2 (3)	C17—C18—H18	118.00
C11—C16—C15	120.8 (2)	C19—C18—H18	121.00
C5—C17—C18	120.0 (2)	C18—C19—H19	120.00
C5—C17—C22	121.5 (2)	C20—C19—H19	120.00
C18—C17—C22	118.5 (2)	C19—C20—H20	119.00
C17—C18—C19	121.0 (2)	C21—C20—H20	122.00
C18—C19—C20	120.0 (2)	C20—C21—H21	121.00
C19—C20—C21	119.6 (2)	C22—C21—H21	118.00
C20—C21—C22	120.7 (3)	C17—C22—H22	118.00
C17—C22—C21	120.3 (2)	C21—C22—H22	121.00
C5—O2—C4—O1	6.5 (4)	C11—C5—C17—C18	−37.2 (3)
C5—O2—C4—C3	−174.2 (2)	C11—C5—C17—C22	146.2 (2)
C4—O2—C5—C6	−72.2 (2)	C6—C5—C11—C16	177.4 (2)
C4—O2—C5—C11	55.9 (3)	C17—C5—C11—C12	120.5 (2)
C4—O2—C5—C17	173.0 (2)	C5—C6—C10—C9	177.2 (2)
C9—N—C8—C7	0.3 (4)	C7—C6—C10—C9	1.6 (3)
C8—N—C9—C10	0.0 (4)	C5—C6—C7—C8	−176.9 (2)
C8—N—C9—H9	179.00	C10—C6—C7—C8	−1.4 (4)
C9—N—C8—H8	180.00	C6—C7—C8—N	0.4 (4)
C1—C3—C4—O2	3.0 (3)	N—C9—C10—C6	−1.0 (4)
C2—C3—C4—O1	2.1 (4)	C5—C11—C12—C13	−179.3 (2)
C1—C3—C4—O1	−177.7 (3)	C12—C11—C16—C15	0.8 (4)
C2—C3—C4—O2	−177.2 (2)	C5—C11—C16—C15	−178.6 (2)
O2—C5—C6—C10	−177.93 (19)	C16—C11—C12—C13	1.4 (4)
O2—C5—C6—C7	−2.6 (3)	C11—C12—C13—C14	−2.3 (4)
C17—C5—C6—C7	109.8 (2)	C12—C13—C14—C15	0.9 (4)
C17—C5—C6—C10	−65.6 (3)	C13—C14—C15—C16	1.3 (4)
O2—C5—C11—C12	−126.8 (2)	C14—C15—C16—C11	−2.2 (4)
O2—C5—C11—C16	52.6 (3)	C5—C17—C18—C19	−177.6 (2)
C6—C5—C11—C12	−2.0 (3)	C18—C17—C22—C21	0.8 (4)
C11—C5—C6—C7	−126.4 (2)	C22—C17—C18—C19	−0.9 (4)
C11—C5—C6—C10	58.3 (3)	C5—C17—C22—C21	177.5 (2)
C17—C5—C11—C16	−60.1 (3)	C17—C18—C19—C20	0.6 (4)
O2—C5—C17—C18	−152.9 (2)	C18—C19—C20—C21	−0.1 (4)
O2—C5—C17—C22	30.5 (3)	C19—C20—C21—C22	0.0 (4)
C6—C5—C17—C18	90.2 (3)	C20—C21—C22—C17	−0.4 (4)
C6—C5—C17—C22	−86.4 (3)

Symmetry codes: (i) x+1/2, y, z−1/2; (ii) −x, −y, z−1; (iii) −x+1/4, y−1/4, z−1/4; (iv) x, y, z−1; (v) −x, −y, z; (vi) −x+1/2, −y, z−1/2; (vii) −x+1/2, −y, z+1/2; (viii) x, y, z+1; (ix) −x+1/4, y+1/4, z+1/4; (x) x−1/4, −y+1/4, z−1/4; (xi) x−1/4, −y+1/4, z+3/4; (xii) x−1/2, y, z−1/2; (xiii) x+1/4, −y+1/4, z+1/4; (xiv) x+1/4, −y+1/4, z−3/4; (xv) x+1/2, y, z+1/2; (xvi) −x, −y, z+1; (xvii) x−1/2, y, z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O2	0.9400	2.4400	2.789 (3)	102.00
C19—H19···N^xvi	0.9800	2.5400	3.497 (4)	165.00

Symmetry code: (xvi) −x, −y, z+1.

(II) diphenyl(4-pyridyl)methyl methacrylate

Crystal data

C22H19NO2	F(000) = 1392
Mr = 329.40	The final unit cell was obtained from the xyz centroids of 2934 reflections after integration using the SAINT software package (Bruker, 2000).
Monoclinic, P21/n	Dx = 1.266 Mg m^−3
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 16.712 (2) Å	Cell parameters from 2934 reflections
b = 11.891 (1) Å	θ = 2.5–26.8°
c = 17.724 (2) Å	µ = 0.08 mm^−1
β = 101.045 (2)°	T = 100 K
V = 3456.9 (6) Å^3	Platelet, colorless
Z = 8	0.20 × 0.18 × 0.06 mm

Data collection

Bruker SMART Apex; area detector diffractometer	6100 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	3615 reflections with I > 2σ(I)
Parallel mounted graphite monochromator	Rint = 0.077
Detector resolution: 4096x4096 / 62x62 (binned 512) pixels mm^-1	θmax = 25.0°, θmin = 2.3°
π and ω scans	h = −19→19
Absorption correction: multi-scan (SADABS, Bruker, 2000)	k = −14→14
Tmin = 0.973, Tmax = 0.995	l = −21→21
24310 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.105	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.265	H-atom parameters constrained
S = 1.46	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
6100 reflections	(Δ/σ)max = 0.032
453 parameters	Δρmax = 0.98 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
O11	0.18023 (16)	0.3926 (2)	0.66896 (17)	0.0378 (10)
O12	0.14257 (15)	0.5487 (2)	0.59952 (14)	0.0319 (9)
N11	0.0699 (2)	0.6533 (3)	0.8565 (2)	0.0400 (12)
C11	0.0868 (2)	0.4259 (3)	0.4727 (2)	0.0340 (12)
C12	0.1215 (3)	0.2523 (3)	0.5459 (3)	0.0495 (17)
C13	0.1155 (2)	0.3729 (3)	0.5373 (2)	0.0310 (14)
C14	0.1501 (2)	0.4379 (3)	0.6091 (2)	0.0300 (12)
C15	0.1864 (2)	0.6231 (3)	0.6587 (2)	0.0276 (12)
C16	0.1440 (2)	0.6304 (3)	0.7270 (2)	0.0244 (11)
C17	0.0807 (2)	0.5592 (3)	0.7374 (2)	0.0268 (11)
C18	0.0463 (2)	0.5738 (3)	0.8021 (3)	0.0365 (14)
C19	0.1301 (2)	0.7228 (3)	0.8447 (2)	0.0353 (12)
C110	0.1673 (2)	0.7145 (3)	0.7817 (2)	0.0294 (12)
C111	0.2761 (2)	0.5870 (3)	0.6779 (2)	0.0233 (11)
C112	0.3190 (2)	0.5718 (3)	0.7524 (2)	0.0313 (12)
C113	0.4013 (2)	0.5449 (3)	0.7666 (2)	0.0282 (12)
C114	0.4423 (2)	0.5346 (3)	0.7075 (2)	0.0312 (14)
C115	0.4002 (2)	0.5475 (3)	0.6327 (2)	0.0347 (14)
C116	0.3183 (2)	0.5727 (3)	0.6183 (2)	0.0302 (12)
C117	0.1790 (2)	0.7379 (3)	0.6175 (2)	0.0280 (12)
C118	0.2424 (3)	0.8174 (3)	0.6298 (2)	0.0367 (14)
C119	0.2330 (3)	0.9207 (3)	0.5931 (3)	0.0386 (16)
C120	0.1613 (3)	0.9513 (3)	0.5471 (2)	0.0403 (16)
C121	0.0986 (3)	0.8770 (3)	0.5369 (2)	0.0402 (16)
C122	0.1059 (2)	0.7703 (3)	0.5725 (2)	0.0305 (12)
O21	0.18284 (16)	0.3557 (2)	0.16962 (17)	0.0379 (10)
O22	0.14905 (14)	0.1995 (2)	0.09936 (14)	0.0296 (8)
N21	0.08157 (19)	0.0917 (3)	0.35931 (19)	0.0337 (11)
C21	0.0866 (2)	0.3216 (3)	−0.0279 (2)	0.0377 (14)
C22	0.1149 (3)	0.4948 (3)	0.0496 (3)	0.0434 (16)
C23	0.1148 (2)	0.3749 (3)	0.0389 (2)	0.0306 (14)
C24	0.1535 (2)	0.3106 (3)	0.1102 (2)	0.0314 (14)
C25	0.1944 (2)	0.1255 (3)	0.1590 (2)	0.0260 (11)
C26	0.1528 (2)	0.1170 (3)	0.2279 (2)	0.0219 (11)
C27	0.1777 (2)	0.0328 (3)	0.2823 (2)	0.0293 (12)
C28	0.1414 (2)	0.0235 (3)	0.3458 (2)	0.0325 (12)
C29	0.0563 (2)	0.1714 (3)	0.3051 (2)	0.0310 (12)
C210	0.0894 (2)	0.1874 (3)	0.2399 (2)	0.0242 (11)
C211	0.2836 (2)	0.1631 (3)	0.1780 (2)	0.0229 (11)
C212	0.3263 (2)	0.1761 (3)	0.1182 (2)	0.0305 (12)
C213	0.4086 (2)	0.2032 (3)	0.1331 (2)	0.0330 (12)
C214	0.4495 (2)	0.2195 (3)	0.2082 (2)	0.0306 (14)
C215	0.4082 (2)	0.2108 (3)	0.2670 (2)	0.0325 (12)
C216	0.3249 (2)	0.1815 (3)	0.2522 (2)	0.0325 (12)
C217	0.1868 (2)	0.0104 (3)	0.1182 (2)	0.0252 (11)
C218	0.1131 (2)	−0.0210 (3)	0.0725 (2)	0.0307 (12)
C219	0.1047 (3)	−0.1271 (3)	0.0373 (2)	0.0374 (16)
C220	0.1682 (3)	−0.2029 (3)	0.0487 (2)	0.0355 (14)
C221	0.2396 (3)	−0.1732 (3)	0.0957 (2)	0.0354 (14)
C222	0.2499 (2)	−0.0686 (3)	0.1308 (2)	0.0311 (12)
H11	0.06803	0.38426	0.42692	0.0408*
H11'	0.08478	0.50571	0.47166	0.0408*
H12	0.09160	0.21618	0.49919	0.0744*
H12'	0.09809	0.22909	0.59003	0.0744*
H12"	0.17896	0.22986	0.55412	0.0744*
H17	0.06145	0.50192	0.70103	0.0324*
H18	0.00331	0.52472	0.80865	0.0436*
H19	0.14776	0.78012	0.88149	0.0423*
H110	0.20889	0.76627	0.77555	0.0357*
H112	0.29157	0.57989	0.79435	0.0375*
H113	0.42934	0.53356	0.81791	0.0342*
H114	0.49905	0.51882	0.71746	0.0374*
H115	0.42801	0.53892	0.59113	0.0414*
H116	0.29014	0.58038	0.56661	0.0361*
H118	0.29215	0.80014	0.66360	0.0436*
H119	0.27761	0.97159	0.60013	0.0462*
H120	0.15547	1.02283	0.52271	0.0485*
H121	0.04827	0.89731	0.50504	0.0483*
H122	0.06050	0.72071	0.56539	0.0366*
H21	0.06471	0.36365	−0.07267	0.0456*
H21'	0.08869	0.24181	−0.03033	0.0456*
H22	0.08761	0.53100	0.00196	0.0648*
H22'	0.17127	0.52169	0.06310	0.0648*
H22"	0.08597	0.51324	0.09115	0.0648*
H27	0.21956	−0.01810	0.27554	0.0347*
H28	0.15982	−0.03431	0.38201	0.0387*
H29	0.01298	0.21945	0.31228	0.0373*
H210	0.06936	0.24501	0.20412	0.0289*
H212	0.29863	0.16632	0.06661	0.0367*
H213	0.43701	0.21064	0.09176	0.0398*
H214	0.50607	0.23663	0.21842	0.0368*
H215	0.43555	0.22453	0.31827	0.0386*
H216	0.29683	0.17441	0.29376	0.0388*
H218	0.06828	0.02956	0.06510	0.0369*
H219	0.05449	−0.14694	0.00509	0.0444*
H220	0.16237	−0.27433	0.02426	0.0424*
H221	0.28339	−0.22554	0.10459	0.0426*
H222	0.30007	−0.05051	0.16366	0.0371*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O11	0.0442 (16)	0.0256 (15)	0.0425 (19)	0.0065 (12)	0.0059 (14)	0.0042 (13)
O12	0.0362 (15)	0.0297 (15)	0.0275 (16)	0.0007 (12)	0.0007 (12)	−0.0021 (12)
N11	0.049 (2)	0.039 (2)	0.035 (2)	0.0144 (17)	0.0158 (17)	0.0086 (17)
C11	0.036 (2)	0.033 (2)	0.032 (2)	−0.0015 (18)	0.0038 (18)	−0.0136 (19)
C12	0.053 (3)	0.034 (3)	0.061 (3)	−0.010 (2)	0.010 (2)	−0.006 (2)
C13	0.028 (2)	0.033 (2)	0.033 (3)	0.0018 (17)	0.0087 (17)	−0.0020 (19)
C14	0.024 (2)	0.041 (2)	0.025 (2)	0.0048 (17)	0.0044 (16)	−0.0053 (19)
C15	0.029 (2)	0.033 (2)	0.020 (2)	0.0011 (16)	0.0026 (16)	−0.0024 (17)
C16	0.0257 (19)	0.0233 (19)	0.024 (2)	0.0033 (15)	0.0041 (16)	0.0040 (16)
C17	0.027 (2)	0.0204 (19)	0.033 (2)	−0.0007 (16)	0.0055 (17)	0.0045 (17)
C18	0.033 (2)	0.032 (2)	0.049 (3)	0.0043 (18)	0.019 (2)	0.019 (2)
C19	0.041 (2)	0.037 (2)	0.027 (2)	0.0112 (19)	0.0044 (19)	0.0026 (18)
C110	0.031 (2)	0.026 (2)	0.030 (2)	−0.0017 (16)	0.0028 (17)	0.0017 (17)
C111	0.028 (2)	0.0196 (18)	0.022 (2)	−0.0002 (15)	0.0037 (16)	0.0012 (15)
C112	0.029 (2)	0.042 (2)	0.024 (2)	0.0016 (18)	0.0081 (16)	0.0046 (18)
C113	0.024 (2)	0.034 (2)	0.026 (2)	0.0048 (16)	0.0030 (16)	−0.0006 (18)
C114	0.0218 (19)	0.034 (2)	0.038 (3)	0.0013 (16)	0.0065 (17)	−0.0029 (19)
C115	0.045 (2)	0.028 (2)	0.036 (3)	0.0072 (18)	0.0203 (19)	0.0006 (18)
C116	0.036 (2)	0.028 (2)	0.026 (2)	0.0067 (17)	0.0046 (17)	0.0004 (17)
C117	0.034 (2)	0.031 (2)	0.020 (2)	−0.0004 (17)	0.0081 (16)	0.0023 (16)
C118	0.043 (2)	0.033 (2)	0.037 (3)	0.0039 (18)	0.0149 (19)	0.0021 (19)
C119	0.051 (3)	0.022 (2)	0.050 (3)	0.0032 (19)	0.028 (2)	0.0040 (19)
C120	0.070 (3)	0.023 (2)	0.032 (3)	0.007 (2)	0.020 (2)	0.0022 (18)
C121	0.065 (3)	0.032 (2)	0.025 (3)	0.006 (2)	0.012 (2)	0.002 (2)
C122	0.041 (2)	0.025 (2)	0.026 (2)	−0.0016 (17)	0.0074 (18)	−0.0031 (17)
O21	0.0425 (16)	0.0273 (15)	0.0417 (19)	−0.0038 (12)	0.0026 (14)	0.0006 (13)
O22	0.0324 (14)	0.0291 (15)	0.0252 (15)	0.0003 (11)	0.0006 (11)	0.0055 (12)
N21	0.0364 (19)	0.0353 (19)	0.029 (2)	−0.0032 (15)	0.0053 (15)	−0.0069 (16)
C21	0.048 (3)	0.032 (2)	0.030 (2)	−0.0003 (19)	−0.0002 (19)	0.0082 (19)
C22	0.047 (3)	0.027 (2)	0.054 (3)	0.0095 (19)	0.004 (2)	0.010 (2)
C23	0.028 (2)	0.024 (2)	0.041 (3)	−0.0026 (16)	0.0099 (18)	0.0090 (19)
C24	0.025 (2)	0.034 (2)	0.035 (3)	−0.0048 (17)	0.0054 (18)	0.006 (2)
C25	0.0269 (19)	0.026 (2)	0.024 (2)	−0.0003 (15)	0.0019 (16)	0.0019 (16)
C26	0.0229 (18)	0.0234 (19)	0.019 (2)	−0.0015 (15)	0.0027 (15)	−0.0039 (15)
C27	0.030 (2)	0.029 (2)	0.029 (2)	0.0082 (16)	0.0058 (17)	0.0006 (17)
C28	0.039 (2)	0.034 (2)	0.024 (2)	0.0020 (18)	0.0047 (18)	0.0027 (17)
C29	0.026 (2)	0.037 (2)	0.031 (2)	0.0031 (17)	0.0082 (17)	−0.0156 (19)
C210	0.0244 (19)	0.0220 (19)	0.026 (2)	0.0037 (15)	0.0047 (16)	−0.0008 (16)
C211	0.0235 (19)	0.0192 (18)	0.025 (2)	0.0027 (14)	0.0025 (16)	−0.0009 (16)
C212	0.035 (2)	0.024 (2)	0.033 (2)	−0.0075 (16)	0.0075 (18)	0.0014 (18)
C213	0.044 (2)	0.026 (2)	0.033 (2)	−0.0061 (18)	0.0176 (19)	0.0007 (18)
C214	0.027 (2)	0.025 (2)	0.039 (3)	−0.0057 (16)	0.0047 (18)	−0.0004 (19)
C215	0.031 (2)	0.036 (2)	0.028 (2)	−0.0060 (17)	−0.0008 (18)	0.0024 (19)
C216	0.029 (2)	0.037 (2)	0.032 (2)	0.0010 (17)	0.0068 (17)	−0.0035 (19)
C217	0.033 (2)	0.0252 (19)	0.019 (2)	0.0001 (16)	0.0089 (16)	0.0024 (16)
C218	0.036 (2)	0.029 (2)	0.026 (2)	0.0034 (17)	0.0029 (17)	0.0024 (18)
C219	0.053 (3)	0.029 (2)	0.027 (3)	−0.0088 (19)	0.000 (2)	−0.0010 (19)
C220	0.060 (3)	0.021 (2)	0.028 (2)	−0.0049 (19)	0.015 (2)	−0.0013 (17)
C221	0.044 (2)	0.024 (2)	0.044 (3)	−0.0006 (18)	0.023 (2)	−0.0031 (19)
C222	0.032 (2)	0.029 (2)	0.034 (2)	−0.0043 (17)	0.0104 (17)	−0.0027 (18)

Geometric parameters (Å, º)

O11—C14	1.210 (5)	C118—H118	0.9494
O12—C14	1.331 (4)	C119—H119	0.9497
O12—C15	1.458 (4)	C120—H120	0.9506
O21—C24	1.200 (5)	C21—C23	1.346 (5)
O22—C25	1.469 (4)	C121—H121	0.9501
O22—C24	1.335 (4)	C122—H122	0.9501
N11—C19	1.349 (5)	C22—C23	1.438 (5)
N11—C18	1.354 (6)	C23—C24	1.512 (5)
N21—C29	1.358 (5)	C25—C26	1.520 (5)
N21—C28	1.344 (5)	C25—C211	1.531 (5)
C11—C13	1.314 (5)	C25—C217	1.542 (5)
C12—C13	1.444 (5)	C26—C27	1.397 (5)
C13—C14	1.506 (5)	C26—C210	1.398 (5)
C15—C111	1.534 (5)	C27—C28	1.382 (5)
C15—C117	1.542 (5)	C29—C210	1.387 (5)
C15—C16	1.518 (5)	C21—H21	0.9499
C16—C17	1.395 (5)	C21—H21'	0.9507
C16—C110	1.395 (5)	C22—H22"	0.9801
C17—C18	1.389 (6)	C22—H22'	0.9801
C19—C110	1.382 (5)	C22—H22	0.9791
C111—C112	1.388 (5)	C27—H27	0.9498
C11—H11'	0.9497	C28—H28	0.9505
C111—C116	1.388 (5)	C29—H29	0.9498
C11—H11	0.9510	C211—C212	1.395 (5)
C12—H12	0.9803	C211—C216	1.381 (5)
C12—H12'	0.9789	C212—C213	1.388 (5)
C112—C113	1.387 (5)	C213—C214	1.389 (5)
C12—H12"	0.9803	C214—C215	1.360 (5)
C113—C114	1.363 (5)	C215—C216	1.410 (5)
C114—C115	1.385 (5)	C217—C222	1.398 (5)
C115—C116	1.376 (5)	C217—C218	1.389 (5)
C17—H17	0.9505	C218—C219	1.403 (5)
C117—C122	1.380 (5)	C219—C220	1.377 (6)
C117—C118	1.406 (6)	C220—C221	1.364 (6)
C118—C119	1.385 (5)	C221—C222	1.387 (5)
C18—H18	0.9498	C210—H210	0.9499
C119—C120	1.363 (7)	C212—H212	0.9494
C19—H19	0.9503	C213—H213	0.9505
C120—C121	1.356 (6)	C214—H214	0.9500
C121—C122	1.412 (5)	C215—H215	0.9498
C110—H110	0.9502	C216—H216	0.9498
C112—H112	0.9502	C218—H218	0.9498
C113—H113	0.9495	C219—H219	0.9498
C114—H114	0.9496	C220—H220	0.9499
C115—H115	0.9489	C221—H221	0.9506
C116—H116	0.9508	C222—H222	0.9494
O11···C16	3.108 (4)	C222···C11^vi	3.569 (5)
O11···C17	2.989 (4)	C122···H213^ii	2.9485
O11···C111	2.800 (4)	C222···C212	3.203 (5)
O11···C112	3.285 (4)	C222···C27	3.371 (5)
O11···C116	3.393 (4)	C210···H114^v	2.8672
O11···C110^i	3.300 (4)	C211···H222	2.5727
O21···C27^ii	3.136 (4)	C211···H27	3.0799
O21···C26	3.094 (4)	C212···H222	2.8701
O21···C211	2.830 (4)	C213···H11'^vi	3.0089
O21···C216	3.277 (4)	C216···H27	3.0303
O21···C210	2.956 (4)	C217···H27	2.7580
O11···H12'	2.6241	C217···H212	2.9019
O11···H17	2.5270	C218···H115^vi	2.9372
O11···H110^i	2.4412	C219···H115^vi	2.9834
O11···H12"	2.8056	C220···H19^xii	2.9245
O12···H17	2.5137	C221···H216^vi	2.8195
O12···H122	2.4724	C222···H27	2.7744
O12···H11'	2.3433	H11···H122^iii	2.5105
O12···H116	2.6675	H11···H12	2.3658
O21···H22"	2.6836	H11'···O12	2.3433
O21···H210	2.4794	H11'···C213^ii	3.0089
O21···H22'	2.7125	H12···H11	2.3658
O21···H27^ii	2.2912	H12···H120^viii	2.5355
O22···H21'	2.3803	H12···N21	2.8647
O22···H210	2.5420	H12'···O11	2.6241
O22···H212	2.7014	H12"···O11	2.8056
O22···H218	2.4413	H12"···H120^viii	2.5379
N11···C210^iii	3.443 (5)	H17···C14	2.5207
N11···H22^iv	2.9252	H17···O11	2.5270
N11···H210^iii	2.6599	H17···O12	2.5137
N21···H12	2.8647	H18···H22"^iii	2.5689
N21···H113^v	2.9179	H19···H220^xiii	2.5778
N21···H114^v	2.9362	H19···C220^xiii	2.9245
C11···C221^ii	3.553 (6)	H21···H22	2.3795
C11···C222^ii	3.569 (5)	H21'···O22	2.3803
C14···C116	3.213 (5)	H21'···C115^vi	2.9655
C14···C17	3.100 (5)	H22···H21	2.3795
C16···O11	3.108 (4)	H22···N11^xiv	2.9252
C17···O11	2.989 (4)	H22'···O21	2.7125
C17···C14	3.100 (5)	H22'···H220^x	2.5179
C24···C210	3.086 (5)	H22"···H18^iii	2.5689
C24···C212	3.280 (5)	H22"···O21	2.6836
C26···O21	3.094 (4)	H27···C217	2.7580
C27···C216	3.157 (5)	H27···C211	3.0799
C27···C222	3.371 (5)	H27···C216	3.0303
C27···O21^vi	3.136 (4)	H27···C222	2.7744
C29···C114^v	3.370 (5)	H27···O21^vi	2.2912
C110···C112	3.175 (5)	H28···H120^viii	2.5991
C110···O11^vii	3.300 (4)	H28···C120^viii	2.9264
C110···C118	3.408 (5)	H110···C111	3.0897
C11···H122^iii	2.9863	H110···C117	2.7703
C111···O11	2.800 (4)	H110···C118	2.8126
C12···H120^viii	2.8330	H110···C112	3.0317
C112···C110	3.175 (5)	H110···O11^vii	2.4412
C112···C119^i	3.521 (6)	H110···H112	2.5992
C112···O11	3.285 (4)	H112···C110	2.5975
C114···C29^ix	3.370 (5)	H112···C16	2.5961
C114···C210^ix	3.578 (5)	H112···C119^i	2.8364
C14···H116	3.0968	H112···H110	2.5992
C14···H17	2.5207	H113···N21^ix	2.9179
C116···C14	3.213 (5)	H114···C29^ix	2.8062
C116···O11	3.393 (4)	H114···C210^ix	2.8672
C116···C118	3.196 (5)	H114···N21^ix	2.9362
C16···H112	2.5961	H114···C26^ix	3.0104
C18···H210^iii	2.8825	H114···C27^ix	3.0490
C118···C116	3.196 (5)	H114···C28^ix	3.0022
C118···C110	3.408 (5)	H115···C218^ii	2.9372
C119···C112^vii	3.521 (6)	H115···C219^ii	2.9834
C22···H220^x	2.9162	H116···O12	2.6675
C24···H210	2.5007	H116···C14	3.0968
C26···H216	2.5585	H116···C117	2.9006
C26···H114^v	3.0104	H118···C116	2.8783
C27···H114^v	3.0490	H118···C111	2.5663
C27···H216	2.5856	H120···H12^x	2.5355
C28···H114^v	3.0022	H120···C12^x	2.8330
C28···H120^viii	3.0991	H120···C28^x	3.0991
C29···H221^ii	3.0981	H120···H12"^x	2.5379
C29···H114^v	2.8062	H120···H28^x	2.5991
C210···N11^iii	3.443 (5)	H122···H11^iii	2.5105
C210···C114^v	3.578 (5)	H122···O12	2.4724
C210···O21	2.956 (4)	H122···C11^iii	2.9863
C110···H112	2.5975	H210···O21	2.4794
C210···C24	3.086 (5)	H210···O22	2.5420
C111···H110	3.0897	H210···C24	2.5007
C211···O21	2.830 (4)	H210···N11^iii	2.6599
C111···H118	2.5663	H210···C18^iii	2.8825
C212···C24	3.280 (5)	H212···O22	2.7014
C212···C222	3.203 (5)	H212···C217	2.9019
C112···H110	3.0317	H213···C121^vi	2.9912
C113···H214^xi	3.0097	H213···C122^vi	2.9485
C114···H214^xi	3.0716	H214···C113^xi	3.0097
C115···H21'^ii	2.9655	H214···C114^xi	3.0715
C116···H118	2.8783	H216···C26	2.5585
C216···O21	3.277 (4)	H216···C27	2.5856
C216···C27	3.157 (5)	H216···C221^ii	2.8195
C216···C221^ii	3.540 (5)	H218···O22	2.4413
C117···H110	2.7703	H218···H219^xv	2.5937
C117···H116	2.9006	H219···H218^xv	2.5937
C118···H110	2.8126	H220···C22^viii	2.9162
C119···H112^vii	2.8364	H220···H19^xii	2.5778
C120···H28^x	2.9264	H220···H22'^viii	2.5179
C221···C11^vi	3.553 (6)	H221···C29^vi	3.0981
C121···H213^ii	2.9912	H222···C211	2.5727
C221···C216^vi	3.540 (5)	H222···C212	2.8701
C14—O12—C15	119.1 (3)	C121—C122—H122	120.00
C24—O22—C25	118.8 (3)	C117—C122—H122	119.97
C18—N11—C19	116.2 (3)	C21—C23—C22	125.0 (4)
C28—N21—C29	115.9 (3)	C21—C23—C24	121.2 (3)
C11—C13—C14	120.5 (3)	C22—C23—C24	113.7 (3)
C11—C13—C12	125.1 (4)	O21—C24—O22	124.8 (3)
C12—C13—C14	114.4 (3)	O21—C24—C23	123.0 (3)
O11—C14—C13	122.7 (3)	O22—C24—C23	112.2 (3)
O12—C14—C13	112.9 (3)	O22—C25—C26	111.4 (3)
O11—C14—O12	124.4 (3)	O22—C25—C211	109.3 (3)
O12—C15—C117	102.3 (3)	O22—C25—C217	102.1 (3)
O12—C15—C16	111.2 (3)	C26—C25—C211	114.8 (3)
O12—C15—C111	109.0 (3)	C26—C25—C217	108.0 (3)
C111—C15—C117	109.8 (3)	C211—C25—C217	110.6 (3)
C16—C15—C117	108.7 (3)	C25—C26—C27	118.7 (3)
C16—C15—C111	115.1 (3)	C25—C26—C210	124.0 (3)
C17—C16—C110	117.5 (3)	C27—C26—C210	117.3 (3)
C15—C16—C110	119.0 (3)	C26—C27—C28	120.0 (3)
C15—C16—C17	123.6 (3)	N21—C28—C27	123.7 (3)
C16—C17—C18	118.5 (3)	N21—C29—C210	124.5 (3)
N11—C18—C17	124.4 (3)	C23—C21—H21'	120.00
N11—C19—C110	123.1 (3)	H21—C21—H21'	119.94
C16—C110—C19	120.3 (3)	C23—C21—H21	120.06
C112—C111—C116	117.6 (3)	C23—C22—H22"	109.43
H11—C11—H11'	119.94	H22—C22—H22'	109.53
C15—C111—C112	123.5 (3)	C23—C22—H22	109.48
C15—C111—C116	118.9 (3)	C23—C22—H22'	109.41
C13—C11—H11	119.95	H22'—C22—H22"	109.45
C13—C11—H11'	120.11	H22—C22—H22"	109.53
C13—C12—H12'	109.52	C26—C27—H27	119.92
C13—C12—H12"	109.41	C28—C27—H27	120.05
C13—C12—H12	109.40	C27—C28—H28	118.16
C111—C112—C113	121.1 (3)	N21—C28—H28	118.15
H12'—C12—H12"	109.55	N21—C29—H29	117.82
H12—C12—H12"	109.42	C210—C29—H29	117.72
H12—C12—H12'	109.52	C26—C210—C29	118.7 (3)
C112—C113—C114	120.6 (3)	C25—C211—C212	118.9 (3)
C113—C114—C115	119.2 (3)	C25—C211—C216	123.0 (3)
C114—C115—C116	120.4 (3)	C212—C211—C216	118.1 (3)
C111—C116—C115	121.2 (3)	C211—C212—C213	120.9 (3)
C18—C17—H17	120.65	C212—C213—C214	120.2 (3)
C16—C17—H17	120.81	C213—C214—C215	119.7 (3)
C118—C117—C122	117.4 (3)	C214—C215—C216	120.3 (3)
C15—C117—C118	122.2 (3)	C211—C216—C215	120.8 (3)
C15—C117—C122	120.2 (3)	C25—C217—C218	119.8 (3)
N11—C18—H18	117.77	C25—C217—C222	122.0 (3)
C17—C18—H18	117.82	C218—C217—C222	118.0 (3)
C117—C118—C119	120.6 (4)	C217—C218—C219	120.2 (3)
N11—C19—H19	118.41	C218—C219—C220	121.0 (4)
C118—C119—C120	121.7 (4)	C219—C220—C221	118.6 (3)
C110—C19—H19	118.49	C220—C221—C222	121.7 (4)
C119—C120—C121	118.3 (3)	C217—C222—C221	120.4 (3)
C120—C121—C122	121.8 (4)	C26—C210—H210	120.72
C117—C122—C121	120.0 (3)	C29—C210—H210	120.63
C19—C110—H110	119.91	C211—C212—H212	119.50
C16—C110—H110	119.83	C213—C212—H212	119.59
C113—C112—H112	119.44	C212—C213—H213	119.88
C111—C112—H112	119.50	C214—C213—H213	119.94
C112—C113—H113	119.78	C213—C214—H214	120.12
C114—C113—H113	119.67	C215—C214—H214	120.19
C113—C114—H114	120.42	C214—C215—H215	119.89
C115—C114—H114	120.39	C216—C215—H215	119.83
C114—C115—H115	119.78	C211—C216—H216	119.58
C116—C115—H115	119.80	C215—C216—H216	119.63
C115—C116—H116	119.38	C217—C218—H218	119.87
C111—C116—H116	119.44	C219—C218—H218	119.93
C117—C118—H118	119.70	C218—C219—H219	119.50
C119—C118—H118	119.67	C220—C219—H219	119.52
C118—C119—H119	119.21	C219—C220—H220	120.62
C120—C119—H119	119.10	C221—C220—H220	120.74
C121—C120—H120	120.87	C220—C221—H221	119.16
C119—C120—H120	120.83	C222—C221—H221	119.18
C120—C121—H121	119.15	C217—C222—H222	119.75
C122—C121—H121	119.01	C221—C222—H222	119.84
C15—O12—C14—O11	12.6 (5)	C15—C117—C118—H118	1.42
C15—O12—C14—C13	−168.5 (3)	C122—C117—C118—H118	175.21
C14—O12—C15—C16	−77.7 (4)	C15—C117—C122—H122	−2.21
C14—O12—C15—C111	50.3 (4)	H118—C118—C119—C120	−176.69
C14—O12—C15—C117	166.5 (3)	H118—C118—C119—H119	3.30
C25—O22—C24—C23	170.9 (3)	C117—C118—C119—H119	−176.71
C24—O22—C25—C26	75.5 (4)	H119—C119—C120—H120	−0.72
C24—O22—C25—C211	−52.4 (4)	C118—C119—C120—H120	179.27
C24—O22—C25—C217	−169.5 (3)	H119—C119—C120—C121	179.14
C25—O22—C24—O21	−10.7 (5)	H120—C120—C121—C122	179.96
C19—N11—C18—C17	1.1 (6)	C119—C120—C121—H121	179.91
C18—N11—C19—C110	−0.7 (5)	H120—C120—C121—H121	−0.23
C29—N21—C28—C27	1.4 (5)	H121—C121—C122—C117	178.42
C28—N21—C29—C210	−1.8 (5)	C120—C121—C122—H122	178.36
C11—C13—C14—O11	−176.9 (3)	H121—C121—C122—H122	−1.45
C11—C13—C14—O12	4.2 (5)	C21—C23—C24—O22	−5.3 (5)
C12—C13—C14—O12	−179.1 (3)	C22—C23—C24—O21	−1.3 (5)
C12—C13—C14—O11	−0.1 (5)	C21—C23—C24—O21	176.3 (3)
C117—C15—C111—C112	117.2 (4)	C22—C23—C24—O22	177.1 (3)
O12—C15—C111—C116	51.1 (4)	O22—C25—C26—C210	−12.0 (5)
C16—C15—C111—C112	−5.8 (5)	O22—C25—C26—C27	166.7 (3)
C117—C15—C16—C110	−55.1 (4)	C217—C25—C26—C27	55.4 (4)
O12—C15—C117—C122	42.7 (4)	C217—C25—C26—C210	−123.4 (4)
C16—C15—C111—C116	176.8 (3)	C26—C25—C211—C212	−178.4 (3)
C117—C15—C111—C116	−60.2 (4)	C217—C25—C211—C212	59.2 (4)
O12—C15—C117—C118	−143.7 (3)	O22—C25—C211—C216	129.7 (3)
O12—C15—C111—C112	−131.5 (3)	C211—C25—C26—C27	−68.5 (4)
C117—C15—C16—C17	122.9 (4)	C211—C25—C26—C210	112.8 (4)
C111—C15—C117—C118	−28.1 (5)	O22—C25—C217—C218	−41.1 (4)
O12—C15—C16—C110	−167.0 (3)	O22—C25—C211—C212	−52.4 (4)
C16—C15—C117—C122	−75.0 (4)	C26—C25—C217—C218	76.5 (4)
O12—C15—C16—C17	11.1 (5)	C211—C25—C217—C218	−157.2 (3)
C111—C15—C16—C110	68.5 (4)	O22—C25—C217—C222	144.6 (3)
C111—C15—C16—C17	−113.4 (4)	C26—C25—C211—C216	3.7 (5)
C16—C15—C117—C118	98.7 (4)	C217—C25—C211—C216	−118.7 (4)
C111—C15—C117—C122	158.3 (3)	C211—C25—C217—C222	28.4 (5)
C15—C16—C17—C18	−179.9 (3)	C26—C25—C217—C222	−97.9 (4)
C17—C16—C110—C19	2.2 (5)	C27—C26—C210—C29	1.3 (5)
C110—C16—C17—C18	−1.8 (5)	C25—C26—C210—C29	−180.0 (3)
C15—C16—C110—C19	−179.6 (3)	C25—C26—C27—C28	179.6 (3)
C16—C17—C18—N11	0.1 (6)	C210—C26—C27—C28	−1.6 (5)
N11—C19—C110—C16	−1.0 (6)	C26—C27—C28—N21	0.3 (6)
C15—C111—C116—H116	−4.30	N21—C29—C210—C26	0.5 (5)
C112—C111—C116—H116	178.16	C216—C211—C212—C213	2.0 (5)
C15—C111—C112—H112	3.53	C25—C211—C212—C213	−176.0 (3)
C116—C111—C112—H112	−179.05	C212—C211—C216—C215	−1.0 (5)
H112—C112—C113—C114	−178.95	C25—C211—C216—C215	176.9 (3)
H112—C112—C113—H113	1.05	C211—C212—C213—C214	−1.0 (5)
C111—C112—C113—H113	−178.91	C212—C213—C214—C215	−1.2 (5)
C112—C113—C114—H114	177.75	C213—C214—C215—C216	2.2 (5)
H113—C113—C114—H114	−2.25	C214—C215—C216—C211	−1.1 (5)
H113—C113—C114—C115	177.80	C25—C217—C218—C219	−177.8 (3)
C113—C114—C115—H115	−178.69	C222—C217—C218—C219	−3.2 (5)
H114—C114—C115—C116	−178.63	C25—C217—C222—C221	177.2 (3)
H114—C114—C115—H115	1.35	C218—C217—C222—C221	2.7 (5)
C114—C115—C116—H116	−179.24	C217—C218—C219—C220	1.6 (6)
H115—C115—C116—H116	0.77	C218—C219—C220—C221	0.6 (6)
H115—C115—C116—C111	−179.28	C219—C220—C221—C222	−1.1 (6)
C118—C117—C122—H122	−176.13	C220—C221—C222—C217	−0.6 (6)

Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x, −y+1, −z+1; (iv) x, y, z+1; (v) x−1/2, −y+1/2, z−1/2; (vi) −x+1/2, y−1/2, −z+1/2; (vii) −x+1/2, y+1/2, −z+3/2; (viii) x, y−1, z; (ix) x+1/2, −y+1/2, z+1/2; (x) x, y+1, z; (xi) −x+1, −y+1, −z+1; (xii) x, y−1, z−1; (xiii) x, y+1, z+1; (xiv) x, y, z−1; (xv) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11′···O12	0.9500	2.3400	2.693 (4)	101.00
C17—H17···O11	0.9500	2.5300	2.989 (4)	110.00
C21—H21′···O22	0.9500	2.3800	2.717 (4)	100.00
C27—H27···O21^vi	0.9500	2.2900	3.136 (4)	148.00
C110—H110···O11^vii	0.9500	2.4400	3.300 (4)	150.00
C210—H210···O21	0.9500	2.4800	2.956 (4)	111.00

Symmetry codes: (vi) −x+1/2, y−1/2, −z+1/2; (vii) −x+1/2, y+1/2, −z+3/2.