(E)-N²-{4-[(E)-2-(4-Chloro­benzoyl)­ethen­yl]-3-methyl-1-phenyl-1H-pyrazol-5-yl}-N¹,N¹-dimethyl­form­amid­ine: polarized mol­ecules within sheets of π-stacked hydrogen-bonded chains

The mol­ecules of the title compound, C₂₂H₂₁ClN₄O, are conformationally chiral, and in the space group P2₁2₁2₁ each crystal contains only one conformational enantio­mer. The intra­molecular dimensions provide evidence for polarization of the electronic structure. Mol­ecules are linked by a single C—H...π(arene) hydrogen bond into chains, which are themselves weakly linked into sheets by an aromatic π–π stacking inter­action.

S1. Comment

We are exploring the use of 5-amino-4-formylpyrazoles as building blocks in the synthesis of new heterocyclic compounds containing fused pyrazole ring systems, as such compounds have a wide range of potential applications (Elguero, 1984, 1996). In connection with this synthetic study, we report here the structure of the title compound, (I) (Fig. 1), which forms an interesting structure consisting of π-stacked hydrogen-bonded chains.

Compound (I) was prepared by base-catalysed condensation of 4'-chloroacetophenone with the intermediate (E)-N'-(4-formyl-3-methyl-1-phenyl-1H-pyrazol-5-yl)-N,N-dimethylformamidine, denoted (A) in the scheme, which itself had been prepared in a single step by reaction of the simple precursor 5-amino-3-methyl-1-phenylpyrazole with an excess of N,N-dimethylformamide and phosphorus(V) trichloride oxide, in a process which leads not only to formylation of the pyrazole ring at the hitherto-vacant 4-position, but also to conversion of the 5-amino group to a formamidine function by condensation with N,N-dimethylformamide.

The molecular conformation of (I) is conveniently considered in terms of the orientations of the various peripheral substituents relative to the central pyrazole ring, as defined by the relevant torsion angles (Table 1). Thus, while the chain between atoms C4 and C41 (Fig. 1) is nearly coplanar with the pyrazole ring, the two phenyl rings are both markedly twisted out of this plane: the dihedral angles between the pyrazole ring and the two aryl rings C11–C16 and C41–C46 are 25.1 (2) and 15.7 (2)°, respectively. Similarly, the dimethylaminomethine unit is significantly twisted out of the plane of the pyrazole ring. Consequently, the molecule of (I) has no internal symmetry and hence it is chiral. In space group P2₁2₁2₁, therefore, each crystal contains only a single conformational enantiomer. However, this has no chemical significance and it may be expected that, in solution for example, all accessible molecular conformations are populated in a dynamic equilibrium.

The intramolecular dimensions (Table 1) provide evidence for polarization of the electronic structure. The C47—O47 and C48—C49 bonds are both long for their types [mean values (Allen et al., 1987) 1.222 and 1.340 Å, respectively; upper quartile values 1.229 and 1.348 Å, respectively], while the C47—C48 and C4—C49 bonds are both short for their types (mean vales 1.464 and 1.455 Å respectively; lower quartile values 1.453 and 1.447 Å, respectively). In addition, the C52—N53 bond is significantly shorter than the N1—C5 bond. The C5—N51 and N51—C52 distances can be compared with the context-specific examples found in the series of simple Schiff bases, (II) (see scheme), where the substituent Ar represents a range of substituted phenyl, or exceptionally pyridyl, groups (Castillo et al., 2010). For the C5—N51 bond, 15 independent values in the series of compounds (II) range from 1.381 (4) to 1.401 (3) Å, all longer than the comparable bond in (I), while for the N51—C52 bond, the values in the series (II) span the range 1.268 (3) to 1.294 (3) Å, all shorter than the corresponding bond in (I). Similarly, in compound (III) [Cambridge Structural Database (CSD; Allen, 2002) refcode CIZQEH; Moreno-Fuquen et al., 1999), the distances corresponding to the C5—N51 and N51—C52 bonds in (I) are 1.383 (2) and 1.289 (2) Å, respectively. The conclusion to be drawn from all of these observations is that the polarized form (Ia) is a significant contributor to the overall electronic structure, in addition to the conventional form (I). Electronic polarization of this type is not possible in the series (II), nor in compound (III).

Despite the polarization of the electronic structure in (I), there are no hydrogen bonds involving the O atom as the acceptor. Instead, molecules related by translation are linked by a single C—H···π(arene) hydrogen bond (Table 2) into simple chains running parallel to the [010] direction (Fig. 2). These chains are weakly linked into sheets by an aromatic π–π stacking interaction. The unsubstituted phenyl ring C11–C16 in the molecule at (x, y, z) makes a dihedral angle of 13.4 (2)° with the substituted phenyl ring C41–C46 in the molecule at (-1 + x, 1 + y, z). The ring centroid separation is 3.867 (2) Å and the interplanar spacing is ca 3.8 Å. The effect of this interaction is to link the hydrogen-bonded chain, albeit weakly, into a sheet parallel to (001) (Fig. 2). Four sheets of this type pass through each unit cell, in the domains 0 < z < 1/4, 1/4 < z < 1/2, 1/2 < z < 3/4 and 3/4 < z < 1.0, respectively, but there are no direction-specific interactions between adjacent sheets.

It is of interest briefly to compare the supramolecular aggregation in (I) with that in the closely related amino-substituted analogues (III) (CSD refcode CIZQEH) and (IV) (CSD refcode YICWUD; Zhang et al., 2007). Neither of the original reports mentioned any intermolecular interactions, but analysis using the deposited atomic coordinates shows that in (III), molecules related by a 2₁ screw axis in space group P2₁/n are linked into chains along [010] by a single C—H···π(arene) hydrogen bond (Fig. 3), while in compound (IV), molecules related by translation are linked by two independent N—H···N hydrogen bonds into a C(7)C(7)[R¹₂(6)] (Bernstein et al., 1995) chain of rings along [100] (Fig. 4).

S2. Experimental

To a solution containing 1 mmol each of 4'-chloroacetophenone and (E)-N'-(4-formyl-3-methyl-1-phenyl-1H-pyrazol-5-yl)-N,N-dimethylformamidine, prepared from 5-amino-3-methyl-1-phenylpyrazole under Vilsmaier conditions (Häufel & Breitmaier, 1974), in absolute ethanol (10 ml), a catalytic quantity of sodium hydroxide (0.5 ml of a 30% w/v aqueous solution) was added, and the mixture was then stirred at room temperature for 2 h. The resulting solid product was collected by filtration and recrystallized by slow evaporation, at ambient temperature and in air, of a solution in ethanol, yielding crystals of (I) suitable for single-crystal X-ray diffraction. MS (70 eV) m/z (%): 392 (M⁺,100), 321 (11), 253 (44), 139 (43), 44 (16); HRMS, found: 392.1404; C₂₂H₂₁³⁵ClN₄O requires: 392.1404.

S3. Refinement

All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic and alkenyl) or 0.98 Å (methyl), and with U_iso(H) = kU_eq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms. The correct enantiomorph in the crystal selected for data collection was established by means of the Flack x parameter (Flack, 1983), x = -0.03 (9), and the Hooft y parameter (Hooft et al., 2008), y = 0.02 (7), calculated from 1620 Bijvoet pairs, equivalent to 99.1% coverage.

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A stereoview of part of the crystal structure of (I), showing the formation of a sheet parallel to (001) built from the π-stacking of hydrogen-bonded chains parallel to [010]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
	Fig. 3. A stereoview of part of the crystal structure of (III) (CSD refcode CIZQEH; Moreno-Fuquen et al., 1999), showing the formation of a hydrogen-bonded chain running parallel to the [010] direction. The deposited atomic coordinates have been used and, for the sake of clarity, H atoms not involved in the motif shown have been omitted.
	Fig. 4. A stereoview of part of the crystal structure of (IV) (CSD refcode YICWUD; Zhang et al., 2007), showing the formation of a hydrogen-bonded chain of rings running parallel to the [100] direction. The deposited atomic coordinates have been used and, for the sake of clarity, H atoms not involved in the motif shown have been omitted.

(E)-N²-{4-[(E)-2-(4-Chlorobenzoyl)ethenyl]-3-methyl- 1-phenyl-1H-pyrazol-5-yl}-N¹,N¹-dimethylformamidine

Crystal data

C22H21ClN4O	F(000) = 824
Mr = 392.88	Dx = 1.324 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3871 reflections
a = 8.2228 (3) Å	θ = 3.2–26.1°
b = 8.3506 (2) Å	µ = 0.21 mm^−1
c = 28.7043 (10) Å	T = 120 K
V = 1970.99 (11) Å^3	Block, colourless
Z = 4	0.12 × 0.06 × 0.06 mm

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	3871 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2849 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.082
Detector resolution: 9.091 pixels mm^-1	θmax = 26.1°, θmin = 3.2°
ϕ and ω scans	h = −10→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −8→10
Tmin = 0.978, Tmax = 0.987	l = −35→35
13638 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.056	H-atom parameters constrained
wR(F^2) = 0.134	w = 1/[σ^2(Fo^2) + (0.0461P)^2 + 0.2898P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
3871 reflections	Δρmax = 0.25 e Å^−3
256 parameters	Δρmin = −0.28 e Å^−3
0 restraints	Absolute structure: Flack (1983), with 1620 Bijvoet pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (9)

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

	x	y	z	Uiso*/Ueq
N1	0.5564 (4)	1.0206 (3)	0.41684 (9)	0.0250 (7)
N2	0.5913 (4)	0.9255 (3)	0.45538 (9)	0.0283 (7)
C3	0.6663 (4)	0.7989 (4)	0.43830 (11)	0.0270 (8)
C4	0.6819 (4)	0.8061 (4)	0.38857 (10)	0.0237 (7)
C5	0.6091 (4)	0.9523 (4)	0.37648 (10)	0.0226 (7)
C11	0.4718 (4)	1.1668 (4)	0.42500 (10)	0.0257 (8)
C12	0.4837 (5)	1.2967 (4)	0.39485 (11)	0.0308 (8)
H12	0.5493	1.2900	0.3677	0.037*
C13	0.3993 (5)	1.4354 (4)	0.40470 (12)	0.0368 (10)
H13	0.4064	1.5239	0.3840	0.044*
C14	0.3045 (5)	1.4475 (4)	0.44432 (12)	0.0348 (9)
H14	0.2468	1.5435	0.4508	0.042*
C15	0.2945 (5)	1.3192 (4)	0.47420 (12)	0.0349 (9)
H15	0.2300	1.3271	0.5015	0.042*
C16	0.3770 (5)	1.1794 (4)	0.46493 (11)	0.0318 (8)
H16	0.3691	1.0915	0.4858	0.038*
C31	0.7189 (5)	0.6694 (4)	0.47107 (11)	0.0374 (9)
H31A	0.6795	0.6937	0.5025	0.056*
H31B	0.8379	0.6631	0.4714	0.056*
H31C	0.6738	0.5667	0.4608	0.056*
C41	0.9566 (4)	0.2875 (4)	0.34752 (11)	0.0257 (8)
C42	0.9335 (5)	0.2233 (4)	0.39144 (11)	0.0306 (8)
H42	0.8665	0.2783	0.4131	0.037*
C43	1.0066 (5)	0.0795 (4)	0.40447 (11)	0.0307 (9)
H43	0.9880	0.0349	0.4344	0.037*
C44	1.1064 (5)	0.0036 (4)	0.37285 (12)	0.0284 (8)
Cl44	1.20021 (12)	−0.17507 (10)	0.38921 (3)	0.0366 (3)
C45	1.1357 (4)	0.0665 (4)	0.32902 (12)	0.0301 (9)
H45	1.2074	0.0139	0.3081	0.036*
C46	1.0592 (5)	0.2071 (4)	0.31624 (11)	0.0313 (9)
H46	1.0762	0.2497	0.2859	0.038*
C47	0.8720 (4)	0.4386 (4)	0.33153 (11)	0.0273 (8)
O47	0.8453 (3)	0.4586 (3)	0.28954 (8)	0.0350 (7)
C48	0.8263 (4)	0.5537 (4)	0.36722 (11)	0.0285 (8)
H48	0.8554	0.5331	0.3987	0.034*
C49	0.7437 (4)	0.6889 (4)	0.35703 (11)	0.0274 (8)
H49	0.7243	0.7084	0.3249	0.033*
N51	0.5738 (4)	1.0229 (3)	0.33425 (9)	0.0252 (7)
C52	0.6879 (5)	1.0237 (4)	0.30291 (10)	0.0260 (8)
H52	0.7903	0.9770	0.3100	0.031*
N53	0.6641 (4)	1.0890 (3)	0.26078 (9)	0.0309 (7)
C54	0.5089 (6)	1.1657 (5)	0.24972 (14)	0.0494 (11)
H54A	0.4635	1.2140	0.2780	0.074*
H54B	0.4330	1.0854	0.2376	0.074*
H54C	0.5263	1.2490	0.2262	0.074*
C55	0.7916 (5)	1.0957 (4)	0.22658 (12)	0.0431 (10)
H55A	0.8890	1.0428	0.2388	0.065*
H55B	0.8167	1.2077	0.2194	0.065*
H55C	0.7561	1.0410	0.1981	0.065*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0270 (18)	0.0222 (14)	0.0257 (14)	−0.0009 (13)	−0.0006 (13)	0.0028 (11)
N2	0.0319 (19)	0.0255 (14)	0.0276 (14)	−0.0021 (14)	−0.0025 (13)	0.0015 (13)
C3	0.031 (2)	0.0220 (17)	0.0286 (17)	0.0019 (16)	−0.0025 (16)	0.0015 (14)
C4	0.0199 (19)	0.0230 (16)	0.0282 (16)	−0.0009 (15)	−0.0029 (15)	0.0002 (15)
C5	0.0197 (19)	0.0236 (16)	0.0246 (17)	−0.0037 (15)	−0.0019 (15)	−0.0031 (14)
C11	0.023 (2)	0.0249 (17)	0.0288 (17)	0.0003 (17)	−0.0033 (15)	−0.0026 (14)
C12	0.035 (2)	0.0265 (18)	0.0306 (17)	0.0023 (17)	0.0042 (17)	−0.0008 (15)
C13	0.044 (3)	0.0302 (19)	0.036 (2)	0.005 (2)	0.0017 (18)	0.0034 (16)
C14	0.037 (2)	0.0270 (19)	0.040 (2)	0.0108 (19)	−0.0007 (19)	−0.0018 (16)
C15	0.037 (2)	0.0351 (19)	0.0324 (18)	0.004 (2)	0.0053 (17)	−0.0038 (16)
C16	0.033 (2)	0.0283 (17)	0.0339 (18)	−0.0002 (18)	0.0023 (17)	0.0032 (16)
C31	0.053 (3)	0.0285 (18)	0.0305 (18)	0.009 (2)	−0.0071 (18)	0.0012 (15)
C41	0.023 (2)	0.0227 (17)	0.0315 (17)	0.0007 (16)	−0.0045 (16)	−0.0022 (14)
C42	0.037 (2)	0.0264 (17)	0.0284 (18)	0.0002 (17)	−0.0006 (18)	−0.0034 (14)
C43	0.033 (2)	0.0298 (18)	0.0291 (18)	0.0038 (18)	−0.0012 (16)	0.0045 (15)
C44	0.025 (2)	0.0240 (17)	0.0362 (19)	0.0015 (16)	−0.0082 (17)	−0.0008 (15)
Cl44	0.0387 (6)	0.0276 (5)	0.0436 (5)	0.0081 (4)	−0.0044 (4)	0.0018 (4)
C45	0.026 (2)	0.0255 (18)	0.039 (2)	0.0034 (17)	0.0032 (17)	−0.0004 (16)
C46	0.034 (2)	0.0299 (18)	0.0300 (18)	0.0041 (18)	0.0015 (17)	0.0025 (14)
C47	0.025 (2)	0.0243 (18)	0.0329 (19)	−0.0027 (16)	−0.0002 (16)	0.0037 (15)
O47	0.0417 (19)	0.0358 (13)	0.0275 (13)	0.0100 (13)	−0.0010 (12)	0.0047 (11)
C48	0.032 (2)	0.0264 (18)	0.0267 (17)	0.0016 (17)	−0.0023 (16)	0.0008 (14)
C49	0.030 (2)	0.0260 (18)	0.0266 (17)	−0.0026 (17)	−0.0021 (15)	0.0039 (15)
N51	0.0269 (19)	0.0233 (15)	0.0255 (14)	0.0028 (13)	−0.0030 (14)	0.0027 (11)
C52	0.031 (2)	0.0209 (17)	0.0255 (17)	−0.0042 (17)	−0.0027 (17)	−0.0017 (13)
N53	0.032 (2)	0.0331 (16)	0.0281 (15)	0.0010 (15)	−0.0032 (13)	0.0056 (13)
C54	0.045 (3)	0.058 (2)	0.045 (2)	0.003 (2)	−0.009 (2)	0.0214 (19)
C55	0.061 (3)	0.039 (2)	0.0293 (19)	−0.001 (2)	0.008 (2)	0.0005 (17)

Geometric parameters (Å, º)

N1—N2	1.392 (3)	C42—H42	0.9500
N2—C3	1.318 (4)	C43—C44	1.378 (5)
C3—C4	1.434 (4)	C43—H43	0.9500
C4—C5	1.404 (4)	C44—C45	1.385 (5)
C5—N1	1.362 (4)	C44—Cl44	1.744 (3)
N1—C11	1.425 (4)	C45—C46	1.381 (5)
C3—C31	1.497 (4)	C45—H45	0.9500
C4—C49	1.427 (4)	C46—H46	0.9500
C11—C16	1.390 (5)	C47—O47	1.236 (4)
C11—C12	1.391 (4)	C47—C48	1.454 (4)
C12—C13	1.379 (5)	C48—C49	1.350 (5)
C12—H12	0.9500	C48—H48	0.9500
C13—C14	1.382 (5)	C49—H49	0.9500
C13—H13	0.9500	C5—N51	1.379 (4)
C14—C15	1.375 (5)	N51—C52	1.300 (4)
C14—H14	0.9500	C52—N53	1.341 (4)
C15—C16	1.376 (5)	C52—H52	0.9500
C15—H15	0.9500	N53—C55	1.438 (5)
C16—H16	0.9500	N53—C54	1.463 (5)
C31—H31A	0.9800	C54—H54A	0.9800
C31—H31B	0.9800	C54—H54B	0.9800
C31—H31C	0.9800	C54—H54C	0.9800
C41—C42	1.383 (4)	C55—H55A	0.9800
C41—C46	1.403 (5)	C55—H55B	0.9800
C41—C47	1.512 (5)	C55—H55C	0.9800
C42—C43	1.394 (5)
C5—N1—N2	111.8 (2)	C43—C42—H42	119.4
C5—N1—C11	130.8 (3)	C44—C43—C42	118.4 (3)
N2—N1—C11	117.3 (2)	C44—C43—H43	120.8
C3—N2—N1	105.0 (2)	C42—C43—H43	120.8
N2—C3—C4	112.2 (3)	C43—C44—C45	121.9 (3)
N2—C3—C31	118.7 (3)	C43—C44—Cl44	118.7 (3)
C4—C3—C31	129.0 (3)	C45—C44—Cl44	119.5 (3)
C5—C4—C49	126.3 (3)	C46—C45—C44	119.0 (3)
C5—C4—C3	104.1 (3)	C46—C45—H45	120.5
C49—C4—C3	129.4 (3)	C44—C45—H45	120.5
N1—C5—N51	120.1 (3)	C45—C46—C41	120.7 (3)
N1—C5—C4	106.8 (3)	C45—C46—H46	119.6
N51—C5—C4	132.8 (3)	C41—C46—H46	119.6
C16—C11—C12	119.5 (3)	O47—C47—C48	123.5 (3)
C16—C11—N1	118.3 (3)	O47—C47—C41	119.4 (3)
C12—C11—N1	122.2 (3)	C48—C47—C41	117.2 (3)
C13—C12—C11	119.5 (3)	C49—C48—C47	122.0 (3)
C13—C12—H12	120.3	C49—C48—H48	119.0
C11—C12—H12	120.3	C47—C48—H48	119.0
C12—C13—C14	120.9 (3)	C48—C49—C4	128.0 (3)
C12—C13—H13	119.6	C48—C49—H49	116.0
C14—C13—H13	119.6	C4—C49—H49	116.0
C15—C14—C13	119.4 (3)	C52—N51—C5	117.3 (3)
C15—C14—H14	120.3	N51—C52—N53	121.4 (3)
C13—C14—H14	120.3	N51—C52—H52	119.3
C14—C15—C16	120.7 (3)	N53—C52—H52	119.3
C14—C15—H15	119.6	C52—N53—C55	121.7 (3)
C16—C15—H15	119.6	C52—N53—C54	120.1 (3)
C15—C16—C11	120.0 (3)	C55—N53—C54	118.1 (3)
C15—C16—H16	120.0	N53—C54—H54A	109.5
C11—C16—H16	120.0	N53—C54—H54B	109.5
C3—C31—H31A	109.5	H54A—C54—H54B	109.5
C3—C31—H31B	109.5	N53—C54—H54C	109.5
H31A—C31—H31B	109.5	H54A—C54—H54C	109.5
C3—C31—H31C	109.5	H54B—C54—H54C	109.5
H31A—C31—H31C	109.5	N53—C55—H55A	109.5
H31B—C31—H31C	109.5	N53—C55—H55B	109.5
C42—C41—C46	118.7 (3)	H55A—C55—H55B	109.5
C42—C41—C47	122.5 (3)	N53—C55—H55C	109.5
C46—C41—C47	118.8 (3)	H55A—C55—H55C	109.5
C41—C42—C43	121.3 (3)	H55B—C55—H55C	109.5
C41—C42—H42	119.4
C5—N1—N2—C3	0.2 (4)	C12—C11—C16—C15	0.6 (5)
C11—N1—N2—C3	179.1 (3)	N1—C11—C16—C15	179.5 (3)
N1—N2—C3—C4	−0.4 (4)	C46—C41—C42—C43	−1.6 (5)
N1—N2—C3—C31	−179.0 (3)	C47—C41—C42—C43	176.7 (3)
N2—C3—C4—C5	0.4 (4)	C41—C42—C43—C44	1.5 (5)
C31—C3—C4—C5	178.9 (4)	C42—C43—C44—C45	0.2 (5)
N2—C3—C4—C49	−174.8 (3)	C42—C43—C44—Cl44	179.2 (3)
C31—C3—C4—C49	3.7 (6)	C43—C44—C45—C46	−1.8 (5)
N2—N1—C5—N51	174.8 (3)	Cl44—C44—C45—C46	179.2 (3)
C11—N1—C5—N51	−3.9 (5)	C44—C45—C46—C41	1.7 (5)
N2—N1—C5—C4	0.0 (4)	C42—C41—C46—C45	−0.1 (5)
C11—N1—C5—C4	−178.7 (3)	C47—C41—C46—C45	−178.4 (3)
C49—C4—C5—N1	175.2 (3)	C42—C41—C47—O47	−152.6 (4)
C3—C4—C5—N1	−0.2 (4)	C46—C41—C47—O47	25.7 (5)
C49—C4—C5—N51	1.3 (6)	C3—C4—C49—C48	−11.8 (6)
C3—C4—C5—N51	−174.1 (4)	C4—C49—C48—C47	175.5 (3)
C5—N1—C11—C16	154.5 (3)	C49—C48—C47—C41	−176.9 (3)
N2—N1—C11—C16	−24.1 (4)	C48—C47—C41—C42	27.4 (5)
C5—N1—C11—C12	−26.6 (6)	C46—C41—C47—C48	−154.4 (3)
N2—N1—C11—C12	154.8 (3)	O47—C47—C48—C49	3.1 (6)
C16—C11—C12—C13	−0.9 (5)	C5—C4—C49—C48	174.0 (4)
N1—C11—C12—C13	−179.8 (3)	N1—C5—N51—C52	139.7 (3)
C11—C12—C13—C14	0.6 (6)	C4—C5—N51—C52	−47.1 (5)
C12—C13—C14—C15	0.0 (6)	C5—N51—C52—N53	179.7 (3)
C13—C14—C15—C16	−0.3 (6)	N51—C52—N53—C54	1.9 (5)
C14—C15—C16—C11	0.1 (6)	N51—C52—N53—C55	177.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C52—H52···Cg1^i	0.95	2.83	3.432 (4)	122

Symmetry code: (i) x, y+1, z.