5-Meth­oxy-2-[(5-meth­oxy-1H-indol-1-yl)carbon­yl]-1H-indole

Attia, M.I.; El-Brollosy, N.R.; El-Emam, A.A.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536812020399

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1775

doi:10.1107/S1600536812020399

Open

access

5-Methoxy-2-[(5-methoxy-1H-indol-1-yl)carbonyl]-1H-indole

Mohamed I. Attia,^a ‡ Nasser R. El-Brollosy,^a Ali A. El-Emam,^a Seik Weng Ng ^b,^c and Edward R. T. Tiekink ^b ^*

^aDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 4 May 2012; accepted 7 May 2012; online 19 May 2012)

The asymmetric unit of the title compound, C₁₉H₁₆N₂O₃, comprises three independent molecules (A, B and C). The inversion-related molecule of A is virtually superimposable upon the other two molecules. In each molecule, there is a twist in the link between the approximately syn carbonyl and amine groups [the N—C—C—O torsion angles range from 19.73 (19) to −21.2 (2)°]. Each molecule has a bent shape quantified in terms of the dihedral angle between the indole and indole fused-ring systems [range = 45.69 (5)–47.91 (5)°]. In the crystal, the A and B molecules form dimeric aggregates via ten-membered {⋯HNC₂O}₂ synthons, while the C molecules self-associate similarly but about a centre of inversion.

Related literature

For background to melatonin and melatonin preparations, see: Barrenetxe et al. (2004 ); Williamson et al. (1998 ). For background to melatonin receptor ligands, see: Bedini et al. (2006 ); Attia et al. (2008 ). For a related structure, see: Attia et al. (2012 ).

Experimental

Crystal data

C₁₉H₁₆N₂O₃
M_r = 320.34
Triclinic, $[P \overline 1]$
a = 11.3153 (4) Å
b = 12.1183 (5) Å
c = 17.1300 (6) Å
α = 76.251 (3)°
β = 79.747 (3)°
γ = 88.913 (3)°
V = 2244.50 (15) Å³
Z = 6
Cu Kα radiation
μ = 0.80 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.02 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.367, T_max = 1.000
17372 measured reflections
9182 independent reflections
7534 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.121
S = 1.02
9182 reflections
661 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯O5	0.91 (2)	1.98 (2)	2.8536 (16)	159 (2)
N3—H3n⋯O2	0.91 (2)	1.97 (2)	2.8384 (16)	159.0 (19)
N5—H5n⋯O8ⁱ	0.90 (2)	2.00 (2)	2.8796 (15)	163.9 (19)
Symmetry code: (i) -x+2, -y, -z+1.

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ), Qmol (Gans & Shalloway, 2001 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812020399/su2424sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812020399/su2424Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812020399/su2424Isup3.cml

checkCIF report

Comment top

Melatonin (N-acetyl-5-methoxytryptamine, MLT) is primarily produced by the pineal gland in the brain with a marked circadian rhythm normally peaking in the dark to regulate sleep patterns (Barrenetxe et al., 2004). It has been reported that commercial melatonin preparations contain N-{2-[1-({3-[2-(acetylamino)ethyl]-5-methoxy-1H-indol-2-yl}-methyl)-5-methoxy-1H-indol-3-yl]ethyl}acetamide (1) as a contaminant (Williamson et al., 1998). The title compound, namely (5-methoxy-1H-indol-1-yl)(5-methoxy-1H-indol-2-yl)methanone (I), can be elaborated to give compound 1, in four steps. The synthesis of compound 1 on a preparative scale is required for the development of an analytical method for the determination of MLT in the presence of this contaminant in commercial MLT preparations. Herein, the crystal and molecular structure of the title compound (I) is described in continuation of on-going studies of melatonin receptor ligands (Bedini et al., 2006; Attia et al., 2008; Attia et al., 2012).

Three crystallographically independent molecules comprises the asymmetric unit of the title compound (I), Fig. 1. In each molecule there is a twist in the link between the carbonyl and amine groups but, each of these is approximately syn with the N1—C9—C10—O2, N3—C28—C29—O5 and N5—C47—C48—O8 torsion angles being 19.73 (19), -20.34 (19) and -21.2 (2)°, respectively. Each molecule has a bent shape quantified in terms of the dihedral angle between the indole and indonyl fused ring systems. For the N1-containing molecule this angle is 45.69 (5)° which compares to 45.86 (5) and 47.91 (5)° in the other two molecules. If the inversion-related N1-containing molecule is overlapped with the N2- and N3-containing molecules, it can be seen that all three molecules are virtually superimposable, as shown in Fig. 2. The major differences are apparent in the relative orientations of the terminal methoxy groups of the indonyl rings. In the N1- and N-3 containing molecules, the methyl group is orientated in almost the opposite direction to that seen in the N2-containing molecule. Further, in the N3-containing molecule, the methoxy group is slightly twisted out of the plane of the benzene ring to which it is connected. This is quantified in the values of the C16—C17—O3—C19, C35—C36—O6—C37 and C54—C55—O9—C57 torsion angles of -179.18 (14), 0.06 (2) and 168.68 (13)°, respectively.

In the crystal, the N1- and N2-containing molecules associate via N—H···O(carbonyl) hydrogen bonds to form dimeric aggregates via 10-membered {···HNC₂O}₂ synthons, Fig. 3. The N3-containing molecules self-associate similarly but about a centre of inversion. Molecules assemble into a three-dimensional architecture via π—π interactions with the closest of these occurring between five-membered (N2,C11–C14) and six-membered C32–C37 rings [inter-centroid distance = 3.5307 (9) Å for symmetry operation (i) = -x+1, -y+1, -z+1].

Related literature top

For background to melatonin and melatonin preparations, see: Barrenetxe et al. (2004); Williamson et al. (1998). For background to melatonin receptor ligands, see: Bedini et al. (2006); Attia et al. (2008). For a related structure, see: Attia et al. (2012).

Experimental top

A mixture of (5-methoxy-2,3-dihydro-1H-indol-1-yl)(5-methoxy-1H-indol-2-yl)- methanone (0.20 g, 0.62 mmol) and 2,3-dichloro-5,6-dicyanobenzoquinone (0.19 g, 0.68 mmol) in ethyl acetate (30 ml) was heated at reflux temperature for 18 h. The reaction mixture was evaporated under reduced pressure and the residue was purified by silica gel chromatography (chloroform/methanol/ammonia, 10:1:0.1) to furnish 0.19 g (96%) of (5-methoxy-1H-indol-1-yl)(5-methoxy-1H-indol-2-yl)methanone as a light-red powder which was recrystallized from ethanol to give colourless crystals of the title compound (I); M.pt: 451–452 K.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997), Qmol (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound (I), showing the atom-labelling and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Overlay diagram of the N1- (red), N3- (green) and N5- (blue) containing molecules in (I) aligned so that the central amide residues are coincident.
	Fig. 3. A view of a dimeric aggregate in (I) sustained by N—H···O hydrogen bonds, shown as blue dashed lines.

5-Methoxy-2-[(5-methoxy-1H-indol-1-yl)carbonyl]-1H-indole top

Crystal data top

C₁₉H₁₆N₂O₃	Z = 6
M_r = 320.34	F(000) = 1008
Triclinic, P1	D_x = 1.422 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 11.3153 (4) Å	Cell parameters from 7164 reflections
b = 12.1183 (5) Å	θ = 2.7–76.2°
c = 17.1300 (6) Å	µ = 0.80 mm⁻¹
α = 76.251 (3)°	T = 100 K
β = 79.747 (3)°	Plate, colourless
γ = 88.913 (3)°	0.30 × 0.20 × 0.02 mm
V = 2244.50 (15) Å³

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	9182 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	7534 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.029
Detector resolution: 10.4041 pixels mm^-1	θ_max = 76.4°, θ_min = 2.7°
ω scan	h = −14→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −10→15
T_min = 0.367, T_max = 1.000	l = −21→21
17372 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0672P)² + 0.3331P] where P = (F_o² + 2F_c²)/3
9182 reflections	(Δ/σ)_max < 0.001
661 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₉H₁₆N₂O₃	γ = 88.913 (3)°
M_r = 320.34	V = 2244.50 (15) Å³
Triclinic, P1	Z = 6
a = 11.3153 (4) Å	Cu Kα radiation
b = 12.1183 (5) Å	µ = 0.80 mm⁻¹
c = 17.1300 (6) Å	T = 100 K
α = 76.251 (3)°	0.30 × 0.20 × 0.02 mm
β = 79.747 (3)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	9182 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	7534 reflections with I > 2σ(I)
T_min = 0.367, T_max = 1.000	R_int = 0.029
17372 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.28 e Å⁻³
9182 reflections	Δρ_min = −0.30 e Å⁻³
661 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.87563 (11)	0.89787 (9)	0.11597 (6)	0.0252 (2)
O2	0.71161 (10)	0.56194 (8)	0.59096 (7)	0.0228 (2)
O3	0.72114 (11)	0.68238 (10)	0.93945 (7)	0.0270 (2)
O4	0.45990 (10)	0.07927 (9)	0.91666 (6)	0.0247 (2)
O5	0.59785 (10)	0.42667 (8)	0.44330 (6)	0.0220 (2)
O6	0.62516 (11)	0.29566 (9)	0.09143 (6)	0.0261 (2)
O7	0.92792 (11)	0.40367 (9)	0.10246 (7)	0.0279 (2)
O8	0.91510 (10)	0.07096 (8)	0.57278 (7)	0.0252 (2)
O9	0.81693 (11)	0.19031 (9)	0.92812 (7)	0.0278 (2)
N1	0.71116 (11)	0.64193 (10)	0.42505 (8)	0.0187 (2)
N2	0.71456 (10)	0.74048 (9)	0.61092 (7)	0.0173 (2)
N3	0.60355 (11)	0.34591 (10)	0.60844 (7)	0.0178 (2)
N4	0.60440 (10)	0.24863 (9)	0.42172 (7)	0.0165 (2)
N5	0.97901 (11)	0.14977 (10)	0.40478 (8)	0.0210 (2)
N6	0.91034 (11)	0.24988 (9)	0.59292 (8)	0.0192 (2)
C1	0.92781 (15)	1.00741 (13)	0.10623 (9)	0.0258 (3)
H1A	0.9528	1.0425	0.0479	0.039*
H1B	0.9979	1.0000	0.1333	0.039*
H1C	0.8686	1.0551	0.1308	0.039*
C2	0.74608 (12)	0.69609 (11)	0.34483 (9)	0.0178 (3)
C3	0.73470 (13)	0.66026 (12)	0.27422 (9)	0.0206 (3)
H3A	0.6974	0.5894	0.2774	0.025*
C4	0.78003 (13)	0.73241 (12)	0.20039 (9)	0.0214 (3)
H4	0.7735	0.7108	0.1515	0.026*
C5	0.83610 (13)	0.83791 (12)	0.19513 (9)	0.0208 (3)
C6	0.84677 (12)	0.87432 (11)	0.26392 (9)	0.0183 (3)
H6	0.8838	0.9456	0.2599	0.022*
C7	0.80051 (12)	0.80150 (11)	0.34081 (9)	0.0174 (3)
C8	0.79569 (12)	0.80978 (11)	0.42263 (9)	0.0176 (3)
H8	0.8252	0.8714	0.4397	0.021*
C9	0.73965 (12)	0.71070 (11)	0.47286 (9)	0.0174 (3)
C10	0.72046 (12)	0.66481 (11)	0.56109 (9)	0.0175 (3)
C11	0.67545 (12)	0.85333 (11)	0.59257 (9)	0.0187 (3)
H11	0.6628	0.8947	0.5403	0.022*
C12	0.65860 (13)	0.89380 (11)	0.66068 (9)	0.0193 (3)
H12	0.6327	0.9677	0.6644	0.023*
C13	0.68686 (12)	0.80492 (11)	0.72678 (9)	0.0180 (3)
C14	0.72090 (12)	0.71065 (11)	0.69460 (9)	0.0171 (3)
C15	0.75692 (12)	0.61024 (11)	0.74267 (9)	0.0194 (3)
H15	0.7817	0.5472	0.7203	0.023*
C16	0.75493 (13)	0.60653 (12)	0.82426 (9)	0.0213 (3)
H16	0.7789	0.5394	0.8586	0.026*
C17	0.71818 (13)	0.69985 (13)	0.85763 (9)	0.0210 (3)
C18	0.68459 (13)	0.79993 (12)	0.80932 (9)	0.0204 (3)
H18	0.6607	0.8632	0.8316	0.024*
C19	0.68398 (19)	0.77366 (16)	0.97647 (11)	0.0368 (4)
H19A	0.6901	0.7517	1.0345	0.055*
H19B	0.6005	0.7915	0.9711	0.055*
H19C	0.7357	0.8407	0.9493	0.055*
C20	0.39862 (14)	−0.02612 (13)	0.92700 (9)	0.0248 (3)
H20A	0.3792	−0.0634	0.9853	0.037*
H20B	0.4501	−0.0751	0.8982	0.037*
H20C	0.3243	−0.0124	0.9047	0.037*
C21	0.57271 (12)	0.29019 (11)	0.68871 (9)	0.0172 (3)
C22	0.58362 (13)	0.32549 (11)	0.75945 (9)	0.0189 (3)
H22	0.6169	0.3981	0.7564	0.023*
C23	0.54416 (13)	0.25078 (12)	0.83326 (9)	0.0204 (3)
H23	0.5508	0.2721	0.8822	0.024*
C24	0.49362 (13)	0.14248 (12)	0.83807 (9)	0.0187 (3)
C25	0.48224 (12)	0.10716 (11)	0.76895 (8)	0.0175 (3)
H25	0.4480	0.0347	0.7726	0.021*
C26	0.52316 (12)	0.18238 (11)	0.69255 (8)	0.0166 (3)
C27	0.52691 (12)	0.17516 (11)	0.61035 (8)	0.0169 (3)
H27	0.4999	0.1127	0.5930	0.020*
C28	0.57739 (12)	0.27657 (11)	0.56054 (8)	0.0166 (3)
C29	0.59421 (12)	0.32370 (11)	0.47242 (8)	0.0172 (3)
C30	0.64991 (13)	0.13806 (11)	0.43902 (9)	0.0191 (3)
H30	0.6616	0.0964	0.4914	0.023*
C31	0.67440 (12)	0.10014 (11)	0.36993 (9)	0.0191 (3)
H31	0.7052	0.0279	0.3656	0.023*
C32	0.64556 (12)	0.18867 (11)	0.30381 (9)	0.0176 (3)
C33	0.60260 (12)	0.28048 (11)	0.33724 (8)	0.0163 (3)
C34	0.56364 (12)	0.37893 (11)	0.28954 (9)	0.0179 (3)
H34	0.5332	0.4398	0.3127	0.022*
C35	0.57070 (12)	0.38537 (12)	0.20640 (9)	0.0193 (3)
H35	0.5448	0.4517	0.1723	0.023*
C36	0.61554 (13)	0.29522 (12)	0.17255 (9)	0.0201 (3)
C37	0.65297 (12)	0.19634 (12)	0.22104 (9)	0.0197 (3)
H37	0.6830	0.1353	0.1979	0.024*
C38	0.58807 (15)	0.39437 (14)	0.03902 (9)	0.0278 (3)
H38A	0.5994	0.3840	−0.0168	0.042*
H38B	0.6362	0.4603	0.0400	0.042*
H38C	0.5030	0.4070	0.0578	0.042*
C39	0.87551 (14)	0.51225 (13)	0.09507 (10)	0.0265 (3)
H39A	0.8735	0.5466	0.0374	0.040*
H39B	0.9234	0.5611	0.1163	0.040*
H39C	0.7935	0.5040	0.1264	0.040*
C40	0.97262 (12)	0.20264 (12)	0.32586 (9)	0.0204 (3)
C41	1.00957 (13)	0.16588 (12)	0.25382 (10)	0.0226 (3)
H41	1.0455	0.0942	0.2548	0.027*
C42	0.99184 (13)	0.23744 (12)	0.18191 (10)	0.0240 (3)
H42	1.0165	0.2149	0.1321	0.029*
C43	0.93764 (13)	0.34427 (12)	0.18016 (10)	0.0227 (3)
C44	0.90086 (12)	0.38164 (12)	0.25020 (9)	0.0205 (3)
H44	0.8648	0.4534	0.2484	0.025*
C45	0.91865 (12)	0.30930 (11)	0.32534 (9)	0.0192 (3)
C46	0.89379 (12)	0.31841 (12)	0.40774 (9)	0.0203 (3)
H46	0.8577	0.3807	0.4269	0.024*
C47	0.93202 (12)	0.21964 (12)	0.45500 (9)	0.0200 (3)
C48	0.91909 (12)	0.17394 (12)	0.54301 (9)	0.0202 (3)
C49	0.96108 (13)	0.36113 (11)	0.57014 (10)	0.0216 (3)
H49	0.9899	0.4022	0.5156	0.026*
C50	0.96235 (13)	0.40024 (11)	0.63750 (9)	0.0213 (3)
H50	0.9916	0.4728	0.6384	0.026*
C51	0.91153 (12)	0.31241 (11)	0.70786 (9)	0.0196 (3)
C52	0.87999 (12)	0.22017 (11)	0.67885 (9)	0.0189 (3)
C53	0.82490 (12)	0.12172 (12)	0.73196 (10)	0.0214 (3)
H53	0.8014	0.0602	0.7121	0.026*
C54	0.80601 (13)	0.11751 (12)	0.81456 (10)	0.0227 (3)
H54	0.7683	0.0517	0.8521	0.027*
C55	0.84108 (13)	0.20794 (12)	0.84477 (9)	0.0223 (3)
C56	0.89355 (13)	0.30686 (12)	0.79158 (9)	0.0212 (3)
H56	0.9164	0.3686	0.8115	0.025*
C57	0.86969 (15)	0.26861 (13)	0.96288 (10)	0.0278 (3)
H57A	0.8459	0.2471	1.0225	0.042*
H57B	0.8421	0.3453	0.9419	0.042*
H57C	0.9574	0.2673	0.9482	0.042*
H1n	0.671 (2)	0.5735 (19)	0.4445 (14)	0.038 (6)*
H3n	0.6380 (19)	0.4170 (18)	0.5893 (13)	0.028 (5)*
H5n	1.0089 (19)	0.0807 (18)	0.4222 (13)	0.027 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0359 (6)	0.0214 (5)	0.0176 (5)	0.0048 (4)	−0.0031 (4)	−0.0048 (4)
O2	0.0308 (5)	0.0136 (5)	0.0236 (5)	0.0013 (4)	−0.0054 (4)	−0.0034 (4)
O3	0.0347 (6)	0.0282 (5)	0.0183 (5)	0.0064 (4)	−0.0064 (4)	−0.0054 (4)
O4	0.0347 (6)	0.0228 (5)	0.0152 (5)	−0.0044 (4)	−0.0024 (4)	−0.0032 (4)
O5	0.0316 (5)	0.0128 (4)	0.0210 (5)	0.0020 (4)	−0.0047 (4)	−0.0032 (4)
O6	0.0355 (6)	0.0267 (5)	0.0155 (5)	0.0019 (4)	−0.0026 (4)	−0.0053 (4)
O7	0.0359 (6)	0.0227 (5)	0.0237 (6)	0.0047 (4)	−0.0032 (4)	−0.0044 (4)
O8	0.0305 (5)	0.0130 (5)	0.0295 (6)	0.0030 (4)	−0.0019 (4)	−0.0028 (4)
O9	0.0310 (6)	0.0265 (5)	0.0225 (5)	−0.0047 (4)	−0.0003 (4)	−0.0020 (4)
N1	0.0203 (5)	0.0151 (5)	0.0213 (6)	0.0019 (4)	−0.0028 (4)	−0.0063 (4)
N2	0.0203 (5)	0.0134 (5)	0.0172 (6)	0.0025 (4)	−0.0018 (4)	−0.0032 (4)
N3	0.0220 (6)	0.0138 (5)	0.0175 (6)	0.0008 (4)	−0.0028 (4)	−0.0039 (4)
N4	0.0187 (5)	0.0137 (5)	0.0163 (6)	0.0026 (4)	−0.0022 (4)	−0.0029 (4)
N5	0.0212 (6)	0.0149 (5)	0.0268 (6)	0.0047 (4)	−0.0042 (5)	−0.0054 (5)
N6	0.0198 (6)	0.0122 (5)	0.0241 (6)	0.0012 (4)	−0.0031 (5)	−0.0023 (4)
C1	0.0313 (8)	0.0222 (7)	0.0214 (7)	0.0047 (6)	−0.0006 (6)	−0.0034 (6)
C2	0.0183 (6)	0.0150 (6)	0.0211 (7)	0.0045 (5)	−0.0036 (5)	−0.0064 (5)
C3	0.0214 (6)	0.0177 (6)	0.0250 (7)	0.0048 (5)	−0.0059 (5)	−0.0087 (5)
C4	0.0244 (7)	0.0213 (7)	0.0220 (7)	0.0070 (5)	−0.0070 (5)	−0.0102 (5)
C5	0.0230 (7)	0.0199 (6)	0.0192 (7)	0.0087 (5)	−0.0044 (5)	−0.0043 (5)
C6	0.0188 (6)	0.0165 (6)	0.0196 (7)	0.0039 (5)	−0.0026 (5)	−0.0051 (5)
C7	0.0162 (6)	0.0163 (6)	0.0203 (7)	0.0036 (5)	−0.0030 (5)	−0.0058 (5)
C8	0.0169 (6)	0.0159 (6)	0.0197 (7)	0.0037 (5)	−0.0013 (5)	−0.0052 (5)
C9	0.0171 (6)	0.0157 (6)	0.0200 (7)	0.0030 (5)	−0.0016 (5)	−0.0067 (5)
C10	0.0167 (6)	0.0147 (6)	0.0209 (7)	0.0023 (5)	−0.0028 (5)	−0.0045 (5)
C11	0.0205 (6)	0.0136 (6)	0.0203 (7)	0.0033 (5)	−0.0021 (5)	−0.0023 (5)
C12	0.0208 (6)	0.0143 (6)	0.0216 (7)	0.0021 (5)	−0.0019 (5)	−0.0036 (5)
C13	0.0161 (6)	0.0155 (6)	0.0213 (7)	0.0008 (5)	−0.0015 (5)	−0.0039 (5)
C14	0.0159 (6)	0.0161 (6)	0.0188 (6)	0.0004 (5)	−0.0022 (5)	−0.0041 (5)
C15	0.0193 (6)	0.0152 (6)	0.0227 (7)	0.0018 (5)	−0.0027 (5)	−0.0034 (5)
C16	0.0208 (6)	0.0184 (6)	0.0227 (7)	0.0030 (5)	−0.0040 (5)	−0.0011 (5)
C17	0.0196 (6)	0.0241 (7)	0.0188 (7)	0.0004 (5)	−0.0031 (5)	−0.0044 (5)
C18	0.0206 (6)	0.0189 (6)	0.0219 (7)	0.0019 (5)	−0.0027 (5)	−0.0063 (5)
C19	0.0534 (11)	0.0373 (9)	0.0236 (8)	0.0136 (8)	−0.0114 (7)	−0.0125 (7)
C20	0.0283 (7)	0.0227 (7)	0.0206 (7)	−0.0027 (6)	−0.0016 (6)	−0.0019 (5)
C21	0.0170 (6)	0.0153 (6)	0.0193 (7)	0.0034 (5)	−0.0024 (5)	−0.0051 (5)
C22	0.0211 (6)	0.0158 (6)	0.0212 (7)	0.0015 (5)	−0.0042 (5)	−0.0067 (5)
C23	0.0236 (7)	0.0205 (7)	0.0190 (7)	0.0018 (5)	−0.0044 (5)	−0.0081 (5)
C24	0.0201 (6)	0.0191 (6)	0.0160 (6)	0.0021 (5)	−0.0020 (5)	−0.0036 (5)
C25	0.0183 (6)	0.0162 (6)	0.0177 (6)	0.0016 (5)	−0.0025 (5)	−0.0041 (5)
C26	0.0158 (6)	0.0152 (6)	0.0189 (7)	0.0026 (5)	−0.0031 (5)	−0.0045 (5)
C27	0.0183 (6)	0.0140 (6)	0.0186 (6)	0.0014 (5)	−0.0030 (5)	−0.0043 (5)
C28	0.0185 (6)	0.0143 (6)	0.0174 (6)	0.0031 (5)	−0.0034 (5)	−0.0049 (5)
C29	0.0177 (6)	0.0148 (6)	0.0189 (7)	0.0024 (5)	−0.0032 (5)	−0.0039 (5)
C30	0.0227 (6)	0.0126 (6)	0.0206 (7)	0.0022 (5)	−0.0031 (5)	−0.0023 (5)
C31	0.0201 (6)	0.0143 (6)	0.0220 (7)	0.0025 (5)	−0.0018 (5)	−0.0044 (5)
C32	0.0166 (6)	0.0150 (6)	0.0202 (7)	−0.0001 (5)	−0.0005 (5)	−0.0041 (5)
C33	0.0154 (6)	0.0149 (6)	0.0178 (6)	−0.0006 (5)	−0.0004 (5)	−0.0040 (5)
C34	0.0180 (6)	0.0159 (6)	0.0187 (6)	0.0017 (5)	−0.0015 (5)	−0.0031 (5)
C35	0.0189 (6)	0.0185 (6)	0.0187 (7)	0.0005 (5)	−0.0029 (5)	−0.0014 (5)
C36	0.0197 (6)	0.0228 (7)	0.0168 (6)	−0.0028 (5)	−0.0005 (5)	−0.0048 (5)
C37	0.0189 (6)	0.0185 (6)	0.0214 (7)	0.0003 (5)	0.0008 (5)	−0.0072 (5)
C38	0.0344 (8)	0.0289 (8)	0.0187 (7)	−0.0026 (6)	−0.0061 (6)	−0.0016 (6)
C39	0.0283 (7)	0.0213 (7)	0.0274 (8)	0.0012 (6)	−0.0039 (6)	−0.0021 (6)
C40	0.0173 (6)	0.0159 (6)	0.0270 (7)	0.0009 (5)	−0.0031 (5)	−0.0039 (5)
C41	0.0210 (6)	0.0167 (6)	0.0298 (8)	0.0027 (5)	−0.0015 (6)	−0.0075 (6)
C42	0.0227 (7)	0.0210 (7)	0.0278 (8)	−0.0001 (5)	0.0000 (6)	−0.0086 (6)
C43	0.0221 (7)	0.0194 (7)	0.0249 (7)	−0.0011 (5)	−0.0022 (5)	−0.0034 (6)
C44	0.0182 (6)	0.0160 (6)	0.0263 (7)	0.0016 (5)	−0.0040 (5)	−0.0034 (5)
C45	0.0164 (6)	0.0161 (6)	0.0247 (7)	0.0010 (5)	−0.0023 (5)	−0.0046 (5)
C46	0.0180 (6)	0.0146 (6)	0.0282 (7)	0.0017 (5)	−0.0037 (5)	−0.0055 (5)
C47	0.0183 (6)	0.0157 (6)	0.0263 (7)	0.0015 (5)	−0.0032 (5)	−0.0065 (5)
C48	0.0173 (6)	0.0150 (6)	0.0276 (7)	0.0030 (5)	−0.0031 (5)	−0.0046 (5)
C49	0.0221 (7)	0.0136 (6)	0.0264 (7)	−0.0003 (5)	−0.0007 (5)	−0.0021 (5)
C50	0.0214 (6)	0.0137 (6)	0.0266 (7)	0.0002 (5)	−0.0015 (5)	−0.0025 (5)
C51	0.0163 (6)	0.0152 (6)	0.0260 (7)	0.0019 (5)	−0.0030 (5)	−0.0031 (5)
C52	0.0167 (6)	0.0144 (6)	0.0244 (7)	0.0036 (5)	−0.0030 (5)	−0.0029 (5)
C53	0.0173 (6)	0.0154 (6)	0.0302 (8)	0.0017 (5)	−0.0030 (5)	−0.0035 (5)
C54	0.0188 (6)	0.0174 (6)	0.0283 (8)	−0.0008 (5)	−0.0013 (5)	0.0000 (5)
C55	0.0192 (6)	0.0208 (7)	0.0240 (7)	0.0024 (5)	−0.0004 (5)	−0.0022 (6)
C56	0.0198 (6)	0.0169 (6)	0.0251 (7)	0.0010 (5)	−0.0018 (5)	−0.0029 (5)
C57	0.0346 (8)	0.0212 (7)	0.0261 (8)	0.0014 (6)	−0.0020 (6)	−0.0050 (6)

Geometric parameters (Å, º) top

O1—C5	1.3765 (18)	C20—H20A	0.9800
O1—C1	1.4240 (19)	C20—H20B	0.9800
O2—C10	1.2285 (17)	C20—H20C	0.9800
O3—C17	1.3732 (18)	C21—C22	1.403 (2)
O3—C19	1.422 (2)	C21—C26	1.4140 (19)
O4—C24	1.3721 (17)	C22—C23	1.374 (2)
O4—C20	1.4232 (18)	C22—H22	0.9500
O5—C29	1.2273 (17)	C23—C24	1.420 (2)
O6—C36	1.3732 (18)	C23—H23	0.9500
O6—C38	1.4204 (19)	C24—C25	1.378 (2)
O7—C43	1.3768 (19)	C25—C26	1.4111 (19)
O7—C39	1.4202 (18)	C25—H25	0.9500
O8—C48	1.2292 (18)	C26—C27	1.4245 (19)
O9—C55	1.3703 (19)	C27—C28	1.3854 (19)
O9—C57	1.424 (2)	C27—H27	0.9500
N1—C2	1.3649 (19)	C28—C29	1.4604 (19)
N1—C9	1.3775 (18)	C30—C31	1.351 (2)
N1—H1n	0.91 (2)	C30—H30	0.9500
N2—C10	1.3868 (18)	C31—C32	1.4426 (19)
N2—C14	1.4070 (18)	C31—H31	0.9500
N2—C11	1.4097 (17)	C32—C37	1.386 (2)
N3—C21	1.3658 (18)	C32—C33	1.4091 (18)
N3—C28	1.3751 (18)	C33—C34	1.3894 (19)
N3—H3n	0.91 (2)	C34—C35	1.396 (2)
N4—C29	1.3897 (18)	C34—H34	0.9500
N4—C30	1.4099 (16)	C35—C36	1.401 (2)
N4—C33	1.4099 (18)	C35—H35	0.9500
N5—C40	1.366 (2)	C36—C37	1.392 (2)
N5—C47	1.3805 (18)	C37—H37	0.9500
N5—H5n	0.90 (2)	C38—H38A	0.9800
N6—C48	1.3886 (19)	C38—H38B	0.9800
N6—C52	1.4096 (19)	C38—H38C	0.9800
N6—C49	1.4139 (18)	C39—H39A	0.9800
C1—H1A	0.9800	C39—H39B	0.9800
C1—H1B	0.9800	C39—H39C	0.9800
C1—H1C	0.9800	C40—C41	1.402 (2)
C2—C3	1.405 (2)	C40—C45	1.4177 (18)
C2—C7	1.4103 (19)	C41—C42	1.372 (2)
C3—C4	1.374 (2)	C41—H41	0.9500
C3—H3A	0.9500	C42—C43	1.418 (2)
C4—C5	1.415 (2)	C42—H42	0.9500
C4—H4	0.9500	C43—C44	1.375 (2)
C5—C6	1.378 (2)	C44—C45	1.420 (2)
C6—C7	1.4167 (19)	C44—H44	0.9500
C6—H6	0.9500	C45—C46	1.420 (2)
C7—C8	1.4202 (19)	C46—C47	1.3855 (19)
C8—C9	1.3884 (19)	C46—H46	0.9500
C8—H8	0.9500	C47—C48	1.459 (2)
C9—C10	1.4591 (19)	C49—C50	1.350 (2)
C11—C12	1.352 (2)	C49—H49	0.9500
C11—H11	0.9500	C50—C51	1.4432 (19)
C12—C13	1.4424 (19)	C50—H50	0.9500
C12—H12	0.9500	C51—C56	1.398 (2)
C13—C18	1.396 (2)	C51—C52	1.402 (2)
C13—C14	1.4016 (18)	C52—C53	1.3965 (19)
C14—C15	1.3961 (19)	C53—C54	1.382 (2)
C15—C16	1.384 (2)	C53—H53	0.9500
C15—H15	0.9500	C54—C55	1.409 (2)
C16—C17	1.408 (2)	C54—H54	0.9500
C16—H16	0.9500	C55—C56	1.391 (2)
C17—C18	1.385 (2)	C56—H56	0.9500
C18—H18	0.9500	C57—H57A	0.9800
C19—H19A	0.9800	C57—H57B	0.9800
C19—H19B	0.9800	C57—H57C	0.9800
C19—H19C	0.9800

C5—O1—C1	116.08 (12)	C26—C25—H25	121.2
C17—O3—C19	116.73 (12)	C25—C26—C21	120.11 (13)
C24—O4—C20	116.84 (12)	C25—C26—C27	133.31 (13)
C36—O6—C38	117.51 (12)	C21—C26—C27	106.58 (12)
C43—O7—C39	116.59 (12)	C28—C27—C26	106.95 (12)
C55—O9—C57	117.19 (12)	C28—C27—H27	126.5
C2—N1—C9	108.82 (12)	C26—C27—H27	126.5
C2—N1—H1n	126.2 (14)	N3—C28—C27	109.16 (12)
C9—N1—H1n	124.9 (14)	N3—C28—C29	117.84 (12)
C10—N2—C14	125.10 (11)	C27—C28—C29	132.63 (13)
C10—N2—C11	126.08 (12)	O5—C29—N4	120.34 (13)
C14—N2—C11	107.48 (11)	O5—C29—C28	121.45 (12)
C21—N3—C28	109.04 (12)	N4—C29—C28	118.21 (11)
C21—N3—H3n	125.8 (13)	C31—C30—N4	109.85 (12)
C28—N3—H3n	125.2 (13)	C31—C30—H30	125.1
C29—N4—C30	125.87 (12)	N4—C30—H30	125.1
C29—N4—C33	124.54 (11)	C30—C31—C32	107.94 (12)
C30—N4—C33	107.51 (11)	C30—C31—H31	126.0
C40—N5—C47	109.01 (12)	C32—C31—H31	126.0
C40—N5—H5n	126.4 (13)	C37—C32—C33	120.10 (13)
C47—N5—H5n	124.6 (13)	C37—C32—C31	132.79 (13)
C48—N6—C52	125.13 (12)	C33—C32—C31	107.11 (12)
C48—N6—C49	125.52 (13)	C34—C33—C32	121.58 (13)
C52—N6—C49	107.23 (12)	C34—C33—N4	130.78 (12)
O1—C1—H1A	109.5	C32—C33—N4	107.59 (11)
O1—C1—H1B	109.5	C33—C34—C35	117.79 (12)
H1A—C1—H1B	109.5	C33—C34—H34	121.1
O1—C1—H1C	109.5	C35—C34—H34	121.1
H1A—C1—H1C	109.5	C34—C35—C36	120.85 (13)
H1B—C1—H1C	109.5	C34—C35—H35	119.6
N1—C2—C3	129.53 (13)	C36—C35—H35	119.6
N1—C2—C7	108.48 (12)	O6—C36—C37	115.04 (12)
C3—C2—C7	121.99 (13)	O6—C36—C35	124.02 (13)
C4—C3—C2	116.96 (13)	C37—C36—C35	120.94 (13)
C4—C3—H3A	121.5	C32—C37—C36	118.72 (13)
C2—C3—H3A	121.5	C32—C37—H37	120.6
C3—C4—C5	121.87 (14)	C36—C37—H37	120.6
C3—C4—H4	119.1	O6—C38—H38A	109.5
C5—C4—H4	119.1	O6—C38—H38B	109.5
O1—C5—C6	125.16 (14)	H38A—C38—H38B	109.5
O1—C5—C4	113.18 (13)	O6—C38—H38C	109.5
C6—C5—C4	121.65 (14)	H38A—C38—H38C	109.5
C5—C6—C7	117.55 (13)	H38B—C38—H38C	109.5
C5—C6—H6	121.2	O7—C39—H39A	109.5
C7—C6—H6	121.2	O7—C39—H39B	109.5
C2—C7—C6	119.98 (13)	H39A—C39—H39B	109.5
C2—C7—C8	106.72 (12)	O7—C39—H39C	109.5
C6—C7—C8	133.31 (13)	H39A—C39—H39C	109.5
C9—C8—C7	106.92 (12)	H39B—C39—H39C	109.5
C9—C8—H8	126.5	N5—C40—C41	129.92 (13)
C7—C8—H8	126.5	N5—C40—C45	108.22 (13)
N1—C9—C8	109.05 (12)	C41—C40—C45	121.86 (14)
N1—C9—C10	118.01 (12)	C42—C41—C40	117.44 (13)
C8—C9—C10	132.49 (13)	C42—C41—H41	121.3
O2—C10—N2	120.42 (13)	C40—C41—H41	121.3
O2—C10—C9	121.34 (13)	C41—C42—C43	121.54 (14)
N2—C10—C9	118.24 (12)	C41—C42—H42	119.2
C12—C11—N2	109.64 (12)	C43—C42—H42	119.2
C12—C11—H11	125.2	C44—C43—O7	125.32 (13)
N2—C11—H11	125.2	C44—C43—C42	121.79 (14)
C11—C12—C13	107.93 (12)	O7—C43—C42	112.89 (14)
C11—C12—H12	126.0	C43—C44—C45	117.73 (13)
C13—C12—H12	126.0	C43—C44—H44	121.1
C18—C13—C14	120.62 (13)	C45—C44—H44	121.1
C18—C13—C12	132.28 (13)	C40—C45—C46	106.58 (13)
C14—C13—C12	107.10 (12)	C40—C45—C44	119.64 (14)
C15—C14—C13	121.68 (13)	C46—C45—C44	133.78 (13)
C15—C14—N2	130.44 (13)	C47—C46—C45	107.27 (12)
C13—C14—N2	107.85 (11)	C47—C46—H46	126.4
C16—C15—C14	117.16 (13)	C45—C46—H46	126.4
C16—C15—H15	121.4	N5—C47—C46	108.92 (13)
C14—C15—H15	121.4	N5—C47—C48	117.63 (12)
C15—C16—C17	121.60 (13)	C46—C47—C48	132.99 (13)
C15—C16—H16	119.2	O8—C48—N6	120.42 (14)
C17—C16—H16	119.2	O8—C48—C47	121.27 (14)
O3—C17—C18	124.65 (13)	N6—C48—C47	118.31 (12)
O3—C17—C16	114.37 (13)	C50—C49—N6	109.76 (13)
C18—C17—C16	120.98 (14)	C50—C49—H49	125.1
C17—C18—C13	117.94 (13)	N6—C49—H49	125.1
C17—C18—H18	121.0	C49—C50—C51	107.98 (13)
C13—C18—H18	121.0	C49—C50—H50	126.0
O3—C19—H19A	109.5	C51—C50—H50	126.0
O3—C19—H19B	109.5	C56—C51—C52	120.89 (13)
H19A—C19—H19B	109.5	C56—C51—C50	131.99 (14)
O3—C19—H19C	109.5	C52—C51—C50	107.11 (13)
H19A—C19—H19C	109.5	C53—C52—C51	121.46 (14)
H19B—C19—H19C	109.5	C53—C52—N6	130.59 (14)
O4—C20—H20A	109.5	C51—C52—N6	107.92 (12)
O4—C20—H20B	109.5	C54—C53—C52	117.24 (14)
H20A—C20—H20B	109.5	C54—C53—H53	121.4
O4—C20—H20C	109.5	C52—C53—H53	121.4
H20A—C20—H20C	109.5	C53—C54—C55	121.91 (14)
H20B—C20—H20C	109.5	C53—C54—H54	119.0
N3—C21—C22	129.94 (13)	C55—C54—H54	119.0
N3—C21—C26	108.27 (12)	O9—C55—C56	124.50 (14)
C22—C21—C26	121.79 (13)	O9—C55—C54	114.82 (13)
C23—C22—C21	117.27 (13)	C56—C55—C54	120.67 (14)
C23—C22—H22	121.4	C55—C56—C51	117.77 (14)
C21—C22—H22	121.4	C55—C56—H56	121.1
C22—C23—C24	121.57 (13)	C51—C56—H56	121.1
C22—C23—H23	119.2	O9—C57—H57A	109.5
C24—C23—H23	119.2	O9—C57—H57B	109.5
O4—C24—C25	124.97 (13)	H57A—C57—H57B	109.5
O4—C24—C23	113.43 (12)	O9—C57—H57C	109.5
C25—C24—C23	121.59 (13)	H57A—C57—H57C	109.5
C24—C25—C26	117.66 (13)	H57B—C57—H57C	109.5
C24—C25—H25	121.2

C9—N1—C2—C3	−179.26 (13)	C27—C28—C29—O5	151.80 (15)
C9—N1—C2—C7	1.13 (15)	N3—C28—C29—N4	160.58 (12)
N1—C2—C3—C4	−179.08 (13)	C27—C28—C29—N4	−27.3 (2)
C7—C2—C3—C4	0.5 (2)	C29—N4—C30—C31	−164.97 (13)
C2—C3—C4—C5	0.2 (2)	C33—N4—C30—C31	−0.85 (16)
C1—O1—C5—C6	−2.1 (2)	N4—C30—C31—C32	0.62 (16)
C1—O1—C5—C4	177.08 (12)	C30—C31—C32—C37	179.82 (15)
C3—C4—C5—O1	179.96 (12)	C30—C31—C32—C33	−0.15 (16)
C3—C4—C5—C6	−0.8 (2)	C37—C32—C33—C34	1.8 (2)
O1—C5—C6—C7	179.79 (12)	C31—C32—C33—C34	−178.19 (13)
C4—C5—C6—C7	0.7 (2)	C37—C32—C33—N4	179.66 (12)
N1—C2—C7—C6	179.02 (12)	C31—C32—C33—N4	−0.36 (15)
C3—C2—C7—C6	−0.6 (2)	C29—N4—C33—C34	−17.3 (2)
N1—C2—C7—C8	−0.76 (14)	C30—N4—C33—C34	178.28 (14)
C3—C2—C7—C8	179.59 (12)	C29—N4—C33—C32	165.11 (12)
C5—C6—C7—C2	0.04 (19)	C30—N4—C33—C32	0.73 (15)
C5—C6—C7—C8	179.74 (14)	C32—C33—C34—C35	−1.3 (2)
C2—C7—C8—C9	0.11 (14)	N4—C33—C34—C35	−178.60 (13)
C6—C7—C8—C9	−179.63 (14)	C33—C34—C35—C36	0.1 (2)
C2—N1—C9—C8	−1.07 (15)	C38—O6—C36—C37	179.90 (13)
C2—N1—C9—C10	−174.29 (11)	C38—O6—C36—C35	0.6 (2)
C7—C8—C9—N1	0.58 (15)	C34—C35—C36—O6	−179.95 (13)
C7—C8—C9—C10	172.45 (13)	C34—C35—C36—C37	0.7 (2)
C14—N2—C10—O2	12.4 (2)	C33—C32—C37—C36	−1.0 (2)
C11—N2—C10—O2	−152.69 (14)	C31—C32—C37—C36	179.04 (15)
C14—N2—C10—C9	−166.47 (12)	O6—C36—C37—C32	−179.63 (12)
C11—N2—C10—C9	28.5 (2)	C35—C36—C37—C32	−0.3 (2)
N1—C9—C10—O2	19.73 (19)	C47—N5—C40—C41	179.54 (15)
C8—C9—C10—O2	−151.56 (15)	C47—N5—C40—C45	−0.65 (16)
N1—C9—C10—N2	−161.42 (12)	N5—C40—C41—C42	179.94 (15)
C8—C9—C10—N2	27.3 (2)	C45—C40—C41—C42	0.1 (2)
C10—N2—C11—C12	167.69 (13)	C40—C41—C42—C43	−0.4 (2)
C14—N2—C11—C12	0.46 (16)	C39—O7—C43—C44	0.0 (2)
N2—C11—C12—C13	−0.26 (16)	C39—O7—C43—C42	−179.45 (13)
C11—C12—C13—C18	−179.61 (15)	C41—C42—C43—C44	0.4 (2)
C11—C12—C13—C14	−0.03 (16)	C41—C42—C43—O7	179.88 (14)
C18—C13—C14—C15	−1.9 (2)	O7—C43—C44—C45	−179.57 (13)
C12—C13—C14—C15	178.45 (13)	C42—C43—C44—C45	−0.1 (2)
C18—C13—C14—N2	179.95 (12)	N5—C40—C45—C46	0.47 (16)
C12—C13—C14—N2	0.31 (15)	C41—C40—C45—C46	−179.70 (13)
C10—N2—C14—C15	14.2 (2)	N5—C40—C45—C44	−179.74 (13)
C11—N2—C14—C15	−178.39 (14)	C41—C40—C45—C44	0.1 (2)
C10—N2—C14—C13	−167.86 (13)	C43—C44—C45—C40	−0.1 (2)
C11—N2—C14—C13	−0.47 (15)	C43—C44—C45—C46	179.62 (15)
C13—C14—C15—C16	1.5 (2)	C40—C45—C46—C47	−0.12 (16)
N2—C14—C15—C16	179.18 (14)	C44—C45—C46—C47	−179.86 (15)
C14—C15—C16—C17	0.0 (2)	C40—N5—C47—C46	0.58 (16)
C19—O3—C17—C18	1.6 (2)	C40—N5—C47—C48	173.82 (12)
C19—O3—C17—C16	−179.52 (15)	C45—C46—C47—N5	−0.27 (16)
C15—C16—C17—O3	179.88 (13)	C45—C46—C47—C48	−172.09 (15)
C15—C16—C17—C18	−1.2 (2)	C52—N6—C48—O8	−9.4 (2)
O3—C17—C18—C13	179.62 (13)	C49—N6—C48—O8	151.94 (14)
C16—C17—C18—C13	0.8 (2)	C52—N6—C48—C47	170.13 (13)
C14—C13—C18—C17	0.7 (2)	C49—N6—C48—C47	−28.6 (2)
C12—C13—C18—C17	−179.75 (15)	N5—C47—C48—O8	−21.2 (2)
C28—N3—C21—C22	179.21 (13)	C46—C47—C48—O8	150.07 (16)
C28—N3—C21—C26	−1.06 (15)	N5—C47—C48—N6	159.32 (13)
N3—C21—C22—C23	179.75 (13)	C46—C47—C48—N6	−29.4 (2)
C26—C21—C22—C23	0.1 (2)	C48—N6—C49—C50	−164.41 (13)
C21—C22—C23—C24	−0.4 (2)	C52—N6—C49—C50	−0.33 (16)
C20—O4—C24—C25	−6.1 (2)	N6—C49—C50—C51	0.33 (16)
C20—O4—C24—C23	174.51 (12)	C49—C50—C51—C56	178.62 (15)
C22—C23—C24—O4	179.66 (13)	C49—C50—C51—C52	−0.20 (16)
C22—C23—C24—C25	0.2 (2)	C56—C51—C52—C53	2.8 (2)
O4—C24—C25—C26	−179.09 (12)	C50—C51—C52—C53	−178.19 (12)
C23—C24—C25—C26	0.3 (2)	C56—C51—C52—N6	−178.98 (12)
C24—C25—C26—C21	−0.59 (19)	C50—C51—C52—N6	−0.01 (15)
C24—C25—C26—C27	179.43 (14)	C48—N6—C52—C53	−17.7 (2)
N3—C21—C26—C25	−179.31 (12)	C49—N6—C52—C53	178.16 (14)
C22—C21—C26—C25	0.4 (2)	C48—N6—C52—C51	164.35 (12)
N3—C21—C26—C27	0.67 (14)	C49—N6—C52—C51	0.20 (15)
C22—C21—C26—C27	−179.57 (12)	C51—C52—C53—C54	−1.9 (2)
C25—C26—C27—C28	179.94 (14)	N6—C52—C53—C54	−179.63 (13)
C21—C26—C27—C28	−0.04 (14)	C52—C53—C54—C55	−0.4 (2)
C21—N3—C28—C27	1.05 (15)	C57—O9—C55—C56	−12.7 (2)
C21—N3—C28—C29	174.94 (11)	C57—O9—C55—C54	168.68 (13)
C26—C27—C28—N3	−0.61 (15)	C53—C54—C55—O9	−179.51 (13)
C26—C27—C28—C29	−173.26 (13)	C53—C54—C55—C56	1.8 (2)
C30—N4—C29—O5	152.36 (14)	O9—C55—C56—C51	−179.45 (13)
C33—N4—C29—O5	−9.2 (2)	C54—C55—C56—C51	−0.9 (2)
C30—N4—C29—C28	−28.5 (2)	C52—C51—C56—C55	−1.4 (2)
C33—N4—C29—C28	169.92 (12)	C50—C51—C56—C55	179.95 (14)
N3—C28—C29—O5	−20.34 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···O5	0.91 (2)	1.98 (2)	2.8536 (16)	159 (2)
N3—H3n···O2	0.91 (2)	1.97 (2)	2.8384 (16)	159.0 (19)
N5—H5n···O8ⁱ	0.90 (2)	2.00 (2)	2.8796 (15)	163.9 (19)

Symmetry code: (i) −x+2, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₆N₂O₃
M_r	320.34
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	11.3153 (4), 12.1183 (5), 17.1300 (6)
α, β, γ (°)	76.251 (3), 79.747 (3), 88.913 (3)
V (Å³)	2244.50 (15)
Z	6
Radiation type	Cu Kα
µ (mm⁻¹)	0.80
Crystal size (mm)	0.30 × 0.20 × 0.02

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.367, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	17372, 9182, 7534
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.630

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.121, 1.02
No. of reflections	9182
No. of parameters	661
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.30

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), Qmol (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···O5	0.91 (2)	1.98 (2)	2.8536 (16)	159 (2)
N3—H3n···O2	0.91 (2)	1.97 (2)	2.8384 (16)	159.0 (19)
N5—H5n···O8ⁱ	0.90 (2)	2.00 (2)	2.8796 (15)	163.9 (19)

Symmetry code: (i) −x+2, −y, −z+1.

Footnotes

‡Additional correspondence author, e-mail: mattia@ksu.edu.sa.

Acknowledgements

The financial support of the Deanship of Scientific Research and the Research Center of the College of Pharmacy, King Saud University is greatly appreciated. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/12).

References

Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Attia, M. I., El-Brollosy, N. R., Ghabbour, H. A., Arshad, S. & Fun, H.-K. (2012). Acta Cryst. E68, o971. CSD CrossRef IUCr Journals Google Scholar
Attia, M. I., Witt-Enderby, P. A. & Julius, J. (2008). Bioorg. Med. Chem. 16, 7654–7661. Web of Science CrossRef PubMed CAS Google Scholar
Barrenetxe, J., Delagrange, P. & Martinez, J. A. (2004). J. Physiol. Biochem. 60, 61–72. CrossRef PubMed CAS Google Scholar
Bedini, A., Spadoni, G., Gatti, G., Lucarini, S., Tarzia, G., Rivara, S., Lorenzi, S., Lodola, A., Mor, M., Lucini, V., Pannacci, M. & Scaglione, F. (2006). J. Med. Chem. 49, 7393–7403. Web of Science CrossRef PubMed CAS Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Gans, J. & Shalloway, D. (2001). J. Mol. Graph. Model. 19, 557–559. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Williamson, B. L., Tomlinson, A. J., Mishra, P. K., Gleich, G. J. & Naylor, S. (1998). Chem. Res. Toxicol. 11, 234–240. Web of Science CrossRef CAS PubMed Google Scholar