Methyl 2-{[(3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-yl­idene)(4-nitro­phen­yl)meth­yl]amino}-3-phenyl­propano­ate

The mol­ecule of the title compound, C₂₇H₂₄N₄O₅, exists in the keto–enamine tautomeric form, stabilized by an intra­molecular N—H...O hydrogen bond. An intra­molecular C—H...·O hydrogen bond also occurs. In the crystal, C—H...O hydrogen bonds link the mol­ecules into chains.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.040
• wR factor = 0.106
• Data-to-parameter ratio = 7.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       7.08
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C4
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C6
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0057 Ang
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595          3

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.03
           From the CIF: _reflns_number_total               2315
           Count of symmetry unique reflns         2319
           Completeness (_total/calc)             99.83%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............          1
PLAT791_ALERT_4_G Note: The Model has Chirality at C18    (Verify)          S
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          46 Perc.
PLAT981_ALERT_1_G No non-zero f" Anomalous Scattering Values Found          ?

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   6 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Comment

In recent years, Schiff bases play an important role in the development of coordination chemistry related to catalysis and enzymatic reactions, magnetism, and molecular architectures (Wu et al., 1993; Harrop et al., 2003; Habibi et al., 2007). In recent years, the Schiff bases derived from 4–acyl–5–pyrazolone and their metal complexes have been studied widely for their high antibacterial activity (Li et al., 1997, 2004). Both 1–phenyl–3–methyl–4–(p–nitro–benzyl)–5–pyrazolone and its metal complexes are widely used and well known for their analgetic activity (Remya et al., 2005). Amino acid esters also demonstrate high antibacterial and biological activity (Xiong et al., 1993). Structure of Schiff base derived from 4–acyl–5–pyrazolone and amino acid ester, closely related to the title compound, has been reported (Zhang et al., 2005).

The molecular structure of the title compound is presented in Fig. 1, and the numerical results are given in tables below. Atoms O1, C9, C8, C11 and N4 form a plane, the largest deviation being 0.021 (4) Å for atom C11. The dihedral angle between this mean plane and the pyrazolone ring is 1.2 (1)°, indicating that they are essentially coplanar, as seen in 4–{[3,4–dihydro–5–methyl–3–oxo–2–phenyl–2H–pyrazol–4–ylidene]–(phenyl)methyl]amino}–1,5–dimethyl–2–phenyl–1H–pyrazol–3(2H)–one [3.56 (3)°; Wang et al., 2003]. The bond lengths within central part of the molecule lie between typical single- and double- bond lengths, indicating extensive conjugation. A strong intramolecular N—H···O hydrogen bond is observed, stabilizing the enamine-keto tautomeric form. In the crystal structure, intermolecular C1—H1···O4 hydrogen bonds link the molecules into chains, shown in Fig. 2.

Related literature

For general background to Schiff bases in coordination chemistry, see: Wu et al. (1993); Harrop et al. (2003); Habibi et al. (2007). For antibacterial properties of Schiff bases derived from 4-acyl-5-pyrazolone and their metal complexes, see: Li et al. (1997, 2004). For the antibacterial and biological activity of amino acid esters, see: Xiong et al. (1993). For related structures, see: Wang et al. (2003); Zhang et al. (2005). For synthetic details, see: Remya et al. (2005). For standard bond lengths, see: Allen et al. (1987).

S2. Experimental

The title compound was synthesized by refluxing a mixture of 1–phenyl–3—methyl–4–(p–nitro–benzyl)–5–pyrazolone (15 mmol) (Remya et al., 2005) and phenylalanine methyl ester (15 mmol) in ethanol (100 ml) for about 5 h. The product was recrystallized from ethanol, affording pale yellow crystals suitable for X–ray analysis.

S3. Refinement

All H atoms were positioned geometrically with N—H = 0.86 Å and C—H = 0.93–0.98 Å, and constrained to ride on their parent atoms, with U_iso(H) = xU_eq(C,N), where x = 1.5 for methyl H and x = 1.2 for other H atoms.

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The chain formed by the intermolecular C—H···O hydrogen bonds (shown by dashed lines).

Methyl 2-{[(3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4- ylidene)(4-nitrophenyl)methyl]amino}-3-phenylpropanoate

Crystal data

C27H24N4O5	F(000) = 508
Mr = 484.50	Dx = 1.312 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2125 reflections
a = 6.7713 (16) Å	θ = 2.5–22.4°
b = 8.917 (2) Å	µ = 0.09 mm^−1
c = 20.339 (5) Å	T = 296 K
β = 92.489 (4)°	Block, colourless
V = 1226.9 (5) Å^3	0.20 × 0.16 × 0.12 mm
Z = 2

Data collection

Bruker APEXII CCD diffractometer	2315 independent reflections
Radiation source: fine-focus sealed tube	1855 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
φ and ω scan	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −8→7
Tmin = 0.980, Tmax = 0.989	k = −10→10
6305 measured reflections	l = −24→16

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0582P)^2 + 0.0914P] where P = (Fo^2 + 2Fc^2)/3
2315 reflections	(Δ/σ)max < 0.001
327 parameters	Δρmax = 0.26 e Å^−3
1 restraint	Δρmin = −0.15 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
O1	0.2384 (4)	−0.1136 (2)	0.34497 (13)	0.0631 (7)
O2	−0.7694 (4)	0.4350 (4)	0.12919 (15)	0.0803 (9)
O3	−0.5325 (5)	0.4977 (5)	0.06804 (18)	0.1058 (12)
O4	−0.3079 (4)	−0.3075 (3)	0.31388 (15)	0.0683 (7)
O5	−0.4842 (5)	−0.3580 (4)	0.22187 (18)	0.1000 (11)
N1	0.3237 (4)	0.1290 (3)	0.38007 (13)	0.0506 (7)
N2	0.2558 (4)	0.2758 (3)	0.36907 (15)	0.0579 (7)
N3	−0.5986 (4)	0.4262 (4)	0.11306 (16)	0.0645 (8)
N4	−0.0863 (4)	−0.0999 (3)	0.26012 (15)	0.0551 (7)
H4	−0.0086	−0.1510	0.2861	0.066*
C1	0.6183 (5)	−0.0145 (5)	0.4130 (2)	0.0709 (11)
H1	0.5785	−0.0909	0.3842	0.085*
C2	0.7941 (6)	−0.0259 (6)	0.4492 (2)	0.0879 (14)
H2	0.8727	−0.1104	0.4444	0.105*
C3	0.8550 (7)	0.0833 (8)	0.4916 (3)	0.1011 (17)
H3	0.9744	0.0747	0.5156	0.121*
C4	0.7377 (8)	0.2064 (9)	0.4983 (3)	0.118 (2)
H4A	0.7776	0.2803	0.5283	0.142*
C5	0.5612 (7)	0.2250 (6)	0.4621 (2)	0.0901 (15)
H5	0.4852	0.3112	0.4661	0.108*
C6	0.5025 (5)	0.1097 (4)	0.41960 (16)	0.0534 (8)
C7	0.1051 (5)	0.2653 (4)	0.32700 (17)	0.0508 (8)
C8	0.0671 (4)	0.1120 (3)	0.30814 (15)	0.0437 (7)
C9	0.2132 (4)	0.0246 (4)	0.34512 (16)	0.0474 (8)
C10	0.0044 (6)	0.4069 (4)	0.3050 (3)	0.0824 (13)
H10A	0.0556	0.4893	0.3310	0.124*
H10B	−0.1352	0.3979	0.3106	0.124*
H10C	0.0281	0.4245	0.2595	0.124*
C11	−0.0733 (4)	0.0480 (4)	0.26523 (15)	0.0449 (8)
C12	−0.2120 (4)	0.1434 (3)	0.22373 (15)	0.0423 (7)
C13	−0.1507 (5)	0.2096 (4)	0.16670 (17)	0.0514 (8)
H13	−0.0236	0.1915	0.1530	0.062*
C14	−0.2753 (5)	0.3019 (4)	0.12978 (17)	0.0545 (9)
H14	−0.2339	0.3465	0.0914	0.065*
C15	−0.4630 (4)	0.3264 (4)	0.15121 (17)	0.0489 (8)
C16	−0.5284 (5)	0.2614 (4)	0.20677 (18)	0.0593 (9)
H16	−0.6562	0.2791	0.2199	0.071*
C17	−0.4023 (5)	0.1686 (4)	0.24343 (17)	0.0564 (9)
H17	−0.4454	0.1231	0.2814	0.068*
C18	−0.2165 (5)	−0.1856 (4)	0.21573 (19)	0.0591 (9)
H18	−0.3020	−0.1133	0.1920	0.071*
C19	−0.3515 (6)	−0.2928 (4)	0.2507 (2)	0.0636 (10)
C20	−0.4402 (7)	−0.4046 (5)	0.3506 (3)	0.0948 (15)
H20A	−0.5692	−0.3599	0.3509	0.142*
H20B	−0.3884	−0.4159	0.3950	0.142*
H20C	−0.4494	−0.5012	0.3299	0.142*
C21	−0.0987 (6)	−0.2697 (4)	0.1635 (2)	0.0731 (11)
H21A	−0.0013	−0.3339	0.1857	0.088*
H21B	−0.1884	−0.3331	0.1375	0.088*
C22	0.0040 (6)	−0.1652 (4)	0.1186 (2)	0.0635 (10)
C23	−0.0986 (7)	−0.0965 (5)	0.0657 (2)	0.0777 (12)
H23	−0.2311	−0.1194	0.0570	0.093*
C24	−0.0046 (8)	0.0060 (6)	0.0261 (2)	0.0874 (14)
H24	−0.0743	0.0508	−0.0091	0.105*
C25	0.1903 (8)	0.0413 (6)	0.0387 (3)	0.0911 (14)
H25	0.2528	0.1109	0.0126	0.109*
C26	0.2911 (7)	−0.0259 (6)	0.0894 (3)	0.0903 (14)
H26	0.4238	−0.0028	0.0976	0.108*
C27	0.2016 (6)	−0.1274 (5)	0.1291 (2)	0.0816 (13)
H27	0.2746	−0.1717	0.1637	0.098*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0668 (15)	0.0396 (15)	0.0809 (17)	0.0042 (11)	−0.0176 (12)	0.0071 (12)
O2	0.0508 (15)	0.087 (2)	0.103 (2)	0.0157 (14)	−0.0078 (14)	0.0168 (17)
O3	0.086 (2)	0.128 (3)	0.104 (2)	0.033 (2)	0.0136 (17)	0.062 (2)
O4	0.0676 (15)	0.0495 (15)	0.088 (2)	−0.0010 (13)	0.0039 (14)	0.0021 (14)
O5	0.093 (2)	0.072 (2)	0.132 (3)	−0.0315 (19)	−0.0316 (19)	0.004 (2)
N1	0.0474 (14)	0.0488 (16)	0.0552 (16)	−0.0002 (13)	−0.0033 (12)	−0.0010 (14)
N2	0.0578 (16)	0.0465 (16)	0.0688 (19)	0.0048 (14)	−0.0034 (14)	−0.0125 (14)
N3	0.0571 (18)	0.064 (2)	0.072 (2)	0.0105 (15)	−0.0038 (15)	0.0147 (17)
N4	0.0621 (17)	0.0311 (15)	0.0703 (19)	0.0030 (13)	−0.0170 (14)	0.0037 (13)
C1	0.066 (2)	0.071 (3)	0.074 (3)	0.007 (2)	−0.0150 (19)	−0.001 (2)
C2	0.064 (2)	0.095 (4)	0.102 (3)	0.009 (3)	−0.020 (2)	0.012 (3)
C3	0.062 (3)	0.145 (5)	0.094 (4)	−0.008 (3)	−0.028 (2)	0.003 (4)
C4	0.089 (4)	0.153 (6)	0.109 (4)	−0.005 (4)	−0.039 (3)	−0.045 (4)
C5	0.073 (3)	0.104 (4)	0.092 (3)	0.004 (2)	−0.018 (2)	−0.034 (3)
C6	0.0458 (17)	0.070 (2)	0.0444 (19)	−0.0047 (18)	0.0009 (13)	0.0002 (17)
C7	0.0468 (18)	0.0410 (17)	0.065 (2)	0.0064 (15)	0.0035 (15)	−0.0057 (16)
C8	0.0424 (16)	0.0355 (17)	0.0530 (19)	0.0032 (14)	−0.0005 (13)	0.0001 (14)
C9	0.0440 (18)	0.046 (2)	0.052 (2)	0.0001 (14)	0.0027 (14)	−0.0001 (15)
C10	0.080 (3)	0.046 (2)	0.119 (4)	0.016 (2)	−0.025 (2)	−0.018 (2)
C11	0.0440 (17)	0.0440 (19)	0.0469 (19)	0.0036 (14)	0.0046 (14)	0.0020 (14)
C12	0.0439 (16)	0.0315 (15)	0.0514 (18)	0.0007 (13)	0.0008 (13)	−0.0007 (14)
C13	0.0421 (17)	0.0472 (18)	0.065 (2)	0.0044 (15)	0.0073 (15)	0.0034 (17)
C14	0.0540 (19)	0.053 (2)	0.057 (2)	0.0031 (16)	0.0082 (15)	0.0122 (16)
C15	0.0441 (16)	0.0418 (18)	0.060 (2)	0.0067 (14)	−0.0031 (15)	0.0012 (15)
C16	0.0439 (17)	0.069 (2)	0.065 (2)	0.0101 (18)	0.0069 (15)	0.011 (2)
C17	0.0525 (18)	0.060 (2)	0.057 (2)	0.0054 (17)	0.0089 (15)	0.0169 (16)
C18	0.067 (2)	0.0341 (17)	0.075 (3)	0.0029 (16)	−0.0178 (19)	−0.0030 (17)
C19	0.064 (2)	0.0346 (17)	0.092 (3)	0.0031 (17)	−0.007 (2)	−0.0013 (19)
C20	0.088 (3)	0.063 (3)	0.136 (4)	−0.007 (2)	0.036 (3)	0.011 (3)
C21	0.086 (3)	0.045 (2)	0.087 (3)	0.0055 (19)	−0.007 (2)	−0.009 (2)
C22	0.072 (2)	0.047 (2)	0.070 (2)	0.0085 (18)	−0.0045 (19)	−0.0138 (18)
C23	0.086 (3)	0.076 (3)	0.070 (3)	0.012 (2)	−0.016 (2)	−0.016 (2)
C24	0.117 (4)	0.091 (4)	0.053 (2)	0.014 (3)	−0.003 (2)	−0.005 (2)
C25	0.106 (4)	0.088 (3)	0.081 (3)	0.011 (3)	0.025 (3)	−0.003 (3)
C26	0.067 (3)	0.091 (3)	0.113 (4)	0.007 (3)	0.012 (3)	−0.003 (3)
C27	0.069 (3)	0.079 (3)	0.096 (3)	0.017 (2)	−0.011 (2)	0.002 (3)

Geometric parameters (Å, º)

O1—C9	1.244 (4)	C11—C12	1.500 (4)
O2—N3	1.218 (4)	C12—C13	1.381 (4)
O3—N3	1.217 (4)	C12—C17	1.384 (4)
O4—C19	1.313 (5)	C13—C14	1.378 (5)
O4—C20	1.473 (5)	C13—H13	0.9300
O5—C19	1.201 (4)	C14—C15	1.379 (4)
N1—C9	1.374 (4)	C14—H14	0.9300
N1—N2	1.403 (4)	C15—C16	1.361 (5)
N1—C6	1.434 (4)	C16—C17	1.384 (5)
N2—C7	1.306 (4)	C16—H16	0.9300
N3—C15	1.474 (4)	C17—H17	0.9300
N4—C11	1.326 (4)	C18—C19	1.520 (6)
N4—C18	1.452 (4)	C18—C21	1.550 (6)
N4—H4	0.8600	C18—H18	0.9800
C1—C6	1.367 (6)	C20—H20A	0.9600
C1—C2	1.376 (5)	C20—H20B	0.9600
C1—H1	0.9300	C20—H20C	0.9600
C2—C3	1.352 (8)	C21—C22	1.497 (6)
C2—H2	0.9300	C21—H21A	0.9700
C3—C4	1.365 (8)	C21—H21B	0.9700
C3—H3	0.9300	C22—C27	1.387 (6)
C4—C5	1.386 (7)	C22—C23	1.396 (6)
C4—H4A	0.9300	C23—C24	1.391 (7)
C5—C6	1.391 (6)	C23—H23	0.9300
C5—H5	0.9300	C24—C25	1.370 (7)
C7—C8	1.440 (5)	C24—H24	0.9300
C7—C10	1.494 (5)	C25—C26	1.352 (7)
C8—C11	1.385 (4)	C25—H25	0.9300
C8—C9	1.445 (4)	C26—C27	1.371 (7)
C10—H10A	0.9600	C26—H26	0.9300
C10—H10B	0.9600	C27—H27	0.9300
C10—H10C	0.9600
C19—O4—C20	116.1 (3)	C12—C13—H13	119.5
C9—N1—N2	112.5 (2)	C13—C14—C15	118.3 (3)
C9—N1—C6	129.5 (3)	C13—C14—H14	120.9
N2—N1—C6	117.7 (3)	C15—C14—H14	120.9
C7—N2—N1	106.2 (3)	C16—C15—C14	122.2 (3)
O3—N3—O2	123.6 (3)	C16—C15—N3	118.5 (3)
O3—N3—C15	118.1 (3)	C14—C15—N3	119.4 (3)
O2—N3—C15	118.2 (3)	C15—C16—C17	119.1 (3)
C11—N4—C18	127.5 (3)	C15—C16—H16	120.4
C11—N4—H4	116.3	C17—C16—H16	120.4
C18—N4—H4	116.3	C16—C17—C12	120.1 (3)
C6—C1—C2	119.6 (4)	C16—C17—H17	119.9
C6—C1—H1	120.2	C12—C17—H17	119.9
C2—C1—H1	120.2	N4—C18—C19	113.7 (3)
C3—C2—C1	121.3 (5)	N4—C18—C21	111.3 (3)
C3—C2—H2	119.3	C19—C18—C21	110.8 (3)
C1—C2—H2	119.3	N4—C18—H18	106.9
C2—C3—C4	118.7 (4)	C19—C18—H18	106.9
C2—C3—H3	120.6	C21—C18—H18	106.9
C4—C3—H3	120.6	O5—C19—O4	124.1 (4)
C3—C4—C5	122.3 (5)	O5—C19—C18	121.9 (4)
C3—C4—H4A	118.8	O4—C19—C18	114.0 (3)
C5—C4—H4A	118.8	O4—C20—H20A	109.5
C4—C5—C6	117.3 (5)	O4—C20—H20B	109.5
C4—C5—H5	121.4	H20A—C20—H20B	109.5
C6—C5—H5	121.4	O4—C20—H20C	109.5
C1—C6—C5	120.7 (3)	H20A—C20—H20C	109.5
C1—C6—N1	121.1 (3)	H20B—C20—H20C	109.5
C5—C6—N1	118.1 (4)	C22—C21—C18	112.6 (3)
N2—C7—C8	111.6 (3)	C22—C21—H21A	109.1
N2—C7—C10	117.9 (3)	C18—C21—H21A	109.1
C8—C7—C10	130.4 (3)	C22—C21—H21B	109.1
C11—C8—C7	132.0 (3)	C18—C21—H21B	109.1
C11—C8—C9	122.8 (3)	H21A—C21—H21B	107.8
C7—C8—C9	105.3 (3)	C27—C22—C23	117.2 (4)
O1—C9—N1	126.9 (3)	C27—C22—C21	121.8 (4)
O1—C9—C8	128.6 (3)	C23—C22—C21	120.9 (4)
N1—C9—C8	104.4 (3)	C24—C23—C22	120.6 (4)
C7—C10—H10A	109.5	C24—C23—H23	119.7
C7—C10—H10B	109.5	C22—C23—H23	119.7
H10A—C10—H10B	109.5	C25—C24—C23	120.3 (5)
C7—C10—H10C	109.5	C25—C24—H24	119.9
H10A—C10—H10C	109.5	C23—C24—H24	119.9
H10B—C10—H10C	109.5	C26—C25—C24	119.4 (5)
N4—C11—C8	120.0 (3)	C26—C25—H25	120.3
N4—C11—C12	118.9 (3)	C24—C25—H25	120.3
C8—C11—C12	121.1 (3)	C25—C26—C27	121.4 (5)
C13—C12—C17	119.4 (3)	C25—C26—H26	119.3
C13—C12—C11	120.7 (3)	C27—C26—H26	119.3
C17—C12—C11	119.8 (3)	C26—C27—C22	121.2 (4)
C14—C13—C12	120.9 (3)	C26—C27—H27	119.4
C14—C13—H13	119.5	C22—C27—H27	119.4
C9—N1—N2—C7	−0.7 (4)	N4—C11—C12—C17	81.3 (4)
C6—N1—N2—C7	173.7 (3)	C8—C11—C12—C17	−99.0 (4)
C6—C1—C2—C3	0.3 (7)	C17—C12—C13—C14	1.0 (5)
C1—C2—C3—C4	0.3 (9)	C11—C12—C13—C14	−177.5 (3)
C2—C3—C4—C5	−1.7 (10)	C12—C13—C14—C15	−0.1 (5)
C3—C4—C5—C6	2.4 (9)	C13—C14—C15—C16	−0.7 (5)
C2—C1—C6—C5	0.5 (6)	C13—C14—C15—N3	179.3 (3)
C2—C1—C6—N1	176.6 (4)	O3—N3—C15—C16	171.5 (4)
C4—C5—C6—C1	−1.7 (7)	O2—N3—C15—C16	−7.0 (5)
C4—C5—C6—N1	−178.0 (4)	O3—N3—C15—C14	−8.5 (5)
C9—N1—C6—C1	18.5 (5)	O2—N3—C15—C14	173.0 (3)
N2—N1—C6—C1	−154.8 (3)	C14—C15—C16—C17	0.6 (6)
C9—N1—C6—C5	−165.3 (4)	N3—C15—C16—C17	−179.4 (3)
N2—N1—C6—C5	21.4 (5)	C15—C16—C17—C12	0.3 (6)
N1—N2—C7—C8	−0.2 (4)	C13—C12—C17—C16	−1.1 (5)
N1—N2—C7—C10	−178.9 (3)	C11—C12—C17—C16	177.4 (3)
N2—C7—C8—C11	−179.3 (3)	C11—N4—C18—C19	−121.9 (4)
C10—C7—C8—C11	−0.9 (7)	C11—N4—C18—C21	112.2 (4)
N2—C7—C8—C9	1.0 (4)	C20—O4—C19—O5	−3.5 (5)
C10—C7—C8—C9	179.4 (4)	C20—O4—C19—C18	177.1 (3)
N2—N1—C9—O1	179.9 (3)	N4—C18—C19—O5	170.7 (4)
C6—N1—C9—O1	6.3 (5)	C21—C18—C19—O5	−63.1 (5)
N2—N1—C9—C8	1.3 (3)	N4—C18—C19—O4	−10.0 (4)
C6—N1—C9—C8	−172.3 (3)	C21—C18—C19—O4	116.3 (4)
C11—C8—C9—O1	0.4 (5)	N4—C18—C21—C22	−64.3 (4)
C7—C8—C9—O1	−179.9 (3)	C19—C18—C21—C22	168.2 (3)
C11—C8—C9—N1	179.0 (3)	C18—C21—C22—C27	97.0 (5)
C7—C8—C9—N1	−1.3 (3)	C18—C21—C22—C23	−80.1 (5)
C18—N4—C11—C8	−176.7 (3)	C27—C22—C23—C24	−0.4 (6)
C18—N4—C11—C12	3.1 (5)	C21—C22—C23—C24	176.9 (4)
C7—C8—C11—N4	−174.9 (4)	C22—C23—C24—C25	−0.3 (7)
C9—C8—C11—N4	4.7 (5)	C23—C24—C25—C26	0.9 (7)
C7—C8—C11—C12	5.3 (5)	C24—C25—C26—C27	−0.8 (7)
C9—C8—C11—C12	−175.1 (3)	C25—C26—C27—C22	0.1 (7)
N4—C11—C12—C13	−100.2 (4)	C23—C22—C27—C26	0.5 (6)
C8—C11—C12—C13	79.5 (4)	C21—C22—C27—C26	−176.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O1	0.86	2.04	2.738 (4)	138
C1—H1···O1	0.93	2.41	3.001 (4)	121
C20—H20A···O1^i	0.96	2.55	3.385 (5)	145

Symmetry code: (i) x−1, y, z.