Dimethyl 1-{4-[4,5-bis­(methoxy­carbon­yl)-1,2,3-triazol-1-ylmethyl­carbon­yl]phen­yl}-1H-pyrazole-3,4-dicarboxyl­ate

In the title mol­ecule, C₂₁H₁₉N₅O₉, the dihedral angle between the mean planes of the triazole and pyrazole rings is 82.4 (1)°. In the solid state, symmetry-related mol­ecules are linked by weak inter­molecular C—H...O and C—H...N hydrogen bonds, having a graph-set motif of R₂²(10), to form chains running parallel to the a axis.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.030
• wR factor = 0.072
• Data-to-parameter ratio = 11.5

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......       0.90

Author Response: ...`see _publ_section_exptl_refinement'

Alert level B
REFLT03_ALERT_3_B  Reflection count < 90% complete (theta max?)
           From the CIF: _diffrn_reflns_theta_max           25.56
           From the CIF: _diffrn_reflns_theta_full          25.00
           From the CIF: _reflns_number_total               3706
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         4134
           Completeness (_total/calc)             89.65%
PLAT022_ALERT_3_B Ratio Unique / Expected Reflections too Low ....       0.90
PLAT432_ALERT_2_B Short Inter X...Y Contact  O13    ..  C29     ..       2.87 Ang.

Alert level C
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H11    ..  O29     ..       2.90 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H10    ..  O26     ..       2.86 Ang.
PLAT481_ALERT_4_C Long D...A H-Bond Reported C11    ..  O29     ..       3.82 Ang.

   1 ALERT level A = In general: serious problem
   3 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

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

---

S1. Comment

Azole derivatives, such as derivatives of pyrazole and triazole have been reported to show analgesic and anti-inflammatory activities (Thamotharan et al., 2003). The title compound, (I), is very useful in organic synthesis and compounds such as (I) are usually regarded as key synthons of oligomeric carboxamides, which are known to bind to DNA by lodging in the groove (Lee et al., 1989; Chambers et al., 1985). The present X-ray crystal structure analysis has been undertaken in order to study the stereochemistry and crystal packing of (I) (Fig. 1).

In (I), the bond lengths and angles of the phenyl-1H-pyrazole-3,4-dicarboxylate moiety are comparable to those found in two related structures – dimethyl 1-(3-chloro-4-methylphenyl)pyrazole-3,4-dicarboxylate (Thamotharan et al., 2003), (II), and dimethyl 1-(7-acetoxy-4-methyl-2-oxo-2H-chromen- 8-ylmethyl)-1H-pyrazole-3,4-dicarboxylate (Thamotharan et al., 2004), (III). In all these three structures the following relations for the bond angles are fulfilled: C5—N1—N2 > C3—N2—N1 and N2—C3—C4 > N1—C5—C4. However, conformational differences are observed in the pyrazole-3,4-dicarboxylate groups of (I), (II) and (III). The least-squares fits between the pyrazol-3,4-dicarboxylate groups of (I) and (II) (Fig. 2a) and (I) and (III) (Fig. 2b) show deviations of 1.336 and 1.108 Å, respectively. The bond lengths and angles of the 1,2,3-triazole-4,5-dicarboxylate group are comparable to those found in two related structures − 5-amino-4-(2,6-dichlorophenyl)-1-(2-nitrophenyl)-1H-1,2,3- triazole (Sen & Venkatesan, 1984), (IV), and diethyl 1-(8-dimethylamino-1-naphthyl)-1H-1,2,3-triazole-4,5- dicarboxylate (Nagawa et al., 1990), (V).

The triazole and pyrazole rings are nearly orthogonal, the dihedral angle between the mean planes of the rings being 82.4 (1)°. The dihedral angle between the mean planes of the pyrazole and phenyl rings is 14.0 (1)°. The exocyclic angle C6—N1—C5 [128.41 (14)°] deviates significantly from the normal value (Lapasset & Falgueirettes, 1972). A similar deviation, 128.28 (12)°, is observed in (II). This deviation may be due to the steric repulsion between the atoms H5 of the pyrazole ring and atom H11 of the phenyl ring (H···H = 2.36 Å). The widening of the exocyclic angles C13—C3—C4 [129.98 (14)°] and C3—C4—C16 [129.31 (15)°] from 120° may be due to the steric interaction between atoms O14 and O17 [O14···O17 = 2.96 (s.u.?) Å]. The dihedral angles between the pyrazole ring and the two 3,4-methoxycarbonyl groups are 53.9 (1) and 22.8 (1)°.

The dihedral angle between the mean planes of triazole and phenyl rings is 68.3 (0)°. The torsion angles C25—C24—C29—O30 [166.06 (15)°] and C24—C25—C26—O27 [151.53 (14)° this is N21—C25—C26—O27] show that the two carbonyl groups are twisted from the mean plane of the triazole ring on opposite sides. A similar observation has been made for structure (V). The dihedral angles between the mean planes of the triazole ring and 4,5-methoxycarbonyl groups are 19.6 (1) and 25.8 (1)°.

In (I), atom C19 acts as a donor for a weak intermolecular C—H···N interaction with atom N23 of the triazole moiety of an adjacent molecule. Atom C8 is involved in a weak intermolecular C—H···O interaction with carboxyl atom O30 of an adjacent molecule. The symmetry-related molecules are linked by intermolecular C—H···O and C—H···N hydrogen bonds (Table 2), having a graph-set motif of R²₂(10) (Bernstein et al., 1995) (Fig. 3), to form a continuous chain, which runs parallel to the a axis.

S2. Experimental

A solution of 1-[4-(2-azido-acetyl)-phenyl-1H-pyrazole-3,4-dicarboxylic acid dimethylester (0.005 mol) in dry xylene (4 ml) was treated with dimethyl acetylene dicarboxylate (0.005 mol), and the reaction mixture was heated at 373 K till the evolution of carbon dioxide ceased (approximately 1 h). The solvent was removed under reduced pressure to obtain an yellow solid, which was recrystallized from dry benzene.

S3. Refinement

All H atoms were treated as riding [C—H = 0.93–0.99 Å and U_iso(H) = 1.5U_eq(C) for methyl H and U_iso(H) = 1.2 U_eq(C) for others]. A short intermolecular contact, with a distance of 2.87 Å, is observed between the atoms O13 and C29^iv [symmetry code: (iv) −1 + x, 1 + y, z]. The TWIN law 1 0 0 0 1 0 0 0 − 1 2 was applied and the structure was refined with one BASF parameter (0.48575) for unequal components, as the monoclinic cell setting with β approximately 90° emulated orthorhombic. 15 systematic violations were indicated by the SHELXS97 (Sheldrick, 1997) program. These violations may be due to the twinning of the crystal. The reflection 109 was a strong reflection, which should have been systematically absent. However, the crystal structure was refined in the space group P2₁/c only, rejecting all the reflections that showed systematic absent violations. Two reflections, 029 and 669, were omitted.

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).

Figures

	Fig. 1. A view of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown by circles of arbitrary radii.
	Fig. 2. Superimposed fit between the pyrazol-3,4-dicarboxylate moieties of (a) (I) in blue and (II) in red, and (b) (I) in blue and (III) in green.
	Fig. 3. The crystal packing, with the intermolecular hydrogen bonds shown as dashed lines.

Dimethyl 1-{4-[4,5-bis(methoxycarbonyl)-1,2,3-triazol-1- ylmethylcarbonyl]phenyl}-1H-pyrazole-3,4-dicarboxylate

Crystal data

C21H19N5O9	F(000) = 1008
Mr = 485.41	Dx = 1.457 Mg m^−3
Monoclinic, P21/c	Melting point: 415 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 12.0798 (12) Å	Cell parameters from 10027 reflections
b = 8.5500 (6) Å	θ = 3.7–25.8°
c = 21.424 (2) Å	µ = 0.12 mm^−1
β = 90.070 (9)°	T = 173 K
V = 2212.7 (4) Å^3	Block, yellow
Z = 4	0.32 × 0.30 × 0.28 mm

Data collection

Stoe IPDS-II diffractometer	3534 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.028
Graphite monochromator	θmax = 25.6°, θmin = 3.7°
ω scans	h = −14→14
10027 measured reflections	k = −10→10
3706 independent reflections	l = −22→25

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.072	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0482P)^2 + 0.1748P] where P = (Fo^2 + 2Fc^2)/3
3706 reflections	(Δ/σ)max < 0.001
321 parameters	Δρmax = 0.14 e Å^−3
0 restraints	Δρmin = −0.20 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
N1	0.46999 (11)	0.72996 (16)	0.49269 (6)	0.0198 (3)
N2	0.54067 (11)	0.79221 (16)	0.44890 (6)	0.0220 (3)
C3	0.61878 (13)	0.86164 (18)	0.48238 (8)	0.0196 (3)
C4	0.60023 (12)	0.84420 (19)	0.54751 (7)	0.0201 (3)
C5	0.50350 (12)	0.75874 (19)	0.55206 (7)	0.0206 (3)
H5	0.4676	0.7265	0.5893	0.025*
C6	0.37712 (13)	0.64068 (18)	0.47204 (8)	0.0193 (3)
C7	0.37412 (14)	0.5938 (2)	0.40975 (8)	0.0244 (3)
H7	0.4331	0.6197	0.3824	0.029*
C8	0.28422 (14)	0.5092 (2)	0.38829 (7)	0.0234 (3)
H8	0.2813	0.4780	0.3458	0.028*
C9	0.19732 (13)	0.46891 (17)	0.42851 (7)	0.0191 (3)
C10	0.20222 (14)	0.5148 (2)	0.49125 (8)	0.0260 (4)
H10	0.1442	0.4865	0.5190	0.031*
C11	0.29127 (15)	0.6012 (2)	0.51307 (8)	0.0275 (4)
H11	0.2941	0.6335	0.5555	0.033*
C12	0.09988 (12)	0.37863 (18)	0.40549 (7)	0.0197 (3)
O12	0.02937 (10)	0.32344 (15)	0.43959 (6)	0.0284 (3)
C13	0.71423 (13)	0.93490 (18)	0.44834 (8)	0.0211 (3)
O13	0.70515 (11)	1.02966 (16)	0.40713 (6)	0.0336 (3)
O14	0.80897 (10)	0.87519 (15)	0.46867 (6)	0.0284 (3)
C15	0.90910 (14)	0.9326 (3)	0.43840 (9)	0.0342 (4)
H15A	0.9065	0.9073	0.3938	0.051*
H15B	0.9740	0.8829	0.4574	0.051*
H15C	0.9141	1.0463	0.4437	0.051*
C16	0.66536 (13)	0.90504 (19)	0.60044 (8)	0.0220 (3)
O16	0.66421 (11)	0.85034 (17)	0.65262 (6)	0.0333 (3)
O17	0.72686 (11)	1.02877 (14)	0.58326 (6)	0.0304 (3)
C18	0.79753 (18)	1.0934 (2)	0.63138 (11)	0.0416 (5)
H18A	0.7524	1.1232	0.6675	0.062*
H18B	0.8359	1.1858	0.6151	0.062*
H18C	0.8521	1.0148	0.6441	0.062*
C19	0.09411 (13)	0.3567 (2)	0.33415 (7)	0.0229 (3)
H19A	0.1016	0.4597	0.3135	0.028*
H19B	0.1565	0.2900	0.3204	0.028*
N21	−0.01013 (10)	0.28467 (16)	0.31543 (6)	0.0199 (3)
N22	−0.01109 (11)	0.13186 (16)	0.29979 (7)	0.0228 (3)
N23	−0.11404 (11)	0.09241 (16)	0.28825 (6)	0.0220 (3)
C24	−0.17963 (12)	0.21995 (17)	0.29617 (7)	0.0178 (3)
C25	−0.11377 (13)	0.34573 (19)	0.31326 (7)	0.0188 (3)
C26	−0.13518 (14)	0.51480 (19)	0.32502 (7)	0.0214 (3)
O26	−0.07727 (12)	0.59593 (16)	0.35712 (7)	0.0374 (3)
O27	−0.22462 (10)	0.56020 (13)	0.29418 (6)	0.0258 (3)
C28	−0.26107 (16)	0.7200 (2)	0.30470 (10)	0.0324 (4)
H28A	−0.2959	0.7277	0.3459	0.049*
H28B	−0.3147	0.7495	0.2724	0.049*
H28C	−0.1972	0.7905	0.3029	0.049*
C29	−0.30246 (13)	0.20803 (18)	0.29351 (7)	0.0188 (3)
O29	−0.36549 (9)	0.29934 (14)	0.31797 (6)	0.0258 (3)
O30	−0.33306 (9)	0.08029 (15)	0.26162 (6)	0.0267 (3)
C31	−0.45088 (14)	0.0455 (3)	0.26312 (12)	0.0406 (5)
H31A	−0.4722	0.0151	0.3055	0.061*
H31B	−0.4670	−0.0405	0.2343	0.061*
H31C	−0.4928	0.1385	0.2506	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0197 (6)	0.0196 (6)	0.0203 (7)	−0.0016 (5)	−0.0005 (5)	0.0008 (5)
N2	0.0230 (6)	0.0224 (7)	0.0206 (6)	−0.0032 (5)	−0.0004 (5)	0.0020 (5)
C3	0.0195 (7)	0.0191 (7)	0.0201 (7)	0.0007 (6)	−0.0017 (6)	0.0007 (6)
C4	0.0206 (7)	0.0211 (8)	0.0186 (8)	0.0029 (6)	−0.0035 (6)	−0.0007 (6)
C5	0.0210 (7)	0.0229 (8)	0.0178 (7)	0.0015 (6)	0.0010 (6)	0.0002 (6)
C6	0.0186 (7)	0.0179 (7)	0.0215 (7)	0.0005 (6)	−0.0036 (6)	0.0006 (6)
C7	0.0232 (8)	0.0289 (8)	0.0210 (8)	−0.0035 (7)	0.0020 (6)	−0.0007 (7)
C8	0.0248 (8)	0.0282 (9)	0.0172 (8)	−0.0044 (7)	0.0010 (6)	−0.0010 (6)
C9	0.0188 (7)	0.0167 (7)	0.0217 (7)	0.0003 (6)	−0.0035 (6)	0.0025 (6)
C10	0.0236 (8)	0.0330 (9)	0.0214 (8)	−0.0078 (7)	0.0025 (7)	−0.0001 (7)
C11	0.0283 (8)	0.0357 (9)	0.0185 (8)	−0.0081 (7)	0.0032 (7)	−0.0045 (7)
C12	0.0196 (7)	0.0173 (8)	0.0221 (8)	0.0001 (6)	−0.0026 (6)	0.0037 (6)
O12	0.0257 (6)	0.0362 (7)	0.0233 (6)	−0.0112 (5)	0.0000 (5)	0.0050 (5)
C13	0.0257 (8)	0.0194 (7)	0.0184 (7)	−0.0031 (6)	−0.0011 (6)	−0.0008 (6)
O13	0.0333 (7)	0.0365 (7)	0.0310 (7)	−0.0008 (6)	0.0011 (6)	0.0144 (6)
O14	0.0194 (5)	0.0362 (7)	0.0295 (6)	−0.0040 (5)	−0.0013 (5)	0.0098 (5)
C15	0.0228 (8)	0.0472 (12)	0.0326 (10)	−0.0105 (8)	0.0005 (7)	0.0031 (8)
C16	0.0190 (7)	0.0247 (8)	0.0224 (7)	0.0035 (6)	−0.0027 (6)	−0.0049 (6)
O16	0.0326 (6)	0.0466 (8)	0.0206 (6)	−0.0029 (6)	−0.0059 (5)	0.0006 (5)
O17	0.0334 (6)	0.0240 (6)	0.0337 (7)	−0.0059 (5)	−0.0096 (6)	−0.0035 (5)
C18	0.0404 (11)	0.0314 (9)	0.0531 (12)	−0.0052 (9)	−0.0231 (10)	−0.0061 (9)
C19	0.0195 (7)	0.0286 (9)	0.0207 (8)	−0.0063 (6)	−0.0028 (6)	0.0018 (6)
N21	0.0191 (6)	0.0228 (7)	0.0179 (6)	−0.0019 (5)	−0.0022 (5)	−0.0006 (5)
N22	0.0228 (6)	0.0218 (7)	0.0239 (6)	0.0003 (5)	0.0000 (6)	−0.0036 (5)
N23	0.0225 (6)	0.0206 (7)	0.0228 (7)	0.0008 (5)	−0.0013 (6)	−0.0049 (5)
C24	0.0204 (7)	0.0179 (7)	0.0149 (7)	−0.0013 (6)	−0.0007 (6)	−0.0004 (6)
C25	0.0220 (7)	0.0203 (8)	0.0142 (7)	0.0004 (6)	−0.0027 (6)	−0.0002 (6)
C26	0.0272 (7)	0.0191 (8)	0.0179 (7)	−0.0027 (6)	−0.0014 (6)	−0.0003 (6)
O26	0.0473 (8)	0.0244 (6)	0.0405 (8)	−0.0002 (6)	−0.0198 (7)	−0.0081 (6)
O27	0.0286 (6)	0.0154 (5)	0.0333 (7)	0.0025 (5)	−0.0077 (5)	−0.0027 (5)
C28	0.0367 (9)	0.0201 (8)	0.0405 (10)	0.0052 (7)	−0.0029 (8)	−0.0037 (7)
C29	0.0215 (7)	0.0199 (7)	0.0149 (7)	−0.0007 (6)	−0.0004 (6)	0.0017 (6)
O29	0.0244 (5)	0.0228 (6)	0.0302 (6)	0.0036 (5)	0.0035 (5)	0.0020 (5)
O30	0.0207 (6)	0.0302 (6)	0.0292 (6)	−0.0058 (5)	−0.0018 (5)	−0.0086 (5)
C31	0.0212 (8)	0.0423 (11)	0.0583 (13)	−0.0090 (8)	−0.0041 (9)	−0.0120 (10)

Geometric parameters (Å, º)

N1—C5	1.357 (2)	C16—O16	1.212 (2)
N1—N2	1.3764 (19)	C16—O17	1.344 (2)
N1—C6	1.427 (2)	O17—C18	1.447 (2)
N2—C3	1.325 (2)	C18—H18A	0.9800
C3—C4	1.421 (2)	C18—H18B	0.9800
C3—C13	1.502 (2)	C18—H18C	0.9800
C4—C5	1.382 (2)	C19—N21	1.4575 (19)
C4—C16	1.474 (2)	C19—H19A	0.9900
C5—H5	0.9500	C19—H19B	0.9900
C6—C7	1.394 (2)	N21—N22	1.349 (2)
C6—C11	1.402 (2)	N21—C25	1.357 (2)
C7—C8	1.383 (2)	N22—N23	1.3117 (19)
C7—H7	0.9500	N23—C24	1.359 (2)
C8—C9	1.402 (2)	C24—C25	1.387 (2)
C8—H8	0.9500	C24—C29	1.488 (2)
C9—C10	1.401 (2)	C25—C26	1.490 (2)
C9—C12	1.491 (2)	C26—O26	1.201 (2)
C10—C11	1.386 (2)	C26—O27	1.324 (2)
C10—H10	0.9500	O27—C28	1.453 (2)
C11—H11	0.9500	C28—H28A	0.9800
C12—O12	1.218 (2)	C28—H28B	0.9800
C12—C19	1.541 (2)	C28—H28C	0.9800
C13—O13	1.203 (2)	C29—O29	1.210 (2)
C13—O14	1.326 (2)	C29—O30	1.340 (2)
O14—C15	1.458 (2)	O30—C31	1.454 (2)
C15—H15A	0.9800	C31—H31A	0.9800
C15—H15B	0.9800	C31—H31B	0.9800
C15—H15C	0.9800	C31—H31C	0.9800
C5—N1—N2	112.60 (12)	O17—C16—C4	111.21 (14)
C5—N1—C6	128.41 (14)	C16—O17—C18	115.53 (15)
N2—N1—C6	118.92 (13)	O17—C18—H18A	109.5
C3—N2—N1	104.25 (13)	O17—C18—H18B	109.5
N2—C3—C4	111.80 (14)	H18A—C18—H18B	109.5
N2—C3—C13	118.08 (14)	O17—C18—H18C	109.5
C4—C3—C13	129.98 (14)	H18A—C18—H18C	109.5
C5—C4—C3	105.02 (14)	H18B—C18—H18C	109.5
C5—C4—C16	125.65 (15)	N21—C19—C12	111.24 (13)
C3—C4—C16	129.31 (15)	N21—C19—H19A	109.4
N1—C5—C4	106.32 (14)	C12—C19—H19A	109.4
N1—C5—H5	126.8	N21—C19—H19B	109.4
C4—C5—H5	126.8	C12—C19—H19B	109.4
C7—C6—C11	120.86 (15)	H19A—C19—H19B	108.0
C7—C6—N1	118.05 (15)	N22—N21—C25	110.87 (13)
C11—C6—N1	121.09 (15)	N22—N21—C19	119.00 (13)
C8—C7—C6	119.22 (16)	C25—N21—C19	130.06 (14)
C8—C7—H7	120.4	N23—N22—N21	107.68 (13)
C6—C7—H7	120.4	N22—N23—C24	108.85 (13)
C7—C8—C9	120.82 (15)	N23—C24—C25	108.72 (13)
C7—C8—H8	119.6	N23—C24—C29	121.46 (13)
C9—C8—H8	119.6	C25—C24—C29	129.41 (14)
C10—C9—C8	119.34 (14)	N21—C25—C24	103.87 (13)
C10—C9—C12	119.64 (15)	N21—C25—C26	121.84 (14)
C8—C9—C12	121.02 (14)	C24—C25—C26	134.23 (14)
C11—C10—C9	120.31 (15)	O26—C26—O27	126.22 (16)
C11—C10—H10	119.8	O26—C26—C25	123.79 (15)
C9—C10—H10	119.8	O27—C26—C25	109.98 (13)
C10—C11—C6	119.44 (15)	C26—O27—C28	116.46 (13)
C10—C11—H11	120.3	O27—C28—H28A	109.5
C6—C11—H11	120.3	O27—C28—H28B	109.5
O12—C12—C9	123.68 (14)	H28A—C28—H28B	109.5
O12—C12—C19	121.12 (14)	O27—C28—H28C	109.5
C9—C12—C19	115.19 (13)	H28A—C28—H28C	109.5
O13—C13—O14	125.32 (15)	H28B—C28—H28C	109.5
O13—C13—C3	124.60 (15)	O29—C29—O30	124.97 (14)
O14—C13—C3	110.04 (13)	O29—C29—C24	124.54 (14)
C13—O14—C15	116.11 (13)	O30—C29—C24	110.47 (13)
O14—C15—H15A	109.5	C29—O30—C31	115.14 (14)
O14—C15—H15B	109.5	O30—C31—H31A	109.5
H15A—C15—H15B	109.5	O30—C31—H31B	109.5
O14—C15—H15C	109.5	H31A—C31—H31B	109.5
H15A—C15—H15C	109.5	O30—C31—H31C	109.5
H15B—C15—H15C	109.5	H31A—C31—H31C	109.5
O16—C16—O17	124.27 (15)	H31B—C31—H31C	109.5
O16—C16—C4	124.52 (15)
C5—N1—N2—C3	−0.45 (17)	C5—C4—C16—O16	24.3 (3)
C6—N1—N2—C3	−177.71 (13)	C3—C4—C16—O16	−157.52 (17)
N1—N2—C3—C4	0.48 (17)	C5—C4—C16—O17	−156.06 (15)
N1—N2—C3—C13	176.55 (13)	C3—C4—C16—O17	22.1 (2)
N2—C3—C4—C5	−0.35 (18)	O16—C16—O17—C18	2.1 (2)
C13—C3—C4—C5	−175.83 (15)	C4—C16—O17—C18	−177.56 (15)
N2—C3—C4—C16	−178.81 (15)	O12—C12—C19—N21	7.9 (2)
C13—C3—C4—C16	5.7 (3)	C9—C12—C19—N21	−172.90 (13)
N2—N1—C5—C4	0.24 (18)	C12—C19—N21—N22	−103.40 (16)
C6—N1—C5—C4	177.19 (14)	C12—C19—N21—C25	73.3 (2)
C3—C4—C5—N1	0.05 (17)	C25—N21—N22—N23	−0.76 (18)
C16—C4—C5—N1	178.59 (15)	C19—N21—N22—N23	176.51 (14)
C5—N1—C6—C7	−164.06 (16)	N21—N22—N23—C24	0.26 (18)
N2—N1—C6—C7	12.7 (2)	N22—N23—C24—C25	0.32 (18)
C5—N1—C6—C11	16.0 (3)	N22—N23—C24—C29	−172.92 (14)
N2—N1—C6—C11	−167.21 (14)	N22—N21—C25—C24	0.92 (17)
C11—C6—C7—C8	0.9 (2)	C19—N21—C25—C24	−175.97 (14)
N1—C6—C7—C8	−179.03 (15)	N22—N21—C25—C26	−176.54 (14)
C6—C7—C8—C9	−0.7 (2)	C19—N21—C25—C26	6.6 (3)
C7—C8—C9—C10	−0.2 (2)	N23—C24—C25—N21	−0.74 (17)
C7—C8—C9—C12	179.58 (15)	C29—C24—C25—N21	171.78 (15)
C8—C9—C10—C11	1.0 (3)	N23—C24—C25—C26	176.24 (17)
C12—C9—C10—C11	−178.80 (16)	C29—C24—C25—C26	−11.2 (3)
C9—C10—C11—C6	−0.8 (3)	N21—C25—C26—O26	−27.3 (3)
C7—C6—C11—C10	−0.1 (3)	C24—C25—C26—O26	156.19 (18)
N1—C6—C11—C10	179.80 (16)	N21—C25—C26—O27	151.53 (14)
C10—C9—C12—O12	−9.9 (2)	C24—C25—C26—O27	−25.0 (2)
C8—C9—C12—O12	170.26 (16)	O26—C26—O27—C28	−5.7 (2)
C10—C9—C12—C19	170.84 (15)	C25—C26—O27—C28	175.54 (15)
C8—C9—C12—C19	−9.0 (2)	N23—C24—C29—O29	156.25 (15)
N2—C3—C13—O13	54.0 (2)	C25—C24—C29—O29	−15.4 (3)
C4—C3—C13—O13	−130.77 (19)	N23—C24—C29—O30	−22.2 (2)
N2—C3—C13—O14	−123.52 (15)	C25—C24—C29—O30	166.06 (15)
C4—C3—C13—O14	51.7 (2)	O29—C29—O30—C31	−6.3 (2)
O13—C13—O14—C15	0.9 (2)	C24—C29—O30—C31	172.15 (15)
C3—C13—O14—C15	178.36 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19A···N23^i	0.99	2.46	3.316 (2)	144
C8—H8···O30^i	0.95	2.54	3.322 (2)	140
C18—H18C···N22^ii	0.98	2.59	3.540 (3)	164
C19—H19B···O16^ii	0.99	2.54	3.426 (2)	149
C5—H5···O29^iii	0.95	2.35	3.285 (2)	168
C11—H11···O29^iii	0.95	2.90	3.824 (2)	164
C10—H10···O26^iii	0.95	2.86	3.707 (2)	148

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1.