(2,2′-Bipyridine-κ²N,N′)oxo(N-vanillylidenetyrosinato-κ³O,N,O′)vanadium(IV) methanol solvate monohydrate

In the title complex {alternative name: (2,2′-bipyridine-κ²N,N′)[3-(4-hydroxyphenyl)-2-(3-methoxy-2-oxidobenzylideneamino)propionato-κ³O,N,O′]oxovanadium(IV) methanol solvate monohydrate}, [V(C₁₇H₁₅NO₅)O(C₁₀H₈N₂)]·CH₄O·H₂O, the V^IV atom is six-coordinated by three O atoms and three N atoms in a distorted octa­hedral configuration. In the crystal structure, the combination of intermolecular hydrogen-bonding (O—H...O) and π-stacking interactions creates a three-dimensional framework structure.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.060
• wR factor = 0.198
• Data-to-parameter ratio = 13.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.77
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.07 Ratio
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          9

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

   0 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
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

The significant role of vanadium in a variety of chemical and biological systems has stimulated the development of vanadium chemistry (Hirao, 1997). Vanadium is a biologically essential trace element, encountered in metalloenzymes such as haloperoxidases or nitrogenases. In addition to this natural relevance, a large variety of biological activities of small vanadium complexes, including enzyme inhibitory, antitumor or insulin-mimetic activities, have been reported. Vanadium–amino acid complexes are receiving considerable attention. However, this type of complex is not stable in the absence of other coordination ligands. Efforts have been made to stabilize vanadium–amino acid complexes by using another ligand, such as a Schiff base of amino acids (Colpas et al., 1994; Gruning & Rehder, 2000; Xu et al., 2005). We report here the synthesis and crystal structure of a new oxovanadium(IV)–amino acid complex with a tridentate Schiff base ligand derived from the condensation of o-vanallin and tyrosine, and with 2,2'-bipyridine.

The molecular structure of the title complex, (I), is shown in Fig. 1. The V^IV atom is six-coordinated with the bipyridine ligand almost perpendicular to the Schiff base chalating plane [dihedral angle 87.62 (11)°], while the phenol group plane makes a dihedral angle of 158.69 (14)° to the Schiff base plane. Selected bond distances are given in Table 1 and show that the V atom is in a distorted octahedral coordination environment with atoms N1 and N2 in the axial positions, and atoms O1, O4, O6 and N3 equatorial. The V atom lies 0.019 Å above the equatorial plane. The biypyridyl ligand is not planar, but rather the two pyridyl rings form an angle of 172.8 (3)° to each other.

In addition to the vanadium complex, the asymmetric unit also contains one molecule of solvated water and one molecule of methanol. All three molecules are involed in O—H···O hydrogen bonding, which links the molecules in a two-dimensional framework (Table 2). Furthermore, pairs of bipyridine ligands related by centers of symmetry have centroid–centroid separations of 3.688 (4) and 3.515 (4) Å (perpendicular distance 3.53 and 3.38 Å) for the N2/C18–C22 and N3/C23–C27 rings, respectively, indicating significant π–π interactions (Tong et al., 1999). The combination of the intermolecular hydrogen bonding and the π-stacking interactions create a three-dimensional framework structure (Fig. 2).

S2. Experimental

Tyrosine (2 mmol, 362 mg) and potassium hydroxide (2 mmol, 112 mg) were dissolved in methanol (10 ml) and added successively to a methanol solution of o-vanillin (2 mmol, 304 mg). The mixture became yellow immediately and was then stirred and refluxed for 2 h. A solution of vanadium sulfate hydrate (2 mmol, 451 mg) in water (4 ml) was added dropwise to the stirring mixture and further refluxed for 3 h. An ethanol solution of 2,2'-bipyridine (2 mmol, 312 mg) was dropped successively and refluxed for 3 h, obtaining a brown solution. It was filtered and held at room temperature for seven days, whereupon yellow crystals suitable for X-ray diffraction were obtained. The elemental analysis result was in agreement with the structure composition of (I).

S3. Refinement

Water H atoms were located in difference Fourier maps and during the refinement the O—H distances were restrained to 0.90 (2) Å with U_iso = 0.08 Ų [please provide s.u. values for O8—H distances in Table 2]. All other H atoms were placed in geometrically calculated positions (O—H = 0.82 Å and C—H = 0.93–0.98 Å) and allowed to ride on their respective parent atoms, with U_iso(H) = 1.2U_eq(C), 1.5U_eq(C_methyl) or 1.5U_eq(O). The maximum residual density peak in the final difference Fourier is 0.56 Å from H28B.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Packing diagram (PLATON; Spek, 2003) of the title compound, with the hydrogen-bonded interactions shown as dashed lines.

(N-vanillylidenetyrosinato-κ³O,N,O')(2,2'-bipyridine-κ²N,N') oxovanadium(IV) methanol solvate hydrate

Crystal data

C27H23N3O6V·CH4O·H2O	F(000) = 1220
Mr = 586.48	Dx = 1.429 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2406 reflections
a = 11.574 (3) Å	θ = 2.3–23.5°
b = 20.210 (5) Å	µ = 0.42 mm^−1
c = 14.919 (3) Å	T = 298 K
β = 128.638 (13)°	Block, yellow
V = 2725.8 (11) Å^3	0.53 × 0.37 × 0.24 mm
Z = 4

Data collection

Siemens SMART CCD area-detector diffractometer	4796 independent reflections
Radiation source: fine-focus sealed tube	2831 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
ϕ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→12
Tmin = 0.808, Tmax = 0.906	k = −23→23
14191 measured reflections	l = −15→17

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.198	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0999P)^2 + 2.8698P] where P = (Fo^2 + 2Fc^2)/3
4796 reflections	(Δ/σ)max = 0.001
362 parameters	Δρmax = 1.03 e Å^−3
0 restraints	Δρmin = −0.37 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
V1	0.53446 (8)	0.95911 (4)	0.72169 (6)	0.0311 (3)
O1	0.3858 (3)	1.02760 (15)	0.6847 (3)	0.0405 (8)
O2	0.1539 (4)	1.06097 (17)	0.5520 (3)	0.0520 (10)
O3	0.0381 (5)	0.6937 (2)	0.2552 (4)	0.0839 (14)
H3	−0.0441	0.6838	0.2343	0.126*
O4	0.6369 (3)	0.87374 (14)	0.7731 (3)	0.0358 (8)
O5	0.8297 (4)	0.78151 (17)	0.9018 (3)	0.0509 (10)
O6	0.5683 (4)	0.98178 (18)	0.6385 (3)	0.0476 (9)
O7	0.7835 (5)	0.6428 (3)	0.1788 (4)	0.0840 (15)
H7	0.7517	0.6254	0.2092	0.126*
O8	0.1019 (5)	0.5801 (3)	0.1831 (4)	0.0982 (17)
H29	0.0442	0.6050	0.1928	0.080*
H30	0.0272	0.5650	0.1128	0.080*
N1	0.3411 (4)	0.90827 (18)	0.6146 (3)	0.0301 (9)
N2	0.7214 (4)	1.01317 (19)	0.8627 (3)	0.0363 (9)
N3	0.5495 (4)	0.94182 (19)	0.8825 (3)	0.0375 (10)
C1	0.2512 (5)	1.0191 (2)	0.5929 (4)	0.0375 (11)
C2	0.2148 (5)	0.9519 (2)	0.5354 (4)	0.0347 (11)
H2	0.1268	0.9341	0.5225	0.042*
C3	0.1861 (6)	0.9557 (2)	0.4202 (4)	0.0432 (12)
H3A	0.1083	0.9876	0.3708	0.052*
H3B	0.2750	0.9706	0.4330	0.052*
C4	0.1415 (6)	0.8895 (3)	0.3629 (4)	0.0437 (13)
C5	0.0037 (6)	0.8632 (3)	0.3158 (4)	0.0528 (14)
H5	−0.0656	0.8902	0.3100	0.063*
C6	−0.0355 (7)	0.7998 (3)	0.2775 (5)	0.0642 (17)
H6	−0.1287	0.7837	0.2470	0.077*
C7	0.0653 (7)	0.7609 (3)	0.2849 (5)	0.0549 (15)
C8	0.2017 (7)	0.7830 (3)	0.3267 (5)	0.0586 (16)
H8	0.2672	0.7552	0.3286	0.070*
C9	0.2428 (7)	0.8496 (3)	0.3676 (5)	0.0546 (15)
H9	0.3354	0.8659	0.3966	0.066*
C10	0.3210 (5)	0.8456 (2)	0.6120 (4)	0.0342 (11)
H10	0.2243	0.8303	0.5601	0.041*
C11	0.4326 (5)	0.7974 (2)	0.6810 (4)	0.0337 (11)
C12	0.5852 (5)	0.8136 (2)	0.7596 (4)	0.0310 (10)
C13	0.6859 (5)	0.7616 (2)	0.8258 (4)	0.0346 (11)
C14	0.6386 (6)	0.6975 (2)	0.8120 (4)	0.0423 (12)
H14	0.7071	0.6641	0.8561	0.051*
C15	0.4886 (6)	0.6819 (3)	0.7324 (5)	0.0489 (14)
H15	0.4573	0.6382	0.7225	0.059*
C16	0.3884 (6)	0.7312 (2)	0.6692 (4)	0.0440 (13)
H16	0.2884	0.7207	0.6171	0.053*
C17	0.9292 (6)	0.7370 (3)	0.9916 (5)	0.0616 (17)
H17A	1.0265	0.7559	1.0393	0.092*
H17B	0.9308	0.6961	0.9596	0.092*
H17C	0.8976	0.7288	1.0367	0.092*
C18	0.8042 (5)	1.0491 (3)	0.8468 (5)	0.0470 (13)
H18	0.7825	1.0477	0.7754	0.056*
C19	0.9190 (6)	1.0879 (3)	0.9303 (5)	0.0587 (16)
H19	0.9730	1.1127	0.9155	0.070*
C20	0.9532 (7)	1.0896 (3)	1.0364 (6)	0.0688 (18)
H20	1.0305	1.1159	1.0944	0.083*
C21	0.8718 (6)	1.0520 (3)	1.0561 (5)	0.0598 (16)
H21	0.8943	1.0520	1.1279	0.072*
C22	0.7554 (5)	1.0140 (2)	0.9671 (4)	0.0410 (12)
C23	0.6645 (5)	0.9710 (2)	0.9802 (4)	0.0371 (11)
C24	0.6921 (6)	0.9601 (3)	1.0839 (4)	0.0523 (14)
H24	0.7700	0.9817	1.1499	0.063*
C25	0.6045 (6)	0.9175 (3)	1.0884 (5)	0.0555 (15)
H25	0.6235	0.9089	1.1578	0.054 (16)*
C26	0.4883 (7)	0.8878 (3)	0.9896 (5)	0.0549 (15)
H26	0.4268	0.8588	0.9906	0.066*
C27	0.4636 (6)	0.9015 (3)	0.8884 (5)	0.0470 (13)
H27	0.3834	0.8816	0.8213	0.056*
C28	0.6716 (9)	0.6464 (5)	0.0614 (6)	0.114 (3)
H28A	0.7122	0.6392	0.0224	0.171*
H28B	0.6264	0.6893	0.0419	0.171*
H28C	0.5987	0.6131	0.0385	0.171*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.0348 (5)	0.0227 (4)	0.0315 (4)	−0.0020 (3)	0.0186 (4)	−0.0009 (3)
O1	0.0402 (19)	0.0281 (19)	0.0344 (18)	0.0007 (15)	0.0141 (16)	−0.0058 (14)
O2	0.046 (2)	0.031 (2)	0.057 (2)	0.0101 (17)	0.0217 (19)	−0.0014 (17)
O3	0.102 (4)	0.052 (3)	0.098 (3)	−0.018 (3)	0.062 (3)	−0.023 (3)
O4	0.0354 (18)	0.0234 (18)	0.0458 (19)	−0.0024 (14)	0.0240 (16)	−0.0011 (14)
O5	0.0339 (19)	0.040 (2)	0.055 (2)	0.0055 (16)	0.0163 (18)	0.0097 (18)
O6	0.058 (2)	0.046 (2)	0.044 (2)	−0.0110 (18)	0.0344 (18)	−0.0009 (17)
O7	0.082 (3)	0.109 (4)	0.076 (3)	−0.026 (3)	0.056 (3)	−0.014 (3)
O8	0.074 (3)	0.122 (5)	0.080 (3)	0.007 (3)	0.039 (3)	−0.024 (3)
N1	0.034 (2)	0.023 (2)	0.028 (2)	0.0005 (16)	0.0167 (17)	−0.0009 (16)
N2	0.041 (2)	0.025 (2)	0.041 (2)	−0.0009 (18)	0.0239 (19)	0.0029 (18)
N3	0.042 (2)	0.032 (2)	0.032 (2)	0.0008 (18)	0.021 (2)	−0.0015 (18)
C1	0.044 (3)	0.024 (3)	0.039 (3)	0.004 (2)	0.023 (3)	0.002 (2)
C2	0.034 (2)	0.024 (3)	0.035 (3)	0.001 (2)	0.016 (2)	−0.001 (2)
C3	0.051 (3)	0.034 (3)	0.036 (3)	0.002 (2)	0.023 (2)	0.004 (2)
C4	0.056 (3)	0.036 (3)	0.033 (3)	0.000 (3)	0.025 (3)	0.001 (2)
C5	0.053 (3)	0.043 (3)	0.042 (3)	−0.006 (3)	0.020 (3)	−0.006 (3)
C6	0.060 (4)	0.059 (4)	0.053 (4)	−0.008 (3)	0.026 (3)	−0.009 (3)
C7	0.065 (4)	0.054 (4)	0.043 (3)	−0.014 (3)	0.032 (3)	−0.018 (3)
C8	0.062 (4)	0.060 (4)	0.057 (4)	0.010 (3)	0.039 (3)	0.003 (3)
C9	0.070 (4)	0.050 (4)	0.047 (3)	0.002 (3)	0.038 (3)	−0.002 (3)
C10	0.033 (2)	0.030 (3)	0.033 (3)	−0.002 (2)	0.017 (2)	−0.002 (2)
C11	0.038 (3)	0.024 (3)	0.036 (3)	0.001 (2)	0.022 (2)	0.001 (2)
C12	0.037 (2)	0.024 (2)	0.031 (2)	−0.001 (2)	0.020 (2)	−0.0008 (19)
C13	0.035 (3)	0.030 (3)	0.034 (3)	0.002 (2)	0.019 (2)	0.004 (2)
C14	0.049 (3)	0.027 (3)	0.047 (3)	0.010 (2)	0.029 (3)	0.012 (2)
C15	0.051 (3)	0.023 (3)	0.063 (4)	0.000 (2)	0.031 (3)	0.003 (2)
C16	0.039 (3)	0.030 (3)	0.050 (3)	−0.003 (2)	0.022 (3)	0.001 (2)
C17	0.041 (3)	0.058 (4)	0.054 (3)	0.005 (3)	0.015 (3)	0.012 (3)
C18	0.043 (3)	0.040 (3)	0.050 (3)	−0.010 (2)	0.025 (3)	−0.004 (3)
C19	0.051 (3)	0.045 (4)	0.072 (4)	−0.016 (3)	0.035 (3)	−0.008 (3)
C20	0.048 (4)	0.054 (4)	0.073 (5)	−0.021 (3)	0.023 (3)	−0.019 (3)
C21	0.055 (4)	0.057 (4)	0.043 (3)	−0.012 (3)	0.018 (3)	−0.013 (3)
C22	0.038 (3)	0.033 (3)	0.037 (3)	0.003 (2)	0.016 (2)	−0.002 (2)
C23	0.039 (3)	0.036 (3)	0.030 (3)	0.006 (2)	0.019 (2)	0.000 (2)
C24	0.054 (3)	0.054 (4)	0.032 (3)	0.002 (3)	0.018 (3)	−0.001 (3)
C25	0.064 (4)	0.064 (4)	0.039 (3)	0.011 (3)	0.033 (3)	0.015 (3)
C26	0.065 (4)	0.053 (4)	0.064 (4)	0.002 (3)	0.049 (3)	0.003 (3)
C27	0.052 (3)	0.044 (3)	0.051 (3)	−0.003 (3)	0.035 (3)	−0.007 (3)
C28	0.110 (6)	0.161 (9)	0.074 (6)	−0.053 (6)	0.059 (5)	−0.007 (5)

Geometric parameters (Å, º)

V1—O6	1.584 (3)	C8—H8	0.9300
V1—O4	1.958 (3)	C9—H9	0.9300
V1—O1	1.999 (3)	C10—C11	1.420 (6)
V1—N1	2.037 (4)	C10—H10	0.9300
V1—N2	2.149 (4)	C11—C16	1.404 (6)
V1—N3	2.321 (4)	C11—C12	1.420 (6)
O1—C1	1.291 (6)	C12—C13	1.415 (6)
O2—C1	1.223 (6)	C13—C14	1.370 (7)
O3—C7	1.402 (7)	C14—C15	1.396 (7)
O3—H3	0.8200	C14—H14	0.9300
O4—C12	1.313 (5)	C15—C16	1.365 (7)
O5—C13	1.364 (5)	C15—H15	0.9300
O5—C17	1.415 (6)	C16—H16	0.9300
O7—C28	1.384 (8)	C17—H17A	0.9600
O7—H7	0.8200	C17—H17B	0.9600
O8—H29	0.9170	C17—H17C	0.9600
O8—H30	0.8990	C18—C19	1.365 (7)
N1—C10	1.285 (6)	C18—H18	0.9300
N1—C2	1.468 (5)	C19—C20	1.372 (9)
N2—C18	1.336 (6)	C19—H19	0.9300
N2—C22	1.348 (6)	C20—C21	1.378 (9)
N3—C27	1.331 (6)	C20—H20	0.9300
N3—C23	1.349 (6)	C21—C22	1.390 (7)
C1—C2	1.519 (6)	C21—H21	0.9300
C2—C3	1.534 (6)	C22—C23	1.470 (7)
C2—H2	0.9800	C23—C24	1.387 (7)
C3—C4	1.495 (7)	C24—C25	1.364 (8)
C3—H3A	0.9700	C24—H24	0.9300
C3—H3B	0.9700	C25—C26	1.367 (8)
C4—C5	1.386 (7)	C25—H25	0.9300
C4—C9	1.389 (7)	C26—C27	1.378 (7)
C5—C6	1.360 (8)	C26—H26	0.9300
C5—H5	0.9300	C27—H27	0.9300
C6—C7	1.352 (8)	C28—H28A	0.9600
C6—H6	0.9300	C28—H28B	0.9600
C7—C8	1.360 (8)	C28—H28C	0.9600
C8—C9	1.432 (8)
O6—V1—O4	100.14 (17)	N1—C10—C11	126.0 (4)
O6—V1—O1	100.05 (17)	N1—C10—H10	117.0
O4—V1—O1	157.62 (14)	C11—C10—H10	117.0
O6—V1—N1	102.66 (16)	C16—C11—C12	119.5 (4)
O4—V1—N1	87.87 (14)	C16—C11—C10	117.8 (4)
O1—V1—N1	78.35 (14)	C12—C11—C10	122.7 (4)
O6—V1—N2	91.69 (17)	O4—C12—C13	118.9 (4)
O4—V1—N2	94.09 (14)	O4—C12—C11	123.6 (4)
O1—V1—N2	94.89 (14)	C13—C12—C11	117.5 (4)
N1—V1—N2	164.96 (15)	O5—C13—C14	124.7 (4)
O6—V1—N3	163.24 (17)	O5—C13—C12	113.9 (4)
O4—V1—N3	80.01 (14)	C14—C13—C12	121.4 (4)
O1—V1—N3	83.44 (14)	C13—C14—C15	120.6 (4)
N1—V1—N3	94.10 (15)	C13—C14—H14	119.7
N2—V1—N3	71.63 (15)	C15—C14—H14	119.7
C1—O1—V1	117.5 (3)	C16—C15—C14	119.4 (5)
C7—O3—H3	109.5	C16—C15—H15	120.3
C12—O4—V1	130.4 (3)	C14—C15—H15	120.3
C13—O5—C17	116.6 (4)	C15—C16—C11	121.5 (5)
C28—O7—H7	109.5	C15—C16—H16	119.2
H29—O8—H30	96.1	C11—C16—H16	119.2
C10—N1—C2	119.8 (4)	O5—C17—H17A	109.5
C10—N1—V1	127.6 (3)	O5—C17—H17B	109.5
C2—N1—V1	112.5 (3)	H17A—C17—H17B	109.5
C18—N2—C22	118.3 (4)	O5—C17—H17C	109.5
C18—N2—V1	119.9 (3)	H17A—C17—H17C	109.5
C22—N2—V1	121.8 (3)	H17B—C17—H17C	109.5
C27—N3—C23	118.0 (4)	N2—C18—C19	123.2 (5)
C27—N3—V1	125.7 (3)	N2—C18—H18	118.4
C23—N3—V1	116.0 (3)	C19—C18—H18	118.4
O2—C1—O1	124.3 (4)	C18—C19—C20	118.9 (6)
O2—C1—C2	119.5 (4)	C18—C19—H19	120.6
O1—C1—C2	116.3 (4)	C20—C19—H19	120.6
N1—C2—C1	107.3 (4)	C19—C20—C21	119.3 (6)
N1—C2—C3	110.0 (4)	C19—C20—H20	120.4
C1—C2—C3	112.2 (4)	C21—C20—H20	120.4
N1—C2—H2	109.1	C20—C21—C22	119.0 (6)
C1—C2—H2	109.1	C20—C21—H21	120.5
C3—C2—H2	109.1	C22—C21—H21	120.5
C4—C3—C2	110.6 (4)	N2—C22—C21	121.4 (5)
C4—C3—H3A	109.5	N2—C22—C23	115.4 (4)
C2—C3—H3A	109.5	C21—C22—C23	123.2 (5)
C4—C3—H3B	109.5	N3—C23—C24	121.4 (5)
C2—C3—H3B	109.5	N3—C23—C22	114.8 (4)
H3A—C3—H3B	108.1	C24—C23—C22	123.8 (5)
C5—C4—C9	118.0 (5)	C25—C24—C23	119.6 (5)
C5—C4—C3	120.8 (5)	C25—C24—H24	120.2
C9—C4—C3	120.8 (5)	C23—C24—H24	120.2
C6—C5—C4	123.5 (6)	C24—C25—C26	119.0 (5)
C6—C5—H5	118.3	C24—C25—H25	120.5
C4—C5—H5	118.3	C26—C25—H25	120.5
C7—C6—C5	118.0 (6)	C25—C26—C27	119.0 (5)
C7—C6—H6	121.0	C25—C26—H26	120.5
C5—C6—H6	121.0	C27—C26—H26	120.5
C6—C7—C8	122.8 (6)	N3—C27—C26	122.9 (5)
C6—C7—O3	121.7 (6)	N3—C27—H27	118.5
C8—C7—O3	115.4 (6)	C26—C27—H27	118.5
C7—C8—C9	119.1 (6)	O7—C28—H28A	109.5
C7—C8—H8	120.5	O7—C28—H28B	109.5
C9—C8—H8	120.5	H28A—C28—H28B	109.5
C4—C9—C8	118.6 (6)	O7—C28—H28C	109.5
C4—C9—H9	120.7	H28A—C28—H28C	109.5
C8—C9—H9	120.7	H28B—C28—H28C	109.5
C4—C5—C6—C7	−0.7 (9)	C6—C7—C8—C9	1.8 (9)
C5—C6—C7—C8	−1.4 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H30···O2^i	0.90	2.00	2.872 (6)	162
O8—H29···O3	0.92	2.04	2.821 (7)	142
O7—H7···O4^ii	0.82	2.06	2.819 (5)	153
O3—H3···O7^iii	0.82	1.81	2.617 (6)	166

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, −y+3/2, z−1/2; (iii) x−1, y, z.