N²,N^2'-Bis[2-(ethoxy­carbonyl­meth­oxy)­benzyl­idene]pyridine-2,6-dicarbohydrazide

In the title compound, C₂₉H₂₉N₅O₈, the ester group is disordered over two sites with site-occupancy factors of 0.91/0.09. The crystal structure is stabilized by inter- and intra­molecular hydrogen-bond inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 299 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.076
• wR factor = 0.231
• Data-to-parameter ratio = 15.4

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT220_ALERT_2_A Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       7.96 Ratio

Author Response: It's the esterified group disorder over two sites.

PLAT222_ALERT_3_A Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       8.05 Ratio

Author Response: It's the esterified group disorder over two sites.

PLAT241_ALERT_2_A Check High      Ueq as Compared to Neighbors for        C16

Author Response: It's the esterified group disorder over two sites.

PLAT241_ALERT_2_A Check High      Ueq as Compared to Neighbors for       C28'

Author Response: It's the esterified group disorder over two sites.

PLAT242_ALERT_2_A Check Low       Ueq as Compared to Neighbors for         O5

Author Response: It's the esterified group disorder over two sites.

PLAT242_ALERT_2_A Check Low       Ueq as Compared to Neighbors for        O8'

Author Response: It's the esterified group disorder over two sites.

PLAT412_ALERT_2_A Short Intra XH3 .. XHn     H16A   ..  H29F    ..       1.44 Ang.

Author Response: It's the esterified group disorder over two sites.

PLAT412_ALERT_2_A Short Intra XH3 .. XHn     H16B   ..  H29F    ..       1.54 Ang.

Author Response: It's the esterified group disorder over two sites.

Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    O5     -   C16     ..      14.47 su
PLAT230_ALERT_2_B Hirshfeld Test Diff for    C16    -   C17     ..       9.17 su
PLAT413_ALERT_2_B Short Inter XH3 .. XHn     H17A   ..  H29A    ..       1.99 Ang.
PLAT432_ALERT_2_B Short Inter X...Y Contact  O2     ..  C17     ..       2.90 Ang.

Alert level C
PLAT194_ALERT_1_C Missing _cell_measurement_reflns_used datum ....          ?
PLAT195_ALERT_1_C Missing _cell_measurement_theta_max   datum ....          ?
PLAT196_ALERT_1_C Missing _cell_measurement_theta_min   datum ....          ?
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       3.30 Ratio

Author Response: It's the esterified group disorder over two sites.

PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C15

Author Response: It's the esterified group disorder over two sites.

PLAT301_ALERT_3_C Main Residue  Disorder .........................       7.00 Perc.
PLAT320_ALERT_2_C Check Hybridisation of  C16    in Main Residue .          ?
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      34.60 Deg.
              O8   -C27  -O8'     1.555   1.555   1.555

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         12

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

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

---

S1. Comment

The tridentate ligands with 2,6-dipicolinoyhydrazone have been intensively studied due to the interesting coordination mode. (Chen et al., 1997; Thompson, 2002; Zhao et al., 2004). We report here the synthesis and crystal structure of a novel tridentate ligand, the title compound (I) (Fig. 1).

The molecular structure contains one pyridine ring and two substitutional benzene rings. The dihedral angles between the pyridine and benzene planes are 6.50 (13)° for C8—C13 and 26.43 (16)° for C20—C25.

The crystal packing is governed by intermolecular hydrogen bonds interactions. Each molecular can serve as donor and acceptor to form the N–H–O hydrogen bonds with two other neighboring molecules, forming chains parallel to the a axis (Fig. 2; Table 1).

Related literature

For related literature, see: Chen et al. (1997); Thompson (2002); Zhao et al. (2004).

S2. Experimental

To a solution of 2-(2-formylphenoxy)acetic acid (1.80 g, 10 mmol) in absolute ethanol (40 ml), a suspension of 2,6-dipicolinoyhydrazine in the same solvent (50 ml) was added at 323 K. The mixture was left to react at reflux for 18 h, then the white needle product was filtered, washed with hot ethanol (20 ml portion) three times and dried in vacuum. Crystals suitable for X-ray diffraction were obtained from acetone-methanol (1:1 v/v) over a period of about three weeks, and unexpecting the carboxyl from the 2-(2-formylphenoxy)acetic acid was esterified in the ethanol solvent.

S3. Refinement

After their location in the difference map, all H-atoms were fixed geometrically at ideal positions and allowed to ride on the parent C or N atoms with C—H = 0.93Å and N—H = 0.86Å and U_iso(H)= 1.2U_eq(C and N). The esterified group is disorder over two sites. So, the site-occupancy factors for the two orientations were refined as 0.905 / 0.095. The SHELX restrains AFIX, FLAT and ISOR were applied.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001).

Figures

	Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 20% probability level.
	Fig. 2. A view of the packing of (I). Hydrogen bonds are shown by dashed lines.

N²,N^2'—Bis[2-(ethoxycarbonylmethoxy)benzylidene]pyridine- 2,6-dicarbohydrazide

Crystal data

C29H29N5O8	Z = 4
Mr = 575.57	F(000) = 1208
Monoclinic, P21/n	Dx = 1.362 Mg m^−3
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 11.5485 (6) Å	µ = 0.10 mm^−1
b = 21.6606 (11) Å	T = 299 K
c = 12.3596 (9) Å	Block, colorless
β = 114.779 (1)°	0.32 × 0.10 × 0.10 mm
V = 2807.1 (3) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4136 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.032
Graphite monochromator	θmax = 27.0°, θmin = 1.9°
phi and ω scans	h = −14→14
23685 measured reflections	k = −27→27
6101 independent reflections	l = −15→15

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.231	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.1307P)^2 + 0.5522P] where P = (Fo^2 + 2Fc^2)/3
6101 reflections	(Δ/σ)max < 0.001
396 parameters	Δρmax = 0.40 e Å^−3
12 restraints	Δρmin = −0.52 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	Occ. (<1)
C1	0.4448 (2)	−0.07839 (10)	1.0814 (2)	0.0440 (5)
C2	0.3444 (3)	−0.09691 (12)	1.1079 (2)	0.0539 (6)
H2	0.3247	−0.0755	1.1632	0.065*
C3	0.2749 (3)	−0.14779 (13)	1.0499 (3)	0.0633 (7)
H3	0.2074	−0.1617	1.0658	0.076*
C4	0.3065 (3)	−0.17779 (12)	0.9680 (3)	0.0605 (7)
H4	0.2622	−0.2129	0.9291	0.073*
C5	0.4054 (3)	−0.15491 (11)	0.9445 (2)	0.0506 (6)
C6	0.5243 (2)	−0.02429 (11)	1.1467 (2)	0.0453 (5)
C7	0.8231 (2)	0.02966 (12)	1.1877 (2)	0.0497 (6)
H7	0.8370	0.0019	1.1370	0.060*
C8	0.9182 (3)	0.07674 (11)	1.2480 (2)	0.0496 (6)
C9	0.9095 (3)	0.11453 (14)	1.3352 (3)	0.0642 (7)
H9	0.8419	0.1094	1.3566	0.077*
C10	0.9998 (3)	0.15966 (15)	1.3905 (3)	0.0721 (8)
H10	0.9925	0.1848	1.4484	0.087*
C11	1.1004 (3)	0.16721 (14)	1.3596 (2)	0.0641 (7)
H11	1.1616	0.1973	1.3974	0.077*
C12	1.1111 (3)	0.13062 (13)	1.2734 (2)	0.0577 (7)
H12	1.1789	0.1363	1.2524	0.069*
C13	1.0217 (2)	0.08554 (12)	1.2180 (2)	0.0499 (6)
C14	1.1296 (3)	0.05037 (14)	1.1008 (3)	0.0640 (7)
H14A	1.1350	0.0124	1.0615	0.077*
H14B	1.2078	0.0546	1.1727	0.077*
C15	1.1167 (3)	0.10434 (17)	1.0195 (3)	0.0712 (8)
C16	1.1906 (13)	0.1507 (5)	0.8951 (12)	0.351 (9)
H16A	1.0988	0.1557	0.8546	0.421*
H16B	1.2167	0.1310	0.8384	0.421*
C17	1.2435 (8)	0.2131 (3)	0.9119 (7)	0.170 (3)
H17A	1.3109	0.2167	0.9905	0.255*
H17B	1.1777	0.2425	0.9025	0.255*
H17C	1.2766	0.2211	0.8538	0.255*
C18	0.4322 (3)	−0.18466 (12)	0.8482 (3)	0.0622 (7)
C19	0.5350 (3)	−0.12858 (14)	0.6412 (3)	0.0598 (7)
H19	0.5493	−0.0881	0.6690	0.072*
C20	0.5563 (3)	−0.14547 (14)	0.5363 (2)	0.0620 (7)
C21	0.5237 (3)	−0.20391 (16)	0.4848 (3)	0.0759 (9)
H21	0.4880	−0.2327	0.5177	0.091*
C22	0.5437 (4)	−0.21969 (19)	0.3858 (3)	0.0829 (10)
H22	0.5205	−0.2586	0.3517	0.100*
C23	0.5977 (4)	−0.17794 (19)	0.3382 (3)	0.0875 (12)
H23	0.6115	−0.1887	0.2718	0.105*
C24	0.6317 (4)	−0.12035 (17)	0.3872 (3)	0.0819 (10)
H24	0.6685	−0.0923	0.3540	0.098*
C25	0.6114 (3)	−0.10395 (14)	0.4863 (2)	0.0665 (8)
C26	0.7136 (5)	−0.00699 (17)	0.5070 (3)	0.0916 (12)
H26A	0.6602	0.0095	0.4288	0.110*
H26B	0.7864	−0.0274	0.5029	0.110*
C27	0.7567 (4)	0.04350 (17)	0.5975 (3)	0.0922 (12)
O5	1.2125 (3)	0.10572 (13)	0.9880 (3)	0.0981 (9)
C28	0.8947 (11)	0.1314 (4)	0.6564 (9)	0.231 (8)	0.905 (13)
H28A	0.9670	0.1425	0.6399	0.278*	0.905 (13)
H28B	0.9264	0.1098	0.7320	0.278*	0.905 (13)
C29	0.8259 (13)	0.1885 (5)	0.6639 (14)	0.306 (9)	0.905 (13)
H29A	0.8077	0.2135	0.5945	0.459*	0.905 (13)
H29B	0.8784	0.2114	0.7339	0.459*	0.905 (13)
H29C	0.7476	0.1774	0.6683	0.459*	0.905 (13)
O8	0.8081 (10)	0.0907 (3)	0.5612 (5)	0.155 (3)	0.905 (13)
O8'	0.8681 (14)	0.0661 (10)	0.589 (2)	0.047 (7)*	0.095 (13)
C28'	0.896 (5)	0.1302 (12)	0.605 (10)	0.23 (7)*	0.095 (13)
H28C	0.8669	0.1504	0.6593	0.277*	0.095 (13)
H28D	0.8721	0.1532	0.5319	0.277*	0.095 (13)
C29'	1.038 (3)	0.111 (6)	0.664 (13)	0.30 (7)*	0.095 (13)
H29D	1.0792	0.1245	0.6148	0.453*	0.095 (13)
H29E	1.0438	0.0668	0.6715	0.453*	0.095 (13)
H29F	1.0786	0.1295	0.7411	0.453*	0.095 (13)
N1	0.47564 (19)	−0.10620 (9)	1.00079 (17)	0.0458 (5)
N2	0.6383 (2)	−0.02049 (9)	1.14131 (17)	0.0475 (5)
H2A	0.6588	−0.0466	1.0999	0.057*
N3	0.7217 (2)	0.02594 (9)	1.20320 (17)	0.0485 (5)
N4	0.4772 (2)	−0.14655 (10)	0.7900 (2)	0.0606 (6)
H4A	0.4935	−0.1087	0.8119	0.073*
N5	0.4975 (2)	−0.16823 (11)	0.6943 (2)	0.0645 (6)
O1	0.48826 (19)	0.01162 (8)	1.20160 (18)	0.0624 (5)
O2	0.4086 (3)	−0.23957 (10)	0.8248 (2)	0.0996 (9)
O3	1.02504 (19)	0.04682 (9)	1.13173 (18)	0.0656 (5)
O4	1.0338 (3)	0.14056 (15)	0.9878 (3)	0.1093 (10)
O6	0.6451 (3)	−0.04805 (10)	0.5434 (2)	0.0817 (7)
O7	0.7445 (4)	0.04619 (14)	0.6864 (3)	0.1194 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0488 (14)	0.0403 (11)	0.0461 (12)	0.0015 (10)	0.0229 (11)	0.0034 (9)
C2	0.0552 (16)	0.0564 (14)	0.0615 (15)	0.0004 (12)	0.0357 (13)	0.0032 (12)
C3	0.0571 (17)	0.0625 (16)	0.0783 (18)	−0.0119 (13)	0.0362 (15)	0.0049 (14)
C4	0.0641 (18)	0.0484 (14)	0.0702 (17)	−0.0156 (12)	0.0294 (15)	−0.0037 (13)
C5	0.0544 (15)	0.0410 (12)	0.0551 (14)	−0.0033 (11)	0.0218 (12)	−0.0011 (10)
C6	0.0559 (15)	0.0435 (12)	0.0435 (11)	−0.0011 (11)	0.0276 (11)	0.0004 (10)
C7	0.0554 (16)	0.0532 (13)	0.0437 (12)	−0.0045 (11)	0.0241 (12)	−0.0040 (10)
C8	0.0541 (16)	0.0523 (13)	0.0404 (12)	−0.0062 (11)	0.0179 (11)	−0.0022 (10)
C9	0.0680 (19)	0.0727 (18)	0.0581 (15)	−0.0111 (15)	0.0326 (14)	−0.0141 (14)
C10	0.081 (2)	0.0769 (19)	0.0575 (16)	−0.0147 (16)	0.0282 (16)	−0.0250 (15)
C11	0.0633 (19)	0.0597 (16)	0.0570 (15)	−0.0138 (13)	0.0132 (14)	−0.0102 (13)
C12	0.0525 (16)	0.0636 (16)	0.0526 (14)	−0.0087 (13)	0.0175 (12)	−0.0044 (12)
C13	0.0470 (15)	0.0558 (14)	0.0430 (12)	−0.0035 (11)	0.0150 (11)	−0.0027 (11)
C14	0.0549 (17)	0.0726 (18)	0.0733 (18)	−0.0041 (14)	0.0354 (15)	−0.0145 (15)
C15	0.067 (2)	0.087 (2)	0.0686 (18)	−0.0041 (18)	0.0376 (17)	−0.0082 (17)
C16	0.193 (11)	0.44 (3)	0.43 (3)	−0.015 (16)	0.141 (14)	0.00 (2)
C17	0.174 (7)	0.146 (5)	0.196 (7)	0.031 (5)	0.084 (6)	0.079 (5)
C18	0.074 (2)	0.0473 (14)	0.0674 (17)	−0.0043 (13)	0.0313 (15)	−0.0132 (13)
C19	0.0563 (17)	0.0623 (16)	0.0621 (15)	−0.0010 (13)	0.0260 (14)	−0.0172 (13)
C20	0.0576 (17)	0.0735 (18)	0.0513 (14)	0.0163 (14)	0.0194 (13)	−0.0088 (13)
C21	0.068 (2)	0.086 (2)	0.0734 (19)	0.0007 (16)	0.0289 (16)	−0.0301 (17)
C22	0.079 (2)	0.094 (2)	0.0650 (19)	0.0171 (19)	0.0195 (18)	−0.0254 (18)
C23	0.107 (3)	0.106 (3)	0.0428 (15)	0.044 (2)	0.0248 (17)	−0.0030 (17)
C24	0.112 (3)	0.086 (2)	0.0483 (15)	0.035 (2)	0.0341 (17)	0.0146 (16)
C25	0.083 (2)	0.0669 (17)	0.0476 (14)	0.0270 (16)	0.0255 (14)	0.0058 (13)
C26	0.147 (4)	0.081 (2)	0.0652 (19)	0.010 (2)	0.063 (2)	0.0169 (17)
C27	0.137 (4)	0.083 (2)	0.077 (2)	0.000 (2)	0.065 (2)	0.0156 (18)
O5	0.0941 (19)	0.0998 (18)	0.129 (2)	0.0022 (15)	0.0749 (19)	0.0165 (16)
C28	0.39 (2)	0.184 (9)	0.194 (9)	−0.151 (12)	0.190 (13)	−0.057 (8)
C29	0.231 (14)	0.303 (19)	0.37 (2)	0.035 (14)	0.113 (15)	0.096 (17)
O8	0.246 (7)	0.139 (4)	0.126 (4)	−0.065 (5)	0.123 (5)	−0.012 (3)
N1	0.0486 (12)	0.0415 (10)	0.0518 (11)	−0.0030 (9)	0.0254 (10)	−0.0039 (9)
N2	0.0548 (13)	0.0465 (10)	0.0472 (10)	−0.0079 (9)	0.0272 (10)	−0.0092 (9)
N3	0.0526 (13)	0.0501 (11)	0.0452 (10)	−0.0082 (9)	0.0230 (9)	−0.0063 (9)
N4	0.0723 (16)	0.0505 (12)	0.0698 (14)	−0.0116 (11)	0.0404 (13)	−0.0221 (11)
N5	0.0727 (17)	0.0625 (14)	0.0621 (13)	−0.0029 (12)	0.0319 (13)	−0.0205 (12)
O1	0.0775 (13)	0.0528 (10)	0.0756 (12)	−0.0095 (9)	0.0504 (11)	−0.0167 (9)
O2	0.162 (3)	0.0512 (12)	0.1062 (18)	−0.0229 (14)	0.0769 (19)	−0.0250 (12)
O3	0.0621 (12)	0.0755 (12)	0.0701 (12)	−0.0208 (10)	0.0384 (10)	−0.0258 (10)
O4	0.108 (2)	0.129 (2)	0.109 (2)	0.0452 (19)	0.0635 (18)	0.0369 (18)
O6	0.126 (2)	0.0663 (13)	0.0724 (13)	0.0102 (13)	0.0610 (14)	0.0051 (11)
O7	0.193 (3)	0.106 (2)	0.0978 (19)	−0.028 (2)	0.099 (2)	−0.0171 (15)

Geometric parameters (Å, º)

C1—N1	1.334 (3)	C18—N4	1.336 (4)
C1—C2	1.389 (3)	C19—N5	1.263 (4)
C1—C6	1.498 (3)	C19—C20	1.463 (4)
C2—C3	1.375 (4)	C19—H19	0.9300
C2—H2	0.9300	C20—C25	1.388 (4)
C3—C4	1.374 (4)	C20—C21	1.396 (4)
C3—H3	0.9300	C21—C22	1.380 (4)
C4—C5	1.383 (4)	C21—H21	0.9300
C4—H4	0.9300	C22—C23	1.363 (6)
C5—N1	1.335 (3)	C22—H22	0.9300
C5—C18	1.496 (4)	C23—C24	1.370 (5)
C6—O1	1.215 (3)	C23—H23	0.9300
C6—N2	1.348 (3)	C24—C25	1.386 (4)
C7—N3	1.267 (3)	C24—H24	0.9300
C7—C8	1.455 (4)	C25—O6	1.373 (4)
C7—H7	0.9300	C26—O6	1.385 (4)
C8—C9	1.390 (4)	C26—C27	1.493 (5)
C8—C13	1.404 (4)	C26—H26A	0.9700
C9—C10	1.383 (4)	C26—H26B	0.9700
C9—H9	0.9300	C27—O7	1.167 (4)
C10—C11	1.377 (4)	C27—O8	1.349 (5)
C10—H10	0.9300	C27—O8'	1.419 (10)
C11—C12	1.375 (4)	C28—O8	1.475 (7)
C11—H11	0.9300	C28—C29	1.494 (9)
C12—C13	1.377 (4)	C28—H28A	0.9700
C12—H12	0.9300	C28—H28B	0.9700
C13—O3	1.370 (3)	C29—H29A	0.9600
C14—O3	1.413 (3)	C29—H29B	0.9600
C14—C15	1.508 (5)	C29—H29C	0.9600
C14—H14A	0.9700	O8'—C28'	1.420 (10)
C14—H14B	0.9700	C28'—C29'	1.540 (11)
C15—O4	1.171 (4)	C28'—H28C	0.9700
C15—O5	1.318 (4)	C28'—H28D	0.9700
C16—O5	1.447 (9)	C29'—H29D	0.9600
C16—C17	1.460 (9)	C29'—H29E	0.9600
C16—H16A	0.9700	C29'—H29F	0.9600
C16—H16B	0.9700	N2—N3	1.381 (3)
C17—H17A	0.9600	N2—H2A	0.8600
C17—H17B	0.9600	N4—N5	1.380 (3)
C17—H17C	0.9600	N4—H4A	0.8600
C18—O2	1.228 (3)
N1—C1—C2	123.8 (2)	N5—C19—H19	119.6
N1—C1—C6	117.4 (2)	C20—C19—H19	119.6
C2—C1—C6	118.9 (2)	C25—C20—C21	118.1 (3)
C3—C2—C1	118.1 (2)	C25—C20—C19	120.7 (3)
C3—C2—H2	120.9	C21—C20—C19	121.2 (3)
C1—C2—H2	120.9	C22—C21—C20	121.1 (4)
C4—C3—C2	119.0 (2)	C22—C21—H21	119.5
C4—C3—H3	120.5	C20—C21—H21	119.5
C2—C3—H3	120.5	C23—C22—C21	119.6 (3)
C3—C4—C5	118.9 (2)	C23—C22—H22	120.2
C3—C4—H4	120.6	C21—C22—H22	120.2
C5—C4—H4	120.6	C22—C23—C24	120.8 (3)
N1—C5—C4	123.3 (2)	C22—C23—H23	119.6
N1—C5—C18	118.1 (2)	C24—C23—H23	119.6
C4—C5—C18	118.5 (2)	C23—C24—C25	120.0 (4)
O1—C6—N2	123.9 (2)	C23—C24—H24	120.0
O1—C6—C1	121.7 (2)	C25—C24—H24	120.0
N2—C6—C1	114.32 (19)	O6—C25—C24	124.3 (3)
N3—C7—C8	121.0 (2)	O6—C25—C20	115.2 (2)
N3—C7—H7	119.5	C24—C25—C20	120.5 (3)
C8—C7—H7	119.5	O6—C26—C27	106.5 (3)
C9—C8—C13	118.1 (2)	O6—C26—H26A	110.4
C9—C8—C7	121.7 (2)	C27—C26—H26A	110.4
C13—C8—C7	120.2 (2)	O6—C26—H26B	110.4
C10—C9—C8	121.0 (3)	C27—C26—H26B	110.4
C10—C9—H9	119.5	H26A—C26—H26B	108.6
C8—C9—H9	119.5	O7—C27—O8	121.3 (4)
C11—C10—C9	119.7 (3)	O7—C27—O8'	121.4 (10)
C11—C10—H10	120.2	O8—C27—O8'	34.6 (7)
C9—C10—H10	120.2	O7—C27—C26	127.5 (3)
C12—C11—C10	120.5 (3)	O8—C27—C26	111.2 (3)
C12—C11—H11	119.7	O8'—C27—C26	103.2 (10)
C10—C11—H11	119.7	C15—O5—C16	111.2 (6)
C11—C12—C13	120.1 (3)	O8—C28—C29	110.2 (9)
C11—C12—H12	120.0	O8—C28—H28A	109.6
C13—C12—H12	120.0	C29—C28—H28A	109.6
O3—C13—C12	124.1 (2)	O8—C28—H28B	109.6
O3—C13—C8	115.3 (2)	C29—C28—H28B	109.6
C12—C13—C8	120.6 (2)	H28A—C28—H28B	108.1
O3—C14—C15	111.4 (3)	C27—O8—C28	115.7 (5)
O3—C14—H14A	109.3	C27—O8'—C28'	119.3 (13)
C15—C14—H14A	109.3	O8'—C28'—C29'	86 (2)
O3—C14—H14B	109.3	O8'—C28'—H28C	114.2
C15—C14—H14B	109.3	C29'—C28'—H28C	114.2
H14A—C14—H14B	108.0	O8'—C28'—H28D	114.2
O4—C15—O5	123.8 (3)	C29'—C28'—H28D	114.2
O4—C15—C14	125.6 (3)	H28C—C28'—H28D	111.4
O5—C15—C14	110.7 (3)	C28'—C29'—H29D	109.5
O5—C16—C17	125.9 (10)	C28'—C29'—H29E	109.5
O5—C16—H16A	105.8	H29D—C29'—H29E	109.5
C17—C16—H16A	105.8	C28'—C29'—H29F	109.5
O5—C16—H16B	105.8	H29D—C29'—H29F	109.5
C17—C16—H16B	105.8	H29E—C29'—H29F	109.5
H16A—C16—H16B	106.2	C1—N1—C5	116.9 (2)
C16—C17—H17A	109.5	C6—N2—N3	119.08 (19)
C16—C17—H17B	109.5	C6—N2—H2A	120.5
H17A—C17—H17B	109.5	N3—N2—H2A	120.5
C16—C17—H17C	109.5	C7—N3—N2	115.9 (2)
H17A—C17—H17C	109.5	C18—N4—N5	119.7 (2)
H17B—C17—H17C	109.5	C18—N4—H4A	120.1
O2—C18—N4	124.7 (3)	N5—N4—H4A	120.1
O2—C18—C5	120.4 (3)	C19—N5—N4	115.6 (2)
N4—C18—C5	114.8 (2)	C13—O3—C14	118.9 (2)
N5—C19—C20	120.8 (3)	C25—O6—C26	118.5 (2)
N1—C1—C2—C3	1.8 (4)	C23—C24—C25—C20	−0.2 (5)
C6—C1—C2—C3	−178.0 (2)	C21—C20—C25—O6	−177.9 (3)
C1—C2—C3—C4	−0.5 (4)	C19—C20—C25—O6	1.1 (4)
C2—C3—C4—C5	−1.6 (4)	C21—C20—C25—C24	0.7 (4)
C3—C4—C5—N1	2.7 (4)	C19—C20—C25—C24	179.7 (3)
C3—C4—C5—C18	−175.0 (3)	O6—C26—C27—O7	5.4 (7)
N1—C1—C6—O1	163.9 (2)	O6—C26—C27—O8	−170.8 (6)
C2—C1—C6—O1	−16.3 (4)	O6—C26—C27—O8'	153.9 (10)
N1—C1—C6—N2	−17.8 (3)	O4—C15—O5—C16	−9.6 (8)
C2—C1—C6—N2	162.0 (2)	C14—C15—O5—C16	170.5 (6)
N3—C7—C8—C9	7.8 (4)	C17—C16—O5—C15	99.1 (12)
N3—C7—C8—C13	−171.5 (2)	O7—C27—O8—C28	25.2 (11)
C13—C8—C9—C10	0.2 (4)	O8'—C27—O8—C28	−75.9 (19)
C7—C8—C9—C10	−179.1 (3)	C26—C27—O8—C28	−158.4 (7)
C8—C9—C10—C11	−0.4 (5)	C29—C28—O8—C27	−99.3 (11)
C9—C10—C11—C12	0.6 (5)	O7—C27—O8'—C28'	−64 (6)
C10—C11—C12—C13	−0.7 (4)	O8—C27—O8'—C28'	37 (5)
C11—C12—C13—O3	−179.7 (3)	C26—C27—O8'—C28'	145 (5)
C11—C12—C13—C8	0.5 (4)	C27—O8'—C28'—C29'	146 (7)
C9—C8—C13—O3	179.9 (2)	C2—C1—N1—C5	−0.8 (4)
C7—C8—C13—O3	−0.8 (4)	C6—C1—N1—C5	179.0 (2)
C9—C8—C13—C12	−0.3 (4)	C4—C5—N1—C1	−1.5 (4)
C7—C8—C13—C12	179.0 (2)	C18—C5—N1—C1	176.2 (2)
O3—C14—C15—O4	2.4 (5)	O1—C6—N2—N3	1.3 (4)
O3—C14—C15—O5	−177.7 (3)	C1—C6—N2—N3	−176.90 (19)
N1—C5—C18—O2	152.8 (3)	C8—C7—N3—N2	179.9 (2)
C4—C5—C18—O2	−29.3 (4)	C6—N2—N3—C7	−175.1 (2)
N1—C5—C18—N4	−29.8 (4)	O2—C18—N4—N5	1.4 (5)
C4—C5—C18—N4	148.0 (3)	C5—C18—N4—N5	−175.8 (2)
N5—C19—C20—C25	−172.5 (3)	C20—C19—N5—N4	−178.2 (2)
N5—C19—C20—C21	6.6 (5)	C18—N4—N5—C19	177.1 (3)
C25—C20—C21—C22	−1.0 (5)	C12—C13—O3—C14	3.5 (4)
C19—C20—C21—C22	179.9 (3)	C8—C13—O3—C14	−176.6 (2)
C20—C21—C22—C23	0.9 (5)	C15—C14—O3—C13	−78.7 (3)
C21—C22—C23—C24	−0.3 (5)	C24—C25—O6—C26	−5.8 (5)
C22—C23—C24—C25	0.0 (5)	C20—C25—O6—C26	172.7 (3)
C23—C24—C25—O6	178.3 (3)	C27—C26—O6—C25	−169.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O5^i	0.86	2.53	3.353 (3)	161
C2—H2···O7^ii	0.93	2.40	3.304 (4)	165
C17—H17C···O2^iii	0.96	2.49	2.896 (8)	105
N2—H2A···N1	0.86	2.34	2.694 (3)	105

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