Candesartan cilexetil, an antihypertensive agent containing an extended double ester chain

In the title compound (systematic name: ()-1-[(cyclo­hex­yloxy)carbonyl­oxy]ethyl 2-ethoxy-1-{[2′-(1H-tetrazol-5-yl)biphenyl-4-yl]methyl}-1H-benzimidazole-7-carboxyl­ate), C₃₃H₃₄N₆O₆, the biphenyl­tetrazole moiety projects almost perpendicularly from the benzimidazole group. The planes of the three rings in the biphenyl­tetrazole moiety are staggered with respect to one another. In the benzimidazole system, the 2-ethoxy group is extended in the opposite direction with respect to the CH(Me)OCOO-c-hexyl double ester chain. An N—H...N hydrogen bond joins [010]-translated molecules to form a chain running along the b axis.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.007 Å
• Disorder in main residue
• R factor = 0.088
• wR factor = 0.292
• Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT220_ALERT_2_A Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       4.51 Ratio

Author Response: this is explained in Experimental Section.

PLAT241_ALERT_2_A Check High      Ueq as Compared to Neighbors for        C29

Author Response: this is explained in Experimental Section.

PLAT241_ALERT_2_A Check High      Ueq as Compared to Neighbors for        C32

Author Response: this is explained in Experimental Section.

Alert level B
PLAT213_ALERT_2_B Atom C261    has ADP max/min Ratio .............       4.80 prolat
PLAT222_ALERT_3_B Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.18 Ratio
PLAT432_ALERT_2_B Short Inter X...Y Contact  O5     ..  C261    ..       2.81 Ang.

Alert level C
DIFMX01_ALERT_2_C  The maximum difference density is > 0.1*ZMAX*0.75
            _refine_diff_density_max given =      0.791
            Test value =      0.600
DIFMX02_ALERT_1_C  The minimum difference density is > 0.1*ZMAX*0.75
            The relevant atom site should be identified.
RFACR01_ALERT_3_C  The value of the weighted R factor is > 0.25
            Weighted R factor given   0.292
PLAT084_ALERT_2_C High R2 Value ..................................       0.29
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.38
PLAT097_ALERT_2_C Maximum (Positive) Residual Density ............       0.79 e/A   3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C22
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C28
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C30
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C31
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C33
PLAT301_ALERT_3_C Main Residue  Disorder .........................       4.00 Perc.
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          7

   3 ALERT level A = In general: serious problem
   3 ALERT level B = Potentially serious problem
  13 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
  14 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

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Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai & Pritzkow, 1995) and GRETEP (Laugier & Bochu, 2004); software used to prepare material for publication: PLATON (Spek, 2003) and WinGX (Farrugia, 1999).

(±)-1-[(cyclohexyloxy)carbonyloxy]ethyl 2-ethoxy-1-{[2'-(1H-tetrazol-5-yl)biphenyl-4-yl]methyl}-1H-benzimidazole- 7-carboxylate

Crystal data

C33H34N6O6	F(000) = 1288
Mr = 610.66	Dx = 1.272 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 10007 reflections
a = 16.3545 (4) Å	θ = 1.0–25°
b = 10.8868 (3) Å	µ = 0.09 mm^−1
c = 18.4635 (5) Å	T = 120 K
β = 104.102 (2)°	Thin plate, colorless
V = 3188.32 (15) Å^3	0.34 × 0.08 × 0.06 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	5575 independent reflections
Radiation source: fine-focus sealed tube	3772 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
φ scans with κ at 0°, and ω scans	θmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = 0→19
Tmin = 0.971, Tmax = 0.997	k = 0→12
10191 measured reflections	l = −21→21

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full with fixed elements per cycle	Hydrogen site location: constr
R[F^2 > 2σ(F^2)] = 0.088	H-atom parameters constrained
wR(F^2) = 0.292	w = 1/[σ^2(Fo^2) + (0.01767P)^2 + 1.1617P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.008
5575 reflections	Δρmax = 0.79 e Å^−3
426 parameters	Δρmin = −0.33 e Å^−3
15 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.030 (5)

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.0100 (2)	−0.1337 (3)	0.31614 (17)	0.0801 (8)
N2	0.0473 (2)	−0.1589 (3)	0.38853 (17)	0.0904 (9)
N3	0.0936 (2)	−0.2567 (3)	0.39389 (16)	0.0819 (8)
N4	0.08563 (18)	−0.2963 (3)	0.32338 (14)	0.0683 (6)
H4	0.1094	−0.3605	0.3106	0.102*
N5	0.25720 (16)	0.3236 (2)	0.30014 (15)	0.0666 (6)
N6	0.18918 (17)	0.4970 (3)	0.31724 (15)	0.0689 (7)
O1	0.20737 (15)	0.4449 (2)	0.19794 (13)	0.0732 (6)
O2	0.39722 (19)	0.1300 (3)	0.40182 (18)	0.1052 (9)
O3	0.3194 (2)	0.0446 (3)	0.4735 (2)	0.1201 (11)
O4	0.3784 (3)	−0.0886 (4)	0.5681 (2)	0.1517 (14)
O5	0.4529 (3)	0.0857 (4)	0.6080 (3)	0.1549 (15)
O6	0.4206 (3)	−0.0626 (4)	0.6866 (3)	0.1622 (16)
C1	0.0350 (2)	−0.2202 (3)	0.27666 (18)	0.0636 (7)
C2	0.00973 (19)	−0.2339 (3)	0.19436 (17)	0.0606 (7)
C3	−0.0470 (2)	−0.3263 (3)	0.16427 (19)	0.0704 (8)
H5	−0.0676	−0.3778	0.1959	0.084*
C4	−0.0730 (2)	−0.3426 (3)	0.0882 (2)	0.0761 (9)
H6	−0.1108	−0.4048	0.0685	0.091*
C5	−0.0427 (2)	−0.2660 (4)	0.0414 (2)	0.0811 (10)
H7	−0.0601	−0.2766	−0.0100	0.097*
C6	0.0133 (2)	−0.1739 (3)	0.07056 (19)	0.0747 (9)
H8	0.0332	−0.1227	0.0383	0.090*
C7	0.0409 (2)	−0.1555 (3)	0.14714 (17)	0.0613 (7)
C8	0.10352 (19)	−0.0573 (3)	0.17634 (17)	0.0618 (7)
C9	0.1768 (2)	−0.0805 (3)	0.2308 (2)	0.0743 (9)
H9	0.1869	−0.1590	0.2508	0.089*
C10	0.2351 (2)	0.0120 (3)	0.2558 (2)	0.0740 (9)
H10	0.2840	−0.0059	0.2921	0.089*
C11	0.22234 (19)	0.1297 (3)	0.22805 (18)	0.0630 (7)
C12	0.1483 (2)	0.1532 (3)	0.17386 (17)	0.0648 (7)
H11	0.1380	0.2321	0.1545	0.078*
C13	0.0902 (2)	0.0622 (3)	0.14857 (18)	0.0648 (8)
H12	0.0413	0.0805	0.1124	0.078*
C14	0.2862 (2)	0.2290 (3)	0.2555 (2)	0.0679 (8)
H13	0.3372	0.1918	0.2855	0.081*
H14	0.3002	0.2679	0.2128	0.081*
C15	0.2150 (2)	0.4265 (3)	0.26992 (18)	0.0637 (7)
C16	0.2157 (2)	0.4352 (3)	0.38498 (19)	0.0705 (8)
C17	0.2046 (3)	0.4695 (4)	0.4542 (2)	0.0858 (10)
H15	0.1776	0.5425	0.4603	0.103*
C18	0.2349 (3)	0.3921 (5)	0.5136 (2)	0.0976 (12)
H16	0.2284	0.4134	0.5607	0.117*
C19	0.2751 (2)	0.2822 (4)	0.5044 (2)	0.0909 (11)
H17	0.2933	0.2303	0.5451	0.109*
C20	0.2884 (2)	0.2490 (4)	0.4361 (2)	0.0775 (9)
C21	0.2579 (2)	0.3259 (3)	0.37580 (18)	0.0672 (8)
C22	0.1638 (3)	0.5546 (3)	0.1650 (2)	0.0785 (9)
H18	0.1943	0.6271	0.1872	0.094*
H19	0.1077	0.5573	0.1736	0.094*
C23	0.1588 (4)	0.5513 (5)	0.0852 (3)	0.1219 (18)
H1	0.1346	0.6266	0.0627	0.183*
H2	0.1240	0.4835	0.0630	0.183*
H3	0.2143	0.5415	0.0774	0.183*
C24	0.3405 (2)	0.1371 (4)	0.4339 (2)	0.0891 (11)
C25	0.3806 (7)	−0.0521 (8)	0.4924 (5)	0.147 (5)	0.75
H20	0.4366	−0.0335	0.4848	0.177*	0.75
C251	0.3734 (14)	−0.071 (2)	0.4842 (9)	0.149 (18)	0.25
H201	0.4264	−0.0250	0.4935	0.179*	0.25
C26	0.3372 (7)	−0.1678 (7)	0.4518 (7)	0.182 (4)	0.75
H21	0.3723	−0.2033	0.4225	0.272*	0.75
H22	0.2838	−0.1454	0.4197	0.272*	0.75
H23	0.3285	−0.2266	0.4880	0.272*	0.75
C261	0.3809 (11)	−0.1161 (15)	0.4058 (12)	0.187 (17)	0.25
H211	0.4092	−0.1940	0.4107	0.280*	0.25
H221	0.4126	−0.0573	0.3850	0.280*	0.25
H231	0.3256	−0.1246	0.3733	0.280*	0.25
C27	0.4186 (4)	−0.0130 (6)	0.6211 (4)	0.144 (2)
C28	0.4578 (4)	0.0093 (10)	0.7539 (3)	0.184 (3)
H24	0.4360	0.0935	0.7478	0.221*
C29	0.5535 (4)	0.0113 (12)	0.7711 (6)	0.266 (6)
H25	0.5760	−0.0715	0.7771	0.319*
H26	0.5726	0.0516	0.7314	0.319*
C30	0.5802 (7)	0.0814 (10)	0.8422 (5)	0.222 (4)
H27	0.5534	0.1616	0.8362	0.267*
H28	0.6408	0.0937	0.8540	0.267*
C31	0.5564 (4)	0.0134 (11)	0.9058 (5)	0.230 (5)
H29	0.5793	0.0549	0.9528	0.277*
H30	0.5781	−0.0699	0.9094	0.277*
C32	0.4600 (5)	0.0123 (13)	0.8880 (4)	0.272 (7)
H31	0.4414	−0.0269	0.9283	0.326*
H32	0.4389	0.0960	0.8831	0.326*
C33	0.4259 (4)	−0.0564 (10)	0.8162 (4)	0.201 (4)
H33	0.3647	−0.0566	0.8041	0.242*
H34	0.4454	−0.1408	0.8211	0.242*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.105 (2)	0.0725 (17)	0.0682 (18)	0.0043 (16)	0.0320 (16)	−0.0076 (14)
N2	0.125 (3)	0.090 (2)	0.0617 (18)	0.0014 (19)	0.0320 (18)	−0.0127 (16)
N3	0.107 (2)	0.0834 (19)	0.0549 (16)	−0.0015 (17)	0.0189 (15)	−0.0070 (14)
N4	0.0846 (17)	0.0685 (15)	0.0519 (14)	0.0009 (14)	0.0168 (12)	−0.0041 (12)
N5	0.0695 (15)	0.0668 (15)	0.0640 (15)	−0.0023 (12)	0.0174 (12)	−0.0008 (12)
N6	0.0730 (16)	0.0729 (16)	0.0613 (15)	0.0016 (13)	0.0175 (13)	−0.0035 (13)
O1	0.0931 (15)	0.0678 (13)	0.0619 (13)	0.0083 (11)	0.0248 (11)	0.0005 (10)
O2	0.0997 (19)	0.106 (2)	0.108 (2)	0.0204 (16)	0.0218 (16)	0.0155 (17)
O3	0.097 (2)	0.104 (2)	0.145 (3)	0.0009 (17)	0.0022 (19)	0.056 (2)
O4	0.158 (3)	0.135 (3)	0.143 (3)	0.006 (3)	0.001 (3)	0.046 (3)
O5	0.153 (3)	0.134 (3)	0.149 (4)	0.008 (3)	−0.020 (3)	0.033 (3)
O6	0.153 (3)	0.175 (4)	0.150 (4)	0.021 (3)	0.021 (3)	0.053 (3)
C1	0.0731 (18)	0.0602 (16)	0.0593 (18)	−0.0035 (14)	0.0195 (14)	−0.0035 (14)
C2	0.0669 (17)	0.0591 (16)	0.0556 (17)	0.0058 (14)	0.0146 (14)	0.0012 (13)
C3	0.076 (2)	0.0694 (19)	0.067 (2)	−0.0060 (16)	0.0199 (16)	0.0014 (16)
C4	0.079 (2)	0.077 (2)	0.068 (2)	−0.0075 (17)	0.0094 (17)	−0.0070 (17)
C5	0.090 (2)	0.091 (2)	0.0546 (19)	−0.004 (2)	0.0021 (17)	−0.0026 (17)
C6	0.081 (2)	0.081 (2)	0.0601 (19)	−0.0016 (18)	0.0144 (16)	0.0067 (16)
C7	0.0659 (17)	0.0634 (17)	0.0536 (16)	0.0047 (14)	0.0129 (13)	0.0032 (13)
C8	0.0645 (17)	0.0650 (18)	0.0574 (17)	0.0029 (14)	0.0181 (14)	0.0019 (14)
C9	0.074 (2)	0.0580 (17)	0.085 (2)	0.0052 (15)	0.0060 (17)	0.0067 (16)
C10	0.0631 (18)	0.0703 (19)	0.083 (2)	0.0076 (16)	0.0068 (16)	0.0035 (17)
C11	0.0668 (18)	0.0637 (17)	0.0638 (18)	0.0040 (14)	0.0259 (15)	0.0005 (14)
C12	0.0745 (19)	0.0625 (17)	0.0584 (17)	0.0041 (15)	0.0183 (15)	0.0069 (14)
C13	0.0716 (18)	0.0647 (18)	0.0571 (18)	0.0044 (15)	0.0142 (14)	0.0054 (14)
C14	0.0646 (18)	0.0676 (18)	0.075 (2)	0.0009 (14)	0.0232 (15)	0.0004 (15)
C15	0.0680 (18)	0.0622 (17)	0.0615 (18)	−0.0021 (14)	0.0171 (14)	−0.0011 (14)
C16	0.0657 (18)	0.082 (2)	0.0628 (19)	−0.0049 (16)	0.0132 (15)	0.0002 (16)
C17	0.087 (2)	0.104 (3)	0.066 (2)	0.001 (2)	0.0185 (18)	−0.007 (2)
C18	0.098 (3)	0.134 (4)	0.060 (2)	−0.002 (3)	0.018 (2)	0.004 (2)
C19	0.085 (2)	0.121 (3)	0.064 (2)	−0.009 (2)	0.0115 (18)	0.019 (2)
C20	0.0652 (19)	0.085 (2)	0.078 (2)	−0.0119 (17)	0.0091 (16)	0.0119 (18)
C21	0.0631 (17)	0.074 (2)	0.0640 (19)	−0.0086 (15)	0.0139 (14)	0.0028 (16)
C22	0.094 (2)	0.073 (2)	0.070 (2)	0.0117 (18)	0.0211 (18)	0.0073 (17)
C23	0.162 (5)	0.132 (4)	0.076 (3)	0.049 (3)	0.038 (3)	0.020 (3)
C24	0.081 (2)	0.092 (3)	0.083 (3)	−0.007 (2)	−0.0016 (19)	0.015 (2)
C25	0.156 (10)	0.120 (6)	0.166 (10)	0.045 (6)	0.037 (7)	0.082 (7)
C251	0.11 (2)	0.15 (3)	0.14 (3)	−0.03 (2)	−0.07 (2)	0.02 (2)
C26	0.227 (11)	0.077 (5)	0.240 (12)	0.026 (6)	0.057 (10)	0.002 (6)
C261	0.079 (11)	0.044 (8)	0.37 (5)	0.031 (8)	−0.077 (19)	−0.003 (15)
C27	0.141 (4)	0.126 (4)	0.146 (5)	0.018 (4)	−0.003 (4)	0.051 (4)
C28	0.154 (6)	0.295 (10)	0.095 (4)	0.067 (6)	0.011 (4)	0.013 (5)
C29	0.143 (6)	0.367 (15)	0.272 (12)	0.078 (8)	0.019 (7)	−0.141 (11)
C30	0.270 (11)	0.242 (10)	0.149 (7)	−0.045 (9)	0.041 (7)	−0.050 (7)
C31	0.174 (8)	0.347 (14)	0.157 (8)	0.091 (9)	0.015 (6)	−0.009 (8)
C32	0.209 (9)	0.49 (2)	0.120 (6)	0.168 (12)	0.038 (6)	0.005 (9)
C33	0.122 (5)	0.313 (12)	0.167 (7)	0.041 (6)	0.032 (5)	0.041 (8)

Geometric parameters (Å, º)

N1—C1	1.316 (3)	C14—H13	0.9700
N1—N2	1.355 (4)	C14—H14	0.9700
N2—N3	1.296 (4)	C16—C17	1.385 (5)
N3—N4	1.348 (4)	C16—C21	1.406 (5)
N4—C1	1.330 (3)	C17—C18	1.376 (6)
N4—H4	0.8600	C17—H15	0.9300
N5—C15	1.362 (3)	C18—C19	1.395 (6)
N5—C21	1.395 (3)	C18—H16	0.9300
N5—C14	1.468 (3)	C19—C20	1.379 (5)
N6—C15	1.308 (3)	C19—H17	0.9300
N6—C16	1.393 (3)	C20—C21	1.386 (5)
O1—C15	1.320 (3)	C20—C24	1.493 (6)
O1—C22	1.447 (3)	C22—C23	1.455 (6)
O2—C24	1.219 (4)	C22—H18	0.9700
O3—C24	1.338 (4)	C22—H19	0.9700
O3—C25	1.435 (9)	C23—H1	0.9600
O3—C251	1.52 (2)	C23—H2	0.9600
O4—C27	1.324 (7)	C23—H3	0.9600
O4—C25	1.462 (9)	C25—C26	1.547 (12)
O4—C251	1.542 (18)	C25—H20	0.9800
O5—C27	1.263 (7)	C251—C261	1.562 (10)
O6—C27	1.318 (6)	C251—H201	0.9800
O6—C28	1.470 (8)	C26—H21	0.9600
C1—C2	1.482 (4)	C26—H22	0.9600
C2—C3	1.389 (4)	C26—H23	0.9600
C2—C7	1.402 (4)	C261—H211	0.9600
C3—C4	1.376 (5)	C261—H221	0.9600
C3—H5	0.9300	C261—H231	0.9600
C4—C5	1.377 (5)	C28—C29	1.519 (5)
C4—H6	0.9300	C28—C33	1.549 (10)
C5—C6	1.376 (5)	C28—H24	0.9800
C5—H7	0.9300	C29—C30	1.489 (11)
C6—C7	1.390 (4)	C29—H25	0.9700
C6—H8	0.9300	C29—H26	0.9700
C7—C8	1.487 (4)	C30—C31	1.518 (8)
C8—C9	1.387 (5)	C30—H27	0.9700
C8—C13	1.397 (4)	C30—H28	0.9700
C9—C10	1.386 (5)	C31—C32	1.530 (11)
C9—H9	0.9300	C31—H29	0.9700
C10—C11	1.377 (5)	C31—H30	0.9700
C10—H10	0.9300	C32—C33	1.505 (12)
C11—C12	1.394 (5)	C32—H31	0.9700
C11—C14	1.503 (5)	C32—H32	0.9700
C12—C13	1.372 (4)	C33—H33	0.9700
C12—H11	0.9300	C33—H34	0.9700
C13—H12	0.9300
C1—N1—N2	106.0 (3)	C20—C21—C16	120.4 (3)
N3—N2—N1	110.9 (3)	N5—C21—C16	104.6 (3)
N2—N3—N4	105.8 (3)	O1—C22—C23	107.8 (3)
C1—N4—N3	109.0 (2)	O1—C22—H18	110.1
C1—N4—H4	125.5	C23—C22—H18	110.1
N3—N4—H4	125.5	O1—C22—H19	110.1
C15—N5—C21	105.97 (19)	C23—C22—H19	110.1
C15—N5—C14	123.2 (2)	H18—C22—H19	108.5
C21—N5—C14	130.5 (2)	C22—C23—H1	109.5
C15—N6—C16	103.7 (2)	C22—C23—H2	109.5
C15—O1—C22	117.7 (2)	H1—C23—H2	109.5
C24—O3—C25	115.3 (4)	C22—C23—H3	109.5
C24—O3—C251	118.4 (9)	H1—C23—H3	109.5
C27—O4—C25	114.4 (5)	H2—C23—H3	109.5
C27—O4—C251	124.1 (10)	O2—C24—O3	123.1 (3)
C27—O6—C28	118.0 (4)	O2—C24—C20	124.9 (3)
N1—C1—N4	108.4 (2)	O3—C24—C20	112.0 (3)
N1—C1—C2	126.4 (3)	O3—C25—O4	104.7 (7)
N4—C1—C2	125.2 (2)	O3—C25—C26	105.6 (8)
C3—C2—C7	120.1 (3)	O4—C25—C26	97.3 (7)
C3—C2—C1	118.4 (3)	O3—C25—H20	115.7
C7—C2—C1	121.6 (3)	O4—C25—H20	115.7
C4—C3—C2	120.7 (3)	C26—C25—H20	115.7
C4—C3—H5	119.6	O3—C251—O4	96.9 (13)
C2—C3—H5	119.6	O3—C251—C261	108.3 (12)
C3—C4—C5	119.6 (3)	O4—C251—C261	154 (2)
C3—C4—H6	120.2	O3—C251—H201	93.3
C5—C4—H6	120.2	O4—C251—H201	93.3
C6—C5—C4	120.2 (3)	C261—C251—H201	93.3
C6—C5—H7	119.9	C25—C26—H21	109.5
C4—C5—H7	119.9	C25—C26—H22	109.5
C5—C6—C7	121.5 (3)	H21—C26—H22	109.5
C5—C6—H8	119.2	C25—C26—H23	109.5
C7—C6—H8	119.2	H21—C26—H23	109.5
C6—C7—C2	117.9 (3)	H22—C26—H23	109.5
C6—C7—C8	119.7 (3)	C251—C261—H211	109.5
C2—C7—C8	122.3 (3)	C251—C261—H221	109.5
C9—C8—C13	117.7 (3)	H211—C261—H221	109.5
C9—C8—C7	122.0 (3)	C251—C261—H231	109.5
C13—C8—C7	120.3 (3)	H211—C261—H231	109.5
C10—C9—C8	120.8 (3)	H221—C261—H231	109.5
C10—C9—H9	119.6	O5—C27—O6	127.7 (6)
C8—C9—H9	119.6	O5—C27—O4	123.5 (5)
C11—C10—C9	121.5 (3)	O6—C27—O4	108.7 (5)
C11—C10—H10	119.3	O6—C28—C29	112.2 (6)
C9—C10—H10	119.3	O6—C28—C33	103.7 (7)
C10—C11—C12	117.7 (3)	C29—C28—C33	111.6 (7)
C10—C11—C14	120.9 (3)	O6—C28—H24	109.8
C12—C11—C14	121.4 (3)	C29—C28—H24	109.8
C13—C12—C11	121.3 (3)	C33—C28—H24	109.8
C13—C12—H11	119.3	C30—C29—C28	104.9 (6)
C11—C12—H11	119.3	C30—C29—H25	110.8
C12—C13—C8	121.0 (3)	C28—C29—H25	110.8
C12—C13—H12	119.5	C30—C29—H26	110.8
C8—C13—H12	119.5	C28—C29—H26	110.8
N5—C14—C11	113.7 (2)	H25—C29—H26	108.8
N5—C14—H13	108.8	C29—C30—C31	110.9 (8)
C11—C14—H13	108.8	C29—C30—H27	109.5
N5—C14—H14	108.8	C31—C30—H27	109.5
C11—C14—H14	108.8	C29—C30—H28	109.5
H13—C14—H14	107.7	C31—C30—H28	109.5
N6—C15—O1	128.1 (3)	H27—C30—H28	108.1
N6—C15—N5	115.0 (2)	C30—C31—C32	106.4 (7)
O1—C15—N5	116.8 (2)	C30—C31—H29	110.5
C17—C16—N6	128.1 (3)	C32—C31—H29	110.5
C17—C16—C21	121.2 (3)	C30—C31—H30	110.5
N6—C16—C21	110.8 (3)	C32—C31—H30	110.5
C18—C17—C16	117.9 (4)	H29—C31—H30	108.6
C18—C17—H15	121.0	C33—C32—C31	109.6 (6)
C16—C17—H15	121.0	C33—C32—H31	109.8
C17—C18—C19	121.1 (4)	C31—C32—H31	109.8
C17—C18—H16	119.5	C33—C32—H32	109.8
C19—C18—H16	119.5	C31—C32—H32	109.8
C20—C19—C18	121.4 (4)	H31—C32—H32	108.2
C20—C19—H17	119.3	C32—C33—C28	107.7 (8)
C18—C19—H17	119.3	C32—C33—H33	110.2
C19—C20—C21	118.0 (4)	C28—C33—H33	110.2
C19—C20—C24	117.3 (4)	C32—C33—H34	110.2
C21—C20—C24	124.6 (4)	C28—C33—H34	110.2
C20—C21—N5	135.0 (3)	H33—C33—H34	108.5
C1—N1—N2—N3	0.0 (4)	N6—C16—C17—C18	178.7 (3)
N1—N2—N3—N4	−0.5 (4)	C21—C16—C17—C18	−1.2 (5)
N2—N3—N4—C1	0.7 (3)	C16—C17—C18—C19	−0.3 (6)
N2—N1—C1—N4	0.4 (3)	C17—C18—C19—C20	2.1 (6)
N2—N1—C1—C2	178.7 (3)	C18—C19—C20—C21	−2.3 (6)
N3—N4—C1—N1	−0.7 (3)	C18—C19—C20—C24	173.2 (4)
N3—N4—C1—C2	−179.0 (2)	C19—C20—C21—N5	−178.6 (3)
N1—C1—C2—C3	−105.5 (3)	C24—C20—C21—N5	6.2 (6)
N4—C1—C2—C3	72.4 (4)	C19—C20—C21—C16	0.8 (5)
N1—C1—C2—C7	73.7 (4)	C24—C20—C21—C16	−174.3 (3)
N4—C1—C2—C7	−108.3 (3)	C15—N5—C21—C20	178.5 (4)
C7—C2—C3—C4	0.3 (5)	C14—N5—C21—C20	4.4 (5)
C1—C2—C3—C4	179.6 (3)	C15—N5—C21—C16	−1.0 (3)
C2—C3—C4—C5	−0.2 (5)	C14—N5—C21—C16	−175.1 (2)
C3—C4—C5—C6	0.0 (6)	C17—C16—C21—C20	0.9 (5)
C4—C5—C6—C7	0.1 (6)	N6—C16—C21—C20	−178.9 (3)
C5—C6—C7—C2	−0.1 (5)	C17—C16—C21—N5	−179.5 (3)
C5—C6—C7—C8	178.0 (3)	N6—C16—C21—N5	0.7 (3)
C3—C2—C7—C6	−0.1 (5)	C15—O1—C22—C23	−176.6 (3)
C1—C2—C7—C6	−179.4 (3)	C25—O3—C24—O2	15.5 (5)
C3—C2—C7—C8	−178.2 (3)	C251—O3—C24—O2	5.1 (8)
C1—C2—C7—C8	2.5 (4)	C25—O3—C24—C20	−162.7 (5)
C6—C7—C8—C9	−128.4 (4)	C251—O3—C24—C20	−173.1 (8)
C2—C7—C8—C9	49.6 (4)	C19—C20—C24—O2	−134.1 (4)
C6—C7—C8—C13	51.0 (4)	C21—C20—C24—O2	41.0 (5)
C2—C7—C8—C13	−131.0 (3)	C19—C20—C24—O3	44.1 (4)
C13—C8—C9—C10	−0.9 (5)	C21—C20—C24—O3	−140.8 (3)
C7—C8—C9—C10	178.5 (3)	C24—O3—C25—O4	141.9 (4)
C8—C9—C10—C11	0.5 (6)	C24—O3—C25—C26	−116.0 (7)
C9—C10—C11—C12	0.2 (5)	C27—O4—C25—O3	−77.5 (7)
C9—C10—C11—C14	−179.9 (3)	C27—O4—C25—C26	174.2 (6)
C10—C11—C12—C13	−0.4 (5)	C27—O4—C251—O3	−67.2 (13)
C14—C11—C12—C13	179.7 (3)	C27—O4—C251—C261	131 (4)
C11—C12—C13—C8	0.0 (5)	C28—O6—C27—O5	8.1 (8)
C9—C8—C13—C12	0.7 (5)	O4—C27—O6—C28	−176.2 (3)
C7—C8—C13—C12	−178.7 (3)	C25—O4—C27—O5	3.1 (8)
C15—N5—C14—C11	−89.4 (3)	C251—O4—C27—O5	4.4 (13)
C21—N5—C14—C11	83.8 (3)	C25—O4—C27—O6	−172.8 (5)
C10—C11—C14—N5	−110.8 (3)	C251—O4—C27—O6	−171.5 (11)
C12—C11—C14—N5	69.2 (4)	C27—O6—C28—C29	−76.0 (8)
C16—N6—C15—O1	−178.4 (3)	C27—O6—C28—C33	163.5 (4)
C16—N6—C15—N5	−0.6 (3)	O6—C28—C29—C30	−177.1 (8)
C22—O1—C15—N6	−1.4 (4)	C33—C28—C29—C30	−61.2 (12)
C22—O1—C15—N5	−179.1 (2)	C28—C29—C30—C31	64.9 (12)
C21—N5—C15—N6	1.1 (3)	C29—C30—C31—C32	−66.3 (11)
C14—N5—C15—N6	175.8 (2)	C30—C31—C32—C33	62.1 (12)
C21—N5—C15—O1	179.1 (2)	C31—C32—C33—C28	−59.1 (11)
C14—N5—C15—O1	−6.2 (3)	O6—C28—C33—C32	−179.2 (6)
C15—N6—C16—C17	−179.9 (4)	C29—C28—C33—C32	59.8 (10)
C15—N6—C16—C21	−0.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N6^i	0.86	2.01	2.835 (4)	160
C14—H13···O2	0.97	2.24	3.061 (4)	142

Symmetry code: (i) x, y−1, z.