Methyl 1-(4-chloro­benzyl)-2-(4-methyl­piperazin-1-yl)-1H-benz­imidazole-5-carboxyl­ate hemihydrate

The title compound, C₂₁H₂₃ClN₄O₂·0.5H₂O, contains two independent mol­ecules in the asymmetric unit. In each mol­ecule the piperazine ring adopts a chair conformation; the deviations of the piperazine N atoms from the best plane through the remaining four C atoms are −0.678 (3) and 0.662 (3) Å in mol­ecule A, and 0.687 (3) and −0.700 (3) Å in mol­ecule B. The mol­ecules are linked by two hydrogen bonds of the O—H...N type involving the O atom of the water mol­ecule of crystallization.

S1. Comment

The benzimidazole nucleus is an essential part of many medicinally useful drugs. For example, omeprazole and lansoprazole are useful drugs in the treatment of peptic ulcers (Nishina et al., 1996), pimobendan is a non-glucosidic cardiotonic drug (Güngör et al., 1992), emedastine difumarate (KG-2413) (Sakai et al., 1989) and astemizole (Hismanal) (Awouters et al., 1983) were discovered for the treatment of allergic diseases and enviroxime is an active drug against rhinoviruses (Victor et al., 1997).

The present compound is also a benzimidazole which was prepared for its antimicrobial activity (Göker et al., 1998). The structure of the title compound, (I), was assigned by NMR, mass spectra and elemental analysis (Göker et al., 1998). Considering the biological importance of the benzimidazole ring system including substances, we describe in this paper the structure of the title compound, (I). \sch

The benzimidazole ring systems of two molecules (I and II) are planar. The bond lengths N1—C2 [1.382 (4) and 1.390 (4) Å] are comparatively longer than the value reported for benzimidazole [1.346 (4) Å; Escande & Galigne, 1974]. The N1—C10 [1.455 (5) and 1.449 (5) Å] and N2—C2 [1.382 (5) and 1.379 (5) Å] bond lengths are normal for Csp³—N and Csp²—N bonds (Allen et al., 1987). The phenyl ring at C10 is also planar and makes an angle of 101.19 (8) for (I) and 79.42 (8)° for (II) with the plane through the complete benzimidazole ring system.

The Cl1 and Cl1' atoms lie almost in the phenyl ring planes with the distance deviations of 0.016 (1) and 0.002 (1) Å from the phenyl planes, respectively.

The C—Cl bond length [Cl1—C14 1.744 (3) for (I) and 1.738 (3) Å for (II)] is within the normal range. In 1-benzyl-2-(2,6-dichloroanilinemethyl)-1H-benzimidazole the C—Cl bond lengths are 1.739 (2) and 1.737 (2) Å (Kendi et al., 1998).

The piperazine ring adopts a perfect chair comformation in (I) and (II) (Velmurugan et al., 1994; Özbey et al., 1998). Best planes through the four non-N atoms make dihedral angles of 42.22 (13) in (I) and 32.81 (17) in (II) with the benzimidazole ring systems. The methyl group at N4 of the piperazine ring is in the equatorial position (Allinger et al., 1965).

The structure shows that the COOCH₃ group at C5 and the benzimidazole ring are almost coplanar with torsion angle C4—C5—C51—O1 7.1 (5)° [173.5 (4) in (II)]. The intramolecular distance C10—N2 of 2.968 (4) Å [3.033 (4) in (II)] is suggestive of a possible C—H···N interaction. Atom C10 is rotated towards to the piperazine ring with the torsion angle C10—N1—C2—N3 of -162.67 (29)°, possibly to enable N2 to interact with the proton of the C10 to form an intramolecular hydrogen bond. This angle is 179.89 (37)° in 6-chloro-1-(phenylmethyl)-2-[N-(phenylmethyl)-N-(2,6-dichlorophenyl)] methyl-1H-benzimidazole (Tunçbilek et al., 1997) and -179.6 (2) in 1-benzyl-2-(2,6-dichloroanilinomethyl)-1H-benzimidazole (Kendi et al., 1998).

The molecules are linked by hydrogen bonds of the O—H···N type involving the O atom of the water molecule of crystallization. The O—N distances [2.873 (4) for (I) and 2.957 (4) Å for (II)] suggest that water acts as a hydrogen-bond donor to the piperazine ring. The H₂O(O3) molecule forms hydrogen bonds to both molecules in the asymmetric unit.

S2. Experimental

The title compound was synthesized by the reaction of methyl 2-chloro-1-(p-chlorophenylmethyl)-1H-benzimidazole-5-carboxylate with N-methylpiperazine, and its structure was assigned by NMR, mass spectra and elemental analysis results (Göker et al., 1998).

S3. Refinement

H atoms were placed geometrically 0.95 Å from their parent atoms. For all H atoms a riding model was used with U_iso(H) = 1.3U_eq(C). Refinement with lower σ(I) cutoffs led to no significant changes in the results. Hydrogen bonds were calculated with PARST (Nardelli, 1995).

Computing details

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1990); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: MolEN; program(s) used to refine structure: MolEN; molecular graphics: MolEN.

Figures

Fig. 1. ORTEP (Johnson, 1965) drawing of the title compound showing the atom-numbering scheme. The displacement ellipsoids are drawn at the 50% probability level.

(I)

Crystal data

C21H23ClN4O2·0.5H2O	V = 2092.3 (3) Å^3
Mr = 407.90	Z = 4
Triclinic, P1	Dx = 1.295 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 11.227 (1) Å	Cell parameters from 25 reflections
b = 13.443 (1) Å	θ = 11–18°
c = 15.835 (2) Å	µ = 0.21 mm^−1
α = 68.06 (1)°	T = 295 K
β = 72.55 (1)°	Prismatic, yellow
γ = 76.30 (1)°	0.40 × 0.40 × 0.40 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.015
ω/2θ scans	θmax = 25.7°, θmin = 2.4°
Absorption correction: empirical (using intensity measurements) ψ scans (North et al., 1968)	h = −13→0
Tmin = 0.853, Tmax = 0.922	k = −16→15
8182 measured reflections	l = −19→18
7754 independent reflections	3 standard reflections every 120 min
5364 reflections with I > 3σ(I)	intensity decay: 3.3%

Refinement

Refinement on F	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.053	w = 1/[σF^2 + (0.02*F)^2 + 1]
wR(F^2) = 0.068	(Δ/σ)max = 0.010
S = 1.24	Δρmax = 0.35 e Å^−3
5364 reflections	Δρmin = −0.10 e Å^−3
514 parameters

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

	x	y	z	Uiso*/Ueq
CL1	0.4418 (1)	0.4189 (1)	0.2599 (1)	0.0828 (5)
O1	1.1370 (3)	0.8364 (2)	0.0784 (2)	0.0915 (10)
O2	0.9395 (3)	0.8999 (2)	0.1381 (2)	0.0836 (11)
O3	0.7534 (3)	0.4752 (3)	0.4440 (2)	0.1045 (17)
N1	0.8342 (2)	0.6966 (2)	−0.1244 (2)	0.0492 (8)
N2	0.9506 (3)	0.5744 (2)	−0.2076 (2)	0.0518 (8)
N3	1.0423 (3)	0.6477 (2)	−0.1287 (2)	0.0496 (8)
N4	1.0033 (3)	0.4630 (2)	−0.3384 (2)	0.0622 (10)
C2	0.9473 (3)	0.6383 (3)	−0.1556 (2)	0.0464 (10)
C4	1.0454 (3)	0.7496 (2)	−0.0243 (2)	0.0489 (10)
C5	0.9679 (3)	0.8152 (2)	0.0274 (2)	0.0509 (10)
C6	0.8401 (3)	0.8441 (3)	0.0298 (2)	0.0595 (12)
C7	0.7827 (3)	0.8111 (3)	−0.0192 (2)	0.0583 (15)
C8	0.8612 (3)	0.7454 (2)	−0.0701 (2)	0.0473 (11)
C9	0.9891 (3)	0.7148 (3)	−0.0733 (2)	0.0459 (11)
C10	0.7077 (3)	0.6825 (3)	−0.1206 (2)	0.0564 (13)
C11	0.6416 (3)	0.6181 (2)	−0.0238 (2)	0.0474 (8)
C12	0.7060 (3)	0.5306 (3)	0.0327 (2)	0.0566 (14)
C13	0.6455 (3)	0.4696 (3)	0.1198 (2)	0.0599 (15)
C14	0.5182 (3)	0.4971 (3)	0.1500 (2)	0.0555 (14)
C15	0.4513 (3)	0.5835 (3)	0.0965 (3)	0.0671 (16)
C16	0.5143 (3)	0.6437 (3)	0.0092 (2)	0.0625 (15)
C20	1.0584 (4)	0.4895 (3)	−0.2103 (2)	0.0639 (15)
C21	1.0300 (4)	0.4101 (3)	−0.2459 (2)	0.0694 (16)
C22	0.8974 (4)	0.5487 (3)	−0.3351 (2)	0.0634 (15)
C23	0.9249 (4)	0.6302 (3)	−0.3014 (2)	0.0570 (13)
C24	0.9766 (5)	0.3825 (3)	−0.3698 (3)	0.0926 (18)
C51	1.0270 (4)	0.8509 (3)	0.0818 (2)	0.0599 (15)
C52	0.9859 (4)	0.9352 (3)	0.1964 (2)	0.0908 (18)
CL1'	0.8824 (1)	0.2067 (1)	0.5581 (1)	0.0930 (4)
O1'	1.4372 (3)	0.0199 (2)	0.9094 (2)	0.1030 (12)
O2'	1.6230 (2)	0.0186 (2)	0.8093 (2)	0.0770 (8)
N1'	1.3717 (2)	−0.1916 (2)	0.6321 (2)	0.0492 (8)
N2'	1.5017 (3)	−0.2213 (2)	0.4894 (2)	0.0488 (8)
N3'	1.5713 (3)	−0.1520 (2)	0.5822 (2)	0.0482 (8)
N4'	1.6005 (3)	−0.3254 (2)	0.3492 (2)	0.0575 (10)
C2'	1.4857 (3)	−0.1893 (2)	0.5658 (2)	0.0455 (10)
C4'	1.5541 (3)	−0.0795 (3)	0.7117 (2)	0.0497 (13)
C5'	1.4721 (3)	−0.0621 (3)	0.7925 (2)	0.0517 (10)
C6'	1.3514 (3)	−0.0921 (3)	0.8249 (2)	0.0573 (14)
C7'	1.3077 (3)	−0.1373 (3)	0.7776 (2)	0.0522 (14)
C8'	1.3884 (3)	−0.1523 (2)	0.6963 (2)	0.0458 (11)
C9'	1.5109 (3)	−0.1258 (2)	0.6638 (2)	0.0447 (11)
C10'	1.2494 (3)	−0.2049 (2)	0.6274 (2)	0.0542 (13)
C11'	1.1583 (3)	−0.1008 (2)	0.6130 (2)	0.0444 (9)
C12'	1.1975 (3)	−0.0038 (3)	0.5503 (2)	0.0532 (15)
C13'	1.1135 (3)	0.0897 (3)	0.5339 (2)	0.0596 (15)
C14'	0.9884 (3)	0.0878 (2)	0.5793 (2)	0.0584 (10)
C15'	0.9471 (3)	−0.0066 (3)	0.6428 (2)	0.0623 (14)
C16'	1.0327 (3)	−0.1003 (2)	0.6599 (2)	0.0519 (13)
C20'	1.6186 (4)	−0.1953 (3)	0.4178 (2)	0.0598 (14)
C21'	1.6153 (4)	−0.2136 (3)	0.3302 (2)	0.0667 (17)
C22'	1.4819 (4)	−0.3480 (3)	0.4192 (2)	0.0602 (12)
C23'	1.4871 (4)	−0.3350 (2)	0.5088 (2)	0.0535 (12)
C24'	1.5985 (4)	−0.3423 (3)	0.2633 (2)	0.0828 (18)
C51'	1.5069 (3)	−0.0051 (3)	0.8449 (2)	0.0635 (15)
C52'	1.6588 (4)	0.0838 (3)	0.8517 (3)	0.0936 (15)
H4	1.133	0.730	−0.026	0.0646*
H6	0.790	0.888	0.066	0.0709*
H7	0.695	0.831	−0.018	0.0722*
H12	0.795	0.513	0.011	0.0722*
H13	0.690	0.409	0.158	0.0773*
H15	0.363	0.601	0.119	0.0848*
H16	0.469	0.705	−0.028	0.0773*
H101	0.714	0.645	−0.163	0.0709*
H102	0.659	0.752	−0.139	0.0709*
H201	1.073	0.454	−0.149	0.0798*
H202	1.132	0.520	−0.251	0.0798*
H211	1.100	0.355	−0.249	0.0862*
H212	0.958	0.379	−0.204	0.0861*
H221	0.824	0.519	−0.294	0.0785*
H222	0.883	0.584	−0.396	0.0785*
H231	0.997	0.662	−0.343	0.0709*
H232	0.854	0.685	−0.298	0.0709*
H521	0.916	0.967	0.234	0.1140*
H522	1.031	0.876	0.236	0.1140*
H523	1.040	0.988	0.158	0.1140*
H241	1.046	0.326	−0.372	0.1165*
H242	0.904	0.353	−0.327	0.1165*
H243	0.960	0.417	−0.430	0.1165*
H31	0.672	0.492	0.480	0.1330*
H32	0.806	0.524	0.438	0.1330*
H4'	1.636	−0.059	0.690	0.0620*
H6'	1.299	−0.082	0.881	0.0697*
H7'	1.225	−0.158	0.799	0.0671*
H12'	1.284	−0.003	0.519	0.0697*
H13'	1.141	0.156	0.491	0.0773*
H15'	0.860	−0.007	0.674	0.0747*
H16'	1.006	−0.165	0.705	0.0697*
H101'	1.214	−0.256	0.684	0.0684*
H102'	1.261	−0.231	0.577	0.0684*
H201'	1.688	−0.242	0.440	0.0773*
H202'	1.628	−0.122	0.405	0.0773*
H211'	1.545	−0.167	0.308	0.0887*
H212'	1.691	−0.197	0.284	0.0887*
H221'	1.469	−0.420	0.431	0.0735*
H222'	1.414	−0.298	0.396	0.0735*
H231'	1.411	−0.352	0.555	0.0684*
H232'	1.557	−0.383	0.530	0.0684*
H241'	1.589	−0.415	0.277	0.1013*
H242'	1.530	−0.296	0.239	0.1013*
H243'	1.675	−0.327	0.218	0.1013*
H521'	1.743	0.098	0.822	0.1127*
H522'	1.604	0.150	0.844	0.1127*
H523'	1.652	0.045	0.917	0.1127*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
CL1	0.066 (1)	0.100 (1)	0.070 (1)	−0.022 (1)	−0.013 (1)	−0.002 (1)
O1	0.071 (1)	0.121 (2)	0.100 (1)	−0.025 (1)	−0.019 (1)	−0.065 (1)
O2	0.081 (2)	0.095 (1)	0.082 (1)	0.000 (1)	−0.031 (1)	−0.058 (1)
O3	0.069 (2)	0.096 (2)	0.112 (2)	−0.017 (2)	0.010 (2)	−0.013 (2)
N1	0.045 (1)	0.054 (1)	0.047 (1)	−0.004 (1)	−0.012 (1)	−0.023 (1)
N2	0.054 (1)	0.048 (1)	0.050 (1)	0.001 (1)	−0.017 (1)	−0.023 (1)
N3	0.046 (1)	0.052 (1)	0.047 (1)	−0.003 (1)	−0.010 (1)	−0.023 (1)
N4	0.064 (2)	0.061 (1)	0.066 (1)	−0.014 (1)	−0.009 (1)	−0.036 (1)
C2	0.048 (2)	0.046 (1)	0.040 (1)	−0.003 (1)	−0.010 (1)	−0.016 (1)
C4	0.048 (2)	0.054 (1)	0.045 (1)	−0.012 (1)	−0.010 (1)	−0.016 (1)
C5	0.061 (2)	0.049 (1)	0.046 (1)	−0.013 (1)	−0.014 (1)	−0.016 (1)
C6	0.061 (2)	0.060 (2)	0.054 (1)	−0.003 (1)	−0.011 (1)	−0.031 (1)
C7	0.048 (2)	0.061 (2)	0.059 (2)	0.002 (1)	−0.013 (1)	−0.030 (1)
C8	0.051 (2)	0.050 (1)	0.041 (1)	−0.009 (1)	−0.010 (1)	−0.018 (1)
C9	0.046 (2)	0.048 (1)	0.041 (1)	−0.009 (1)	−0.007 (1)	−0.015 (1)
C10	0.046 (2)	0.068 (2)	0.053 (1)	−0.001 (1)	−0.021 (1)	−0.023 (1)
C11	0.041 (1)	0.051 (1)	0.051 (1)	−0.002 (1)	−0.017 (1)	−0.024 (1)
C12	0.040 (2)	0.061 (2)	0.061 (2)	−0.000 (1)	−0.014 (1)	−0.023 (1)
C13	0.053 (2)	0.056 (2)	0.064 (2)	−0.000 (1)	−0.023 (1)	−0.016 (1)
C14	0.052 (2)	0.061 (2)	0.056 (2)	−0.013 (1)	−0.017 (1)	−0.017 (1)
C15	0.039 (2)	0.080 (2)	0.070 (2)	−0.004 (2)	−0.014 (1)	−0.018 (2)
C20	0.065 (2)	0.056 (2)	0.068 (2)	−0.000 (2)	−0.021 (1)	−0.030 (1)
C21	0.075 (2)	0.053 (2)	0.078 (2)	−0.005 (2)	−0.018 (2)	−0.032 (1)
C22	0.061 (2)	0.076 (2)	0.057 (2)	−0.014 (2)	−0.011 (1)	−0.033 (1)
C23	0.064 (2)	0.057 (2)	0.046 (1)	−0.005 (2)	−0.012 (1)	−0.022 (1)
C24	0.110 (3)	0.087 (2)	0.095 (2)	−0.024 (2)	−0.019 (2)	−0.056 (1)
C51	0.073 (2)	0.059 (2)	0.055 (2)	−0.019 (1)	−0.016 (1)	−0.021 (1)
C52	0.111 (3)	0.093 (2)	0.081 (2)	−0.007 (2)	−0.037 (2)	−0.054 (1)
C16	0.047 (2)	0.062 (2)	0.066 (2)	0.006 (2)	−0.025 (1)	−0.014 (1)
CL1'	0.092 (1)	0.074 (1)	0.114 (1)	0.023 (1)	−0.059 (1)	−0.055 (1)
O1'	0.082 (2)	0.154 (2)	0.086 (1)	−0.022 (1)	−0.012 (1)	−0.079 (1)
O2'	0.068 (1)	0.098 (1)	0.078 (1)	−0.021 (1)	−0.019 (1)	−0.046 (1)
N1'	0.042 (1)	0.050 (1)	0.052 (1)	−0.007 (1)	−0.010 (1)	−0.023 (1)
N2'	0.055 (1)	0.041 (1)	0.048 (1)	−0.010 (1)	−0.005 (1)	−0.019 (1)
N3'	0.046 (1)	0.047 (1)	0.050 (1)	−0.012 (1)	−0.005 (1)	−0.018 (1)
N4'	0.067 (2)	0.051 (1)	0.050 (1)	−0.005 (1)	−0.010 (1)	−0.024 (1)
C2'	0.047 (2)	0.039 (1)	0.048 (1)	−0.007 (1)	−0.010 (1)	−0.015 (1)
C4'	0.048 (2)	0.048 (1)	0.055 (2)	−0.010 (1)	−0.018 (1)	−0.014 (1)
C5'	0.059 (2)	0.050 (1)	0.046 (1)	−0.003 (1)	−0.022 (1)	−0.016 (1)
C6'	0.051 (2)	0.066 (2)	0.048 (1)	−0.002 (2)	−0.011 (1)	−0.024 (1)
C7'	0.045 (2)	0.066 (2)	0.051 (2)	−0.010 (1)	−0.007 (1)	−0.022 (1)
C8'	0.042 (1)	0.043 (1)	0.049 (1)	−0.004 (1)	−0.012 (1)	−0.016 (1)
C9'	0.045 (2)	0.041 (1)	0.045 (1)	−0.006 (1)	−0.012 (1)	−0.012 (1)
C10'	0.047 (2)	0.054 (2)	0.065 (2)	−0.012 (1)	−0.013 (1)	−0.026 (1)
C11'	0.042 (1)	0.050 (1)	0.047 (1)	−0.011 (1)	−0.012 (1)	−0.023 (1)
C12'	0.044 (2)	0.060 (2)	0.052 (2)	−0.012 (1)	−0.010 (1)	−0.013 (1)
C13'	0.070 (2)	0.053 (2)	0.059 (2)	−0.012 (1)	−0.025 (1)	−0.012 (1)
C14'	0.061 (2)	0.056 (1)	0.065 (1)	0.002 (1)	−0.033 (1)	−0.033 (1)
C15'	0.039 (2)	0.075 (2)	0.076 (2)	−0.004 (1)	−0.015 (1)	−0.046 (1)
C16'	0.050 (2)	0.056 (1)	0.056 (2)	−0.021 (1)	−0.006 (1)	−0.023 (1)
C20'	0.068 (2)	0.054 (2)	0.056 (2)	−0.019 (1)	−0.001 (2)	−0.022 (1)
C21'	0.088 (3)	0.060 (2)	0.048 (2)	−0.019 (2)	−0.001 (2)	−0.020 (1)
C22'	0.065 (2)	0.049 (1)	0.067 (2)	−0.007 (1)	−0.015 (1)	−0.029 (1)
C23'	0.063 (2)	0.041 (1)	0.053 (2)	−0.011 (1)	−0.006 (1)	−0.018 (1)
C24'	0.100 (3)	0.084 (2)	0.064 (2)	−0.009 (2)	−0.018 (2)	−0.039 (1)
C51'	0.055 (2)	0.074 (2)	0.058 (2)	−0.003 (2)	−0.022 (1)	−0.022 (1)
C52'	0.099 (2)	0.105 (2)	0.103 (2)	−0.030 (2)	−0.040 (2)	−0.048 (2)

Geometric parameters (Å, º)

CL1—C14	1.744 (3)	C16—H16	0.950
O1—C51	1.188 (5)	CL1'—C14'	1.738 (3)
O2—C51	1.343 (4)	O1'—C51'	1.192 (5)
O2—C52	1.440 (7)	O2'—C51'	1.317 (5)
O3—H31	0.950	O2'—C52'	1.463 (7)
O3—H32	0.950	N1'—C2'	1.390 (4)
N1—C2	1.382 (4)	N1'—C8'	1.383 (5)
N1—C8	1.389 (5)	N1'—C10'	1.449 (5)
N1—C10	1.455 (5)	N2'—C2'	1.379 (5)
N2—C2	1.382 (5)	N2'—C23'	1.479 (5)
N2—C20	1.455 (4)	N2'—C20'	1.471 (4)
N2—C23	1.476 (4)	N3'—C2'	1.309 (5)
N3—C2	1.304 (5)	N3'—C9'	1.398 (4)
N3—C9	1.403 (5)	N4'—C22'	1.467 (4)
N4—C21	1.461 (5)	N4'—C21'	1.458 (5)
N4—C22	1.449 (4)	N4'—C24'	1.468 (6)
N4—C24	1.466 (7)	C4'—C5'	1.400 (5)
C4—C5	1.397 (5)	C4'—C9'	1.383 (6)
C4—C9	1.385 (6)	C4'—H4'	0.950
C4—H4	0.950	C5'—C6'	1.393 (5)
C5—C6	1.385 (5)	C5'—C51'	1.496 (7)
C5—C51	1.488 (7)	C6'—C7'	1.369 (7)
C6—C7	1.380 (7)	C6'—H6'	0.950
C6—H6	0.950	C7'—C8'	1.387 (5)
C7—C8	1.395 (5)	C7'—H7'	0.950
C7—H7	0.950	C8'—C9'	1.396 (5)
C8—C9	1.385 (5)	C10'—C11'	1.509 (4)
C10—C11	1.512 (4)	C10'—H101'	0.950
C10—H101	0.950	C10'—H102'	0.950
C10—H102	0.950	C11'—C16'	1.382 (4)
C11—C12	1.382 (4)	C11'—C12'	1.386 (4)
C11—C16	1.374 (4)	C16'—C15'	1.380 (4)
C12—C13	1.376 (4)	C16'—H16'	0.950
C12—H12	0.950	C15'—C14'	1.373 (4)
C13—C14	1.370 (5)	C15'—H15'	0.950
C13—H13	0.950	C14'—C13'	1.372 (5)
C14—C15	1.366 (5)	C12'—C13'	1.369 (5)
C15—C16	1.384 (5)	C13'—H13'	0.950
C15—H15	0.950	C12'—H12'	0.950
C20—C21	1.508 (7)	C23'—C22'	1.510 (6)
C20—H201	0.950	C23'—H231'	0.950
C20—H202	0.950	C23'—H232'	0.950
C21—H211	0.950	C22'—H221'	0.950
C21—H212	0.950	C22'—H222'	0.950
C22—C23	1.507 (7)	C21'—C20'	1.508 (6)
C22—H221	0.950	C21'—H211'	0.950
C22—H222	0.950	C21'—H212'	0.950
C23—H231	0.950	C20'—H201'	0.950
C23—H232	0.950	C20'—H202'	0.950
C24—H241	0.950	C24'—H241'	0.950
C24—H242	0.950	C24'—H242'	0.950
C24—H243	0.950	C24'—H243'	0.950
C52—H521	0.950	C52'—H521'	0.950
C52—H522	0.950	C52'—H522'	0.950
C52—H523	0.950	C52'—H523'	0.950
C51—O2—C52	116.1 (3)	C51'—O2'—C52'	115.0 (3)
H31—O3—H32	109.5	C2'—N1'—C8'	105.6 (3)
C2—N1—C8	105.3 (3)	C2'—N1'—C10'	129.1 (3)
C2—N1—C10	127.4 (3)	C8'—N1'—C10'	123.7 (3)
C8—N1—C10	124.4 (3)	C2'—N2'—C23'	117.1 (2)
C2—N2—C20	115.7 (3)	C2'—N2'—C20'	114.1 (3)
C2—N2—C23	117.2 (3)	C23'—N2'—C20'	109.3 (3)
C20—N2—C23	110.8 (3)	C2'—N3'—C9'	104.5 (3)
C2—N3—C9	104.4 (3)	C22'—N4'—C21'	108.0 (3)
C21—N4—C22	109.7 (3)	C22'—N4'—C24'	110.1 (4)
C21—N4—C24	109.3 (3)	C21'—N4'—C24'	110.8 (3)
C22—N4—C24	111.2 (4)	N1'—C2'—N2'	121.2 (3)
N1—C2—N2	119.6 (3)	N1'—C2'—N3'	113.7 (3)
N1—C2—N3	114.0 (3)	N2'—C2'—N3'	125.1 (3)
N2—C2—N3	126.3 (3)	C5'—C4'—C9'	117.9 (3)
C5—C4—C9	117.3 (3)	C5'—C4'—H4'	121.3
C5—C4—H4	121.6	C9'—C4'—H4'	120.8
C9—C4—H4	121.2	C4'—C5'—C6'	121.2 (4)
C4—C5—C6	121.4 (4)	C4'—C5'—C51'	121.6 (3)
C4—C5—C51	117.5 (3)	C6'—C5'—C51'	117.1 (3)
C6—C5—C51	121.1 (3)	C5'—C6'—C7'	121.3 (3)
C5—C6—C7	122.1 (4)	C5'—C6'—H6'	119.5
C5—C6—H6	118.9	C7'—C6'—H6'	119.2
C7—C6—H6	119.0	C6'—C7'—C8'	117.2 (3)
C6—C7—C8	115.8 (3)	C6'—C7'—H7'	121.9
C6—C7—H7	122.4	C8'—C7'—H7'	120.8
C8—C7—H7	121.8	N1'—C8'—C7'	131.3 (3)
N1—C8—C7	130.6 (3)	N1'—C8'—C9'	106.0 (3)
N1—C8—C9	106.2 (3)	C7'—C8'—C9'	122.7 (4)
C7—C8—C9	123.2 (4)	N3'—C9'—C4'	130.2 (3)
N3—C9—C4	129.7 (3)	N3'—C9'—C8'	110.2 (4)
N3—C9—C8	110.1 (4)	C4'—C9'—C8'	119.7 (3)
C4—C9—C8	120.2 (3)	N1'—C10'—C11'	112.8 (3)
N1—C10—C11	112.4 (3)	N1'—C10'—H101'	108.5
N1—C10—H101	108.6	N1'—C10'—H102'	108.5
N1—C10—H102	108.8	C11'—C10'—H101'	108.6
C11—C10—H101	108.6	C11'—C10'—H102'	109.0
C11—C10—H102	109.0	H101'—C10'—H102'	109.5
H101—C10—H102	109.5	C10'—C11'—C16'	120.7 (3)
C10—C11—C12	121.4 (3)	C10'—C11'—C12'	121.1 (3)
C10—C11—C16	120.4 (3)	C16'—C11'—C12'	118.2 (3)
C12—C11—C16	118.2 (3)	C11'—C16'—C15'	121.1 (3)
C11—C12—C13	121.6 (3)	C11'—C16'—H16'	119.0
C11—C12—H12	118.9	C15'—C16'—H16'	119.9
C13—C12—H12	119.5	C16'—C15'—C14'	119.3 (3)
C12—C13—C14	118.5 (3)	C16'—C15'—H15'	120.6
C12—C13—H13	121.3	C14'—C15'—H15'	120.1
C14—C13—H13	120.2	CL1'—C14'—C15'	119.9 (2)
CL1—C14—C13	118.3 (2)	CL1'—C14'—C13'	119.6 (2)
CL1—C14—C15	120.0 (3)	C15'—C14'—C13'	120.5 (3)
C13—C14—C15	121.7 (3)	C14'—C13'—C12'	119.8 (3)
C14—C15—C16	118.8 (3)	C14'—C13'—H13'	119.9
C14—C15—H15	120.1	C12'—C13'—H13'	120.3
C16—C15—H15	121.1	C11'—C12'—C13'	121.1 (3)
N2—C20—C21	108.6 (4)	C11'—C12'—H12'	118.7
N2—C20—H201	109.4	C13'—C12'—H12'	120.3
N2—C20—H202	109.9	N2'—C23'—C22'	109.1 (2)
C21—C20—H201	110.1	N2'—C23'—H231'	109.3
C21—C20—H202	109.4	N2'—C23'—H232'	110.1
H201—C20—H202	109.5	C22'—C23'—H231'	109.9
N4—C21—C20	111.5 (3)	C22'—C23'—H232'	108.9
N4—C21—H211	109.3	H231'—C23'—H232'	109.5
N4—C21—H212	108.6	N4'—C22'—C23'	109.7 (4)
C20—C21—H211	109.5	N4'—C22'—H221'	109.5
C20—C21—H212	108.4	N4'—C22'—H222'	109.5
H211—C21—H212	109.5	C23'—C22'—H221'	109.8
N4—C22—C23	110.8 (4)	C23'—C22'—H222'	108.9
N4—C22—H221	109.3	H221'—C22'—H222'	109.5
N4—C22—H222	109.1	N4'—C21'—C20'	111.4 (3)
C23—C22—H221	109.3	N4'—C21'—H211'	108.9
C23—C22—H222	108.9	N4'—C21'—H212'	109.2
H221—C22—H222	109.5	C20'—C21'—H211'	108.0
N2—C23—C22	108.9 (3)	C20'—C21'—H212'	109.8
N2—C23—H231	109.4	H211'—C21'—H212'	109.5
N2—C23—H232	109.6	N2'—C20'—C21'	109.8 (4)
C22—C23—H231	109.5	N2'—C20'—H201'	109.1
C22—C23—H232	110.0	N2'—C20'—H202'	109.8
H231—C23—H232	109.5	C21'—C20'—H201'	108.1
N4—C24—H241	111.3	C21'—C20'—H202'	110.6
N4—C24—H242	108.4	H201'—C20'—H202'	109.5
N4—C24—H243	108.7	N4'—C24'—H241'	109.8
H241—C24—H242	109.5	N4'—C24'—H242'	109.5
H241—C24—H243	109.5	N4'—C24'—H243'	109.1
H242—C24—H243	109.5	H241'—C24'—H242'	109.5
O1—C51—O2	123.4 (4)	H241'—C24'—H243'	109.5
O1—C51—C5	125.4 (4)	H242'—C24'—H243'	109.5
O2—C51—C5	111.2 (3)	O1'—C51'—O2'	123.2 (5)
O2—C52—H521	108.5	O1'—C51'—C5'	124.5 (4)
O2—C52—H522	110.9	O2'—C51'—C5'	112.2 (3)
O2—C52—H523	109.0	O2'—C52'—H521'	110.1
H521—C52—H522	109.5	O2'—C52'—H522'	109.4
H521—C52—H523	109.5	O2'—C52'—H523'	108.9
H522—C52—H523	109.5	H521'—C52'—H522'	109.5
C11—C16—C15	121.2 (3)	H521'—C52'—H523'	109.5
C11—C16—H16	119.6	H522'—C52'—H523'	109.5
C15—C16—H16	119.2
C52—O2—C51—O1	−0.1 (5)	C52'—O2'—C51'—O1'	−3.2 (5)
C52—O2—C51—C5	178.2 (3)	C52'—O2'—C51'—C5'	174.3 (3)
C51—O2—C52—H521	−178.80	C51'—O2'—C52'—H521'	−179.9
C51—O2—C52—H522	−58.44	C51'—O2'—C52'—H522'	−59.6
C51—O2—C52—H523	62.11	C51'—O2'—C52'—H523'	60.1
C8—N1—C2—N2	176.2 (3)	C8'—N1'—C2'—N2'	−178.6 (3)
C8—N1—C2—N3	−1.7 (3)	C8'—N1'—C2'—N3'	−0.3 (4)
C10—N1—C2—N2	15.1 (4)	C10'—N1'—C2'—N2'	−13.0 (5)
C10—N1—C2—N3	−162.7 (3)	C10'—N1'—C2'—N3'	165.3 (3)
C2—N1—C8—C7	−178.1 (3)	C2'—N1'—C8'—C7'	−179.2 (4)
C2—N1—C8—C9	0.9 (3)	C2'—N1'—C8'—C9'	1.4 (3)
C10—N1—C8—C7	−16.3 (5)	C10'—N1'—C8'—C7'	14.2 (6)
C10—N1—C8—C9	162.7 (3)	C10'—N1'—C8'—C9'	−165.2 (3)
C2—N1—C10—C11	99.5 (4)	C2'—N1'—C10'—C11'	−105.9 (4)
C2—N1—C10—H101	−20.70	C2'—N1'—C10'—H101'	133.9
C2—N1—C10—H102	−139.72	C2'—N1'—C10'—H102'	15.03
C8—N1—C10—C11	−58.2 (4)	C8'—N1'—C10'—C11'	57.4 (4)
C8—N1—C10—H101	−178.39	C8'—N1'—C10'—H101'	−62.9
C8—N1—C10—H102	62.59	C8'—N1'—C10'—H102'	178.3
C20—N2—C2—N1	−159.8 (3)	C23'—N2'—C2'—N1'	−61.2 (4)
C20—N2—C2—N3	17.7 (5)	C23'—N2'—C2'—N3'	120.7 (4)
C23—N2—C2—N1	66.6 (4)	C20'—N2'—C2'—N1'	169.3 (3)
C23—N2—C2—N3	−115.9 (4)	C20'—N2'—C2'—N3'	−8.7 (5)
C2—N2—C20—C21	164.6 (3)	C2'—N2'—C23'—C22'	168.8 (3)
C2—N2—C20—H201	44.37	C2'—N2'—C23'—H231'	48.5
C2—N2—C20—H202	−75.90	C2'—N2'—C23'—H232'	−71.9
C23—N2—C20—C21	−58.96 (4)	C20'—N2'—C23'—C22'	−59.6 (4)
C23—N2—C20—H201	−179.19	C20'—N2'—C23'—H231'	−179.8
C23—N2—C20—H202	60.53	C20'—N2'—C23'—H232'	59.8
C2—N2—C23—C22	−164.6 (3)	C2'—N2'—C20'—C21'	−169.2 (3)
C2—N2—C23—H231	75.68	C2'—N2'—C20'—H201'	72.6
C2—N2—C23—H232	−44.40	C2'—N2'—C20'—H202'	−47.4
C20—N2—C23—C22	59.7 (4)	C23'—N2'—C20'—C21'	57.7 (4)
C20—N2—C23—H231	−59.95	C23'—N2'—C20'—H201'	−60.6
C20—N2—C23—H232	179.97	C23'—N2'—C20'—H202'	179.5
C9—N3—C2—N1	1.6 (3)	C9'—N3'—C2'—N1'	−1.0 (4)
C9—N3—C2—N2	−176.0 (3)	C9'—N3'—C2'—N2'	177.2 (3)
C2—N3—C9—C4	178.0 (3)	C2'—N3'—C9'—C4'	−177.4 (3)
C2—N3—C9—C8	−1.0 (3)	C2'—N3'—C9'—C8'	1.9 (3)
C22—N4—C21—C20	−58.2 (4)	C21'—N4'—C22'—C23'	−61.3 (4)
C22—N4—C21—H211	−179.4	C21'—N4'—C22'—H221'	178.1
C22—N4—C21—H212	61.3	C21'—N4'—C22'—H222'	58.1
C24—N4—C21—C20	179.9 (4)	C24'—N4'—C22'—C23'	177.6 (3)
C24—N4—C21—H211	58.6	C24'—N4'—C22'—H221'	57.1
C24—N4—C21—H212	−60.8	C24'—N4'—C22'—H222'	−62.9
C21—N4—C22—C23	58.1 (4)	C22'—N4'—C21'—C20'	59.7 (4)
C21—N4—C22—H221	−62.4	C22'—N4'—C21'—H211'	−59.2
C21—N4—C22—H222	177.9	C22'—N4'—C21'—H212'	−178.7
C24—N4—C22—C23	179.1 (3)	C24'—N4'—C21'—C20'	−179.5 (4)
C24—N4—C22—H221	58.6	C24'—N4'—C21'—H211'	61.6
C24—N4—C22—H222	−61.1	C24'—N4'—C21'—H212'	−58.0
C21—N4—C24—H241	−58.6	C22'—N4'—C24'—H241'	−60.8
C21—N4—C24—H242	61.8	C22'—N4'—C24'—H242'	59.5
C21—N4—C24—H243	−179.3	C22'—N4'—C24'—H243'	179.3
C22—N4—C24—H241	−179.8	C21'—N4'—C24'—H241'	179.8
C22—N4—C24—H242	−59.4	C21'—N4'—C24'—H242'	−60.0
C22—N4—C24—H243	59.5	C21'—N4'—C24'—H243'	59.8
C9—C4—C5—C6	0.1 (4)	C9'—C4'—C5'—C6'	1.1 (5)
C9—C4—C5—C51	178.7 (3)	C9'—C4'—C5'—C51'	−175.4 (3)
H4—C4—C5—C6	179.9	H4'—C4'—C5'—C6'	−179.7
H4—C4—C5—C51	−1.4	H4'—C4'—C5'—C51'	3.8
C5—C4—C9—N3	−178.7 (3)	C5'—C4'—C9'—N3'	−179.9 (3)
C5—C4—C9—C8	0.3 (5)	C5'—C4'—C9'—C8'	0.7 (5)
H4—C4—C9—N3	1.5	H4'—C4'—C9'—N3'	0.8
H4—C4—C9—C8	−179.6	H4'—C4'—C9'—C8'	−178.5
C4—C5—C6—C7	−0.7 (5)	C4'—C5'—C6'—C7'	−1.6 (5)
C4—C5—C6—H6	179.1	C4'—C5'—C6'—H6'	177.7
C51—C5—C6—C7	−179.3 (3)	C51'—C5'—C6'—C7'	175.1 (3)
C51—C5—C6—H6	0.5	C51'—C5'—C6'—H6'	−5.7
C4—C5—C51—O1	7.1 (5)	C4'—C5'—C51'—O1'	173.5 (4)
C4—C5—C51—O2	−171.2 (3)	C4'—C5'—C51'—O2'	−4.0 (5)
C6—C5—C51—O1	−174.3 (3)	C6'—C5'—C51'—O1'	−3.1 (6)
C6—C5—C51—O2	7.4 (4)	C6'—C5'—C51'—O2'	179.3 (3)
C5—C6—C7—C8	0.9 (5)	C5'—C6'—C7'—C8'	0.1 (5)
C5—C6—C7—H7	−179.6	C5'—C6'—C7'—H7'	−179.5
H6—C6—C7—C8	−178.9	H6'—C6'—C7'—C8'	−179.1
H6—C6—C7—H7	0.6	H6'—C6'—C7'—H7'	1.2
C6—C7—C8—N1	178.2 (3)	C6'—C7'—C8'—N1'	−177.6 (3)
C6—C7—C8—C9	−0.6 (5)	C6'—C7'—C8'—C9'	1.7 (5)
H7—C7—C8—N1	−1.2	H7'—C7'—C8'—N1'	2.1
H7—C7—C8—C9	180.0	H7'—C7'—C8'—C9'	−178.6
N1—C8—C9—N3	0.1 (3)	N1'—C8'—C9'—N3'	−2.1 (4)
N1—C8—C9—C4	−179.1 (3)	N1'—C8'—C9'—C4'	177.3 (3)
C7—C8—C9—N3	179.1 (3)	C7'—C8'—C9'—N3'	178.5 (3)
C7—C8—C9—C4	−0.0 (6)	C7'—C8'—C9'—C4'	−2.1 (5)
N1—C10—C11—C12	−38.6 (5)	N1'—C10'—C11'—C16'	−139.7 (3)
N1—C10—C11—C16	143.2 (3)	N1'—C10'—C11'—C12'	42.3 (4)
H101—C10—C11—C12	81.6	H101'—C10'—C11'—C16'	−19.4
H101—C10—C11—C16	−96.6	H101'—C10'—C11'—C12'	162.5
H102—C10—C11—C12	−159.2	H102'—C10'—C11'—C16'	99.8
H102—C10—C11—C16	22.6	H102'—C10'—C11'—C12'	−78.3
C10—C11—C12—C13	−178.0 (3)	C10'—C11'—C16'—C15'	−175.9 (3)
C10—C11—C12—H12	3.5	C10'—C11'—C16'—H16'	5.3
C16—C11—C12—C13	0.3 (5)	C12'—C11'—C16'—C15'	2.2 (5)
C16—C11—C12—H12	−178.3	C12'—C11'—C16'—H16'	−176.6
C10—C11—C16—C15	177.9 (4)	C10'—C11'—C12'—C13'	176.9 (3)
C10—C11—C16—H16	−3.6	C10'—C11'—C12'—H12'	−3.2
C12—C11—C16—C15	−0.4 (6)	C16'—C11'—C12'—C13'	−1.2 (5)
C12—C11—C16—H16	178.1	C16'—C11'—C12'—H12'	178.7
C11—C12—C13—C14	−0.2 (6)	C11'—C16'—C15'—C14'	−1.3 (5)
C11—C12—C13—H13	179.1	C11'—C16'—C15'—H15'	178.3
H12—C12—C13—C14	178.7	H16'—C16'—C15'—C14'	177.5
H12—C12—C13—H13	−2.3	H16'—C16'—C15'—H15'	−2.9
C12—C13—C14—CL1	179.5 (3)	C16'—C15'—C14'—CL1'	−179.1 (3)
C12—C13—C14—C15	−0.6 (6)	C16'—C15'—C14'—C13'	−0.7 (5)
H13—C13—C14—CL1	0.5	H15'—C15'—C14'—CL1'	1.3
H13—C13—C14—C15	−179.6	H15'—C15'—C14'—C13'	179.8
CL1—C14—C15—C16	−179.5 (3)	CL1'—C14'—C13'—C12'	−179.9 (3)
CL1—C14—C15—H15	−0.6	CL1'—C14'—C13'—H13'	0.1
C13—C14—C15—C16	0.5 (6)	C15'—C14'—C13'—C12'	1.7 (5)
C13—C14—C15—H15	179.5	C15'—C14'—C13'—H13'	−178.4
C14—C15—C16—C11	−0.0 (7)	C14'—C13'—C12'—C11'	−0.7 (5)
C14—C15—C16—H16	−178.5	C14'—C13'—C12'—H12'	179.4
H15—C15—C16—C11	−178.9	H13'—C13'—C12'—C11'	179.3
H15—C15—C16—H16	2.6	H13'—C13'—C12'—H12'	−0.6
N2—C20—C21—N4	58.2 (4)	N2'—C23'—C22'—N4'	62.0 (4)
N2—C20—C21—H211	179.4	N2'—C23'—C22'—H221'	−177.6
N2—C20—C21—H212	−61.3	N2'—C23'—C22'—H222'	−57.8
H201—C20—C21—N4	178.0	H231'—C23'—C22'—N4'	−178.1
H201—C20—C21—H211	−60.8	H231'—C23'—C22'—H221'	−57.7
H201—C20—C21—H212	58.5	H231'—C23'—C22'—H222'	62.1
H202—C20—C21—N4	−61.6	H232'—C23'—C22'—N4'	−58.2
H202—C20—C21—H211	59.6	H232'—C23'—C22'—H221'	62.3
H202—C20—C21—H212	178.9	H232'—C23'—C22'—H222'	−177.9
N4—C22—C23—N2	−58.8 (4)	N4'—C21'—C20'—N2'	−58.6 (4)
N4—C22—C23—H231	60.9	N4'—C21'—C20'—H201'	60.3
N4—C22—C23—H232	−178.8	N4'—C21'—C20'—H202'	−180.0
H221—C22—C23—N2	61.7	H211'—C21'—C20'—N2'	60.9
H221—C22—C23—H231	−178.6	H211'—C21'—C20'—H201'	179.8
H221—C22—C23—H232	−58.3	H211'—C21'—C20'—H202'	−60.5
H222—C22—C23—N2	−178.7	H212'—C21'—C20'—N2'	−179.8
H222—C22—C23—H231	−59.0	H212'—C21'—C20'—H201'	−60.9
H222—C22—C23—H232	61.3	H212'—C21'—C20'—H202'	58.9