Crystal structure of propaquizafop

Jeon, Y.; Kim, J.; Lee, S.; Kim, T.H.

doi:10.1107/S1600536814024751

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 12| December 2014| Pages o1266-o1267

doi:10.1107/S1600536814024751

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Crystal structure of propaquizafop

Youngeun Jeon,^a Jineun Kim,^a ^* Sangjin Lee ^a and Tae Ho Kim ^a ^*

^aDepartment of Chemistry and Research Institute of Natural Sciences, Gyeongsang National University, Jinju 660-701, Republic of Korea
^*Correspondence e-mail: jekim@gnu.ac.kr, thkim@gnu.ac.kr

Edited by P. C. Healy, Griffith University, Australia (Received 6 November 2014; accepted 11 November 2014; online 19 November 2014)

The title compound, C₂₂H₂₂ClN₃O₅ {systematic name: 2-(propan-2-ylideneaminooxy)ethyl (R)-2-[4-(6-chloroquinoxalin-2-yloxy)phenoxy]propionate}, is a herbicide. The asymmetric unit comprises two independent molecules in which the dihedral angles between the phenyl ring and the quinoxaline ring plane are 75.93 (7) and 82.77 (8)°. The crystal structure features C—H⋯O, C—H⋯N, and C—H⋯Cl hydrogen bonds, as well as weak π–π interactions [ring-centroid separation = 3.782 (2) and 3.5952 (19) Å], resulting in a three-dimensional architecture.

Keywords: crystal structure; propaquizafop; herbicide; hydrogen bonding; π–π interactions.

CCDC reference: 1033575

1. Related literature

For information on the herbicidal properties of the title compound, see: Bergkvist & Ledin (1997 ). For a related crystal structure, see: Hu et al. (2009 ).

2. Experimental

2.1. Crystal data

C₂₂H₂₂ClN₃O₅
M_r = 443.88
Monoclinic, P 2₁
a = 4.6205 (2) Å
b = 21.9423 (10) Å
c = 21.1737 (10) Å
β = 93.263 (2)°
V = 2143.20 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 173 K
0.47 × 0.05 × 0.04 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.905, T_max = 0.991
20815 measured reflections
8319 independent reflections
5996 reflections with I > 2σ(I)
R_int = 0.063

2.3. Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.103
S = 0.99
8319 reflections
565 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ), 4004 Friedel pairs
Absolute structure parameter: 0.05 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4B⋯O2ⁱ	0.99	2.60	3.337 (4)	131
C7—H7⋯O3ⁱⁱ	1.00	2.33	3.264 (4)	154
C14—H14⋯O3ⁱⁱ	0.95	2.47	3.389 (4)	164
C22—H22⋯O8ⁱ	0.95	2.53	3.468 (4)	170
C27—H27A⋯O5ⁱⁱ	0.99	2.56	3.284 (4)	130
C29—H29⋯O8ⁱ	1.00	2.33	3.173 (4)	142
C44—H44⋯N1ⁱⁱⁱ	0.95	2.51	3.430 (5)	162
C10—H10⋯Cl2^iv	0.95	2.91	3.855 (4)	174
C25—H25A⋯Cl2^v	0.98	2.99	3.368 (4)	105
C32—H32⋯Cl1^vi	0.95	2.89	3.748 (4)	151
Symmetry codes: (i) x-1, y, z; (ii) x+1, y, z; (iii) x+1, y, z-1; (iv) $[-x-1, y-{\script{1\over 2}}, -z]$ ; (v) x+1, y, z+1; (vi) $[-x+2, y+{\script{1\over 2}}, -z]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2010 ); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 1033575

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814024751/hg5418sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814024751/hg5418Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814024751/hg5418Isup3.cml

checkCIF report

Comment top

Propaquizafop, C₂₂H₂₂ClN₃O₅, is a herbicide of the aryloxy phenoxy propionate family. It is used for the post emergence control of a wide range of annual and perennial grasses. It is used for selective weed control in many broadleaf crops such as sugarbeet, oilseed rape, soybeans, sunflower, other field crops, vegetables, fruit trees, vineyards and forestry. (Bergkvist & Ledin, 1997). Its crystal structure is reported herein. In this compound (Scheme 1, Fig. 1), there are two independent and conformationally similar molecules (A and B) in the asymmetric unit, with the dihedral angle between the phenyl ring and quinoxaline ring planes are 75.93 (7) and 82.77 (8)°. All bond lengths and bond angles are normal and comparable to those observed in the crystal structure of a similar compound (Hu et al., 2009).

In the crystal structure (Fig. 2), The crystal structure is stabilized by C—H···O, C—H···N, and C—H···Cl hydrogen bonds (Table 1), as well as two weak intermolecular π–π interactions between the quinoxaline rings [Cg1···Cg2ⁱ = 3.782 (2) Å. Cg1 and Cg2 are the centroids of the C15—N2—C16—C21—N3—C22 and the C16—C21 rings, respectively. Cg3···Cg4ⁱⁱ = 3.5952 (19) Å. Cg3 and Cg4 are the centroid of the C37—N5—C38—C43—N6—C44 and the C38—C43 rings, respectively. (Symmetry codes: (i), x - 1, y, z and (ii), x + 1, y, z)], resulting in a three-dimensional architecture.

Related literature top

For information on the herbicidal properties of the title compound, see: Bergkvist & Ledin (1997). For a related crystal structure, see: Hu et al. (2009).

Experimental top

The title compound was purchased from the Dr. Ehrenstorfer GmbH Company. Slow evaporation of a solution in CH₃OH gave single crystals suitable for X-ray analysis.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The asymmetric unit of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius.

Fig. 2. Crystal packing viewed along the a axis. The intermolecular C—H···N, C—H···O, and C—H···Cl hydrogen bonds are shown as dashed lines.

2-(Propan-2-ylideneaminooxy)ethyl (R)-2-[4-(6-chloroquinoxalin-2-yloxy)phenoxy]propionate top

Crystal data top

C₂₂H₂₂ClN₃O₅	F(000) = 928
M_r = 443.88	D_x = 1.376 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2323 reflections
a = 4.6205 (2) Å	θ = 2.7–19.3°
b = 21.9423 (10) Å	µ = 0.22 mm⁻¹
c = 21.1737 (10) Å	T = 173 K
β = 93.263 (2)°	Needle, colourless
V = 2143.20 (17) Å³	0.47 × 0.05 × 0.04 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	8319 independent reflections
Radiation source: fine-focus sealed tube	5996 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −5→5
T_min = 0.905, T_max = 0.991	k = −26→27
20815 measured reflections	l = −26→26

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.054	H-atom parameters constrained
wR(F²) = 0.103	w = 1/[σ²(F_o²) + (0.0354P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max < 0.001
8319 reflections	Δρ_max = 0.26 e Å⁻³
565 parameters	Δρ_min = −0.24 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 4004 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (6)

Crystal data top

C₂₂H₂₂ClN₃O₅	V = 2143.20 (17) Å³
M_r = 443.88	Z = 4
Monoclinic, P2₁	Mo Kα radiation
a = 4.6205 (2) Å	µ = 0.22 mm⁻¹
b = 21.9423 (10) Å	T = 173 K
c = 21.1737 (10) Å	0.47 × 0.05 × 0.04 mm
β = 93.263 (2)°

Data collection top

Bruker APEXII CCD diffractometer	8319 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	5996 reflections with I > 2σ(I)
T_min = 0.905, T_max = 0.991	R_int = 0.063
20815 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	H-atom parameters constrained
wR(F²) = 0.103	Δρ_max = 0.26 e Å⁻³
S = 0.99	Δρ_min = −0.24 e Å⁻³
8319 reflections	Absolute structure: Flack (1983), 4004 Friedel pairs
565 parameters	Absolute structure parameter: 0.05 (6)
1 restraint

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.8646 (2)	0.58056 (5)	−0.01482 (4)	0.0403 (3)
Cl2	−0.2992 (2)	0.91749 (4)	−0.39805 (4)	0.0328 (2)
O1	−0.0906 (5)	0.62880 (10)	0.75631 (10)	0.0300 (6)
O2	0.1079 (5)	0.64050 (10)	0.62762 (10)	0.0263 (6)
O3	−0.2656 (5)	0.63233 (11)	0.55516 (10)	0.0296 (6)
O4	−0.0116 (6)	0.53477 (11)	0.49904 (10)	0.0282 (6)
O5	−0.0140 (6)	0.67388 (11)	0.28083 (10)	0.0305 (6)
O6	0.6212 (6)	0.84357 (11)	0.39165 (11)	0.0323 (6)
O7	0.3833 (5)	0.83763 (10)	0.25968 (10)	0.0254 (6)
O8	0.7468 (5)	0.84570 (11)	0.19415 (10)	0.0291 (6)
O9	0.4940 (5)	0.94441 (10)	0.13532 (10)	0.0281 (6)
O10	0.6648 (5)	0.82773 (10)	−0.09140 (10)	0.0315 (6)
N1	−0.0042 (7)	0.67417 (13)	0.80229 (13)	0.0281 (7)
N2	0.2541 (6)	0.60906 (13)	0.22060 (12)	0.0235 (7)
N3	0.2624 (7)	0.70563 (13)	0.13081 (13)	0.0286 (7)
N4	0.5470 (7)	0.79627 (13)	0.43496 (13)	0.0328 (8)
N5	0.3225 (6)	0.88493 (13)	−0.14960 (12)	0.0241 (7)
N6	0.4407 (7)	0.80739 (13)	−0.25283 (14)	0.0264 (7)
C1	0.2912 (9)	0.58894 (17)	0.84480 (18)	0.0407 (10)
H1A	0.1313	0.5597	0.8463	0.061*
H1B	0.4244	0.5834	0.8821	0.061*
H1C	0.3954	0.5821	0.8064	0.061*
C2	0.1739 (8)	0.65195 (16)	0.84430 (16)	0.0260 (8)
C3	0.2718 (9)	0.69528 (17)	0.89626 (16)	0.0369 (10)
H3A	0.1748	0.7346	0.8894	0.055*
H3B	0.4821	0.7009	0.8960	0.055*
H3C	0.2222	0.6785	0.9372	0.055*
C4	−0.2490 (8)	0.65898 (18)	0.70522 (16)	0.0330 (9)
H4A	−0.3731	0.6910	0.7226	0.040*
H4B	−0.3770	0.6292	0.6823	0.040*
C5	−0.0510 (8)	0.68746 (16)	0.65971 (16)	0.0288 (9)
H5A	−0.1664	0.7120	0.6281	0.035*
H5B	0.0873	0.7150	0.6829	0.035*
C6	−0.0370 (8)	0.61396 (16)	0.57733 (15)	0.0231 (8)
C7	0.1219 (8)	0.55835 (15)	0.55631 (15)	0.0239 (8)
H7	0.3296	0.5684	0.5504	0.029*
C8	0.1005 (10)	0.50749 (17)	0.60594 (16)	0.0375 (10)
H8A	−0.1038	0.4994	0.6129	0.056*
H8B	0.2005	0.5203	0.6458	0.056*
H8C	0.1912	0.4703	0.5907	0.056*
C9	0.0115 (8)	0.56995 (15)	0.44475 (15)	0.0220 (8)
C10	−0.1660 (8)	0.55205 (16)	0.39339 (16)	0.0293 (9)
H10	−0.2871	0.5173	0.3964	0.035*
C11	−0.1670 (8)	0.58495 (17)	0.33742 (16)	0.0291 (9)
H11	−0.2895	0.5732	0.3019	0.035*
C12	0.0091 (8)	0.63397 (16)	0.33417 (15)	0.0253 (9)
C13	0.1930 (8)	0.65152 (18)	0.38381 (16)	0.0332 (9)
H13	0.3166	0.6858	0.3799	0.040*
C14	0.1968 (8)	0.61839 (16)	0.44033 (16)	0.0278 (9)
H14	0.3257	0.6293	0.4751	0.033*
C15	0.1284 (8)	0.66053 (16)	0.22798 (15)	0.0234 (8)
C16	0.3954 (7)	0.60351 (15)	0.16469 (15)	0.0219 (8)
C17	0.5290 (8)	0.54843 (15)	0.15090 (16)	0.0252 (8)
H17	0.5228	0.5155	0.1800	0.030*
C18	0.6692 (8)	0.54103 (17)	0.09599 (16)	0.0289 (9)
H18	0.7572	0.5032	0.0866	0.035*
C19	0.6801 (8)	0.59032 (17)	0.05409 (15)	0.0279 (9)
C20	0.5540 (8)	0.64459 (17)	0.06578 (16)	0.0282 (9)
H20	0.5678	0.6775	0.0369	0.034*
C21	0.4019 (7)	0.65187 (16)	0.12123 (15)	0.0213 (8)
C22	0.1234 (8)	0.70974 (17)	0.18315 (15)	0.0289 (9)
H22	0.0181	0.7458	0.1915	0.035*
C23	0.2920 (10)	0.77216 (18)	0.52389 (18)	0.0457 (12)
H23A	0.3871	0.7331	0.5164	0.069*
H23B	0.0812	0.7666	0.5207	0.069*
H23C	0.3522	0.7871	0.5662	0.069*
C24	0.3764 (8)	0.81741 (17)	0.47554 (17)	0.0305 (9)
C25	0.2581 (9)	0.88020 (18)	0.47602 (18)	0.0398 (10)
H25A	0.4160	0.9095	0.4721	0.060*
H25B	0.1652	0.8873	0.5158	0.060*
H25C	0.1149	0.8853	0.4405	0.060*
C26	0.7593 (8)	0.81513 (19)	0.34125 (16)	0.0341 (10)
H26A	0.8859	0.7819	0.3583	0.041*
H26B	0.8828	0.8453	0.3207	0.041*
C27	0.5417 (8)	0.78956 (17)	0.29305 (16)	0.0278 (9)
H27A	0.6428	0.7643	0.2624	0.033*
H27B	0.4042	0.7630	0.3144	0.033*
C28	0.5173 (7)	0.86318 (16)	0.21119 (15)	0.0212 (8)
C29	0.3410 (7)	0.91649 (16)	0.18402 (14)	0.0255 (8)
H29	0.1471	0.9020	0.1668	0.031*
C30	0.3044 (9)	0.96437 (17)	0.23452 (17)	0.0403 (10)
H30A	0.4955	0.9787	0.2506	0.060*
H30B	0.2015	0.9466	0.2693	0.060*
H30C	0.1926	0.9987	0.2163	0.060*
C31	0.5158 (8)	0.91335 (16)	0.07887 (15)	0.0246 (8)
C32	0.6921 (9)	0.93993 (17)	0.03696 (16)	0.0409 (11)
H32	0.7851	0.9774	0.0477	0.049*
C33	0.7369 (9)	0.91307 (18)	−0.02070 (16)	0.0377 (10)
H33	0.8607	0.9316	−0.0495	0.045*
C34	0.6009 (8)	0.85980 (16)	−0.03539 (15)	0.0268 (9)
C35	0.4212 (9)	0.83233 (18)	0.00528 (17)	0.0390 (10)
H35	0.3267	0.7952	−0.0062	0.047*
C36	0.3778 (9)	0.85927 (18)	0.06367 (17)	0.0386 (10)
H36	0.2550	0.8406	0.0925	0.046*
C37	0.5101 (8)	0.84137 (16)	−0.14593 (15)	0.0243 (8)
C38	0.1798 (7)	0.89193 (15)	−0.20807 (15)	0.0200 (8)
C39	−0.0240 (8)	0.93925 (15)	−0.21804 (15)	0.0261 (9)
H39	−0.0634	0.9656	−0.1840	0.031*
C40	−0.1663 (8)	0.94788 (16)	−0.27590 (16)	0.0279 (9)
H40	−0.2995	0.9806	−0.2825	0.034*
C41	−0.1115 (7)	0.90744 (16)	−0.32525 (14)	0.0240 (8)
C42	0.0835 (8)	0.86119 (15)	−0.31783 (15)	0.0238 (8)
H42	0.1156	0.8344	−0.3520	0.029*
C43	0.2374 (7)	0.85328 (14)	−0.25905 (15)	0.0201 (8)
C44	0.5739 (8)	0.80277 (16)	−0.19749 (16)	0.0259 (9)
H44	0.7195	0.7725	−0.1910	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0453 (6)	0.0483 (6)	0.0288 (5)	0.0108 (5)	0.0144 (5)	0.0064 (5)
Cl2	0.0361 (5)	0.0393 (6)	0.0225 (5)	0.0037 (5)	−0.0025 (4)	−0.0023 (4)
O1	0.0389 (16)	0.0270 (14)	0.0235 (13)	0.0008 (12)	−0.0035 (12)	−0.0057 (11)
O2	0.0294 (14)	0.0267 (14)	0.0223 (13)	0.0021 (12)	−0.0034 (11)	−0.0083 (11)
O3	0.0254 (15)	0.0379 (16)	0.0249 (13)	0.0003 (13)	−0.0017 (12)	−0.0050 (12)
O4	0.0424 (16)	0.0261 (14)	0.0157 (12)	−0.0112 (12)	−0.0006 (11)	−0.0004 (11)
O5	0.0466 (17)	0.0275 (14)	0.0178 (13)	0.0077 (12)	0.0063 (12)	0.0043 (11)
O6	0.0375 (16)	0.0358 (15)	0.0241 (13)	−0.0003 (13)	0.0052 (12)	0.0088 (12)
O7	0.0231 (13)	0.0284 (14)	0.0250 (13)	0.0026 (12)	0.0038 (11)	0.0060 (11)
O8	0.0222 (14)	0.0377 (15)	0.0276 (14)	0.0018 (12)	0.0035 (12)	0.0045 (12)
O9	0.0397 (16)	0.0276 (14)	0.0170 (12)	−0.0090 (12)	0.0032 (11)	0.0008 (11)
O10	0.0419 (16)	0.0302 (15)	0.0216 (13)	0.0092 (13)	−0.0050 (12)	−0.0034 (12)
N1	0.0331 (19)	0.0289 (17)	0.0220 (16)	−0.0028 (15)	−0.0009 (14)	−0.0100 (14)
N2	0.0311 (18)	0.0234 (16)	0.0158 (15)	0.0000 (14)	−0.0011 (13)	0.0029 (13)
N3	0.0353 (19)	0.0267 (17)	0.0235 (17)	−0.0002 (15)	−0.0017 (15)	0.0017 (14)
N4	0.043 (2)	0.0327 (19)	0.0233 (16)	−0.0008 (16)	0.0065 (15)	0.0046 (14)
N5	0.0247 (17)	0.0284 (17)	0.0193 (16)	−0.0030 (14)	0.0013 (13)	0.0013 (13)
N6	0.0309 (18)	0.0244 (17)	0.0243 (16)	0.0005 (14)	0.0055 (14)	−0.0015 (13)
C1	0.053 (3)	0.030 (2)	0.038 (2)	0.012 (2)	−0.011 (2)	0.0010 (19)
C2	0.028 (2)	0.026 (2)	0.0237 (19)	−0.0005 (18)	0.0001 (17)	0.0068 (17)
C3	0.048 (3)	0.034 (2)	0.027 (2)	−0.013 (2)	−0.0103 (19)	0.0029 (18)
C4	0.034 (2)	0.040 (2)	0.024 (2)	0.0076 (19)	−0.0062 (18)	−0.0059 (18)
C5	0.035 (2)	0.027 (2)	0.024 (2)	0.0032 (18)	−0.0065 (18)	−0.0080 (17)
C6	0.029 (2)	0.025 (2)	0.0155 (18)	−0.0086 (17)	0.0015 (17)	0.0016 (15)
C7	0.032 (2)	0.022 (2)	0.0173 (18)	−0.0014 (17)	−0.0016 (16)	0.0011 (15)
C8	0.059 (3)	0.033 (2)	0.020 (2)	−0.002 (2)	−0.0043 (19)	0.0050 (17)
C9	0.032 (2)	0.0193 (19)	0.0152 (17)	0.0006 (17)	0.0040 (16)	−0.0033 (15)
C10	0.042 (3)	0.022 (2)	0.023 (2)	−0.0073 (18)	−0.0009 (18)	−0.0033 (16)
C11	0.038 (2)	0.030 (2)	0.0189 (19)	−0.0020 (19)	−0.0052 (17)	−0.0034 (17)
C12	0.037 (2)	0.024 (2)	0.0153 (18)	0.0048 (18)	0.0052 (17)	0.0036 (16)
C13	0.038 (2)	0.034 (2)	0.028 (2)	−0.008 (2)	0.0040 (18)	0.0044 (18)
C14	0.034 (2)	0.030 (2)	0.0196 (19)	−0.0085 (18)	0.0007 (17)	−0.0008 (16)
C15	0.029 (2)	0.027 (2)	0.0139 (18)	−0.0001 (17)	−0.0020 (16)	−0.0030 (16)
C16	0.0194 (19)	0.027 (2)	0.0194 (18)	0.0013 (16)	0.0000 (15)	0.0009 (16)
C17	0.026 (2)	0.025 (2)	0.0254 (19)	−0.0038 (17)	0.0040 (17)	0.0040 (16)
C18	0.027 (2)	0.029 (2)	0.030 (2)	0.0049 (18)	0.0011 (17)	0.0008 (18)
C19	0.026 (2)	0.036 (2)	0.0222 (19)	0.0042 (18)	0.0059 (16)	0.0016 (18)
C20	0.031 (2)	0.034 (2)	0.0192 (19)	−0.0055 (19)	0.0001 (16)	0.0060 (17)
C21	0.0196 (19)	0.0236 (19)	0.0201 (18)	−0.0028 (16)	−0.0040 (15)	−0.0018 (16)
C22	0.039 (2)	0.029 (2)	0.0194 (19)	0.0053 (18)	0.0025 (18)	0.0009 (17)
C23	0.068 (3)	0.037 (2)	0.033 (2)	−0.003 (2)	0.016 (2)	0.003 (2)
C24	0.031 (2)	0.036 (2)	0.024 (2)	0.0034 (19)	0.0017 (18)	−0.0006 (18)
C25	0.040 (3)	0.045 (3)	0.033 (2)	0.008 (2)	−0.0057 (19)	0.002 (2)
C26	0.028 (2)	0.054 (3)	0.0202 (19)	0.005 (2)	0.0053 (18)	0.0095 (19)
C27	0.031 (2)	0.031 (2)	0.0220 (19)	0.0077 (18)	0.0042 (17)	0.0046 (17)
C28	0.017 (2)	0.030 (2)	0.0165 (18)	−0.0079 (17)	−0.0005 (16)	−0.0017 (16)
C29	0.027 (2)	0.029 (2)	0.0208 (18)	−0.0007 (18)	0.0049 (15)	0.0035 (17)
C30	0.057 (3)	0.031 (2)	0.034 (2)	0.009 (2)	0.017 (2)	0.0004 (19)
C31	0.031 (2)	0.0233 (19)	0.0184 (18)	0.0026 (18)	−0.0036 (16)	0.0040 (17)
C32	0.064 (3)	0.030 (2)	0.029 (2)	−0.021 (2)	0.014 (2)	−0.0051 (19)
C33	0.058 (3)	0.028 (2)	0.029 (2)	−0.010 (2)	0.015 (2)	−0.0014 (19)
C34	0.034 (2)	0.028 (2)	0.0175 (19)	0.0055 (18)	−0.0023 (17)	0.0023 (16)
C35	0.053 (3)	0.035 (2)	0.028 (2)	−0.018 (2)	−0.002 (2)	−0.0017 (19)
C36	0.047 (3)	0.044 (3)	0.024 (2)	−0.018 (2)	0.0026 (19)	−0.0025 (19)
C37	0.029 (2)	0.023 (2)	0.0212 (19)	−0.0014 (18)	0.0015 (16)	0.0007 (16)
C38	0.026 (2)	0.0174 (17)	0.0166 (18)	−0.0062 (16)	0.0021 (15)	−0.0030 (15)
C39	0.030 (2)	0.026 (2)	0.0219 (19)	0.0020 (17)	0.0033 (17)	−0.0062 (16)
C40	0.027 (2)	0.028 (2)	0.029 (2)	0.0051 (17)	0.0014 (17)	−0.0040 (17)
C41	0.0268 (19)	0.030 (2)	0.0154 (17)	−0.0042 (18)	−0.0004 (15)	0.0016 (16)
C42	0.028 (2)	0.0245 (19)	0.0199 (19)	−0.0019 (17)	0.0064 (16)	−0.0062 (16)
C43	0.024 (2)	0.0132 (17)	0.0236 (19)	−0.0045 (15)	0.0032 (16)	0.0005 (15)
C44	0.029 (2)	0.022 (2)	0.027 (2)	0.0024 (17)	0.0046 (18)	0.0017 (16)

Geometric parameters (Å, º) top

Cl1—C19	1.745 (3)	C12—C13	1.369 (5)
Cl2—C41	1.739 (3)	C13—C14	1.399 (5)
O1—C4	1.433 (4)	C13—H13	0.9500
O1—N1	1.433 (3)	C14—H14	0.9500
O2—C6	1.357 (4)	C15—C22	1.437 (5)
O2—C5	1.456 (4)	C16—C17	1.396 (4)
O3—C6	1.201 (4)	C16—C21	1.406 (4)
O4—C9	1.394 (4)	C17—C18	1.372 (5)
O4—C7	1.426 (4)	C17—H17	0.9500
O5—C15	1.362 (4)	C18—C19	1.402 (5)
O5—C12	1.428 (4)	C18—H18	0.9500
O6—C26	1.419 (4)	C19—C20	1.355 (5)
O6—N4	1.439 (3)	C20—C21	1.411 (5)
O7—C28	1.351 (4)	C20—H20	0.9500
O7—C27	1.445 (4)	C22—H22	0.9500
O8—C28	1.202 (4)	C23—C24	1.494 (5)
O9—C31	1.384 (4)	C23—H23A	0.9800
O9—C29	1.422 (4)	C23—H23B	0.9800
O10—C37	1.356 (4)	C23—H23C	0.9800
O10—C34	1.424 (4)	C24—C25	1.482 (5)
N1—C2	1.274 (4)	C25—H25A	0.9800
N2—C15	1.283 (4)	C25—H25B	0.9800
N2—C16	1.390 (4)	C25—H25C	0.9800
N3—C22	1.315 (4)	C26—C27	1.500 (5)
N3—C21	1.365 (4)	C26—H26A	0.9900
N4—C24	1.285 (4)	C26—H26B	0.9900
N5—C37	1.290 (4)	C27—H27A	0.9900
N5—C38	1.378 (4)	C27—H27B	0.9900
N6—C44	1.296 (4)	C28—C29	1.520 (5)
N6—C43	1.378 (4)	C29—C30	1.515 (5)
C1—C2	1.485 (5)	C29—H29	1.0000
C1—H1A	0.9800	C30—H30A	0.9800
C1—H1B	0.9800	C30—H30B	0.9800
C1—H1C	0.9800	C30—H30C	0.9800
C2—C3	1.504 (5)	C31—C32	1.369 (5)
C3—H3A	0.9800	C31—C36	1.376 (5)
C3—H3B	0.9800	C32—C33	1.382 (5)
C3—H3C	0.9800	C32—H32	0.9500
C4—C5	1.502 (5)	C33—C34	1.355 (5)
C4—H4A	0.9900	C33—H33	0.9500
C4—H4B	0.9900	C34—C35	1.370 (5)
C5—H5A	0.9900	C35—C36	1.395 (5)
C5—H5B	0.9900	C35—H35	0.9500
C6—C7	1.504 (5)	C36—H36	0.9500
C7—C8	1.540 (4)	C37—C44	1.426 (5)
C7—H7	1.0000	C38—C39	1.410 (5)
C8—H8A	0.9800	C38—C43	1.410 (4)
C8—H8B	0.9800	C39—C40	1.370 (5)
C8—H8C	0.9800	C39—H39	0.9500
C9—C14	1.371 (5)	C40—C41	1.405 (5)
C9—C10	1.381 (5)	C40—H40	0.9500
C10—C11	1.387 (5)	C41—C42	1.360 (5)
C10—H10	0.9500	C42—C43	1.409 (5)
C11—C12	1.353 (5)	C42—H42	0.9500
C11—H11	0.9500	C44—H44	0.9500

C4—O1—N1	107.6 (3)	C21—C20—H20	120.3
C6—O2—C5	115.5 (3)	N3—C21—C16	121.8 (3)
C9—O4—C7	116.8 (2)	N3—C21—C20	118.9 (3)
C15—O5—C12	120.0 (3)	C16—C21—C20	119.3 (3)
C26—O6—N4	107.2 (3)	N3—C22—C15	121.0 (3)
C28—O7—C27	115.7 (3)	N3—C22—H22	119.5
C31—O9—C29	118.5 (3)	C15—C22—H22	119.5
C37—O10—C34	118.4 (3)	C24—C23—H23A	109.5
C2—N1—O1	110.6 (3)	C24—C23—H23B	109.5
C15—N2—C16	114.7 (3)	H23A—C23—H23B	109.5
C22—N3—C21	116.2 (3)	C24—C23—H23C	109.5
C24—N4—O6	110.1 (3)	H23A—C23—H23C	109.5
C37—N5—C38	115.0 (3)	H23B—C23—H23C	109.5
C44—N6—C43	115.4 (3)	N4—C24—C25	125.5 (3)
C2—C1—H1A	109.5	N4—C24—C23	114.3 (3)
C2—C1—H1B	109.5	C25—C24—C23	120.1 (3)
H1A—C1—H1B	109.5	C24—C25—H25A	109.5
C2—C1—H1C	109.5	C24—C25—H25B	109.5
H1A—C1—H1C	109.5	H25A—C25—H25B	109.5
H1B—C1—H1C	109.5	C24—C25—H25C	109.5
N1—C2—C1	125.6 (3)	H25A—C25—H25C	109.5
N1—C2—C3	115.1 (3)	H25B—C25—H25C	109.5
C1—C2—C3	119.3 (3)	O6—C26—C27	111.3 (3)
C2—C3—H3A	109.5	O6—C26—H26A	109.4
C2—C3—H3B	109.5	C27—C26—H26A	109.4
H3A—C3—H3B	109.5	O6—C26—H26B	109.4
C2—C3—H3C	109.5	C27—C26—H26B	109.4
H3A—C3—H3C	109.5	H26A—C26—H26B	108.0
H3B—C3—H3C	109.5	O7—C27—C26	111.2 (3)
O1—C4—C5	111.9 (3)	O7—C27—H27A	109.4
O1—C4—H4A	109.2	C26—C27—H27A	109.4
C5—C4—H4A	109.2	O7—C27—H27B	109.4
O1—C4—H4B	109.2	C26—C27—H27B	109.4
C5—C4—H4B	109.2	H27A—C27—H27B	108.0
H4A—C4—H4B	107.9	O8—C28—O7	123.1 (3)
O2—C5—C4	110.3 (3)	O8—C28—C29	126.5 (3)
O2—C5—H5A	109.6	O7—C28—C29	110.4 (3)
C4—C5—H5A	109.6	O9—C29—C30	107.1 (3)
O2—C5—H5B	109.6	O9—C29—C28	109.2 (3)
C4—C5—H5B	109.6	C30—C29—C28	110.2 (3)
H5A—C5—H5B	108.1	O9—C29—H29	110.1
O3—C6—O2	123.1 (3)	C30—C29—H29	110.1
O3—C6—C7	126.2 (3)	C28—C29—H29	110.1
O2—C6—C7	110.7 (3)	C29—C30—H30A	109.5
O4—C7—C6	110.6 (3)	C29—C30—H30B	109.5
O4—C7—C8	106.0 (3)	H30A—C30—H30B	109.5
C6—C7—C8	109.6 (3)	C29—C30—H30C	109.5
O4—C7—H7	110.2	H30A—C30—H30C	109.5
C6—C7—H7	110.2	H30B—C30—H30C	109.5
C8—C7—H7	110.2	C32—C31—C36	120.0 (3)
C7—C8—H8A	109.5	C32—C31—O9	115.2 (3)
C7—C8—H8B	109.5	C36—C31—O9	124.8 (3)
H8A—C8—H8B	109.5	C31—C32—C33	121.0 (4)
C7—C8—H8C	109.5	C31—C32—H32	119.5
H8A—C8—H8C	109.5	C33—C32—H32	119.5
H8B—C8—H8C	109.5	C34—C33—C32	118.7 (3)
C14—C9—C10	120.8 (3)	C34—C33—H33	120.7
C14—C9—O4	124.3 (3)	C32—C33—H33	120.7
C10—C9—O4	115.0 (3)	C33—C34—C35	121.7 (3)
C9—C10—C11	119.8 (3)	C33—C34—O10	120.1 (3)
C9—C10—H10	120.1	C35—C34—O10	117.9 (3)
C11—C10—H10	120.1	C34—C35—C36	119.6 (4)
C12—C11—C10	119.0 (3)	C34—C35—H35	120.2
C12—C11—H11	120.5	C36—C35—H35	120.2
C10—C11—H11	120.5	C31—C36—C35	119.0 (4)
C11—C12—C13	122.3 (3)	C31—C36—H36	120.5
C11—C12—O5	120.6 (3)	C35—C36—H36	120.5
C13—C12—O5	116.7 (3)	N5—C37—O10	122.3 (3)
C12—C13—C14	119.2 (3)	N5—C37—C44	124.2 (3)
C12—C13—H13	120.4	O10—C37—C44	113.5 (3)
C14—C13—H13	120.4	N5—C38—C39	119.9 (3)
C9—C14—C13	118.9 (3)	N5—C38—C43	121.3 (3)
C9—C14—H14	120.5	C39—C38—C43	118.8 (3)
C13—C14—H14	120.5	C40—C39—C38	121.2 (3)
N2—C15—O5	122.2 (3)	C40—C39—H39	119.4
N2—C15—C22	124.8 (3)	C38—C39—H39	119.4
O5—C15—C22	113.0 (3)	C39—C40—C41	118.7 (3)
N2—C16—C17	119.3 (3)	C39—C40—H40	120.7
N2—C16—C21	121.3 (3)	C41—C40—H40	120.7
C17—C16—C21	119.4 (3)	C42—C41—C40	122.1 (3)
C18—C17—C16	121.0 (3)	C42—C41—Cl2	119.4 (3)
C18—C17—H17	119.5	C40—C41—Cl2	118.5 (3)
C16—C17—H17	119.5	C41—C42—C43	119.5 (3)
C17—C18—C19	118.7 (3)	C41—C42—H42	120.3
C17—C18—H18	120.6	C43—C42—H42	120.3
C19—C18—H18	120.6	N6—C43—C42	118.8 (3)
C20—C19—C18	122.1 (3)	N6—C43—C38	121.6 (3)
C20—C19—Cl1	119.8 (3)	C42—C43—C38	119.6 (3)
C18—C19—Cl1	118.1 (3)	N6—C44—C37	122.5 (3)
C19—C20—C21	119.4 (3)	N6—C44—H44	118.7
C19—C20—H20	120.3	C37—C44—H44	118.7

C4—O1—N1—C2	−170.3 (3)	O5—C15—C22—N3	176.7 (3)
C26—O6—N4—C24	−168.5 (3)	O6—N4—C24—C25	3.3 (5)
O1—N1—C2—C1	3.1 (5)	O6—N4—C24—C23	−178.5 (3)
O1—N1—C2—C3	−178.1 (3)	N4—O6—C26—C27	82.3 (3)
N1—O1—C4—C5	82.1 (3)	C28—O7—C27—C26	82.3 (3)
C6—O2—C5—C4	82.2 (3)	O6—C26—C27—O7	68.3 (4)
O1—C4—C5—O2	66.0 (4)	C27—O7—C28—O8	3.6 (4)
C5—O2—C6—O3	9.0 (4)	C27—O7—C28—C29	−175.0 (3)
C5—O2—C6—C7	−168.6 (3)	C31—O9—C29—C30	−169.9 (3)
C9—O4—C7—C6	68.8 (4)	C31—O9—C29—C28	70.8 (4)
C9—O4—C7—C8	−172.5 (3)	O8—C28—C29—O9	−1.5 (5)
O3—C6—C7—O4	9.4 (5)	O7—C28—C29—O9	177.0 (2)
O2—C6—C7—O4	−173.0 (3)	O8—C28—C29—C30	−118.8 (4)
O3—C6—C7—C8	−107.1 (4)	O7—C28—C29—C30	59.7 (4)
O2—C6—C7—C8	70.5 (4)	C29—O9—C31—C32	−173.2 (3)
C7—O4—C9—C14	13.2 (5)	C29—O9—C31—C36	6.1 (5)
C7—O4—C9—C10	−167.8 (3)	C36—C31—C32—C33	−0.5 (6)
C14—C9—C10—C11	−2.9 (5)	O9—C31—C32—C33	178.8 (3)
O4—C9—C10—C11	178.1 (3)	C31—C32—C33—C34	0.5 (6)
C9—C10—C11—C12	0.5 (5)	C32—C33—C34—C35	0.1 (6)
C10—C11—C12—C13	1.4 (6)	C32—C33—C34—O10	−173.6 (3)
C10—C11—C12—O5	−171.3 (3)	C37—O10—C34—C33	−88.6 (4)
C15—O5—C12—C11	−85.1 (4)	C37—O10—C34—C35	97.5 (4)
C15—O5—C12—C13	101.8 (4)	C33—C34—C35—C36	−0.6 (6)
C11—C12—C13—C14	−1.0 (6)	O10—C34—C35—C36	173.3 (3)
O5—C12—C13—C14	172.0 (3)	C32—C31—C36—C35	0.1 (6)
C10—C9—C14—C13	3.2 (5)	O9—C31—C36—C35	−179.2 (3)
O4—C9—C14—C13	−177.8 (3)	C34—C35—C36—C31	0.5 (6)
C12—C13—C14—C9	−1.3 (6)	C38—N5—C37—O10	−178.7 (3)
C16—N2—C15—O5	−178.5 (3)	C38—N5—C37—C44	0.6 (5)
C16—N2—C15—C22	0.9 (5)	C34—O10—C37—N5	4.8 (5)
C12—O5—C15—N2	9.3 (5)	C34—O10—C37—C44	−174.6 (3)
C12—O5—C15—C22	−170.1 (3)	C37—N5—C38—C39	−178.2 (3)
C15—N2—C16—C17	−177.4 (3)	C37—N5—C38—C43	0.6 (5)
C15—N2—C16—C21	1.4 (5)	N5—C38—C39—C40	179.1 (3)
N2—C16—C17—C18	179.6 (3)	C43—C38—C39—C40	0.3 (5)
C21—C16—C17—C18	0.8 (5)	C38—C39—C40—C41	1.7 (5)
C16—C17—C18—C19	1.0 (5)	C39—C40—C41—C42	−1.8 (5)
C17—C18—C19—C20	−0.8 (6)	C39—C40—C41—Cl2	178.5 (3)
C17—C18—C19—Cl1	178.9 (3)	C40—C41—C42—C43	−0.2 (5)
C18—C19—C20—C21	−1.2 (5)	Cl2—C41—C42—C43	179.5 (3)
Cl1—C19—C20—C21	179.2 (3)	C44—N6—C43—C42	180.0 (3)
C22—N3—C21—C16	0.5 (5)	C44—N6—C43—C38	−0.3 (5)
C22—N3—C21—C20	179.7 (3)	C41—C42—C43—N6	−178.0 (3)
N2—C16—C21—N3	−2.2 (5)	C41—C42—C43—C38	2.3 (5)
C17—C16—C21—N3	176.6 (3)	N5—C38—C43—N6	−0.8 (5)
N2—C16—C21—C20	178.5 (3)	C39—C38—C43—N6	178.0 (3)
C17—C16—C21—C20	−2.7 (5)	N5—C38—C43—C42	178.9 (3)
C19—C20—C21—N3	−176.5 (3)	C39—C38—C43—C42	−2.4 (5)
C19—C20—C21—C16	2.9 (5)	C43—N6—C44—C37	1.5 (5)
C21—N3—C22—C15	1.8 (5)	N5—C37—C44—N6	−1.8 (6)
N2—C15—C22—N3	−2.7 (6)	O10—C37—C44—N6	177.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···O2ⁱ	0.99	2.60	3.337 (4)	131
C7—H7···O3ⁱⁱ	1.00	2.33	3.264 (4)	154
C14—H14···O3ⁱⁱ	0.95	2.47	3.389 (4)	164
C22—H22···O8ⁱ	0.95	2.53	3.468 (4)	170
C27—H27A···O5ⁱⁱ	0.99	2.56	3.284 (4)	130
C29—H29···O8ⁱ	1.00	2.33	3.173 (4)	142
C44—H44···N1ⁱⁱⁱ	0.95	2.51	3.430 (5)	162
C10—H10···Cl2^iv	0.95	2.91	3.855 (4)	174
C25—H25A···Cl2^v	0.98	2.99	3.368 (4)	105
C32—H32···Cl1^vi	0.95	2.89	3.748 (4)	151

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···O2ⁱ	0.99	2.60	3.337 (4)	131.4
C7—H7···O3ⁱⁱ	1.00	2.33	3.264 (4)	154.1
C14—H14···O3ⁱⁱ	0.95	2.47	3.389 (4)	163.9
C22—H22···O8ⁱ	0.95	2.53	3.468 (4)	170.4
C27—H27A···O5ⁱⁱ	0.99	2.56	3.284 (4)	130.2
C29—H29···O8ⁱ	1.00	2.33	3.173 (4)	141.9
C44—H44···N1ⁱⁱⁱ	0.95	2.51	3.430 (5)	161.7
C10—H10···Cl2^iv	0.95	2.91	3.855 (4)	174.4
C25—H25A···Cl2^v	0.98	2.99	3.368 (4)	104.6
C32—H32···Cl1^vi	0.95	2.89	3.748 (4)	150.8

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

Acknowledgements

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No. 2012R1A1B3003337).

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