supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

xu2661 scheme

Acta Cryst. (2009). E65, o2983    [ doi:10.1107/S160053680904553X ]

1-(3-Chlorobenzyloxy)urea

X. Mai, H.-Y. Xia, Y.-S. Cao, W. Tong and G.-G. Tu

Abstract top

The asymmetric unit of the crystal structure of the title compound, C8H9ClN2O2, contains four independent molecules. The dihedral angles between the urea N-(C=O)-N planes and the benzene rings are 83.3 (3), 87.8 (1), 89.1 (1) and 17.5 (2)° in the four molecules. Extensive N-H...O hydrogen bonding is present in the crystal structure.

Comment top

Hydroxyurea (HU) is a substance used in cancer chemotherapy for many years, but it has several disadvantages, such as short half-life, extremely polar nature, the rapid development of resistance and so on. To obtain more potent compound, we have designed and synthesized HU derivatives, and evaluated their in vitro antitumor activities in our previous work (Mai et al., 2009). Here we report the crystal structure of the title compound, 3-chlorobenzyloxyurea.

The structure of 3-chlorobenzyloxyurea is shown in Fig. 1. The conformations of the N–O and C=O bonds are opposite to each other, similar to that observed in N-hydroxyurea (Howard et al., 1967; Thiessen et al., 1978; Armagan et al., 1976; Berman et al., 1967; Larsen & Jerslev, 1966), 1-hydroxy-1-methylurea, 1-hydroxy-3-methylurea (Nielsen et al., 1993), N-(6-phenoxy-2H-chromen-3-ylmethyl)-N-hydroxyurea (Yoshitaka et al., 1993) and 1-(2-fluorobenzyl)-1-(2-fluorobenzyloxy) urea (Mai et al., 2009). The bond parameters are similar to 1-(2-fluorobenzyl)-1-(2-fluorobenzyloxy)urea (Mai et al., 2009). The asymmetric unit of the title compound contains four independent molecules. The dihedral angles between the urea N-(C=O)–N planes and benzene ring are 83.3 (3)°, 87.8 (1)°, 89.1 (1)° and 17.5 (2)° for the four molecules. The N–O bonds are twisted out of the urea N–(C=O)–N planes by 18.4 (3)°, 17.9 (3)°, 19.2 (4)° and -17.8 (3)°, respectively in the four molecules. In the crystal structure, molecules are linked through intermolecular N–H···O hydrogen bonds, forming the zigzig chain.

Related literature top

For general background to the design and synthesis of hydroxyurea derivatives and their in vitro antitumor activity, see: Mai et al. (2009). For related structures, see: Armagan et al. (1976); Nielsen et al. (1993); Berman & Kim (1967); Howard et al. (1967); Larsen & Jerslev (1966); Thiessen et al. (1978); Yoshitaka et al. (1993).

Experimental top

The title compound was synthesized by hydroxyurea (0.026 mol) with 3-chlorobenzyl chloride (0.034 mol) in methanol (80 ml) in the presence of potassium hydroxide (0.034 mol). After refluxing for 13 h, solvent was removed under reduced pressure at 308 K. The resulting crude solid was filtered and washed in trichloromethane, then recrystallized in acetone and trichloromethane solution (5:2), filtered and dried. Colorless platelet single crystals of the title compound were recrystallized from the mixed solvent acetone and n-hexane (5:10).

Refinement top

H atoms were placed in calculated positions with N—H = 0.90 (imino), 0.86 Å (amino), C—H = 0.93 (aromatic) and 0.97 Å (methylene), and refined in riding mode with Uiso(H) = 1.2Ueq(C,N).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The unit cell diagram showing intermolecular hydrogen bonding as dashed lines
1-(3-Chlorobenzyloxy)urea top
Crystal data top
C8H9ClN2O2Z = 8
Mr = 200.62F(000) = 832
Triclinic, P1Dx = 1.415 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.830 (1) ÅCell parameters from 1978 reflections
b = 13.9410 (14) Åθ = 2.2–22.6°
c = 14.2750 (15) ŵ = 0.37 mm−1
α = 69.672 (1)°T = 298 K
β = 75.828 (2)°Platelet, colourless
γ = 70.388 (1)°0.43 × 0.40 × 0.05 mm
V = 1883.6 (3) Å3
Data collection top
Bruker APEXII CCD area-detector
diffractometer		6533 independent reflections
Radiation source: fine-focus sealed tube3124 reflections with I > 2σ(I)
graphiteRint = 0.029
φ and ω scansθmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −12→11
Tmin = 0.856, Tmax = 0.982k = −16→16
9908 measured reflectionsl = −16→16
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0205P)2]
where P = (Fo2 + 2Fc2)/3
6533 reflections(Δ/σ)max = 0.001
469 parametersΔρmax = 0.23 e Å−3
0 restraintsΔρmin = −0.24 e Å−3
Crystal data top
C8H9ClN2O2γ = 70.388 (1)°
Mr = 200.62V = 1883.6 (3) Å3
Triclinic, P1Z = 8
a = 10.830 (1) ÅMo Kα radiation
b = 13.9410 (14) ŵ = 0.37 mm−1
c = 14.2750 (15) ÅT = 298 K
α = 69.672 (1)°0.43 × 0.40 × 0.05 mm
β = 75.828 (2)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		6533 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3124 reflections with I > 2σ(I)
Tmin = 0.856, Tmax = 0.982Rint = 0.029
9908 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.094Δρmax = 0.23 e Å−3
S = 1.01Δρmin = −0.24 e Å−3
6533 reflectionsAbsolute structure: ?
469 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Cl11.11832 (10)0.31531 (8)−0.02808 (6)0.0839 (3)
Cl20.25832 (11)0.58558 (9)−0.04798 (7)0.0998 (4)
Cl30.39222 (11)0.83726 (9)−0.04386 (7)0.1020 (4)
Cl40.16163 (12)1.13164 (10)0.84040 (10)0.1271 (5)
N10.8146 (2)0.36994 (18)0.39732 (16)0.0401 (6)
H10.84180.30290.43700.048*
N20.6676 (2)0.51825 (17)0.44071 (16)0.0419 (6)
H2A0.59000.55220.46310.050*
H2B0.73010.54910.41770.050*
N30.0506 (2)0.61462 (18)0.39981 (16)0.0380 (6)
H30.07570.54890.44240.046*
N4−0.0889 (2)0.76897 (17)0.43587 (16)0.0453 (7)
H4A−0.16470.80540.45830.054*
H4B−0.02510.79800.40890.054*
N50.2948 (2)0.86095 (18)0.39097 (17)0.0438 (6)
H50.32030.79480.43270.053*
N60.1619 (2)1.01583 (18)0.42966 (17)0.0529 (7)
H6A0.08821.05240.45490.063*
H6B0.22521.04480.39910.063*
N70.4342 (2)0.89042 (18)0.59283 (16)0.0422 (6)
H70.41190.95740.55200.051*
N80.5745 (2)0.73892 (17)0.55203 (16)0.0447 (6)
H8A0.65130.70250.53090.054*
H8B0.50930.71110.57350.054*
O10.60499 (19)0.36862 (15)0.47386 (15)0.0501 (6)
O20.91190 (18)0.42284 (15)0.38500 (13)0.0421 (5)
O3−0.15777 (19)0.62023 (14)0.48081 (14)0.0462 (5)
O40.15349 (18)0.66423 (15)0.38002 (14)0.0440 (5)
O50.09142 (19)0.86693 (15)0.48084 (15)0.0524 (6)
O60.4015 (2)0.90763 (15)0.36655 (15)0.0510 (6)
O70.64654 (19)0.88364 (14)0.52150 (14)0.0469 (5)
O80.33178 (18)0.84381 (15)0.60348 (14)0.0458 (5)
C10.6909 (3)0.4182 (2)0.4417 (2)0.0379 (7)
C20.9543 (3)0.4670 (2)0.2794 (2)0.0463 (8)
H2C0.99400.52270.27140.056*
H2D0.87740.49920.24440.056*
C31.0527 (3)0.3856 (2)0.2309 (2)0.0400 (8)
C41.0418 (3)0.3863 (2)0.1359 (2)0.0473 (8)
H40.97150.43480.10320.057*
C51.1353 (3)0.3151 (3)0.0903 (2)0.0489 (8)
C61.2408 (3)0.2433 (3)0.1353 (2)0.0573 (9)
H61.30380.19640.10280.069*
C71.2522 (3)0.2418 (3)0.2306 (3)0.0619 (10)
H7A1.32300.19310.26270.074*
C81.1592 (3)0.3119 (3)0.2776 (2)0.0551 (9)
H81.16750.31000.34160.066*
C9−0.0704 (3)0.6681 (2)0.4428 (2)0.0373 (7)
C100.1852 (3)0.7051 (2)0.2732 (2)0.0506 (9)
H10A0.24430.74900.25910.061*
H10B0.10450.75030.24560.061*
C110.2494 (3)0.6202 (3)0.2204 (2)0.0462 (8)
C120.2222 (3)0.6366 (3)0.1247 (2)0.0552 (9)
H120.15900.69750.09570.066*
C130.2892 (4)0.5626 (3)0.0729 (2)0.0578 (9)
C140.3784 (4)0.4728 (3)0.1150 (3)0.0694 (11)
H140.42330.42340.07950.083*
C150.4031 (4)0.4544 (3)0.2107 (3)0.0804 (12)
H150.46320.39150.24030.096*
C160.3399 (3)0.5278 (3)0.2632 (2)0.0659 (10)
H160.35820.51510.32750.079*
C170.1778 (3)0.9153 (3)0.4379 (2)0.0424 (8)
C180.4308 (3)0.9459 (3)0.2589 (2)0.0649 (10)
H18A0.50390.97730.24200.078*
H18B0.35441.00160.23330.078*
C190.4666 (3)0.8607 (3)0.2068 (2)0.0498 (9)
C200.4215 (3)0.8854 (3)0.1150 (3)0.0608 (10)
H200.37100.95370.08580.073*
C210.4533 (3)0.8067 (3)0.0688 (2)0.0625 (10)
C220.5279 (3)0.7067 (3)0.1085 (3)0.0665 (10)
H220.54890.65520.07540.080*
C230.5723 (3)0.6827 (3)0.1992 (3)0.0687 (10)
H230.62250.61410.22780.082*
C240.5427 (3)0.7592 (3)0.2471 (2)0.0575 (9)
H240.57440.74240.30740.069*
C250.5569 (3)0.8378 (2)0.5515 (2)0.0364 (7)
C260.2837 (3)0.8033 (2)0.7081 (2)0.0504 (9)
H26A0.35820.77270.74560.061*
H26B0.24610.74650.71570.061*
C270.1814 (3)0.8842 (2)0.7541 (2)0.0443 (8)
C280.2123 (3)0.9650 (3)0.7696 (2)0.0560 (9)
H280.29680.97420.74590.067*
C290.1197 (4)1.0319 (3)0.8198 (3)0.0605 (10)
C30−0.0046 (4)1.0205 (3)0.8561 (3)0.0815 (12)
H30−0.06581.06430.89260.098*
C31−0.0373 (4)0.9426 (3)0.8373 (4)0.1146 (18)
H31−0.12300.93560.85870.137*
C320.0543 (4)0.8753 (3)0.7876 (3)0.0877 (13)
H320.03040.82260.77630.105*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.1008 (8)0.0997 (8)0.0604 (6)−0.0235 (7)−0.0021 (6)−0.0446 (6)
Cl20.0901 (8)0.1568 (11)0.0720 (7)−0.0397 (8)−0.0086 (6)−0.0533 (7)
Cl30.1091 (9)0.1371 (11)0.0636 (6)−0.0405 (8)−0.0252 (6)−0.0189 (6)
Cl40.1133 (10)0.1276 (11)0.1915 (13)−0.0182 (8)−0.0241 (10)−0.1208 (10)
N10.0363 (16)0.0381 (16)0.0505 (15)−0.0135 (14)0.0008 (13)−0.0199 (13)
N20.0341 (15)0.0312 (16)0.0625 (16)−0.0105 (13)0.0005 (13)−0.0198 (13)
N30.0380 (16)0.0337 (15)0.0433 (15)−0.0127 (13)−0.0003 (13)−0.0134 (12)
N40.0397 (16)0.0333 (17)0.0641 (17)−0.0126 (13)0.0039 (13)−0.0209 (13)
N50.0432 (17)0.0370 (17)0.0543 (16)−0.0154 (14)−0.0014 (14)−0.0168 (13)
N60.0454 (17)0.0355 (17)0.0766 (19)−0.0135 (14)0.0034 (15)−0.0211 (14)
N70.0389 (16)0.0341 (16)0.0532 (16)−0.0117 (14)−0.0013 (14)−0.0144 (13)
N80.0382 (16)0.0316 (16)0.0665 (17)−0.0097 (13)−0.0005 (13)−0.0218 (13)
O10.0376 (13)0.0378 (13)0.0820 (16)−0.0174 (11)0.0014 (12)−0.0260 (11)
O20.0374 (12)0.0513 (14)0.0452 (12)−0.0174 (11)0.0006 (10)−0.0226 (10)
O30.0372 (13)0.0399 (13)0.0690 (14)−0.0186 (11)0.0037 (11)−0.0250 (11)
O40.0387 (13)0.0486 (14)0.0505 (13)−0.0196 (11)0.0025 (11)−0.0201 (11)
O50.0414 (14)0.0408 (14)0.0827 (16)−0.0187 (12)0.0033 (12)−0.0283 (12)
O60.0466 (14)0.0544 (15)0.0578 (14)−0.0230 (12)0.0024 (11)−0.0215 (11)
O70.0359 (13)0.0333 (13)0.0743 (14)−0.0120 (11)−0.0013 (11)−0.0211 (11)
O80.0391 (13)0.0521 (14)0.0522 (13)−0.0186 (11)0.0001 (11)−0.0212 (11)
C10.040 (2)0.034 (2)0.0448 (19)−0.0074 (17)−0.0077 (17)−0.0187 (16)
C20.051 (2)0.046 (2)0.0417 (19)−0.0195 (18)0.0019 (17)−0.0133 (16)
C30.042 (2)0.039 (2)0.0374 (18)−0.0149 (17)0.0032 (16)−0.0115 (15)
C40.047 (2)0.043 (2)0.050 (2)−0.0110 (17)−0.0046 (17)−0.0145 (17)
C50.053 (2)0.051 (2)0.045 (2)−0.0189 (19)0.0003 (18)−0.0179 (17)
C60.061 (3)0.047 (2)0.057 (2)−0.012 (2)0.011 (2)−0.0221 (18)
C70.056 (2)0.055 (2)0.058 (2)0.0005 (19)−0.004 (2)−0.0146 (19)
C80.054 (2)0.060 (3)0.047 (2)−0.012 (2)−0.0039 (19)−0.0160 (18)
C90.037 (2)0.037 (2)0.0447 (19)−0.0107 (17)−0.0061 (16)−0.0193 (16)
C100.051 (2)0.042 (2)0.050 (2)−0.0157 (17)0.0065 (18)−0.0099 (17)
C110.045 (2)0.044 (2)0.043 (2)−0.0166 (18)0.0088 (17)−0.0103 (17)
C120.046 (2)0.053 (2)0.059 (2)−0.0114 (18)0.0005 (19)−0.0160 (19)
C130.055 (2)0.064 (3)0.050 (2)−0.022 (2)0.0023 (19)−0.014 (2)
C140.086 (3)0.058 (3)0.056 (2)−0.022 (2)0.021 (2)−0.025 (2)
C150.096 (3)0.047 (3)0.056 (3)0.014 (2)0.005 (2)−0.008 (2)
C160.076 (3)0.053 (3)0.045 (2)0.004 (2)−0.002 (2)−0.0105 (19)
C170.041 (2)0.038 (2)0.053 (2)−0.0084 (18)−0.0080 (18)−0.0211 (17)
C180.075 (3)0.052 (2)0.062 (2)−0.027 (2)0.011 (2)−0.013 (2)
C190.051 (2)0.046 (2)0.047 (2)−0.0181 (19)0.0096 (18)−0.0128 (18)
C200.054 (2)0.053 (2)0.057 (2)−0.0084 (19)0.001 (2)−0.006 (2)
C210.053 (2)0.080 (3)0.048 (2)−0.021 (2)0.0020 (19)−0.015 (2)
C220.062 (3)0.076 (3)0.060 (2)−0.014 (2)0.006 (2)−0.034 (2)
C230.066 (3)0.060 (3)0.063 (2)0.004 (2)−0.005 (2)−0.020 (2)
C240.057 (2)0.057 (3)0.052 (2)−0.009 (2)−0.0074 (19)−0.015 (2)
C250.036 (2)0.030 (2)0.0425 (18)−0.0054 (17)−0.0067 (16)−0.0129 (15)
C260.054 (2)0.041 (2)0.054 (2)−0.0180 (18)0.0034 (18)−0.0124 (17)
C270.039 (2)0.043 (2)0.0460 (19)−0.0100 (17)−0.0013 (16)−0.0103 (16)
C280.043 (2)0.069 (3)0.063 (2)−0.015 (2)−0.0005 (18)−0.033 (2)
C290.067 (3)0.056 (3)0.060 (2)−0.009 (2)−0.011 (2)−0.0252 (19)
C300.078 (3)0.057 (3)0.083 (3)−0.002 (2)0.022 (2)−0.026 (2)
C310.061 (3)0.078 (3)0.195 (5)−0.027 (3)0.048 (3)−0.067 (3)
C320.060 (3)0.062 (3)0.142 (4)−0.025 (2)0.024 (3)−0.049 (3)
Geometric parameters (Å, °) top
Cl1—C51.742 (3)C6—C71.388 (4)
Cl2—C131.737 (3)C6—H60.9300
Cl3—C211.750 (3)C7—C81.372 (4)
Cl4—C291.732 (3)C7—H7A0.9300
N1—C11.387 (3)C8—H80.9300
N1—O21.424 (2)C10—C111.504 (4)
N1—H10.9000C10—H10A0.9700
N2—C11.327 (3)C10—H10B0.9700
N2—H2A0.8600C11—C161.376 (4)
N2—H2B0.8600C11—C121.392 (4)
N3—C91.385 (3)C12—C131.380 (4)
N3—O41.424 (2)C12—H120.9300
N3—H30.9000C13—C141.346 (4)
N4—C91.323 (3)C14—C151.376 (4)
N4—H4A0.8600C14—H140.9300
N4—H4B0.8600C15—C161.375 (4)
N5—C171.386 (3)C15—H150.9300
N5—O61.426 (3)C16—H160.9300
N5—H50.9000C18—C191.510 (4)
N6—C171.320 (3)C18—H18A0.9700
N6—H6A0.8600C18—H18B0.9700
N6—H6B0.8600C19—C241.377 (4)
N7—C251.384 (3)C19—C201.400 (4)
N7—O81.417 (2)C20—C211.378 (4)
N7—H70.9000C20—H200.9300
N8—C251.324 (3)C21—C221.355 (4)
N8—H8A0.8600C22—C231.383 (4)
N8—H8B0.8600C22—H220.9300
O1—C11.247 (3)C23—C241.371 (4)
O2—C21.439 (3)C23—H230.9300
O3—C91.247 (3)C24—H240.9300
O4—C101.428 (3)C26—C271.500 (4)
O5—C171.249 (3)C26—H26A0.9700
O6—C181.432 (3)C26—H26B0.9700
O7—C251.248 (3)C27—C321.374 (4)
O8—C261.432 (3)C27—C281.377 (4)
C2—C31.507 (4)C28—C291.369 (4)
C2—H2C0.9700C28—H280.9300
C2—H2D0.9700C29—C301.360 (4)
C3—C41.387 (4)C30—C311.372 (5)
C3—C81.391 (4)C30—H300.9300
C4—C51.374 (4)C31—C321.364 (5)
C4—H40.9300C31—H310.9300
C5—C61.366 (4)C32—H320.9300
C1—N1—O2113.2 (2)C13—C12—H12120.0
C1—N1—H1108.3C11—C12—H12120.0
O2—N1—H1108.2C14—C13—C12120.6 (3)
C1—N2—H2A120.0C14—C13—Cl2119.7 (3)
C1—N2—H2B120.0C12—C13—Cl2119.7 (3)
H2A—N2—H2B120.0C13—C14—C15119.8 (3)
C9—N3—O4114.3 (2)C13—C14—H14120.1
C9—N3—H3108.1C15—C14—H14120.1
O4—N3—H3108.1C16—C15—C14120.8 (3)
C9—N4—H4A120.0C16—C15—H15119.6
C9—N4—H4B120.0C14—C15—H15119.6
H4A—N4—H4B120.0C15—C16—C11119.8 (3)
C17—N5—O6114.9 (2)C15—C16—H16120.1
C17—N5—H5108.0C11—C16—H16120.1
O6—N5—H5107.9O5—C17—N6124.3 (3)
C17—N6—H6A120.0O5—C17—N5117.3 (3)
C17—N6—H6B120.0N6—C17—N5118.2 (3)
H6A—N6—H6B120.0O6—C18—C19113.6 (2)
C25—N7—O8114.0 (2)O6—C18—H18A108.8
C25—N7—H7107.9C19—C18—H18A108.8
O8—N7—H7107.9O6—C18—H18B108.8
C25—N8—H8A120.0C19—C18—H18B108.8
C25—N8—H8B120.0H18A—C18—H18B107.7
H8A—N8—H8B120.0C24—C19—C20119.1 (3)
N1—O2—C2110.04 (18)C24—C19—C18121.7 (3)
N3—O4—C10108.3 (2)C20—C19—C18119.2 (3)
N5—O6—C18108.6 (2)C21—C20—C19118.7 (3)
N7—O8—C26110.3 (2)C21—C20—H20120.7
O1—C1—N2123.4 (3)C19—C20—H20120.7
O1—C1—N1118.8 (3)C22—C21—C20122.2 (3)
N2—C1—N1117.6 (3)C22—C21—Cl3119.4 (3)
O2—C2—C3113.2 (2)C20—C21—Cl3118.4 (3)
O2—C2—H2C108.9C21—C22—C23118.9 (3)
C3—C2—H2C108.9C21—C22—H22120.6
O2—C2—H2D108.9C23—C22—H22120.6
C3—C2—H2D108.9C24—C23—C22120.5 (3)
H2C—C2—H2D107.7C24—C23—H23119.8
C4—C3—C8118.5 (3)C22—C23—H23119.8
C4—C3—C2120.1 (3)C23—C24—C19120.6 (3)
C8—C3—C2121.4 (3)C23—C24—H24119.7
C5—C4—C3119.8 (3)C19—C24—H24119.7
C5—C4—H4120.1O7—C25—N8123.8 (3)
C3—C4—H4120.1O7—C25—N7118.3 (3)
C6—C5—C4121.9 (3)N8—C25—N7117.8 (3)
C6—C5—Cl1118.9 (3)O8—C26—C27114.8 (2)
C4—C5—Cl1119.2 (3)O8—C26—H26A108.6
C5—C6—C7118.7 (3)C27—C26—H26A108.6
C5—C6—H6120.7O8—C26—H26B108.6
C7—C6—H6120.7C27—C26—H26B108.6
C8—C7—C6120.2 (3)H26A—C26—H26B107.5
C8—C7—H7A119.9C32—C27—C28117.9 (3)
C6—C7—H7A119.9C32—C27—C26120.1 (3)
C7—C8—C3121.0 (3)C28—C27—C26121.9 (3)
C7—C8—H8119.5C29—C28—C27120.5 (3)
C3—C8—H8119.5C29—C28—H28119.8
O3—C9—N4123.9 (3)C27—C28—H28119.8
O3—C9—N3118.1 (3)C30—C29—C28121.4 (3)
N4—C9—N3117.9 (3)C30—C29—Cl4118.9 (3)
O4—C10—C11113.7 (2)C28—C29—Cl4119.7 (3)
O4—C10—H10A108.8C29—C30—C31118.2 (4)
C11—C10—H10A108.8C29—C30—H30120.9
O4—C10—H10B108.8C31—C30—H30120.9
C11—C10—H10B108.8C32—C31—C30120.8 (4)
H10A—C10—H10B107.7C32—C31—H31119.6
C16—C11—C12119.0 (3)C30—C31—H31119.6
C16—C11—C10120.9 (3)C31—C32—C27121.1 (4)
C12—C11—C10120.0 (3)C31—C32—H32119.5
C13—C12—C11120.0 (3)C27—C32—H32119.5
C1—N1—O2—C2−114.4 (2)C12—C11—C16—C150.9 (5)
C9—N3—O4—C10−110.6 (3)C10—C11—C16—C15−176.0 (3)
C17—N5—O6—C18−112.7 (3)O6—N5—C17—O5−164.4 (2)
C25—N7—O8—C26114.6 (3)O6—N5—C17—N619.2 (4)
O2—N1—C1—O1−166.4 (2)N5—O6—C18—C19−58.1 (3)
O2—N1—C1—N218.4 (3)O6—C18—C19—C24−38.7 (4)
N1—O2—C2—C3−79.1 (3)O6—C18—C19—C20141.4 (3)
O2—C2—C3—C4137.8 (3)C24—C19—C20—C210.9 (5)
O2—C2—C3—C8−45.1 (4)C18—C19—C20—C21−179.2 (3)
C8—C3—C4—C5−0.1 (4)C19—C20—C21—C22−0.8 (5)
C2—C3—C4—C5177.0 (3)C19—C20—C21—Cl3178.1 (2)
C3—C4—C5—C6−0.7 (5)C20—C21—C22—C230.8 (5)
C3—C4—C5—Cl1178.8 (2)Cl3—C21—C22—C23−178.0 (3)
C4—C5—C6—C70.9 (5)C21—C22—C23—C24−0.9 (5)
Cl1—C5—C6—C7−178.5 (2)C22—C23—C24—C191.1 (5)
C5—C6—C7—C8−0.5 (5)C20—C19—C24—C23−1.1 (5)
C6—C7—C8—C3−0.3 (5)C18—C19—C24—C23179.0 (3)
C4—C3—C8—C70.5 (5)O8—N7—C25—O7166.5 (2)
C2—C3—C8—C7−176.5 (3)O8—N7—C25—N8−17.8 (3)
O4—N3—C9—O3−165.9 (2)N7—O8—C26—C2783.7 (3)
O4—N3—C9—N417.9 (3)O8—C26—C27—C32114.8 (3)
N3—O4—C10—C11−67.9 (3)O8—C26—C27—C28−69.1 (4)
O4—C10—C11—C16−38.4 (4)C32—C27—C28—C292.0 (5)
O4—C10—C11—C12144.7 (3)C26—C27—C28—C29−174.2 (3)
C16—C11—C12—C13−2.2 (5)C27—C28—C29—C300.3 (5)
C10—C11—C12—C13174.7 (3)C27—C28—C29—Cl4178.9 (2)
C11—C12—C13—C141.7 (5)C28—C29—C30—C31−2.8 (6)
C11—C12—C13—Cl2−178.1 (2)Cl4—C29—C30—C31178.6 (3)
C12—C13—C14—C150.2 (5)C29—C30—C31—C322.9 (7)
Cl2—C13—C14—C15180.0 (3)C30—C31—C32—C27−0.7 (7)
C13—C14—C15—C16−1.6 (6)C28—C27—C32—C31−1.8 (6)
C14—C15—C16—C111.0 (6)C26—C27—C32—C31174.4 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O5i0.902.203.096 (3)173
N2—H2A···O1i0.862.163.023 (3)177
N2—H2B···O3ii0.862.292.971 (3)136
N4—H4A···O7iii0.862.112.971 (3)176
N4—H4B···O50.862.393.017 (3)130
N5—H5···O1i0.902.193.090 (3)176
N6—H6A···O5iv0.862.072.925 (3)177
N7—H7···O7v0.902.042.937 (3)171
N8—H8A···O3ii0.862.092.947 (3)177
N8—H8B···O1i0.862.252.976 (3)142
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z; (iii) x−1, y, z; (iv) −x, −y+2, −z+1; (v) −x+1, −y+2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O5i0.902.203.096 (3)173
N2—H2A···O1i0.862.163.023 (3)177
N2—H2B···O3ii0.862.292.971 (3)136
N4—H4A···O7iii0.862.112.971 (3)176
N4—H4B···O50.862.393.017 (3)130
N5—H5···O1i0.902.193.090 (3)176
N6—H6A···O5iv0.862.072.925 (3)177
N7—H7···O7v0.902.042.937 (3)171
N8—H8A···O3ii0.862.092.947 (3)177
N8—H8B···O1i0.862.252.976 (3)142
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z; (iii) x−1, y, z; (iv) −x, −y+2, −z+1; (v) −x+1, −y+2, −z+1.
Acknowledgements top

The authors gratefully acknowledge the financial support of this study by the National Key S&T Special Project of China: Grand New Drug R&D (NO. 2009ZX09103–087) and the program of Nanchang Department of Science and Technology, China (No. 2008368).

references
References top

Armagan, N., Richards, J. P. G. & Uraz, A. A. (1976). Acta Cryst. B32, 1042–1047.

Berman, H. & Kim, S. H. (1967). Acta Cryst. 23, 180–181.

Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Howard, W., Shields, P. J., Hamrick, J. & Welby, R. (1967). J. Chem. Phys. 46, 2510–2514.

Larsen, I. K. & Jerslev, B. (1966). Acta Chem. Scand. 20, 983–991.

Mai, X., Xia, H.-Y., Cao, Y.-S., Lu, X.-S. & Fang, X.-N. (2009). Acta Cryst. E65, o442.

Nielsen, B. B., Frydenvang, K. & Larsen, I. K. (1993). Acta Cryst. C49, 1018–1022.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Thiessen, W. E., Levy, H. A. & Flaig, B. D. (1978). Acta Cryst. B34, 2495–2502.

Yoshitaka, S., James, L. S., Alan, J. H., Adam, H. L., Timothy, J. K., Warren, H. L. D., Hope, W. & Earl, F. K. (1993). J. Med. Chem. 36, 3580–3594.