organic papers
o804
Pınaret al. C31H26N2O5 doi:10.1107/S1600536806002595 Acta Cryst.(2006). E62, o804–o806Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
1
000-Benzyl-1-(2,4-dimethoxyphenyl)-3-phenoxy-spiro[azetidine-2,3
000(3
H
)-indole]-2
000,4(1
H
)-dione
S
¸erife Pınar,aMehmet Akkurt,a* Ali Asghar Jarrahpour,b
Dariush Khaliliband Orhan Bu¨yu¨kgu¨ngo¨rc
aDepartment of Physics, Faculty of Arts and Sciences, Erciyes University, 38039 Kayseri, Turkey,bDepartment of Chemistry, College of Sciences, Shiraz University, 71454 Shiraz, Iran, andcDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139 Samsun, Turkey
Correspondence e-mail: akkurt@erciyes.edu.tr
Key indicators
Single-crystal X-ray study T= 296 K
Mean(C–C) = 0.002 A˚ Rfactor = 0.038 wRfactor = 0.102
Data-to-parameter ratio = 14.5
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
Received 16 January 2006 Accepted 20 January 2006
#2006 International Union of Crystallography All rights reserved
The title compound, C31H26N2O5, is a compound with a spiro
junction between -lactam and isatin ring systems. Its four-and five-membered rings are nearly planar, with maximum deviations of0.020 (1) and 0.050 (1) A˚ for their carbonyl C atoms, respectively. The dihedral angle between these two rings is 86.44 (5). The crystal structure is stabilized by intramolecular C—H O hydrogen-bonding and van der Waals interactions.
Comment
The four-membered-lactam ring of the title compound, (I) (Fig. 1), is nearly planar, with a maximum deviation of 0.020 (1) A˚ for the carbonyl atom C9. Within the lactam ring, the bond lengths (Table 1) are similar to those observed in previous studies (Ercanet al., 1996a,b; Kabaket al., 1999). The N1—C9 bond, conjugated with the carbonyl group, is shorter than the N1—C1 and N1—C11 bonds and the C9 O3 bond is longer than the standard value of 1.198 (12) A˚ given by Allen
et al.(1987).
The dihedral angles between the ring systems are listed in Table 2. The sum of the bond angles about atom N1 is 357.21.
The packing of (I), viewed down the a axis, is shown in Fig. 2. The crystal structure of (I) is stabilized by intra-molecular C—H O hydrogen bonding (Table 3) and van der Waals interactions.
Experimental
Treatment of N-benzyl-3-(2,4-dimethoxyphenylimino)isatin with phenoxyacetyl chloride and triethylamine in dry dichloromethane at 263 K gave the title spiro monocyclic-lactam (Bhawalet al., 1997). Compound (I) was recrystallized from dichloromethane to give single
lactam carbonyl at 1766 cm1and CO of isatin at 1728 cm1. The 1H NMR spectrum showed the methoxy H atoms at 3.39 and 3.75
p.p.m., the diastereotopic benzyl H atoms at 4.73 p.p.m (J= 15 Hz) and 5.10 p.p.m (J= 15 Hz), COCHOPh at 5.64 p.p.m, and aromatic H atoms at 6.29–7.93 p.p.m. The 13C NMR spectrum exhibited the following signals: CH2benzylic at 44.2, OMe at 55.2 and 55.5, C— OPh at 69.9, spiro C at 86.0, aromatic C at 99.5–159.3, CO of-lactam at 163.4 and CO of isatin at 173.8 p.p.m. The mass spectrum showed molecular ion atm/e506 and the base peak atm/e85.
Crystal data
C31H26N2O5 Mr= 506.54
Monoclinic, P21=c a= 9.3547 (7) A˚
b= 10.0777 (5) A˚
c= 28.193 (2) A˚ = 106.838 (5)
V= 2543.9 (3) A˚3
Z= 4
Dx= 1.323 Mg m
3
MoKradiation
Cell parameters from 29809 reflections
= 1.5–27.3
= 0.09 mm1
T= 296 K Prism, colourless 0.650.500.29 mm
Data collection
Stoe IPDS2 diffractometer !scans
Absorption correction: none 26901 measured reflections 4995 independent reflections 3963 reflections withI> 2(I)
Rint= 0.042 max= 26.0
h=11!11
k=12!12
l=34!32
Refinement
Refinement onF2 R[F2> 2(F2)] = 0.038 wR(F2) = 0.102
S= 1.05 4995 reflections 345 parameters
H-atom parameters constrained
w= 1/[2
(Fo2) + (0.0537P)2 + 0.2246P]
whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001
max= 0.14 e A˚
3 min=0.18 e A˚
3
Table 1
Selected geometric parameters (A˚ ,).
O1—C8 1.414 (2)
O2—C7 1.415 (2)
O3—C9 1.2083 (17)
O4—C10 1.4015 (15)
O4—C26 1.3836 (16)
O5—C18 1.2154 (16)
N1—C1 1.4166 (16)
N1—C9 1.3673 (17)
N1—C11 1.4774 (16)
N2—C13 1.4116 (18)
N2—C18 1.3645 (17)
N2—C19 1.4627 (19)
C1—N1—C9 130.19 (11)
C1—N1—C11 131.68 (10)
C9—N1—C11 95.44 (10)
C13—N2—C18 110.80 (11)
C13—N2—C19 124.66 (11)
[image:2.610.46.298.68.272.2]C18—N2—C19 124.21 (12)
Table 2
Dihedral angles () between the planes of the ring systems of (I).
Adenotes the ring system N1/C9–C11,BC1–C6,CC13–C17/C12/C11/C18/N2,
DC20–C25 andEC26–C31.
Rings A B C D E
A 26.81 (5) 84.60 (5) 35.01 (6) 54.04 (5)
B 69.26 (4) 57.04 (5) 51.12 (5)
C 81.68 (4) 64.88 (4)
D 85.54 (5)
Figure 1
[image:2.610.44.294.317.442.2]A view of (I), with the atom-numbering scheme and 30% probability displacement ellipsoids. All H atoms have been omitted for clarity.
Figure 2
[image:2.610.312.566.673.728.2]Table 3
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
C6—H6 O3 0.93 2.47 3.0909 (18) 124
C19—H19A O5 0.97 2.60 2.9254 (18) 100
All H atoms were positioned geometrically and constrained to an idealized geometry, with C—H distances of 0.93 (aromatic H), 0.96 (methyl H), 0.97 (methylene H) or 0.98 A˚ (methine H), and with Uiso(H) = 1.2Ueq(C-aromatic, C-methylene and C-methine) or 1.5Ueq(C-methyl).
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction:X-RED32(Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication:WinGX(Farrugia, 1999).
The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS2 diffractometer (purchased under grant F.279 of the University Research Fund). AAJ and DK acknowledge the Shiraz University Research Council (grant No. 84-GR-SC-23).
References
Alcaide, B. & Almendros, P. (2001).Chem. Soc. Rev.30, 226–240.
Alcaide, B. & Almendros, P. (2002).Synlett, pp. 381–393.
Alcaide, B. & Almendros, P. (2004).Curr. Med. Chem.11, 1921–1949. Alcaide, B., Almendros, P. & Salgado, N. R. (2001).Tetrahedron Lett.42, 1503–
1505.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L. & Orpen, A. G. (1987).
J. Chem. Soc. Perkin Trans. 2, pp. S1–S19.
Alonso, E., Del Pozo, C. & Gonzalez, J. (2002).Synlett, pp. 69–72.
Alonso, E., Lopez-Ortiz, F., del Pozo, C., Peralta, E., Macias, A. & Gonzalez, J. (2001).J. Org. Chem.66, 6333–6338.
Bhawal, B. M., Deshmukh, A. R. A. S., Srirajan, V. & Karupaiyan, K. (1997).
Tetrahedron Lett.38, 4281–4284.
Deshmukh, A. R. A. S., Bhawal, B. M., Krishnaswamy, D., Govande, V. V., Shinkre, B. A. & Jayanthi, A. (2004).Curr. Med. Chem.11, 1889–1920. Durkheimer, W., Blumbach, J., Lattrell, R. & Scheunemann, K. H. (1985).
Angew. Chem. Int. Ed. Engl.24, 180–202.
Ercan, F., U¨ lku¨, D. & Gu¨ner, V. (1996a).Acta Cryst.C52, 1779–1780. Ercan, F., U¨ lku¨, D. & Gu¨ner, V. (1996b).Z. Kristallogr.211, 735–736. Farrugia, L. J. (1997).J. Appl. Cryst.30, 565.
Farrugia, L. J. (1999).J. Appl. Cryst.32, 837–838.
Gomez-Gallego, M., Mancheno, M. J. & Sierra, M. A. (2000).Tetrahedron,56, 5743–5774.
Jarrahpour, A. A. & Jahaniani, A. R. (2005).Molbank, M439.
Jarrahpour, A. A., Shekarriz, M. & Taslimi, A. (2004a).Molecules,9, 29–38. Jarrahpour, A. A., Shekarriz, M. & Taslimi, A. (2004b).Molecules,9, 939–
948.
Kabak, M., Elerman, Y., Gu¨ner, V., Yıldırır, S. & Durlu, T. N. (1999).Acta Cryst.C55, 1511–1512.
Kambara, T. & Tomioka, K. (1999).J. Org. Chem.64, 9282–9285.
Lopez, J. R., Martinez, J. C. G. & Barra, E. D. (2003).Synlett, pp. 1587– 1590.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.
Singh, G. S. (2003).Tetrahedron,59, 7631–7649.
Stoe & Cie (2002).X-AREA(Version 1.18) andX-RED32(Version 1.04). Stoe & Cie, Darmstadt, Germany.
organic papers
supporting information
Acta Cryst. (2006). E62, o804–o806 [https://doi.org/10.1107/S1600536806002595]
1
′
-Benzyl-1-(2,4-dimethoxyphenyl)-3-phenoxyspiro[azetidine-2,3
′
(3
H
)-indole]-2
′
,4(1
H
)-dione
Ş
erife P
ı
nar, Mehmet Akkurt, Ali Asghar Jarrahpour, Dariush Khalili and Orhan B
ü
y
ü
kg
ü
ng
ö
r
1′-Benzyl-1-(2,4-dimethoxyphenyl)-3-phenoxyspiro[azetidine-2,3′(3H)- indole]-2′,4(1H)-dione
Crystal data
C31H26N2O5
Mr = 506.54
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 9.3547 (7) Å
b = 10.0777 (5) Å
c = 28.193 (2) Å
β = 106.838 (5)°
V = 2543.9 (3) Å3
Z = 4
F(000) = 1064
Dx = 1.323 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 29809 reflections
θ = 1.5–27.3°
µ = 0.09 mm−1
T = 296 K Prism, colourless 0.65 × 0.50 × 0.29 mm
Data collection
Stoe IPDS2 diffractometer
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus
Plane graphite monochromator Detector resolution: 6.67 pixels mm-1
ω scans
26901 measured reflections
4995 independent reflections 3963 reflections with I > 2σ(I)
Rint = 0.042
θmax = 26.0°, θmin = 1.5°
h = −11→11
k = −12→12
l = −34→32
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.038
wR(F2) = 0.102
S = 1.05 4995 reflections 345 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained
w = 1/[σ2(F
o2) + (0.0537P)2 + 0.2246P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.14 e Å−3
Δρmin = −0.18 e Å−3
Special details
supporting information
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Acta Cryst. (2006). E62, o804–o806
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors.
Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to
zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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)
x y z Uiso*/Ueq
H5 1.04400 0.49740 0.26790 0.0670* H6 0.93310 0.45040 0.32940 0.0600* H7A 0.47170 0.79190 0.20440 0.1080* H7B 0.56170 0.89210 0.24450 0.1080* H7C 0.40180 0.84630 0.24480 0.1080* H8A 1.08640 0.52940 0.19270 0.1050* H8B 1.16640 0.64290 0.22870 0.1050* H8C 1.12640 0.66320 0.17120 0.1050* H10 0.57390 0.48590 0.42170 0.0570* H14 0.41430 1.02670 0.36200 0.0740* H15 0.64030 1.13940 0.38880 0.0810* H16 0.86250 1.02810 0.40760 0.0750* H17 0.86770 0.79820 0.40040 0.0630* H19A 0.16860 0.72290 0.32190 0.0680* H19B 0.21010 0.87410 0.32400 0.0680* H21 0.20190 1.00300 0.39510 0.0790* H22 0.16310 1.01890 0.47210 0.0920* H23 0.12570 0.82960 0.51320 0.0890* H24 0.13060 0.62470 0.47740 0.0830* H25 0.17720 0.60770 0.40200 0.0720* H27 0.50490 0.66610 0.46120 0.0730* H28 0.45220 0.74940 0.53090 0.0830* H29 0.63660 0.76260 0.60510 0.0850* H30 0.87840 0.70690 0.60890 0.0820* H31 0.93420 0.62780 0.53970 0.0700*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
supporting information
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Acta Cryst. (2006). E62, o804–o806
C13 0.0462 (7) 0.0462 (7) 0.0534 (7) −0.0007 (5) 0.0168 (5) 0.0003 (5) C14 0.0580 (8) 0.0474 (8) 0.0835 (10) 0.0049 (6) 0.0250 (7) 0.0001 (7) C15 0.0722 (10) 0.0463 (8) 0.0896 (11) −0.0079 (7) 0.0338 (9) −0.0055 (7) C16 0.0567 (8) 0.0584 (9) 0.0746 (10) −0.0143 (7) 0.0235 (7) −0.0095 (7) C17 0.0458 (7) 0.0568 (8) 0.0563 (7) −0.0041 (6) 0.0162 (6) −0.0034 (6) C18 0.0448 (6) 0.0478 (7) 0.0430 (6) −0.0002 (5) 0.0124 (5) −0.0010 (5) C19 0.0410 (7) 0.0602 (8) 0.0642 (8) 0.0062 (6) 0.0091 (6) 0.0021 (7) C20 0.0367 (6) 0.0543 (8) 0.0663 (8) 0.0034 (5) 0.0119 (6) −0.0021 (6) C21 0.0583 (8) 0.0557 (9) 0.0875 (11) −0.0012 (7) 0.0260 (8) −0.0057 (8) C22 0.0713 (10) 0.0709 (11) 0.0906 (12) −0.0057 (8) 0.0290 (9) −0.0259 (9) C23 0.0659 (10) 0.0896 (13) 0.0681 (10) 0.0022 (9) 0.0207 (8) −0.0080 (9) C24 0.0636 (9) 0.0708 (10) 0.0734 (10) 0.0080 (8) 0.0214 (8) 0.0089 (8) C25 0.0528 (8) 0.0527 (8) 0.0746 (9) 0.0056 (6) 0.0185 (7) 0.0003 (7) C26 0.0550 (7) 0.0491 (7) 0.0430 (6) 0.0016 (6) 0.0127 (5) 0.0050 (5) C27 0.0543 (8) 0.0751 (10) 0.0517 (7) 0.0049 (7) 0.0116 (6) 0.0020 (7) C28 0.0687 (10) 0.0733 (10) 0.0703 (10) 0.0088 (8) 0.0263 (8) −0.0039 (8) C29 0.0945 (12) 0.0630 (9) 0.0579 (9) 0.0041 (9) 0.0264 (8) −0.0088 (7) C30 0.0828 (11) 0.0607 (9) 0.0510 (8) 0.0063 (8) 0.0036 (7) −0.0058 (7) C31 0.0578 (8) 0.0565 (8) 0.0524 (7) 0.0035 (6) 0.0044 (6) −0.0003 (6)
Geometric parameters (Å, º)
O1—C4 1.3671 (19) C23—C24 1.373 (3)
O1—C8 1.414 (2) C24—C25 1.376 (2)
O2—C2 1.3601 (17) C26—C27 1.370 (2)
O2—C7 1.415 (2) C26—C31 1.383 (2)
O3—C9 1.2083 (17) C27—C28 1.385 (2) O4—C10 1.4015 (15) C28—C29 1.370 (2) O4—C26 1.3836 (16) C29—C30 1.374 (3) O5—C18 1.2154 (16) C30—C31 1.374 (2)
N1—C1 1.4166 (16) C3—H3 0.9300
N1—C9 1.3673 (17) C5—H5 0.9300
N1—C11 1.4774 (16) C6—H6 0.9300
N2—C13 1.4116 (18) C7—H7A 0.9600
N2—C18 1.3645 (17) C7—H7B 0.9600
N2—C19 1.4627 (19) C7—H7C 0.9600
C1—C2 1.3993 (17) C8—H8A 0.9600
C1—C6 1.3784 (19) C8—H8B 0.9600
C2—C3 1.3804 (19) C8—H8C 0.9600
C3—C4 1.388 (2) C10—H10 0.9800
C4—C5 1.378 (2) C14—H14 0.9300
C5—C6 1.386 (2) C15—H15 0.9300
C9—C10 1.5244 (18) C16—H16 0.9300
C13—C14 1.3772 (19) C23—H23 0.9300
C14—C15 1.388 (2) C24—H24 0.9300
C15—C16 1.372 (2) C25—H25 0.9300
C16—C17 1.390 (2) C27—H27 0.9300
C19—C20 1.5071 (19) C28—H28 0.9300
C20—C21 1.384 (2) C29—H29 0.9300
C20—C25 1.389 (2) C30—H30 0.9300
C21—C22 1.383 (3) C31—H31 0.9300
C22—C23 1.379 (3)
O2···C11 2.8195 (14) C19···H14 2.8900 O2···N1 2.7079 (14) C21···H14 3.0200 O2···N2 3.1231 (15) C22···H16x 2.9200
O2···C18 2.8145 (15) C23···H28 2.9200 O2···C12 2.9790 (14) C23···H17x 2.9300
O2···C13 3.1746 (16) C24···H17x 2.8500
O3···O4 3.0612 (14) C24···H28 3.0000 O3···C6 3.0909 (18) C25···H27 3.0000 O3···C31i 3.3846 (19) C25···H17x 2.9700
O4···N1 3.0200 (14) C26···H24v 2.9500
O4···O3 3.0612 (14) C27···H10 2.7100 O4···C17 3.2181 (17) C28···H10v 2.8700
O5···N1 3.0338 (15) C29···H21xi 2.9700
O1···H30ii 2.6500 C31···H24v 2.8300
O3···H15iii 2.6800 H3···C7 2.5500
O3···H31i 2.6800 H3···H7A 2.3000
O3···H6 2.4700 H3···H7B 2.4100
O3···H8Civ 2.7300 H5···C8 2.5200
O4···H24v 2.7600 H5···H8A 2.2900
O5···H10 2.7700 H5···H8B 2.3300
O5···H19A 2.6000 H6···O3 2.4700
O5···H7Bvi 2.8300 H6···C9 2.7000
N1···O2 2.7079 (14) H7A···C3 2.7600 N1···O4 3.0200 (14) H7A···H3 2.3000 N1···O5 3.0338 (15) H7B···C3 2.7900 N1···C7vi 3.397 (2) H7B···H3 2.4100
N2···O2 3.1231 (15) H7B···O5vii 2.8300
C1···C7vi 3.447 (2) H7C···C1vii 2.8700
C2···C12 3.4303 (16) H8A···C5 2.7500 C6···O3 3.0909 (18) H8A···H5 2.2900 C7···N1vii 3.397 (2) H8B···C5 2.7200
C7···C13 3.572 (2) H8B···H5 2.3300 C7···C1vii 3.447 (2) H8C···O3viii 2.7300
C8···C16iv 3.549 (3) H8C···C16iv 3.0000
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Acta Cryst. (2006). E62, o804–o806
C12···C27 3.5779 (18) H14···C19 2.8900 C12···O2 2.9790 (14) H14···C21 3.0200 C13···O2 3.1746 (16) H14···H19B 2.4400 C13···C7 3.572 (2) H14···H21 2.4400 C14···C21 3.522 (2) H14···H29xi 2.4200
C14···C20 3.581 (2) H15···O3xii 2.6800
C16···C8viii 3.549 (3) H16···C22ix 2.9200
C16···C22ix 3.593 (3) H17···C23ix 2.9300
C17···O4 3.2181 (17) H17···C24ix 2.8500
C18···O2 2.8145 (15) H17···C25ix 2.9700
C20···C14 3.581 (2) H19A···O5 2.6000 C21···C14 3.522 (2) H19A···C5x 2.7900
C22···C16x 3.593 (3) H19A···H25 2.5200
C24···C31v 3.540 (2) H19B···C14 2.8900
C26···C12 3.4665 (18) H19B···H14 2.4400 C27···C12 3.5779 (18) H19B···H21 2.4100 C27···C11 3.5453 (18) H19B···C4vii 3.1000
C31···C24v 3.540 (2) H21···H14 2.4400
C31···O3i 3.3846 (19) H21···H19B 2.4100
C1···H7Cvi 2.8700 H21···C29xi 2.9700
C3···H7A 2.7600 H23···C16xi 3.0900
C3···H7B 2.7900 H24···O4v 2.7600
C4···H19Bvi 3.1000 H24···C26v 2.9500
C5···H8A 2.7500 H24···C31v 2.8300
C5···H8B 2.7200 H25···H19A 2.5200
C5···H19Aix 2.7900 H27···C10 2.5800
C7···H3 2.5500 H27···C11 3.0400
C8···H5 2.5200 H27···C25 3.0000
C9···H6 2.7000 H27···H10 2.3200
C10···H27 2.5800 H28···C23 2.9200
C11···H27 3.0400 H28···C24 3.0000
C14···H19B 2.8900 H29···C14xi 3.0700
C14···H29xi 3.0700 H29···H14xi 2.4200
C16···H23xi 3.0900 H30···O1xiii 2.6500
C16···H8Cviii 3.0000 H31···O3i 2.6800
supporting information
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Acta Cryst. (2006). E62, o804–o806
N1—C9—C10—C11 2.37 (10) C28—C29—C30—C31 −1.8 (3) O3—C9—C10—C11 −179.93 (17) C29—C30—C31—C26 −1.0 (2)
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, −y+3/2, z−1/2; (iii) x, y−1, z; (iv) −x+2, y−1/2, −z+1/2; (v) −x+1, −y+1, −z+1; (vi) −x+1, y−1/2, −z+1/2; (vii) −x+1, y+1/2, −z+1/2; (viii) −x+2, y+1/2, −z+1/2; (ix) x+1, y, z; (x) x−1, y, z; (xi) −x+1, −y+2, −z+1; (xii) x, y+1, z; (xiii) x, −y+3/2, z+1/2.
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A