metal-organic papers
m1362
Ivor Wharfet al. [Ge(C6H5)3(N3)] DOI: 10.1107/S1600536804021221 Acta Cryst.(2004). E60, m1362±m1364 Acta Crystallographica Section EStructure Reports Online
ISSN 1600-5368
Azidotriphenylgermane
Ivor Wharfa* and Francine BeÂlanger-GarieÂpyb
aDepartment of Chemistry, Otto Maass Chemistry Building, McGill University, 801 Sherbrooke St. West, Montreal, Quebec, Canada H3A 2K6, andbDeÂpartement de Chimie, Universite de MontreÂal, CP 6128, Succ. Centre-ville, MontreÂal, QueÂbec, Canada H3C 3J7
Correspondence e-mail: [email protected]
Key indicators Single-crystal X-ray study
T= 220 K
Mean(C±C) = 0.003 AÊ Disorder in main residue
Rfactor = 0.033
wRfactor = 0.101
Data-to-parameter ratio = 14.3
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved
The title compound, [Ge(C6H5)3(N3)], (I), is monomeric with
quasi-tetrahedral geometry around germanium. The azide group (ÐNÐNÐN) is disordered. One form hasd(NÐ
N) >d(NÐN), the other has d(NÐN) <d(NÐN). In
contrast, the mesityl analogue, (II), hasd(NÐN) >d(NÐ
N). As expected, on going from (I) to (II), angle (CÐGeÐ
C)ave increases while angle (CÐGeÐN)ave decreases.
However, in contrast to the silicon case, d(GeÐN) and d(GeÐC)averemain effectively unchanged on going from (I)
to (II).
Comment
A few years ago, we determined the structures of several pseudohalotrimesitylgermanes [(Mes)3GeX: Mes =
2,4,6-tri-methylphenyl;X= CN, NCS, NCO, N3and OH] (Hiharaet al.,
2000) with the aim of comparing the geometries of these molecules with those of related phenylgermanium systems. However, only the structures of Ph3GeNCO (Tarkhovaet al.,
1976) and Ph3GeOH (Fergusonet al., 1992) were available for
this purpose at the time and only recently has the structure of Ph3GeH (McGrady et al., 2002) become available for
comparison with that of (Mes)3GeH (Lambert et al., 1998).
Thus, to enable a further comparison of this type to be made, we now report the structure of Ph3GeN3, (I).
Compound (I) is monomeric (Fig. 1) and is isostructural with Ph3SiN3(Wharf & Belanger-GarieÂpy, 2004). The average
CÐGeÐC angle [113.4 (1)] is greater than the average CÐ
GeÐN angle [105.1 (1)] (Table 1), with averaged (GeÐC) =
1.936 (2) AÊ and d(GeÐN1) = 1.8968 (17) AÊ. A similar geometry has been found for Ph3GeNCO (Tarkhova et al.,
1976), although the data are less precise than those given here. For (Mes)3GeN3, (II), the corresponding data are 115.6 (4),
102.2 (4), 1.95 (1) AÊ and 1.895 (9) AÊ, respectively. Thus, while
on going from (I) to (II), changes in average angles around Ge follow the trends predicted by Andose & Mislow (1974), for Ph3CH(Mes)3CH, no change in average d(GeÐC) and
d(GeÐN1) is apparent. In contrast, when comparing Ph3SiN3
with (Mes)3SiN3(Zigleret al., 1989), we found both average
d(SiÐC) andd(SiÐN1) to increase when Ph is replaced by Mes. Presumably, the longer GeÐC and GeÐN1 bonds are able to accommodate the distalo-CH3 N1interactions in (II)
without lengthening. However, the proximal o-CH3 o-CH3
interactions increase the average CÐGeÐC angle on going
from (I) to (II) to the same extent as found for the two analogous silicon compounds.
The azide group in (I) is disordered (50/50); one component
has d(N1ÐN21) > d(N21ÐN31) with GeÐN1ÐN21 =
118.1 (9) and N1ÐN21ÐN31 = 171.2 (2), while the second
component hasd(N1ÐN22) <d(N22ÐN32), GeÐN1ÐN22 = 121.3 (1) and N1ÐN22ÐN32 = 171 (3). This situation is
exactly comparable to that found for Ph3SiN3 (Wharf &
Belanger-GarieÂpy, 2004) and the same structural interpret-ation will thus apply. This may also account for the largeUeq
values noted for atoms N31 and N32.
Experimental
The title compound was prepared by re¯uxing chlorotriphenyl-germane (12.9 mmol, 4.36 g) in dry tetrahydrofuran (300 ml) with dried sodium azide (0.14 mol, 9.4 g) for 4 d. Evaporation of the ®ltrate under reduced pressure gave crude (I), which was recrys-tallized from hexane [m.p. 380±381 K; literature 380±380.5 K (Reichle, 1964)]. Analysis calculated for C18H15GeN3: C 62.50, H
4.37%; found: C 62.22, H 4.30%. X-ray quality crystals were obtained by slow evaporation of a hexane solution of (I).
Crystal data
[Ge(C6H5)3(N3)]
Mr= 345.92 Monoclinic,P21=n
a= 9.7428 (2) AÊ
b= 17.0689 (3) AÊ
c= 10.3630 (2) AÊ = 110.449 (1)
V= 1614.76 (5) AÊ3
Z= 4
Dx= 1.423 Mg mÿ3 CuKradiation
Cell parameters from 11289 re¯ections
= 4.6±72.9
= 2.56 mmÿ1
T= 220 (2) K Block, colourless 0.500.200.15 mm
Data collection
Bruker AXS SMART 2K/Platform diffractometer
!scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin= 0.403,Tmax= 0.681 13062 measured re¯ections
3097 independent re¯ections 2939 re¯ections withI> 2(I)
Rint= 0.026 max= 73.0
h=ÿ12!11
k=ÿ20!20
l=ÿ12!12
Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.033
wR(F2) = 0.101
S= 1.05 3097 re¯ections 217 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.084P)2] whereP= (Fo2+ 2Fc2)/3 (/)max= 0.001
max= 0.29 e AÊÿ3
min=ÿ0.62 e AÊÿ3
Table 1
Selected geometric parameters (AÊ,).
GeÐN1 1.8968 (17)
GeÐC11 1.9317 (18)
GeÐC21 1.9370 (16)
GeÐC31 1.9378 (17)
N1ÐN22 1.14 (2)
N1ÐN21 1.24 (2)
N21ÐN31 1.10 (2)
N22ÐN32 1.20 (3)
N1ÐGeÐC11 101.69 (9) N1ÐGeÐC21 107.51 (7) C11ÐGeÐC21 113.31 (7) N1ÐGeÐC31 106.27 (7) C11ÐGeÐC31 114.02 (7)
C21ÐGeÐC31 112.91 (7) N22ÐN1ÐGe 121.3 (1) N21ÐN1ÐGe 118.1 (9) N31ÐN21ÐN1 171.20 (19) N1ÐN22ÐN32 171 (3)
C11ÐGeÐN1ÐN22 158.20 (16) C21ÐGeÐN1ÐN22 38.90 (16) C31ÐGeÐN1ÐN22 ÿ82.20 (16) C11ÐGeÐN1ÐN21 169.90 (12) C21ÐGeÐN1ÐN21 50.60 (12) C31ÐGeÐN1ÐN21 ÿ70.60 (12)
N1ÐGeÐC11ÐC12 18.08 (17) N1ÐGeÐC11ÐC16 ÿ160.86 (15) N1ÐGeÐC21ÐC22 37.05 (16) N1ÐGeÐC21ÐC26 ÿ147.37 (14) N1ÐGeÐC31ÐC32 75.48 (16) N1ÐGeÐC31ÐC36 ÿ101.80 (15)
The azide group is found to be disordered with two sets of N atoms. The occupancy factor was originally re®ned but was then ®xed at 0.5 for each atom set in the ®nal cycles. All the H atoms were positioned geometrically (CÐH = 0.94 AÊ) and were included in the re®nement in the riding-model approximation, with Uiso(H) = 1.2Ueq(parent
atom).
Data collection:SMART(Bruker, 1999); cell re®nement:SAINT
(Bruker, 1999); data reduction:SAINT; program(s) used to solve structure:SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
SHELXTL (Bruker, 1997); software used to prepare material for publication: UdMX (Maris, 2004).
Financial support from the Fonds FQRNT du MinisteÁre de l'EÂducation du QueÂbec is gratefully acknowledged.
References
Andose, J. D. & Mislow, K. (1974).J. Am. Chem. Soc.96, 2168±2176. Bruker (1997). SHELXTL. Version 5.10. Bruker AXS Inc., Madison,
Wisconsin, USA.
Bruker (1999).SMART(Version 5.059) andSAINT(Version 6.06). Bruker AXS Inc., Madison, Wisconsin, USA.
Ferguson, G., Gallagher, J. F., Murphy, D., Spalding, T. R., Glidewell, C. & Holden, H. D. (1992).Acta Cryst.C48, 1228±1231.
Hihara, G., Hynes, R. C., Lebuis, A.-M., RivieÁre-Baudet, M., Wharf, I. & Onyszchuk, M. (2000).J. Organomet. Chem.598, 276±285.
Lambert, J. B., Stern, C. L., Zhao, Y., Tse, W. C., Shawl, C. E., Lentz, K. T. & Kania, L. (1998).J. Organomet. Chem.568, 21±31.
Maris, T. (2004).UdMX. Version 6.2. University of Montreal, Quebec, Canada.
metal-organic papers
Acta Cryst.(2004). E60, m1362±m1364 Ivor Wharfet al. [Ge(C6H5)3(N3)]
m1363
Figure 1
McGrady, G. S., Odlyha, M., Prince, P. & Steed, J. W. (2002).CrystEngComm.
4, 271±276.
Reichle, W. T. (1964).Inorg. Chem.3, 402±406.
Sheldrick, G. M. (1996).SADABS.Bruker AXS Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.
Tarkhova, T. N., Nikdaeva, L. E., Chupninov, E. V., Simonov, M. A. & Belov, N. V. (1976).Sov. Phys. Crystallogr.21, 216±218.
Wharf, I. & Belanger-GarieÂpy, F. (2004). Acta Cryst. E60, o1643± o1645.
Zigler, S. S., Haller, K. J. & West, R. (1989). Organometallics, 8, 1656± 1660.
metal-organic papers
supporting information
sup-1 Acta Cryst. (2004). E60, m1362–m1364
supporting information
Acta Cryst. (2004). E60, m1362–m1364 [https://doi.org/10.1107/S1600536804021221]
Azidotriphenylgermane
Ivor Wharf and Francine B
é
langer-Gari
é
py
azidotriphenylgermane
Crystal data [Ge(C6H5)3(N3)] Mr = 345.92 Monoclinic, P21/n Hall symbol: -P 2yn a = 9.7428 (2) Å b = 17.0689 (3) Å c = 10.3630 (2) Å β = 110.449 (1)° V = 1614.76 (5) Å3 Z = 4
F(000) = 704 Dx = 1.423 Mg m−3
Cu Kα radiation, λ = 1.54178 Å Cell parameters from 11289 reflections θ = 4.6–72.9°
µ = 2.56 mm−1 T = 220 K Block, colourless 0.50 × 0.20 × 0.15 mm
Data collection
Bruker AXS SMART 2K/Platform diffractometer
Radiation source: Sealed Tube Graphite monochromator
Detector resolution: 5.5 pixels mm-1 ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.403, Tmax = 0.681
13062 measured reflections 3097 independent reflections 2939 reflections with I > 2σ(I) Rint = 0.026
θmax = 73.0°, θmin = 5.2° h = −12→11
k = −20→20 l = −12→12
Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.033 wR(F2) = 0.101 S = 1.05 3097 reflections 217 parameters 48 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) + (0.084P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.001
supporting information
sup-2 Acta Cryst. (2004). E60, m1362–m1364
Special details
Experimental. X-ray crystallographic data for (A) were collected from a single-crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker Platform diffractometer, equipped with a Bruker SMART 2 K Charged-Coupled Device (CCD) Area Detector using the program SMART and normal focus sealed tube source graphite monochromated Cu—Kα radiation. The crystal-to-detector distance was 4.908 cm, and the data collection was carried out in 512 x 512 pixel mode, utilizing 4 x 4 pixel binning. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 9.0 degree scan in 30 frames over four different parts of the reciprocal space (120 frames total). One complete sphere of data was collected, to better than 0.8 Å resolution. Upon completion of the data collection, the first 101 frames were recollected in order to improve the decay correction analysis.
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)
x y z Uiso*/Ueq Occ. (<1)
Ge 0.601550 (19) 0.157792 (10) 0.247136 (18) 0.03403 (12) N1 0.5977 (2) 0.07986 (10) 0.11545 (17) 0.0478 (4)
N21 0.714 (2) 0.0634 (12) 0.099 (2) 0.050 (2) 0.50 N31 0.8132 (12) 0.0394 (6) 0.0859 (10) 0.080 (2) 0.50 N22 0.695 (3) 0.0702 (13) 0.081 (3) 0.070 (6) 0.50 N32 0.7848 (14) 0.0630 (7) 0.0263 (11) 0.100 (3) 0.50 C11 0.39515 (19) 0.17474 (11) 0.20953 (19) 0.0394 (4)
C12 0.2910 (2) 0.12018 (13) 0.1358 (2) 0.0505 (5)
H12 0.3207 0.0733 0.1058 0.061*
C13 0.1436 (3) 0.1353 (2) 0.1067 (3) 0.0709 (7)
H13 0.0735 0.0991 0.0544 0.085*
C14 0.0981 (3) 0.20283 (19) 0.1535 (3) 0.0734 (8)
H14 −0.0021 0.2118 0.1353 0.088*
C15 0.2001 (3) 0.25657 (17) 0.2266 (3) 0.0700 (7)
H15 0.1694 0.3028 0.2579 0.084*
C16 0.3488 (3) 0.24339 (13) 0.2549 (2) 0.0520 (5)
H16 0.4180 0.2807 0.3047 0.062*
C21 0.70042 (18) 0.24861 (9) 0.20908 (16) 0.0343 (3) C22 0.6816 (2) 0.27043 (11) 0.07444 (18) 0.0399 (4)
H22 0.6257 0.2386 0.0008 0.048*
C23 0.7443 (3) 0.33838 (10) 0.0478 (2) 0.0458 (4)
H23 0.7319 0.3523 −0.0433 0.055*
C24 0.8252 (2) 0.38585 (10) 0.1558 (2) 0.0456 (4)
H24 0.8664 0.4326 0.1378 0.055*
C25 0.8457 (2) 0.36478 (12) 0.2900 (2) 0.0473 (4)
H25 0.9016 0.3969 0.3632 0.057*
C26 0.7842 (2) 0.29643 (11) 0.31699 (18) 0.0424 (4)
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sup-3 Acta Cryst. (2004). E60, m1362–m1364
C31 0.7044 (2) 0.11211 (10) 0.42617 (17) 0.0368 (3) C32 0.8547 (2) 0.10394 (12) 0.4735 (2) 0.0478 (4)
H32 0.9083 0.1227 0.4201 0.057*
C33 0.9273 (2) 0.06822 (13) 0.5993 (2) 0.0562 (5)
H33 1.0298 0.0631 0.6312 0.067*
C34 0.8488 (3) 0.04029 (13) 0.6771 (2) 0.0561 (5)
H34 0.8979 0.0164 0.7625 0.067*
C35 0.6988 (2) 0.04728 (13) 0.6303 (2) 0.0533 (5)
H35 0.6454 0.0270 0.6828 0.064*
C36 0.6261 (2) 0.08424 (11) 0.50562 (19) 0.0440 (4)
H36 0.5238 0.0904 0.4751 0.053*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Ge 0.03553 (18) 0.03323 (17) 0.03152 (17) −0.00267 (5) 0.00942 (12) −0.00067 (5) N1 0.0491 (10) 0.0462 (8) 0.0462 (9) −0.0038 (7) 0.0142 (8) −0.0138 (7) N21 0.043 (4) 0.049 (3) 0.062 (5) −0.004 (3) 0.022 (4) −0.016 (3) N31 0.052 (3) 0.089 (5) 0.101 (6) −0.004 (3) 0.028 (4) −0.038 (4) N22 0.071 (9) 0.062 (7) 0.072 (7) −0.011 (5) 0.017 (6) −0.038 (6) N32 0.090 (7) 0.109 (8) 0.123 (8) −0.021 (5) 0.066 (7) −0.059 (6) C11 0.0372 (9) 0.0429 (8) 0.0357 (9) 0.0023 (7) 0.0098 (7) 0.0123 (7) C12 0.0428 (10) 0.0556 (11) 0.0466 (10) −0.0085 (8) 0.0076 (8) 0.0112 (8) C13 0.0439 (13) 0.0951 (19) 0.0633 (14) −0.0141 (12) 0.0057 (11) 0.0295 (14) C14 0.0445 (12) 0.0979 (19) 0.0799 (16) 0.0197 (12) 0.0242 (12) 0.0481 (15) C15 0.0674 (16) 0.0741 (15) 0.0806 (16) 0.0298 (12) 0.0412 (14) 0.0367 (13) C16 0.0532 (11) 0.0484 (10) 0.0576 (11) 0.0088 (8) 0.0233 (9) 0.0117 (9) C21 0.0340 (8) 0.0347 (8) 0.0336 (7) −0.0007 (6) 0.0111 (7) −0.0014 (6) C22 0.0418 (9) 0.0429 (9) 0.0340 (8) −0.0020 (7) 0.0119 (7) −0.0022 (7) C23 0.0508 (12) 0.0456 (11) 0.0445 (10) 0.0023 (7) 0.0210 (9) 0.0068 (6) C24 0.0445 (10) 0.0364 (8) 0.0595 (11) −0.0028 (6) 0.0228 (9) 0.0031 (7) C25 0.0453 (10) 0.0417 (9) 0.0486 (10) −0.0067 (8) 0.0084 (8) −0.0079 (8) C26 0.0493 (10) 0.0402 (8) 0.0344 (8) −0.0033 (7) 0.0103 (7) −0.0012 (6) C31 0.0391 (9) 0.0331 (8) 0.0345 (8) 0.0004 (6) 0.0084 (7) 0.0004 (6) C32 0.0401 (10) 0.0524 (10) 0.0486 (10) −0.0015 (7) 0.0125 (8) 0.0076 (8) C33 0.0407 (11) 0.0584 (12) 0.0596 (12) 0.0030 (8) 0.0049 (9) 0.0121 (9) C34 0.0583 (13) 0.0522 (11) 0.0461 (10) 0.0009 (9) 0.0037 (9) 0.0152 (9) C35 0.0581 (12) 0.0570 (11) 0.0454 (10) −0.0018 (9) 0.0188 (9) 0.0122 (8) C36 0.0418 (10) 0.0467 (9) 0.0427 (9) −0.0002 (7) 0.0139 (8) 0.0032 (7)
Geometric parameters (Å, º)
Ge—N1 1.8968 (17) C22—C23 1.383 (3)
Ge—C11 1.9317 (18) C22—H22 0.94
Ge—C21 1.9370 (16) C23—C24 1.383 (3)
Ge—C31 1.9378 (17) C23—H23 0.94
N1—N22 1.14 (2) C24—C25 1.382 (3)
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sup-4 Acta Cryst. (2004). E60, m1362–m1364
N21—N31 1.10 (2) C25—C26 1.384 (3)
N22—N32 1.20 (3) C25—H25 0.94
C11—C12 1.392 (3) C26—H26 0.94
C11—C16 1.395 (3) C31—C32 1.379 (3)
C12—C13 1.385 (3) C31—C36 1.388 (3)
C12—H12 0.94 C32—C33 1.388 (3)
C13—C14 1.382 (5) C32—H32 0.94
C13—H13 0.94 C33—C34 1.376 (3)
C14—C15 1.370 (4) C33—H33 0.94
C14—H14 0.94 C34—C35 1.375 (3)
C15—C16 1.392 (3) C34—H34 0.94
C15—H15 0.94 C35—C36 1.389 (3)
C16—H16 0.94 C35—H35 0.94
C21—C22 1.393 (2) C36—H36 0.94
C21—C26 1.395 (2)
N1—Ge—C11 101.69 (9) C23—C22—H22 119.6
N1—Ge—C21 107.51 (7) C21—C22—H22 119.6
C11—Ge—C21 113.31 (7) C22—C23—C24 119.79 (19)
N1—Ge—C31 106.27 (7) C22—C23—H23 120.1
C11—Ge—C31 114.02 (7) C24—C23—H23 120.1
C21—Ge—C31 112.91 (7) C25—C24—C23 120.18 (17)
N22—N1—Ge 121.3 (1) C25—C24—H24 119.9
N21—N1—Ge 118.1 (9) C23—C24—H24 119.9
N31—N21—N1 171.20 (19) C24—C25—C26 120.13 (17)
N1—N22—N32 171 (3) C24—C25—H25 119.9
C12—C11—C16 119.15 (19) C26—C25—H25 119.9 C12—C11—Ge 121.20 (16) C25—C26—C21 120.32 (17)
C16—C11—Ge 119.64 (15) C25—C26—H26 119.8
C13—C12—C11 119.7 (2) C21—C26—H26 119.8
C13—C12—H12 120.1 C32—C31—C36 119.35 (16)
C11—C12—H12 120.1 C32—C31—Ge 120.72 (14)
C14—C13—C12 121.0 (3) C36—C31—Ge 119.88 (14)
C14—C13—H13 119.5 C31—C32—C33 120.51 (18)
C12—C13—H13 119.5 C31—C32—H32 119.7
C15—C14—C13 119.5 (2) C33—C32—H32 119.7
C15—C14—H14 120.2 C34—C33—C32 119.8 (2)
C13—C14—H14 120.2 C34—C33—H33 120.1
C14—C15—C16 120.6 (3) C32—C33—H33 120.1
C14—C15—H15 119.7 C35—C34—C33 120.21 (18)
C16—C15—H15 119.7 C35—C34—H34 119.9
C15—C16—C11 120.0 (2) C33—C34—H34 119.9
C15—C16—H16 120 C34—C35—C36 120.09 (19)
C11—C16—H16 120 C34—C35—H35 120
C22—C21—C26 118.82 (16) C36—C35—H35 120
C22—C21—Ge 121.14 (12) C31—C36—C35 119.99 (18)
C26—C21—Ge 119.89 (13) C31—C36—H36 120
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sup-5 Acta Cryst. (2004). E60, m1362–m1364
