L Phenyl­alanine L phenyl­alaninium malonate

organic papers

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9H11NO2C9H12NO2+C3H3O4 doi:10.1107/S1600536805007014 Acta Cryst.(2005). E61, o992–o994 Acta Crystallographica Section E

Structure Reports

Online

ISSN 1600-5368

L

-Phenylalanine

-phenylalaninium malonate

M. Alagar,aR. V. Krishnakumar,b P. Parimala Deviaand

S. Natarajanc*

a_{Department of Physics, Ayya Nadar Janaki}

Ammal College, Sivakasi 626 123, India,

b_{Department of Physics, Thiagarajar College,}

Madurai 625 009, India, andc_{Department of}

Physics, Madurai Kamaraj University, Madurai 625 021, India

Correspondence e-mail: s_natarajan50@yahoo.com

Key indicators

Single-crystal X-ray study T= 293 K

Mean(C–C) = 0.006 A˚ Rfactor = 0.035 wRfactor = 0.101 Data-to-parameter ratio = 6.9

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography Printed in Great Britain – all rights reserved

The asymmetric unit of the title compound, C9H11NO2C9H12NO2

+

C3H3O4

, consists of two phenyl-alanine molecules, one as a zwitterion (P) and the other as a cation (P+), in addition to a malonate anion (Mal). The phenylalaninium and phenylalanine molecules are linked by a very shortsyn–syncarboxyl–carboxylate (–COO HOOC–) hydrogen bond [O O = 2.429 (4) A˚ ]. The Mal anion is stabilized by a strong intramolecular O—H O hydrogen bond. The aggregation of P and P+is mediated through Mal, leading to an infinite double chain along thecaxis.

Comment

l-Phenylalanine, an essential amino acid, forms many proton

transfer complexes with organic and inorganic acids. Inter-estingly, the crystal structure ofl-phenylalanine itself has not

yet been reported, but that of d-phenylalanine has been

published, with a highRfactor of 0.15 (Weissbuchet al., 1990). Precise X-ray crystal structure determinations of complexes of amino acids with carboxylic acids are expected to provide information regarding preferences of specific aggregation patterns, stoichiometry and ionization states of the constituent molecules. In a few instances, such complexes are also found to exhibit non-linear optical (NLO) properties. The present study reports the crystal structure of l-phenylalaninium

malonatel-phenylalanine, (I). Recently, the crystal structures

of l-phenylalaninium maleate (Alagar et al., 2001), dl

-phenylalaninium maleate (Alagar, Subha Nandhini et al., 2003) and l-phenylalanine fumaric acid (Alagar,

Krishna-kumaret al., 2003) have been reported.

Fig. 1 shows the molecular structure with the atom-numbering scheme. The asymmetric unit consists of two phenylalanine molecules, one as a zwitterion (P) and the other as a cation (P+), in addition to a malonate anion (Mal). The phenylalaninium and phenylalanine molecules are linked by a very shortsyn–syncarboxyl–carboxylate (–COO HOOC–) Speakman-salt-type hydrogen bond [O O = 2.429 (4) A˚ ]. Such strong interactions (with a normal range of 2.50–2.60 A˚ and a minimum of 2.40 A˚ ) have already been thoroughly investigated (Speakman, 1972). The preferential formation of a PP+aggregate, as observed in the case ofl-phenylalaninium

formate l-phenylalanine (henceforth PHEFOR) (Go¨rbitz &

Etter, 1992), may be attributed to the specific stability asso-ciated with the nearly symmetric short hydrogen bonds between chemically identical groups. The geometry of the carboxylate group of P is unusual, with unequal C1A—O1A

and C1A—O2A bonds [1.217 (4) and 1.285 (3) A˚ , respec-tively], presumably as a result of the participation of O2Ain the formation of the PP+ aggregate. The side-chain confor-mations of P and P+_{are found to begauche}+_{, as observed in}

PHEFOR (Table 1). The Mal anion is essentially planar, except for the methylene H atoms, and is stabilized by a strong intramolecular O—H O hydrogen bond. The O3 O6 distance, 2.413 (4) A˚ , agrees well with the values expected for

a symmetrical hydrogen bond (Gilliet al., 1994). However, as evidenced in Table 2, the intramolecular hydrogen bond is asymmetric. Similar instances involving Mal have been observed in several other crystal structures (Briggman & Oskarsson, 1978; Djinovic´et al., 1990; Kalsbeek, 1992; Barnes & Weakley, 2000; Saraswathi & Vijayan, 2002a,b).

Fig. 2 shows the packing of molecules, viewed along theb

axis. The further aggregation of P and P+is mediated through Mal, leading to an infinite double chain along the c axis. There are no direct hydrogen-bonded head-to-tail P—P or P+—P+interactions. However, the amino group of P forms a hydrogen bond with the carboxylic acid group of P+andvice versa. The double chain on either side is flanked by the hydrophobic side chains of P and P+, both occurring alter-nately along theaandcaxes. Thus, the double chain is char-acterized by thick layers of alternating hydrophilic and hydrophobic zones along theaaxis. The distance between the centroids of P and P+ [8.943 (4) A˚ ] and the angle between their planes [70.2 (1)_{] leads to edge-to-face phenyl–phenyl}

interactions among P—P and P+—P+, a phenomenon observed in PHEFOR. The aggregation pattern, stoichiometry and ionization states of individual molecules show striking similarities with other phenylalanine–carboxylic acid complexes.

Experimental

Colourless single crystals of (I) were grown, as transparent needles, from a saturated aqueous solution containingl-phenylalanine and malonic acid in a 1:1 stoichiometric ratio.

Crystal data

C9H11NO2C9H12NO2+C3H3O4

Mr= 434.44

Monoclinic,P21 a= 14.031 (3) A˚ b= 5.5082 (10) A˚ c= 14.601 (3) A˚ = 107.412 (3)

V= 1076.7 (4) A˚3 Z= 2

Dx= 1.340 Mg m 3 Dm= 1.35 Mg m

3

Dmmeasured by flotation in a

mixture of xylene and bromoform MoKradiation

Cell parameters from 25 reflections

= 7.4–16.3

= 0.10 mm1 T= 293 (2) K

Block cut from a needle, colourless 0.300.220.15 mm

Data collection

Nonius MACH3 four-circle diffractometer

!/2scans

Absorption correction: scan (Northet al., 1968) Tmin= 0.89,Tmax= 0.98 2761 measured reflections 2032 independent reflections 1921 reflections withI> 2(I)

Rint= 0.049 max= 25.0 h=1!16 k=1!5 l=17!16 3 standard reflections

frequency: 60 min intensity decay: none

Refinement

Refinement onF2 R[F2> 2(F2)] = 0.035 wR(F2_{) = 0.101} S= 1.06 2032 reflections 296 parameters

H atoms treated by a mixture of independent and constrained refinement

w= 1/[2_(F

o2) + (0.0587P)2 + 0.0894P]

whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001

max= 0.16 e A˚

3

min=0.17 e A˚

3

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Acta Cryst.(2005). E61, o992–o994 Alagaret al. _C

9H11NO2C9H12NO2+C3H3O4

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Figure 2

Packing diagram of the molecules of (I), viewed down thebaxis. Dashed lines indicate hydrogen bonds. C-bound H atoms have been omitted.

Figure 1

Table 1

Selected geometric parameters (A˚ ,_).

O1A—C1A 1.217 (4) O2A—C1A 1.285 (3) N1A—C2A 1.480 (4) O1B—C1B 1.226 (4) O2B—C1B 1.271 (4) O2B—H2B 0.91 (8) N1B—C2B 1.484 (4) O3—C10 1.284 (5)

O3—H3 1.05 (4)

O4—C10 1.204 (5) O5—C12 1.213 (4) O6—C12 1.291 (5) C10—C11 1.496 (5) C11—C12 1.501 (5) C11—H1 1.01 (6) C11—H2 0.95 (5)

O1A—C1A—C2A—N1A 2.7 (4) O2A—C1A—C2A—N1A 177.6 (2) N1A—C2A—C3A—C4A 66.9 (4) C2A—C3A—C4A—C5A 90.0 (4) C2A—C3A—C4A—C9A 89.3 (4)

O1B—C1B—C2B—N1B 2.4 (4) O2B—C1B—C2B—N1B 177.4 (3) N1B—C2B—C3B—C4B 61.7 (4) C2B—C3B—C4B—C5B 85.8 (4) C2B—C3B—C4B—C9B 94.5 (4)

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

N1A—H5 O4i

0.89 1.90 2.699 (4) 148 N1A—H6 O3ii 0.89 2.06 2.889 (4) 154 N1A—H7 O1Biii

0.89 1.90 2.757 (3) 160 N1B—H16 O5iv

0.89 2.12 3.005 (4) 174 N1B—H17 O5 0.89 2.35 3.167 (5) 152 N1B—H18 O1Av

0.89 2.05 2.864 (3) 152 O2B—H2B O2Avi

0.91 (8) 1.53 (8) 2.429 (4) 175 (6) O3—H3 O6 1.04 (4) 1.41 (4) 2.413 (4) 160 (4)

Symmetry codes: (i) x;y;zþ1; (ii) x;y1;zþ1; (iii) xþ1;y1

2;zþ1; (iv)

x;y1;z; (v)xþ1;yþ1

2;zþ1; (vi)x;yþ1;z.

The H atoms attached to O2B, O3 and C11 were located in a difference map and refined freely; the O—H and C—H distances are listed in Table 1. All other H atoms were positioned geometrically and were allowed to ride on their parent atoms, with C—H = 0.93– 0.98 A˚ , N—H = 0.89 A˚, andUiso(H) = 1.2Ueq(C) and 1.5Ueq(N). The absolute configuration of (I) was not established by the analysis but is known from the configuration of the starting reagents. In the absence

of significant anomalous dispersion effects, Friedel pairs were aver-aged.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement:CAD-4 EXPRESS; data reduction:XCAD4(Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS97

(Sheldrick, 1990); program(s) used to refine structure:SHELXL97

(Sheldrick, 1997); molecular graphics:PLATON(Spek, 2003); soft-ware used to prepare material for publication:SHELXL97.

MA thanks the Management and Principal of Ayya Nadar Janaki Ammal College, Sivakasi, for permission to use the computer facility of the FIST laboratory. The authors thank the UGC for the DRS programme and the DST, Government of India, for the FIST programme.

References

Alagar, M., Krishnakumar, R. V. & Natarajan, S. (2001).Acta Cryst.E57, o968–970.

Alagar, M., Krishnakumar, R. V., Rajagopal, K., Subha Nandhini, M. & Natarajan, S. (2003).Acta Cryst.E59, o952–o954.

Alagar, M., Subha Nandhini, M., Krishnakumar, R. V., Mostad, A. & Natarajan, S. (2003).Acta Cryst.E59, o209–211.

Barnes, J. C. & Weakley, T. J. R. (2000).Acta Cryst.C56, e346–e347. Briggman, B. & Oskarsson, A. (1978).Acta Cryst.B34, 3357–3359. Djinovic´, K., Golic, L. & Leban, I. (1990).Acta Cryst.C46, 281–286. Enraf–Nonius (1994). CAD-4 EXPRESS. Version 5.1/1.2. Enraf–Nonius,

Delft, The Netherlands.

Gilli, P., Bertolasi, V., Ferretti, V. & Gilli, G. (1994).J. Am. Chem. Soc.116, 909–915.

Go¨rbitz, C. H. & Etter, M. C. (1992).Acta Cryst.C48, 1317–1320.

Harms, K. & Wocadlo, S. (1996).XCAD4. University of Marburg, Germany. Kalsbeek, N. (1992).Acta Cryst.C48, 878–883.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst.A24, 351– 359.

Saraswathi, N. T. & Vijayan, M. (2002a).Acta Cryst.B58, 734–739. Saraswathi, N. T. & Vijayan, M. (2002b).Acta Cryst.B58, 1051–1056. Sheldrick, G. M. (1990).Acta Cryst.A46, 467–473.

Sheldrick, G. M. (1997).SHELXL97. University of Go¨ttingen, Germany. Speakman, J. C. (1972).Struct. Bonding,12, 141–199.

Spek, A. L. (2003).J. Appl. Cryst.36, 7–13.

Weissbuch, I., Frolow, F., Addadi, L., Lahav, M. & Leiserowitz, L. (1990).J. Am. Chem. Soc.112, 7718–7724.

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Acta Cryst. (2005). E61, o992–o994

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Acta Cryst. (2005). E61, o992–o994 [https://doi.org/10.1107/S1600536805007014]

L

-Phenylalanine

-phenylalaninium malonate

M. Alagar, R. V. Krishnakumar, P. Parimala Devi and S. Natarajan

L-Phenylalaninium malonate L-phenylalanine

Crystal data

C9H12NO2+·C3H3O4−·C9H11NO2 Mr = 434.44

Monoclinic, P21 Hall symbol: P 2yb a = 14.031 (3) Å b = 5.5082 (10) Å c = 14.601 (3) Å β = 107.412 (3)° V = 1076.7 (4) Å3 Z = 2

F(000) = 460

Dx = 1.340 Mg m−3 Dm = 1.35 Mg m−3

Dm measured by flotation in a mixture of xylene and bromoform

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 25 reflections θ = 7.4–16.3°

µ = 0.10 mm−1 T = 293 K

Block cut from a needle, colourless 0.30 × 0.22 × 0.15 mm

Data collection

Nonius MACH3 four-circle diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω/2θ scans

Absorption correction: ψ scans (North et al., 1968)

Tmin = 0.89, Tmax = 0.98 2761 measured reflections

2032 independent reflections 1921 reflections with I > 2σ(I) Rint = 0.049

θmax = 25.0°, θmin = 2.4° h = −1→16

k = −1→5 l = −17→16

3 standard reflections every 60 min min intensity decay: none

Refinement

Refinement on F2 Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.035} wR(F2_{) = 0.101} S = 1.06 2032 reflections 296 parameters 1 restraint

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(F

o2) + (0.0587P)2 + 0.0894P] where P = (Fo2 + 2Fc2)/3

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Acta Cryst. (2005). E61, o992–o994

Special details

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 F}2_, conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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

O1A 0.58881 (16) −0.0208 (4) 0.67715 (16) 0.0451 (6)

O2A 0.69402 (18) 0.0977 (5) 0.59800 (15) 0.0516 (6)

N1A 0.58236 (18) 0.4156 (5) 0.75437 (17) 0.0398 (6)

H5 0.5865 0.5664 0.7771 0.060*

H6 0.6008 0.3114 0.8031 0.060*

H7 0.5197 0.3848 0.7197 0.060*

C1A 0.6407 (2) 0.1314 (7) 0.65476 (18) 0.0350 (7)

C2A 0.6491 (2) 0.3891 (6) 0.6933 (2) 0.0367 (7)

H8 0.6247 0.4988 0.6384 0.044*

C3A 0.7560 (2) 0.4637 (7) 0.7471 (2) 0.0445 (8)

H9 0.7945 0.4673 0.7019 0.053*

H10 0.7549 0.6273 0.7713 0.053*

C4A 0.8083 (2) 0.3008 (7) 0.8296 (2) 0.0419 (8)

C5A 0.8034 (2) 0.3435 (8) 0.9211 (2) 0.0517 (9)

H11 0.7689 0.4782 0.9328 0.062*

C6A 0.8496 (3) 0.1871 (10) 0.9961 (3) 0.0637 (12)

H12 0.8449 0.2157 1.0573 0.076*

C7A 0.9020 (3) −0.0091 (9) 0.9792 (3) 0.0670 (12)

H13 0.9335 −0.1127 1.0295 0.080*

C8A 0.9083 (3) −0.0533 (9) 0.8897 (3) 0.0648 (11)

H14 0.9437 −0.1872 0.8786 0.078*

C9A 0.8618 (2) 0.1018 (8) 0.8150 (3) 0.0518 (9)

H15 0.8667 0.0713 0.7539 0.062*

O1B 0.59595 (16) 0.8585 (4) 0.38890 (14) 0.0454 (6)

O2B 0.6945 (2) 0.7031 (5) 0.52394 (15) 0.0511 (7)

N1B 0.59996 (19) 0.4656 (6) 0.28503 (18) 0.0498 (8)

H16 0.6046 0.3242 0.2572 0.075*

H17 0.6260 0.5824 0.2578 0.075*

H18 0.5360 0.4985 0.2778 0.075*

C1B 0.6462 (2) 0.6927 (6) 0.4353 (2) 0.0351 (7)

C2B 0.6554 (2) 0.4516 (6) 0.3888 (2) 0.0405 (8)

H19 0.6226 0.3286 0.4174 0.049*

C3B 0.7628 (3) 0.3704 (7) 0.4048 (2) 0.0509 (9)

H20 0.7948 0.3542 0.4733 0.061*

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C4B 0.8251 (2) 0.5363 (7) 0.3644 (2) 0.0476 (9)

C5B 0.8746 (3) 0.7326 (8) 0.4152 (3) 0.0642 (11)

H22 0.8697 0.7637 0.4763 0.077*

C6B 0.9320 (3) 0.8860 (10) 0.3767 (4) 0.0876 (16)

H23 0.9642 1.0193 0.4116 0.105*

C7B 0.9407 (4) 0.8400 (12) 0.2874 (5) 0.0956 (17)

H24 0.9800 0.9402 0.2622 0.115*

C8B 0.8923 (3) 0.6490 (13) 0.2360 (4) 0.0869 (16)

H25 0.8972 0.6196 0.1749 0.104*

C9B 0.8359 (3) 0.4981 (10) 0.2742 (3) 0.0669 (12)

H26 0.8039 0.3661 0.2382 0.080*

O3 0.5881 (2) 1.1472 (6) −0.07408 (19) 0.0589 (7)

O4 0.6056 (3) 0.7746 (8) −0.1150 (2) 0.0960 (12)

O5 0.6289 (2) 0.9821 (7) 0.20181 (17) 0.0725 (9)

O6 0.6179 (3) 1.2600 (6) 0.0918 (2) 0.0754 (9)

C10 0.6087 (3) 0.9229 (7) −0.0535 (2) 0.0469 (9)

C11 0.6397 (3) 0.8519 (7) 0.0501 (2) 0.0479 (9)

C12 0.6273 (3) 1.0375 (8) 0.1209 (2) 0.0478 (9)

H2B 0.695 (4) 0.846 (15) 0.555 (4) 0.13 (2)*

H3 0.598 (3) 1.232 (8) −0.008 (3) 0.063 (11)*

H1 0.604 (4) 0.698 (12) 0.059 (4) 0.11 (2)*

H2 0.708 (4) 0.807 (12) 0.070 (3) 0.105 (17)*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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C8B 0.075 (3) 0.104 (5) 0.094 (3) 0.000 (3) 0.046 (3) 0.004 (4) C9B 0.060 (2) 0.079 (3) 0.068 (2) −0.009 (3) 0.0290 (19) −0.013 (2) O3 0.0733 (17) 0.0552 (19) 0.0512 (14) 0.0043 (15) 0.0234 (13) 0.0085 (14) O4 0.137 (3) 0.097 (3) 0.0601 (17) −0.001 (2) 0.0377 (18) −0.040 (2) O5 0.0910 (18) 0.093 (2) 0.0364 (12) −0.003 (2) 0.0235 (12) −0.0102 (15) O6 0.122 (3) 0.0373 (18) 0.079 (2) −0.0065 (17) 0.0494 (19) −0.0192 (15) C10 0.0553 (19) 0.046 (3) 0.0431 (18) −0.0014 (19) 0.0206 (15) −0.0072 (17) C11 0.067 (2) 0.035 (2) 0.0446 (18) 0.006 (2) 0.0211 (17) −0.0050 (17) C12 0.0516 (19) 0.058 (3) 0.0367 (17) −0.0084 (19) 0.0176 (14) −0.0102 (18)

Geometric parameters (Å, º)

O1A—C1A 1.217 (4) N1B—H17 0.8900

O2A—C1A 1.285 (3) N1B—H18 0.8900

N1A—C2A 1.480 (4) C1B—C2B 1.514 (4)

N1A—H5 0.8900 C2B—C3B 1.521 (5)

N1A—H6 0.8900 C2B—H19 0.9800

N1A—H7 0.8900 C3B—C4B 1.502 (5)

C1A—C2A 1.519 (5) C3B—H20 0.9700

C2A—C3A 1.526 (4) C3B—H21 0.9700

C2A—H8 0.9800 C4B—C5B 1.376 (6)

C3A—C4A 1.505 (5) C4B—C9B 1.387 (5)

C3A—H9 0.9700 C5B—C6B 1.397 (7)

C3A—H10 0.9700 C5B—H22 0.9300

C4A—C5A 1.378 (4) C6B—C7B 1.368 (8)

C4A—C9A 1.381 (5) C6B—H23 0.9300

C5A—C6A 1.391 (6) C7B—C8B 1.351 (8)

C5A—H11 0.9300 C7B—H24 0.9300

C6A—C7A 1.371 (6) C8B—C9B 1.375 (7)

C6A—H12 0.9300 C8B—H25 0.9300

C7A—C8A 1.358 (6) C9B—H26 0.9300

C7A—H13 0.9300 O3—C10 1.284 (5)

C8A—C9A 1.386 (6) O3—H3 1.05 (4)

C8A—H14 0.9300 O4—C10 1.204 (5)

C9A—H15 0.9300 O5—C12 1.213 (4)

O1B—C1B 1.226 (4) O6—C12 1.291 (5)

O2B—C1B 1.271 (4) C10—C11 1.496 (5)

O2B—H2B 0.91 (8) C11—C12 1.501 (5)

N1B—C2B 1.484 (4) C11—H1 1.01 (6)

N1B—H16 0.8900 C11—H2 0.95 (5)

C2A—N1A—H5 109.5 O1B—C1B—C2B 121.2 (3)

C2A—N1A—H6 109.5 O2B—C1B—C2B 113.9 (3)

H5—N1A—H6 109.5 N1B—C2B—C1B 108.9 (3)

C2A—N1A—H7 109.5 N1B—C2B—C3B 111.4 (2)

H5—N1A—H7 109.5 C1B—C2B—C3B 113.8 (3)

H6—N1A—H7 109.5 N1B—C2B—H19 107.5

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O1A—C1A—C2A 122.0 (3) C3B—C2B—H19 107.5

O2A—C1A—C2A 112.3 (3) C4B—C3B—C2B 115.3 (3)

N1A—C2A—C1A 108.8 (3) C4B—C3B—H20 108.4

N1A—C2A—C3A 111.4 (2) C2B—C3B—H20 108.4

C1A—C2A—C3A 113.4 (3) C4B—C3B—H21 108.4

N1A—C2A—H8 107.7 C2B—C3B—H21 108.4

C1A—C2A—H8 107.7 H20—C3B—H21 107.5

C3A—C2A—H8 107.7 C5B—C4B—C9B 116.8 (4)

C4A—C3A—C2A 114.8 (3) C5B—C4B—C3B 121.7 (3)

C4A—C3A—H9 108.6 C9B—C4B—C3B 121.5 (4)

C2A—C3A—H9 108.6 C4B—C5B—C6B 121.1 (4)

C4A—C3A—H10 108.6 C4B—C5B—H22 119.4

C2A—C3A—H10 108.6 C6B—C5B—H22 119.4

H9—C3A—H10 107.5 C7B—C6B—C5B 119.9 (5)

C5A—C4A—C9A 118.1 (3) C7B—C6B—H23 120.0

C5A—C4A—C3A 121.4 (3) C5B—C6B—H23 120.0

C9A—C4A—C3A 120.5 (3) C8B—C7B—C6B 120.0 (5)

C4A—C5A—C6A 120.7 (4) C8B—C7B—H24 120.0

C4A—C5A—H11 119.6 C6B—C7B—H24 120.0

C6A—C5A—H11 119.6 C7B—C8B—C9B 120.0 (5)

C7A—C6A—C5A 119.7 (4) C7B—C8B—H25 120.0

C7A—C6A—H12 120.1 C9B—C8B—H25 120.0

C5A—C6A—H12 120.1 C8B—C9B—C4B 122.2 (5)

C8A—C7A—C6A 120.4 (4) C8B—C9B—H26 118.9

C8A—C7A—H13 119.8 C4B—C9B—H26 118.9

C6A—C7A—H13 119.8 C10—O3—H3 105 (2)

C7A—C8A—C9A 119.8 (4) C12—O6—H3 101.9 (19)

C7A—C8A—H14 120.1 O4—C10—O3 121.6 (4)

C9A—C8A—H14 120.1 O4—C10—C11 120.7 (4)

C4A—C9A—C8A 121.2 (4) O3—C10—C11 117.7 (3)

C4A—C9A—H15 119.4 C10—C11—C12 117.4 (3)

C8A—C9A—H15 119.4 C10—C11—H1 110 (3)

C1B—O2B—H2B 118 (4) C12—C11—H1 108 (3)

C2B—N1B—H16 109.5 C10—C11—H2 110 (3)

C2B—N1B—H17 109.5 C12—C11—H2 107 (3)

H16—N1B—H17 109.5 H1—C11—H2 104 (5)

C2B—N1B—H18 109.5 O5—C12—O6 122.0 (4)

H16—N1B—H18 109.5 O5—C12—C11 121.8 (4)

H17—N1B—H18 109.5 O6—C12—C11 116.2 (3)

O1B—C1B—O2B 124.9 (3)

O1A—C1A—C2A—N1A −2.7 (4) O1B—C1B—C2B—C3B 127.3 (3)

O2A—C1A—C2A—N1A 177.6 (2) O2B—C1B—C2B—C3B −52.6 (4)

O1A—C1A—C2A—C3A 121.9 (3) N1B—C2B—C3B—C4B 61.7 (4)

O2A—C1A—C2A—C3A −57.8 (3) C1B—C2B—C3B—C4B −61.7 (4)

N1A—C2A—C3A—C4A 66.9 (4) C2B—C3B—C4B—C5B 85.8 (4)

C1A—C2A—C3A—C4A −56.3 (3) C2B—C3B—C4B—C9B −94.5 (4)

supporting information

sup-6

Acta Cryst. (2005). E61, o992–o994

C2A—C3A—C4A—C9A 89.3 (4) C3B—C4B—C5B—C6B −179.7 (4)

C9A—C4A—C5A—C6A −1.3 (5) C4B—C5B—C6B—C7B −0.9 (7)

C3A—C4A—C5A—C6A 178.0 (3) C5B—C6B—C7B—C8B 1.2 (8)

C4A—C5A—C6A—C7A 1.2 (6) C6B—C7B—C8B—C9B −1.3 (8)

C5A—C6A—C7A—C8A −0.7 (6) C7B—C8B—C9B—C4B 1.0 (8)

C6A—C7A—C8A—C9A 0.3 (6) C5B—C4B—C9B—C8B −0.6 (6)

C5A—C4A—C9A—C8A 0.9 (5) C3B—C4B—C9B—C8B 179.7 (4)

C3A—C4A—C9A—C8A −178.4 (3) O4—C10—C11—C12 −171.2 (4)

C7A—C8A—C9A—C4A −0.4 (6) O3—C10—C11—C12 10.4 (5)

O1B—C1B—C2B—N1B 2.4 (4) C10—C11—C12—O5 163.4 (3)

O2B—C1B—C2B—N1B −177.4 (3) C10—C11—C12—O6 −18.7 (5)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N1A—H5···O4i _{0.89 1.90 2.699 (4) 148}

N1A—H6···O3ii _{0.89 2.06 2.889 (4) 154}

N1A—H7···O1Biii _{0.89 1.90 2.757 (3) 160}

N1B—H16···O5iv _{0.89 2.12 3.005 (4) 174}

N1B—H17···O5 0.89 2.35 3.167 (5) 152

N1B—H18···O1Av _{0.89 2.05 2.864 (3) 152}

O2B—H2B···O2Avi _{0.91 (8) 1.53 (8) 2.429 (4) 175 (6)}

O3—H3···O6 1.04 (4) 1.41 (4) 2.413 (4) 160 (4)