DL Valinium perchlorate

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organic papers

o28

B. Sridharet al. C5H12NO2+ClO4ÿ DOI: 10.1107/S1600536802022225 Acta Cryst.(2003). E59, o28±o30

Acta Crystallographica Section E

Structure Reports

Online

ISSN 1600-5368

DL

-Valinium perchlorate

B. Sridhar,a_{N. Srinivasan,}b

Bjoern Dalhusc_{and R. K.}

Rajarama_*

a_{Department of Physics, Madurai Kamaraj}

University, Madurai 625 021, India,b

Depart-ment of Physics, Thiagarajar College, Madurai 625 009, India, andc_{Department of Chemistry,}

University of Oslo, Blindern, N-0315 Oslo, Norway

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 105 K

Mean(C±C) = 0.002 AÊ

Rfactor = 0.036

wRfactor = 0.105

Data-to-parameter ratio = 32.2

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

The title compound, C5H12NO2+ClO4ÿ, crystallizes in the

triclinic space group P1 with four valinium cations and four perchlorate anions in the asymmetric unit. In the crystal, three of the four crystallographically independent valinium residues are linked to the perchlorate anionsviaOÐH O hydrogen bonds. The fourth residue, on the other hand, forms OÐ H O hydrogen bonds with an inversion-related residue, thereby forming a dimer. Both class I and class III hydrogen-bonding patterns are observed. All the four residues have similargaucheII±gaucheI side-chain conformations.

Comment

Valine is a chain amino acid. Generally branched-chain amino acids (BCAA) such as leucine, isoleucine and valine play a vital role in tissue repair and also provide energy directly to muscle tissue. The crystal structures of l-valine hydrochloride (Parthasarathy, 1966; Ando et al., 1967), l -valine hydrochloride monohydrate (Rao, 1969), dl-valine (Mallikarjunan & Rao, 1969; Dalhus & GoÈrbitz, 1996a), l -valine (Torri & Iitaka, 1970; Dalhus & GoÈrbitz, 1996b),dl -valine nitrate (Rao & Parthasarathy, 1974), l-valine nitrate (Srinivasanet al., 1997) and l-valine l-valinium perchlorate monohydrate (Pandiarajanet al., 2001) have been reported. In the present study, the crystal structure of dl-valinium perchlorate, (I), was undertaken. Recently, a closely related crystal structure of dl-valinium nitrate, in the triclinic space groupP1 withz= 8, was solved in our laboratory (Srinivasan

et al., 2002).

The asymmetric unit contains four crystallographically independent valinium residues (I, II, III and IV) and four independent perchlorate anions (1, 2, 3 and 4). The ClÐO bond distances and OÐClÐO bond angles show nearly ideal tetrahedral geometry. The CÐO distances and OÐCÐC angles show the existence of the carboxyl group in all four valinium residues. The backbone torsion angle 1_{indicates a}

cisconformation for all four valinium residues. The deviations of -amino nitrogen atoms N1, N2, N3 and N4 from the corresponding carboxyl planes are 0.052 (2), 0.022 (2), 0.477 (2) and 0.006 (2) AÊ, respectively. This tendency of the CÐN bond to twist is commonly found in amino acids (Lakshminarayananet al., 1967). All three possible side-chain

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rotamers (gauche I/gauche II, gauche I/trans andgauche II/

trans) are observed for valine residues in crystals (Torri & Iitaka, 1970). In the present structure, the torsion angles11

and12_are _gauche_{II and}_gauche_{I, respectively, for all four}

valinium residues.

Only 11 of the 16 O atoms in the perchlorate anions take part in hydrogen bonding. The perchlorate anions connect the carboxyl group of valinium residues I, II and IV by OÐH O hydrogen bonding. Interestingly, in residue III, the carboxyl O atom forms a rather strong OÐH O [2.638 (1) AÊ] hydrogen bond with its inversion-related equivalent, resulting in a dimer. Since the H atom, H3B, is closer to the donor carboxyl O atom, it may be termed an asymmetric hydrogen bond (Olovssonet al., 2001). Further, the H atom shows asyn-syn

orientation with respect to the donor and acceptor carboxyl groups [H3BÐO3BÐC31ÐO3A is ÿ0.6 (14) _and

H3B O3Biii_±C31iii_±O3_Aiii _is_{ÿ4.2 (4)}_{; symmetry code: (iii)}

2ÿx, 1ÿy,ÿz]. This type ofsyn-synorientation is also found in betaine betainium oxalate (Rodrigueset al., 2001).

The amino N atoms of residues I and III form NÐH O hydrogen bonds with carboxyl groups of neighbouring val-inium residues, as well as O atoms of the surrounding perchlorate anions. In contrast, the amino N atoms of residues II and IV interact only with perchlorate anions. A class I hydrogen-bonding pattern, with three two-centered hydrogen bonds, is observed for residues I and III. Chelated and three-centered hydrogen bonds are observed in residues II and IV, leading to a class III hydrogen-bonding pattern, with two three-centered and one two-centered hydrogen bonds (Jeffrey & Saenger, 1991). The aggregation of hydrophilic double layers, stacked between hydrophobic double layers parallel to thebcplane at x= 0 plane, is observed. Similar aggregation patterns are also observed indl-valinium nitrate (Srinivasan

et al., 2002).

Experimental

The title compound was crystallized by slow evaporation from an aqueous solution ofdl-valine and perchloric acid in a 1:1 stoichio-metric ratio.

Crystal data

C5H12NO2+ClO4ÿ

Mr= 217.61 Triclinic,P1 a= 10.3005 (6) AÊ b= 13.0905 (8) AÊ c= 14.6105 (9) AÊ = 81.288 (2) = 88.4473 (19) = 75.9648 (19)

V= 1889.1 (2) AÊ3

Z= 8

Dx= 1.530 Mg mÿ3

Dm= 1.50 Mg mÿ3

Dmmeasured by ¯otation in a mixture of carbon tetrachloride and xylene

MoKradiation Cell parameters from 8152

re¯ections = 2.5±35.0 = 0.41 mmÿ1

T= 105 (2) K Plate, colorless 0.700.500.15 mm

Data collection

Bruker SMART CCD diffractometer !scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

T = 0.76,T = 0.94

15604 independent re¯ections 12138 re¯ections withI> 2(I) Rint= 0.020

max= 35.1

h=ÿ16!16 k=ÿ21!21

Re®nement

Re®nement onF2

R[F2_{> 2}₍_F2_{)] = 0.036}

wR(F2_{) = 0.105}

S= 1.02 15604 re¯ections 485 parameters

H-atom parameters constrained

w= 1/[2₍_F

o2) + (0.0522P)2 + 0.6779P]

whereP= (Fo2+ 2Fc2)/3 (/)max= 0.002

max= 0.78 e AÊÿ3

min=ÿ0.54 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,_).

O1AÐC11 1.2132 (14)

O1BÐC11 1.3161 (14)

O2AÐC21 1.2141 (13)

O2BÐC21 1.3209 (13)

O3AÐC31 1.2248 (13)

O3BÐC31 1.3064 (13)

O4AÐC41 1.2121 (14)

O4BÐC41 1.3262 (14)

O1AÐC11ÐC12ÐN1 2.09 (14)

N1ÐC12ÐC13ÐC14 ÿ73.50 (12)

N1ÐC12ÐC13ÐC15 52.77 (12)

O2AÐC21ÐC22ÐN2 1.11 (14)

N2ÐC22ÐC23ÐC24 ÿ53.19 (12)

N2ÐC22ÐC23ÐC25 72.66 (12)

O3AÐC31ÐC32ÐN3 ÿ20.98 (14)

N3ÐC32ÐC33ÐC34 ÿ64.56 (13)

N3ÐC32ÐC33ÐC35 62.85 (13)

O4AÐC41ÐC42ÐN4 0.30 (15)

N4ÐC42ÐC43ÐC44 ÿ75.99 (12)

N4ÐC42ÐC43ÐC45 49.37 (12)

Table 2

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

O1BÐH1B O34i _{0.86 (2)} _{1.89 (2)} _{2.7503 (14)} _{177 (2)}

N1ÐH1A O24ii _0.89 _2.15 _{2.8349 (13)} ₁₃₃

N1ÐH1C O2A 0.89 2.15 2.8670 (12) 137

N1ÐH1D O12ii _0.89 _2.27 _{2.9264 (13)} ₁₃₀

O2BÐH2B O44i _{0.87 (2)} _{1.88 (2)} _{2.7395 (12)} _{175 (2)}

N2ÐH2A O13i _0.89 _2.19 _{2.9124 (13)} ₁₃₈

N2ÐH2A O12i _0.89 _2.51 _{3.3055 (13)} ₁₄₉

N2ÐH2C O23i _0.89 _2.02 _{2.8695 (13)} ₁₅₉

N2ÐH2D O24ii _0.89 _2.15 _{2.9234 (13)} ₁₄₅

N2ÐH2D O43 0.89 2.31 2.9731 (13) 132

O3BÐH3B O3Aiii _{0.90 (2)} _{1.74 (2)} _{2.6381 (11)} _{174 (2)}

N3ÐH3A O1Ai _0.89 _2.09 _{2.9288 (12)} ₁₅₈

N3ÐH3D O33iv _0.89 _2.25 _{2.9745 (13)} ₁₃₉

N3ÐH3C O42 0.89 2.10 2.9546 (13) 161

O4BÐH4B O14ii _{0.86 (2)} _{1.93 (2)} _{2.7913 (13)} _{172 (2)}

N4ÐH4A O43v _0.89 _2.20 _{2.9049 (12)} ₁₃₅

N4ÐH4A O42v _0.89 _2.51 _{3.3032 (13)} ₁₄₈

N4ÐH4C O13vi _0.89 _2.16 _{2.8827 (13)} ₁₃₈

N4ÐH4C O33v _0.89 _2.32 _{2.9834 (13)} ₁₃₂

N4ÐH4D O31i _0.89 _1.95 _{2.8208 (14)} ₁₆₅

Symmetry codes: (i) 1ÿx;1ÿy;1ÿz; (ii) x;yÿ1;z; (iii) 2ÿx;1ÿy;ÿz; (iv)

Figure 1

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organic papers

o30

B. Sridharet al. C5H12NO2+ClO4ÿ Acta Cryst.(2003). E59, o28±o30

The carboxyl H atoms (H1B, H2B, H3Band H4B) were located from a difference Fourier map and re®ned isotropically (OÐH = 0.86±0.90 AÊ). All other H atoms were placed in geometrically calculated positions and included in the re®nement in a riding-model approximation, withUisoequal to 1.2Ueqof the carrier atom. The O

atoms of perchlorate anion 3 have slightly higher Uiso values

compared to the other three perchlorate anions. Attempts to re®ne these O atoms with a split model resulted in site-occupation factors for major and minor components of 0.93 and 0.07. However, due to unsuccessful convergence, the re®nement of this split model could not be con®rmed and hence is not reported.

Data collection:SMART(Bruker, 1998); cell re®nement:SAINT

(Bruker, 1998); data reduction: SAINT; program(s) used to solve structure:SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:

PLATON (Spek, 1999); software used to prepare material for publication:SHELXL97.

BS thanks the Council of Scienti®c & Industrial Research (CSIR), Government of India, for ®nancial assistance and RKR thanks the Department of Science and Technology (DST), Government of India, for ®nancial support. The ®nancial support of the UGC is acknowledged.

References

Ando, Q., Ashida, T., Sasada, Y. & Kakudo, M. (1967).Acta Cryst.23, 172±173. Bruker (1998).SMARTandSAINT. Bruker AXS Inc., Madison, Wisconsin,

USA.

Dalhus, B. & GoÈrbitz, C. H. (1996a).Acta Cryst.C52, 1759±1761. Dalhus, B. & GoÈrbitz, C. H. (1996b).Acta Chem. Scand.50, 544±548. Jeffrey, G. A. & Saenger, W. (1991). In Hydrogen Bonding in Biological

Structures. Berlin, Heidelberg, New York: Springer-Verlag.

Johnson, C. K. (1976).ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.

Lakshminarayanan, A. V., Sashisekaran, V. & Ramachandran, G. N. (1967). In Conformation of Biopolymers, edited by G. N. Ramachandran. London: Academic Press.

Mallikarjunan, M. & Rao, S. T. (1969).Acta Cryst.B25, 296±303.

Olovsson, I., Ptasiewicz-Bak, H., Gustafsson, T. & Majerz, I. (2001).Acta Cryst.B57, 311±316.

Pandiarajan, S., Sridhar, B. & Rajaram, R. K. (2001).Acta Cryst.E57, o466± o468.

Parthasarathy, R. (1966).Acta Cryst.21, 422±426.

Rao, S. N. & Parthasarathy, R. (1974).Am. Crystallogr. Assoc. Meet.(Spring), p. 129.

Rao, S. T. (1969).Z. Kristallogr.128, 339±351.

Rodrigues, V. H., PaixaÄo, J. A., Costa, M. M. R. R. & Matos Beja, A. (2001). Acta Cryst.C57, 213±215.

Sheldrick, G. M. (1996).SADABS. University of GoÈttingen, Germany. Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of

GoÈttingen, Germany.

Spek, A. L. (1999). PLATON for Windows. Utretch University, The Netherlands.

Srinivasan, N., Rajaram, R. K. & Jebaraj, D. D. (1997).Z. Kristallogr.212, 311± 312.

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supporting information

Acta Cryst. (2003). E59, o28–o30 [https://doi.org/10.1107/S1600536802022225]

DL

-Valinium perchlorate

B. Sridhar, N. Srinivasan, Bjoern Dalhus and R. K. Rajaram

DL-valinium perchlorate

Crystal data

C5H12NO2+·ClO4−

Mr = 217.61

Triclinic, P1 Hall symbol: -P 1

a = 10.3005 (6) Å

b = 13.0905 (8) Å

c = 14.6105 (9) Å

α = 81.288 (2)°

β = 88.4473 (19)°

γ = 75.9648 (19)°

V = 1889.1 (2) Å3

Z = 8

F(000) = 912

Dx = 1.530 Mg m−3

Dm = 1.50 Mg m−3

Dm measured by flotation in a mixture of carbon

tetrachloride and xylene Mo Kα radiation, λ = 0.71070 Å Cell parameters from 8152 reflections

θ = 2.5–35.0°

µ = 0.41 mm−1

T = 105 K Plate, colorless 0.7 × 0.5 × 0.15 mm

Data collection

Bruker SMART CCD diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

Detector resolution: 8.33 pixels mm-1

ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin = 0.76, Tmax = 0.94

35831 measured reflections 15604 independent reflections 12138 reflections with I > 2σ(I)

Rint = 0.020

θmax = 35.1°, θmin = 1.4°

h = −16→16

k = −21→21

l = −23→23

Refinement

Refinement on F2

Least-squares matrix: full

R[F2_{> 2}_σ₍_F2_{)] = 0.036}

wR(F2_{) = 0.105}

S = 1.02

15604 reflections 485 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) + (0.0522P)2 + 0.6779P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.002

Δρmax = 0.78 e Å−3

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supporting information

sup-2 Acta Cryst. (2003). E59, o28–o30

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}_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

Cl1 0.66873 (2) 0.893149 (19) 0.817212 (17) 0.01552 (5) O11 0.76072 (9) 0.84376 (8) 0.89155 (6) 0.02528 (18) O12 0.73948 (9) 0.92487 (7) 0.73479 (6) 0.02430 (17) O13 0.59270 (9) 0.82024 (7) 0.79486 (6) 0.02318 (17) O14 0.57590 (10) 0.98674 (8) 0.84367 (7) 0.0308 (2) Cl2 0.66344 (2) 1.005117 (19) 0.408864 (17) 0.01586 (5) O21 0.74562 (10) 1.01445 (8) 0.32912 (7) 0.0295 (2) O22 0.54022 (10) 0.98222 (9) 0.38580 (8) 0.0347 (2) O23 0.73582 (10) 0.92302 (8) 0.47938 (8) 0.0338 (2) O24 0.63256 (9) 1.10502 (7) 0.44624 (6) 0.02397 (17) Cl3 0.33296 (3) 0.501837 (19) 0.098497 (17) 0.01683 (5) O31 0.36925 (14) 0.57718 (9) 0.02752 (10) 0.0550 (4) O32 0.19527 (10) 0.53822 (9) 0.12232 (7) 0.0322 (2) O33 0.35737 (9) 0.39904 (7) 0.06830 (7) 0.02488 (18) O34 0.41625 (12) 0.49198 (9) 0.17972 (8) 0.0414 (3) Cl4 0.67119 (2) 0.378808 (19) 0.330192 (16) 0.01480 (5) O41 0.76844 (9) 0.33058 (8) 0.40217 (6) 0.02494 (17) O42 0.73619 (9) 0.41280 (7) 0.24598 (6) 0.02373 (17) O43 0.59667 (9) 0.30374 (7) 0.31094 (6) 0.02147 (16) O44 0.57803 (9) 0.47075 (7) 0.35974 (7) 0.02634 (19) O1A 0.56652 (9) 0.27665 (7) 0.75114 (6) 0.02522 (18) O1B 0.71043 (10) 0.37587 (7) 0.69865 (7) 0.02738 (19) H1B 0.670 (2) 0.4151 (16) 0.7383 (14) 0.041 (5)* C11 0.65508 (11) 0.29506 (8) 0.69959 (7) 0.01787 (19) C12 0.71516 (10) 0.22531 (8) 0.62752 (7) 0.01470 (17)

H12 0.6977 0.2688 0.5663 0.018*

N1 0.64138 (9) 0.13933 (7) 0.63272 (6) 0.01647 (16)

H1A 0.6742 0.0968 0.5912 0.025*

H1C 0.5549 0.1684 0.6209 0.025*

H1D 0.6511 0.1016 0.6892 0.025*

C13 0.86793 (11) 0.18040 (9) 0.63866 (8) 0.01858 (19)

H13 0.9095 0.2405 0.6222 0.022*

C14 0.91084 (13) 0.13110 (11) 0.73832 (9) 0.0260 (2)

H14A 0.8770 0.1823 0.7791 0.039*

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H14C 0.8757 0.0695 0.7559 0.039* C15 0.91918 (12) 0.10227 (11) 0.56990 (10) 0.0276 (3)

H15A 0.8904 0.1361 0.5084 0.041*

H15B 0.8841 0.0404 0.5858 0.041*

H15C 1.0152 0.0815 0.5725 0.041*

O2A 0.43593 (9) 0.30578 (7) 0.53587 (6) 0.02418 (17) O2B 0.31609 (10) 0.47309 (7) 0.49077 (6) 0.02417 (17) H2B 0.352 (2) 0.4873 (15) 0.5387 (14) 0.038 (5)* C21 0.36053 (11) 0.37166 (8) 0.48176 (7) 0.01643 (18) C22 0.30666 (10) 0.34589 (8) 0.39431 (7) 0.01484 (17)

H22 0.3428 0.3849 0.3410 0.018*

N2 0.36225 (9) 0.22939 (7) 0.39283 (6) 0.01628 (16)

H2A 0.3328 0.2112 0.3424 0.024*

H2C 0.3358 0.1924 0.4430 0.024*

H2D 0.4512 0.2153 0.3922 0.024*

C23 0.15237 (10) 0.37941 (9) 0.38645 (7) 0.01732 (18)

H23 0.1266 0.4574 0.3764 0.021*

C24 0.10323 (13) 0.34255 (11) 0.30178 (9) 0.0254 (2)

H24A 0.1482 0.3671 0.2475 0.038*

H24B 0.0085 0.3713 0.2941 0.038*

H24C 0.1223 0.2662 0.3107 0.038*

C25 0.08330 (12) 0.34197 (12) 0.47498 (9) 0.0271 (2)

H25A 0.1160 0.3662 0.5267 0.041*

H25B 0.1022 0.2656 0.4852 0.041*

H25C −0.0116 0.3707 0.4686 0.041*

O3A 0.87416 (8) 0.50013 (6) 0.07502 (6) 0.01906 (15) O3B 0.93978 (8) 0.64102 (7) −0.00291 (6) 0.02141 (16) H3B 1.004 (2) 0.5902 (16) −0.0235 (14) 0.042 (5)* C31 0.86245 (10) 0.59610 (8) 0.05362 (7) 0.01574 (17) C32 0.75478 (10) 0.67735 (8) 0.09498 (7) 0.01546 (17)

H32 0.7168 0.7358 0.0457 0.019*

N3 0.64675 (9) 0.62359 (7) 0.13106 (6) 0.01619 (16)

H3A 0.5823 0.6696 0.1557 0.024*

H3C 0.6809 0.5684 0.1741 0.024*

H3D 0.6129 0.6008 0.0848 0.024*

C33 0.81640 (12) 0.72299 (9) 0.17046 (8) 0.0203 (2)

H33 0.8855 0.7557 0.1401 0.024*

C34 0.71305 (15) 0.81187 (13) 0.20703 (13) 0.0395 (4)

H34A 0.6715 0.8636 0.1560 0.059*

H34B 0.7564 0.8454 0.2471 0.059*

H34C 0.6462 0.7825 0.2410 0.059*

C35 0.88633 (18) 0.63760 (12) 0.24833 (10) 0.0361 (3)

H35A 0.9502 0.5834 0.2224 0.054*

H35B 0.8212 0.6065 0.2827 0.054*

H35C 0.9316 0.6693 0.2888 0.054*

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supporting information

C41 0.62229 (11) 0.12492 (9) 1.02561 (7) 0.01772 (18) C42 0.68971 (10) 0.14625 (8) 1.11005 (7) 0.01526 (17)

H42 0.6682 0.0998 1.1645 0.018*

N4 0.62721 (9) 0.25923 (7) 1.12166 (6) 0.01644 (16)

H4A 0.6638 0.2752 1.1705 0.025*

H4C 0.5397 0.2673 1.1303 0.025*

H4D 0.6410 0.3024 1.0711 0.025*

C43 0.84372 (11) 0.12400 (9) 1.10210 (8) 0.01909 (19)

H43 0.8784 0.0465 1.1103 0.023*

C44 0.88945 (14) 0.16861 (12) 1.00713 (10) 0.0302 (3)

H44A 0.8505 0.1418 0.9597 0.045*

H44B 0.9852 0.1471 1.0039 0.045*

H44C 0.8614 0.2450 0.9982 0.045*

C45 0.90418 (12) 0.16514 (11) 1.18006 (9) 0.0258 (2)

H45A 0.8741 0.1361 1.2388 0.039*

H45B 0.8762 0.2415 1.1721 0.039*

H45C 1.0000 0.1435 1.1779 0.039*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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C15 0.0169 (5) 0.0326 (6) 0.0342 (6) −0.0020 (4) 0.0050 (4) −0.0149 (5) O2A 0.0265 (4) 0.0216 (4) 0.0223 (4) 0.0001 (3) −0.0088 (3) −0.0048 (3) O2B 0.0306 (5) 0.0187 (4) 0.0231 (4) −0.0012 (3) −0.0062 (3) −0.0090 (3) C21 0.0161 (4) 0.0173 (4) 0.0165 (4) −0.0037 (3) 0.0001 (3) −0.0049 (3) C22 0.0160 (4) 0.0143 (4) 0.0143 (4) −0.0033 (3) −0.0001 (3) −0.0029 (3) N2 0.0169 (4) 0.0159 (4) 0.0164 (4) −0.0029 (3) −0.0004 (3) −0.0048 (3) C23 0.0146 (4) 0.0175 (4) 0.0189 (4) −0.0019 (3) −0.0015 (3) −0.0024 (4) C24 0.0209 (5) 0.0303 (6) 0.0253 (5) −0.0045 (4) −0.0060 (4) −0.0069 (5) C25 0.0184 (5) 0.0363 (7) 0.0254 (6) −0.0059 (5) 0.0051 (4) −0.0028 (5) O3A 0.0195 (4) 0.0162 (3) 0.0193 (4) −0.0013 (3) 0.0048 (3) −0.0016 (3) O3B 0.0185 (4) 0.0178 (4) 0.0258 (4) −0.0023 (3) 0.0085 (3) −0.0014 (3) C31 0.0143 (4) 0.0178 (4) 0.0140 (4) −0.0019 (3) 0.0009 (3) −0.0022 (3) C32 0.0145 (4) 0.0154 (4) 0.0157 (4) −0.0020 (3) 0.0025 (3) −0.0026 (3) N3 0.0153 (4) 0.0166 (4) 0.0165 (4) −0.0032 (3) 0.0024 (3) −0.0036 (3) C33 0.0198 (5) 0.0212 (5) 0.0224 (5) −0.0070 (4) 0.0031 (4) −0.0078 (4) C34 0.0291 (7) 0.0372 (7) 0.0588 (10) −0.0060 (6) 0.0056 (6) −0.0325 (7) C35 0.0504 (9) 0.0354 (7) 0.0241 (6) −0.0115 (6) −0.0136 (6) −0.0055 (5) O4A 0.0236 (4) 0.0264 (4) 0.0212 (4) −0.0023 (3) −0.0058 (3) −0.0057 (3) O4B 0.0318 (5) 0.0237 (4) 0.0295 (5) −0.0026 (4) −0.0044 (4) −0.0148 (4) C41 0.0179 (4) 0.0199 (5) 0.0170 (4) −0.0054 (4) 0.0015 (3) −0.0068 (4) C42 0.0163 (4) 0.0152 (4) 0.0145 (4) −0.0034 (3) 0.0004 (3) −0.0032 (3) N4 0.0173 (4) 0.0165 (4) 0.0160 (4) −0.0034 (3) −0.0003 (3) −0.0049 (3) C43 0.0153 (4) 0.0197 (5) 0.0219 (5) −0.0036 (4) 0.0012 (4) −0.0032 (4) C44 0.0257 (6) 0.0394 (7) 0.0266 (6) −0.0111 (5) 0.0096 (5) −0.0039 (5) C45 0.0185 (5) 0.0312 (6) 0.0295 (6) −0.0077 (4) −0.0041 (4) −0.0064 (5)

Geometric parameters (Å, º)

Cl1—O11 1.4287 (9) C23—C24 1.5339 (16)

Cl1—O12 1.4497 (9) C23—H23 0.98

Cl1—O13 1.4498 (9) C24—H24A 0.96

Cl1—O14 1.4560 (9) C24—H24B 0.96

Cl2—O21 1.4292 (9) C24—H24C 0.96

Cl2—O22 1.4327 (10) C25—H25A 0.96

Cl2—O23 1.4456 (10) C25—H25B 0.96

Cl2—O24 1.4543 (9) C25—H25C 0.96

Cl3—O31 1.4269 (11) O3A—C31 1.2248 (13) Cl3—O32 1.4337 (10) O3B—C31 1.3064 (13)

Cl3—O33 1.4416 (9) O3B—H3B 0.90 (2)

Cl3—O34 1.4547 (10) C31—C32 1.5208 (14)

Cl4—O41 1.4342 (9) C32—N3 1.4989 (14)

Cl4—O42 1.4471 (9) C32—C33 1.5484 (16)

Cl4—O43 1.4475 (8) C32—H32 0.98

Cl4—O44 1.4596 (9) N3—H3A 0.89

O1A—C11 1.2132 (14) N3—H3C 0.89

O1B—C11 1.3161 (14) N3—H3D 0.89

O1B—H1B 0.86 (2) C33—C34 1.5261 (17)

(9)

supporting information

C12—N1 1.4953 (13) C33—H33 0.98

C12—C13 1.5443 (15) C34—H34A 0.96

C12—H12 0.98 C34—H34B 0.96

N1—H1A 0.89 C34—H34C 0.96

N1—H1C 0.89 C35—H35A 0.96

N1—H1D 0.89 C35—H35B 0.96

C13—C14 1.5309 (17) C35—H35C 0.96

C13—C15 1.5345 (17) O4A—C41 1.2121 (14)

C13—H13 0.98 O4B—C41 1.3262 (14)

C14—H14A 0.96 O4B—H4B 0.86 (2)

C14—H14B 0.96 C41—C42 1.5254 (15)

C14—H14C 0.96 C42—N4 1.4962 (13)

C15—H15A 0.96 C42—C43 1.5463 (15)

C15—H15B 0.96 C42—H42 0.98

C15—H15C 0.96 N4—H4A 0.89

O2A—C21 1.2141 (13) N4—H4C 0.89

O2B—C21 1.3209 (13) N4—H4D 0.89

O2B—H2B 0.87 (2) C43—C44 1.5301 (17)

C21—C22 1.5212 (15) C43—C45 1.5369 (17)

C22—N2 1.4966 (13) C43—H43 0.98

C22—C23 1.5453 (15) C44—H44A 0.96

C22—H22 0.98 C44—H44B 0.96

N2—H2A 0.89 C44—H44C 0.96

N2—H2C 0.89 C45—H45A 0.96

N2—H2D 0.89 C45—H45B 0.96

C23—C25 1.5320 (16) C45—H45C 0.96

(10)

O41—Cl4—O44 109.33 (5) C33—C32—H32 108.6 O42—Cl4—O44 109.40 (6) C32—N3—H3A 109.5 O43—Cl4—O44 108.78 (5) C32—N3—H3C 109.5 C11—O1B—H1B 108.8 (13) H3A—N3—H3C 109.5 O1A—C11—O1B 125.16 (10) C32—N3—H3D 109.5 O1A—C11—C12 122.82 (10) H3A—N3—H3D 109.5 O1B—C11—C12 112.02 (9) H3C—N3—H3D 109.5 N1—C12—C11 107.12 (8) C34—C33—C35 112.19 (12) N1—C12—C13 112.34 (8) C34—C33—C32 111.18 (10) C11—C12—C13 113.40 (9) C35—C33—C32 113.27 (10)

N1—C12—H12 107.9 C34—C33—H33 106.6

C11—C12—H12 107.9 C35—C33—H33 106.6

C13—C12—H12 107.9 C32—C33—H33 106.6

C12—N1—H1A 109.5 C33—C34—H34A 109.5

C12—N1—H1C 109.5 C33—C34—H34B 109.5

H1A—N1—H1C 109.5 H34A—C34—H34B 109.5

C12—N1—H1D 109.5 C33—C34—H34C 109.5

H1A—N1—H1D 109.5 H34A—C34—H34C 109.5

H1C—N1—H1D 109.5 H34B—C34—H34C 109.5

C14—C13—C15 112.01 (10) C33—C35—H35A 109.5 C14—C13—C12 112.93 (9) C33—C35—H35B 109.5 C15—C13—C12 110.41 (9) H35A—C35—H35B 109.5

C14—C13—H13 107.0 C33—C35—H35C 109.5

C15—C13—H13 107.0 H35A—C35—H35C 109.5 C12—C13—H13 107.0 H35B—C35—H35C 109.5 C13—C14—H14A 109.5 C41—O4B—H4B 109.7 (14) C13—C14—H14B 109.5 O4A—C41—O4B 125.17 (10) H14A—C14—H14B 109.5 O4A—C41—C42 123.30 (10) C13—C14—H14C 109.5 O4B—C41—C42 111.53 (9) H14A—C14—H14C 109.5 N4—C42—C41 106.44 (8) H14B—C14—H14C 109.5 N4—C42—C43 112.39 (9) C13—C15—H15A 109.5 C41—C42—C43 113.14 (9)

C13—C15—H15B 109.5 N4—C42—H42 108.2

H15A—C15—H15B 109.5 C41—C42—H42 108.2

C13—C15—H15C 109.5 C43—C42—H42 108.2

H15A—C15—H15C 109.5 C42—N4—H4A 109.5

H15B—C15—H15C 109.5 C42—N4—H4C 109.5

C21—O2B—H2B 110.7 (13) H4A—N4—H4C 109.5 O2A—C21—O2B 124.84 (10) C42—N4—H4D 109.5 O2A—C21—C22 123.15 (10) H4A—N4—H4D 109.5 O2B—C21—C22 112.02 (9) H4C—N4—H4D 109.5 N2—C22—C21 106.83 (8) C44—C43—C45 111.04 (10) N2—C22—C23 113.00 (8) C44—C43—C42 112.87 (10) C21—C22—C23 113.28 (9) C45—C43—C42 110.94 (9)

N2—C22—H22 107.8 C44—C43—H43 107.2

C21—C22—H22 107.8 C45—C43—H43 107.2

C23—C22—H22 107.8 C42—C43—H43 107.2

(11)

supporting information

C22—N2—H2C 109.5 C43—C44—H44B 109.5

H2A—N2—H2C 109.5 H44A—C44—H44B 109.5

C22—N2—H2D 109.5 C43—C44—H44C 109.5

H2A—N2—H2D 109.5 H44A—C44—H44C 109.5

H2C—N2—H2D 109.5 H44B—C44—H44C 109.5

C25—C23—C24 111.38 (10) C43—C45—H45A 109.5 C25—C23—C22 112.90 (9) C43—C45—H45B 109.5 C24—C23—C22 110.96 (9) H45A—C45—H45B 109.5

C25—C23—H23 107.1 C43—C45—H45C 109.5

C24—C23—H23 107.1 H45A—C45—H45C 109.5 C22—C23—H23 107.1 H45B—C45—H45C 109.5

O1A—C11—C12—N1 2.09 (14) O3A—C31—C32—N3 −20.98 (14) O1B—C11—C12—N1 −177.91 (9) O3B—C31—C32—N3 161.07 (9) O1A—C11—C12—C13 −122.43 (12) O3A—C31—C32—C33 102.72 (12) O1B—C11—C12—C13 57.57 (12) O3B—C31—C32—C33 −75.23 (11) N1—C12—C13—C14 −73.50 (12) N3—C32—C33—C34 −64.56 (13) C11—C12—C13—C14 48.14 (13) C31—C32—C33—C34 174.92 (11) N1—C12—C13—C15 52.77 (12) N3—C32—C33—C35 62.85 (13) C11—C12—C13—C15 174.41 (10) C31—C32—C33—C35 −57.67 (13) O2A—C21—C22—N2 1.11 (14) O4A—C41—C42—N4 0.30 (15) O2B—C21—C22—N2 −179.21 (9) O4B—C41—C42—N4 −179.76 (9) O2A—C21—C22—C23 126.19 (12) O4A—C41—C42—C43 −123.63 (12) O2B—C21—C22—C23 −54.14 (12) O4B—C41—C42—C43 56.32 (13) N2—C22—C23—C24 −53.19 (12) N4—C42—C43—C44 −75.99 (12) C21—C22—C23—C24 −174.87 (9) C41—C42—C43—C44 44.61 (13) N2—C22—C23—C25 72.66 (12) N4—C42—C43—C45 49.37 (12) C21—C22—C23—C25 −49.02 (13) C41—C42—C43—C45 169.97 (10)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O1B—H1B···O34i _{0.86 (2)} _{1.89 (2)} _{2.7503 (14)} _{177 (2)}

N1—H1A···O24ii _0.89 _2.15 _{2.8349 (13)} ₁₃₃

N1—H1C···O2A 0.89 2.15 2.8670 (12) 137 N1—H1D···O12ii _0.89 _2.27 _{2.9264 (13)} ₁₃₀

O2B—H2B···O44i _{0.87 (2)} _{1.88 (2)} _{2.7395 (12)} _{175 (2)}

N2—H2A···O13i _0.89 _2.19 _{2.9124 (13)} ₁₃₈

N2—H2A···O12i _0.89 _2.51 _{3.3055 (13)} ₁₄₉

N2—H2C···O23i _0.89 _2.02 _{2.8695 (13)} ₁₅₉

N2—H2D···O24ii _0.89 _2.15 _{2.9234 (13)} ₁₄₅

N2—H2D···O43 0.89 2.31 2.9731 (13) 132 O3B—H3B···O3Aiii _{0.90 (2)} _{1.74 (2)} _{2.6381 (11)} _{174 (2)}

N3—H3A···O1Ai _0.89 _2.09 _{2.9288 (12)} ₁₅₈

N3—H3D···O33iv _0.89 _2.25 _{2.9745 (13)} ₁₃₉

N3—H3C···O42 0.89 2.10 2.9546 (13) 161 O4B—H4B···O14ii _{0.86 (2)} _{1.93 (2)} _{2.7913 (13)} _{172 (2)}

(12)

N4—H4A···O42v _0.89 _2.51 _{3.3032 (13)} ₁₄₈

N4—H4C···O13vi _0.89 _2.16 _{2.8827 (13)} ₁₃₈

N4—H4C···O33v _0.89 _2.32 _{2.9834 (13)} ₁₃₂

N4—H4D···O31i _0.89 _1.95 _{2.8208 (14)} ₁₆₅