Risperidone chloride 2 5 hydrate: a new crystalline form

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organic papers

o768

Wang and Pan _C

23H28FN4O2+Cl2.5H2O doi:10.1107/S1600536806002157 Acta Cryst.(2006). E62, o768–o770 Acta Crystallographica Section E

Structure Reports

Online

ISSN 1600-5368

Risperidone chloride 2.5-hydrate: a new crystalline

form

Dan-Hua Wanga,b* and Yuan-Jiang Pana

a

Chemistry Department, Zhejiang University, Hangzhou, Zhejiang 310027, People’s Republic of China, andb_{Zhejiang Huahai Pharmaceutical} Co. Ltd, Linhai, Zhejiang 317024, People’s Republic of China

Correspondence e-mail:

[email protected]

Key indicators

Single-crystal X-ray study

T= 298 K

Mean(C–C) = 0.002 A˚ Disorder in solvent or counterion

Rfactor = 0.041

wRfactor = 0.101

Data-to-parameter ratio = 18.1

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

Received 3 January 2006 Accepted 18 January 2006

The asymmetric unit of the title compound,

C23H28FN4O2 +

Cl2.5H2O, contain one risperidone cation

{systematic name: 4-(6-fluoro-1,2-benzisoxazol-3-yl)-1-[2-(2-methyl-4-oxo-3,4,6,7,8,9-hexahydro-2H-pyrido[1,2-a ]pyrim-idin-3-yl)ethyl]piperidinium}, one Cl anion, and two and a half water molecules. The piperidine ring adopts a chair conformation, while the tetrahydropyridine ring has a sofa conformation. Each Cl _{anion and the water molecules are}

linked to the risperidone moleculesviaO—H O, O—H N, O—H Cl and N—H Cl hydrogen bonds which stabilize the crystal packing.

Comment

Risperidone is an antipsychotic agent belonging to a new chemical class of benzisoxazole derivatives, available world-wide since the early 1990s (Callaghanet al., 1999; Kennedyet al., 2000; Tandon, 2002). It has useful central nervous system activity and shows a wide range of therapeutic effects. Phar-maceutical formulations contain solid crystalline risperidone. For this reason, well documented characteristics of its crys-talline form are required. To date, four solid forms of risper-idone have been reported (Krochmalet al., 2004; Reddyet al., 2004) and characterized by X-ray powder diffraction patterns, but only one of their crystal structures has been determined (Peeterset al., 1993). In the course of our studies, we report here the crystal structure of a new 2.5-hydrate, (I).

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of risperidone (Peeters et al., 1993) and risperidoneN-oxide (Ravikumaret al., 2005).

The conformation of compound (I) is also similar to those of the above two compounds. The piperidine ring has the expected chair conformation, atoms C1 and N1 having deviations of 0.631 (2) and 0.710 (2) A˚ , respectively, from the least-squares plane through the other four atoms. The tetrahydropyridine ring adopts a sofa conformation, similar to that of risperidone N-oxide, with atom C19 displaced by 0.578 (3) A˚ from the mean plane defined by atoms C20/C21/ N3/C17/C18. Interestingly, in the structure of risperidone, a half-chair conformation is reported for this ring. Similarly, the ethyl bridge between the piperidine and pyridopyrimine groups has an antiperiplanar conformation, with an N1— C13—C14—C15 torsion angle of 167.1 (1)_{. The}

benzisox-azole ring system is almost planar.

In the crystal structure of the title compound, an elaborate hydrogen-bond network is formed. Each Cl anion, each water molecule, two amino groups and one carbonyl group in the risperidone molecule are involved in the hydrogen-bond network (Table 2). O—H Cl, N—H Cl, O—H O and O—H N hydrogen bonds link three molecules into a ring

linear hydrogen-bonded chain is formed along the a axis (Fig. 3). Atom O5 from a solvent water molecule forms a hydrogen bond with another solvent water molecule, O4. Therefore, atom O5 has a larger displacement parameter. The crystal packing is stabilized by these hydrogen bonds.

Experimental

The crude risperidone was supplied by Zhejiang Huahai Pharma-ceutical Co. Ltd. The compound was recrystallized from a solution in a mixture of acetone and water (4:1v/v), with the pH adjusted to 6–7 using 1.0 mol l1_{HCl, giving brown crystals of (I) suitable for X-ray} diffraction.

Crystal data

C23H28FN4O2+Cl

2.5H2O

Mr= 491.99

Monoclinic, P21=n

a= 10.027 (3) A˚

b= 18.431 (4) A˚

c= 13.394 (4) A˚

= 100.613 (11)

V= 2433.0 (11) A˚3

Z= 4

Dx= 1.343 Mg m

3

MoKradiation

Cell parameters from 19056 reflections

= 3.0–27.5

= 0.20 mm1

T= 298 (1) K Block, brown 0.300.260.20 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

!scans

Absorption correction: multi-scan (ABSCOR; Higashi, 1995)

Tmin= 0.913,Tmax= 0.960

23832 measured reflections

5562 independent reflections 3581 reflections withF2_{> 2}₍_F2₎

Rint= 0.031 max= 27.5

h=13!12

k=23!23

l=17!17

Refinement

Refinement onF2

R[F2_{> 2}₍_F2_{)] = 0.041}

wR(F2_{) = 0.102}

S= 1.04 5562 reflections

w= 1/[0.0005Fo2+(Fo2)]/(4Fo2)

(/)max< 0.001

max= 0.51 e A˚

3

min=0.33 e A˚

3

[image:2.610.46.298.67.207.2]

Extinction correction:

Figure 1

[image:2.610.317.562.73.270.2]

The structure and atom-numbering scheme for the asymmetric unit of (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

Figure 2

A partial packing diagram for (I), showing the linking of the water molecules, risperidone cations and Cl _{anions. Hydrogen bonds are}

shown as dashed lines. [Symmetry codes: (i) 1 +x,y,z; (ii)1 2+x,

1 2y,

1 2+z; (iii)1

2+x, 1 2y,

1 2+z.]

Figure 3

[image:2.610.45.294.257.412.2]

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Table 1

Selected geometric parameters (A˚ ,_).

O1—N2 1.4275 (19)

O1—C12 1.355 (2)

O2—C16 1.2320 (19) N1—C3 1.4929 (19) N1—C4 1.4948 (19) N1—C13 1.5004 (19)

N2—C6 1.3023 (18) N3—C16 1.4079 (19)

N3—C17 1.483 (2)

N3—C21 1.363 (2)

N4—C21 1.297 (2)

N4—C22 1.3772 (19)

C3—N1—C4 109.77 (10) C3—N1—C13 114.52 (12)

[image:3.610.45.296.238.328.2]

C4—N1—C13 111.61 (10)

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

N1—H111 Cl1 0.86 2.17 3.0351 (12) 179 O3—H311 Cl1 0.90 2.21 3.1047 (14) 170 O3—H312 O2i

0.93 1.93 2.8421 (18) 167 O4—H411 O3 0.98 1.95 2.909 (2) 167 O4—H412 N4ii 0.96 2.04 2.997 (2) 178 O5—H511 O4 0.91 1.87 2.775 (4) 173 O5—H512 O4iii

0.92 1.90 2.754 (5) 153 O5—H512 O5iii 0.92 1.85 2.320 (5) 109

Symmetry codes: (i)x1;y;z; (ii)x1

2;yþ12;zþ12; (iii)x;yþ1;zþ2.

The H atoms of the amino group and the water molecules were located in difference Fourier maps and included in the refinement based on the as-found N—H and O—H bond lengths, but their isotropic displacement parameters were refined and then fixed in the final stage. All other H atoms were placed in calculated positions, with C—H = 0.93–0.98 A˚ , and included in the refinement in the riding model, withUiso(H) = 1.2Ueq(carrier atom).

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refine-ment:PROCESS-AUTO; data reduction:CrystalStructure(Rigaku/ MSC, 2004); program(s) used to solve structure:SIR97(Altomareet al., 1999); program(s) used to refine structure:CRYSTALS (Better-idge et al., 2003); molecular graphics: ORTEP-3 for Windows

(Farrugia, 1997); software used to prepare material for publication:

CrystalStructure.

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999).J. Appl. Cryst.32, 115–119.

Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, C. K. & Watkin, D. J. (2003).J. Appl. Cryst.36, 1487.

Callaghan, J. T., Bergstrom, R. F., Ptak, L. R. & Beasley, C. M. (1999).Clin. Pharm.37, 177–193.

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

Higashi, T. (1995).ABSCOR. Rigaku Corporation, Tokyo, Japan.

Kennedy, J. S., Bymaster, F. P., Schuh, L., Calligaro, D. O., Nomikos, G., Felder, C. C., Bernauer, M., Kinon, B. J., Baker, R. W., Hay, D., Roth, H. J., Dossenbach, M., Kaiser, C., Beasley, C. M., Holcombe, J. H., Effron, M. B. & Breier, A. (2000).Int. J. Geriatr. Psych. Suppl. 1,16, S33–S61.

Krochmal, B., Diller, D., Dolitzky, B.-Z. & Aronhime, J. (2004). US Patent No. 2004/0229905.

Larson, A. C. (1970).Crystallographic Computing, edited by F. R. Ahmed, S. R. Hall & C. P. Huber, pp. 291–294. Copenhagen: Munksgaard.

Peeters, O. M., Blaton, N. M. & Ranter, C. J. (1993).Acta Cryst.C49, 1698– 1700.

Ravikumar, K., Sridhar, B., Manjunatha, S. G. & Thomas, S. (2005).Acta Cryst.

E61, o2515–o2517.

Reddy, R. B., Ramesh, C., Reddy, T. R. & Kumar, K. V. R. (2004). US Patent No. 2004/0209898.

Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, 3-9-12 Akishima, Tokyo 196-8666, Japan.

Rigaku/MSC (2004).CrystalStructure. Version 3.6.0. Rigaku/MSC, 9009 New Trails Drive, The Woodlands, TX 77381-5209, USA.

Tandon, R. (2002).Psychiatr. Q.73, 297–311.

organic papers

o770

Wang and Pan _C

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supporting information

Acta Cryst. (2006). E62, o768–o770 [https://doi.org/10.1107/S1600536806002157]

Risperidone chloride 2.5-hydrate: a new crystalline form

Dan-Hua Wang and Yuan-Jiang Pan

4-(6-fluoro-1,2-benzisoxazol-3-yl)-1-[2-(2-methyl-4-oxo-3,4,6,7,8,9- hexahydro-2H-pyrido[1,2-a

]pyrimidin-3-yl)ethyl]piperidinium chloride 2.5-hydrate

Crystal data

C23H28FN4O2+·Cl−·2.5H2O Mr = 491.99

Monoclinic, P21/n Hall symbol: -P 2yn a = 10.027 (3) Å b = 18.431 (4) Å c = 13.394 (4) Å β = 100.613 (11)° V = 2433.0 (11) Å3 Z = 4

F(000) = 1044.00 Dx = 1.343 Mg m−3

Mo Kα radiation, λ = 0.71075 Å Cell parameters from 19056 reflections θ = 3.0–27.5°

µ = 0.20 mm−1 T = 298 K Block, brown

0.30 × 0.26 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Detector resolution: 10.00 pixels mm-1 ω scans

Absorption correction: multi-scan (ABSCOR; Higashi, 1995) Tmin = 0.913, Tmax = 0.960 23832 measured reflections

5562 independent reflections 3581 reflections with F2_{> 2}_σ₍_F2₎ Rint = 0.031

θmax = 27.5°

h = −13→12

k = −23→23

l = −17→17

Refinement

Refinement on F2 R[F2_{> 2}_σ₍_F2_{)] = 0.041} wR(F2_{) = 0.102} S = 1.04 5562 reflections 308 parameters

H-atom parameters constrained

w = 1/[0.0005Fo2 + 1σ(Fo2)]/(4Fo2) (Δ/σ)max < 0.001

Δρmax = 0.51 e Å−3 Δρmin = −0.33 e Å−3

Extinction correction: Larson (1970) Extinction coefficient: 99 (21)

Special details

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

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supporting information

sup-2 Acta Cryst. (2006). E62, o768–o770

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq Occ. (<1)

Cl1 0.46396 (4) 0.41240 (2) 0.66523 (4) 0.05455 (13)

F1 0.02999 (12) 0.69441 (6) 0.76030 (10) 0.0766 (4)

O1 0.47576 (12) 0.78289 (6) 0.75840 (10) 0.0535 (3)

O2 1.03858 (12) 0.36035 (6) 0.49888 (10) 0.0539 (3)

O3 0.16081 (13) 0.44177 (6) 0.67188 (12) 0.0752 (4)

O4 0.1315 (2) 0.43621 (9) 0.88382 (14) 0.1169 (7)

O5 0.0347 (4) 0.5558 (2) 0.9741 (3) 0.1377 (18) 0.50

N1 0.74081 (12) 0.47731 (6) 0.66009 (9) 0.0328 (3)

N2 0.59673 (14) 0.74596 (6) 0.74586 (12) 0.0491 (4)

N3 1.01137 (13) 0.23864 (6) 0.47595 (10) 0.0396 (3)

N4 0.80844 (14) 0.18132 (6) 0.49170 (11) 0.0433 (4)

C1 0.67478 (16) 0.62490 (8) 0.71696 (12) 0.0387 (4)

C2 0.63629 (17) 0.59535 (8) 0.60874 (12) 0.0408 (4)

C3 0.73354 (17) 0.53766 (8) 0.58494 (12) 0.0406 (4)

C4 0.79240 (16) 0.50553 (8) 0.76470 (12) 0.0399 (4)

C5 0.69638 (17) 0.56216 (8) 0.79342 (12) 0.0400 (4)

C6 0.56730 (17) 0.67718 (6) 0.73657 (12) 0.0383 (4)

C7 0.42758 (17) 0.66399 (8) 0.74123 (12) 0.0383 (4)

C8 0.34043 (17) 0.60384 (8) 0.73419 (12) 0.0449 (4)

C9 0.20728 (18) 0.61562 (10) 0.74066 (13) 0.0515 (5)

C10 0.16310 (19) 0.68616 (10) 0.75505 (13) 0.0527 (5)

C11 0.24287 (19) 0.74639 (9) 0.76278 (12) 0.0505 (5)

C12 0.37643 (18) 0.73260 (8) 0.75525 (12) 0.0431 (4)

C13 0.81998 (16) 0.41241 (8) 0.63667 (12) 0.0414 (4)

C14 0.77004 (18) 0.38422 (8) 0.52978 (12) 0.0443 (4)

C15 0.82572 (17) 0.31013 (8) 0.51264 (12) 0.0385 (4)

C16 0.96252 (17) 0.30763 (8) 0.49650 (12) 0.0398 (4)

C17 1.15257 (18) 0.23649 (9) 0.45730 (14) 0.0517 (5)

C18 1.1889 (2) 0.16528 (11) 0.41497 (19) 0.0734 (7)

C19 1.1395 (2) 0.10295 (11) 0.46773 (19) 0.0730 (7)

C20 0.9888 (2) 0.10563 (9) 0.45534 (16) 0.0593 (6)

C21 0.93185 (18) 0.17862 (8) 0.47537 (12) 0.0414 (4)

C22 0.75375 (17) 0.24736 (8) 0.51052 (12) 0.0410 (4)

C23 0.6117 (2) 0.24280 (10) 0.53038 (17) 0.0593 (6)

H1 0.7605 0.6515 0.7224 0.046*

H411 0.1321 0.4318 0.8111 0.142*

H412 0.1861 0.3978 0.9181 0.142*

H8 0.3721 0.5573 0.7254 0.053*

H9 0.1468 0.5770 0.7355 0.062*

H11 0.2105 0.7927 0.7723 0.060*

H21 0.5461 0.5745 0.6002 0.048*

H22 0.6360 0.6352 0.5615 0.049*

H31 0.7017 0.5189 0.5171 0.049*

H32 0.8230 0.5587 0.5887 0.049*

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H42 0.8000 0.4657 0.8127 0.047*

H51 0.7342 0.5813 0.8601 0.048*

H52 0.6096 0.5395 0.7953 0.047*

H111 0.6619 0.4594 0.6620 0.040*

H131 0.9147 0.4259 0.6434 0.050*

H132 0.8111 0.3742 0.6848 0.050*

H141 0.7977 0.4179 0.4818 0.053*

H142 0.6718 0.3814 0.5181 0.053*

H171 1.2140 0.2452 0.5211 0.063*

H172 1.1633 0.2746 0.4094 0.063*

H181 1.2869 0.1621 0.4227 0.091*

H182 1.1486 0.1631 0.3434 0.092*

H191 1.1791 0.1050 0.5394 0.090*

H192 1.1661 0.0581 0.4390 0.089*

H201 0.9612 0.0710 0.5021 0.074*

H202 0.9507 0.0917 0.3861 0.074*

H231 0.5988 0.1969 0.5611 0.073*

H232 0.5968 0.2813 0.5753 0.073*

H233 0.5486 0.2473 0.4674 0.074*

H311 0.2503 0.4394 0.6708 0.092*

H312 0.1343 0.4154 0.6128 0.092*

H511 0.0590 0.5152 0.9434 0.171* 0.50

H512 −0.0290 0.5442 1.0134 0.171* 0.50

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Cl1 0.0390 (2) 0.0677 (2) 0.0570 (2) −0.0095 (2) 0.0090 (2) 0.0000 (2)

F1 0.0521 (7) 0.1004 (8) 0.0808 (9) 0.0184 (6) 0.0215 (6) −0.0043 (6)

O1 0.0605 (8) 0.0327 (5) 0.0653 (8) 0.0041 (5) 0.0062 (6) −0.0089 (5)

O2 0.0586 (8) 0.0417 (6) 0.0636 (8) −0.0138 (5) 0.0169 (6) −0.0068 (5)

O3 0.0525 (8) 0.0836 (9) 0.0930 (12) −0.0131 (7) 0.0221 (7) −0.0336 (8)

O4 0.1565 (18) 0.1035 (12) 0.0945 (14) 0.0740 (12) 0.0330 (12) 0.0066 (10)

O5 0.128 (3) 0.113 (2) 0.187 (4) −0.006 (2) 0.069 (3) −0.063 (2)

N1 0.0302 (6) 0.0348 (6) 0.0338 (7) 0.0007 (5) 0.0072 (5) 0.0018 (5)

N2 0.0520 (9) 0.0364 (7) 0.0569 (9) −0.0022 (6) 0.0052 (7) −0.0075 (6)

N3 0.0438 (7) 0.0385 (6) 0.0382 (8) −0.0016 (5) 0.0120 (6) −0.0015 (5)

N4 0.0509 (8) 0.0375 (7) 0.0437 (8) −0.0048 (5) 0.0147 (6) −0.0015 (5)

C1 0.0379 (8) 0.0349 (7) 0.0430 (9) −0.0032 (6) 0.0063 (7) −0.0026 (6)

C2 0.0508 (10) 0.0353 (7) 0.0359 (9) 0.0054 (6) 0.0070 (7) 0.0047 (6)

C3 0.0486 (9) 0.0392 (8) 0.0359 (9) 0.0033 (6) 0.0127 (7) 0.0061 (6)

C4 0.0397 (9) 0.0446 (8) 0.0331 (8) 0.0032 (6) 0.0007 (7) −0.0001 (6)

C5 0.0429 (9) 0.0435 (8) 0.0322 (8) 0.0040 (6) 0.0036 (7) −0.0030 (6)

C6 0.0459 (9) 0.0337 (7) 0.0336 (8) −0.0009 (6) 0.0032 (7) −0.0028 (6)

C7 0.0471 (9) 0.0340 (7) 0.0330 (8) 0.0032 (6) 0.0054 (7) −0.0039 (6)

C8 0.0485 (10) 0.0388 (8) 0.0474 (10) 0.0002 (7) 0.0092 (8) −0.0021 (7)

C9 0.0487 (10) 0.0534 (9) 0.0528 (11) −0.0045 (8) 0.0107 (8) −0.0021 (8)

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supporting information

C11 0.0598 (11) 0.0483 (9) 0.0423 (10) 0.0171 (8) 0.0067 (8) −0.0055 (7)

C12 0.0541 (10) 0.0373 (8) 0.0356 (9) 0.0046 (7) 0.0022 (7) −0.0053 (6)

C13 0.0394 (9) 0.0422 (8) 0.0428 (9) 0.0098 (6) 0.0083 (7) −0.0013 (7)

C14 0.0506 (10) 0.0410 (8) 0.0405 (9) 0.0066 (7) 0.0061 (7) −0.0013 (7)

C15 0.0462 (9) 0.0379 (7) 0.0311 (8) 0.0011 (6) 0.0065 (7) −0.0014 (6)

C16 0.0490 (9) 0.0365 (8) 0.0342 (8) −0.0018 (7) 0.0087 (7) −0.0019 (6)

C17 0.0447 (10) 0.0587 (10) 0.0533 (11) 0.0006 (8) 0.0135 (8) −0.0022 (8)

C18 0.0671 (14) 0.0723 (13) 0.0891 (18) 0.0069 (10) 0.0363 (13) −0.0094 (11)

C19 0.0787 (15) 0.0589 (11) 0.0861 (17) 0.0198 (10) 0.0278 (13) −0.0052 (10)

C20 0.0775 (14) 0.0393 (9) 0.0673 (13) 0.0023 (8) 0.0296 (11) −0.0053 (8)

C21 0.0550 (10) 0.0370 (8) 0.0341 (9) −0.0028 (7) 0.0132 (7) −0.0013 (6)

C22 0.0461 (9) 0.0450 (8) 0.0325 (8) −0.0004 (7) 0.0086 (7) 0.0003 (6)

C23 0.0516 (11) 0.0590 (10) 0.0700 (14) −0.0015 (8) 0.0183 (10) 0.0037 (9)

Geometric parameters (Å, º)

F1—C10 1.358 (2) O3—H311 0.901

O1—N2 1.4275 (19) O3—H312 0.925

O1—C12 1.355 (2) O4—H411 0.979

O2—C16 1.2320 (19) O4—H412 0.959

N1—C3 1.4929 (19) O5—H511 0.909

N1—C4 1.4948 (19) O5—H512 0.924

N1—C13 1.5004 (19) N1—H111 0.862

N2—C6 1.3023 (18) C1—H1 0.980

N3—C16 1.4079 (19) C2—H21 0.970

N3—C17 1.483 (2) C2—H22 0.970

N3—C21 1.363 (2) C3—H31 0.970

N4—C21 1.297 (2) C3—H32 0.970

N4—C22 1.3772 (19) C4—H41 0.970

C1—C2 1.530 (2) C4—H42 0.970

C1—C5 1.533 (2) C5—H51 0.970

C1—C6 1.504 (2) C5—H52 0.970

C2—C3 1.516 (2) C8—H8 0.930

C4—C5 1.517 (2) C9—H9 0.930

C6—C7 1.435 (2) C11—H11 0.930

C7—C8 1.404 (2) C13—H131 0.970

C7—C12 1.390 (2) C13—H132 0.970

C8—C9 1.371 (2) C14—H141 0.970

C9—C10 1.398 (2) C14—H142 0.970

C10—C11 1.361 (2) C17—H171 0.970

C11—C12 1.385 (2) C17—H172 0.970

C13—C14 1.519 (2) C18—H181 0.970

C14—C15 1.509 (2) C18—H182 0.970

C15—C16 1.428 (2) C19—H191 0.970

C15—C22 1.361 (2) C19—H192 0.970

C17—C18 1.501 (2) C20—H201 0.970

C18—C19 1.481 (3) C20—H202 0.970

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C20—C21 1.505 (2) C23—H232 0.960

C22—C23 1.498 (2) C23—H233 0.960

Cl1···O3 3.1048 (14) H11···H411ii _3.310

Cl1···N1 3.0351 (12) H11···H412ii _3.507

F1···O2i _{3.5586 (18)} _{H11···H171}iii _2.869

F1···N3i _{3.3503 (18)} _{H11···H202}i _3.223

F1···C16i _{3.454 (2)} _{H11···H311}ii _2.817

F1···C17i _{3.392 (2)} _{H11···H312}ii _3.003

F1···C23ii _{3.485 (2)} _H21···Cl1 _3.260

O1···O2iii _{3.5778 (18)} _H21···Cl1i _3.546

O1···O3ii _{3.4342 (18)} _H21···C14i _3.410

O1···O4ii _{3.466 (2)} _H21···H31i _3.188

O1···C13iii _{3.2876 (18)} _{H21···H141}i _3.422

O1···C15iii _{3.3720 (19)} _{H21···H142}i _2.583

O1···C16iii _{3.259 (2)} _{H21···H233}i _3.492

O2···F1i _{3.5586 (18)} _H22···Cl1i _3.142

O2···O1iv _{3.5778 (18)} _H22···O2vi _3.504

O2···O3v _{2.8421 (18)} _H22···C17vi _3.216

O2···C3vi _{3.311 (2)} _H22···C23i _3.407

O3···Cl1 3.1048 (14) H22···H142i _3.089

O3···O1vii _{3.4342 (18)} _{H22···H171}vi _2.992

O3···O2viii _{2.8421 (18)} _{H22···H172}vi _2.584

O3···O4 2.909 (2) H22···H232i _3.098

O3···C8 3.5085 (19) H22···H233i _2.829

O3···C9 3.343 (2) H31···Cl1i _2.971

O3···C13viii _{3.406 (2)} _H31···O2vi _3.462

O4···O1vii _{3.466 (2)} _H31···O3i _3.181

O4···O3 2.909 (2) H31···H8i _3.490

O4···O5 2.775 (4) H31···H21i _3.188

O4···O5ix _{2.754 (5)} _{H31···H311}i _2.758

O4···N4x _{2.997 (2)} _{H31···H312}i _2.873

O5···O4 2.775 (4) H32···O2vi _2.476

O5···O4ix _{2.754 (5)} _H32···O3i _3.524

O5···O5ix _{2.320 (5)} _H32···C16vi _3.592

O5···C4viii _{3.481 (4)} _H32···H9v _3.488

O5···C18iii _{3.527 (4)} _{H32···H172}vi _3.076

O5···C19iii _{3.331 (4)} _{H32···H311}i _3.419

N1···Cl1 3.0351 (12) H32···H312i _2.850

N2···C13iii _{3.4786 (19)} _H41···F1v _3.432

N2···C15iii _{3.397 (2)} _H41···O4v _3.182

N2···C22iii _{3.331 (2)} _H41···O5v _2.963

N3···F1i _{3.3503 (18)} _{H41···H411}v _3.039

N3···C10i _{3.544 (2)} _H41···H9v _2.921

N3···C12iv _{3.571 (2)} _{H41···H511}v _2.697

N4···O4xi _{2.997 (2)} _{H41···H512}v _3.274

C3···O2vi _{3.311 (2)} _{H41···H512}xii _3.315

(9)

supporting information

C8···O3 3.5085 (19) H42···O5v _3.332

C8···C14i _{3.512 (2)} _H42···O5xii _3.052

C9···O3 3.343 (2) H42···C18x _3.083

C10···N3i _{3.544 (2)} _H42···C19x _3.120

C10···C16i _{3.375 (2)} _{H42···H411}v _3.392

C12···N3iii _{3.571 (2)} _{H42···H181}x _2.794

C12···C22i _{3.578 (2)} _{H42···H182}x _2.887

C13···O1iv _{3.2876 (18)} _{H42···H192}x _2.386

C13···O3v _{3.406 (2)} _{H42···H511}v _2.995

C13···N2iv _{3.4786 (19)} _{H42···H511}xii _3.330

C14···C8i _{3.512 (2)} _{H42···H512}v _3.251

C15···O1iv _{3.3720 (19)} _{H42···H512}xii _2.960

C15···N2iv _{3.397 (2)} _H51···O4xii _3.461

C16···F1i _{3.454 (2)} _H51···O5v _3.152

C16···O1iv _{3.259 (2)} _H51···N4iii _2.799

C16···C10i _{3.375 (2)} _H51···C21iii _3.493

C17···F1i _{3.392 (2)} _H51···C22iii _3.509

C18···O5iv _{3.527 (4)} _H51···C23iii _3.545

C19···O5iv _{3.331 (4)} _{H51···H412}xii _2.956

C22···N2iv _{3.331 (2)} _{H51···H201}iii _2.935

C22···C12i _{3.578 (2)} _{H51···H231}iii _2.794

C23···F1vii _{3.485 (2)} _{H51···H511}v _3.464

Cl1···H8 2.983 H51···H511xii _3.518

Cl1···H11vii _3.028 _{H51···H512}v _2.920

Cl1···H21 3.260 H52···Cl1 3.117

Cl1···H21i _3.546 _H52···C19x _3.473

Cl1···H22i _3.142 _{H52···H192}x _2.618

Cl1···H31i _2.971 _{H52···H201}iii _2.986

Cl1···H52 3.117 H52···H202x _3.252

Cl1···H111 2.173 H111···Cl1 2.173

Cl1···H132 3.513 H111···H182x _3.337

Cl1···H142 3.173 H131···O1iv _3.058

Cl1···H182x _3.071 _H131···O3v _2.444

Cl1···H202x _2.987 _H131···O4v _3.543

Cl1···H232 3.107 H131···H411v _2.829

Cl1···H311 2.214 H131···H311v _3.326

Cl1···H312 3.251 H131···H312v _2.321

F1···H1viii _2.772 _{H132···Cl1} _3.513

F1···H41viii _3.432 _H132···O1iv _2.717

F1···H172i _2.762 _H132···N2iv _2.643

F1···H182i _3.334 _{H132···C18}x _3.595

F1···H231ii _2.921 _{H132···H411}v _3.513

F1···H232ii _3.171 _{H132···H181}x _3.309

O1···H411ii _3.032 _{H132···H182}x _2.986

O1···H412ii _3.360 _H141···O3i _3.379

O1···H131iii _3.058 _H141···C8i _2.996

O1···H132iii _2.717 _H141···C9i _3.035

(10)

O1···H312ii _3.295 _H141···H9i _3.065

O2···H9i _3.535 _{H141···H21}i _3.422

O2···H22vi _3.504 _{H141···H311}i _3.311

O2···H31vi _3.462 _{H141···H312}v _3.506

O2···H32vi _2.476 _{H141···H312}i _3.439

O2···H311v _3.183 _{H142···Cl1} _3.173

O2···H312v _1.934 _H142···C2i _3.268

O3···H411 1.947 H142···C7i _3.533

O3···H412 3.360 H142···C8i _3.370

O3···H8 2.996 H142···H8i _3.402

O3···H9 2.646 H142···H21i _2.583

O3···H11vii _3.069 _{H142···H22}i _3.089

O3···H31i _3.181 _{H171···C10}iv _3.214

O3···H32i _3.524 _{H171···C11}iv _2.847

O3···H131viii _2.444 _{H171···C12}iv _3.294

O3···H141i _3.379 _{H171···H11}iv _2.869

O4···H9 3.288 H171···H22vi _2.992

O4···H41viii _3.182 _{H171···H233}v _3.559

O4···H42viii _3.329 _{H171···H312}v _3.514

O4···H51xii _3.461 _H172···F1i _2.762

O4···H131viii _3.543 _H172···N2vi _3.478

O4···H201x _3.395 _H172···C1vi _3.154

O4···H202x _3.236 _H172···C2vi _3.166

O4···H231x _3.471 _H172···H1vi _2.461

O4···H311 3.288 H172···H22vi _2.584

O4···H511 1.871 H172···H32vi _3.076

O4···H511ix _3.381 _H181···O5iv _2.835

O4···H512 3.255 H181···N2vi _3.210

O4···H512ix _1.898 _{H181···H42}xi _2.794

O5···H411 3.426 H181···H132xi _3.309

O5···H411ix _3.591 _{H181···H231}v _3.390

O5···H412 3.432 H181···H233v _3.022

O5···H412ix _2.982 _{H181···H511}iv _3.452

O5···H9 3.598 H181···H512iv _3.253

O5···H41viii _2.963 _{H182···Cl1}xi _3.071

O5···H42viii _3.332 _H182···F1i _3.334

O5···H42xii _3.052 _H182···N2vi _3.448

O5···H51viii _3.152 _{H182···H42}xi _2.887

O5···H181iii _2.835 _{H182···H111}xi _3.337

O5···H191iii _3.046 _{H182···H132}xi _2.986

O5···H192iii _3.013 _H191···O5iv _3.046

O5···H231ii _2.922 _H191···C7iv _3.481

O5···H511ix _2.050 _H191···C8iv _3.074

O5···H512ix _1.854 _H191···C9iv _2.963

N2···H132iii _2.643 _{H191···C10}iv _3.274

N2···H172vi _3.478 _H191···H8iv _3.399

N2···H181vi _3.210 _H191···H9iv _3.234

(11)

supporting information

N2···H232iii _3.591 _{H191···H511}iv _3.076

N2···H233i _2.961 _H192···O5iv _3.013

N4···H411xi _3.428 _H192···C4xi _3.085

N4···H412xi _2.039 _H192···C5xi _3.004

N4···H11i _3.538 _{H192···H42}xi _2.386

N4···H51iv _2.799 _{H192···H51}xi _2.907

C1···H172vi _3.154 _{H192···H52}xi _2.618

C2···H142i _3.268 _{H192···H201}xiii _2.877

C2···H172vi _3.166 _{H192···H511}iv _3.017

C2···H233i _3.492 _{H192···H512}iv _3.586

C3···H311i _3.485 _{H192···H512}xiv _3.575

C3···H312i _3.288 _H201···O4xi _3.395

C4···H192x _3.085 _H201···C5iv _3.409

C4···H511v _3.249 _{H201···C19}xiii _3.407

C4···H512v _3.552 _{H201···C20}xiii _3.326

C4···H512xii _3.564 _{H201···H412}xi _2.840

C5···H192x _3.004 _{H201···H51}iv _2.935

C5···H201iii _3.409 _{H201···H52}iv _2.986

C5···H231iii _3.565 _{H201···H191}xiii _3.537

C6···H233i _3.096 _{H201···H192}xiii _2.877

C7···H142i _3.533 _{H201···H201}xiii _2.733

C7···H191iii _3.481 _{H201···H202}xiii _3.395

C7···H233i _3.284 _{H202···Cl1}xi _2.987

C8···H141i _2.996 _H202···O4xi _3.236

C8···H142i _3.370 _{H202···H411}xi _3.197

C8···H191iii _3.074 _{H202···H412}xi _2.771

C8···H311 3.231 H202···H8xi _3.489

C9···H141i _3.035 _{H202···H11}i _3.223

C9···H191iii _2.963 _{H202···H52}xi _3.252

C9···H311 3.429 H202···H201xiii _3.395

C10···H171iii _3.214 _{H202···H311}xi _3.247

C10···H191iii _3.274 _H231···F1vii _2.921

C11···H171iii _2.847 _H231···O4xi _3.471

C12···H171iii _3.294 _H231···O5vii _2.922

C12···H233i _3.229 _H231···C5iv _3.565

C13···H411v _3.561 _H231···H1iv _3.097

C13···H312v _3.226 _{H231···H412}xi _2.845

C14···H21i _3.410 _{H231···H51}iv _2.794

C16···H32vi _3.592 _{H231···H512}vii _3.024

C16···H312v _2.889 _{H232···Cl1} _3.107

C17···H1vi _3.405 _H232···F1vii _3.171

C17···H22vi _3.216 _H232···N2iv _3.591

C18···H42xi _3.083 _{H232···H22}i _3.098

C18···H132xi _3.595 _H233···O1i _3.041

C19···H42xi _3.120 _H233···N2i _2.961

C19···H52xi _3.473 _H233···C2i _3.492

C19···H201xiii _3.407 _H233···C6i _3.096

(12)

C20···H412xi _2.985 _{H233···C12}i _3.229

C20···H201xiii _3.326 _{H233···H412}xi _3.134

C21···H412xi _2.819 _{H233···H21}i _3.492

C21···H11i _3.402 _{H233···H22}i _2.829

C21···H51iv _3.493 _{H233···H171}viii _3.559

C22···H412xi _2.973 _{H233···H181}viii _3.022

C22···H51iv _3.509 _{H311···Cl1} _2.214

C23···H412xi _3.153 _H311···O2viii _3.183

C23···H22i _3.407 _H311···O4 _3.288

C23···H51iv _3.545 _H311···C3i _3.485

H1···F1v _2.772 _H311···C8 _3.231

H1···C17vi _3.405 _H311···C9 _3.429

H1···H172vi _2.461 _{H311···H411} _2.403

H1···H231iii _3.097 _{H311···H412} _3.572

H411···O1vii _3.032 _H311···H8 _2.533

H411···O3 1.947 H311···H9 2.931

H411···O5 3.426 H311···H11vii _2.817

H411···O5ix _3.591 _{H311···H31}i _2.758

H411···N4x _3.428 _{H311···H32}i _3.419

H411···C13viii _3.561 _{H311···H131}viii _3.326

H411···H9 2.875 H311···H141i _3.311

H411···H11vii _3.310 _{H311···H202}x _3.247

H411···H41viii _3.039 _{H312···Cl1} _3.251

H411···H42viii _3.392 _H312···O1vii _3.295

H411···H131viii _2.829 _H312···O2viii _1.934

H411···H132viii _3.513 _H312···C3i _3.288

H411···H202x _3.197 _{H312···C13}viii _3.226

H411···H311 2.403 H312···C16viii _2.889

H411···H312 2.677 H312···H411 2.677

H411···H511 2.554 H312···H9 3.393

H411···H512ix _2.772 _{H312···H11}vii _3.003

H412···O1vii _3.360 _{H312···H31}i _2.873

H412···O3 3.360 H312···H32i _2.850

H412···O5 3.432 H312···H131viii _2.321

H412···O5ix _2.982 _{H312···H141}viii _3.506

H412···N4x _2.039 _{H312···H141}i _3.439

H412···C20x _2.985 _{H312···H171}viii _3.514

H412···C21x _2.819 _H511···O4 _1.871

H412···C22x _2.973 _H511···O4ix _3.381

H412···C23x _3.153 _H511···O5ix _2.050

H412···H11vii _3.507 _H511···C4viii _3.249

H412···H51xii _2.956 _{H511···C19}iii _3.441

H412···H201x _2.840 _{H511···H411} _2.554

H412···H202x _2.771 _{H511···H412} _2.566

H412···H231x _2.845 _H511···H9 _3.275

H412···H233x _3.134 _{H511···H41}viii _2.697

H412···H311 3.572 H511···H42viii _2.995

(13)

supporting information

H412···H512ix _2.236 _{H511···H51}viii _3.464

H8···Cl1 2.983 H511···H51xii _3.518

H8···O3 2.996 H511···H181iii _3.452

H8···H31i _3.490 _{H511···H191}iii _3.076

H8···H141i _3.012 _{H511···H192}iii _3.017

H8···H142i _3.402 _{H511···H511}ix _2.162

H8···H191iii _3.399 _{H511···H512}ix _1.300

H8···H202x _3.489 _H512···O4 _3.255

H8···H311 2.533 H512···O4ix _1.898

H9···O2i _3.535 _H512···O5ix _1.854

H9···O3 2.646 H512···C4viii _3.552

H9···O4 3.288 H512···C4xii _3.564

H9···O5 3.598 H512···H411ix _2.772

H9···H411 2.875 H512···H412ix _2.236

H9···H32viii _3.488 _{H512···H41}viii _3.274

H9···H41viii _2.921 _{H512···H41}xii _3.315

H9···H141i _3.065 _{H512···H42}viii _3.251

H9···H191iii _3.234 _{H512···H42}xii _2.960

H9···H311 2.931 H512···H51viii _2.920

H9···H312 3.393 H512···H181iii _3.253

H9···H511 3.275 H512···H192iii _3.586

H11···Cl1ii _3.028 _{H512···H192}xv _3.575

H11···O3ii _3.069 _{H512···H231}ii _3.024

H11···N4i _3.538 _{H512···H511}ix _1.300

H11···C21i _3.402 _{H512···H512}ix _1.789

N2—O1—C12 107.80 (11) C3—C2—H21 108.6

C3—N1—C4 109.77 (10) C3—C2—H22 108.6

C3—N1—C13 114.52 (12) H21—C2—H22 109.5

C4—N1—C13 111.61 (10) N1—C3—H31 109.5

O1—N2—C6 107.03 (13) N1—C3—H32 109.4

C16—N3—C17 115.75 (12) C2—C3—H31 109.5

C16—N3—C21 120.66 (14) C2—C3—H32 109.4

C17—N3—C21 123.58 (13) H31—C3—H32 109.5

C21—N4—C22 119.30 (13) N1—C4—H41 109.2

C2—C1—C5 110.14 (12) N1—C4—H42 109.2

C2—C1—C6 109.25 (12) C5—C4—H41 109.2

C5—C1—C6 112.58 (14) C5—C4—H42 109.2

C1—C2—C3 112.90 (12) H41—C4—H42 109.5

N1—C3—C2 109.53 (13) C1—C5—H51 108.9

N1—C4—C5 110.54 (11) C1—C5—H52 109.0

C1—C5—C4 111.58 (14) C4—C5—H51 108.9

N2—C6—C1 118.89 (15) C4—C5—H52 108.9

N2—C6—C7 111.51 (14) H51—C5—H52 109.5

C1—C6—C7 129.48 (12) C7—C8—H8 120.9

C6—C7—C8 137.02 (14) C9—C8—H8 120.9

C6—C7—C12 103.84 (13) C8—C9—H9 120.2

(14)

C7—C8—C9 118.16 (14) C10—C11—H11 123.0

C8—C9—C10 119.53 (16) C12—C11—H11 123.0

F1—C10—C9 116.78 (16) N1—C13—H131 108.8

F1—C10—C11 118.31 (16) N1—C13—H132 108.8

C9—C10—C11 124.91 (18) C14—C13—H131 108.8

C10—C11—C12 114.04 (15) C14—C13—H132 108.9

O1—C12—C7 109.81 (15) H131—C13—H132 109.5

O1—C12—C11 125.95 (14) C13—C14—H141 108.7

C7—C12—C11 124.23 (15) C13—C14—H142 108.6

N1—C13—C14 112.00 (11) C15—C14—H141 108.7

C13—C14—C15 112.71 (12) C15—C14—H142 108.7

C14—C15—C16 116.41 (13) H141—C14—H142 109.5

C14—C15—C22 124.26 (15) N3—C17—H171 108.6

C16—C15—C22 119.32 (14) N3—C17—H172 108.5

O2—C16—N3 118.78 (15) C18—C17—H171 108.5

O2—C16—C15 125.30 (14) C18—C17—H172 108.6

N3—C16—C15 115.92 (13) H171—C17—H172 109.5

N3—C17—C18 113.13 (14) C17—C18—H181 108.9

C17—C18—C19 111.8 (2) C17—C18—H182 108.9

C18—C19—C20 110.04 (17) C19—C18—H181 108.9

C19—C20—C21 114.85 (15) C19—C18—H182 108.9

N3—C21—N4 122.92 (14) H181—C18—H182 109.5

N3—C21—C20 119.06 (16) C18—C19—H191 109.3

N4—C21—C20 118.02 (14) C18—C19—H192 109.3

N4—C22—C15 121.85 (16) C20—C19—H191 109.3

N4—C22—C23 113.98 (13) C20—C19—H192 109.3

C15—C22—C23 124.16 (15) H191—C19—H192 109.5

H311—O3—H312 95.3 C19—C20—H201 108.1

H411—O4—H412 107.9 C19—C20—H202 108.1

H511—O5—H512 109.7 C21—C20—H201 108.1

C3—N1—H111 112.0 C21—C20—H202 108.1

C4—N1—H111 105.5 H201—C20—H202 109.5

C13—N1—H111 103.0 C22—C23—H231 109.5

C2—C1—H1 108.3 C22—C23—H232 109.5

C5—C1—H1 108.3 C22—C23—H233 109.5

C6—C1—H1 108.3 H231—C23—H232 109.5

C1—C2—H21 108.7 H231—C23—H233 109.5

C1—C2—H22 108.6 H232—C23—H233 109.5

N2—O1—C12—C7 0.07 (13) N1—C4—C5—C1 −56.97 (16)

N2—O1—C12—C11 −178.81 (16) N2—C6—C7—C8 178.56 (18)

C12—O1—N2—C6 −0.37 (17) N2—C6—C7—C12 −0.48 (18)

C3—N1—C4—C5 61.91 (16) C1—C6—C7—C8 2.6 (3)

C4—N1—C3—C2 −61.05 (15) C1—C6—C7—C12 −176.46 (15)

C3—N1—C13—C14 −53.41 (16) C6—C7—C8—C9 −178.39 (18)

C13—N1—C3—C2 172.50 (11) C6—C7—C12—O1 0.23 (17)

C4—N1—C13—C14 −178.90 (12) C6—C7—C12—C11 179.13 (16)

(15)

supporting information

O1—N2—C6—C1 176.99 (12) C8—C7—C12—C11 −0.1 (2)

O1—N2—C6—C7 0.53 (18) C12—C7—C8—C9 0.5 (2)

C16—N3—C17—C18 −168.04 (15) C7—C8—C9—C10 −0.7 (2)

C17—N3—C16—O2 −0.9 (2) C8—C9—C10—F1 179.65 (16)

C17—N3—C16—C15 178.88 (13) C8—C9—C10—C11 0.5 (2)

C16—N3—C21—N4 1.1 (2) F1—C10—C11—C12 −179.21 (15)

C16—N3—C21—C20 −178.67 (14) C9—C10—C11—C12 −0.1 (2)

C21—N3—C16—O2 178.19 (14) C10—C11—C12—O1 178.61 (16)

C21—N3—C16—C15 −2.1 (2) C10—C11—C12—C7 −0.1 (2)

C17—N3—C21—N4 −179.92 (14) N1—C13—C14—C15 −167.07 (13)

C17—N3—C21—C20 0.3 (2) C13—C14—C15—C16 −77.62 (18)

C21—N3—C17—C18 12.9 (2) C13—C14—C15—C22 103.24 (18)

C21—N4—C22—C15 −0.09 (18) C14—C15—C16—O2 2.5 (2)

C21—N4—C22—C23 −178.73 (15) C14—C15—C16—N3 −177.18 (13)

C22—N4—C21—N3 0.04 (17) C14—C15—C22—N4 178.13 (14)

C22—N4—C21—C20 179.82 (14) C14—C15—C22—C23 −3.4 (2)

C2—C1—C5—C4 50.89 (17) C16—C15—C22—N4 −1.0 (2)

C5—C1—C2—C3 −51.38 (18) C16—C15—C22—C23 177.51 (15)

C2—C1—C6—N2 −110.61 (16) C22—C15—C16—O2 −178.28 (15)

C2—C1—C6—C7 65.1 (2) C22—C15—C16—N3 2.0 (2)

C6—C1—C2—C3 −175.53 (13) N3—C17—C18—C19 −43.5 (2)

C5—C1—C6—N2 126.70 (15) C17—C18—C19—C20 60.7 (2)

C5—C1—C6—C7 −57.6 (2) C18—C19—C20—C21 −47.0 (2)

C6—C1—C5—C4 173.09 (12) C19—C20—C21—N3 17.1 (2)

C1—C2—C3—N1 56.74 (16) C19—C20—C21—N4 −162.66 (17)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x+3/2, y+1/2, −z+3/2; (iv) −x+3/2, y−1/2, −z+3/2; (v) x+1, y, z; (vi) −x+2, −y+1, −z+1; (vii) −x+1/2, y−1/2, −z+3/2; (viii) x−1, y, z; (ix) −x, −y+1, −z+2; (x) x−1/2, −y+1/2, z+1/2; (xi) x+1/2, −y+1/2, z−1/2; (xii) −x+1, −y+1, −z+2; (xiii) −x+2, −y, −z+1; (xiv) x+3/2, −y+1/2, z−1/2; (xv) x−3/2, −y+1/2, z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N1—H111···Cl1 0.86 2.17 3.0351 (12) 179

O3—H311···Cl1 0.90 2.21 3.1047 (14) 170

O3—H312···O2viii _0.93 _1.93 _{2.8421 (18)} ₁₆₇

O4—H411···O3 0.98 1.95 2.909 (2) 167

O4—H412···N4x _0.96 _2.04 _{2.997 (2)} ₁₇₈

O5—H511···O4 0.91 1.87 2.775 (4) 173

O5—H512···O4ix _0.92 _1.90 _{2.754 (5)} ₁₅₃

O5—H512···O5ix _0.92 _1.85 _{2.320 (5)} ₁₀₉