Morpholinium 5 chloro 2 nitro­benzoate

organic papers

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Structure Reports Online

ISSN 1600-5368

Morpholinium 5-chloro-2-nitrobenzoate

Hiroyuki Ishida,* Bilkish Rahman and Setsuo Kashino

Department of Chemistry, Faculty of Science, Okayama University, Okayama 700-8530, Japan

Correspondence e-mail: [email protected]

Key indicators Single-crystal X-ray study

T= 298 K

Mean(C±C) = 0.004 AÊ

Rfactor = 0.057

wRfactor = 0.090

Data-to-parameter ratio = 13.3

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

#2001 International Union of Crystallography Printed in Great Britain ± all rights reserved

In the title compound, C4H10NO+C7H3ClNO4ÿ, two cations

and two anions are connected by NÐH O hydrogen bonds to afford a ring with descriptorR44(12), which is located on an

inversion center. There are four CÐH O interactions which connect the ring units to form a three-dimensional network.

Comment

The title compound, (I), was investigated as part of a study on

DÐH Ahydrogen bonding (D: N, O or C;A: N, O or Cl) in chloro- and nitro-substituted benzoic acid±amine systems (Ishidaet al., 2001). To our knowledge, this is the ®rst struc-tural report of a 5-chloro-2-nitrobenzoic acid±amine system.

In the crystal, two cations and two anions are held together by short NÐH O hydrogen bonds (Table 2), forming a centrosymmetric hydrogen-bonded ring (Fig. 1) with graph-set descriptor R44(12) (Bernstein et al., 1995). The nitro and

carboxyl groups are considerably twisted out of the benzene ring plane. The dihedral angle between the nitro group and the benzene ring is 51.8 (2)_{and that between the carboxyl group}

and the benzene ring is 46.1 (2)_{. There are four CÐH O}

interactions involving O atoms of the nitro group and of the cation. TheR44(12) rings are arranged along thea,bandcaxes

through C6ÐH3 O5iii _{and C9ÐH9 O5}iv _{interactions, a}

C11ÐH13 O3v_{interaction, and a C4ÐH2 O4}ii_interaction

(symmetry codes are as in Table 2), respectively, to form a three-dimensional network (Fig. 2).

Experimental

Crystals of (I) were obtained by slow evaporation from an aceto-nitrile solution of morpholine and the benzoic acid in a molar ratio of 1:1.

Crystal data

C4H10NO+C7H3ClNO4ÿ

Mr= 288.69

Monoclinic,P21/n

a= 10.6482 (15) AÊ b= 5.9079 (12) AÊ c= 21.084 (3) AÊ = 102.722 (10) V= 1293.8 (3) AÊ3

Z= 4

Dx= 1.482 Mg mÿ3

MoKradiation Cell parameters from 25

re¯ections = 11.1±12.0

= 0.31 mmÿ1

T= 298 K Prismatic, colorless 0.500.300.20 mm

Data collection

Rigaku AFC-5Rdiffractometer !±2scans

Absorption correction: scan (Northet al., 1968) Tmin= 0.894,Tmax= 0.939 3789 measured re¯ections 2980 independent re¯ections 1667 re¯ections withI> 2(I)

Rint= 0.024 max= 27.5

h=ÿ1!13 k= 0!7 l=ÿ27!27 3 standard re¯ections

every 97 re¯ections intensity decay: 0.5%

Re®nement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.057}

wR(F2_{) = 0.090}

S= 1.14 2979 re¯ections 224 parameters

All H-atom parameters re®ned w= 1/[2_(F

o) + 0.00029|Fo|2]

(/)max= 0.001

max= 0.48 e AÊÿ3

min=ÿ0.61 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,_).

ClÐC5 1.742 (3)

O1ÐC7 1.238 (3)

O2ÐC7 1.240 (3)

O3ÐN1 1.215 (3)

O4ÐN1 1.222 (3)

N1ÐC2 1.474 (3)

C1ÐC2 1.383 (3)

C1ÐC6 1.387 (3)

C1ÐC7 1.523 (3)

C2ÐC3 1.377 (4)

C3ÐC4 1.376 (4)

C4ÐC5 1.367 (4)

C5ÐC6 1.380 (4)

O5ÐC9 1.417 (4)

O5ÐC10 1.423 (3)

N2ÐC8 1.479 (3)

N2ÐC11 1.492 (4)

C8ÐC9 1.503 (4)

C10ÐC11 1.505 (4)

C9ÐO5ÐC10 109.7 (2) C8ÐN2ÐC11 110.3 (2)

N2ÐC8ÐC9 109.5 (2)

O5ÐC9ÐC8 111.7 (3)

O5ÐC10ÐC11 110.9 (2) N2ÐC11ÐC10 109.5 (3)

Table 2

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

N2ÐH4 O2 1.02 (3) 1.71 (3) 2.696 (3) 164 (3) N2ÐH5 O1i _{0.89 (3) 1.86 (3) 2.734 (3) 169 (2)} C4ÐH2 O4ii _{0.91 (3) 2.74 (3) 3.408 (4) 132 (2)} C6ÐH3 O5iii _{0.95 (2) 2.63 (2) 3.339 (3) 131 (2)} C9ÐH9 O5iv _{1.04 (3) 2.68 (3) 3.455 (4) 132 (2)} C11ÐH13 O3v _{1.01 (2) 2.51 (2) 3.447 (4) 155 (2)}

Symmetry codes: (i) 1ÿx;ÿy;ÿz; (ii)3

2ÿx;12‡y;12ÿz; (iii) 1‡x;y;z; (iv)ÿx;ÿy;ÿz; (v) 1ÿx;1ÿy;ÿz.

H atoms were located in difference Fourier maps and re®ned isotropically. Re®ned distances: CÐH = 0.89 (2)±1.04 (3) AÊ and NÐ H = 0.89 (3)±1.02 (3) AÊ.

Data collection: MSC/FC Diffractometer Control Software (Molecular Structure Corporation, 1990); cell re®nement:MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows(Molecular Structure Corporation, 1997±1999); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to re®ne structure: TEXSAN for Windows; software used to prepare material for publication:TEXSAN for Windows.

X-ray measurements were made at the X-ray Laboratory of Okayama University.

Acta Cryst.(2001). E57, o630±o632 Hiroyuki Ishidaet al. C₄H₁₀NO+C₇H₃ClNO₄ÿ

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organic papers

Figure 2

Packing diagram showing a three-dimensional hydrogen-bond network formed via NÐH O and CÐH O hydrogen bonds indicated by dashed and dotted lines, respectively [symmetry codes are as in Table 2].

Figure 1

organic papers

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Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993).J. Appl. Cryst.26, 343±350.

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995).Angew. Chem. Int. Ed. Engl.34, 1555±1573.

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

Ishida, H., Rahman, B. & Kashino, S. (2001)Acta Cryst.C57.In the press. Molecular Structure Corporation (1990).MSC/AFC Diffractometer Control

Software.MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.

Molecular Structure Corporation (1997±1999). TEXSAN for Windows. Version 1.06. MSC, 9009 New Trails Drive, The Woodlands, TX 77381, USA. North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst.A24, 351±

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Acta Cryst. (2001). E57, o630–o632

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Acta Cryst. (2001). E57, o630–o632 [doi:10.1107/S1600536801009953]

Morpholinium 5-chloro-2-nitrobenzoate

Hiroyuki Ishida, Bilkish Rahman and Setsuo Kashino

S1. Comment

The title compound, (I), was investigated as part of a study on D—H···A hydrogen bonding (D: N, O or C; A: N, O or Cl)

in chloro- and nitro-substituted benzoic acid–amine systems (Ishida et al., 2001). To our knowledge, this is the first

structural report of a 5-chloro-2-nitrobenzoic acid–amine system.

In the crystal, two cations and two anions are held together by short N—H···O hydrogen bonds (Tables 2), forming a

centrosymmetric hydrogen-bonded ring (Fig. 1) with graph-set descriptor R44(12) (Bernstein et al., 1995). The nitro and

carboxyl groups are considerably twisted out of the benzene ring. The dihedral angle between the nitro group and the

benzene ring is 51.8 (2)° and that between the carboxyl group and the benzene ring is 46.1 (2)°. There are four C—H···O

interactions involving O atoms of the nitro group and of the cation. The R44(12) rings are arranged along the a, b and c

axes through C6—H3···O5iii _{and C9—H9···O5}iv _{interactions, a C11—H13···O3}v _{interaction, and a C4—H2···O4}ii

interaction (symmetry codes are as in Table 2), respectively, to form a three-dimensional network (Fig. 2).

S2. Experimental

Crystals of (I) were obtained by slow evaporation from an acetonitrile solution of morpholine with the benzoic acid with

a molar ratio of 1:1.

S3. Refinement

H atoms were found in difference Fourier maps and refined isotropically. Refined distances: C—H = 0.89 (2)–1.04 (3) Å

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Acta Cryst. (2001). E57, o630–o632

Figure 1

ORTEP-3 (Farrugia, 1997) drawing of a hydrogen-bonded ring with the atom-labeling. Displacement ellipsoids of non-H

atoms are drawn at the 50% probability level. N—H···O hydrogen bonds are indicated by dashed lines [symmetry code:

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Acta Cryst. (2001). E57, o630–o632

Figure 2

Packing diagram showing a three-dimensional hydrogen-bond network formed via N—H···O and C—H···O hydrogen

bonds indicated by dashed and dotted lines, respectively [symmetry codes are as Table 2].

(I)

Crystal data

C4H10NO+·C7H3ClNO4− Mr = 288.69

Monoclinic, P21/n Hall symbol: -P 2yn

a = 10.6482 (15) Å

b = 5.9079 (12) Å

c = 21.084 (3) Å

β = 102.722 (10)°

V = 1293.8 (3) Å3 Z = 4

F(000) = 600.0

Dx = 1.482 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 25 reflections

θ = 11.1–12.0°

µ = 0.31 mm−1

T = 298 K

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Acta Cryst. (2001). E57, o630–o632

Data collection

Rigaku AFC-5R diffractometer

Radiation source: Rigaku rotating anode Graphite monochromator

ω–2θ scans

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

Tmin = 0.894, Tmax = 0.939 3789 measured reflections

2980 independent reflections 1667 reflections with I > 2σ(I)

Rint = 0.024

θmax = 27.5°, θmin = 2.0°

h = −1→13

k = 0→7

l = −27→27

3 standard reflections every 97 reflections intensity decay: 0.5%

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.057} wR(F2_{) = 0.090} S = 1.14 2979 reflections 224 parameters 0 restraints

0 constraints

All H-atom parameters refined

Weighting scheme based on measured s.u.'s w =

1/[σ2_(F

o) + 0.00029|Fo|2] (Δ/σ)max = 0.001

Δρmax = 0.48 e Å−3 Δρmin = −0.61 e Å−3

Special details

Experimental. The scan width was (1.68 + 0.30tanθ)° with an ω scan speed of 6° per minute (up to 3 scans to achieve

I/σ(I) > 10). Stationary background counts were recorded at each end of the scan, and the scan time:background time

ratio was 2:1.

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

x y z Uiso*/Ueq

Cl 1.15180 (6) 0.51623 (16) 0.20486 (4) 0.0733 (3)

O1 0.71434 (17) 0.1900 (4) 0.04790 (9) 0.0652 (6)

O2 0.59263 (15) 0.2039 (3) 0.12135 (8) 0.0512 (5)

O3 0.53246 (16) 0.6782 (3) 0.09021 (9) 0.0533 (5)

O4 0.54071 (17) 0.7205 (4) 0.19264 (9) 0.0676 (7)

O5 0.09276 (16) 0.2138 (4) 0.05282 (9) 0.0593 (6)

N1 0.59015 (19) 0.6798 (4) 0.14677 (10) 0.0438 (6)

N2 0.35291 (19) 0.0935 (4) 0.05658 (10) 0.0389 (6)

C1 0.7737 (2) 0.4405 (4) 0.13564 (10) 0.0317 (6)

C2 0.7294 (2) 0.6321 (4) 0.16144 (10) 0.0352 (6)

C3 0.8090 (3) 0.7874 (5) 0.19918 (12) 0.0458 (8)

C4 0.9397 (3) 0.7502 (5) 0.21209 (13) 0.0513 (8)

C5 0.9861 (2) 0.5619 (5) 0.18731 (11) 0.0432 (7)

C6 0.9059 (2) 0.4086 (4) 0.14874 (11) 0.0389 (7)

C7 0.6844 (2) 0.2622 (4) 0.09767 (11) 0.0382 (7)

C8 0.2824 (3) 0.0022 (6) 0.10408 (14) 0.0529 (9)

C9 0.1407 (3) −0.0036 (6) 0.07399 (17) 0.0613 (10)

C10 0.1564 (3) 0.2956 (6) 0.00470 (14) 0.0541 (9)

C11 0.2989 (3) 0.3179 (5) 0.03186 (15) 0.0511 (9)

H1 0.774 (2) 0.908 (4) 0.2139 (10) 0.039 (7)*

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H3 0.939 (2) 0.274 (4) 0.1336 (10) 0.039 (6)*

H4 0.448 (3) 0.109 (5) 0.0777 (12) 0.074 (8)*

H5 0.342 (2) −0.004 (4) 0.0237 (12) 0.050 (7)*

H6 0.301 (2) 0.108 (5) 0.1410 (12) 0.067 (8)*

H7 0.318 (3) −0.152 (5) 0.1192 (13) 0.075 (9)*

H8 0.094 (3) −0.052 (5) 0.1049 (13) 0.086 (9)*

H9 0.122 (3) −0.120 (5) 0.0363 (14) 0.078 (9)*

H10 0.123 (2) 0.449 (5) −0.0065 (12) 0.070 (8)*

H11 0.138 (2) 0.194 (4) −0.0350 (11) 0.054 (7)*

H12 0.317 (3) 0.420 (5) 0.0702 (13) 0.072 (9)*

H13 0.345 (2) 0.372 (5) −0.0022 (12) 0.067 (8)*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Cl 0.0376 (3) 0.1031 (7) 0.0715 (5) −0.0035 (4) −0.0048 (3) −0.0109 (5)

O1 0.0681 (12) 0.0687 (14) 0.0588 (12) −0.0133 (11) 0.0140 (10) −0.0336 (11)

O2 0.0406 (10) 0.0476 (11) 0.0631 (12) −0.0115 (9) 0.0064 (9) −0.0029 (10)

O3 0.0462 (10) 0.0547 (12) 0.0531 (11) 0.0110 (9) −0.0017 (8) −0.0074 (10)

O4 0.0661 (12) 0.0817 (15) 0.0637 (12) 0.0221 (12) 0.0331 (10) 0.0018 (12)

O5 0.0416 (10) 0.0778 (15) 0.0626 (12) 0.0162 (10) 0.0204 (9) 0.0077 (11)

N1 0.0457 (12) 0.0347 (12) 0.0522 (13) 0.0064 (10) 0.0133 (11) −0.0018 (11)

N2 0.0351 (11) 0.0411 (13) 0.0418 (12) −0.0031 (10) 0.0114 (9) −0.0112 (11)

C1 0.0389 (12) 0.0277 (13) 0.0278 (11) −0.0002 (10) 0.0058 (9) −0.0006 (10)

C2 0.0391 (12) 0.0345 (14) 0.0318 (12) 0.0003 (11) 0.0072 (10) 0.0006 (11)

C3 0.0597 (17) 0.0353 (15) 0.0421 (14) 0.0014 (14) 0.0101 (12) −0.0100 (13)

C4 0.0532 (16) 0.0491 (19) 0.0449 (16) −0.0143 (15) −0.0039 (12) −0.0106 (14)

C5 0.0392 (12) 0.0502 (16) 0.0365 (13) −0.0053 (12) 0.0009 (10) 0.0009 (12)

C6 0.0397 (13) 0.0370 (15) 0.0390 (14) 0.0022 (12) 0.0064 (11) −0.0009 (12)

C7 0.0399 (13) 0.0254 (13) 0.0439 (15) 0.0059 (11) −0.0027 (11) −0.0013 (11)

C8 0.0468 (14) 0.065 (2) 0.0504 (17) 0.0073 (16) 0.0174 (13) 0.0104 (17)

C9 0.0428 (14) 0.070 (2) 0.077 (2) 0.0010 (17) 0.0264 (15) 0.016 (2)

C10 0.0492 (16) 0.060 (2) 0.0524 (18) 0.0098 (15) 0.0103 (13) 0.0050 (17)

C11 0.0507 (16) 0.0456 (17) 0.0581 (18) −0.0038 (14) 0.0147 (14) 0.0030 (16)

Geometric parameters (Å, º)

Cl—C5 1.742 (3) O5—C9 1.417 (4)

O1—C7 1.238 (3) O5—C10 1.423 (3)

O2—C7 1.240 (3) N2—C8 1.479 (3)

O3—N1 1.215 (3) N2—C11 1.492 (4)

O4—N1 1.222 (3) N2—H4 1.02 (3)

N1—C2 1.474 (3) N2—H5 0.89 (3)

C1—C2 1.383 (3) C8—C9 1.503 (4)

C1—C6 1.387 (3) C8—H6 0.98 (3)

C1—C7 1.523 (3) C8—H7 1.01 (3)

C2—C3 1.377 (4) C9—H8 0.95 (3)

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C3—H1 0.89 (2) C10—C11 1.505 (4)

C4—C5 1.367 (4) C10—H10 0.98 (3)

C4—H2 0.91 (3) C10—H11 1.01 (3)

C5—C6 1.380 (4) C11—H12 0.99 (3)

C6—H3 0.95 (2) C11—H13 1.01 (3)

O1···N2i _{2.734 (3) O3···N2}iv _{3.096 (3)}

O1···C11ii _{3.346 (4) O3···C11 3.299 (4)}

O1···C8i _{3.407 (4) O3···C8}iv _{3.344 (4)}

O1···C11i _{3.427 (4) O3···C11}ii _{3.447 (4)}

O1···C9i _{3.457 (4) O4···C5}v _{3.297 (3)}

O1···C10i _{3.468 (4) O4···C8}iv _{3.400 (4)}

O1···O3ii _{3.553 (3) O4···C4}vi _{3.408 (4)}

O2···N2 2.696 (3) O4···C6v _{3.450 (3)}

O2···N1iii _{3.143 (3) O4···C3}vi _{3.564 (4)}

O2···O3iii _{3.210 (3) O5···C6}vii _{3.339 (3)}

O2···O4iii _{3.330 (3) O5···C9}viii _{3.455 (4)}

O2···C11 3.346 (3) N2···C7 3.586 (3)

O2···C8 3.454 (3) C1···C10ii _{3.565 (4)}

O2···C3iii _{3.520 (4) C3···C7}iv _{3.600 (4)}

C9—O5—C10 109.7 (2) O1—C7—O2 128.2 (2)

O3—N1—O4 124.4 (2) O1—C7—C1 115.9 (2)

O3—N1—C2 118.2 (2) O2—C7—C1 115.9 (2)

O4—N1—C2 117.4 (2) N2—C8—C9 109.5 (2)

C8—N2—C11 110.3 (2) N2—C8—H6 105.0 (16)

C8—N2—H4 109.9 (16) N2—C8—H7 109.4 (17)

C8—N2—H5 107.1 (16) C9—C8—H6 111.2 (16)

C11—N2—H4 110.1 (17) C9—C8—H7 112.5 (17)

C11—N2—H5 109.2 (17) H6—C8—H7 109 (2)

H4—N2—H5 110 (2) O5—C9—C8 111.7 (3)

C2—C1—C6 116.9 (2) O5—C9—H8 106 (2)

C2—C1—C7 123.1 (2) O5—C9—H9 111.3 (17)

C6—C1—C7 120.0 (2) C8—C9—H8 110.5 (19)

N1—C2—C1 119.2 (2) C8—C9—H9 110.1 (16)

N1—C2—C3 117.2 (2) H8—C9—H9 107 (3)

C1—C2—C3 123.6 (2) O5—C10—C11 110.9 (2)

C2—C3—C4 118.3 (3) O5—C10—H10 106.1 (17)

C2—C3—H1 118.7 (15) O5—C10—H11 110.5 (14)

C4—C3—H1 122.9 (15) C11—C10—H10 107.3 (17)

C3—C4—C5 119.3 (3) C11—C10—H11 111.2 (14)

C3—C4—H2 121.8 (16) H10—C10—H11 111 (2)

C5—C4—H2 118.9 (16) N2—C11—C10 109.5 (3)

Cl—C5—C4 118.6 (2) N2—C11—H12 105.3 (17)

Cl—C5—C6 119.3 (2) N2—C11—H13 108.7 (17)

C4—C5—C6 122.1 (3) C10—C11—H12 111.4 (16)

C1—C6—C5 119.8 (3) C10—C11—H13 111.5 (16)

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C5—C6—H3 120.9 (14)

Cl—C5—C4—C3 −179.4 (2) N1—C2—C3—C4 −178.2 (2)

Cl—C5—C6—C1 178.57 (19) C1—C2—C3—C4 −0.1 (4)

O1—C7—C1—C2 137.0 (3) C1—C6—C5—C4 −1.8 (4)

O1—C7—C1—C6 −46.6 (3) C2—C1—C6—C5 1.6 (4)

O2—C7—C1—C2 −44.7 (3) C2—C3—C4—C5 −0.0 (4)

O2—C7—C1—C6 131.8 (3) C3—C2—C1—C6 −0.7 (4)

O3—N1—C2—C1 −51.3 (3) C3—C2—C1—C7 175.9 (2)

O3—N1—C2—C3 126.9 (3) C3—C4—C5—C6 1.0 (4)

O4—N1—C2—C1 129.3 (2) C5—C6—C1—C7 −175.1 (2)

O4—N1—C2—C3 −52.5 (3) C8—N2—C11—C10 −54.8 (3)

O5—C9—C8—N2 −57.8 (4) C8—C9—O5—C10 61.0 (4)

O5—C10—C11—N2 58.3 (4) C9—O5—C10—C11 −61.2 (4)

N1—C2—C1—C6 177.4 (2) C9—C8—N2—C11 54.2 (4)

N1—C2—C1—C7 −6.0 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N2—H4···O2 1.02 (3) 1.71 (3) 2.696 (3) 164 (3)

N2—H5···O1i _{0.89 (3) 1.86 (3) 2.734 (3) 169 (2)}

C4—H2···O4v _{0.91 (3) 2.74 (3) 3.408 (4) 132 (2)}

C6—H3···O5ix _{0.95 (2) 2.63 (2) 3.339 (3) 131 (2)}

C9—H9···O5viii _{1.04 (3) 2.68 (3) 3.455 (4) 132 (2)}

C11—H13···O3ii _{1.01 (2) 2.51 (2) 3.447 (4) 155 (2)}