Acta Cryst.(2001). E57, o627±o629 DOI: 10.1107/S1600536801009941 Hiroyuki Ishidaet al. C4H10NO+C7H3ClNO4ÿ
o627
organic papers
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
Morpholinium 4-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= 299 K
Mean(C±C) = 0.003 AÊ
Rfactor = 0.050
wRfactor = 0.098
Data-to-parameter ratio = 13.4
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 three 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 4-chloro-2-nitrobenzoic acid±amine system.
An acid±base interaction involving a proton transfer is observed as expected from the high basicity of this present amine. Two cations and two anions are held together by short NÐH O hydrogen bonds (Table 2), forming a centrosym-metric 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 plane is 50.7 (2)and that between the carboxyl
group and the benzene ring is 43.6 (2). The macro rings are
arranged along theaaxis by a CÐH O interaction formed between the cation and the nitro group (C8ÐH7 O3iii; Table
2). The rings are also linked along thebandcaxes by two CÐ H O interactions (C5ÐH2 O5ii and C11ÐH12 O2iv;
Table 2), formed between the benzene ring and the cation, and between the cation and the carboxyl group (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.
organic papers
o628
Hiroyuki Ishidaet al. C4H10NO+C7H3ClNO4ÿ Acta Cryst.(2001). E57, o627±o629Crystal data
C4H10NO+C7H3ClNO4ÿ
Mr= 288.69
Monoclinic,P21/n
a= 6.0475 (10) AÊ b= 25.808 (4) AÊ c= 8.6101 (10) AÊ = 101.853 (11)
V= 1315.2 (3) AÊ3
Z= 4
Dx= 1.458 Mg mÿ3
MoKradiation Cell parameters from 25
re¯ections = 11.0±12.1 = 0.31 mmÿ1
T= 299 K Plate, colorless 0.450.350.18 mm
Data collection
Rigaku AFC-5Rdiffractometer !±2scans
Absorption correction: scan (Northet al., 1968) Tmin= 0.881,Tmax= 0.946 3948 measured re¯ections 3006 independent re¯ections 1740 re¯ections withI> 2(I)
Rint= 0.028 max= 27.5
h=ÿ1!7 k= 0!33 l=ÿ11!11 3 standard re¯ections
every 97 re¯ections intensity decay: 4.7% Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.050
wR(F2) = 0.098
S= 1.19 3005 re¯ections 225 parameters
All H-atom parameters re®ned w= 1/[2(F
o) + 0.00032|Fo|2]
(/)max= 0.01
max= 0.50 e AÊÿ3
min=ÿ0.41 e AÊÿ3
Extinction correction: Zachariasen (1967)
Extinction coef®cient: 9.9 (16)10ÿ7
Table 1
Selected geometric parameters (AÊ,).
ClÐC4 1.735 (2)
O1ÐC7 1.238 (3)
O2ÐC7 1.231 (3)
O3ÐN1 1.213 (2)
O4ÐN1 1.219 (2)
N1ÐC2 1.472 (3)
C1ÐC2 1.390 (3)
C1ÐC6 1.385 (3)
C1ÐC7 1.519 (3)
C2ÐC3 1.379 (3)
C3ÐC4 1.375 (3)
C4ÐC5 1.384 (4)
C5ÐC6 1.380 (4)
O5ÐC9 1.420 (4)
O5ÐC10 1.418 (3)
N2ÐC8 1.483 (3)
N2ÐC11 1.478 (3)
C8ÐC9 1.496 (4)
C10ÐC11 1.509 (4)
C9ÐO5ÐC10 109.6 (2) C8ÐN2ÐC11 110.1 (2)
N2ÐC8ÐC9 110.1 (2)
O5ÐC9ÐC8 111.5 (3)
O5ÐC10ÐC11 111.2 (2) N2ÐC11ÐC10 109.5 (2) 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. NÐH O hydrogen bonds are indicated by dashed lines [symmetry code: (i) 1ÿx, 1ÿy, 1ÿz].
Figure 2
Table 2
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
N2ÐH4 O2 1.02 (3) 1.72 (3) 2.710 (2) 163 (2) N2ÐH5 O1i 0.95 (3) 1.80 (3) 2.733 (3) 166 (2) C5ÐH2 O5ii 1.01 (2) 2.57 (2) 3.575 (2) 171.4 (19) C8ÐH7 O3iii 1.00 (2) 2.54 (3) 3.391 (3) 143.6 (19) C11ÐH12 O2iv 0.97 (2) 2.55 (3) 3.398 (3) 146.4 (17)
Symmetry codes: (i) 1ÿx;1ÿy;1ÿz; (ii)3
2ÿx;12y;12ÿz; (iii) 2ÿx;1ÿy;1ÿz; (iv) 1ÿx;1ÿy;ÿz.
H atoms were located in difference Fourier maps and re®ned isotropically. Re®ned distances: CÐH = 0.88 (2)±1.06 (3) AÊ and NÐ H = 0.95 (3)±1.02 (3) AÊ.
Data collection: MSC/AFC 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: SAPI91 (Fan, 1991); 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.
References
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995).Angew. Chem. Int. Ed. Engl.34, 1555±1573.
Fan, H.-F. (1991).SAPI91. Rigaku Corporation, Tokyo, Japan. 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±
359.
Zachariasen, W. H. (1967).Acta Cryst.23, 558±564.
supporting information
sup-1
Acta Cryst. (2001). E57, o627–o629
supporting information
Acta Cryst. (2001). E57, o627–o629 [doi:10.1107/S1600536801009941]
Morpholinium 4-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 4-chloro-2-nitrobenzoic acid–amine system.
An acid–base interaction involving a proton transfer is observed as expected from the high basicity of the present amine.
Two cations and two anions are held together by short N—H···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. The dihedral angle between the nitro group and the benzene ring is
50.7 (2)° and that between the carboxyl group and the benzene ring is 43.6 (2)°. The macro rings are arranged along the a
axis by a C—H···O interaction formed between the cation and the nitro group (C8—H7···O3iii; Table 2). The rings are also
linked along the b and c axes by two C—H···O interactions (C5—H2···O5ii and C11—H12···O2iv; Table 2), formed
between the benzene ring and the cation, and between the cation and the carboxyl group (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 = 0.88 (2)–1.06 (3) Å
supporting information
sup-2
[image:5.610.134.482.75.277.2]Acta Cryst. (2001). E57, o627–o629
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:
(i) 1 - x, 1 - y, 1 - z].
Figure 2
Packing diagram showing a three-dimensional hydrogen-bond network formed via N—H···O and C—H···O hydrogen
[image:5.610.131.482.358.590.2]supporting information
sup-3
Acta Cryst. (2001). E57, o627–o629
(I)
Crystal data
C4H10NO+·C7H3ClNO4− Mr = 288.69
Monoclinic, P21/n Hall symbol: -P 2yn
a = 6.0475 (10) Å
b = 25.808 (4) Å
c = 8.6101 (10) Å
β = 101.853 (11)°
V = 1315.2 (3) Å3 Z = 4
F(000) = 600.0
Dx = 1.458 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 25 reflections
θ = 11.0–12.1°
µ = 0.31 mm−1
T = 299 K
Plate, colorless 0.45 × 0.35 × 0.18 mm
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 = 0.881, Tmax = 0.946 3948 measured reflections
3006 independent reflections 1740 reflections with I > 2σ(I)
Rint = 0.028
θmax = 27.5°, θmin = 1.6°
h = −1→7
k = 0→33
l = −11→11
3 standard reflections every 97 reflections intensity decay: 4.7%
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.050 wR(F2) = 0.098 S = 1.19 3005 reflections 225 parameters 0 restraints 0 constraints
All H-atom parameters refined
Weighting scheme based on measured s.u.'s w =
1/[σ2(F
o) + 0.00032|Fo|2] (Δ/σ)max = 0.01
Δρmax = 0.50 e Å−3 Δρmin = −0.41 e Å−3
Extinction correction: Zachariasen (1967), equ(3) Acta Cryst.(1968) A24, p213. Extinction coefficient: 9.9 (16)E-7
Special details
Experimental. The scan width was (0.73 + 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 1.32441 (14) 0.74864 (3) 0.17158 (11) 0.0882 (3)
O1 0.6661 (3) 0.58811 (7) 0.4824 (2) 0.0688 (6)
O2 0.6557 (3) 0.54952 (6) 0.25025 (19) 0.0565 (5)
O3 1.1413 (3) 0.52815 (6) 0.3214 (2) 0.0585 (6)
O4 1.1436 (3) 0.54705 (7) 0.0779 (2) 0.0606 (6)
O5 0.5976 (3) 0.35006 (6) 0.1573 (2) 0.0611 (6)
N1 1.1170 (3) 0.55805 (7) 0.2105 (2) 0.0420 (6)
N2 0.5440 (3) 0.44930 (7) 0.2885 (2) 0.0413 (6)
supporting information
sup-4
Acta Cryst. (2001). E57, o627–o629
C2 1.0606 (4) 0.61226 (7) 0.2387 (2) 0.0353 (6)
C3 1.1960 (4) 0.64980 (9) 0.1924 (3) 0.0465 (7)
C4 1.1530 (4) 0.70060 (9) 0.2242 (3) 0.0517 (7)
C5 0.9778 (5) 0.71391 (9) 0.2976 (3) 0.0559 (8)
C6 0.8457 (4) 0.67506 (9) 0.3409 (3) 0.0472 (7)
C7 0.7204 (4) 0.58265 (8) 0.3523 (3) 0.0391 (6)
C8 0.7686 (4) 0.42453 (11) 0.3034 (3) 0.0522 (8)
C9 0.7443 (5) 0.36683 (11) 0.2989 (4) 0.0634 (10)
C10 0.3799 (5) 0.37174 (10) 0.1486 (4) 0.0564 (9)
C11 0.3881 (5) 0.43015 (10) 0.1448 (3) 0.0497 (8)
H1 1.307 (4) 0.6404 (8) 0.145 (2) 0.040 (6)*
H2 0.950 (4) 0.7516 (9) 0.321 (3) 0.058 (7)*
H3 0.719 (4) 0.6836 (9) 0.385 (3) 0.060 (7)*
H4 0.562 (4) 0.4884 (10) 0.284 (3) 0.075 (8)*
H5 0.487 (4) 0.4398 (9) 0.379 (3) 0.054 (7)*
H6 0.826 (4) 0.4375 (9) 0.218 (3) 0.053 (7)*
H7 0.865 (4) 0.4389 (10) 0.402 (3) 0.071 (8)*
H8 0.892 (5) 0.3492 (11) 0.303 (3) 0.088 (9)*
H9 0.681 (4) 0.3563 (10) 0.392 (3) 0.075 (8)*
H10 0.286 (5) 0.3610 (11) 0.057 (3) 0.082 (9)*
H11 0.314 (4) 0.3591 (9) 0.247 (3) 0.068 (7)*
H12 0.437 (3) 0.4426 (9) 0.051 (3) 0.049 (6)*
H13 0.241 (4) 0.4463 (10) 0.143 (3) 0.067 (8)*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Cl 0.0969 (6) 0.0466 (4) 0.1354 (8) −0.0153 (4) 0.0570 (5) 0.0197 (4)
O1 0.0876 (14) 0.0713 (12) 0.0608 (12) −0.0193 (10) 0.0467 (11) −0.0036 (10)
O2 0.0697 (12) 0.0480 (10) 0.0545 (11) −0.0216 (8) 0.0190 (9) −0.0077 (8)
O3 0.0767 (13) 0.0391 (9) 0.0661 (12) 0.0120 (8) 0.0300 (10) 0.0142 (9)
O4 0.0772 (12) 0.0576 (11) 0.0512 (11) 0.0007 (9) 0.0231 (9) −0.0132 (9)
O5 0.0749 (13) 0.0470 (10) 0.0628 (12) 0.0113 (9) 0.0176 (10) −0.0131 (9)
N1 0.0397 (11) 0.0400 (10) 0.0497 (12) −0.0012 (8) 0.0169 (9) −0.0015 (10)
N2 0.0519 (12) 0.0374 (11) 0.0391 (11) −0.0045 (9) 0.0200 (10) −0.0033 (9)
C1 0.0383 (12) 0.0366 (12) 0.0345 (12) −0.0002 (9) 0.0080 (10) 0.0029 (9)
C2 0.0386 (12) 0.0330 (11) 0.0345 (12) 0.0011 (9) 0.0080 (10) 0.0014 (9)
C3 0.0500 (15) 0.0417 (13) 0.0534 (15) −0.0000 (11) 0.0239 (12) 0.0056 (11)
C4 0.0602 (16) 0.0343 (12) 0.0652 (17) −0.0074 (11) 0.0233 (13) 0.0100 (11)
C5 0.0676 (18) 0.0325 (13) 0.0715 (18) 0.0024 (12) 0.0234 (14) 0.0025 (12)
C6 0.0522 (16) 0.0398 (13) 0.0550 (16) 0.0027 (11) 0.0234 (13) −0.0011 (11)
C7 0.0380 (12) 0.0389 (12) 0.0425 (13) 0.0035 (10) 0.0132 (10) 0.0086 (11)
C8 0.0447 (15) 0.0642 (17) 0.0488 (16) −0.0039 (13) 0.0122 (13) −0.0015 (13)
C9 0.0632 (19) 0.0570 (17) 0.069 (2) 0.0180 (15) 0.0116 (16) 0.0067 (15)
C10 0.0619 (18) 0.0455 (14) 0.0589 (18) −0.0057 (13) 0.0061 (15) −0.0117 (14)
supporting information
sup-5
Acta Cryst. (2001). E57, o627–o629
Geometric parameters (Å, º)
Cl—C4 1.735 (2) O5—C9 1.420 (4)
O1—C7 1.238 (3) O5—C10 1.418 (3)
O2—C7 1.231 (3) N2—C8 1.483 (3)
O3—N1 1.213 (2) N2—C11 1.478 (3)
O4—N1 1.219 (2) N2—H4 1.02 (3)
N1—C2 1.472 (3) N2—H5 0.95 (3)
C1—C2 1.390 (3) C8—C9 1.496 (4)
C1—C6 1.385 (3) C8—H6 0.94 (3)
C1—C7 1.519 (3) C8—H7 1.00 (3)
C2—C3 1.379 (3) C9—H8 1.00 (3)
C3—C4 1.375 (3) C9—H9 1.00 (3)
C3—H1 0.88 (2) C10—C11 1.509 (4)
C4—C5 1.384 (4) C10—H10 0.91 (3)
C5—C6 1.380 (4) C10—H11 1.06 (3)
C5—H2 1.01 (2) C11—H12 0.97 (2)
C6—H3 0.95 (2) C11—H13 0.98 (3)
O1···N2i 2.733 (3) O2···C11 3.512 (3)
O1···C11i 3.327 (4) O3···N2v 3.230 (3)
O1···C10i 3.407 (4) O3···C8ii 3.391 (4)
O1···O3ii 3.522 (3) O3···C11v 3.445 (3)
O1···C8i 3.523 (3) O3···C8 3.480 (3)
O1···O3iii 3.547 (3) O3···N2ii 3.552 (3)
O1···C8ii 3.550 (4) O4···O4vi 3.124 (4)
O2···N2 2.710 (3) O4···C11v 3.357 (3)
O2···O4iii 3.148 (3) O4···C11iv 3.439 (4)
O2···N1iii 3.213 (3) O4···C8vi 3.509 (4)
O2···C8 3.309 (4) O5···C3vi 3.489 (3)
O2···O3iii 3.338 (3) O5···C5vii 3.575 (3)
O2···C11iv 3.398 (3)
C9—O5—C10 109.6 (2) O1—C7—O2 128.3 (2)
O3—N1—O4 124.8 (2) O1—C7—C1 115.4 (2)
O3—N1—C2 118.00 (19) O2—C7—C1 116.3 (2)
O4—N1—C2 117.1 (2) N2—C8—C9 110.1 (2)
C8—N2—C11 110.1 (2) N2—C8—H6 104.9 (15)
C8—N2—H4 109.0 (15) N2—C8—H7 106.1 (16)
C8—N2—H5 107.4 (15) C9—C8—H6 112.6 (15)
C11—N2—H4 110.9 (16) C9—C8—H7 115.4 (16)
C11—N2—H5 109.0 (15) H6—C8—H7 107 (2)
H4—N2—H5 110 (2) O5—C9—C8 111.5 (3)
C2—C1—C6 116.3 (2) O5—C9—H8 106.9 (17)
C2—C1—C7 124.0 (2) O5—C9—H9 109.5 (17)
C6—C1—C7 119.5 (2) C8—C9—H8 111.8 (18)
N1—C2—C1 119.82 (19) C8—C9—H9 107.5 (17)
supporting information
sup-6
Acta Cryst. (2001). E57, o627–o629
C1—C2—C3 123.5 (2) O5—C10—C11 111.2 (2)
C2—C3—C4 117.7 (2) O5—C10—H10 110 (2)
C2—C3—H1 119.3 (15) O5—C10—H11 109.6 (14)
C4—C3—H1 123.0 (15) C11—C10—H10 107.6 (19)
Cl—C4—C3 118.8 (2) C11—C10—H11 110.2 (14)
Cl—C4—C5 119.8 (2) H10—C10—H11 109 (3)
C3—C4—C5 121.4 (2) N2—C11—C10 109.5 (2)
C4—C5—C6 118.9 (2) N2—C11—H12 109.4 (14)
C4—C5—H2 120.2 (14) N2—C11—H13 107.1 (15)
C6—C5—H2 120.9 (14) C10—C11—H12 111.5 (14)
C1—C6—C5 122.2 (2) C10—C11—H13 113.1 (16)
C1—C6—H3 117.7 (16) H12—C11—H13 106 (2)
C5—C6—H3 120.0 (16)
Cl—C4—C3—C2 178.5 (2) N1—C2—C3—C4 −177.1 (2)
Cl—C4—C5—C6 −178.9 (2) C1—C2—C3—C4 1.2 (4)
O1—C7—C1—C2 139.9 (2) C1—C6—C5—C4 −0.3 (5)
O1—C7—C1—C6 −44.4 (3) C2—C1—C6—C5 0.4 (4)
O2—C7—C1—C2 −42.0 (3) C2—C3—C4—C5 −1.0 (4)
O2—C7—C1—C6 133.8 (3) C3—C2—C1—C6 −0.9 (4)
O3—N1—C2—C1 −50.8 (3) C3—C2—C1—C7 175.0 (2)
O3—N1—C2—C3 127.5 (2) C3—C4—C5—C6 0.6 (5)
O4—N1—C2—C1 131.7 (2) C5—C6—C1—C7 −175.6 (3)
O4—N1—C2—C3 −50.0 (3) C8—N2—C11—C10 54.5 (3)
O5—C9—C8—N2 57.5 (3) C8—C9—O5—C10 −60.7 (3)
O5—C10—C11—N2 −58.6 (3) C9—O5—C10—C11 61.1 (3)
N1—C2—C1—C6 177.3 (2) C9—C8—N2—C11 −54.3 (3)
N1—C2—C1—C7 −6.8 (4)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1; (iii) x−1, y, z; (iv) −x+1, −y+1, −z; (v) x+1, y, z; (vi) −x+2, −y+1, −z; (vii) −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
N2—H4···O2 1.02 (3) 1.72 (3) 2.710 (2) 163 (2)
N2—H5···O1i 0.95 (3) 1.80 (3) 2.733 (3) 166 (2)
C5—H2···O5viii 1.01 (2) 2.57 (2) 3.575 (2) 171 (2)
C8—H7···O3ii 1.00 (2) 2.54 (3) 3.391 (3) 144 (2)
C11—H12···O2iv 0.97 (2) 2.55 (3) 3.398 (3) 146 (2)
