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In the title compound, C4H10NO+·C7H3ClNO4, two cations and two anions are connected by N—H...O hydrogen bonds to afford a ring with descriptor R44(12), which is located on an inversion center. There are three C—H...O interactions which connect the ring units to form a three-dimensional network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801009941/ob6054sup1.cif
Contains datablocks General, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801009941/ob6054Isup2.hkl
Contains datablock I

CCDC reference: 170776

Key indicators

  • Single-crystal X-ray study
  • T = 299 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.050
  • wR factor = 0.098
  • Data-to-parameter ratio = 13.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_353 Alert C Long N-H Bond (0.87A) N(2) - H(4) = 1.02 Ang.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

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).

Experimental top

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.

Refinement top

H atoms were found in difference Fourier maps and refined isotropically. Refined distances: C—H = 0.88 (2)–1.06 (3) Å and N—H = 0.95 (3)–1.02 (3) Å.

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1990); cell refinement: 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 refine structure: TEXSAN for Windows; software used to prepare material for publication: TEXSAN for Windows.

Figures top
[Figure 1] Fig. 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] Fig. 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) top
Crystal data top
C4H10NO+·C7H3ClNO4F(000) = 600.0
Mr = 288.69Dx = 1.458 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 6.0475 (10) Åθ = 11.0–12.1°
b = 25.808 (4) ŵ = 0.31 mm1
c = 8.6101 (10) ÅT = 299 K
β = 101.853 (11)°Plate, colorless
V = 1315.2 (3) Å30.45 × 0.35 × 0.18 mm
Z = 4
Data collection top
Rigaku AFC-5R
diffractometer
1740 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anodeRint = 0.028
Graphite monochromatorθmax = 27.5°, θmin = 1.6°
ω–2θ scansh = 17
Absorption correction: ψ scan
(North et al., 1968)
k = 033
Tmin = 0.881, Tmax = 0.946l = 1111
3948 measured reflections3 standard reflections every 97 reflections
3006 independent reflections intensity decay: 4.7%
Refinement top
Refinement on F20 constraints
Least-squares matrix: fullAll H-atom parameters refined
R[F2 > 2σ(F2)] = 0.050Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.00032|Fo|2]
wR(F2) = 0.098(Δ/σ)max = 0.01
S = 1.19Δρmax = 0.50 e Å3
3005 reflectionsΔρmin = 0.41 e Å3
225 parametersExtinction correction: Zachariasen (1967), equ(3) Acta Cryst.(1968) A24, p213.
0 restraintsExtinction coefficient: 9.9 (16)E-7
Crystal data top
C4H10NO+·C7H3ClNO4V = 1315.2 (3) Å3
Mr = 288.69Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.0475 (10) ŵ = 0.31 mm1
b = 25.808 (4) ÅT = 299 K
c = 8.6101 (10) Å0.45 × 0.35 × 0.18 mm
β = 101.853 (11)°
Data collection top
Rigaku AFC-5R
diffractometer
1740 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.028
Tmin = 0.881, Tmax = 0.9463 standard reflections every 97 reflections
3948 measured reflections intensity decay: 4.7%
3006 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.098All H-atom parameters refined
S = 1.19Δρmax = 0.50 e Å3
3005 reflectionsΔρmin = 0.41 e Å3
225 parameters
Special details top

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) top
xyzUiso*/Ueq
Cl1.32441 (14)0.74864 (3)0.17158 (11)0.0882 (3)
O10.6661 (3)0.58811 (7)0.4824 (2)0.0688 (6)
O20.6557 (3)0.54952 (6)0.25025 (19)0.0565 (5)
O31.1413 (3)0.52815 (6)0.3214 (2)0.0585 (6)
O41.1436 (3)0.54705 (7)0.0779 (2)0.0606 (6)
O50.5976 (3)0.35006 (6)0.1573 (2)0.0611 (6)
N11.1170 (3)0.55805 (7)0.2105 (2)0.0420 (6)
N20.5440 (3)0.44930 (7)0.2885 (2)0.0413 (6)
C10.8821 (3)0.62323 (8)0.3125 (2)0.0364 (6)
C21.0606 (4)0.61226 (7)0.2387 (2)0.0353 (6)
C31.1960 (4)0.64980 (9)0.1924 (3)0.0465 (7)
C41.1530 (4)0.70060 (9)0.2242 (3)0.0517 (7)
C50.9778 (5)0.71391 (9)0.2976 (3)0.0559 (8)
C60.8457 (4)0.67506 (9)0.3409 (3)0.0472 (7)
C70.7204 (4)0.58265 (8)0.3523 (3)0.0391 (6)
C80.7686 (4)0.42453 (11)0.3034 (3)0.0522 (8)
C90.7443 (5)0.36683 (11)0.2989 (4)0.0634 (10)
C100.3799 (5)0.37174 (10)0.1486 (4)0.0564 (9)
C110.3881 (5)0.43015 (10)0.1448 (3)0.0497 (8)
H11.307 (4)0.6404 (8)0.145 (2)0.040 (6)*
H20.950 (4)0.7516 (9)0.321 (3)0.058 (7)*
H30.719 (4)0.6836 (9)0.385 (3)0.060 (7)*
H40.562 (4)0.4884 (10)0.284 (3)0.075 (8)*
H50.487 (4)0.4398 (9)0.379 (3)0.054 (7)*
H60.826 (4)0.4375 (9)0.218 (3)0.053 (7)*
H70.865 (4)0.4389 (10)0.402 (3)0.071 (8)*
H80.892 (5)0.3492 (11)0.303 (3)0.088 (9)*
H90.681 (4)0.3563 (10)0.392 (3)0.075 (8)*
H100.286 (5)0.3610 (11)0.057 (3)0.082 (9)*
H110.314 (4)0.3591 (9)0.247 (3)0.068 (7)*
H120.437 (3)0.4426 (9)0.051 (3)0.049 (6)*
H130.241 (4)0.4463 (10)0.143 (3)0.067 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.0969 (6)0.0466 (4)0.1354 (8)0.0153 (4)0.0570 (5)0.0197 (4)
O10.0876 (14)0.0713 (12)0.0608 (12)0.0193 (10)0.0467 (11)0.0036 (10)
O20.0697 (12)0.0480 (10)0.0545 (11)0.0216 (8)0.0190 (9)0.0077 (8)
O30.0767 (13)0.0391 (9)0.0661 (12)0.0120 (8)0.0300 (10)0.0142 (9)
O40.0772 (12)0.0576 (11)0.0512 (11)0.0007 (9)0.0231 (9)0.0132 (9)
O50.0749 (13)0.0470 (10)0.0628 (12)0.0113 (9)0.0176 (10)0.0131 (9)
N10.0397 (11)0.0400 (10)0.0497 (12)0.0012 (8)0.0169 (9)0.0015 (10)
N20.0519 (12)0.0374 (11)0.0391 (11)0.0045 (9)0.0200 (10)0.0033 (9)
C10.0383 (12)0.0366 (12)0.0345 (12)0.0002 (9)0.0080 (10)0.0029 (9)
C20.0386 (12)0.0330 (11)0.0345 (12)0.0011 (9)0.0080 (10)0.0014 (9)
C30.0500 (15)0.0417 (13)0.0534 (15)0.0000 (11)0.0239 (12)0.0056 (11)
C40.0602 (16)0.0343 (12)0.0652 (17)0.0074 (11)0.0233 (13)0.0100 (11)
C50.0676 (18)0.0325 (13)0.0715 (18)0.0024 (12)0.0234 (14)0.0025 (12)
C60.0522 (16)0.0398 (13)0.0550 (16)0.0027 (11)0.0234 (13)0.0011 (11)
C70.0380 (12)0.0389 (12)0.0425 (13)0.0035 (10)0.0132 (10)0.0086 (11)
C80.0447 (15)0.0642 (17)0.0488 (16)0.0039 (13)0.0122 (13)0.0015 (13)
C90.0632 (19)0.0570 (17)0.069 (2)0.0180 (15)0.0116 (16)0.0067 (15)
C100.0619 (18)0.0455 (14)0.0589 (18)0.0057 (13)0.0061 (15)0.0117 (14)
C110.0539 (16)0.0440 (14)0.0486 (16)0.0051 (12)0.0047 (13)0.0027 (12)
Geometric parameters (Å, º) top
Cl—C41.735 (2)O5—C91.420 (4)
O1—C71.238 (3)O5—C101.418 (3)
O2—C71.231 (3)N2—C81.483 (3)
O3—N11.213 (2)N2—C111.478 (3)
O4—N11.219 (2)N2—H41.02 (3)
N1—C21.472 (3)N2—H50.95 (3)
C1—C21.390 (3)C8—C91.496 (4)
C1—C61.385 (3)C8—H60.94 (3)
C1—C71.519 (3)C8—H71.00 (3)
C2—C31.379 (3)C9—H81.00 (3)
C3—C41.375 (3)C9—H91.00 (3)
C3—H10.88 (2)C10—C111.509 (4)
C4—C51.384 (4)C10—H100.91 (3)
C5—C61.380 (4)C10—H111.06 (3)
C5—H21.01 (2)C11—H120.97 (2)
C6—H30.95 (2)C11—H130.98 (3)
O1···N2i2.733 (3)O2···C113.512 (3)
O1···C11i3.327 (4)O3···N2v3.230 (3)
O1···C10i3.407 (4)O3···C8ii3.391 (4)
O1···O3ii3.522 (3)O3···C11v3.445 (3)
O1···C8i3.523 (3)O3···C83.480 (3)
O1···O3iii3.547 (3)O3···N2ii3.552 (3)
O1···C8ii3.550 (4)O4···O4vi3.124 (4)
O2···N22.710 (3)O4···C11v3.357 (3)
O2···O4iii3.148 (3)O4···C11iv3.439 (4)
O2···N1iii3.213 (3)O4···C8vi3.509 (4)
O2···C83.309 (4)O5···C3vi3.489 (3)
O2···O3iii3.338 (3)O5···C5vii3.575 (3)
O2···C11iv3.398 (3)
C9—O5—C10109.6 (2)O1—C7—O2128.3 (2)
O3—N1—O4124.8 (2)O1—C7—C1115.4 (2)
O3—N1—C2118.00 (19)O2—C7—C1116.3 (2)
O4—N1—C2117.1 (2)N2—C8—C9110.1 (2)
C8—N2—C11110.1 (2)N2—C8—H6104.9 (15)
C8—N2—H4109.0 (15)N2—C8—H7106.1 (16)
C8—N2—H5107.4 (15)C9—C8—H6112.6 (15)
C11—N2—H4110.9 (16)C9—C8—H7115.4 (16)
C11—N2—H5109.0 (15)H6—C8—H7107 (2)
H4—N2—H5110 (2)O5—C9—C8111.5 (3)
C2—C1—C6116.3 (2)O5—C9—H8106.9 (17)
C2—C1—C7124.0 (2)O5—C9—H9109.5 (17)
C6—C1—C7119.5 (2)C8—C9—H8111.8 (18)
N1—C2—C1119.82 (19)C8—C9—H9107.5 (17)
N1—C2—C3116.6 (2)H8—C9—H9110 (2)
C1—C2—C3123.5 (2)O5—C10—C11111.2 (2)
C2—C3—C4117.7 (2)O5—C10—H10110 (2)
C2—C3—H1119.3 (15)O5—C10—H11109.6 (14)
C4—C3—H1123.0 (15)C11—C10—H10107.6 (19)
Cl—C4—C3118.8 (2)C11—C10—H11110.2 (14)
Cl—C4—C5119.8 (2)H10—C10—H11109 (3)
C3—C4—C5121.4 (2)N2—C11—C10109.5 (2)
C4—C5—C6118.9 (2)N2—C11—H12109.4 (14)
C4—C5—H2120.2 (14)N2—C11—H13107.1 (15)
C6—C5—H2120.9 (14)C10—C11—H12111.5 (14)
C1—C6—C5122.2 (2)C10—C11—H13113.1 (16)
C1—C6—H3117.7 (16)H12—C11—H13106 (2)
C5—C6—H3120.0 (16)
Cl—C4—C3—C2178.5 (2)N1—C2—C3—C4177.1 (2)
Cl—C4—C5—C6178.9 (2)C1—C2—C3—C41.2 (4)
O1—C7—C1—C2139.9 (2)C1—C6—C5—C40.3 (5)
O1—C7—C1—C644.4 (3)C2—C1—C6—C50.4 (4)
O2—C7—C1—C242.0 (3)C2—C3—C4—C51.0 (4)
O2—C7—C1—C6133.8 (3)C3—C2—C1—C60.9 (4)
O3—N1—C2—C150.8 (3)C3—C2—C1—C7175.0 (2)
O3—N1—C2—C3127.5 (2)C3—C4—C5—C60.6 (5)
O4—N1—C2—C1131.7 (2)C5—C6—C1—C7175.6 (3)
O4—N1—C2—C350.0 (3)C8—N2—C11—C1054.5 (3)
O5—C9—C8—N257.5 (3)C8—C9—O5—C1060.7 (3)
O5—C10—C11—N258.6 (3)C9—O5—C10—C1161.1 (3)
N1—C2—C1—C6177.3 (2)C9—C8—N2—C1154.3 (3)
N1—C2—C1—C76.8 (4)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+2, y+1, z+1; (iii) x1, y, z; (iv) x+1, y+1, z; (v) x+1, y, z; (vi) x+2, y+1, z; (vii) x+3/2, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H4···O21.02 (3)1.72 (3)2.710 (2)163 (2)
N2—H5···O1i0.95 (3)1.80 (3)2.733 (3)166 (2)
C5—H2···O5viii1.01 (2)2.57 (2)3.575 (2)171 (2)
C8—H7···O3ii1.00 (2)2.54 (3)3.391 (3)144 (2)
C11—H12···O2iv0.97 (2)2.55 (3)3.398 (3)146 (2)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+2, y+1, z+1; (iv) x+1, y+1, z; (viii) x+3/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC4H10NO+·C7H3ClNO4
Mr288.69
Crystal system, space groupMonoclinic, P21/n
Temperature (K)299
a, b, c (Å)6.0475 (10), 25.808 (4), 8.6101 (10)
β (°) 101.853 (11)
V3)1315.2 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.31
Crystal size (mm)0.45 × 0.35 × 0.18
Data collection
DiffractometerRigaku AFC-5R
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.881, 0.946
No. of measured, independent and
observed [I > 2σ(I)] reflections
3948, 3006, 1740
Rint0.028
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.098, 1.19
No. of reflections3005
No. of parameters225
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.50, 0.41

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1990), MSC/AFC Diffractometer Control Software, TEXSAN for Windows (Molecular Structure Corporation, 1997-1999), SAPI91 (Fan, 1991), TEXSAN for Windows.

Selected geometric parameters (Å, º) top
Cl—C41.735 (2)C3—C41.375 (3)
O1—C71.238 (3)C4—C51.384 (4)
O2—C71.231 (3)C5—C61.380 (4)
O3—N11.213 (2)O5—C91.420 (4)
O4—N11.219 (2)O5—C101.418 (3)
N1—C21.472 (3)N2—C81.483 (3)
C1—C21.390 (3)N2—C111.478 (3)
C1—C61.385 (3)C8—C91.496 (4)
C1—C71.519 (3)C10—C111.509 (4)
C2—C31.379 (3)
C9—O5—C10109.6 (2)O5—C9—C8111.5 (3)
C8—N2—C11110.1 (2)O5—C10—C11111.2 (2)
N2—C8—C9110.1 (2)N2—C11—C10109.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H4···O21.02 (3)1.72 (3)2.710 (2)163 (2)
N2—H5···O1i0.95 (3)1.80 (3)2.733 (3)166 (2)
C5—H2···O5ii1.01 (2)2.57 (2)3.575 (2)171.4 (19)
C8—H7···O3iii1.00 (2)2.54 (3)3.391 (3)143.6 (19)
C11—H12···O2iv0.97 (2)2.55 (3)3.398 (3)146.4 (17)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+3/2, y+1/2, z+1/2; (iii) x+2, y+1, z+1; (iv) x+1, y+1, z.
 

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