In the title compound, C
4H
10NO
+·C
7H
3ClNO
4−, 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 four C—H
O interactions which connect the ring units to form a three-dimensional network.
Supporting information
CCDC reference: 170777
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- R factor = 0.057
- wR factor = 0.090
- Data-to-parameter ratio = 13.3
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
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
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.
H atoms were found in difference Fourier maps and refined isotropically. Refined
distances: C—H = 0.89 (2)–1.04 (3) Å and N—H = 0.89 (3)–1.02 (3) Å.
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: SIR92 (Altomare, et al. 1993); program(s) used to refine structure: TEXSAN for Windows; software used to prepare material for publication: TEXSAN for Windows.
Crystal data top
C4H10NO+·C7H3ClNO4− | F(000) = 600.0 |
Mr = 288.69 | Dx = 1.482 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 10.6482 (15) Å | θ = 11.1–12.0° |
b = 5.9079 (12) Å | µ = 0.31 mm−1 |
c = 21.084 (3) Å | T = 298 K |
β = 102.722 (10)° | Prismatic, colorless |
V = 1293.8 (3) Å3 | 0.50 × 0.30 × 0.20 mm |
Z = 4 | |
Data collection top
Rigaku AFC-5R diffractometer | 1667 reflections with I > 2σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.024 |
Graphite monochromator | θmax = 27.5°, θmin = 2.0° |
ω–2θ scans | h = −1→13 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→7 |
Tmin = 0.894, Tmax = 0.939 | l = −27→27 |
3789 measured reflections | 3 standard reflections every 97 reflections |
2980 independent reflections | intensity decay: 0.5% |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.057 | All H-atom parameters refined |
wR(F2) = 0.090 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.00029|Fo|2] |
S = 1.14 | (Δ/σ)max = 0.001 |
2979 reflections | Δρmax = 0.48 e Å−3 |
224 parameters | Δρmin = −0.61 e Å−3 |
Crystal data top
C4H10NO+·C7H3ClNO4− | V = 1293.8 (3) Å3 |
Mr = 288.69 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.6482 (15) Å | µ = 0.31 mm−1 |
b = 5.9079 (12) Å | T = 298 K |
c = 21.084 (3) Å | 0.50 × 0.30 × 0.20 mm |
β = 102.722 (10)° | |
Data collection top
Rigaku AFC-5R diffractometer | 1667 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.024 |
Tmin = 0.894, Tmax = 0.939 | 3 standard reflections every 97 reflections |
3789 measured reflections | intensity decay: 0.5% |
2980 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.090 | All H-atom parameters refined |
S = 1.14 | Δρmax = 0.48 e Å−3 |
2979 reflections | Δρmin = −0.61 e Å−3 |
224 parameters | |
Special details top
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) top | 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)* | |
H2 | 0.996 (2) | 0.846 (4) | 0.2371 (11) | 0.049 (7)* | |
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) top | 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) top
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) |
C3—C4 | 1.376 (4) | C9—H9 | 1.04 (3) |
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···N2iv | 3.096 (3) |
O1···C11ii | 3.346 (4) | O3···C11 | 3.299 (4) |
O1···C8i | 3.407 (4) | O3···C8iv | 3.344 (4) |
O1···C11i | 3.427 (4) | O3···C11ii | 3.447 (4) |
O1···C9i | 3.457 (4) | O4···C5v | 3.297 (3) |
O1···C10i | 3.468 (4) | O4···C8iv | 3.400 (4) |
O1···O3ii | 3.553 (3) | O4···C4vi | 3.408 (4) |
O2···N2 | 2.696 (3) | O4···C6v | 3.450 (3) |
O2···N1iii | 3.143 (3) | O4···C3vi | 3.564 (4) |
O2···O3iii | 3.210 (3) | O5···C6vii | 3.339 (3) |
O2···O4iii | 3.330 (3) | O5···C9viii | 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···C7iv | 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) |
C1—C6—H3 | 119.1 (14) | H12—C11—H13 | 110 (2) |
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) top
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) |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, −y+1, −z; (v) −x+3/2, y+1/2, −z+1/2; (viii) −x, −y, −z; (ix) x+1, y, z. |
Experimental details
Crystal data |
Chemical formula | C4H10NO+·C7H3ClNO4− |
Mr | 288.69 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 10.6482 (15), 5.9079 (12), 21.084 (3) |
β (°) | 102.722 (10) |
V (Å3) | 1293.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.31 |
Crystal size (mm) | 0.50 × 0.30 × 0.20 |
|
Data collection |
Diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.894, 0.939 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3789, 2980, 1667 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.090, 1.14 |
No. of reflections | 2979 |
No. of parameters | 224 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.48, −0.61 |
Selected geometric parameters (Å, º) topCl—C5 | 1.742 (3) | C3—C4 | 1.376 (4) |
O1—C7 | 1.238 (3) | C4—C5 | 1.367 (4) |
O2—C7 | 1.240 (3) | C5—C6 | 1.380 (4) |
O3—N1 | 1.215 (3) | O5—C9 | 1.417 (4) |
O4—N1 | 1.222 (3) | O5—C10 | 1.423 (3) |
N1—C2 | 1.474 (3) | N2—C8 | 1.479 (3) |
C1—C2 | 1.383 (3) | N2—C11 | 1.492 (4) |
C1—C6 | 1.387 (3) | C8—C9 | 1.503 (4) |
C1—C7 | 1.523 (3) | C10—C11 | 1.505 (4) |
C2—C3 | 1.377 (4) | | |
| | | |
C9—O5—C10 | 109.7 (2) | O5—C9—C8 | 111.7 (3) |
C8—N2—C11 | 110.3 (2) | O5—C10—C11 | 110.9 (2) |
N2—C8—C9 | 109.5 (2) | N2—C11—C10 | 109.5 (3) |
Hydrogen-bond geometry (Å, º) top
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···O4ii | 0.91 (3) | 2.74 (3) | 3.408 (4) | 132 (2) |
C6—H3···O5iii | 0.95 (2) | 2.63 (2) | 3.339 (3) | 131 (2) |
C9—H9···O5iv | 1.04 (3) | 2.68 (3) | 3.455 (4) | 132 (2) |
C11—H13···O3v | 1.01 (2) | 2.51 (2) | 3.447 (4) | 155 (2) |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x+1, y, z; (iv) −x, −y, −z; (v) −x+1, −y+1, −z. |
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···O5iv interactions, a C11—H13···O3v interaction, and a C4—H2···O4ii interaction (symmetry codes are as in Table 2), respectively, to form a three-dimensional network (Fig. 2).