Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805029077/hg6245sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805029077/hg6245Isup2.hkl |
CCDC reference: 287600
Single crystals of the title salt were obtained from ethanol solutions (20 ml) of 2-amino-5-iodobenzoic acid (0.7 g) and 1-methylpiperazine (0.5 g) by slow concentration over a period of 2 d at room temperature.
The H atoms involved in N—H···O hydrogen bonds were found in difference Fourier maps; however, during refinement, N—H distances were fixed at 0.86 or 0.90 Å and the Uiso values were set at 1.2Ueq(N). H atoms bonded to C atoms were included in the refinement in the riding-model approximation, with C—H = 0.93–0.97 Å and Uiso(H) = 1.2Ueq(C) for the non-methyl C atoms and C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl atom C12.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C5H13N2+·C7H5INO2− | F(000) = 720 |
Mr = 363.19 | Dx = 1.622 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2209 reflections |
a = 14.829 (3) Å | θ = 2.8–24.1° |
b = 7.3472 (14) Å | µ = 2.15 mm−1 |
c = 13.713 (3) Å | T = 294 K |
β = 95.313 (3)° | Prism, colorless |
V = 1487.6 (5) Å3 | 0.26 × 0.22 × 0.20 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2655 independent reflections |
Radiation source: fine-focus sealed tube | 1678 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ϕ and ω scans | θmax = 25.1°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −17→17 |
Tmin = 0.578, Tmax = 0.656 | k = −8→8 |
7380 measured reflections | l = −16→13 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.039P)2 + 0.5464P] where P = (Fo2 + 2Fc2)/3 |
2655 reflections | (Δ/σ)max < 0.001 |
164 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.65 e Å−3 |
C5H13N2+·C7H5INO2− | V = 1487.6 (5) Å3 |
Mr = 363.19 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.829 (3) Å | µ = 2.15 mm−1 |
b = 7.3472 (14) Å | T = 294 K |
c = 13.713 (3) Å | 0.26 × 0.22 × 0.20 mm |
β = 95.313 (3)° |
Bruker SMART CCD area-detector diffractometer | 2655 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1678 reflections with I > 2σ(I) |
Tmin = 0.578, Tmax = 0.656 | Rint = 0.029 |
7380 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.33 e Å−3 |
2655 reflections | Δρmin = −0.65 e Å−3 |
164 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
I1 | 0.014263 (19) | 0.86525 (5) | 0.85945 (3) | 0.08959 (18) | |
N1 | 0.3687 (2) | 0.7581 (5) | 0.6555 (2) | 0.0729 (10) | |
H1A | 0.3651 | 0.7455 | 0.5929 | 0.087* | |
H1B | 0.4207 | 0.7536 | 0.6890 | 0.087* | |
O1 | 0.38083 (18) | 0.8577 (3) | 0.95581 (17) | 0.0581 (7) | |
O2 | 0.45410 (19) | 0.7625 (6) | 0.8329 (2) | 0.0887 (10) | |
C1 | 0.2932 (3) | 0.7848 (5) | 0.7010 (3) | 0.0479 (9) | |
C2 | 0.2963 (2) | 0.8082 (4) | 0.8032 (2) | 0.0389 (8) | |
C3 | 0.2153 (3) | 0.8327 (5) | 0.8445 (3) | 0.0479 (9) | |
H3 | 0.2170 | 0.8480 | 0.9120 | 0.057* | |
C4 | 0.1334 (3) | 0.8355 (5) | 0.7907 (3) | 0.0515 (10) | |
C5 | 0.1304 (3) | 0.8171 (5) | 0.6901 (3) | 0.0642 (11) | |
H5 | 0.0752 | 0.8217 | 0.6521 | 0.077* | |
C6 | 0.2086 (3) | 0.7922 (6) | 0.6470 (3) | 0.0615 (11) | |
H6 | 0.2056 | 0.7797 | 0.5793 | 0.074* | |
C7 | 0.3828 (3) | 0.8099 (5) | 0.8681 (3) | 0.0497 (9) | |
N2 | 0.3973 (2) | 0.1996 (4) | 1.0425 (2) | 0.0574 (8) | |
H2A | 0.4512 | 0.2047 | 1.0782 | 0.069* | |
H2B | 0.3901 | 0.0862 | 1.0182 | 0.069* | |
N3 | 0.2346 (2) | 0.3752 (5) | 0.9684 (3) | 0.0742 (11) | |
C8 | 0.3961 (3) | 0.3304 (6) | 0.9613 (3) | 0.0670 (11) | |
H8A | 0.4415 | 0.2970 | 0.9180 | 0.080* | |
H8B | 0.4103 | 0.4512 | 0.9868 | 0.080* | |
C9 | 0.3035 (4) | 0.3308 (6) | 0.9052 (3) | 0.0747 (13) | |
H9A | 0.3023 | 0.4190 | 0.8525 | 0.090* | |
H9B | 0.2912 | 0.2117 | 0.8765 | 0.090* | |
C10 | 0.2346 (3) | 0.2444 (7) | 1.0477 (4) | 0.0780 (13) | |
H10A | 0.2201 | 0.1246 | 1.0209 | 0.094* | |
H10B | 0.1884 | 0.2774 | 1.0901 | 0.094* | |
C11 | 0.3247 (3) | 0.2387 (6) | 1.1060 (3) | 0.0669 (11) | |
H11A | 0.3363 | 0.3548 | 1.1384 | 0.080* | |
H11B | 0.3241 | 0.1454 | 1.1560 | 0.080* | |
C12 | 0.1445 (4) | 0.3812 (7) | 0.9143 (6) | 0.130 (3) | |
H12A | 0.1252 | 0.2598 | 0.8971 | 0.195* | |
H12B | 0.1471 | 0.4522 | 0.8558 | 0.195* | |
H12C | 0.1023 | 0.4357 | 0.9546 | 0.195* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0505 (2) | 0.0945 (3) | 0.1271 (3) | 0.00456 (17) | 0.02630 (18) | −0.0012 (2) |
N1 | 0.069 (2) | 0.112 (3) | 0.0385 (19) | 0.004 (2) | 0.0117 (17) | −0.0143 (19) |
O1 | 0.0651 (17) | 0.0755 (18) | 0.0328 (15) | −0.0052 (14) | −0.0008 (12) | −0.0003 (13) |
O2 | 0.0454 (17) | 0.165 (3) | 0.0541 (18) | 0.0159 (19) | −0.0017 (14) | −0.0237 (19) |
C1 | 0.059 (3) | 0.047 (2) | 0.038 (2) | −0.0048 (18) | 0.0082 (19) | −0.0024 (17) |
C2 | 0.044 (2) | 0.0400 (19) | 0.032 (2) | −0.0020 (15) | 0.0014 (15) | 0.0016 (15) |
C3 | 0.057 (2) | 0.048 (2) | 0.040 (2) | −0.0029 (17) | 0.0093 (18) | 0.0008 (16) |
C4 | 0.043 (2) | 0.049 (2) | 0.062 (3) | −0.0047 (17) | 0.0048 (18) | 0.0032 (19) |
C5 | 0.054 (3) | 0.068 (3) | 0.067 (3) | −0.002 (2) | −0.013 (2) | 0.004 (2) |
C6 | 0.067 (3) | 0.076 (3) | 0.038 (2) | −0.007 (2) | −0.010 (2) | −0.0037 (19) |
C7 | 0.049 (2) | 0.057 (2) | 0.043 (2) | −0.0018 (18) | 0.0027 (18) | 0.0030 (18) |
N2 | 0.0411 (18) | 0.065 (2) | 0.065 (2) | 0.0076 (15) | −0.0011 (15) | −0.0071 (17) |
N3 | 0.047 (2) | 0.058 (2) | 0.114 (3) | 0.0006 (17) | −0.013 (2) | 0.008 (2) |
C8 | 0.058 (3) | 0.075 (3) | 0.070 (3) | −0.005 (2) | 0.012 (2) | 0.004 (2) |
C9 | 0.092 (4) | 0.058 (3) | 0.069 (3) | −0.008 (2) | −0.018 (3) | 0.009 (2) |
C10 | 0.048 (3) | 0.069 (3) | 0.119 (4) | 0.003 (2) | 0.017 (3) | −0.002 (3) |
C11 | 0.067 (3) | 0.071 (3) | 0.066 (3) | 0.011 (2) | 0.021 (2) | −0.004 (2) |
C12 | 0.070 (4) | 0.072 (3) | 0.233 (7) | 0.003 (3) | −0.065 (4) | 0.027 (4) |
I1—C4 | 2.090 (4) | N2—H2A | 0.9000 |
N1—C1 | 1.346 (5) | N2—H2B | 0.9000 |
N1—H1A | 0.8600 | N3—C9 | 1.436 (6) |
N1—H1B | 0.8600 | N3—C10 | 1.451 (6) |
O1—C7 | 1.257 (4) | N3—C12 | 1.468 (6) |
O2—C7 | 1.251 (4) | C8—C9 | 1.511 (6) |
C1—C6 | 1.397 (5) | C8—H8A | 0.9700 |
C1—C2 | 1.409 (5) | C8—H8B | 0.9700 |
C2—C3 | 1.386 (5) | C9—H9A | 0.9700 |
C2—C7 | 1.493 (5) | C9—H9B | 0.9700 |
C3—C4 | 1.362 (5) | C10—C11 | 1.492 (6) |
C3—H3 | 0.9300 | C10—H10A | 0.9700 |
C4—C5 | 1.382 (6) | C10—H10B | 0.9700 |
C5—C6 | 1.362 (6) | C11—H11A | 0.9700 |
C5—H5 | 0.9300 | C11—H11B | 0.9700 |
C6—H6 | 0.9300 | C12—H12A | 0.9600 |
N2—C8 | 1.470 (5) | C12—H12B | 0.9600 |
N2—C11 | 1.474 (5) | C12—H12C | 0.9600 |
C1—N1—H1A | 120.0 | C10—N3—C12 | 109.6 (4) |
C1—N1—H1B | 120.0 | N2—C8—C9 | 109.4 (3) |
H1A—N1—H1B | 120.0 | N2—C8—H8A | 109.8 |
N1—C1—C6 | 120.3 (3) | C9—C8—H8A | 109.8 |
N1—C1—C2 | 121.8 (3) | N2—C8—H8B | 109.8 |
C6—C1—C2 | 117.8 (4) | C9—C8—H8B | 109.8 |
C3—C2—C1 | 118.3 (3) | H8A—C8—H8B | 108.2 |
C3—C2—C7 | 119.0 (3) | N3—C9—C8 | 110.9 (4) |
C1—C2—C7 | 122.7 (3) | N3—C9—H9A | 109.5 |
C4—C3—C2 | 122.9 (3) | C8—C9—H9A | 109.5 |
C4—C3—H3 | 118.6 | N3—C9—H9B | 109.5 |
C2—C3—H3 | 118.6 | C8—C9—H9B | 109.5 |
C3—C4—C5 | 119.0 (4) | H9A—C9—H9B | 108.0 |
C3—C4—I1 | 120.4 (3) | N3—C10—C11 | 111.0 (4) |
C5—C4—I1 | 120.7 (3) | N3—C10—H10A | 109.4 |
C6—C5—C4 | 119.8 (4) | C11—C10—H10A | 109.4 |
C6—C5—H5 | 120.1 | N3—C10—H10B | 109.4 |
C4—C5—H5 | 120.1 | C11—C10—H10B | 109.4 |
C5—C6—C1 | 122.2 (4) | H10A—C10—H10B | 108.0 |
C5—C6—H6 | 118.9 | N2—C11—C10 | 110.8 (3) |
C1—C6—H6 | 118.9 | N2—C11—H11A | 109.5 |
O2—C7—O1 | 122.8 (3) | C10—C11—H11A | 109.5 |
O2—C7—C2 | 118.6 (3) | N2—C11—H11B | 109.5 |
O1—C7—C2 | 118.5 (3) | C10—C11—H11B | 109.5 |
C8—N2—C11 | 111.2 (3) | H11A—C11—H11B | 108.1 |
C8—N2—H2A | 109.4 | N3—C12—H12A | 109.5 |
C11—N2—H2A | 109.4 | N3—C12—H12B | 109.5 |
C8—N2—H2B | 109.4 | H12A—C12—H12B | 109.5 |
C11—N2—H2B | 109.4 | N3—C12—H12C | 109.5 |
H2A—N2—H2B | 108.0 | H12A—C12—H12C | 109.5 |
C9—N3—C10 | 110.5 (3) | H12B—C12—H12C | 109.5 |
C9—N3—C12 | 111.6 (5) | ||
N1—C1—C2—C3 | −179.2 (3) | C3—C2—C7—O2 | 170.0 (4) |
C6—C1—C2—C3 | 1.6 (5) | C1—C2—C7—O2 | −10.7 (5) |
N1—C1—C2—C7 | 1.5 (5) | C3—C2—C7—O1 | −9.5 (5) |
C6—C1—C2—C7 | −177.7 (3) | C1—C2—C7—O1 | 169.8 (3) |
C1—C2—C3—C4 | −0.1 (5) | C11—N2—C8—C9 | −55.4 (4) |
C7—C2—C3—C4 | 179.1 (3) | C10—N3—C9—C8 | −59.4 (5) |
C2—C3—C4—C5 | −1.5 (5) | C12—N3—C9—C8 | 178.4 (3) |
C2—C3—C4—I1 | 178.1 (3) | N2—C8—C9—N3 | 57.9 (5) |
C3—C4—C5—C6 | 1.6 (6) | C9—N3—C10—C11 | 58.3 (5) |
I1—C4—C5—C6 | −178.0 (3) | C12—N3—C10—C11 | −178.4 (4) |
C4—C5—C6—C1 | −0.2 (6) | C8—N2—C11—C10 | 55.0 (5) |
N1—C1—C6—C5 | 179.3 (4) | N3—C10—C11—N2 | −55.7 (5) |
C2—C1—C6—C5 | −1.4 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.86 | 2.06 | 2.889 (4) | 162 |
N1—H1B···O2 | 0.86 | 1.99 | 2.637 (4) | 131 |
N2—H2B···O1ii | 0.90 | 1.88 | 2.780 (4) | 174 |
N2—H2A···O2iii | 0.90 | 1.79 | 2.675 (4) | 168 |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, y−1, z; (iii) −x+1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C5H13N2+·C7H5INO2− |
Mr | 363.19 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 14.829 (3), 7.3472 (14), 13.713 (3) |
β (°) | 95.313 (3) |
V (Å3) | 1487.6 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.15 |
Crystal size (mm) | 0.26 × 0.22 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.578, 0.656 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7380, 2655, 1678 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.088, 1.02 |
No. of reflections | 2655 |
No. of parameters | 164 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.65 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXTL (Bruker, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.86 | 2.06 | 2.889 (4) | 162 |
N1—H1B···O2 | 0.86 | 1.99 | 2.637 (4) | 131 |
N2—H2B···O1ii | 0.90 | 1.88 | 2.780 (4) | 174 |
N2—H2A···O2iii | 0.90 | 1.79 | 2.675 (4) | 168 |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, y−1, z; (iii) −x+1, −y+1, −z+2. |
Our interest in piperazine derivatives stems from their application in host–guest systems. We have recently reported the crystal structure of 1-methylpiperazine-1,4-diium 4-nitrophthalate(2-) 4-nitrophthalic acid monohydrate (Guo, 2004). The structure of 4-methylpiperazin-1-ium 2-amino-5-iodobenzoate, (I), is reported here.
The title salt, (I), is composed of a cation which is a monoprotonated 1-methylpiperazine molecule, and an anion, which is a deprotonated 2-amino-5-iodobenzoic acid molecule. The structures of the cation and anion are shown in Fig. 1.
The cation adopts a normal chair conformation, as reported previously (Guo, 2004), and participates in hydrogen bonds formed between the N2—H2B group and atom O1ii of a 2-amino-5-iodobenzoate anion and the N2—H2A group and atom O2iii of another anion (see Table 1 for symmetry codes). Within the anion, the amino (NH2) and carboxy (C7/O1/O2) groups are almost coplanar with respect to the central six-membered ring. Atom H1B is involved in an intramolecular N1—H1B···O2 hydrogen bond, while atom H1A is responsible for the formation of an N1—H1A···O1i hydrogen bond (see Table 1 for symmetry code), which joins another anion. These hydrogen-bond contacts build up a number of different sized rings and further aggregate into a three-dimensional framework. A packing diagram for the structure of (I) is shown in Fig. 2.