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In the title salt, C5H13N2+·C7H5INO2, the packing of the ions is stabilized by N—H...O hydrogen bonds and van der Waals forces.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805029077/hg6245sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805029077/hg6245Isup2.hkl
Contains datablock I

CCDC reference: 287600

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.032
  • wR factor = 0.088
  • Data-to-parameter ratio = 16.2

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N3 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C4
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

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.

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A view of the structure of (I), showing the atom-numbering scheme; displacement ellipsoids for non-H atoms are drawn at the 30% probability level. H atoms are represented by circles of arbitrary size
[Figure 2] Fig. 2. Packing diagram, showing the hydrogen-bond interactions as dashed lines, viewed down the a axis.
4-Methylpiperazin-1-ium 2-amino-5-iodobenzoate top
Crystal data top
C5H13N2+·C7H5INO2F(000) = 720
Mr = 363.19Dx = 1.622 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2209 reflections
a = 14.829 (3) Åθ = 2.8–24.1°
b = 7.3472 (14) ŵ = 2.15 mm1
c = 13.713 (3) ÅT = 294 K
β = 95.313 (3)°Prism, colorless
V = 1487.6 (5) Å30.26 × 0.22 × 0.20 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
2655 independent reflections
Radiation source: fine-focus sealed tube1678 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
ϕ and ω scansθmax = 25.1°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1717
Tmin = 0.578, Tmax = 0.656k = 88
7380 measured reflectionsl = 1613
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.088H-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 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.65 e Å3
Crystal data top
C5H13N2+·C7H5INO2V = 1487.6 (5) Å3
Mr = 363.19Z = 4
Monoclinic, P21/cMo Kα radiation
a = 14.829 (3) ŵ = 2.15 mm1
b = 7.3472 (14) ÅT = 294 K
c = 13.713 (3) Å0.26 × 0.22 × 0.20 mm
β = 95.313 (3)°
Data collection top
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 = 0.656Rint = 0.029
7380 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.088H-atom parameters constrained
S = 1.02Δρmax = 0.33 e Å3
2655 reflectionsΔρmin = 0.65 e Å3
164 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I10.014263 (19)0.86525 (5)0.85945 (3)0.08959 (18)
N10.3687 (2)0.7581 (5)0.6555 (2)0.0729 (10)
H1A0.36510.74550.59290.087*
H1B0.42070.75360.68900.087*
O10.38083 (18)0.8577 (3)0.95581 (17)0.0581 (7)
O20.45410 (19)0.7625 (6)0.8329 (2)0.0887 (10)
C10.2932 (3)0.7848 (5)0.7010 (3)0.0479 (9)
C20.2963 (2)0.8082 (4)0.8032 (2)0.0389 (8)
C30.2153 (3)0.8327 (5)0.8445 (3)0.0479 (9)
H30.21700.84800.91200.057*
C40.1334 (3)0.8355 (5)0.7907 (3)0.0515 (10)
C50.1304 (3)0.8171 (5)0.6901 (3)0.0642 (11)
H50.07520.82170.65210.077*
C60.2086 (3)0.7922 (6)0.6470 (3)0.0615 (11)
H60.20560.77970.57930.074*
C70.3828 (3)0.8099 (5)0.8681 (3)0.0497 (9)
N20.3973 (2)0.1996 (4)1.0425 (2)0.0574 (8)
H2A0.45120.20471.07820.069*
H2B0.39010.08621.01820.069*
N30.2346 (2)0.3752 (5)0.9684 (3)0.0742 (11)
C80.3961 (3)0.3304 (6)0.9613 (3)0.0670 (11)
H8A0.44150.29700.91800.080*
H8B0.41030.45120.98680.080*
C90.3035 (4)0.3308 (6)0.9052 (3)0.0747 (13)
H9A0.30230.41900.85250.090*
H9B0.29120.21170.87650.090*
C100.2346 (3)0.2444 (7)1.0477 (4)0.0780 (13)
H10A0.22010.12461.02090.094*
H10B0.18840.27741.09010.094*
C110.3247 (3)0.2387 (6)1.1060 (3)0.0669 (11)
H11A0.33630.35481.13840.080*
H11B0.32410.14541.15600.080*
C120.1445 (4)0.3812 (7)0.9143 (6)0.130 (3)
H12A0.12520.25980.89710.195*
H12B0.14710.45220.85580.195*
H12C0.10230.43570.95460.195*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.0505 (2)0.0945 (3)0.1271 (3)0.00456 (17)0.02630 (18)0.0012 (2)
N10.069 (2)0.112 (3)0.0385 (19)0.004 (2)0.0117 (17)0.0143 (19)
O10.0651 (17)0.0755 (18)0.0328 (15)0.0052 (14)0.0008 (12)0.0003 (13)
O20.0454 (17)0.165 (3)0.0541 (18)0.0159 (19)0.0017 (14)0.0237 (19)
C10.059 (3)0.047 (2)0.038 (2)0.0048 (18)0.0082 (19)0.0024 (17)
C20.044 (2)0.0400 (19)0.032 (2)0.0020 (15)0.0014 (15)0.0016 (15)
C30.057 (2)0.048 (2)0.040 (2)0.0029 (17)0.0093 (18)0.0008 (16)
C40.043 (2)0.049 (2)0.062 (3)0.0047 (17)0.0048 (18)0.0032 (19)
C50.054 (3)0.068 (3)0.067 (3)0.002 (2)0.013 (2)0.004 (2)
C60.067 (3)0.076 (3)0.038 (2)0.007 (2)0.010 (2)0.0037 (19)
C70.049 (2)0.057 (2)0.043 (2)0.0018 (18)0.0027 (18)0.0030 (18)
N20.0411 (18)0.065 (2)0.065 (2)0.0076 (15)0.0011 (15)0.0071 (17)
N30.047 (2)0.058 (2)0.114 (3)0.0006 (17)0.013 (2)0.008 (2)
C80.058 (3)0.075 (3)0.070 (3)0.005 (2)0.012 (2)0.004 (2)
C90.092 (4)0.058 (3)0.069 (3)0.008 (2)0.018 (3)0.009 (2)
C100.048 (3)0.069 (3)0.119 (4)0.003 (2)0.017 (3)0.002 (3)
C110.067 (3)0.071 (3)0.066 (3)0.011 (2)0.021 (2)0.004 (2)
C120.070 (4)0.072 (3)0.233 (7)0.003 (3)0.065 (4)0.027 (4)
Geometric parameters (Å, º) top
I1—C42.090 (4)N2—H2A0.9000
N1—C11.346 (5)N2—H2B0.9000
N1—H1A0.8600N3—C91.436 (6)
N1—H1B0.8600N3—C101.451 (6)
O1—C71.257 (4)N3—C121.468 (6)
O2—C71.251 (4)C8—C91.511 (6)
C1—C61.397 (5)C8—H8A0.9700
C1—C21.409 (5)C8—H8B0.9700
C2—C31.386 (5)C9—H9A0.9700
C2—C71.493 (5)C9—H9B0.9700
C3—C41.362 (5)C10—C111.492 (6)
C3—H30.9300C10—H10A0.9700
C4—C51.382 (6)C10—H10B0.9700
C5—C61.362 (6)C11—H11A0.9700
C5—H50.9300C11—H11B0.9700
C6—H60.9300C12—H12A0.9600
N2—C81.470 (5)C12—H12B0.9600
N2—C111.474 (5)C12—H12C0.9600
C1—N1—H1A120.0C10—N3—C12109.6 (4)
C1—N1—H1B120.0N2—C8—C9109.4 (3)
H1A—N1—H1B120.0N2—C8—H8A109.8
N1—C1—C6120.3 (3)C9—C8—H8A109.8
N1—C1—C2121.8 (3)N2—C8—H8B109.8
C6—C1—C2117.8 (4)C9—C8—H8B109.8
C3—C2—C1118.3 (3)H8A—C8—H8B108.2
C3—C2—C7119.0 (3)N3—C9—C8110.9 (4)
C1—C2—C7122.7 (3)N3—C9—H9A109.5
C4—C3—C2122.9 (3)C8—C9—H9A109.5
C4—C3—H3118.6N3—C9—H9B109.5
C2—C3—H3118.6C8—C9—H9B109.5
C3—C4—C5119.0 (4)H9A—C9—H9B108.0
C3—C4—I1120.4 (3)N3—C10—C11111.0 (4)
C5—C4—I1120.7 (3)N3—C10—H10A109.4
C6—C5—C4119.8 (4)C11—C10—H10A109.4
C6—C5—H5120.1N3—C10—H10B109.4
C4—C5—H5120.1C11—C10—H10B109.4
C5—C6—C1122.2 (4)H10A—C10—H10B108.0
C5—C6—H6118.9N2—C11—C10110.8 (3)
C1—C6—H6118.9N2—C11—H11A109.5
O2—C7—O1122.8 (3)C10—C11—H11A109.5
O2—C7—C2118.6 (3)N2—C11—H11B109.5
O1—C7—C2118.5 (3)C10—C11—H11B109.5
C8—N2—C11111.2 (3)H11A—C11—H11B108.1
C8—N2—H2A109.4N3—C12—H12A109.5
C11—N2—H2A109.4N3—C12—H12B109.5
C8—N2—H2B109.4H12A—C12—H12B109.5
C11—N2—H2B109.4N3—C12—H12C109.5
H2A—N2—H2B108.0H12A—C12—H12C109.5
C9—N3—C10110.5 (3)H12B—C12—H12C109.5
C9—N3—C12111.6 (5)
N1—C1—C2—C3179.2 (3)C3—C2—C7—O2170.0 (4)
C6—C1—C2—C31.6 (5)C1—C2—C7—O210.7 (5)
N1—C1—C2—C71.5 (5)C3—C2—C7—O19.5 (5)
C6—C1—C2—C7177.7 (3)C1—C2—C7—O1169.8 (3)
C1—C2—C3—C40.1 (5)C11—N2—C8—C955.4 (4)
C7—C2—C3—C4179.1 (3)C10—N3—C9—C859.4 (5)
C2—C3—C4—C51.5 (5)C12—N3—C9—C8178.4 (3)
C2—C3—C4—I1178.1 (3)N2—C8—C9—N357.9 (5)
C3—C4—C5—C61.6 (6)C9—N3—C10—C1158.3 (5)
I1—C4—C5—C6178.0 (3)C12—N3—C10—C11178.4 (4)
C4—C5—C6—C10.2 (6)C8—N2—C11—C1055.0 (5)
N1—C1—C6—C5179.3 (4)N3—C10—C11—N255.7 (5)
C2—C1—C6—C51.4 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.862.062.889 (4)162
N1—H1B···O20.861.992.637 (4)131
N2—H2B···O1ii0.901.882.780 (4)174
N2—H2A···O2iii0.901.792.675 (4)168
Symmetry codes: (i) x, y+3/2, z1/2; (ii) x, y1, z; (iii) x+1, y+1, z+2.

Experimental details

Crystal data
Chemical formulaC5H13N2+·C7H5INO2
Mr363.19
Crystal system, space groupMonoclinic, P21/c
Temperature (K)294
a, b, c (Å)14.829 (3), 7.3472 (14), 13.713 (3)
β (°) 95.313 (3)
V3)1487.6 (5)
Z4
Radiation typeMo Kα
µ (mm1)2.15
Crystal size (mm)0.26 × 0.22 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.578, 0.656
No. of measured, independent and
observed [I > 2σ(I)] reflections
7380, 2655, 1678
Rint0.029
(sin θ/λ)max1)0.597
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.088, 1.02
No. of reflections2655
No. of parameters164
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.33, 0.65

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXTL (Bruker, 2000), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.862.062.889 (4)162
N1—H1B···O20.861.992.637 (4)131
N2—H2B···O1ii0.901.882.780 (4)174
N2—H2A···O2iii0.901.792.675 (4)168
Symmetry codes: (i) x, y+3/2, z1/2; (ii) x, y1, z; (iii) x+1, y+1, z+2.
 

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