In the title compound, C
5H
10NH
2+·C
6HO
4Cl
2−, two chloranilate ions are connected by O—H
O hydrogen bonds to form a dimeric unit. The piperidinium ions are linked on both sides of the dimer
via a bifurcated N—H
O hydrogen bond to afford a 2:2 complex of chloranilic acid and piperidine. The 2:2 complexes are linked together to form a hydrogen-bonded molecular tape.
Supporting information
CCDC reference: 227013
Key indicators
- Single-crystal X-ray study
- T = 299 K
- Mean (C-C) = 0.004 Å
- R factor = 0.035
- wR factor = 0.093
- Data-to-parameter ratio = 13.3
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT333_ALERT_2_C Large Av Benzene C-C Dist. C1 - C6 = 1.44 Ang.
PLAT335_ALERT_2_C Large Benzene C-C Range C1 - C6 = 0.20 Ang.
PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C1 - C6 = 1.54 Ang.
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 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
3 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
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. 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: TEXSAN for Windows.
Crystal data top
C5H12N+·C6HCl2O4− | F(000) = 1216.00 |
Mr = 294.13 | Dx = 1.559 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 25 reflections |
a = 17.263 (5) Å | θ = 11.7–12.0° |
b = 6.800 (4) Å | µ = 0.52 mm−1 |
c = 22.832 (8) Å | T = 299 K |
β = 110.80 (2)° | Prismatic, dark purple |
V = 2505.5 (19) Å3 | 0.30 × 0.30 × 0.25 mm |
Z = 8 | |
Data collection top
Rigaku AFC-5R diffractometer | 2029 reflections with I > 2σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.028 |
Graphite monochromator | θmax = 27.5°, θmin = 3.3° |
ω–2θ scans | h = 0→22 |
Absorption correction: ψ scan (North et al., 1968) | k = −2→8 |
Tmin = 0.816, Tmax = 0.877 | l = −29→27 |
3924 measured reflections | 3 standard reflections every 97 reflections |
2866 independent reflections | intensity decay: 1.1% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.035 | All H-atom parameters refined |
wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.031P)2 + 2.03P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.01 |
2866 reflections | Δρmax = 0.31 e Å−3 |
216 parameters | Δρmin = −0.27 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 1.4E-3 (3) |
Special details top
Experimental. The scan width was (1.68 + 0.30tanθ)° with an ω scan speed of 6° per minute
(up to 4 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. |
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. 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.19360 (3) | −0.07182 (9) | −0.10353 (3) | 0.03969 (17) | |
Cl2 | 0.42847 (3) | 0.12311 (11) | 0.17429 (3) | 0.04382 (19) | |
O1 | 0.14759 (9) | −0.0208 (3) | 0.01009 (8) | 0.0420 (4) | |
O2 | 0.37363 (10) | −0.0034 (3) | −0.05712 (8) | 0.0394 (4) | |
O3 | 0.47215 (9) | 0.0848 (3) | 0.05631 (7) | 0.0397 (4) | |
O4 | 0.24660 (9) | 0.0672 (3) | 0.12676 (7) | 0.0437 (4) | |
N | 0.09638 (13) | −0.1059 (3) | 0.12238 (9) | 0.0392 (5) | |
C1 | 0.22073 (12) | 0.0047 (3) | 0.01936 (10) | 0.0289 (4) | |
C2 | 0.25685 (12) | −0.0105 (3) | −0.02863 (10) | 0.0280 (4) | |
C3 | 0.33890 (12) | 0.0152 (3) | −0.01421 (9) | 0.0273 (4) | |
C4 | 0.39751 (12) | 0.0641 (3) | 0.05101 (10) | 0.0283 (4) | |
C5 | 0.36400 (12) | 0.0800 (3) | 0.09781 (9) | 0.0289 (4) | |
C6 | 0.27886 (13) | 0.0547 (3) | 0.08662 (10) | 0.0292 (4) | |
C7 | 0.13646 (16) | −0.2011 (4) | 0.18518 (12) | 0.0409 (6) | |
C8 | 0.17747 (16) | −0.0509 (4) | 0.23478 (11) | 0.0432 (6) | |
C9 | 0.1196 (2) | 0.1136 (5) | 0.23617 (14) | 0.0576 (8) | |
C10 | 0.0817 (2) | 0.2062 (5) | 0.17120 (15) | 0.0584 (8) | |
C11 | 0.03792 (16) | 0.0553 (5) | 0.12241 (15) | 0.0534 (7) | |
H1 | 0.423 (2) | 0.009 (5) | −0.0424 (15) | 0.071 (11)* | |
H2 | 0.1382 (18) | −0.058 (4) | 0.1102 (13) | 0.056 (8)* | |
H3 | 0.0716 (19) | −0.198 (5) | 0.0990 (15) | 0.061 (9)* | |
H4 | 0.1757 (18) | −0.298 (5) | 0.1814 (13) | 0.061 (9)* | |
H5 | 0.0934 (17) | −0.267 (4) | 0.1938 (12) | 0.053 (8)* | |
H6 | 0.2228 (16) | 0.003 (4) | 0.2262 (12) | 0.047 (7)* | |
H7 | 0.1985 (17) | −0.122 (4) | 0.2756 (14) | 0.058 (8)* | |
H8 | 0.148 (2) | 0.223 (7) | 0.2676 (19) | 0.112 (14)* | |
H9 | 0.0776 (18) | 0.059 (4) | 0.2467 (13) | 0.050 (8)* | |
H10 | 0.127 (2) | 0.272 (5) | 0.1591 (15) | 0.077 (10)* | |
H11 | 0.0436 (18) | 0.291 (4) | 0.1683 (13) | 0.055 (8)* | |
H12 | 0.0211 (18) | 0.109 (5) | 0.0813 (15) | 0.064 (9)* | |
H13 | −0.0071 (19) | −0.009 (4) | 0.1277 (13) | 0.055 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0388 (3) | 0.0451 (3) | 0.0306 (3) | −0.0028 (3) | 0.0066 (2) | −0.0056 (2) |
Cl2 | 0.0340 (3) | 0.0664 (5) | 0.0291 (3) | −0.0003 (3) | 0.0089 (2) | −0.0068 (3) |
O1 | 0.0265 (7) | 0.0572 (11) | 0.0438 (9) | −0.0039 (8) | 0.0145 (7) | −0.0015 (8) |
O2 | 0.0327 (9) | 0.0574 (11) | 0.0337 (8) | −0.0018 (8) | 0.0184 (7) | −0.0068 (8) |
O3 | 0.0256 (7) | 0.0557 (11) | 0.0419 (9) | −0.0036 (7) | 0.0172 (6) | −0.0097 (8) |
O4 | 0.0367 (8) | 0.0648 (12) | 0.0382 (8) | −0.0072 (8) | 0.0238 (7) | −0.0080 (8) |
N | 0.0359 (10) | 0.0464 (13) | 0.0329 (10) | −0.0078 (10) | 0.0093 (8) | −0.0062 (10) |
C1 | 0.0271 (10) | 0.0276 (11) | 0.0341 (11) | 0.0012 (9) | 0.0136 (8) | 0.0026 (9) |
C2 | 0.0286 (10) | 0.0260 (11) | 0.0293 (10) | 0.0001 (8) | 0.0102 (8) | −0.0015 (8) |
C3 | 0.0307 (10) | 0.0264 (11) | 0.0290 (10) | 0.0014 (8) | 0.0156 (8) | −0.0011 (8) |
C4 | 0.0257 (9) | 0.0268 (11) | 0.0340 (10) | 0.0019 (8) | 0.0124 (8) | −0.0026 (9) |
C5 | 0.0268 (9) | 0.0329 (12) | 0.0273 (10) | 0.0007 (9) | 0.0098 (8) | −0.0024 (9) |
C6 | 0.0306 (10) | 0.0286 (11) | 0.0323 (11) | 0.0007 (9) | 0.0159 (8) | 0.0013 (9) |
C7 | 0.0391 (12) | 0.0389 (15) | 0.0451 (13) | 0.0013 (11) | 0.0153 (11) | 0.0058 (11) |
C8 | 0.0434 (13) | 0.0541 (17) | 0.0319 (12) | −0.0025 (12) | 0.0131 (10) | 0.0020 (11) |
C9 | 0.075 (2) | 0.061 (2) | 0.0455 (15) | 0.0085 (17) | 0.0325 (15) | −0.0019 (14) |
C10 | 0.0680 (19) | 0.0494 (19) | 0.0617 (18) | 0.0212 (16) | 0.0275 (16) | 0.0049 (15) |
C11 | 0.0345 (13) | 0.065 (2) | 0.0562 (17) | 0.0075 (13) | 0.0102 (12) | 0.0157 (15) |
Geometric parameters (Å, º) top
Cl1—C2 | 1.722 (2) | C5—C6 | 1.410 (3) |
Cl2—C5 | 1.730 (2) | C7—C8 | 1.503 (4) |
O1—C1 | 1.216 (2) | C7—H4 | 0.97 (3) |
O2—C3 | 1.324 (2) | C7—H5 | 0.95 (3) |
O2—H1 | 0.79 (3) | C8—C9 | 1.508 (4) |
O3—C4 | 1.259 (2) | C8—H6 | 0.95 (3) |
O4—C6 | 1.233 (2) | C8—H7 | 1.00 (3) |
N—C11 | 1.490 (4) | C9—C10 | 1.528 (4) |
N—C7 | 1.500 (3) | C9—H8 | 1.03 (4) |
N—H2 | 0.92 (3) | C9—H9 | 0.92 (3) |
N—H3 | 0.83 (3) | C10—C11 | 1.506 (5) |
C1—C2 | 1.444 (3) | C10—H10 | 1.02 (3) |
C1—C6 | 1.545 (3) | C10—H11 | 0.86 (3) |
C2—C3 | 1.347 (3) | C11—H12 | 0.95 (3) |
C3—C4 | 1.511 (3) | C11—H13 | 0.93 (3) |
C4—C5 | 1.388 (3) | | |
| | | |
O1···N | 3.049 (3) | O4···C8 | 3.200 (4) |
O1···C3i | 3.369 (3) | O4···C7 | 3.244 (3) |
O1···C4ii | 3.380 (3) | C1···C2i | 3.381 (4) |
O2···O3iii | 2.713 (3) | C1···C3ii | 3.413 (4) |
O2···Ni | 3.177 (3) | C1···C2ii | 3.459 (4) |
O3···Niv | 3.000 (3) | C2···C6ii | 3.341 (4) |
O4···N | 2.817 (3) | C2···C2i | 3.549 (5) |
| | | |
C3—O2—H1 | 112 (2) | N—C7—H5 | 105.9 (16) |
C11—N—C7 | 113.6 (2) | C8—C7—H5 | 111.2 (17) |
C11—N—H2 | 110.0 (18) | H4—C7—H5 | 109 (2) |
C7—N—H2 | 107.4 (18) | C7—C8—C9 | 112.4 (2) |
C11—N—H3 | 111 (2) | C7—C8—H6 | 108.2 (16) |
C7—N—H3 | 104 (2) | C9—C8—H6 | 108.6 (17) |
H2—N—H3 | 111 (3) | C7—C8—H7 | 107.1 (17) |
O1—C1—C2 | 124.0 (2) | C9—C8—H7 | 111.3 (16) |
O1—C1—C6 | 118.17 (18) | H6—C8—H7 | 109 (2) |
C2—C1—C6 | 117.83 (17) | C8—C9—C10 | 110.1 (2) |
C3—C2—C1 | 120.35 (19) | C8—C9—H8 | 113 (2) |
C3—C2—Cl1 | 121.01 (16) | C10—C9—H8 | 108 (2) |
C1—C2—Cl1 | 118.59 (15) | C8—C9—H9 | 107.3 (18) |
O2—C3—C2 | 121.35 (19) | C10—C9—H9 | 108.4 (18) |
O2—C3—C4 | 115.44 (17) | H8—C9—H9 | 110 (3) |
C2—C3—C4 | 123.21 (18) | C11—C10—C9 | 111.5 (3) |
O3—C4—C5 | 127.55 (19) | C11—C10—H10 | 109.3 (19) |
O3—C4—C3 | 115.08 (18) | C9—C10—H10 | 109.8 (19) |
C5—C4—C3 | 117.36 (17) | C11—C10—H11 | 103 (2) |
C4—C5—C6 | 122.92 (19) | C9—C10—H11 | 114 (2) |
C4—C5—Cl2 | 119.71 (15) | H10—C10—H11 | 109 (3) |
C6—C5—Cl2 | 117.32 (15) | N—C11—C10 | 109.8 (2) |
O4—C6—C5 | 125.0 (2) | N—C11—H12 | 104.6 (18) |
O4—C6—C1 | 116.65 (18) | C10—C11—H12 | 111.4 (19) |
C5—C6—C1 | 118.31 (17) | N—C11—H13 | 104.6 (18) |
N—C7—C8 | 111.1 (2) | C10—C11—H13 | 116.3 (18) |
N—C7—H4 | 107.9 (17) | H12—C11—H13 | 109 (2) |
C8—C7—H4 | 111.9 (17) | | |
| | | |
O1—C1—C2—C3 | −178.3 (2) | C3—C4—C5—Cl2 | 176.66 (16) |
C6—C1—C2—C3 | 1.1 (3) | C4—C5—C6—O4 | 179.8 (2) |
O1—C1—C2—Cl1 | −1.0 (3) | Cl2—C5—C6—O4 | 2.5 (3) |
C6—C1—C2—Cl1 | 178.49 (15) | C4—C5—C6—C1 | 0.7 (3) |
C1—C2—C3—O2 | 178.2 (2) | Cl2—C5—C6—C1 | −176.68 (16) |
Cl1—C2—C3—O2 | 0.8 (3) | O1—C1—C6—O4 | −0.6 (3) |
C1—C2—C3—C4 | −1.1 (3) | C2—C1—C6—O4 | 179.9 (2) |
Cl1—C2—C3—C4 | −178.45 (16) | O1—C1—C6—C5 | 178.6 (2) |
O2—C3—C4—O3 | 1.3 (3) | C2—C1—C6—C5 | −0.9 (3) |
C2—C3—C4—O3 | −179.4 (2) | C11—N—C7—C8 | −53.6 (3) |
O2—C3—C4—C5 | −178.5 (2) | N—C7—C8—C9 | 52.7 (3) |
C2—C3—C4—C5 | 0.9 (3) | C7—C8—C9—C10 | −54.3 (4) |
O3—C4—C5—C6 | 179.7 (2) | C8—C9—C10—C11 | 56.3 (4) |
C3—C4—C5—C6 | −0.7 (3) | C7—N—C11—C10 | 55.5 (3) |
O3—C4—C5—Cl2 | −3.0 (3) | C9—C10—C11—N | −56.5 (3) |
Symmetry codes: (i) −x+1/2, −y−1/2, −z; (ii) −x+1/2, −y+1/2, −z; (iii) −x+1, −y, −z; (iv) x+1/2, y+1/2, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O3 | 0.80 (4) | 2.17 (3) | 2.614 (3) | 115 (3) |
O2—H1···O3iii | 0.80 (4) | 2.05 (4) | 2.713 (3) | 140 (3) |
N—H2···O1 | 0.92 (3) | 2.36 (3) | 3.049 (3) | 131 (2) |
N—H2···O4 | 0.92 (3) | 1.97 (3) | 2.817 (3) | 153 (2) |
N—H3···O3v | 0.84 (3) | 2.21 (3) | 3.000 (3) | 157 (3) |
N—H3···O2i | 0.84 (3) | 2.56 (3) | 3.177 (3) | 131 (3) |
C7—H5···Cl2v | 0.95 (3) | 2.82 (3) | 3.708 (4) | 156 (2) |
C8—H6···O4 | 0.95 (3) | 2.49 (3) | 3.200 (4) | 132 (2) |
Symmetry codes: (i) −x+1/2, −y−1/2, −z; (iii) −x+1, −y, −z; (v) x−1/2, y−1/2, z. |