The molecule of the title compound, C
9H
9Cl
2NO
2, is a zwitterion with cationic iminium and an anionic phenolate group, which form an intramolecular N—H
O hydrogen bond closing a six-membered pseudocycle. Intermolecular O—H
O hydrogen bonds link the molecules into infinite chains running along the
c axis.
Supporting information
CCDC reference: 628437
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.003 Å
- R factor = 0.030
- wR factor = 0.073
- Data-to-parameter ratio = 10.6
checkCIF/PLATON results
No syntax errors found
Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 25.20
From the CIF: _reflns_number_total 1730
Count of symmetry unique reflns 990
Completeness (_total/calc) 174.75%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 740
Fraction of Friedel pairs measured 0.747
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
0 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 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
1 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL(Bruker, 2002); software used to prepare material for publication: SHELXL97.
(
E)-2,4-dichloro-6-[(2-hydroxyethyliminio)methyl]phenolate
top
Crystal data top
C9H9Cl2NO2 | Dx = 1.596 Mg m−3 |
Mr = 234.07 | Melting point: 409.7 K |
Orthorhombic, Aba2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: A 2 -2ac | Cell parameters from 250 reflections |
a = 18.619 (3) Å | θ = 2.0–27.5° |
b = 21.447 (4) Å | µ = 0.64 mm−1 |
c = 4.8779 (9) Å | T = 295 K |
V = 1947.9 (6) Å3 | Block, orange |
Z = 8 | 0.28 × 0.23 × 0.15 mm |
F(000) = 960 | |
Data collection top
Siemens SMART CCD area detector diffractometer | 1730 independent reflections |
Radiation source: fine-focus sealed tube | 1690 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ω and φ scans | θmax = 25.2°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −15→22 |
Tmin = 0.834, Tmax = 0.902 | k = −23→25 |
5027 measured reflections | l = −5→5 |
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)] = 0.030 | All H-atom parameters refined |
wR(F2) = 0.073 | w = 1/[σ2(Fo2) + (0.0388P)2 + 1.0811P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
1730 reflections | Δρmax = 0.20 e Å−3 |
163 parameters | Δρmin = −0.19 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 740 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.07 (7) |
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 | x | y | z | Uiso*/Ueq | |
N1 | 0.44604 (11) | 0.56740 (11) | 0.2954 (5) | 0.0348 (5) | |
Cl1 | 0.68249 (3) | 0.61415 (3) | 0.89565 (15) | 0.03919 (17) | |
Cl2 | 0.65019 (4) | 0.80138 (3) | 0.17326 (17) | 0.0494 (2) | |
O1 | 0.54686 (8) | 0.56780 (7) | 0.6568 (4) | 0.0396 (4) | |
O2 | 0.28677 (9) | 0.58035 (8) | 0.3931 (5) | 0.0422 (4) | |
C1 | 0.53147 (12) | 0.64954 (10) | 0.3328 (5) | 0.0325 (5) | |
C2 | 0.56863 (12) | 0.61922 (10) | 0.5514 (5) | 0.0307 (5) | |
C3 | 0.63230 (11) | 0.64990 (10) | 0.6408 (5) | 0.0315 (5) | |
C4 | 0.65576 (13) | 0.70519 (11) | 0.5319 (5) | 0.0345 (6) | |
C5 | 0.61663 (12) | 0.73280 (10) | 0.3204 (5) | 0.0345 (6) | |
C6 | 0.55630 (14) | 0.70623 (11) | 0.2209 (6) | 0.0357 (6) | |
C7 | 0.47060 (13) | 0.61942 (11) | 0.2113 (6) | 0.0359 (6) | |
C8 | 0.38820 (13) | 0.53270 (12) | 0.1588 (6) | 0.0404 (6) | |
C9 | 0.32451 (14) | 0.52399 (12) | 0.3444 (6) | 0.0391 (6) | |
H9B | 0.2941 (16) | 0.4949 (12) | 0.262 (6) | 0.046 (8)* | |
H4 | 0.6999 (15) | 0.7229 (11) | 0.602 (7) | 0.043 (7)* | |
H9A | 0.3408 (16) | 0.5101 (14) | 0.515 (7) | 0.043 (8)* | |
H8B | 0.3771 (15) | 0.5576 (13) | −0.005 (6) | 0.046 (8)* | |
H6 | 0.5321 (16) | 0.7221 (12) | 0.078 (7) | 0.044 (8)* | |
H2 | 0.2667 (16) | 0.5894 (12) | 0.256 (7) | 0.045 (9)* | |
H7 | 0.4505 (17) | 0.6384 (12) | 0.057 (8) | 0.057 (10)* | |
H8A | 0.4081 (16) | 0.4901 (13) | 0.111 (7) | 0.058 (9)* | |
H1 | 0.4721 (19) | 0.5530 (14) | 0.401 (11) | 0.071 (11)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0277 (11) | 0.0406 (12) | 0.0361 (12) | 0.0016 (9) | −0.0033 (9) | −0.0040 (8) |
Cl1 | 0.0353 (3) | 0.0473 (3) | 0.0350 (3) | −0.0005 (2) | −0.0062 (3) | 0.0058 (3) |
Cl2 | 0.0552 (4) | 0.0356 (3) | 0.0575 (4) | −0.0058 (3) | 0.0059 (4) | 0.0104 (3) |
O1 | 0.0393 (9) | 0.0386 (8) | 0.0411 (10) | −0.0085 (7) | −0.0048 (8) | 0.0090 (8) |
O2 | 0.0405 (9) | 0.0456 (9) | 0.0406 (10) | 0.0051 (8) | 0.0002 (10) | −0.0074 (10) |
C1 | 0.0277 (11) | 0.0355 (12) | 0.0343 (14) | 0.0030 (9) | 0.0004 (10) | 0.0001 (10) |
C2 | 0.0265 (10) | 0.0334 (11) | 0.0320 (13) | 0.0022 (9) | 0.0046 (9) | −0.0014 (10) |
C3 | 0.0317 (11) | 0.0359 (12) | 0.0269 (11) | 0.0047 (9) | 0.0029 (10) | −0.0018 (10) |
C4 | 0.0328 (14) | 0.0348 (13) | 0.0360 (13) | −0.0013 (10) | 0.0045 (10) | −0.0049 (10) |
C5 | 0.0359 (12) | 0.0284 (11) | 0.0391 (15) | −0.0001 (10) | 0.0071 (11) | 0.0021 (10) |
C6 | 0.0359 (14) | 0.0347 (13) | 0.0366 (14) | 0.0061 (10) | 0.0016 (11) | 0.0048 (11) |
C7 | 0.0310 (13) | 0.0413 (13) | 0.0355 (15) | 0.0055 (10) | −0.0022 (11) | −0.0019 (11) |
C8 | 0.0351 (13) | 0.0436 (14) | 0.0424 (15) | −0.0039 (10) | −0.0018 (12) | −0.0130 (14) |
C9 | 0.0366 (13) | 0.0388 (13) | 0.0417 (18) | −0.0065 (11) | −0.0055 (12) | −0.0032 (12) |
Geometric parameters (Å, º) top
Cl1—C3 | 1.734 (2) | C3—C4 | 1.371 (3) |
Cl2—C5 | 1.752 (2) | C4—C5 | 1.395 (4) |
O1—C2 | 1.283 (3) | C4—H4 | 0.97 (3) |
O2—C9 | 1.418 (3) | C5—C6 | 1.350 (4) |
N1—C7 | 1.274 (3) | C6—H6 | 0.90 (3) |
N1—C8 | 1.469 (3) | C7—H7 | 0.93 (4) |
N1—H1 | 0.77 (4) | C8—C9 | 1.503 (4) |
O2—H2 | 0.79 (3) | C8—H8B | 0.98 (3) |
C1—C6 | 1.411 (3) | C8—H8A | 1.01 (3) |
C1—C2 | 1.428 (3) | C9—H9B | 0.93 (3) |
C1—C7 | 1.433 (3) | C9—H9A | 0.93 (3) |
C2—C3 | 1.424 (3) | | |
| | | |
C7—N1—C8 | 124.1 (3) | C5—C6—C1 | 119.8 (2) |
C7—N1—H1 | 110 (3) | C5—C6—H6 | 122.5 (19) |
C8—N1—H1 | 124 (2) | C1—C6—H6 | 117.5 (19) |
C9—O2—H2 | 108 (2) | N1—C7—C1 | 123.1 (2) |
C6—C1—C2 | 121.5 (2) | N1—C7—H7 | 119.8 (18) |
C6—C1—C7 | 119.2 (2) | C1—C7—H7 | 117.0 (18) |
C2—C1—C7 | 119.1 (2) | N1—C8—C9 | 111.6 (2) |
O1—C2—C3 | 122.5 (2) | N1—C8—H8B | 104.4 (17) |
O1—C2—C1 | 122.5 (2) | C9—C8—H8B | 113.1 (17) |
C3—C2—C1 | 114.9 (2) | N1—C8—H8A | 107.0 (18) |
C4—C3—C2 | 123.1 (2) | C9—C8—H8A | 108.3 (17) |
C4—C3—Cl1 | 119.25 (19) | H8B—C8—H8A | 112 (2) |
C2—C3—Cl1 | 117.63 (17) | O2—C9—C8 | 112.7 (2) |
C3—C4—C5 | 119.2 (2) | O2—C9—H9B | 109.9 (18) |
C3—C4—H4 | 118.3 (17) | C8—C9—H9B | 107.6 (18) |
C5—C4—H4 | 122.5 (17) | O2—C9—H9A | 106.5 (19) |
C6—C5—C4 | 121.4 (2) | C8—C9—H9A | 108.7 (19) |
C6—C5—Cl2 | 120.3 (2) | H9B—C9—H9A | 112 (3) |
C4—C5—Cl2 | 118.24 (19) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.77 (4) | 1.89 (4) | 2.575 (3) | 147 (3) |
O2—H2···O2i | 0.79 (3) | 2.04 (3) | 2.7970 (18) | 160 (3) |
Symmetry code: (i) −x+1/2, y, z−1/2. |