Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032473/bt2426sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032473/bt2426Isup2.hkl |
CCDC reference: 657715
Key indicators
- Single-crystal X-ray study
- T = 130 K
- Mean (C-C) = 0.010 Å
- R factor = 0.076
- wR factor = 0.197
- Data-to-parameter ratio = 12.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.89 Ratio PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 10 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety N1A PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety N1B PLAT417_ALERT_2_C Short Inter D-H..H-D H21C .. H22W .. 2.11 Ang.
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 25.00 From the CIF: _reflns_number_total 4197 Count of symmetry unique reflns 2346 Completeness (_total/calc) 178.90% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1851 Fraction of Friedel pairs measured 0.789 Are heavy atom types Z>Si present yes PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2C = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2D = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3C = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3D = . R PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 6 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The structure of the title compound is different from those of the L-tartrates of the parent aniline (Chen et al., 2005), p-toluidine and m-anisidine (Renuka et al., 1995). For related literature, see: Aakeröy et al. (1992); Bijvoet et al. (1951); Bott et al. (1993); Fuller et al. (1995); Manivannan et al. (1995); Smith et al. (2006).
Compound (I) was synthesized by heating for 10 min under reflux, 1 mmol quantities of L-tartaric acid and 4-chloroaniline in 50 ml of 50% 2-propanol-water. Colourless needles (m.p. 443 K) were obtained after partial room-temperature evaporation of solvent.
Hydrogen atoms potentially involved in hydrogen-bonding interactions were located by difference methods and their positional and isotropic displacement parameters were refined but these were constrained in the final refinement cycles. Other H atoms were included at calculated positions [C—H (aromatic) = 0.95 Å and C—H (aliphatic) = 0.98–1.00 Å] and treated as riding with Uiso(H) = 1.2Ueq(C). The absolute configuration determined for the parent L-(+)-tartaric acid (2R,3R) (Bijvoet et al., 1951) was invoked.
The utility of L-tartaric acid as an agent for the introduction of chirality in organic compounds for the generation of crystalline materials with potentially useful nonlinear optical properties has been recognized (Aakeröy et al., 1992; Fuller et al., 1995; Renuka et al., 1995; Chen et al., 2005; Manivannan et al., 1995). The product from the 1:1 reaction with aniline (Chen et al., 2005), p-toluidine and m-anisidine (a monohydrate) (Renuka et al., 1995) have been determined so that our similar reaction of L-tartaric acid with 4-chloroaniline in aqueous propan-2-ol not unexpectedly gave good crystals of the proton-transfer compound 4-chloroanilinium hydrogen (2R,3R)-tartrate monohydrate C6H7ClN+ C4H5O6-. H2O, (I) and the structure is reported here.
In (I), the asymmetric unit comprises two 4-chloroanilinium cations (A and B), two hydrogen L-tartarate anions (C and D) and two water molecules of solvation (O1W and O2W) (Fig. 1). The two hydrogen tartrate anions and the water molecules form duplex hydrogen-bonded substructures through homomeric A and B chain carboxylate interactions with other tartrate carboxylic acid and hydroxyl groups as well as with the water molecules (Table 1). These include the C11(7) head-to-tail carboxylic acid–carboxylate associations (O11–H11···O42) which extend down the a cell direction in the unit cell (Figs. 2, 3). These carboxyl associations typify the hydrogen-bonded framework substructures in the majority of the anhydrous hydrogen tartrates (Aakeröy et al., 1992). The two independent 4-chloroanilinium cations in (I) form a π-associated dimer through partial overlapping of the offset benzene rings [ring centroid separation, 3.576 (4) Å; inter-ring dihedral angle, 0.5 (1)°]. However, the inter-dimer separation down the a cell direction [4.242 (4) Å] does not give stacks such as is found in the structure of quinolinium hydrogen-L-tartrate (Smith et al., 2006). In (I), these dimers are accommodated between the substructures and are peripherally hydrogen-bonded to them through aminium N+—H···O interactions with water and both carboxyl and hydroxyl O acceptors of the anions, including the R34(8) cyclic system seen in the asymmetric unit in Fig. 1. The result is a two-dimensional network structure.
The accepted (2R,3R) absolute configuration for the L-tartrate residues in (I) (Bijvoet et al., 1951) was assumed and both anions C and D adopt the common extended conformation. The intramolecular hydroxyl O–H···O(carboxyl) hydrogen bond which is also common in hydrogen tartrates is absent in the C anion but present in the D anion [O···O, [2.554 (6) Å]. In addition, in the D anion there is an unusual intramolecular hydroxyl–hydroxyl O–H···O contact [O···O, 2.936 (7) Å]. However, there are no significant conformational differences in the two anions, the O21–C2–C3–O31 torsion angles being -61.7 (7) ° (C) and -69.5 (6) ° (D), comparing with -66.8 (2) ° in sodium hydrogen L-tartrate monohydrate (Bott et al., 1993).
The structure of the title compound is different from those of the L-tartrates of the parent aniline (Chen et al., 2005), p-toluidine and m-anisidine (Renuka et al., 1995). For related literature, see: Aakeröy et al. (1992); Bijvoet et al. (1951); Bott et al. (1993); Fuller et al. (1995); Manivannan et al. (1995); Smith et al. (2006).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.
C6H7ClN+·C4H5O6−·H2O | F(000) = 616 |
Mr = 295.67 | Dx = 1.558 Mg m−3 |
Monoclinic, P21 | Melting point: 443 K |
Hall symbol: P 2yb | Mo Kα radiation, λ = 0.71073 Å |
a = 7.3437 (15) Å | Cell parameters from 1450 reflections |
b = 10.850 (2) Å | θ = 2.9–22.5° |
c = 15.971 (3) Å | µ = 0.33 mm−1 |
β = 97.880 (4)° | T = 130 K |
V = 1260.5 (4) Å3 | Needle, colourless |
Z = 4 | 0.45 × 0.15 × 0.05 mm |
Bruker SMART CCD diffractometer | 4197 independent reflections |
Radiation source: sealed tube | 3319 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.087 |
φ and ω scans | θmax = 25.0°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −8→8 |
Tmin = 0.93, Tmax = 0.98 | k = −12→11 |
6196 measured reflections | l = −18→11 |
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)] = 0.076 | H-atom parameters not refined |
wR(F2) = 0.197 | w = 1/[σ2(Fo2) + (0.0989P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
4197 reflections | Δρmax = 0.79 e Å−3 |
342 parameters | Δρmin = −0.59 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 1857 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.02 (6) |
C6H7ClN+·C4H5O6−·H2O | V = 1260.5 (4) Å3 |
Mr = 295.67 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.3437 (15) Å | µ = 0.33 mm−1 |
b = 10.850 (2) Å | T = 130 K |
c = 15.971 (3) Å | 0.45 × 0.15 × 0.05 mm |
β = 97.880 (4)° |
Bruker SMART CCD diffractometer | 4197 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 3319 reflections with I > 2σ(I) |
Tmin = 0.93, Tmax = 0.98 | Rint = 0.087 |
6196 measured reflections |
R[F2 > 2σ(F2)] = 0.076 | H-atom parameters not refined |
wR(F2) = 0.197 | Δρmax = 0.79 e Å−3 |
S = 1.06 | Δρmin = −0.59 e Å−3 |
4197 reflections | Absolute structure: Flack (1983), 1857 Friedel pairs |
342 parameters | Absolute structure parameter: 0.02 (6) |
1 restraint |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
Cl4A | 0.9564 (3) | 0.55789 (17) | 0.48663 (12) | 0.0366 (6) | |
N1A | 0.6345 (8) | 0.9058 (5) | 0.2194 (3) | 0.0197 (17) | |
C1A | 0.7105 (9) | 0.8202 (7) | 0.2862 (4) | 0.0203 (19) | |
C2A | 0.7486 (10) | 0.8612 (6) | 0.3678 (5) | 0.026 (2) | |
C3A | 0.8266 (10) | 0.7810 (6) | 0.4301 (4) | 0.024 (2) | |
C4A | 0.8612 (10) | 0.6607 (6) | 0.4076 (4) | 0.024 (2) | |
C5A | 0.8207 (9) | 0.6193 (6) | 0.3260 (4) | 0.025 (2) | |
C6A | 0.7471 (9) | 0.6994 (6) | 0.2644 (4) | 0.022 (2) | |
Cl4B | 0.3364 (3) | 0.82187 (19) | 0.47195 (13) | 0.0439 (7) | |
N1B | 0.3270 (7) | 0.4358 (5) | 0.2080 (3) | 0.0192 (17) | |
C1B | 0.3282 (9) | 0.5305 (6) | 0.2730 (4) | 0.020 (2) | |
C2B | 0.2610 (10) | 0.6462 (6) | 0.2512 (5) | 0.024 (2) | |
C3B | 0.2671 (10) | 0.7368 (7) | 0.3126 (5) | 0.028 (3) | |
C4B | 0.3326 (10) | 0.7061 (7) | 0.3945 (5) | 0.027 (3) | |
C5B | 0.3993 (10) | 0.5903 (7) | 0.4180 (5) | 0.031 (3) | |
C6B | 0.3935 (10) | 0.5014 (6) | 0.3561 (5) | 0.027 (2) | |
O11D | 1.3279 (6) | 0.1806 (4) | 0.3335 (3) | 0.0205 (14) | |
O12D | 1.2998 (6) | 0.0308 (4) | 0.2370 (3) | 0.0227 (16) | |
O21D | 0.9331 (6) | 0.0562 (5) | 0.2059 (3) | 0.0213 (16) | |
O31D | 1.0026 (6) | 0.3206 (4) | 0.2331 (3) | 0.0255 (16) | |
O41D | 0.6701 (6) | 0.1617 (4) | 0.3335 (3) | 0.0240 (16) | |
O42D | 0.6568 (6) | 0.3134 (5) | 0.2385 (3) | 0.0280 (17) | |
C1D | 1.2342 (9) | 0.1077 (6) | 0.2827 (4) | 0.0173 (19) | |
C2D | 1.0252 (8) | 0.1109 (6) | 0.2818 (4) | 0.0146 (17) | |
C3D | 0.9500 (9) | 0.2378 (6) | 0.2957 (4) | 0.0197 (19) | |
C4D | 0.7397 (9) | 0.2382 (6) | 0.2880 (4) | 0.020 (2) | |
O11C | 0.7704 (6) | 0.7011 (4) | −0.0581 (3) | 0.0223 (14) | |
O12C | 0.8064 (6) | 0.7839 (5) | 0.0707 (3) | 0.0281 (16) | |
O21C | 0.4577 (6) | 0.8208 (5) | 0.0689 (3) | 0.0251 (17) | |
O31C | 0.5071 (6) | 0.5544 (5) | 0.0801 (3) | 0.0248 (17) | |
O41C | 0.1507 (6) | 0.5520 (5) | 0.0570 (3) | 0.0273 (16) | |
O42C | 0.1257 (6) | 0.6830 (4) | −0.0542 (3) | 0.0197 (12) | |
C1C | 0.7086 (9) | 0.7465 (6) | 0.0082 (4) | 0.018 (2) | |
C2C | 0.5001 (9) | 0.7479 (6) | 0.0013 (4) | 0.0174 (17) | |
C3C | 0.4269 (9) | 0.6155 (6) | 0.0054 (4) | 0.0209 (19) | |
C4C | 0.2190 (10) | 0.6152 (6) | 0.0028 (4) | 0.021 (2) | |
O1W | 0.8354 (7) | 0.4453 (5) | 0.0895 (3) | 0.0276 (17) | |
O2W | 0.1433 (8) | 0.8814 (5) | 0.1023 (4) | 0.042 (2) | |
H2A | 0.7218 | 0.9438 | 0.3816 | 0.032* | |
H3A | 0.8558 | 0.8078 | 0.4869 | 0.029* | |
H5A | 0.8435 | 0.5360 | 0.3125 | 0.030* | |
H6A | 0.7213 | 0.6729 | 0.2073 | 0.026* | |
H11A | 0.617 | 0.865 | 0.169 | 0.035* | |
H12A | 0.714 | 0.970 | 0.215 | 0.036* | |
H13A | 0.526 | 0.934 | 0.231 | 0.030* | |
H2B | 0.2108 | 0.6637 | 0.1944 | 0.029* | |
H3B | 0.2269 | 0.8183 | 0.2983 | 0.033* | |
H5B | 0.4475 | 0.5725 | 0.4750 | 0.037* | |
H6B | 0.4343 | 0.4201 | 0.3705 | 0.032* | |
H11B | 0.375 | 0.366 | 0.233 | 0.029* | |
H12B | 0.390 | 0.460 | 0.168 | 0.031* | |
H13B | 0.209 | 0.424 | 0.183 | 0.033* | |
H2D | 0.9973 | 0.0583 | 0.3298 | 0.018* | |
H3D | 1.0024 | 0.2678 | 0.3532 | 0.024* | |
H11D | 1.450 | 0.174 | 0.334 | 0.060* | |
H21D | 0.908 | 0.108 | 0.176 | 0.070* | |
H31D | 0.890 | 0.360 | 0.215 | 0.041* | |
H2C | 0.4472 | 0.7867 | −0.0534 | 0.021* | |
H3C | 0.4585 | 0.5688 | −0.0446 | 0.025* | |
H11C | 0.893 | 0.695 | −0.056 | 0.042* | |
H21C | 0.345 | 0.842 | 0.058 | 0.051* | |
H31C | 0.609 | 0.525 | 0.073 | 0.060* | |
H11W | 0.847 | 0.364 | 0.079 | 0.062* | |
H12W | 0.948 | 0.478 | 0.091 | 0.061* | |
H21W | 0.031 | 0.873 | 0.099 | 0.040* | |
H22W | 0.193 | 0.928 | 0.145 | 0.052* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl4A | 0.0468 (12) | 0.0268 (10) | 0.0363 (11) | 0.0033 (9) | 0.0056 (9) | 0.0137 (9) |
N1A | 0.021 (3) | 0.016 (3) | 0.024 (3) | −0.002 (2) | 0.010 (2) | −0.002 (2) |
C1A | 0.020 (3) | 0.017 (3) | 0.023 (4) | −0.003 (3) | 0.000 (3) | −0.001 (3) |
C2A | 0.034 (4) | 0.018 (4) | 0.028 (4) | −0.010 (3) | 0.007 (3) | 0.000 (3) |
C3A | 0.028 (4) | 0.023 (4) | 0.021 (4) | −0.007 (3) | 0.005 (3) | −0.003 (3) |
C4A | 0.023 (4) | 0.020 (4) | 0.027 (4) | 0.000 (3) | 0.002 (3) | 0.009 (3) |
C5A | 0.026 (4) | 0.013 (3) | 0.038 (4) | −0.004 (3) | 0.011 (3) | −0.002 (3) |
C6A | 0.019 (4) | 0.017 (4) | 0.030 (4) | −0.004 (3) | 0.007 (3) | −0.009 (3) |
Cl4B | 0.0475 (13) | 0.0352 (11) | 0.0515 (13) | −0.0046 (10) | 0.0158 (10) | −0.0212 (10) |
N1B | 0.019 (3) | 0.013 (3) | 0.026 (3) | −0.003 (2) | 0.005 (2) | 0.001 (2) |
C1B | 0.019 (3) | 0.019 (4) | 0.022 (4) | −0.009 (3) | 0.008 (3) | −0.001 (3) |
C2B | 0.033 (4) | 0.019 (4) | 0.024 (4) | −0.001 (3) | 0.014 (3) | 0.004 (3) |
C3B | 0.028 (4) | 0.016 (4) | 0.043 (5) | −0.001 (3) | 0.017 (3) | −0.003 (3) |
C4B | 0.021 (4) | 0.024 (4) | 0.038 (5) | −0.006 (3) | 0.012 (3) | −0.014 (3) |
C5B | 0.031 (4) | 0.037 (5) | 0.023 (4) | 0.004 (3) | 0.002 (3) | 0.001 (3) |
C6B | 0.031 (4) | 0.014 (3) | 0.036 (4) | 0.002 (3) | 0.007 (3) | 0.001 (3) |
O11D | 0.011 (2) | 0.024 (2) | 0.027 (3) | 0.002 (2) | 0.0040 (19) | −0.006 (2) |
O12D | 0.015 (2) | 0.020 (3) | 0.035 (3) | 0.004 (2) | 0.010 (2) | −0.003 (2) |
O21D | 0.020 (3) | 0.014 (2) | 0.028 (3) | 0.002 (2) | −0.003 (2) | −0.005 (2) |
O31D | 0.029 (3) | 0.011 (2) | 0.039 (3) | 0.002 (2) | 0.014 (2) | 0.000 (2) |
O41D | 0.026 (3) | 0.016 (2) | 0.032 (3) | 0.007 (2) | 0.011 (2) | 0.001 (2) |
O42D | 0.023 (3) | 0.026 (3) | 0.036 (3) | 0.004 (2) | 0.008 (2) | 0.006 (3) |
C1D | 0.025 (4) | 0.014 (3) | 0.013 (3) | −0.003 (3) | 0.003 (3) | 0.002 (3) |
C2D | 0.018 (3) | 0.013 (3) | 0.013 (3) | −0.004 (3) | 0.003 (3) | −0.004 (3) |
C3D | 0.021 (3) | 0.011 (3) | 0.027 (4) | −0.001 (3) | 0.003 (3) | −0.005 (3) |
C4D | 0.025 (4) | 0.012 (3) | 0.025 (4) | 0.002 (3) | 0.006 (3) | −0.003 (3) |
O11C | 0.021 (2) | 0.025 (3) | 0.022 (2) | −0.001 (2) | 0.007 (2) | −0.006 (2) |
O12C | 0.016 (2) | 0.044 (3) | 0.024 (3) | −0.001 (2) | 0.002 (2) | −0.009 (2) |
O21C | 0.020 (3) | 0.026 (3) | 0.030 (3) | 0.010 (2) | 0.006 (2) | −0.008 (2) |
O31C | 0.021 (3) | 0.024 (3) | 0.031 (3) | 0.006 (2) | 0.009 (2) | 0.007 (2) |
O41C | 0.020 (2) | 0.030 (3) | 0.032 (3) | −0.006 (2) | 0.004 (2) | 0.005 (2) |
O42C | 0.018 (2) | 0.021 (2) | 0.019 (2) | 0.004 (2) | −0.0018 (19) | −0.003 (2) |
C1C | 0.025 (4) | 0.014 (3) | 0.018 (4) | 0.004 (3) | 0.013 (3) | 0.003 (3) |
C2C | 0.020 (3) | 0.014 (3) | 0.020 (3) | 0.005 (3) | 0.009 (3) | −0.005 (3) |
C3C | 0.029 (4) | 0.018 (3) | 0.017 (3) | 0.006 (3) | 0.008 (3) | 0.001 (3) |
C4C | 0.032 (4) | 0.011 (3) | 0.021 (4) | 0.000 (3) | 0.011 (3) | −0.006 (3) |
O1W | 0.022 (3) | 0.027 (3) | 0.034 (3) | −0.004 (2) | 0.005 (2) | 0.001 (2) |
O2W | 0.036 (3) | 0.044 (4) | 0.045 (4) | −0.001 (3) | 0.007 (3) | −0.002 (3) |
Cl4A—C4A | 1.756 (7) | N1B—H11B | 0.90 |
Cl4B—C4B | 1.760 (8) | C1A—C2A | 1.369 (10) |
O11C—C1C | 1.305 (8) | C1A—C6A | 1.392 (10) |
O12C—C1C | 1.217 (8) | C2A—C3A | 1.385 (10) |
O21C—C2C | 1.407 (8) | C3A—C4A | 1.387 (9) |
O31C—C3C | 1.420 (8) | C4A—C5A | 1.372 (9) |
O41C—C4C | 1.261 (8) | C5A—C6A | 1.367 (9) |
O42C—C4C | 1.292 (8) | C2A—H2A | 0.9500 |
O11C—H11C | 0.90 | C3A—H3A | 0.9500 |
O21C—H21C | 0.85 | C5A—H5A | 0.9500 |
O31C—H31C | 0.84 | C6A—H6A | 0.9500 |
O11D—C1D | 1.267 (8) | C1B—C6B | 1.384 (10) |
O12D—C1D | 1.248 (8) | C1B—C2B | 1.376 (9) |
O21D—C2D | 1.433 (8) | C2B—C3B | 1.385 (11) |
O31D—C3D | 1.436 (8) | C3B—C4B | 1.371 (11) |
O41D—C4D | 1.257 (8) | C4B—C5B | 1.382 (11) |
O42D—C4D | 1.237 (8) | C5B—C6B | 1.378 (11) |
O11D—H11D | 0.90 | C2B—H2B | 0.9500 |
O21D—H21D | 0.74 | C3B—H3B | 0.9500 |
O31D—H31D | 0.94 | C5B—H5B | 0.9500 |
O1W—H11W | 0.90 | C6B—H6B | 0.9500 |
O1W—H12W | 0.90 | C1C—C2C | 1.520 (9) |
N1A—C1A | 1.466 (9) | C2C—C3C | 1.538 (9) |
N1A—H11A | 0.91 | C3C—C4C | 1.522 (10) |
N1A—H13A | 0.90 | C2C—H2C | 1.0000 |
N1A—H12A | 0.92 | C3C—H3C | 1.0000 |
O2W—H21W | 0.82 | C1D—C2D | 1.533 (9) |
O2W—H22W | 0.89 | C2D—C3D | 1.511 (9) |
N1B—C1B | 1.460 (8) | C3D—C4D | 1.532 (9) |
N1B—H13B | 0.91 | C2D—H2D | 1.0000 |
N1B—H12B | 0.88 | C3D—H3D | 1.0000 |
C1C—O11C—H11C | 117 | C4B—C5B—C6B | 117.8 (7) |
C2C—O21C—H21C | 108 | C1B—C6B—C5B | 120.1 (6) |
C3C—O31C—H31C | 110 | C3B—C2B—H2B | 120.00 |
C1D—O11D—H11D | 114 | C1B—C2B—H2B | 120.00 |
C2D—O21D—H21D | 106 | C4B—C3B—H3B | 121.00 |
C3D—O31D—H31D | 101 | C2B—C3B—H3B | 121.00 |
H11W—O1W—H12W | 106 | C6B—C5B—H5B | 121.00 |
H12A—N1A—H13A | 110 | C4B—C5B—H5B | 121.00 |
H11A—N1A—H13A | 109 | C1B—C6B—H6B | 120.00 |
H11A—N1A—H12A | 108 | C5B—C6B—H6B | 120.00 |
C1A—N1A—H11A | 109 | O11C—C1C—C2C | 113.8 (5) |
C1A—N1A—H12A | 111 | O12C—C1C—C2C | 122.1 (6) |
C1A—N1A—H13A | 109 | O11C—C1C—O12C | 124.1 (6) |
H21W—O2W—H22W | 115 | O21C—C2C—C3C | 112.1 (5) |
H12B—N1B—H13B | 107 | C1C—C2C—C3C | 110.0 (5) |
C1B—N1B—H11B | 108 | O21C—C2C—C1C | 106.1 (5) |
C1B—N1B—H12B | 111 | C2C—C3C—C4C | 110.9 (5) |
H11B—N1B—H12B | 111 | O31C—C3C—C4C | 108.7 (5) |
H11B—N1B—H13B | 111 | O31C—C3C—C2C | 111.4 (5) |
C1B—N1B—H13B | 109 | O41C—C4C—C3C | 118.3 (6) |
N1A—C1A—C2A | 119.6 (6) | O41C—C4C—O42C | 124.8 (7) |
N1A—C1A—C6A | 118.8 (6) | O42C—C4C—C3C | 116.8 (6) |
C2A—C1A—C6A | 121.5 (6) | C1C—C2C—H2C | 110.00 |
C1A—C2A—C3A | 119.3 (6) | C3C—C2C—H2C | 110.00 |
C2A—C3A—C4A | 118.5 (6) | O21C—C2C—H2C | 109.00 |
C3A—C4A—C5A | 122.1 (6) | C4C—C3C—H3C | 109.00 |
Cl4A—C4A—C5A | 119.2 (5) | O31C—C3C—H3C | 109.00 |
Cl4A—C4A—C3A | 118.7 (5) | C2C—C3C—H3C | 109.00 |
C4A—C5A—C6A | 119.2 (6) | O12D—C1D—C2D | 118.4 (6) |
C1A—C6A—C5A | 119.3 (6) | O11D—C1D—C2D | 116.6 (6) |
C3A—C2A—H2A | 120.00 | O11D—C1D—O12D | 124.9 (6) |
C1A—C2A—H2A | 120.00 | O21D—C2D—C1D | 110.8 (5) |
C4A—C3A—H3A | 121.00 | C1D—C2D—C3D | 113.9 (5) |
C2A—C3A—H3A | 121.00 | O21D—C2D—C3D | 111.2 (5) |
C6A—C5A—H5A | 120.00 | C2D—C3D—C4D | 112.1 (5) |
C4A—C5A—H5A | 120.00 | O31D—C3D—C4D | 107.9 (5) |
C5A—C6A—H6A | 120.00 | O31D—C3D—C2D | 109.2 (5) |
C1A—C6A—H6A | 120.00 | O41D—C4D—C3D | 115.9 (6) |
C2B—C1B—C6B | 121.0 (6) | O42D—C4D—C3D | 117.1 (6) |
N1B—C1B—C6B | 119.3 (6) | O41D—C4D—O42D | 127.0 (6) |
N1B—C1B—C2B | 119.7 (6) | C1D—C2D—H2D | 107.00 |
C1B—C2B—C3B | 119.5 (7) | C3D—C2D—H2D | 107.00 |
C2B—C3B—C4B | 118.4 (7) | O21D—C2D—H2D | 107.00 |
Cl4B—C4B—C3B | 117.8 (6) | C4D—C3D—H3D | 109.00 |
C3B—C4B—C5B | 123.0 (7) | O31D—C3D—H3D | 109.00 |
Cl4B—C4B—C5B | 119.2 (6) | C2D—C3D—H3D | 109.00 |
N1A—C1A—C2A—C3A | −177.7 (6) | O12C—C1C—C2C—O21C | 12.0 (9) |
C6A—C1A—C2A—C3A | 0.5 (11) | O12C—C1C—C2C—C3C | −109.5 (7) |
N1A—C1A—C6A—C5A | 179.0 (6) | O21C—C2C—C3C—O31C | −61.7 (7) |
C2A—C1A—C6A—C5A | 0.8 (10) | O21C—C2C—C3C—C4C | 59.6 (7) |
C1A—C2A—C3A—C4A | −0.9 (11) | C1C—C2C—C3C—O31C | 56.1 (7) |
C2A—C3A—C4A—Cl4A | −178.9 (6) | C1C—C2C—C3C—C4C | 177.3 (5) |
C2A—C3A—C4A—C5A | 0.0 (11) | O31C—C3C—C4C—O41C | −8.5 (8) |
Cl4A—C4A—C5A—C6A | −179.8 (5) | O31C—C3C—C4C—O42C | 169.8 (5) |
C3A—C4A—C5A—C6A | 1.3 (11) | C2C—C3C—C4C—O41C | −131.2 (6) |
C4A—C5A—C6A—C1A | −1.7 (10) | C2C—C3C—C4C—O42C | 47.1 (7) |
N1B—C1B—C2B—C3B | −178.2 (6) | O11D—C1D—C2D—O21D | 161.6 (5) |
C6B—C1B—C2B—C3B | 3.2 (11) | O11D—C1D—C2D—C3D | 35.4 (8) |
N1B—C1B—C6B—C5B | 178.6 (6) | O12D—C1D—C2D—O21D | −21.6 (8) |
C2B—C1B—C6B—C5B | −2.8 (11) | O12D—C1D—C2D—C3D | −147.8 (6) |
C1B—C2B—C3B—C4B | −3.1 (11) | O21D—C2D—C3D—O31D | −69.5 (6) |
C2B—C3B—C4B—Cl4B | −179.1 (6) | O21D—C2D—C3D—C4D | 49.9 (7) |
C2B—C3B—C4B—C5B | 2.6 (12) | C1D—C2D—C3D—O31D | 56.5 (7) |
Cl4B—C4B—C5B—C6B | 179.6 (6) | C1D—C2D—C3D—C4D | 175.9 (5) |
C3B—C4B—C5B—C6B | −2.1 (11) | O31D—C3D—C4D—O41D | 173.8 (5) |
C4B—C5B—C6B—C1B | 2.2 (11) | O31D—C3D—C4D—O42D | −6.5 (8) |
O11C—C1C—C2C—O21C | −168.5 (5) | C2D—C3D—C4D—O41D | 53.6 (7) |
O11C—C1C—C2C—C3C | 70.0 (7) | C2D—C3D—C4D—O42D | −126.8 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O12C | 0.91 | 2.40 | 3.131 (7) | 137 |
N1A—H11A···O21C | 0.91 | 1.91 | 2.731 (7) | 149 |
N1A—H12A···O21Di | 0.92 | 1.889 | 2.765 (8) | 160 |
N1A—H13A···O12Dii | 0.90 | 1.98 | 2.855 (7) | 165 |
N1B—H11B···O42D | 0.90 | 2.14 | 2.747 (7) | 124 |
N1B—H12B···O31C | 0.88 | 2.02 | 2.884 (7) | 166 |
N1B—H12B···O41C | 0.88 | 2.52 | 2.868 (7) | 104 |
N1B—H13B···O31Diii | 0.91 | 2.13 | 2.768 (7) | 126 |
N1B—H13B···O41C | 0.91 | 2.43 | 2.868 (7) | 109 |
O11C—H11C···O42Civ | 0.90 | 1.71 | 2.609 (6) | 179 |
O11D—H11D···O41Div | 0.90 | 1.62 | 2.521 (6) | 179 |
O21C—H21C···O2W | 0.85 | 1.78 | 2.527 (7) | 145 |
O31C—H31C···O1W | 0.84 | 1.86 | 2.672 (7) | 163 |
O21D—H21D···O31D | 0.74 | 2.54 | 2.936 (7) | 115 |
O21D—H21D···O42Cv | 0.74 | 2.09 | 2.768 (7) | 151 |
O31D—H31D···O1W | 0.94 | 2.19 | 2.798 (7) | 121 |
O31D—H31D···O42D | 0.94 | 1.87 | 2.554 (6) | 127 |
O1W—H11W···O42Cv | 0.90 | 2.02 | 2.923 (7) | 179 |
O1W—H12W···O41Civ | 0.90 | 1.84 | 2.702 (7) | 161 |
O2W—H21W···O12Ciii | 0.82 | 1.91 | 2.674 (8) | 153 |
O2W—H22W···O12Dii | 0.89 | 1.92 | 2.810 (8) | 179 |
C2A—H2A···O41Di | 0.95 | 2.50 | 3.343 (8) | 148 |
C2B—H2B···O41C | 0.95 | 2.49 | 3.261 (9) | 138 |
C3B—H3B···O12Dii | 0.95 | 2.59 | 3.431 (9) | 148 |
Symmetry codes: (i) x, y+1, z; (ii) x−1, y+1, z; (iii) x−1, y, z; (iv) x+1, y, z; (v) −x+1, y−1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C6H7ClN+·C4H5O6−·H2O |
Mr | 295.67 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 130 |
a, b, c (Å) | 7.3437 (15), 10.850 (2), 15.971 (3) |
β (°) | 97.880 (4) |
V (Å3) | 1260.5 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.33 |
Crystal size (mm) | 0.45 × 0.15 × 0.05 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.93, 0.98 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6196, 4197, 3319 |
Rint | 0.087 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.076, 0.197, 1.06 |
No. of reflections | 4197 |
No. of parameters | 342 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.79, −0.59 |
Absolute structure | Flack (1983), 1857 Friedel pairs |
Absolute structure parameter | 0.02 (6) |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 1999), SAINT, SHELXS97 Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), PLATON.
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O12C | 0.91 | 2.40 | 3.131 (7) | 137 |
N1A—H11A···O21C | 0.91 | 1.91 | 2.731 (7) | 149 |
N1A—H12A···O21Di | 0.92 | 1.889 | 2.765 (8) | 160 |
N1A—H13A···O12Dii | 0.90 | 1.98 | 2.855 (7) | 165 |
N1B—H11B···O42D | 0.90 | 2.14 | 2.747 (7) | 124 |
N1B—H12B···O31C | 0.88 | 2.02 | 2.884 (7) | 166 |
N1B—H12B···O41C | 0.88 | 2.52 | 2.868 (7) | 104 |
N1B—H13B···O31Diii | 0.91 | 2.13 | 2.768 (7) | 126 |
N1B—H13B···O41C | 0.91 | 2.43 | 2.868 (7) | 109 |
O11C—H11C···O42Civ | 0.90 | 1.71 | 2.609 (6) | 179 |
O11D—H11D···O41Div | 0.90 | 1.62 | 2.521 (6) | 179 |
O21C—H21C···O2W | 0.85 | 1.78 | 2.527 (7) | 145 |
O31C—H31C···O1W | 0.84 | 1.86 | 2.672 (7) | 163 |
O21D—H21D···O31D | 0.74 | 2.54 | 2.936 (7) | 115 |
O21D—H21D···O42Cv | 0.74 | 2.09 | 2.768 (7) | 151 |
O31D—H31D···O1W | 0.94 | 2.19 | 2.798 (7) | 121 |
O31D—H31D···O42D | 0.94 | 1.87 | 2.554 (6) | 127 |
O1W—H11W···O42Cv | 0.90 | 2.02 | 2.923 (7) | 179 |
O1W—H12W···O41Civ | 0.90 | 1.84 | 2.702 (7) | 161 |
O2W—H21W···O12Ciii | 0.82 | 1.91 | 2.674 (8) | 153 |
O2W—H22W···O12Dii | 0.89 | 1.92 | 2.810 (8) | 179 |
Symmetry codes: (i) x, y+1, z; (ii) x−1, y+1, z; (iii) x−1, y, z; (iv) x+1, y, z; (v) −x+1, y−1/2, −z. |
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The utility of L-tartaric acid as an agent for the introduction of chirality in organic compounds for the generation of crystalline materials with potentially useful nonlinear optical properties has been recognized (Aakeröy et al., 1992; Fuller et al., 1995; Renuka et al., 1995; Chen et al., 2005; Manivannan et al., 1995). The product from the 1:1 reaction with aniline (Chen et al., 2005), p-toluidine and m-anisidine (a monohydrate) (Renuka et al., 1995) have been determined so that our similar reaction of L-tartaric acid with 4-chloroaniline in aqueous propan-2-ol not unexpectedly gave good crystals of the proton-transfer compound 4-chloroanilinium hydrogen (2R,3R)-tartrate monohydrate C6H7ClN+ C4H5O6-. H2O, (I) and the structure is reported here.
In (I), the asymmetric unit comprises two 4-chloroanilinium cations (A and B), two hydrogen L-tartarate anions (C and D) and two water molecules of solvation (O1W and O2W) (Fig. 1). The two hydrogen tartrate anions and the water molecules form duplex hydrogen-bonded substructures through homomeric A and B chain carboxylate interactions with other tartrate carboxylic acid and hydroxyl groups as well as with the water molecules (Table 1). These include the C11(7) head-to-tail carboxylic acid–carboxylate associations (O11–H11···O42) which extend down the a cell direction in the unit cell (Figs. 2, 3). These carboxyl associations typify the hydrogen-bonded framework substructures in the majority of the anhydrous hydrogen tartrates (Aakeröy et al., 1992). The two independent 4-chloroanilinium cations in (I) form a π-associated dimer through partial overlapping of the offset benzene rings [ring centroid separation, 3.576 (4) Å; inter-ring dihedral angle, 0.5 (1)°]. However, the inter-dimer separation down the a cell direction [4.242 (4) Å] does not give stacks such as is found in the structure of quinolinium hydrogen-L-tartrate (Smith et al., 2006). In (I), these dimers are accommodated between the substructures and are peripherally hydrogen-bonded to them through aminium N+—H···O interactions with water and both carboxyl and hydroxyl O acceptors of the anions, including the R34(8) cyclic system seen in the asymmetric unit in Fig. 1. The result is a two-dimensional network structure.
The accepted (2R,3R) absolute configuration for the L-tartrate residues in (I) (Bijvoet et al., 1951) was assumed and both anions C and D adopt the common extended conformation. The intramolecular hydroxyl O–H···O(carboxyl) hydrogen bond which is also common in hydrogen tartrates is absent in the C anion but present in the D anion [O···O, [2.554 (6) Å]. In addition, in the D anion there is an unusual intramolecular hydroxyl–hydroxyl O–H···O contact [O···O, 2.936 (7) Å]. However, there are no significant conformational differences in the two anions, the O21–C2–C3–O31 torsion angles being -61.7 (7) ° (C) and -69.5 (6) ° (D), comparing with -66.8 (2) ° in sodium hydrogen L-tartrate monohydrate (Bott et al., 1993).