The title solvate, C
7H
6O
4·C
2H
3N, comprises two molecules, one acid and one solvent. The main molecules are arranged in layers by a two-dimensional hydrogen-bond network. In this way, channels are formed along the [100] axis, which are occupied by tail-to-tail solvent molecules in a manner similar to that observed previously in related structures. However, the hydrogen bond between an acetonitrile N atom and one of the hydroxyl groups is relatively normal, with an N
O separation of 2.8189 (10) Å. The placement of the solvent molecules makes the whole structure unstable under ambient conditions. Several minutes after removing the crystal from the mother solution it became milky, which probably indicates release of the solvent from the crystal structure.
Supporting information
CCDC reference: 655014
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.001 Å
- R factor = 0.045
- wR factor = 0.131
- Data-to-parameter ratio = 26.0
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.17 Ratio
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.42
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
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
An amount of 3,4-dihydroxybenzoic acid monohydrate (0.2 g) were diluted in 6 ml
of acetonitrile. The resulting mixture was warmed to 333 K and then slowly
cooled to 293 K. After several hours, colourless crystals were formed.
All H atoms for the 3,4-dihydroxybenzoic acid molecule were found in a
difference map and refined isotropically. H atoms of the methyl group in
acetonitrile were placed in idealized positions, with C—H bond lengths
constrained to 0.98 Å and Uiso(H) = 1.5Ueq(C14). This
group was considered as a rigid group but allowed to rotate about C13—C14 σ
bond.
Structure description
top
Related structures have been described, in which solvent molecules fill channels
generated by a supramolecular arrangement (Aitipamula & Nangia, 2005;
Gerkensmeier et al., 1999).
Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: HKL (Otwinowski & Minor, 1997); data reduction: DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
3,4-Dihydroxybenozic acid acetonitile solvate
top
Crystal data top
C7H6O4·C2H3N | F(000) = 408 |
Mr = 195.17 | Dx = 1.427 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2242 reflections |
a = 6.3792 (6) Å | θ = 1.0–35.0° |
b = 10.4941 (8) Å | µ = 0.11 mm−1 |
c = 13.7634 (12) Å | T = 120 K |
β = 99.4790 (14)° | Parallelepiped, colourless |
V = 908.80 (14) Å3 | 0.4 × 0.2 × 0.2 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD diffractometer | 3466 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.026 |
Graphite monochromator | θmax = 35.0°, θmin = 3.6° |
CCD scans | h = −10→10 |
9774 measured reflections | k = −12→16 |
3948 independent reflections | l = −22→18 |
Refinement top
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.131 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0745P)2 + 0.1499P] where P = (Fo2 + 2Fc2)/3 |
3948 reflections | (Δ/σ)max = 0.025 |
152 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
Crystal data top
C7H6O4·C2H3N | V = 908.80 (14) Å3 |
Mr = 195.17 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.3792 (6) Å | µ = 0.11 mm−1 |
b = 10.4941 (8) Å | T = 120 K |
c = 13.7634 (12) Å | 0.4 × 0.2 × 0.2 mm |
β = 99.4790 (14)° | |
Data collection top
Nonius KappaCCD diffractometer | 3466 reflections with I > 2σ(I) |
9774 measured reflections | Rint = 0.026 |
3948 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.131 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.49 e Å−3 |
3948 reflections | Δρmin = −0.37 e Å−3 |
152 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | −0.25161 (9) | 1.05508 (6) | 0.06328 (5) | 0.02453 (13) | |
H1 | −0.381 (4) | 1.080 (2) | 0.0265 (17) | 0.073 (6)* | |
C2 | −0.24757 (11) | 0.93132 (7) | 0.07528 (5) | 0.01851 (13) | |
O3 | −0.39826 (10) | 0.86069 (6) | 0.04151 (5) | 0.02659 (14) | |
C4 | −0.04961 (10) | 0.87984 (7) | 0.13234 (5) | 0.01694 (13) | |
C5 | 0.12150 (11) | 0.96085 (7) | 0.16568 (5) | 0.01803 (13) | |
H5 | 0.113 (2) | 1.0546 (14) | 0.1515 (10) | 0.030 (3)* | |
C6 | 0.30668 (11) | 0.91081 (7) | 0.21885 (5) | 0.01761 (13) | |
O7 | 0.48099 (9) | 0.98127 (6) | 0.25608 (5) | 0.02552 (14) | |
H7 | 0.464 (3) | 1.059 (2) | 0.2347 (13) | 0.052 (5)* | |
C8 | 0.32202 (10) | 0.77978 (7) | 0.23852 (5) | 0.01706 (13) | |
O9 | 0.50348 (9) | 0.72937 (5) | 0.29073 (5) | 0.02233 (13) | |
H9 | 0.596 (3) | 0.7824 (19) | 0.3070 (14) | 0.056 (5)* | |
C10 | 0.15149 (11) | 0.69939 (7) | 0.20561 (6) | 0.01884 (13) | |
H10 | 0.1655 (19) | 0.6080 (12) | 0.2212 (9) | 0.023 (3)* | |
C11 | −0.03439 (11) | 0.74969 (7) | 0.15260 (5) | 0.01867 (13) | |
H11 | −0.155 (2) | 0.6970 (14) | 0.1283 (10) | 0.030 (3)* | |
N12 | 0.88052 (13) | 0.84338 (8) | 0.38793 (6) | 0.02975 (16) | |
C13 | 1.05256 (13) | 0.86299 (8) | 0.42443 (6) | 0.02431 (15) | |
C14 | 1.26991 (13) | 0.89099 (10) | 0.47069 (7) | 0.02865 (18) | |
H14A | 1.3432 | 0.9365 | 0.4239 | 0.043* | |
H14B | 1.3448 | 0.8111 | 0.4902 | 0.043* | |
H14C | 1.2680 | 0.9442 | 0.5291 | 0.043* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0197 (2) | 0.0181 (3) | 0.0325 (3) | 0.00133 (19) | −0.0057 (2) | 0.0037 (2) |
C2 | 0.0154 (3) | 0.0175 (3) | 0.0212 (3) | 0.0009 (2) | −0.0013 (2) | −0.0003 (2) |
O3 | 0.0183 (3) | 0.0207 (3) | 0.0363 (3) | −0.00038 (19) | −0.0086 (2) | −0.0010 (2) |
C4 | 0.0134 (3) | 0.0165 (3) | 0.0196 (3) | 0.0007 (2) | −0.0014 (2) | −0.0001 (2) |
C5 | 0.0147 (3) | 0.0148 (3) | 0.0232 (3) | 0.0003 (2) | −0.0010 (2) | 0.0014 (2) |
C6 | 0.0135 (3) | 0.0138 (3) | 0.0241 (3) | −0.00094 (19) | −0.0012 (2) | 0.0004 (2) |
O7 | 0.0162 (2) | 0.0147 (2) | 0.0414 (3) | −0.00371 (18) | −0.0077 (2) | 0.0035 (2) |
C8 | 0.0130 (2) | 0.0140 (3) | 0.0227 (3) | 0.00081 (19) | −0.0012 (2) | 0.0000 (2) |
O9 | 0.0148 (2) | 0.0150 (2) | 0.0338 (3) | 0.00113 (17) | −0.00611 (19) | 0.00066 (19) |
C10 | 0.0158 (3) | 0.0135 (3) | 0.0257 (3) | −0.0006 (2) | −0.0012 (2) | −0.0003 (2) |
C11 | 0.0151 (3) | 0.0157 (3) | 0.0237 (3) | −0.0012 (2) | −0.0014 (2) | −0.0011 (2) |
N12 | 0.0237 (3) | 0.0309 (4) | 0.0329 (4) | 0.0007 (3) | −0.0004 (3) | −0.0005 (3) |
C13 | 0.0226 (3) | 0.0236 (3) | 0.0258 (3) | 0.0024 (3) | 0.0012 (3) | −0.0013 (3) |
C14 | 0.0204 (3) | 0.0325 (4) | 0.0312 (4) | 0.0012 (3) | −0.0013 (3) | −0.0052 (3) |
Geometric parameters (Å, º) top
O1—C2 | 1.3089 (9) | C8—O9 | 1.3646 (8) |
O1—H1 | 0.93 (2) | C8—C10 | 1.3922 (10) |
C2—O3 | 1.2419 (9) | O9—H9 | 0.82 (2) |
C2—C4 | 1.4753 (10) | C10—C11 | 1.3900 (10) |
C4—C11 | 1.3942 (10) | C10—H10 | 0.983 (13) |
C4—C5 | 1.3999 (10) | C11—H11 | 0.960 (14) |
C5—C6 | 1.3864 (10) | N12—C13 | 1.1478 (12) |
C5—H5 | 1.003 (14) | C13—C14 | 1.4572 (12) |
C6—O7 | 1.3631 (9) | C14—H14A | 0.9800 |
C6—C8 | 1.4017 (10) | C14—H14B | 0.9800 |
O7—H7 | 0.87 (2) | C14—H14C | 0.9800 |
| | | |
C2—O1—H1 | 110.1 (14) | C10—C8—C6 | 120.37 (6) |
O3—C2—O1 | 123.16 (7) | C8—O9—H9 | 113.2 (13) |
O3—C2—C4 | 121.51 (7) | C11—C10—C8 | 119.60 (6) |
O1—C2—C4 | 115.33 (6) | C11—C10—H10 | 121.6 (7) |
C11—C4—C5 | 120.30 (6) | C8—C10—H10 | 118.8 (7) |
C11—C4—C2 | 119.37 (6) | C10—C11—C4 | 120.16 (6) |
C5—C4—C2 | 120.33 (6) | C10—C11—H11 | 121.9 (9) |
C6—C5—C4 | 119.58 (6) | C4—C11—H11 | 118.0 (9) |
C6—C5—H5 | 119.2 (8) | N12—C13—C14 | 178.69 (10) |
C4—C5—H5 | 121.2 (8) | C13—C14—H14A | 109.5 |
O7—C6—C5 | 124.35 (6) | C13—C14—H14B | 109.5 |
O7—C6—C8 | 115.65 (6) | H14A—C14—H14B | 109.5 |
C5—C6—C8 | 119.99 (6) | C13—C14—H14C | 109.5 |
C6—O7—H7 | 109.3 (12) | H14A—C14—H14C | 109.5 |
O9—C8—C10 | 119.08 (6) | H14B—C14—H14C | 109.5 |
O9—C8—C6 | 120.54 (6) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.93 (2) | 1.68 (2) | 2.6056 (9) | 174 (2) |
O7—H7···O9ii | 0.87 (2) | 1.84 (2) | 2.6878 (8) | 164.8 (17) |
O9—H9···N12 | 0.82 (2) | 2.07 (2) | 2.8189 (10) | 153.0 (18) |
Symmetry codes: (i) −x−1, −y+2, −z; (ii) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data |
Chemical formula | C7H6O4·C2H3N |
Mr | 195.17 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 6.3792 (6), 10.4941 (8), 13.7634 (12) |
β (°) | 99.4790 (14) |
V (Å3) | 908.80 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.4 × 0.2 × 0.2 |
|
Data collection |
Diffractometer | Nonius KappaCCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9774, 3948, 3466 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.806 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.131, 1.05 |
No. of reflections | 3948 |
No. of parameters | 152 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.49, −0.37 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.93 (2) | 1.68 (2) | 2.6056 (9) | 174 (2) |
O7—H7···O9ii | 0.87 (2) | 1.84 (2) | 2.6878 (8) | 164.8 (17) |
O9—H9···N12 | 0.82 (2) | 2.07 (2) | 2.8189 (10) | 153.0 (18) |
Symmetry codes: (i) −x−1, −y+2, −z; (ii) −x+1, y+1/2, −z+1/2. |