We report the crystal structure and crystallization conditions of a first hydrated form of metacetamol (a hemihydrate), C8H9NO2·0.5H2O. It crystallizes from metacetamol-saturated 1:1 (v/v) water–ethanol solutions in a monoclinic structure (space group P21/n) and contains eight metacetamol and four water molecules per unit cell. The conformations of the molecules are the same as in polymorph II of metacetamol, which ensures the formation of hydrogen-bonded dimers and R22(16) ring motifs in its crystal structure similar to those in polymorph II. Unlike in form II, however, these dimers in the hemihydrate are connected through water molecules into infinite hydrogen-bonded molecular chains. Different chains are linked to each other by metacetamol–water and metacetamol–metacetamol hydrogen bonds, the latter type being also present in polymorph I. The overall noncovalent network of the hemihydrate is well developed and several types of hydrogen bonds are responsible for its formation.
Supporting information
CCDC reference: 1954774
Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
N-(3-Hydroxyphenyl)acetamide hemihydrate
top
Crystal data top
2C8H9NO2·H2O | F(000) = 680 |
Mr = 320.34 | Dx = 1.262 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 12.7626 (4) Å | Cell parameters from 4399 reflections |
b = 6.92827 (14) Å | θ = 1.7–24.2° |
c = 19.7011 (4) Å | µ = 0.09 mm−1 |
β = 104.619 (3)° | T = 295 K |
V = 1685.62 (8) Å3 | Block, colourless |
Z = 4 | 0.3 × 0.2 × 0.1 mm |
Data collection top
Rigaku Xcalibur Ruby Gemini ultra diffractometer | 3209 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 2204 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
Detector resolution: 10.3457 pixels mm-1 | θmax = 25.7°, θmin = 1.7° |
ω scans | h = −15→15 |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015) | k = −8→8 |
Tmin = 0.968, Tmax = 1.000 | l = −24→24 |
20645 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.121 | w = 1/[σ2(Fo2) + (0.0471P)2 + 0.2986P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
3209 reflections | Δρmax = 0.15 e Å−3 |
274 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
O11 | 0.13102 (15) | 0.0755 (2) | 0.52095 (8) | 0.0861 (6) | |
H11 | 0.095 (2) | 0.167 (4) | 0.4888 (14) | 0.110 (9)* | |
O21 | −0.03939 (16) | 0.6558 (2) | 0.57158 (7) | 0.0899 (6) | |
N11 | 0.00908 (14) | 0.5130 (2) | 0.67710 (8) | 0.0543 (5) | |
H11A | 0.0053 (15) | 0.523 (3) | 0.7214 (12) | 0.064 (6)* | |
C11 | 0.06446 (15) | 0.3468 (3) | 0.66289 (9) | 0.0470 (5) | |
C21 | 0.06817 (17) | 0.2941 (3) | 0.59582 (10) | 0.0543 (5) | |
H21 | 0.0323 (16) | 0.366 (3) | 0.5570 (11) | 0.068 (6)* | |
C31 | 0.12470 (17) | 0.1302 (3) | 0.58617 (10) | 0.0577 (5) | |
C41 | 0.17654 (19) | 0.0186 (3) | 0.64273 (12) | 0.0657 (6) | |
H41 | 0.2146 (18) | −0.092 (3) | 0.6337 (11) | 0.081 (7)* | |
C51 | 0.17180 (18) | 0.0722 (4) | 0.70877 (12) | 0.0657 (6) | |
H51 | 0.2070 (17) | −0.003 (3) | 0.7490 (12) | 0.081 (7)* | |
C61 | 0.11587 (16) | 0.2345 (3) | 0.71957 (10) | 0.0563 (5) | |
H61 | 0.1118 (14) | 0.274 (3) | 0.7663 (11) | 0.058 (5)* | |
C71 | −0.03749 (17) | 0.6556 (3) | 0.63367 (10) | 0.0556 (5) | |
C81 | −0.08655 (19) | 0.8159 (3) | 0.66606 (11) | 0.0664 (6) | |
H81A | −0.0500 | 0.9346 | 0.6617 | 0.100* | |
H81B | −0.0793 | 0.7882 | 0.7148 | 0.100* | |
H81C | −0.1619 | 0.8278 | 0.6425 | 0.100* | |
O12 | 0.52609 (13) | 0.9883 (2) | 0.67514 (7) | 0.0685 (5) | |
O22 | 0.56527 (14) | 0.8283 (2) | 0.44372 (7) | 0.0729 (5) | |
N12 | 0.63940 (14) | 0.5709 (2) | 0.50799 (8) | 0.0521 (4) | |
C12 | 0.63225 (14) | 0.6233 (2) | 0.57617 (9) | 0.0454 (4) | |
C22 | 0.58092 (16) | 0.7885 (3) | 0.59045 (9) | 0.0471 (5) | |
C32 | 0.57719 (15) | 0.8275 (3) | 0.65887 (9) | 0.0474 (5) | |
C42 | 0.62505 (16) | 0.7049 (3) | 0.71278 (10) | 0.0525 (5) | |
C52 | 0.67631 (18) | 0.5425 (3) | 0.69765 (11) | 0.0604 (6) | |
C62 | 0.67959 (17) | 0.4988 (3) | 0.63012 (11) | 0.0572 (5) | |
C72 | 0.60799 (16) | 0.6689 (3) | 0.44774 (10) | 0.0499 (5) | |
C82 | 0.62801 (18) | 0.5726 (3) | 0.38414 (10) | 0.0636 (6) | |
H82A | 0.5600 | 0.5447 | 0.3515 | 0.095* | |
H82B | 0.6671 | 0.4545 | 0.3977 | 0.095* | |
H82C | 0.6698 | 0.6567 | 0.3624 | 0.095* | |
O1WA | 0.7127 (3) | 0.1769 (4) | 0.50402 (18) | 0.0986 (12) | 0.736 (6) |
H1WA | 0.6658 | 0.0860 | 0.4966 | 0.148* | 0.736 (6) |
H1WB | 0.7715 | 0.1242 | 0.4993 | 0.148* | 0.736 (6) |
O1WB | 0.7969 (8) | 0.2862 (14) | 0.5064 (6) | 0.128 (5) | 0.264 (6) |
H1WC | 0.8641 | 0.3133 | 0.5107 | 0.192* | 0.264 (6) |
H1WD | 0.7865 | 0.1836 | 0.4819 | 0.192* | 0.264 (6) |
H42 | 0.6227 (15) | 0.738 (3) | 0.7588 (11) | 0.063 (6)* | |
H22 | 0.5436 (14) | 0.874 (3) | 0.5526 (10) | 0.054 (5)* | |
H62 | 0.7149 (17) | 0.385 (3) | 0.6185 (11) | 0.075 (7)* | |
H52 | 0.7091 (16) | 0.457 (3) | 0.7332 (11) | 0.072 (6)* | |
H12A | 0.6737 (18) | 0.458 (3) | 0.5056 (12) | 0.087 (8)* | |
H12 | 0.494 (2) | 1.054 (4) | 0.6328 (14) | 0.098 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O11 | 0.1278 (15) | 0.0825 (11) | 0.0536 (9) | 0.0563 (11) | 0.0333 (9) | 0.0077 (8) |
O21 | 0.1552 (16) | 0.0758 (11) | 0.0434 (9) | 0.0521 (10) | 0.0339 (9) | 0.0078 (7) |
N11 | 0.0766 (12) | 0.0542 (10) | 0.0353 (9) | 0.0008 (8) | 0.0199 (8) | −0.0050 (8) |
C11 | 0.0527 (11) | 0.0477 (11) | 0.0402 (10) | −0.0037 (9) | 0.0111 (8) | −0.0011 (8) |
C21 | 0.0676 (14) | 0.0547 (12) | 0.0401 (11) | 0.0110 (10) | 0.0125 (10) | 0.0039 (9) |
C31 | 0.0691 (13) | 0.0607 (13) | 0.0465 (11) | 0.0150 (11) | 0.0204 (10) | 0.0027 (10) |
C41 | 0.0713 (15) | 0.0655 (14) | 0.0627 (14) | 0.0212 (12) | 0.0212 (11) | 0.0129 (12) |
C51 | 0.0651 (14) | 0.0771 (16) | 0.0523 (13) | 0.0143 (12) | 0.0101 (11) | 0.0174 (12) |
C61 | 0.0599 (13) | 0.0684 (14) | 0.0396 (11) | −0.0052 (11) | 0.0105 (10) | 0.0030 (10) |
C71 | 0.0741 (14) | 0.0519 (12) | 0.0435 (11) | 0.0015 (10) | 0.0197 (10) | −0.0065 (9) |
C81 | 0.0843 (15) | 0.0552 (13) | 0.0657 (14) | 0.0019 (11) | 0.0300 (12) | −0.0159 (10) |
O12 | 0.1140 (13) | 0.0569 (9) | 0.0377 (8) | 0.0214 (8) | 0.0248 (8) | 0.0040 (7) |
O22 | 0.1237 (13) | 0.0544 (9) | 0.0421 (8) | 0.0323 (9) | 0.0238 (8) | 0.0049 (6) |
N12 | 0.0652 (11) | 0.0423 (9) | 0.0492 (10) | 0.0113 (8) | 0.0151 (8) | −0.0006 (8) |
C12 | 0.0525 (11) | 0.0402 (10) | 0.0430 (10) | 0.0008 (8) | 0.0113 (8) | 0.0022 (8) |
C22 | 0.0635 (13) | 0.0408 (10) | 0.0355 (10) | 0.0051 (9) | 0.0097 (9) | 0.0050 (8) |
C32 | 0.0593 (12) | 0.0427 (10) | 0.0399 (10) | −0.0008 (9) | 0.0121 (9) | 0.0027 (8) |
C42 | 0.0567 (12) | 0.0621 (13) | 0.0371 (11) | −0.0042 (10) | 0.0088 (9) | 0.0101 (9) |
C52 | 0.0611 (13) | 0.0653 (14) | 0.0539 (13) | 0.0110 (11) | 0.0130 (10) | 0.0257 (11) |
C62 | 0.0609 (13) | 0.0512 (12) | 0.0606 (13) | 0.0134 (10) | 0.0174 (10) | 0.0142 (10) |
C72 | 0.0611 (12) | 0.0443 (11) | 0.0457 (11) | 0.0027 (9) | 0.0160 (9) | −0.0040 (9) |
C82 | 0.0814 (15) | 0.0609 (13) | 0.0533 (12) | −0.0013 (11) | 0.0257 (11) | −0.0134 (10) |
O1WA | 0.093 (2) | 0.0519 (15) | 0.160 (3) | 0.0120 (14) | 0.050 (2) | −0.0140 (15) |
O1WB | 0.095 (7) | 0.078 (7) | 0.205 (10) | 0.029 (6) | 0.024 (6) | −0.034 (6) |
Geometric parameters (Å, º) top
O11—H11 | 0.93 (3) | O22—C72 | 1.225 (2) |
O11—C31 | 1.361 (2) | N12—C12 | 1.416 (2) |
O21—C71 | 1.217 (2) | N12—C72 | 1.338 (2) |
N11—H11A | 0.89 (2) | N12—H12A | 0.91 (2) |
N11—C11 | 1.416 (2) | C12—C22 | 1.383 (2) |
N11—C71 | 1.343 (2) | C12—C62 | 1.384 (3) |
C11—C21 | 1.383 (3) | C22—C32 | 1.387 (2) |
C11—C61 | 1.383 (3) | C22—H22 | 0.978 (18) |
C21—H21 | 0.93 (2) | C32—C42 | 1.377 (2) |
C21—C31 | 1.384 (3) | C42—C52 | 1.371 (3) |
C31—C41 | 1.380 (3) | C42—H42 | 0.94 (2) |
C41—H41 | 0.95 (2) | C52—C62 | 1.375 (3) |
C41—C51 | 1.369 (3) | C52—H52 | 0.93 (2) |
C51—H51 | 0.96 (2) | C62—H62 | 0.96 (2) |
C51—C61 | 1.377 (3) | C72—C82 | 1.498 (2) |
C61—H61 | 0.98 (2) | C82—H82A | 0.9600 |
C71—C81 | 1.495 (3) | C82—H82B | 0.9600 |
C81—H81A | 0.9600 | C82—H82C | 0.9600 |
C81—H81B | 0.9600 | O1WA—H1WA | 0.8558 |
C81—H81C | 0.9600 | O1WA—H1WB | 0.8604 |
O12—C32 | 1.369 (2) | O1WB—H1WC | 0.8613 |
O12—H12 | 0.95 (3) | O1WB—H1WD | 0.8502 |
| | | |
C31—O11—H11 | 108.5 (16) | C12—N12—H12A | 114.8 (15) |
C11—N11—H11A | 114.2 (13) | C72—N12—C12 | 129.36 (16) |
C71—N11—H11A | 116.4 (13) | C72—N12—H12A | 115.8 (15) |
C71—N11—C11 | 129.42 (16) | C22—C12—N12 | 123.55 (16) |
C21—C11—N11 | 122.86 (17) | C22—C12—C62 | 119.83 (17) |
C61—C11—N11 | 117.16 (17) | C62—C12—N12 | 116.63 (17) |
C61—C11—C21 | 119.97 (19) | C12—C22—C32 | 119.55 (17) |
C11—C21—H21 | 121.1 (12) | C12—C22—H22 | 120.7 (10) |
C11—C21—C31 | 119.49 (19) | C32—C22—H22 | 119.6 (10) |
C31—C21—H21 | 119.4 (12) | O12—C32—C22 | 121.40 (16) |
O11—C31—C21 | 121.00 (18) | O12—C32—C42 | 117.80 (17) |
O11—C31—C41 | 118.40 (18) | C42—C32—C22 | 120.80 (18) |
C41—C31—C21 | 120.60 (19) | C32—C42—H42 | 118.5 (12) |
C31—C41—H41 | 117.8 (14) | C52—C42—C32 | 118.79 (19) |
C51—C41—C31 | 119.2 (2) | C52—C42—H42 | 122.7 (12) |
C51—C41—H41 | 123.0 (13) | C42—C52—C62 | 121.59 (19) |
C41—C51—H51 | 120.8 (13) | C42—C52—H52 | 120.4 (12) |
C41—C51—C61 | 121.1 (2) | C62—C52—H52 | 118.0 (12) |
C61—C51—H51 | 118.0 (13) | C12—C62—H62 | 117.9 (13) |
C11—C61—H61 | 118.5 (11) | C52—C62—C12 | 119.43 (19) |
C51—C61—C11 | 119.55 (19) | C52—C62—H62 | 122.7 (12) |
C51—C61—H61 | 122.0 (11) | O22—C72—N12 | 122.94 (17) |
O21—C71—N11 | 122.31 (18) | O22—C72—C82 | 120.98 (18) |
O21—C71—C81 | 121.57 (19) | N12—C72—C82 | 116.08 (17) |
N11—C71—C81 | 116.11 (17) | C72—C82—H82A | 109.5 |
C71—C81—H81A | 109.5 | C72—C82—H82B | 109.5 |
C71—C81—H81B | 109.5 | C72—C82—H82C | 109.5 |
C71—C81—H81C | 109.5 | H82A—C82—H82B | 109.5 |
H81A—C81—H81B | 109.5 | H82A—C82—H82C | 109.5 |
H81A—C81—H81C | 109.5 | H82B—C82—H82C | 109.5 |
H81B—C81—H81C | 109.5 | H1WA—O1WA—H1WB | 105.1 |
C32—O12—H12 | 107.9 (15) | H1WC—O1WB—H1WD | 104.3 |
| | | |
O11—C31—C41—C51 | 179.5 (2) | O12—C32—C42—C52 | 179.75 (18) |
N11—C11—C21—C31 | 179.51 (18) | N12—C12—C22—C32 | 179.50 (17) |
N11—C11—C61—C51 | −179.39 (19) | N12—C12—C62—C52 | 179.39 (18) |
C11—N11—C71—O21 | 1.7 (3) | C12—N12—C72—O22 | −0.4 (3) |
C11—N11—C71—C81 | −177.90 (18) | C12—N12—C72—C82 | 179.53 (18) |
C11—C21—C31—O11 | −179.24 (19) | C12—C22—C32—O12 | −179.24 (17) |
C11—C21—C31—C41 | 0.5 (3) | C12—C22—C32—C42 | 0.7 (3) |
C21—C11—C61—C51 | 0.9 (3) | C22—C12—C62—C52 | −0.9 (3) |
C21—C31—C41—C51 | −0.2 (3) | C22—C32—C42—C52 | −0.2 (3) |
C31—C41—C51—C61 | 0.3 (4) | C32—C42—C52—C62 | −0.9 (3) |
C41—C51—C61—C11 | −0.7 (3) | C42—C52—C62—C12 | 1.5 (3) |
C61—C11—C21—C31 | −0.8 (3) | C62—C12—C22—C32 | −0.1 (3) |
C71—N11—C11—C21 | −7.8 (3) | C72—N12—C12—C22 | 5.4 (3) |
C71—N11—C11—C61 | 172.50 (19) | C72—N12—C12—C62 | −174.95 (19) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11···O21i | 0.93 (3) | 1.73 (3) | 2.660 (2) | 175 (3) |
N11—H11A···O12ii | 0.89 (2) | 2.19 (2) | 3.060 (2) | 167.1 (18) |
O1WA—H1WA···O22iii | 0.86 | 2.29 | 3.108 (4) | 160 |
O1WA—H1WB···O11iv | 0.86 | 1.97 | 2.788 (3) | 159 |
O1WB—H1WD···O11iv | 0.85 | 2.09 | 2.769 (8) | 137 |
N12—H12A···O1WA | 0.91 (2) | 2.01 (2) | 2.893 (3) | 165 (2) |
N12—H12A···O1WB | 0.91 (2) | 1.97 (2) | 2.822 (7) | 157 (2) |
O12—H12···O22v | 0.95 (3) | 1.71 (3) | 2.6605 (19) | 179 (2) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, y−1/2, −z+3/2; (iii) x, y−1, z; (iv) −x+1, −y, −z+1; (v) −x+1, −y+2, −z+1. |