The crystal structures of the first stable α-diol from the α-halogenopyruvamide series, 3-chloro-2,2-dihydroxy-3-phenylpropanamide, C9H10ClNO3, and three products [3-(4-chlorophenyl)-2-cyano-2,3-epoxypropanamide, C10H7ClN2O2, 3-bromo-2-cyano-2-hydroxy-3-p-tolylpropanamide, C11H11BrN2O2, 3-bromo-2-oxo-3-p-tolylpropanamide, C10H10BrNO2] obtained during the systematic synthesis of α-halogenopyruvamides are reported. The crystal structures are dominated by hydrogen bonds involving an amide group. The stability of the geminal diol could be ascribed to hydrogen bonds which involve both hydroxyl groups.
Supporting information
CCDC references: 150865; 150866; 150867; 150868
Data collection: DIF4 (Stoe, 1992) for (I); CAD-4 Software (Enraf-Nonius, 1994) for (II); COLLECT Software (Nonius BV, 1998) for (III); COLLECT Software (Nonius, 1998) for (IV). Cell refinement: DIF4 for (I); PARAM (Stewart et al., 1976) for (II); DENZO and SCALEPACK (Otwinowski & Minor, 1997) for (III), (IV). Data reduction: REDU4 (Stoe, 1992) for (I); DATRD2 in NRCVAX (Gabe et al., 1989) for (II); DENZO and SCALEPACK for (III), (IV). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.
(I) '3-(4-chlorophenyl)-2-cyano-2,3-epoxypropanamide'
top
Crystal data top
C10H7ClN2O2 | F(000) = 456 |
Mr = 222.63 | Dx = 1.420 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 4.9992 (8) Å | Cell parameters from 25 reflections |
b = 12.694 (3) Å | θ = 10–15° |
c = 16.442 (3) Å | µ = 0.35 mm−1 |
β = 93.54 (1)° | T = 293 K |
V = 1041.4 (4) Å3 | Prismatic, colourless |
Z = 4 | 0.30 × 0.30 × 0.25 mm |
Data collection top
STADI4(STOE) diffractometer | Rint = 0.025 |
Radiation source: fine-focus sealed tube | θmax = 28.0°, θmin = 2.0° |
Graphite monochromator | h = −6→6 |
ω/2θ scans | k = −16→15 |
3492 measured reflections | l = −22→21 |
2533 independent reflections | 3 standard reflections every 300 reflections |
1852 reflections with I > 2σ(I) | intensity decay: 0.8% |
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)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.152 | Calculated w = 1/[σ2(Fo2) + (0.0811P)2 + 0.2445P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
2533 reflections | Δρmax = 0.29 e Å−3 |
147 parameters | Δρmin = −0.34 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.061 (6) |
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 >
2σ(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 | 0.7265 (3) | 0.03484 (16) | −0.41529 (10) | 0.0612 (5) | |
H1 | 0.7222 | 0.0306 | −0.4676 | 0.068 (7)* | |
H2 | 0.8713 | 0.0541 | −0.3884 | 0.083 (8)* | |
C1 | 0.5113 (3) | 0.01177 (14) | −0.37641 (11) | 0.0460 (4) | |
O1 | 0.2951 (2) | −0.01638 (12) | −0.40846 (8) | 0.0591 (4) | |
C2 | 0.5379 (3) | 0.02381 (14) | −0.28500 (10) | 0.0458 (4) | |
C10 | 0.3935 (4) | −0.05536 (15) | −0.24065 (11) | 0.0534 (4) | |
N2 | 0.2806 (5) | −0.11797 (15) | −0.20777 (13) | 0.0795 (6) | |
C3 | 0.5770 (4) | 0.13093 (15) | −0.24897 (12) | 0.0521 (4) | |
H3 | 0.5857 | 0.1889 | −0.2882 | 0.065 (6)* | |
O2 | 0.7912 (2) | 0.05587 (13) | −0.24926 (8) | 0.0618 (4) | |
C4 | 0.4738 (4) | 0.15929 (14) | −0.16894 (11) | 0.0508 (4) | |
C5 | 0.2670 (4) | 0.23174 (16) | −0.16634 (13) | 0.0577 (5) | |
H5 | 0.1976 | 0.2631 | −0.2142 | 0.054 (5)* | |
C6 | 0.1631 (4) | 0.25776 (17) | −0.09257 (15) | 0.0644 (5) | |
H6 | 0.0219 | 0.3052 | −0.0907 | 0.092 (8)* | |
C7 | 0.2730 (4) | 0.21197 (17) | −0.02199 (13) | 0.0607 (5) | |
C8 | 0.4810 (5) | 0.14142 (18) | −0.02315 (12) | 0.0642 (5) | |
H8 | 0.5532 | 0.1118 | 0.0251 | 0.081 (7)* | |
C9 | 0.5820 (4) | 0.11482 (17) | −0.09691 (12) | 0.0601 (5) | |
H9 | 0.7226 | 0.0670 | −0.0983 | 0.075 (7)* | |
Cl | 0.13798 (15) | 0.24047 (7) | 0.07086 (4) | 0.0936 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0338 (7) | 0.0949 (13) | 0.0556 (9) | −0.0122 (7) | 0.0080 (6) | −0.0042 (8) |
C1 | 0.0327 (7) | 0.0515 (9) | 0.0544 (9) | 0.0011 (6) | 0.0065 (6) | −0.0012 (7) |
O1 | 0.0327 (6) | 0.0863 (10) | 0.0589 (7) | −0.0083 (6) | 0.0072 (5) | −0.0086 (7) |
C2 | 0.0344 (7) | 0.0494 (9) | 0.0537 (9) | 0.0004 (6) | 0.0045 (6) | 0.0023 (7) |
C10 | 0.0597 (10) | 0.0432 (9) | 0.0586 (10) | 0.0059 (8) | 0.0140 (8) | 0.0004 (8) |
N2 | 0.1039 (15) | 0.0507 (10) | 0.0877 (13) | −0.0041 (10) | 0.0376 (11) | 0.0039 (9) |
C3 | 0.0487 (9) | 0.0516 (10) | 0.0560 (10) | −0.0070 (7) | 0.0028 (7) | 0.0024 (8) |
O2 | 0.0366 (6) | 0.0857 (10) | 0.0626 (7) | 0.0000 (6) | −0.0006 (5) | −0.0085 (7) |
C4 | 0.0502 (9) | 0.0456 (9) | 0.0567 (10) | −0.0089 (7) | 0.0044 (7) | −0.0022 (7) |
C5 | 0.0561 (10) | 0.0504 (10) | 0.0665 (11) | −0.0034 (8) | 0.0026 (8) | 0.0027 (9) |
C6 | 0.0577 (11) | 0.0549 (11) | 0.0815 (14) | 0.0004 (9) | 0.0117 (9) | −0.0070 (10) |
C7 | 0.0627 (11) | 0.0571 (11) | 0.0635 (11) | −0.0100 (9) | 0.0119 (9) | −0.0127 (9) |
C8 | 0.0729 (13) | 0.0637 (12) | 0.0555 (11) | −0.0009 (10) | 0.0009 (9) | −0.0017 (9) |
C9 | 0.0600 (10) | 0.0581 (11) | 0.0618 (11) | 0.0051 (9) | 0.0017 (8) | −0.0028 (9) |
Cl | 0.0949 (5) | 0.1114 (6) | 0.0768 (4) | 0.0013 (4) | 0.0235 (3) | −0.0278 (4) |
Geometric parameters (Å, º) top
N1—C1 | 1.318 (2) | C4—C5 | 1.386 (3) |
N1—H1 | 0.8600 | C4—C9 | 1.391 (3) |
N1—H2 | 0.8600 | C5—C6 | 1.389 (3) |
C1—O1 | 1.226 (2) | C5—H5 | 0.9300 |
C1—C2 | 1.508 (2) | C6—C7 | 1.381 (3) |
C2—O2 | 1.422 (2) | C6—H6 | 0.9300 |
C2—C10 | 1.459 (2) | C7—C8 | 1.373 (3) |
C2—C3 | 1.491 (3) | C7—Cl | 1.745 (2) |
C10—N2 | 1.132 (3) | C8—C9 | 1.384 (3) |
C3—O2 | 1.434 (2) | C8—H8 | 0.9300 |
C3—C4 | 1.487 (3) | C9—H9 | 0.9300 |
C3—H3 | 0.9800 | | |
| | | |
C1—N1—H1 | 120.0 | C2—O2—C3 | 62.96 (11) |
C1—N1—H2 | 120.0 | C5—C4—C9 | 119.63 (18) |
H1—N1—H2 | 120.0 | C5—C4—C3 | 119.20 (17) |
O1—C1—N1 | 125.49 (17) | C9—C4—C3 | 121.16 (18) |
O1—C1—C2 | 118.63 (14) | C4—C5—C6 | 120.31 (19) |
N1—C1—C2 | 115.87 (15) | C4—C5—H5 | 119.8 |
O2—C2—C10 | 116.49 (15) | C6—C5—H5 | 119.8 |
O2—C2—C3 | 58.89 (11) | C7—C6—C5 | 118.9 (2) |
C10—C2—C3 | 119.11 (15) | C7—C6—H6 | 120.6 |
O2—C2—C1 | 117.53 (13) | C5—C6—H6 | 120.6 |
C10—C2—C1 | 114.35 (15) | C8—C7—C6 | 121.66 (19) |
C3—C2—C1 | 119.31 (15) | C8—C7—Cl | 118.78 (17) |
N2—C10—C2 | 178.5 (2) | C6—C7—Cl | 119.51 (17) |
O2—C3—C4 | 117.63 (16) | C7—C8—C9 | 119.3 (2) |
O2—C3—C2 | 58.15 (11) | C7—C8—H8 | 120.4 |
C4—C3—C2 | 121.88 (16) | C9—C8—H8 | 120.4 |
O2—C3—H3 | 115.7 | C8—C9—C4 | 120.2 (2) |
C4—C3—H3 | 115.7 | C8—C9—H9 | 119.9 |
C2—C3—H3 | 115.7 | C4—C9—H9 | 119.9 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2···O2 | 0.86 | 2.35 | 2.742 (2) | 108 |
N1—H2···O1i | 0.86 | 2.34 | 2.911 (2) | 124 |
N1—H1···O1ii | 0.86 | 2.04 | 2.903 (2) | 178 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y, −z−1. |
(II) '3-bromo-2-cyano-3-(4-methylphenyl)-2-hydroxypropanamide'
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Crystal data top
C11H11BrN2O2 | F(000) = 568 |
Mr = 283.13 | Dx = 1.595 Mg m−3 |
Monoclinic, P21/a | Mo Kα radiation, λ = 0.71073 Å |
a = 5.934 (3) Å | Cell parameters from 25 reflections |
b = 33.653 (6) Å | θ = 8–16° |
c = 6.177 (1) Å | µ = 3.47 mm−1 |
β = 107.12 (3)° | T = 293 K |
V = 1178.9 (7) Å3 | Prismatic, colourless |
Z = 4 | 0.12 × 0.10 × 0.05 mm |
Data collection top
NONIUS CAD4 diffractometer | 1851 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.077 |
Graphite monochromator | θmax = 27.9°, θmin = 1.2° |
ω/2θ scans | h = −7→7 |
Absorption correction: part of the refinement model (ΔF) Walker & Stuart, D (1983) Acta. Cryst. A39, 158-166 | k = −44→44 |
Tmin = 0.631, Tmax = 0.855 | l = −8→8 |
11169 measured reflections | 3 standard reflections every 500 reflections |
2836 independent reflections | intensity decay: 1.9% |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 0.97 | Calculated w = 1/[σ2(Fo2) + (0.0705P)2 + ] where P = (Fo2 + 2Fc2)/3 |
2836 reflections | (Δ/σ)max = 0.001 |
146 parameters | Δρmax = 0.54 e Å−3 |
0 restraints | Δρmin = −0.51 e Å−3 |
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 >
2σ(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 | 0.3428 (5) | 0.20386 (11) | −0.0062 (5) | 0.0629 (9) | |
H2A | 0.2006 | 0.2102 | −0.0799 | 0.076* | |
H2B | 0.4532 | 0.2058 | −0.0699 | 0.076* | |
C1 | 0.3912 (5) | 0.19116 (10) | 0.2027 (6) | 0.0423 (7) | |
O1 | 0.2511 (4) | 0.18707 (9) | 0.3114 (5) | 0.0628 (7) | |
C2 | 0.6521 (5) | 0.17985 (9) | 0.3159 (5) | 0.0335 (6) | |
O2 | 0.7794 (4) | 0.18555 (8) | 0.1622 (4) | 0.0458 (6) | |
H1 | 0.9209 | 0.1853 | 0.2295 | 0.069* | |
C10 | 0.7393 (5) | 0.20611 (11) | 0.5167 (5) | 0.0430 (7) | |
N2 | 0.8137 (6) | 0.22568 (11) | 0.6711 (5) | 0.0665 (9) | |
C3 | 0.6489 (5) | 0.13651 (10) | 0.3992 (5) | 0.0344 (6) | |
H4 | 0.5452 | 0.1359 | 0.4968 | 0.041* | |
Br | 0.96866 (5) | 0.122066 (11) | 0.58896 (5) | 0.04902 (14) | |
C4 | 0.5573 (5) | 0.10630 (10) | 0.2155 (5) | 0.0365 (6) | |
C5 | 0.6653 (6) | 0.09796 (11) | 0.0501 (5) | 0.0476 (8) | |
H11 | 0.8029 | 0.1112 | 0.0504 | 0.057* | |
C6 | 0.5689 (6) | 0.06988 (11) | −0.1165 (5) | 0.0501 (8) | |
H15 | 0.6417 | 0.0650 | −0.2281 | 0.060* | |
C7 | 0.3659 (6) | 0.04903 (11) | −0.1195 (6) | 0.0490 (8) | |
C8 | 0.2618 (6) | 0.05736 (11) | 0.0473 (6) | 0.0528 (9) | |
H12 | 0.1258 | 0.0438 | 0.0488 | 0.063* | |
C9 | 0.3546 (6) | 0.08542 (11) | 0.2123 (6) | 0.0466 (8) | |
H10 | 0.2804 | 0.0904 | 0.3228 | 0.056* | |
C11 | 0.2620 (8) | 0.01864 (13) | −0.2993 (6) | 0.0695 (12) | |
H17A | 0.3568 | 0.0169 | −0.4009 | 0.104* | |
H17B | 0.1045 | 0.0264 | −0.3823 | 0.104* | |
H17C | 0.2582 | −0.0068 | −0.2296 | 0.104* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0498 (15) | 0.066 (2) | 0.0641 (18) | 0.0076 (15) | 0.0025 (14) | 0.0218 (17) |
C1 | 0.0355 (14) | 0.0292 (19) | 0.0597 (18) | 0.0006 (12) | 0.0101 (13) | 0.0060 (15) |
O1 | 0.0347 (10) | 0.071 (2) | 0.0892 (18) | 0.0031 (11) | 0.0282 (12) | 0.0118 (15) |
C2 | 0.0303 (12) | 0.0346 (18) | 0.0370 (13) | −0.0006 (11) | 0.0119 (10) | 0.0040 (12) |
O2 | 0.0402 (10) | 0.0551 (16) | 0.0482 (11) | −0.0055 (11) | 0.0225 (9) | 0.0114 (11) |
C10 | 0.0392 (14) | 0.039 (2) | 0.0520 (18) | 0.0018 (14) | 0.0150 (13) | 0.0036 (16) |
N2 | 0.0647 (18) | 0.062 (3) | 0.0671 (18) | −0.0017 (17) | 0.0112 (16) | −0.0132 (18) |
C3 | 0.0355 (13) | 0.0327 (17) | 0.0388 (14) | 0.0069 (12) | 0.0168 (11) | 0.0085 (13) |
Br | 0.04734 (18) | 0.0540 (3) | 0.04557 (18) | 0.01574 (15) | 0.01338 (13) | 0.01061 (16) |
C4 | 0.0400 (14) | 0.0302 (17) | 0.0434 (15) | 0.0054 (12) | 0.0184 (12) | 0.0070 (13) |
C5 | 0.0512 (16) | 0.045 (2) | 0.0555 (18) | −0.0054 (16) | 0.0291 (15) | −0.0004 (17) |
C6 | 0.066 (2) | 0.041 (2) | 0.0496 (18) | 0.0000 (17) | 0.0272 (16) | −0.0012 (16) |
C7 | 0.0592 (18) | 0.032 (2) | 0.0503 (17) | 0.0059 (15) | 0.0080 (15) | 0.0051 (15) |
C8 | 0.0468 (17) | 0.041 (2) | 0.071 (2) | −0.0048 (15) | 0.0183 (16) | 0.0024 (18) |
C9 | 0.0448 (15) | 0.042 (2) | 0.0577 (19) | 0.0010 (14) | 0.0229 (14) | 0.0027 (16) |
C11 | 0.090 (3) | 0.050 (3) | 0.060 (2) | −0.005 (2) | 0.007 (2) | −0.0055 (19) |
Geometric parameters (Å, º) top
N1—C1 | 1.308 (4) | C4—C9 | 1.388 (4) |
N1—H2A | 0.8600 | C5—C6 | 1.390 (5) |
N1—H2B | 0.8600 | C5—H11 | 0.9300 |
C1—O1 | 1.221 (4) | C6—C7 | 1.390 (5) |
C1—C2 | 1.547 (4) | C6—H15 | 0.9300 |
C2—O2 | 1.390 (3) | C7—C8 | 1.377 (5) |
C2—C10 | 1.486 (4) | C7—C11 | 1.502 (5) |
C2—C3 | 1.548 (4) | C8—C9 | 1.380 (5) |
O2—H1 | 0.8200 | C8—H12 | 0.9300 |
C10—N2 | 1.136 (4) | C9—H10 | 0.9300 |
C3—C4 | 1.501 (4) | C11—H17A | 0.9600 |
C3—Br | 1.975 (3) | C11—H17B | 0.9600 |
C3—H4 | 0.9800 | C11—H17C | 0.9600 |
C4—C5 | 1.386 (4) | | |
| | | |
C1—N1—H2A | 120.0 | C9—C4—C3 | 118.2 (2) |
C1—N1—H2B | 120.0 | C4—C5—C6 | 120.3 (3) |
H2A—N1—H2B | 120.0 | C4—C5—H11 | 119.8 |
O1—C1—N1 | 126.3 (3) | C6—C5—H11 | 119.8 |
O1—C1—C2 | 118.4 (3) | C7—C6—C5 | 121.3 (3) |
N1—C1—C2 | 115.2 (3) | C7—C6—H15 | 119.3 |
O2—C2—C10 | 111.2 (2) | C5—C6—H15 | 119.3 |
O2—C2—C1 | 109.3 (2) | C8—C7—C6 | 117.7 (3) |
C10—C2—C1 | 106.7 (2) | C8—C7—C11 | 121.0 (3) |
O2—C2—C3 | 114.8 (2) | C6—C7—C11 | 121.3 (3) |
C10—C2—C3 | 108.6 (2) | C7—C8—C9 | 121.5 (3) |
C1—C2—C3 | 105.9 (2) | C7—C8—H12 | 119.3 |
C2—O2—H1 | 109.5 | C9—C8—H12 | 119.3 |
N2—C10—C2 | 177.6 (3) | C8—C9—C4 | 120.9 (3) |
C4—C3—C2 | 115.1 (2) | C8—C9—H10 | 119.6 |
C4—C3—Br | 110.67 (19) | C4—C9—H10 | 119.6 |
C2—C3—Br | 108.98 (18) | C7—C11—H17A | 109.5 |
C4—C3—H4 | 107.3 | C7—C11—H17B | 109.5 |
C2—C3—H4 | 107.3 | H17A—C11—H17B | 109.5 |
Br—C3—H4 | 107.3 | C7—C11—H17C | 109.5 |
C5—C4—C9 | 118.3 (3) | H17A—C11—H17C | 109.5 |
C5—C4—C3 | 123.5 (3) | H17B—C11—H17C | 109.5 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2B···O2 | 0.86 | 2.15 | 2.567 (4) | 109 |
N1—H2A···N2i | 0.86 | 2.41 | 3.269 (5) | 173 |
O2—H1···O1ii | 0.82 | 1.87 | 2.677 (3) | 166 |
Symmetry codes: (i) x−1, y, z−1; (ii) x+1, y, z. |
(III) '3-bromo-3-(4-metylphenyl)-2-oxopropanamide'
top
Crystal data top
C10H10BrNO2 | F(000) = 1024 |
Mr = 256.10 | Dx = 1.594 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 22.614 (5) Å | Cell parameters from 3833 reflections |
b = 10.257 (2) Å | θ = 2.8–26.0° |
c = 10.099 (2) Å | µ = 3.83 mm−1 |
β = 114.32 (3)° | T = 293 K |
V = 2134.6 (8) Å3 | Prismatic, colourless |
Z = 8 | 0.22 × 0.20 × 0.20 mm |
Data collection top
Nonius-Kappa CCD diffractometer | 1372 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.021 |
Graphite monochromator | θmax = 26.0°, θmin = 2.8° |
1° φ and ω scans | h = −27→27 |
3833 measured reflections | k = −12→12 |
1966 independent reflections | l = −10→10 |
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)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.109 | Calculated w = 1/[σ2(Fo2) + (0.0678P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max < 0.001 |
1966 reflections | Δρmax = 0.64 e Å−3 |
139 parameters | Δρmin = −0.39 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0038 (6) |
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 >
2σ(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 | |
Br | 0.33339 (2) | 0.18643 (4) | 0.33990 (4) | 0.0648 (2) | |
O2 | 0.30305 (12) | 0.4924 (3) | 0.4623 (3) | 0.0706 (8) | |
O1 | 0.42285 (11) | 0.4607 (3) | 0.3368 (2) | 0.0521 (7) | |
N1 | 0.43410 (14) | 0.5051 (3) | 0.5646 (3) | 0.0548 (8) | |
H1 | 0.4749 | 0.5213 | 0.5951 | 0.055 (11)* | |
H2 | 0.4154 | 0.5109 | 0.6232 | 0.072 (13)* | |
C1 | 0.40018 (15) | 0.4713 (3) | 0.4276 (3) | 0.0422 (8) | |
C2 | 0.32834 (16) | 0.4462 (3) | 0.3879 (3) | 0.0433 (8) | |
C3 | 0.29390 (15) | 0.3588 (4) | 0.2601 (4) | 0.0432 (8) | |
H3 | 0.3065 | 0.3832 | 0.1815 | 0.037 (8)* | |
C4 | 0.22207 (16) | 0.3498 (4) | 0.2005 (4) | 0.0458 (9) | |
C5 | 0.18556 (18) | 0.3691 (4) | 0.0542 (4) | 0.0563 (10) | |
H5 | 0.2062 | 0.3876 | −0.0066 | 0.053 (10)* | |
C6 | 0.1187 (2) | 0.3614 (5) | −0.0030 (5) | 0.0701 (12) | |
H6 | 0.0951 | 0.3758 | −0.1019 | 0.086 (14)* | |
C7 | 0.0863 (2) | 0.3332 (4) | 0.0816 (5) | 0.0705 (13) | |
C8 | 0.1225 (2) | 0.3145 (5) | 0.2288 (6) | 0.0780 (14) | |
H8 | 0.1014 | 0.2965 | 0.2886 | 0.098 (16)* | |
C9 | 0.1894 (2) | 0.3219 (4) | 0.2885 (5) | 0.0690 (13) | |
H9 | 0.2128 | 0.3083 | 0.3876 | 0.080 (14)* | |
C11 | 0.0134 (2) | 0.3201 (6) | 0.0186 (8) | 0.103 (2) | |
H11A | −0.0040 | 0.3333 | −0.0846 | 0.11 (2)* | |
H11B | −0.0042 | 0.3842 | 0.0616 | 0.16 (3)* | |
H11C | 0.0020 | 0.2345 | 0.0388 | 0.105 (19)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br | 0.0559 (3) | 0.0615 (3) | 0.0704 (3) | 0.0063 (2) | 0.0194 (2) | −0.0018 (2) |
O2 | 0.0413 (15) | 0.107 (2) | 0.0689 (18) | −0.0057 (15) | 0.0278 (13) | −0.0322 (16) |
O1 | 0.0370 (13) | 0.085 (2) | 0.0362 (12) | −0.0090 (12) | 0.0174 (10) | −0.0044 (11) |
N1 | 0.0329 (17) | 0.095 (3) | 0.0370 (15) | −0.0141 (16) | 0.0149 (13) | −0.0121 (15) |
C1 | 0.0331 (18) | 0.054 (2) | 0.0375 (18) | −0.0009 (15) | 0.0129 (14) | 0.0007 (14) |
C2 | 0.0336 (18) | 0.049 (2) | 0.0448 (18) | −0.0003 (16) | 0.0140 (14) | 0.0004 (15) |
C3 | 0.0295 (18) | 0.057 (2) | 0.0427 (19) | −0.0011 (15) | 0.0141 (14) | 0.0027 (15) |
C4 | 0.0313 (18) | 0.056 (2) | 0.0463 (19) | −0.0050 (16) | 0.0120 (15) | −0.0016 (15) |
C5 | 0.039 (2) | 0.069 (3) | 0.053 (2) | −0.0091 (19) | 0.0119 (17) | −0.0049 (18) |
C6 | 0.046 (2) | 0.083 (3) | 0.060 (3) | −0.002 (2) | 0.001 (2) | −0.003 (2) |
C7 | 0.036 (2) | 0.066 (3) | 0.099 (3) | −0.0085 (19) | 0.017 (2) | −0.007 (2) |
C8 | 0.046 (2) | 0.100 (4) | 0.095 (4) | −0.014 (2) | 0.037 (3) | 0.006 (3) |
C9 | 0.045 (2) | 0.100 (4) | 0.061 (3) | −0.011 (2) | 0.021 (2) | 0.010 (2) |
C11 | 0.037 (3) | 0.100 (5) | 0.152 (6) | −0.009 (3) | 0.019 (3) | −0.005 (4) |
Geometric parameters (Å, º) top
Br—C3 | 1.995 (4) | C5—C6 | 1.381 (6) |
O2—C2 | 1.212 (4) | C5—H5 | 0.9300 |
O1—C1 | 1.225 (4) | C6—C7 | 1.366 (6) |
N1—C1 | 1.322 (4) | C6—H6 | 0.9300 |
N1—H1 | 0.8600 | C7—C8 | 1.384 (7) |
N1—H2 | 0.8600 | C7—C11 | 1.510 (6) |
C1—C2 | 1.526 (5) | C8—C9 | 1.380 (6) |
C2—C3 | 1.500 (5) | C8—H8 | 0.9300 |
C3—C4 | 1.485 (5) | C9—H9 | 0.9300 |
C3—H3 | 0.9800 | C11—H11A | 0.9600 |
C4—C5 | 1.379 (5) | C11—H11B | 0.9600 |
C4—C9 | 1.399 (5) | C11—H11C | 0.9600 |
| | | |
C1—N1—H1 | 120.0 | C6—C5—H5 | 119.7 |
C1—N1—H2 | 120.0 | C7—C6—C5 | 121.8 (4) |
H1—N1—H2 | 120.0 | C7—C6—H6 | 119.1 |
O1—C1—N1 | 124.4 (3) | C5—C6—H6 | 119.1 |
O1—C1—C2 | 121.1 (3) | C6—C7—C8 | 118.0 (4) |
N1—C1—C2 | 114.5 (3) | C6—C7—C11 | 122.0 (5) |
O2—C2—C3 | 123.8 (3) | C8—C7—C11 | 120.0 (5) |
O2—C2—C1 | 119.6 (3) | C9—C8—C7 | 121.2 (4) |
C3—C2—C1 | 116.5 (3) | C9—C8—H8 | 119.4 |
C4—C3—C2 | 118.7 (3) | C7—C8—H8 | 119.4 |
C4—C3—Br | 110.0 (3) | C8—C9—C4 | 120.3 (4) |
C2—C3—Br | 101.2 (2) | C8—C9—H9 | 119.9 |
C4—C3—H3 | 108.8 | C4—C9—H9 | 119.9 |
C2—C3—H3 | 108.8 | C7—C11—H11A | 109.5 |
Br—C3—H3 | 108.8 | C7—C11—H11B | 109.5 |
C5—C4—C9 | 118.0 (3) | H11A—C11—H11B | 109.5 |
C5—C4—C3 | 119.8 (3) | C7—C11—H11C | 109.5 |
C9—C4—C3 | 122.1 (3) | H11A—C11—H11C | 109.5 |
C4—C5—C6 | 120.6 (4) | H11B—C11—H11C | 109.5 |
C4—C5—H5 | 119.7 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2···O2 | 0.86 | 2.39 | 2.710 (4) | 102 |
N1—H2···O1i | 0.86 | 2.11 | 2.885 (4) | 149 |
N1—H1···O1ii | 0.86 | 2.13 | 2.988 (4) | 173 |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) −x+1, −y+1, −z+1. |
(IV) '3-chloro-3-phenyl-2,2-dihydroxypropanamide'
top
Crystal data top
C9H10ClNO3 | F(000) = 448 |
Mr = 215.63 | Dx = 1.515 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
a = 5.526 (1) Å | Cell parameters from 1798 reflections |
b = 29.989 (6) Å | θ = 2.7–26.0° |
c = 5.997 (1) Å | µ = 0.38 mm−1 |
β = 107.96 (3)° | T = 293 K |
V = 945.4 (3) Å3 | Prismatic, colourless |
Z = 4 | 0.40 × 0.35 × 0.25 mm |
Data collection top
Nonius-Kappa CCD diffractometer | 1550 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.023 |
Graphite monochromator | θmax = 26.0°, θmin = 2.7° |
1° φ and ω scans | h = −6→6 |
1798 measured reflections | k = −36→36 |
1781 independent reflections | l = −7→7 |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.028 | Calculated w = 1/[σ2(Fo2) + (0.0287P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.063 | (Δ/σ)max = 0.001 |
S = 1.01 | Δρmax = 0.17 e Å−3 |
1781 reflections | Δρmin = −0.16 e Å−3 |
137 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
2 restraints | Extinction coefficient: 0.024 (2) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.50 (5) |
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 >
2σ(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 | |
Cl | 0.16258 (8) | 0.124077 (19) | 0.21761 (8) | 0.05386 (18) | |
O2 | −0.3113 (2) | 0.06060 (5) | 0.03079 (18) | 0.0496 (4) | |
H21 | −0.2398 | 0.0616 | 0.1725 | 0.073 (9)* | |
O1 | −0.1405 (2) | 0.05041 (5) | −0.48339 (19) | 0.0561 (4) | |
C4 | −0.2056 (4) | 0.14729 (6) | −0.1812 (3) | 0.0384 (4) | |
O3 | 0.0723 (3) | 0.03416 (5) | 0.0011 (3) | 0.0550 (4) | |
H31 | 0.0174 | 0.0087 | −0.0038 | 0.106 (13)* | |
N1 | −0.5146 (4) | 0.04729 (7) | −0.4077 (4) | 0.0606 (5) | |
H1 | −0.5987 | 0.0412 | −0.5508 | 0.091 (10)* | |
H2 | −0.5925 | 0.0496 | −0.3042 | 0.069 (8)* | |
C3 | −0.0171 (4) | 0.11083 (6) | −0.0800 (3) | 0.0386 (5) | |
H3 | 0.1032 | 0.1099 | −0.1714 | 0.052 (6)* | |
C2 | −0.1314 (4) | 0.06384 (7) | −0.0872 (3) | 0.0391 (4) | |
C9 | −0.2038 (4) | 0.16836 (7) | −0.3868 (4) | 0.0468 (5) | |
H9 | −0.0877 | 0.1595 | −0.4622 | 0.047 (6)* | |
C5 | −0.3815 (4) | 0.16089 (7) | −0.0730 (4) | 0.0465 (5) | |
H5 | −0.3859 | 0.1470 | 0.0643 | 0.057 (6)* | |
C1 | −0.2683 (4) | 0.05304 (6) | −0.3474 (4) | 0.0429 (5) | |
C8 | −0.3733 (5) | 0.20236 (8) | −0.4799 (4) | 0.0610 (6) | |
H8 | −0.3711 | 0.2163 | −0.6177 | 0.071 (8)* | |
C7 | −0.5452 (5) | 0.21557 (8) | −0.3691 (5) | 0.0621 (6) | |
H7 | −0.6585 | 0.2386 | −0.4316 | 0.096 (9)* | |
C6 | −0.5500 (4) | 0.19488 (7) | −0.1670 (4) | 0.0564 (6) | |
H6 | −0.6671 | 0.2038 | −0.0930 | 0.075 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl | 0.0438 (2) | 0.0725 (4) | 0.0405 (2) | −0.0043 (3) | 0.00592 (19) | −0.0035 (3) |
O2 | 0.0480 (8) | 0.0600 (10) | 0.0461 (9) | −0.0068 (7) | 0.0224 (7) | 0.0063 (7) |
O1 | 0.0775 (11) | 0.0505 (9) | 0.0483 (8) | −0.0010 (7) | 0.0315 (8) | −0.0006 (7) |
C4 | 0.0415 (10) | 0.0366 (11) | 0.0351 (9) | −0.0055 (8) | 0.0087 (9) | −0.0034 (8) |
O3 | 0.0460 (9) | 0.0489 (10) | 0.0672 (10) | 0.0082 (7) | 0.0131 (8) | 0.0163 (8) |
N1 | 0.0483 (11) | 0.0662 (14) | 0.0605 (13) | −0.0020 (9) | 0.0067 (11) | −0.0141 (10) |
C3 | 0.0355 (10) | 0.0451 (12) | 0.0367 (10) | −0.0031 (8) | 0.0134 (9) | 0.0004 (8) |
C2 | 0.0330 (9) | 0.0437 (12) | 0.0409 (11) | 0.0019 (8) | 0.0117 (8) | 0.0064 (8) |
C9 | 0.0536 (12) | 0.0475 (13) | 0.0410 (11) | −0.0073 (11) | 0.0171 (10) | −0.0031 (9) |
C5 | 0.0434 (11) | 0.0500 (12) | 0.0483 (12) | 0.0009 (10) | 0.0176 (10) | 0.0010 (10) |
C1 | 0.0513 (12) | 0.0324 (11) | 0.0461 (11) | 0.0011 (8) | 0.0167 (10) | 0.0004 (8) |
C8 | 0.0828 (16) | 0.0474 (13) | 0.0422 (11) | −0.0028 (12) | 0.0037 (12) | 0.0060 (10) |
C7 | 0.0594 (13) | 0.0495 (14) | 0.0636 (14) | 0.0059 (11) | −0.0015 (11) | −0.0016 (12) |
C6 | 0.0492 (12) | 0.0553 (15) | 0.0630 (15) | 0.0058 (10) | 0.0147 (12) | −0.0044 (12) |
Geometric parameters (Å, º) top
Cl—C3 | 1.7987 (19) | C3—C2 | 1.539 (3) |
O2—C2 | 1.390 (2) | C3—H3 | 0.9800 |
O2—H21 | 0.8200 | C2—C1 | 1.544 (3) |
O1—C1 | 1.235 (2) | C9—C8 | 1.381 (3) |
C4—C5 | 1.386 (3) | C9—H9 | 0.9300 |
C4—C9 | 1.388 (3) | C5—C6 | 1.378 (3) |
C4—C3 | 1.503 (3) | C5—H5 | 0.9300 |
O3—C2 | 1.404 (2) | C8—C7 | 1.375 (3) |
O3—H31 | 0.8200 | C8—H8 | 0.9300 |
N1—C1 | 1.308 (3) | C7—C6 | 1.369 (4) |
N1—H1 | 0.8600 | C7—H7 | 0.9300 |
N1—H2 | 0.8600 | C6—H6 | 0.9300 |
| | | |
C2—O2—H21 | 109.5 | C3—C2—C1 | 106.81 (15) |
C5—C4—C9 | 118.68 (18) | C8—C9—C4 | 120.4 (2) |
C5—C4—C3 | 121.58 (17) | C8—C9—H9 | 119.8 |
C9—C4—C3 | 119.74 (17) | C4—C9—H9 | 119.8 |
C2—O3—H31 | 109.5 | C6—C5—C4 | 120.6 (2) |
C1—N1—H1 | 120.0 | C6—C5—H5 | 119.7 |
C1—N1—H2 | 120.0 | C4—C5—H5 | 119.7 |
H1—N1—H2 | 120.0 | O1—C1—N1 | 124.6 (2) |
C4—C3—C2 | 115.30 (17) | O1—C1—C2 | 118.62 (17) |
C4—C3—Cl | 109.99 (13) | N1—C1—C2 | 116.80 (19) |
C2—C3—Cl | 109.04 (13) | C7—C8—C9 | 120.0 (2) |
C4—C3—H3 | 107.5 | C7—C8—H8 | 120.0 |
C2—C3—H3 | 107.5 | C9—C8—H8 | 120.0 |
Cl—C3—H3 | 107.5 | C6—C7—C8 | 120.1 (2) |
O2—C2—O3 | 112.33 (15) | C6—C7—H7 | 119.9 |
O2—C2—C3 | 113.66 (16) | C8—C7—H7 | 119.9 |
O3—C2—C3 | 107.19 (15) | C7—C6—C5 | 120.2 (2) |
O2—C2—C1 | 107.17 (15) | C7—C6—H6 | 119.9 |
O3—C2—C1 | 109.50 (16) | C5—C6—H6 | 119.9 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2···O2 | 0.86 | 2.15 | 2.552 (3) | 108 |
O2—H21···O1i | 0.82 | 1.99 | 2.789 (2) | 163 |
O3—H31···O1ii | 0.82 | 1.99 | 2.809 (2) | 172 |
Symmetry codes: (i) x, y, z+1; (ii) x, −y, z+1/2. |