From α-carbamoyl-α-cyano­oxiranes to 3-halogenopyruv­amides

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.

Computing details

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'

Crystal data

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) Å^3	Prismatic, colourless
Z = 4	0.30 × 0.30 × 0.25 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.152	Calculated w = 1/[σ^2(Fo^2) + (0.0811P)^2 + 0.2445P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.061 (6)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···O1^i	0.86	2.34	2.911 (2)	124
N1—H1···O1^ii	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'

Crystal data

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) Å^3	Prismatic, colourless
Z = 4	0.12 × 0.10 × 0.05 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H-atom parameters constrained
S = 0.97	Calculated w = 1/[σ^2(Fo^2) + (0.0705P)^2 + ] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···N2^i	0.86	2.41	3.269 (5)	173
O2—H1···O1^ii	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'

Crystal data

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) Å^3	Prismatic, colourless
Z = 8	0.22 × 0.20 × 0.20 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.109	Calculated w = 1/[σ^2(Fo^2) + (0.0678P)^2] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0038 (6)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···O1^i	0.86	2.11	2.885 (4)	149
N1—H1···O1^ii	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'

Crystal data

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) Å^3	Prismatic, colourless
Z = 4	0.40 × 0.35 × 0.25 mm

Data collection

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

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.028	Calculated w = 1/[σ^2(Fo^2) + (0.0287P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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+0.001xFc^2λ^3/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···O1^i	0.82	1.99	2.789 (2)	163
O3—H31···O1^ii	0.82	1.99	2.809 (2)	172

Symmetry codes: (i) x, y, z+1; (ii) x, −y, z+1/2.