Two 2,2-dihalo-N-(1-phenyl­ethyl)­cyclo­propane-1-carbox­amides

The crystal structures of (1R,1′S)-2′,2′-di­chloro-N-(1-phenyl­ethyl)­cyclo­propane-1′-carbox­amide, C₁₂H₁₃Cl₂NO, (I), and (1R,1′R)-2′,2′-di­fluoro-N-(1-phenyl­ethyl)­cyclo­propane-1′-car­box­amide, C₁₂H₁₃F₂NO, (II), have been determined. Both crystals contain two independent mol­ecules with different conformations of the phenyl­ethyl groups. In the crystals of both compounds, the mol­ecules are linked together by N—H...O hydrogen bonds, thus forming chains in the a direction.

S1. Comment

The title compounds have been synthesized as intermediate products in the synthesis of novel ferroelectric liquid crystals with optically active dihaloid-substituted cyclopropanecarboxylic acids in their side chain (Miyazawa & de Meijere, 2001). An X-ray structural study has confirmed the absolute configuration of the molecules, which was proposed on the basis of chemical information.

The structures of (I) and (II) are similar but not isostructural. The structures of both compounds contain two independent molecules, and the conformations of these independent molecules are different. However, in (II) the two independent molecules differ mainly by the orientation of the phenyl ring, whereas in (I) the conformation around the N—C7 bonds in the two independent molecules is also different (Fig. 1). The replacement of chlorine substitutents in the cyclopropane cycle of (I) with more electronegative fluorine substitutents in (II) results in a predictable (e.g. Allen, 1980; Cremer & Kraka, 1985) increase in the asymmetry of the three-membered ring, with a significant elongation of the distal bond C10—C11(C30—C31) and a shortening of the vicinal bonds C12—C10(C32—C30) and C12—C11(C32—C31).

In crystals, the molecules of both compounds form infinite chains along the a axis. The molecules in these chains are connected by strong N—H···O hydrogen bonds. Because the molecules of (I) and (II) have different configurations, the arrangement of the molecules in the chains is also different (Fig. 2). In (I), the phenyl rings and methyl groups of adjacent molecules are in close vicinity, whereas in (II) the C11 methylene groups of the cyclopropane rings are located between the benzene rings. As a result, the chains in (I) are packed together so as to form hydrophobic areas in which the phenylethyl groups are located (Fig. 3), which is not the case in (II).

S2. Experimental

Crystals of (I) were obtained by the slow evaporation of a hexane/methanol solution. Crystals of (II) were similarly obtained from a hexane/diethyl ether solution.

Computing details

For both compounds, data collection: Bruker SMART; cell refinement: Bruker SMART; data reduction: Bruker SHELXTL; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.

Figures

	Fig. 1. The overlapping of the two independent molecules of (a) (I) and (b) (II). Thermal ellipsoids are at the 50% probability level; H atoms are omitted for clarity.
	Fig. 2. The arrangement of the molecules in hydrogen-bonded chains in (a) (I) and (b) (II).
	Fig. 3. The packing diagrams of (a) (I) and (b) (II) viewed along the a axis.

(I) (1R,1'S)-2',2'-dichloro-N-(1-phenylethyl)cyclopropane-1'-carboxamide

Crystal data

C12H13Cl2NO	F(000) = 536
Mr = 258.13	Dx = 1.349 Mg m^−3
Monoclinic, P21	Melting point = 138–140 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 9.4157 (3) Å	Cell parameters from 999 reflections
b = 9.6893 (3) Å	θ = 10.3–20.8°
c = 13.9473 (4) Å	µ = 0.49 mm^−1
β = 92.91 (1)°	T = 100 K
V = 1270.8 (1) Å^3	Plate, colourless
Z = 4	0.48 × 0.20 × 0.06 mm

Data collection

Bruker SMART CCD 1K diffractometer	6176 independent reflections
Radiation source: fine-focus sealed tube	5373 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ω–scan	θmax = 30.4°, θmin = 2.6°
Absorption correction: multi-scan SADABS (Sheldrick, 1998)	h = −13→12
Tmin = 0.799, Tmax = 0.971	k = −13→11
12790 measured reflections	l = −19→18

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	All H-atom parameters refined
wR(F^2) = 0.071	w = 1/[σ^2(Fo^2) + (0.04P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
6176 reflections	Δρmax = 0.27 e Å^−3
393 parameters	Δρmin = −0.21 e Å^−3
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (4)

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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.90658 (5)	0.95555 (5)	0.14039 (3)	0.02506 (11)
Cl2	1.19172 (5)	0.92227 (5)	0.07430 (3)	0.02897 (12)
Cl3	0.63731 (5)	0.19208 (5)	0.10898 (4)	0.03026 (12)
Cl4	0.38863 (5)	0.25411 (5)	0.21764 (4)	0.02986 (12)
O1	1.20002 (13)	1.11590 (14)	−0.11012 (9)	0.0215 (3)
O2	0.30541 (14)	0.56336 (16)	0.15745 (10)	0.0253 (3)
N1	0.99728 (17)	1.03222 (18)	−0.18427 (11)	0.0202 (3)
N2	0.52478 (17)	0.65041 (16)	0.19571 (11)	0.0184 (3)
C1	0.9813 (2)	0.8907 (2)	−0.32829 (13)	0.0252 (4)
C2	1.0304 (2)	0.7553 (3)	−0.31640 (15)	0.0312 (5)
C3	0.9560 (3)	0.6457 (3)	−0.35890 (17)	0.0362 (5)
C4	0.8311 (3)	0.6693 (2)	−0.41342 (15)	0.0329 (5)
C5	0.7810 (3)	0.8027 (2)	−0.42590 (16)	0.0333 (5)
C6	0.8554 (2)	0.9130 (2)	−0.38334 (16)	0.0303 (4)
C7	1.0610 (2)	1.0077 (2)	−0.27739 (14)	0.0262 (4)
C8	1.0652 (3)	1.1418 (3)	−0.33433 (17)	0.0411 (6)
C9	1.07273 (19)	1.08525 (18)	−0.10888 (12)	0.0173 (3)
C10	0.98923 (19)	1.10025 (19)	−0.02023 (12)	0.0182 (4)
C11	1.0532 (2)	1.1791 (2)	0.06502 (14)	0.0222 (4)
C12	1.03969 (19)	1.02698 (19)	0.07068 (13)	0.0184 (4)
C21	0.42350 (19)	0.72534 (19)	0.34949 (13)	0.0199 (4)
C22	0.3144 (2)	0.7995 (2)	0.38976 (15)	0.0279 (4)
C23	0.2760 (3)	0.7734 (2)	0.48309 (16)	0.0353 (5)
C24	0.3458 (2)	0.6720 (3)	0.53688 (15)	0.0329 (5)
C25	0.4535 (2)	0.5956 (2)	0.49750 (15)	0.0314 (5)
C26	0.4919 (2)	0.6218 (2)	0.40382 (14)	0.0257 (4)
C27	0.46959 (19)	0.7669 (2)	0.25029 (13)	0.0195 (4)
C28	0.5837 (2)	0.8802 (2)	0.25918 (15)	0.0276 (4)
C29	0.43618 (18)	0.5592 (2)	0.15185 (12)	0.0188 (4)
C30	0.50897 (19)	0.4506 (2)	0.09521 (12)	0.0198 (3)
C31	0.4174 (2)	0.3562 (2)	0.03031 (14)	0.0242 (4)
C32	0.4880 (2)	0.3009 (2)	0.11986 (13)	0.0210 (4)
H1N	0.910 (3)	1.019 (3)	−0.182 (2)	0.050 (8)*
H2	1.115 (3)	0.740 (3)	−0.2738 (17)	0.034 (6)*
H3	0.998 (3)	0.555 (3)	−0.3507 (19)	0.046 (8)*
H4	0.779 (3)	0.599 (3)	−0.4421 (18)	0.036 (7)*
H5	0.693 (3)	0.820 (3)	−0.4618 (18)	0.035 (7)*
H6	0.825 (3)	1.004 (3)	−0.3950 (19)	0.039 (7)*
H7	1.149 (3)	0.985 (2)	−0.2617 (16)	0.020 (6)*
H81	0.976 (3)	1.179 (3)	−0.3482 (16)	0.028 (6)*
H82	1.112 (3)	1.127 (3)	−0.393 (2)	0.055 (8)*
H83	1.113 (3)	1.211 (3)	−0.2974 (18)	0.034 (6)*
H10	0.886 (2)	1.100 (2)	−0.0321 (14)	0.018 (5)*
H111	1.142 (2)	1.207 (2)	0.0581 (14)	0.016 (5)*
H112	0.988 (2)	1.230 (2)	0.1018 (15)	0.021 (5)*
H2N	0.610 (3)	0.645 (2)	0.1827 (17)	0.030 (6)*
H22	0.265 (3)	0.864 (3)	0.3481 (18)	0.036 (7)*
H23	0.195 (3)	0.820 (3)	0.5046 (19)	0.043 (7)*
H24	0.326 (3)	0.657 (3)	0.6006 (18)	0.033 (6)*
H25	0.503 (3)	0.520 (3)	0.5356 (17)	0.030 (6)*
H26	0.566 (3)	0.568 (3)	0.3773 (17)	0.034 (7)*
H27	0.382 (2)	0.797 (2)	0.2138 (15)	0.022 (6)*
H281	0.612 (2)	0.905 (2)	0.1949 (14)	0.015 (5)*
H282	0.538 (3)	0.964 (3)	0.2847 (17)	0.033 (6)*
H283	0.674 (3)	0.842 (3)	0.3017 (19)	0.040 (7)*
H30	0.599 (2)	0.471 (2)	0.0753 (14)	0.020 (5)*
H311	0.318 (3)	0.366 (2)	0.0299 (17)	0.031 (6)*
H312	0.451 (2)	0.326 (2)	−0.0243 (16)	0.023 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0270 (2)	0.0261 (2)	0.0226 (2)	−0.00523 (19)	0.00588 (17)	0.00172 (18)
Cl2	0.0229 (2)	0.0334 (3)	0.0304 (2)	0.0088 (2)	−0.00033 (18)	0.0076 (2)
Cl3	0.0295 (3)	0.0220 (2)	0.0399 (3)	0.0035 (2)	0.0080 (2)	−0.0010 (2)
Cl4	0.0294 (3)	0.0319 (3)	0.0290 (2)	−0.0002 (2)	0.00840 (19)	0.0083 (2)
O1	0.0127 (6)	0.0259 (7)	0.0259 (6)	−0.0003 (5)	0.0014 (5)	0.0012 (6)
O2	0.0133 (7)	0.0315 (8)	0.0312 (7)	0.0000 (6)	0.0017 (5)	0.0000 (6)
N1	0.0116 (8)	0.0298 (9)	0.0193 (7)	−0.0003 (7)	0.0026 (6)	−0.0011 (6)
N2	0.0142 (7)	0.0210 (8)	0.0201 (7)	0.0001 (6)	0.0035 (6)	−0.0026 (6)
C1	0.0232 (10)	0.0346 (12)	0.0183 (8)	−0.0004 (8)	0.0068 (7)	−0.0025 (8)
C2	0.0332 (11)	0.0382 (12)	0.0225 (9)	0.0057 (11)	0.0033 (8)	0.0044 (9)
C3	0.0483 (15)	0.0288 (12)	0.0319 (11)	0.0056 (11)	0.0048 (10)	0.0056 (9)
C4	0.0448 (13)	0.0306 (13)	0.0238 (10)	−0.0075 (10)	0.0051 (9)	−0.0033 (9)
C5	0.0338 (12)	0.0347 (13)	0.0310 (11)	−0.0013 (10)	−0.0021 (9)	−0.0050 (10)
C6	0.0281 (11)	0.0281 (12)	0.0344 (10)	0.0026 (9)	−0.0024 (8)	−0.0060 (9)
C7	0.0177 (10)	0.0400 (12)	0.0215 (9)	−0.0035 (9)	0.0063 (7)	−0.0056 (8)
C8	0.0474 (16)	0.0521 (16)	0.0237 (10)	−0.0225 (14)	0.0017 (10)	0.0016 (11)
C9	0.0159 (8)	0.0150 (9)	0.0210 (8)	0.0018 (7)	0.0023 (7)	0.0018 (7)
C10	0.0138 (8)	0.0202 (9)	0.0206 (8)	0.0003 (7)	0.0006 (6)	−0.0002 (7)
C11	0.0218 (10)	0.0206 (10)	0.0241 (9)	−0.0031 (8)	0.0019 (7)	−0.0031 (8)
C12	0.0165 (9)	0.0191 (9)	0.0197 (8)	−0.0008 (7)	0.0024 (6)	0.0005 (7)
C21	0.0193 (9)	0.0202 (10)	0.0204 (8)	−0.0031 (7)	0.0017 (7)	−0.0020 (7)
C22	0.0308 (11)	0.0235 (11)	0.0301 (10)	0.0043 (9)	0.0102 (8)	0.0017 (9)
C23	0.0421 (13)	0.0326 (13)	0.0328 (11)	0.0021 (11)	0.0182 (10)	−0.0036 (10)
C24	0.0376 (12)	0.0407 (14)	0.0212 (9)	−0.0069 (10)	0.0085 (8)	0.0004 (9)
C25	0.0298 (11)	0.0386 (13)	0.0257 (9)	0.0006 (10)	−0.0010 (8)	0.0090 (9)
C26	0.0216 (10)	0.0300 (11)	0.0255 (9)	0.0029 (9)	0.0014 (7)	0.0022 (8)
C27	0.0184 (9)	0.0186 (9)	0.0216 (8)	0.0044 (7)	0.0029 (7)	0.0006 (7)
C28	0.0345 (12)	0.0215 (10)	0.0279 (10)	−0.0039 (9)	0.0107 (9)	−0.0032 (8)
C29	0.0147 (9)	0.0241 (10)	0.0175 (8)	0.0007 (7)	0.0004 (6)	0.0016 (7)
C30	0.0161 (8)	0.0210 (9)	0.0224 (8)	−0.0033 (8)	0.0030 (6)	−0.0022 (8)
C31	0.0272 (11)	0.0245 (10)	0.0208 (9)	−0.0049 (8)	−0.0013 (8)	−0.0015 (8)
C32	0.0186 (9)	0.0205 (9)	0.0239 (9)	−0.0015 (7)	0.0021 (7)	−0.0007 (7)

Geometric parameters (Å, º)

Cl1—C12	1.7661 (18)	C10—C12	1.509 (3)
Cl2—C12	1.7532 (19)	C10—C11	1.512 (3)
Cl3—C32	1.769 (2)	C10—H10	0.98 (2)
Cl4—C32	1.7524 (19)	C11—C12	1.482 (3)
O1—C9	1.236 (2)	C11—H111	0.89 (2)
O2—C29	1.238 (2)	C11—H112	0.95 (2)
N1—C9	1.341 (2)	C21—C22	1.394 (3)
N1—C7	1.478 (2)	C21—C26	1.395 (3)
N1—H1N	0.84 (3)	C21—C27	1.525 (2)
N2—C29	1.341 (2)	C22—C23	1.392 (3)
N2—C27	1.471 (2)	C22—H22	0.95 (3)
N2—H2N	0.83 (3)	C23—C24	1.382 (3)
C1—C6	1.396 (3)	C23—H23	0.95 (3)
C1—C2	1.398 (3)	C24—C25	1.391 (3)
C1—C7	1.516 (3)	C24—H24	0.93 (2)
C2—C3	1.389 (4)	C25—C26	1.397 (3)
C2—H2	0.98 (2)	C25—H25	1.01 (3)
C3—C4	1.387 (4)	C26—H26	0.96 (3)
C3—H3	0.96 (3)	C27—C28	1.537 (3)
C4—C5	1.385 (3)	C27—H27	0.99 (2)
C4—H4	0.92 (3)	C28—H281	0.98 (2)
C5—C6	1.394 (3)	C28—H282	1.00 (3)
C5—H5	0.96 (2)	C28—H283	1.08 (3)
C6—H6	0.94 (3)	C29—C30	1.502 (3)
C7—C8	1.524 (3)	C30—C32	1.506 (3)
C7—H7	0.87 (2)	C30—C31	1.523 (3)
C8—H81	0.92 (3)	C30—H30	0.92 (2)
C8—H82	0.96 (3)	C31—C32	1.485 (3)
C8—H83	0.94 (3)	C31—H311	0.94 (3)
C9—C10	1.506 (2)	C31—H312	0.89 (2)
C9—N1—C7	121.88 (16)	C11—C12—Cl1	118.96 (14)
C9—N1—H1N	121 (2)	C10—C12—Cl1	116.43 (13)
C7—N1—H1N	117 (2)	Cl2—C12—Cl1	111.01 (10)
C29—N2—C27	120.91 (15)	C22—C21—C26	118.74 (18)
C29—N2—H2N	116.3 (17)	C22—C21—C27	118.61 (17)
C27—N2—H2N	122.0 (17)	C26—C21—C27	122.54 (16)
C6—C1—C2	118.5 (2)	C23—C22—C21	121.0 (2)
C6—C1—C7	121.9 (2)	C23—C22—H22	123.2 (15)
C2—C1—C7	119.54 (19)	C21—C22—H22	115.7 (15)
C3—C2—C1	120.7 (2)	C24—C23—C22	119.9 (2)
C3—C2—H2	121.2 (15)	C24—C23—H23	122.2 (16)
C1—C2—H2	118.0 (15)	C22—C23—H23	117.5 (16)
C4—C3—C2	120.2 (2)	C23—C24—C25	120.01 (19)
C4—C3—H3	122.9 (17)	C23—C24—H24	121.2 (15)
C2—C3—H3	116.8 (17)	C25—C24—H24	118.7 (15)
C5—C4—C3	119.8 (2)	C24—C25—C26	120.1 (2)
C5—C4—H4	117.5 (16)	C24—C25—H25	120.6 (14)
C3—C4—H4	122.7 (16)	C26—C25—H25	119.3 (14)
C4—C5—C6	120.1 (2)	C21—C26—C25	120.31 (19)
C4—C5—H5	120.8 (16)	C21—C26—H26	120.3 (15)
C6—C5—H5	119.1 (16)	C25—C26—H26	119.4 (15)
C5—C6—C1	120.7 (2)	N2—C27—C21	113.04 (15)
C5—C6—H6	120.5 (16)	N2—C27—C28	109.02 (15)
C1—C6—H6	118.7 (16)	C21—C27—C28	110.20 (15)
N1—C7—C1	108.55 (16)	N2—C27—H27	105.6 (13)
N1—C7—C8	110.07 (19)	C21—C27—H27	106.1 (12)
C1—C7—C8	114.76 (18)	C28—C27—H27	112.8 (13)
N1—C7—H7	104.0 (14)	C27—C28—H281	109.0 (12)
C1—C7—H7	111.5 (15)	C27—C28—H282	107.6 (14)
C8—C7—H7	107.5 (15)	H281—C28—H282	105.7 (18)
C7—C8—H81	113.3 (15)	C27—C28—H283	109.2 (14)
C7—C8—H82	110.1 (19)	H281—C28—H283	110.1 (18)
H81—C8—H82	109 (2)	H282—C28—H283	115 (2)
C7—C8—H83	110.1 (15)	O2—C29—N2	123.17 (17)
H81—C8—H83	104 (2)	O2—C29—C30	122.52 (17)
H82—C8—H83	110 (2)	N2—C29—C30	114.31 (15)
O1—C9—N1	123.83 (16)	C29—C30—C32	119.10 (15)
O1—C9—C10	122.38 (16)	C29—C30—C31	118.25 (16)
N1—C9—C10	113.76 (15)	C32—C30—C31	58.73 (12)
C9—C10—C12	119.31 (15)	C29—C30—H30	117.3 (14)
C9—C10—C11	119.40 (16)	C32—C30—H30	113.9 (14)
C12—C10—C11	58.74 (12)	C31—C30—H30	116.6 (13)
C9—C10—H10	114.7 (12)	C32—C31—C30	60.07 (13)
C12—C10—H10	114.2 (12)	C32—C31—H311	116.4 (15)
C11—C10—H10	119.0 (12)	C30—C31—H311	118.5 (15)
C12—C11—C10	60.51 (12)	C32—C31—H312	116.1 (14)
C12—C11—H111	113.0 (14)	C30—C31—H312	119.7 (14)
C10—C11—H111	114.0 (13)	H311—C31—H312	115 (2)
C12—C11—H112	115.1 (13)	C31—C32—C30	61.21 (13)
C10—C11—H112	116.3 (12)	C31—C32—Cl4	120.90 (14)
H111—C11—H112	122.4 (18)	C30—C32—Cl4	120.53 (13)
C11—C12—C10	60.75 (12)	C31—C32—Cl3	117.83 (14)
C11—C12—Cl2	120.34 (14)	C30—C32—Cl3	116.14 (13)
C10—C12—Cl2	121.22 (13)	Cl4—C32—Cl3	111.76 (11)
C6—C1—C2—C3	0.4 (3)	C26—C21—C22—C23	1.4 (3)
C7—C1—C2—C3	177.26 (19)	C27—C21—C22—C23	−174.7 (2)
C1—C2—C3—C4	−0.4 (3)	C21—C22—C23—C24	−0.4 (4)
C2—C3—C4—C5	0.4 (3)	C22—C23—C24—C25	−0.5 (4)
C3—C4—C5—C6	−0.4 (3)	C23—C24—C25—C26	0.4 (3)
C4—C5—C6—C1	0.4 (3)	C22—C21—C26—C25	−1.4 (3)
C2—C1—C6—C5	−0.4 (3)	C27—C21—C26—C25	174.55 (19)
C7—C1—C6—C5	−177.18 (19)	C24—C25—C26—C21	0.5 (3)
C9—N1—C7—C1	152.73 (18)	C29—N2—C27—C21	78.3 (2)
C9—N1—C7—C8	−80.9 (2)	C29—N2—C27—C28	−158.78 (17)
C6—C1—C7—N1	84.2 (2)	C22—C21—C27—N2	−150.49 (18)
C2—C1—C7—N1	−92.5 (2)	C26—C21—C27—N2	33.6 (2)
C6—C1—C7—C8	−39.4 (3)	C22—C21—C27—C28	87.2 (2)
C2—C1—C7—C8	143.9 (2)	C26—C21—C27—C28	−88.7 (2)
C7—N1—C9—O1	−1.0 (3)	C27—N2—C29—O2	−3.0 (3)
C7—N1—C9—C10	−179.11 (17)	C27—N2—C29—C30	177.14 (15)
O1—C9—C10—C12	−57.0 (2)	O2—C29—C30—C32	−58.4 (2)
N1—C9—C10—C12	121.17 (18)	N2—C29—C30—C32	121.48 (18)
O1—C9—C10—C11	11.5 (3)	O2—C29—C30—C31	9.6 (3)
N1—C9—C10—C11	−170.34 (17)	N2—C29—C30—C31	−170.57 (16)
C9—C10—C11—C12	−108.37 (18)	C29—C30—C31—C32	−108.63 (18)
C10—C11—C12—Cl2	111.14 (16)	C30—C31—C32—Cl4	110.27 (17)
C10—C11—C12—Cl1	−105.85 (15)	C30—C31—C32—Cl3	−106.16 (16)
C9—C10—C12—C11	108.53 (19)	C29—C30—C32—C31	107.21 (19)
C9—C10—C12—Cl2	−1.2 (2)	C29—C30—C32—Cl4	−3.7 (2)
C11—C10—C12—Cl2	−109.73 (17)	C31—C30—C32—Cl4	−110.87 (17)
C9—C10—C12—Cl1	−141.51 (15)	C29—C30—C32—Cl3	−143.90 (14)
C11—C10—C12—Cl1	109.96 (16)	C31—C30—C32—Cl3	108.89 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2^i	0.84 (3)	2.11 (3)	2.909 (2)	158 (3)
N2—H2N···O1^ii	0.83 (3)	2.12 (3)	2.927 (2)	163 (2)

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

(II) (1R,1'R)-2',2'-difluoro-N-(1-phenylethyl)cyclopropane-1'-carboxamide

Crystal data

C12H13F2NO	F(000) = 472
Mr = 225.23	Dx = 1.286 Mg m^−3
Monoclinic, P21	Melting point = 103–107 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 9.2402 (4) Å	Cell parameters from 998 reflections
b = 14.2669 (5) Å	θ = 10.2–20.8°
c = 9.3542 (4) Å	µ = 0.10 mm^−1
β = 109.33 (1)°	T = 120 K
V = 1163.6 (1) Å^3	Plate, colourless
Z = 4	0.42 × 0.22 × 0.04 mm

Data collection

Bruker SMART CCD 1K diffractometer	3738 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.051
Graphite monochromator	θmax = 30.3°, θmin = 2.3°
ω–scan	h = −12→13
11953 measured reflections	k = −20→17
5647 independent reflections	l = −12→12

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	All H-atom parameters refined
wR(F^2) = 0.084	w = 1/[σ^2(Fo^2) + (0.034P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max < 0.001
5647 reflections	Δρmax = 0.15 e Å^−3
393 parameters	Δρmin = −0.22 e Å^−3
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 1.0 (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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
F1	0.62539 (16)	0.03015 (10)	0.25394 (15)	0.0418 (4)
F2	0.86380 (16)	0.01065 (10)	0.39734 (15)	0.0474 (4)
F3	0.09259 (16)	−0.01905 (10)	−0.28357 (15)	0.0429 (4)
F4	0.31949 (17)	−0.07215 (10)	−0.26885 (15)	0.0458 (4)
O1	0.58366 (17)	0.17844 (11)	0.01546 (16)	0.0304 (4)
O2	0.08026 (16)	0.06551 (10)	0.00394 (16)	0.0323 (4)
N1	0.7615 (2)	0.11682 (13)	−0.0752 (2)	0.0281 (4)
N2	0.2897 (2)	0.15807 (13)	0.0464 (2)	0.0297 (5)
C1	0.7271 (2)	0.23260 (15)	−0.2767 (2)	0.0243 (5)
C2	0.6215 (3)	0.30311 (17)	−0.3392 (3)	0.0347 (6)
C3	0.6697 (3)	0.38934 (18)	−0.3742 (3)	0.0418 (6)
C4	0.8227 (3)	0.40720 (19)	−0.3474 (3)	0.0383 (6)
C5	0.9285 (3)	0.33740 (17)	−0.2860 (3)	0.0325 (5)
C6	0.8821 (3)	0.25057 (16)	−0.2524 (2)	0.0284 (5)
C7	0.6765 (3)	0.13861 (16)	−0.2341 (2)	0.0265 (5)
C8	0.6945 (3)	0.05950 (18)	−0.3362 (3)	0.0352 (6)
C9	0.7113 (2)	0.14259 (15)	0.0375 (2)	0.0238 (5)
C10	0.8187 (3)	0.12467 (17)	0.1938 (2)	0.0303 (5)
C11	0.7812 (3)	0.17008 (19)	0.3279 (3)	0.0383 (6)
C12	0.7657 (2)	0.07081 (17)	0.3017 (2)	0.0302 (5)
C21	0.2263 (2)	0.23036 (15)	0.2604 (2)	0.0279 (5)
C22	0.2869 (3)	0.15399 (17)	0.3511 (3)	0.0329 (5)
C23	0.2774 (3)	0.14595 (19)	0.4957 (3)	0.0382 (6)
C24	0.2075 (3)	0.21638 (18)	0.5516 (3)	0.0418 (7)
C25	0.1485 (3)	0.29374 (19)	0.4625 (3)	0.0430 (7)
C26	0.1568 (3)	0.30095 (17)	0.3182 (3)	0.0363 (6)
C27	0.2263 (3)	0.24080 (16)	0.0975 (3)	0.0313 (5)
C28	0.3135 (4)	0.3266 (2)	0.0746 (4)	0.0447 (7)
C29	0.2132 (3)	0.07792 (16)	0.0046 (2)	0.0265 (5)
C30	0.3009 (3)	0.00220 (15)	−0.0419 (2)	0.0283 (5)
C31	0.2391 (3)	−0.09912 (17)	−0.0495 (3)	0.0347 (6)
C32	0.2288 (3)	−0.04759 (16)	−0.1862 (2)	0.0327 (6)
H1N	0.846 (3)	0.0975 (16)	−0.058 (2)	0.027 (7)*
H2	0.513 (3)	0.2879 (17)	−0.357 (3)	0.042 (7)*
H3	0.596 (3)	0.4392 (19)	−0.419 (3)	0.054 (8)*
H4	0.852 (3)	0.467 (2)	−0.363 (3)	0.058 (8)*
H5	1.032 (3)	0.3490 (19)	−0.266 (3)	0.049 (8)*
H6	0.956 (3)	0.1994 (16)	−0.210 (2)	0.032 (6)*
H7	0.574 (2)	0.1453 (14)	−0.242 (2)	0.015 (5)*
H81	0.663 (3)	0.0009 (18)	−0.308 (2)	0.033 (6)*
H82	0.638 (3)	0.0739 (16)	−0.445 (3)	0.032 (6)*
H83	0.799 (3)	0.0540 (19)	−0.329 (3)	0.056 (8)*
H10	0.916 (3)	0.1185 (16)	0.204 (2)	0.029 (6)*
H111	0.863 (3)	0.1903 (16)	0.415 (3)	0.030 (6)*
H112	0.691 (3)	0.206 (2)	0.298 (3)	0.060 (9)*
H2N	0.374 (3)	0.1623 (17)	0.036 (3)	0.034 (7)*
H22	0.330 (3)	0.1057 (16)	0.308 (3)	0.033 (6)*
H23	0.311 (3)	0.0875 (18)	0.554 (3)	0.037 (7)*
H24	0.208 (3)	0.2097 (17)	0.649 (3)	0.039 (7)*
H25	0.099 (3)	0.3375 (18)	0.497 (3)	0.040 (7)*
H26	0.117 (3)	0.3559 (19)	0.258 (3)	0.038 (7)*
H27	0.115 (3)	0.2499 (16)	0.028 (3)	0.034 (6)*
H281	0.306 (3)	0.3286 (19)	−0.037 (3)	0.055 (8)*
H282	0.415 (3)	0.3261 (18)	0.145 (3)	0.037 (7)*
H283	0.269 (3)	0.383 (2)	0.094 (3)	0.052 (8)*
H30	0.410 (3)	0.0101 (16)	−0.011 (2)	0.035 (6)*
H311	0.142 (3)	−0.1015 (17)	−0.018 (3)	0.048 (7)*
H312	0.306 (3)	−0.145 (2)	−0.024 (3)	0.049 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0384 (8)	0.0488 (9)	0.0399 (8)	−0.0131 (7)	0.0152 (6)	0.0077 (6)
F2	0.0520 (9)	0.0564 (10)	0.0349 (8)	0.0189 (8)	0.0161 (7)	0.0194 (7)
F3	0.0387 (8)	0.0478 (9)	0.0342 (7)	0.0038 (7)	0.0013 (6)	−0.0018 (6)
F4	0.0560 (10)	0.0491 (9)	0.0371 (8)	0.0113 (7)	0.0219 (7)	−0.0066 (7)
O1	0.0225 (8)	0.0381 (9)	0.0334 (9)	0.0051 (7)	0.0132 (7)	0.0042 (7)
O2	0.0214 (8)	0.0330 (9)	0.0428 (9)	0.0005 (7)	0.0108 (7)	−0.0046 (8)
N1	0.0208 (11)	0.0359 (12)	0.0298 (11)	0.0056 (9)	0.0115 (8)	0.0054 (8)
N2	0.0195 (10)	0.0283 (11)	0.0432 (12)	−0.0015 (9)	0.0129 (9)	−0.0088 (8)
C1	0.0277 (12)	0.0271 (12)	0.0194 (10)	0.0030 (10)	0.0094 (9)	−0.0003 (9)
C2	0.0281 (14)	0.0358 (15)	0.0374 (14)	0.0007 (11)	0.0072 (10)	0.0028 (11)
C3	0.0382 (15)	0.0328 (15)	0.0489 (16)	0.0067 (12)	0.0069 (12)	0.0094 (12)
C4	0.0409 (16)	0.0298 (15)	0.0442 (15)	−0.0035 (12)	0.0139 (12)	0.0075 (11)
C5	0.0312 (14)	0.0383 (15)	0.0301 (13)	−0.0030 (12)	0.0131 (11)	−0.0001 (10)
C6	0.0313 (14)	0.0291 (14)	0.0265 (12)	0.0033 (11)	0.0120 (10)	0.0037 (10)
C7	0.0227 (12)	0.0309 (13)	0.0266 (11)	0.0027 (10)	0.0092 (9)	0.0049 (10)
C8	0.0447 (16)	0.0275 (15)	0.0358 (15)	−0.0014 (12)	0.0165 (12)	0.0010 (12)
C9	0.0235 (12)	0.0243 (11)	0.0258 (11)	−0.0052 (9)	0.0110 (9)	0.0042 (9)
C10	0.0213 (13)	0.0431 (15)	0.0277 (12)	−0.0005 (11)	0.0096 (10)	0.0069 (10)
C11	0.0406 (16)	0.0437 (17)	0.0271 (13)	−0.0056 (13)	0.0065 (12)	−0.0035 (12)
C12	0.0254 (12)	0.0377 (14)	0.0274 (12)	0.0011 (11)	0.0085 (9)	0.0059 (11)
C21	0.0190 (11)	0.0244 (12)	0.0401 (13)	−0.0023 (10)	0.0094 (10)	−0.0077 (11)
C22	0.0258 (12)	0.0289 (14)	0.0414 (14)	0.0012 (10)	0.0076 (11)	−0.0102 (11)
C23	0.0342 (14)	0.0323 (14)	0.0428 (14)	−0.0025 (12)	0.0058 (12)	−0.0063 (12)
C24	0.0385 (15)	0.0460 (17)	0.0474 (16)	−0.0084 (12)	0.0227 (13)	−0.0101 (13)
C25	0.0456 (17)	0.0353 (15)	0.0589 (18)	0.0029 (13)	0.0319 (14)	−0.0070 (13)
C26	0.0340 (14)	0.0252 (14)	0.0541 (17)	0.0019 (11)	0.0205 (12)	−0.0023 (12)
C27	0.0252 (13)	0.0255 (13)	0.0428 (14)	0.0047 (10)	0.0105 (11)	−0.0061 (11)
C28	0.058 (2)	0.0294 (15)	0.0529 (19)	0.0002 (14)	0.0266 (16)	−0.0017 (13)
C29	0.0235 (11)	0.0273 (12)	0.0279 (11)	0.0025 (10)	0.0076 (9)	−0.0016 (9)
C30	0.0233 (12)	0.0268 (13)	0.0340 (13)	0.0030 (10)	0.0083 (10)	−0.0042 (10)
C31	0.0387 (15)	0.0253 (14)	0.0405 (15)	0.0045 (12)	0.0135 (12)	−0.0001 (11)
C32	0.0339 (14)	0.0321 (14)	0.0317 (13)	0.0061 (11)	0.0105 (11)	−0.0021 (10)

Geometric parameters (Å, º)

F1—C12	1.354 (3)	C10—C12	1.476 (3)
F2—C12	1.350 (3)	C10—C11	1.549 (3)
F3—C32	1.350 (3)	C10—H10	0.88 (2)
F4—C32	1.361 (2)	C11—C12	1.436 (4)
O1—C9	1.238 (2)	C11—H111	0.96 (2)
O2—C29	1.239 (2)	C11—H112	0.94 (3)
N1—C9	1.336 (3)	C21—C22	1.380 (3)
N1—C7	1.467 (3)	C21—C26	1.396 (3)
N1—H1N	0.79 (2)	C21—C27	1.531 (3)
N2—C29	1.333 (3)	C22—C23	1.390 (3)
N2—C27	1.466 (3)	C22—H22	0.95 (2)
N2—H2N	0.82 (2)	C23—C24	1.387 (3)
C1—C2	1.389 (3)	C23—H23	0.99 (3)
C1—C6	1.398 (3)	C24—C25	1.382 (4)
C1—C7	1.516 (3)	C24—H24	0.91 (2)
C2—C3	1.384 (3)	C25—C26	1.381 (4)
C2—H2	0.99 (3)	C25—H25	0.89 (3)
C3—C4	1.375 (4)	C26—H26	0.96 (3)
C3—H3	0.98 (3)	C27—C28	1.520 (4)
C4—C5	1.381 (4)	C27—H27	1.02 (2)
C4—H4	0.92 (3)	C28—H281	1.03 (3)
C5—C6	1.381 (3)	C28—H282	0.95 (3)
C5—H5	0.92 (3)	C28—H283	0.95 (3)
C6—H6	0.99 (2)	C29—C30	1.499 (3)
C7—C8	1.522 (3)	C30—C32	1.474 (3)
C7—H7	0.93 (2)	C30—C31	1.547 (3)
C8—H81	0.95 (2)	C30—H30	0.96 (2)
C8—H82	1.00 (2)	C31—C32	1.450 (3)
C8—H83	0.95 (3)	C31—H311	1.03 (3)
C9—C10	1.493 (3)	C31—H312	0.88 (3)
C9—N1—C7	122.16 (19)	F2—C12—C10	118.81 (19)
C9—N1—H1N	121.0 (16)	F1—C12—C10	119.73 (18)
C7—N1—H1N	115.8 (16)	C11—C12—C10	64.28 (17)
C29—N2—C27	123.78 (19)	C22—C21—C26	118.4 (2)
C29—N2—H2N	117.5 (17)	C22—C21—C27	123.70 (19)
C27—N2—H2N	118.6 (17)	C26—C21—C27	117.8 (2)
C2—C1—C6	118.4 (2)	C21—C22—C23	121.3 (2)
C2—C1—C7	121.10 (19)	C21—C22—H22	117.1 (13)
C6—C1—C7	120.54 (19)	C23—C22—H22	121.5 (13)
C3—C2—C1	120.5 (2)	C24—C23—C22	119.6 (3)
C3—C2—H2	123.1 (14)	C24—C23—H23	120.4 (13)
C1—C2—H2	116.4 (14)	C22—C23—H23	119.7 (13)
C4—C3—C2	120.9 (3)	C25—C24—C23	119.4 (2)
C4—C3—H3	118.2 (15)	C25—C24—H24	123.7 (16)
C2—C3—H3	120.9 (15)	C23—C24—H24	116.8 (16)
C3—C4—C5	119.1 (2)	C26—C25—C24	120.7 (2)
C3—C4—H4	119.0 (17)	C26—C25—H25	120.0 (16)
C5—C4—H4	121.7 (17)	C24—C25—H25	119.2 (16)
C4—C5—C6	120.8 (2)	C25—C26—C21	120.4 (2)
C4—C5—H5	119.8 (17)	C25—C26—H26	120.0 (14)
C6—C5—H5	119.4 (17)	C21—C26—H26	119.5 (14)
C5—C6—C1	120.4 (2)	N2—C27—C28	108.37 (19)
C5—C6—H6	121.9 (13)	N2—C27—C21	112.17 (19)
C1—C6—H6	117.7 (13)	C28—C27—C21	113.2 (2)
N1—C7—C1	110.21 (18)	N2—C27—H27	108.4 (12)
N1—C7—C8	110.21 (19)	C28—C27—H27	105.8 (13)
C1—C7—C8	112.56 (17)	C21—C27—H27	108.6 (12)
N1—C7—H7	107.0 (11)	C27—C28—H281	107.7 (16)
C1—C7—H7	106.4 (12)	C27—C28—H282	110.1 (15)
C8—C7—H7	110.2 (12)	H281—C28—H282	115 (2)
C7—C8—H81	111.6 (13)	C27—C28—H283	111.8 (17)
C7—C8—H82	111.0 (13)	H281—C28—H283	107 (2)
H81—C8—H82	111.0 (19)	H282—C28—H283	105 (2)
C7—C8—H83	109.7 (16)	O2—C29—N2	123.5 (2)
H81—C8—H83	108 (2)	O2—C29—C30	121.7 (2)
H82—C8—H83	105 (2)	N2—C29—C30	114.75 (19)
O1—C9—N1	122.85 (19)	C32—C30—C29	119.3 (2)
O1—C9—C10	121.45 (18)	C32—C30—C31	57.31 (15)
N1—C9—C10	115.70 (19)	C29—C30—C31	117.4 (2)
C12—C10—C9	119.69 (19)	C32—C30—H30	116.1 (13)
C12—C10—C11	56.63 (16)	C29—C30—H30	116.4 (13)
C9—C10—C11	117.8 (2)	C31—C30—H30	117.3 (14)
C12—C10—H10	115.8 (15)	C32—C31—C30	58.81 (16)
C9—C10—H10	116.7 (14)	C32—C31—H311	117.2 (14)
C11—C10—H10	116.8 (14)	C30—C31—H311	111.1 (14)
C12—C11—C10	59.09 (16)	C32—C31—H312	117.0 (18)
C12—C11—H111	116.7 (13)	C30—C31—H312	117.8 (19)
C10—C11—H111	119.5 (13)	H311—C31—H312	120 (2)
C12—C11—H112	117.1 (17)	F3—C32—F4	107.82 (17)
C10—C11—H112	113.6 (17)	F3—C32—C31	121.5 (2)
H111—C11—H112	118 (2)	F4—C32—C31	119.8 (2)
F2—C12—F1	107.82 (18)	F3—C32—C30	120.68 (19)
F2—C12—C11	120.5 (2)	F4—C32—C30	117.9 (2)
F1—C12—C11	120.6 (2)	C31—C32—C30	63.88 (16)
C6—C1—C2—C3	−1.0 (3)	C26—C21—C22—C23	1.1 (3)
C7—C1—C2—C3	178.5 (2)	C27—C21—C22—C23	−176.9 (2)
C1—C2—C3—C4	−0.3 (4)	C21—C22—C23—C24	−0.8 (4)
C2—C3—C4—C5	0.6 (4)	C22—C23—C24—C25	−0.1 (4)
C3—C4—C5—C6	0.3 (4)	C23—C24—C25—C26	0.8 (4)
C4—C5—C6—C1	−1.6 (3)	C24—C25—C26—C21	−0.6 (4)
C2—C1—C6—C5	1.9 (3)	C22—C21—C26—C25	−0.4 (3)
C7—C1—C6—C5	−177.56 (19)	C27—C21—C26—C25	177.7 (2)
C9—N1—C7—C1	89.8 (2)	C29—N2—C27—C28	−157.5 (2)
C9—N1—C7—C8	−145.3 (2)	C29—N2—C27—C21	76.8 (3)
C2—C1—C7—N1	−125.6 (2)	C22—C21—C27—N2	3.4 (3)
C6—C1—C7—N1	53.8 (2)	C26—C21—C27—N2	−174.6 (2)
C2—C1—C7—C8	110.9 (2)	C22—C21—C27—C28	−119.6 (3)
C6—C1—C7—C8	−69.7 (3)	C26—C21—C27—C28	62.4 (3)
C7—N1—C9—O1	7.1 (3)	C27—N2—C29—O2	0.4 (3)
C7—N1—C9—C10	−173.47 (19)	C27—N2—C29—C30	−179.36 (19)
O1—C9—C10—C12	53.3 (3)	O2—C29—C30—C32	50.0 (3)
N1—C9—C10—C12	−126.2 (2)	N2—C29—C30—C32	−130.3 (2)
O1—C9—C10—C11	−12.2 (3)	O2—C29—C30—C31	−16.0 (3)
N1—C9—C10—C11	168.3 (2)	N2—C29—C30—C31	163.7 (2)
C9—C10—C11—C12	108.8 (2)	C29—C30—C31—C32	108.8 (2)
C10—C11—C12—F2	109.7 (2)	C30—C31—C32—F3	−111.5 (2)
C10—C11—C12—F1	−110.8 (2)	C30—C31—C32—F4	108.6 (2)
C9—C10—C12—F2	142.3 (2)	C29—C30—C32—F3	7.2 (3)
C11—C10—C12—F2	−112.2 (3)	C31—C30—C32—F3	112.7 (2)
C9—C10—C12—F1	6.6 (3)	C29—C30—C32—F4	143.0 (2)
C11—C10—C12—F1	112.1 (3)	C31—C30—C32—F4	−111.6 (2)
C9—C10—C12—C11	−105.5 (3)	C29—C30—C32—C31	−105.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2^i	0.79 (2)	2.10 (2)	2.884 (2)	171 (2)
N2—H2N···O1	0.82 (2)	2.02 (3)	2.840 (2)	177 (2)

Symmetry code: (i) x+1, y, z.