Formation of isostructural solid solutions in 2,6-disubstituted N-phenylformamides and N-phenylthioamides

In order to investigate possible isostructural solid solutions of disubstituted N-phenylformamides and thioamides, we have studied the re-crystallization of pairs of compounds selected from 2,6-difluoro-N-phenylformamide (I), 2,6-dichloro-N-phenylformamide (II), 2,6-dimethyl-N-phenylformamide (III), 2,6-dichloro-N-phenylthioamide (IV), 2,6-dimethyl-N-phenylthioamide (V), 2,6-diisopropyl-N-phenylformamide (VI) and 2,6-diisopropyl-N-phenylthioamide (VII). For single-component 2,6-disubstituted-N-phenylformamides only the trans form occurs in the pure crystal, while for thioamides the cis form occurs, with only one exception. By forming solid solutions of pairs of these molecules the resulting structures all adopt similar N—H...O/S chains in the crystals. Solid solutions (1), (2) and (3), resulting from the mixing of (I) and (II), (II) and (III), and (IV) and (V), respectively, are all isostructural with each other (space group Pbca). Only co-crystal (1) is isostructural to both starting materials, while (2) is isostructural to only one of the starting pair, (II). Solid solution (3), which adopts the same Pbca structure as (1) and (2), is different to the monoclinic structures of both the reactants. Solid solution (4) is monoclinic, with similar hydrogen-bonded chains, and isostructural to the two components, resulting from the composition from the mixing of (VI) and (VII). Isostructural indices were used to quantify crystal-packing similarities and differences. Occupancy factors of the reactants in each co-crystal differ widely.

Computing details

For all compounds, data collection: Bruker SMART, Bruker (1998); cell refinement: Bruker SAINT+, Bruker (1999); data reduction: Bruker SAINT+; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999) and PLATON (Spek, 2009).

Figures

(1) (N-(2,6-difluorophenyl)formamide).(N-(2,6-dichlorophenyl)formamide) 0.73:0.27

Crystal data

C7H5Cl1.46F0.54NO	F(000) = 733.2
Mr = 181.07	Dx = 1.605 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5727 reflections
a = 8.5220 (2) Å	θ = 2.9–28.4°
b = 12.2910 (3) Å	µ = 0.61 mm^−1
c = 14.3090 (4) Å	T = 173 K
V = 1498.78 (7) Å^3	Block, colourless
Z = 8	0.45 × 0.19 × 0.18 mm

Data collection

Bruker SMART 1K CCD area detector diffractometer	1706 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
ω scans	θmax = 28°, θmin = 2.9°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −10→11
Tmin = 0.765, Tmax = 0.895	k = −16→15
17793 measured reflections	l = −18→18
1811 independent reflections

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.25	w = 1/[σ^2(Fo^2) + (0.0212P)^2 + 1.2505P] where P = (Fo^2 + 2Fc^2)/3
1811 reflections	(Δ/σ)max < 0.001
122 parameters	Δρmax = 0.22 e Å^−3
26 restraints	Δρmin = −0.22 e Å^−3

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996).

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	Occ. (<1)
C1	0.55412 (18)	0.41372 (14)	0.65058 (12)	0.0238 (4)
C2	0.56802 (18)	0.36432 (14)	0.56340 (13)	0.0264 (4)
C3	0.6658 (2)	0.40402 (18)	0.49453 (14)	0.0350 (5)
H3	0.6718	0.369	0.4354	0.042*
C4	0.7549 (3)	0.4955 (2)	0.51292 (15)	0.0392 (5)
H4	0.823	0.5235	0.4662	0.047*
C5	0.7456 (2)	0.54661 (18)	0.59882 (15)	0.0368 (5)
H5	0.8084	0.6087	0.6116	0.044*
C6	0.6446 (2)	0.50675 (16)	0.66595 (13)	0.0294 (4)
C7	0.4956 (2)	0.33346 (17)	0.80107 (13)	0.0295 (4)
H7	0.4162	0.3066	0.8416	0.035*
O1	0.63083 (16)	0.32872 (14)	0.82907 (10)	0.0367 (4)
Cl1	0.45573 (16)	0.25127 (11)	0.53968 (7)	0.0273 (2)	0.728 (4)
Cl2	0.62585 (16)	0.57954 (10)	0.76865 (9)	0.0347 (3)	0.728 (4)
F1	0.4829 (10)	0.2728 (5)	0.5474 (6)	0.062 (4)	0.272 (4)
F2	0.6341 (11)	0.5535 (7)	0.7512 (4)	0.065 (4)	0.272 (4)
N1	0.44897 (18)	0.37314 (14)	0.71833 (11)	0.0263 (3)
H1	0.351 (3)	0.3664 (19)	0.7027 (16)	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0172 (7)	0.0292 (9)	0.0249 (8)	0.0031 (7)	−0.0025 (6)	0.0017 (7)
C2	0.0212 (8)	0.0301 (9)	0.0280 (9)	0.0028 (7)	−0.0026 (7)	0.0008 (7)
C3	0.0305 (10)	0.0492 (12)	0.0252 (9)	0.0062 (9)	0.0015 (8)	0.0038 (8)
C4	0.0293 (9)	0.0522 (13)	0.0362 (10)	−0.0005 (9)	0.0023 (9)	0.0165 (10)
C5	0.0283 (9)	0.0368 (11)	0.0453 (11)	−0.0060 (8)	−0.0062 (9)	0.0110 (9)
C6	0.0267 (9)	0.0311 (9)	0.0303 (9)	0.0009 (7)	−0.0052 (7)	0.0017 (8)
C7	0.0218 (9)	0.0407 (11)	0.0262 (9)	−0.0048 (8)	0.0024 (7)	−0.0007 (8)
O1	0.0210 (6)	0.0572 (10)	0.0318 (7)	−0.0045 (6)	−0.0021 (5)	0.0101 (7)
Cl1	0.0287 (4)	0.0277 (4)	0.0255 (4)	−0.0023 (4)	−0.0007 (3)	−0.0052 (3)
Cl2	0.0423 (5)	0.0302 (4)	0.0317 (5)	−0.0033 (3)	−0.0041 (3)	−0.0080 (4)
F1	0.056 (6)	0.062 (7)	0.068 (6)	−0.006 (4)	−0.013 (4)	−0.010 (4)
F2	0.054 (4)	0.084 (8)	0.057 (5)	0.007 (4)	0.002 (3)	−0.032 (4)
N1	0.0162 (7)	0.0373 (9)	0.0255 (7)	−0.0017 (6)	−0.0005 (6)	−0.0026 (6)

Geometric parameters (Å, º)

C1—C2	1.392 (2)	C4—H4	0.95
C1—C6	1.396 (3)	C5—C6	1.380 (3)
C1—N1	1.411 (2)	C5—H5	0.95
C2—F1	1.358 (5)	C6—F2	1.351 (5)
C2—C3	1.380 (3)	C6—Cl2	1.728 (2)
C2—Cl1	1.721 (2)	C7—O1	1.222 (2)
C3—C4	1.382 (3)	C7—N1	1.341 (2)
C3—H3	0.95	C7—H7	0.95
C4—C5	1.382 (3)	N1—H1	0.87 (3)
C2—C1—C6	116.82 (17)	C6—C5—C4	119.6 (2)
C2—C1—N1	121.02 (16)	C6—C5—H5	120.2
C6—C1—N1	122.12 (16)	C4—C5—H5	120.2
F1—C2—C3	119.7 (4)	F2—C6—C5	121.2 (4)
F1—C2—C1	117.8 (4)	F2—C6—C1	117.0 (4)
C3—C2—C1	122.48 (18)	C5—C6—C1	121.70 (18)
C3—C2—Cl1	118.72 (16)	C5—C6—Cl2	117.76 (16)
C1—C2—Cl1	118.78 (15)	C1—C6—Cl2	120.47 (15)
C2—C3—C4	118.92 (19)	O1—C7—N1	125.91 (18)
C2—C3—H3	120.5	O1—C7—H7	117
C4—C3—H3	120.5	N1—C7—H7	117
C3—C4—C5	120.48 (19)	C7—N1—C1	123.17 (15)
C3—C4—H4	119.8	C7—N1—H1	118.5 (15)
C5—C4—H4	119.8	C1—N1—H1	117.9 (15)
C6—C1—C2—F1	179.1 (5)	C4—C5—C6—C1	1.9 (3)
N1—C1—C2—F1	−3.2 (5)	C4—C5—C6—Cl2	−175.03 (17)
C6—C1—C2—C3	0.03 (16)	C2—C1—C6—F2	−178.5 (5)
N1—C1—C2—C3	177.82 (16)	N1—C1—C6—F2	3.7 (5)
C6—C1—C2—Cl1	−178.47 (14)	C2—C1—C6—C5	−1.4 (2)
N1—C1—C2—Cl1	−0.69 (18)	N1—C1—C6—C5	−179.16 (17)
F1—C2—C3—C4	−178.2 (5)	C2—C1—C6—Cl2	175.49 (12)
C1—C2—C3—C4	0.77 (19)	N1—C1—C6—Cl2	−2.3 (2)
Cl1—C2—C3—C4	179.27 (16)	O1—C7—N1—C1	1.3 (3)
C2—C3—C4—C5	−0.2 (3)	C2—C1—N1—C7	116.98 (18)
C3—C4—C5—C6	−1.1 (3)	C6—C1—N1—C7	−65.4 (2)
C4—C5—C6—F2	178.9 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.87 (3)	1.98 (3)	2.848 (2)	172 (2)
C4—H4···O1^ii	0.95	2.70	3.540 (3)	148

Symmetry codes: (i) x−1/2, y, −z+3/2; (ii) −x+3/2, −y+1, z−1/2.

(2) (N-(2,6-dichlorophenyl)formamide).(N-(2,6-dimethylphenyl)formamide) 0.48:0.52

Crystal data

C8.03H8.10Cl0.97NO	F(000) = 702.0
Mr = 168.95	Dx = 1.395 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1886 reflections
a = 8.5073 (12) Å	θ = 2.8–24.7°
b = 13.093 (2) Å	µ = 0.40 mm^−1
c = 14.448 (2) Å	T = 293 K
V = 1609.3 (4) Å^3	Block, colourless
Z = 8	0.36 × 0.25 × 0.15 mm

Data collection

Bruker SMART 1K CCD area detector diffractometer	972 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
ω scans	θmax = 25.5°, θmin = 2.8°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −3→10
Tmin = 0.89, Tmax = 0.94	k = −15→15
7672 measured reflections	l = −17→17
1475 independent reflections

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.154	H atoms treated by a mixture of independent and constrained refinement
S = 0.86	w = 1/[σ^2(Fo^2) + (0.0849P)^2 + 1.8237P] where P = (Fo^2 + 2Fc^2)/3
1475 reflections	(Δ/σ)max < 0.001
124 parameters	Δρmax = 0.16 e Å^−3
26 restraints	Δρmin = −0.20 e Å^−3

Special details

Experimental. absorption corrections were made using the program SADABS (Sheldrick, 1996).

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	Occ. (<1)
C1	0.4461 (3)	0.4211 (2)	0.64854 (18)	0.0422 (7)
C2	0.3610 (3)	0.5098 (2)	0.66262 (19)	0.0504 (8)
C3	0.2593 (3)	0.5452 (3)	0.5950 (2)	0.0656 (10)
H3	0.2015	0.6045	0.6049	0.079*
C4	0.2440 (4)	0.4924 (3)	0.5131 (2)	0.0707 (11)
H4	0.1753	0.5161	0.4679	0.085*
C5	0.3294 (4)	0.4051 (3)	0.4977 (2)	0.0626 (10)
H5	0.32	0.3707	0.4416	0.075*
C6	0.4295 (3)	0.3681 (2)	0.5655 (2)	0.0472 (8)
C7	0.5081 (3)	0.3470 (3)	0.7984 (2)	0.0529 (8)
H7	0.5873	0.3225	0.8368	0.063*
N1	0.5513 (3)	0.3835 (2)	0.71673 (17)	0.0472 (7)
H1	0.645 (4)	0.376 (2)	0.700 (2)	0.057*
O1	0.3740 (2)	0.3425 (2)	0.82761 (15)	0.0710 (8)
Cl1	0.3873 (6)	0.5805 (3)	0.7605 (3)	0.0717 (14)	0.484 (6)
Cl2	0.5368 (4)	0.2580 (3)	0.5438 (3)	0.0604 (10)	0.484 (6)
C8	0.3797 (18)	0.5706 (11)	0.7505 (6)	0.075 (7)	0.516 (6)
H8A	0.4893	0.5827	0.7619	0.113*	0.516 (6)
H8B	0.3355	0.5332	0.8014	0.113*	0.516 (6)
H8C	0.3261	0.6348	0.7443	0.113*	0.516 (6)
C9	0.5223 (14)	0.2716 (6)	0.5499 (11)	0.085 (8)	0.516 (6)
H9A	0.5124	0.228	0.6031	0.127*	0.516 (6)
H9B	0.631	0.2884	0.5406	0.127*	0.516 (6)
H9C	0.4826	0.2368	0.4963	0.127*	0.516 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0314 (13)	0.0570 (18)	0.0382 (15)	−0.0030 (13)	0.0032 (11)	0.0049 (13)
C2	0.0417 (15)	0.0596 (19)	0.0500 (17)	−0.0023 (14)	0.0051 (13)	0.0079 (14)
C3	0.0507 (18)	0.075 (2)	0.071 (2)	0.0102 (17)	0.0103 (18)	0.028 (2)
C4	0.0510 (18)	0.105 (3)	0.056 (2)	−0.003 (2)	−0.0088 (17)	0.033 (2)
C5	0.0517 (17)	0.093 (3)	0.0432 (17)	−0.0184 (19)	−0.0058 (15)	0.0094 (18)
C6	0.0411 (15)	0.0582 (19)	0.0422 (16)	−0.0113 (14)	0.0031 (13)	0.0028 (14)
C7	0.0403 (15)	0.075 (2)	0.0435 (17)	0.0089 (14)	−0.0066 (14)	0.0028 (15)
N1	0.0316 (11)	0.0666 (17)	0.0434 (14)	0.0028 (12)	0.0003 (11)	−0.0007 (12)
O1	0.0417 (12)	0.116 (2)	0.0559 (14)	0.0112 (12)	0.0059 (10)	0.0242 (13)
Cl1	0.083 (3)	0.068 (2)	0.064 (2)	0.012 (2)	0.0043 (19)	−0.0125 (16)
Cl2	0.0648 (17)	0.0609 (17)	0.055 (2)	−0.0034 (14)	0.0019 (14)	−0.0089 (14)
C8	0.072 (11)	0.059 (9)	0.095 (13)	0.003 (7)	0.017 (8)	−0.037 (8)
C9	0.114 (14)	0.080 (12)	0.060 (10)	−0.019 (8)	0.026 (8)	−0.026 (7)

Geometric parameters (Å, º)

C1—C2	1.384 (4)	C6—C9	1.507 (5)
C1—C6	1.394 (4)	C6—Cl2	1.735 (5)
C1—N1	1.419 (4)	C7—O1	1.218 (4)
C2—C3	1.385 (4)	C7—N1	1.325 (4)
C2—C8	1.507 (5)	C7—H7	0.93
C2—Cl1	1.705 (5)	N1—H1	0.84 (4)
C3—C4	1.376 (5)	C8—H8A	0.96
C3—H3	0.93	C8—H8B	0.96
C4—C5	1.373 (5)	C8—H8C	0.96
C4—H4	0.93	C9—H9A	0.96
C5—C6	1.385 (4)	C9—H9B	0.96
C5—H5	0.93	C9—H9C	0.96
C2—C1—C6	119.4 (3)	C5—C6—Cl2	119.1 (3)
C2—C1—N1	121.2 (3)	C1—C6—Cl2	121.1 (3)
C6—C1—N1	119.3 (3)	O1—C7—N1	125.9 (3)
C1—C2—C3	120.2 (3)	O1—C7—H7	117.1
C1—C2—C8	120.8 (7)	N1—C7—H7	117.1
C3—C2—C8	118.9 (7)	C7—N1—C1	124.6 (2)
C1—C2—Cl1	120.6 (3)	C7—N1—H1	119 (2)
C3—C2—Cl1	119.1 (3)	C1—N1—H1	116 (2)
C4—C3—C2	119.9 (3)	C2—C8—H8A	109.5
C4—C3—H3	120.1	C2—C8—H8B	109.5
C2—C3—H3	120.1	H8A—C8—H8B	109.5
C5—C4—C3	120.5 (3)	C2—C8—H8C	109.5
C5—C4—H4	119.7	H8A—C8—H8C	109.5
C3—C4—H4	119.7	H8B—C8—H8C	109.5
C4—C5—C6	120.1 (3)	C6—C9—H9A	109.5
C4—C5—H5	119.9	C6—C9—H9B	109.5
C6—C5—H5	119.9	H9A—C9—H9B	109.5
C5—C6—C1	119.8 (3)	C6—C9—H9C	109.5
C5—C6—C9	120.7 (7)	H9A—C9—H9C	109.5
C1—C6—C9	119.5 (7)	H9B—C9—H9C	109.5
C6—C1—C2—C3	0.5 (2)	C4—C5—C6—C9	179.2 (6)
N1—C1—C2—C3	179.8 (2)	C4—C5—C6—Cl2	−179.6 (3)
C6—C1—C2—C8	−178.2 (6)	C2—C1—C6—C5	0.6 (3)
N1—C1—C2—C8	1.1 (6)	N1—C1—C6—C5	−178.7 (2)
C6—C1—C2—Cl1	−176.1 (3)	C2—C1—C6—C9	179.9 (5)
N1—C1—C2—Cl1	3.2 (3)	N1—C1—C6—C9	0.5 (6)
C1—C2—C3—C4	−0.6 (2)	C2—C1—C6—Cl2	178.6 (2)
C8—C2—C3—C4	178.1 (6)	N1—C1—C6—Cl2	−0.7 (3)
Cl1—C2—C3—C4	176.0 (3)	O1—C7—N1—C1	−1.9 (5)
C2—C3—C4—C5	−0.3 (4)	C2—C1—N1—C7	67.7 (4)
C3—C4—C5—C6	1.4 (5)	C6—C1—N1—C7	−113.0 (3)
C4—C5—C6—C1	−1.5 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.84 (4)	2.03 (4)	2.870 (3)	172 (3)
C4—H4···O1^ii	0.93	2.78	3.586 (4)	146

Symmetry codes: (i) x+1/2, y, −z+3/2; (ii) −x+1/2, −y+1, z−1/2.

(3) (N-(2,6-dichlorophenyl)thioamide).(N-(2,6-dimethylphenyl)thioamide) 0.11:0.89

Crystal data

C8.78H10.35Cl0.22NS	F(000) = 718.0
Mr = 169.71	Dx = 1.275 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 8770 reflections
a = 9.2080 (1) Å	θ = 2.8–28.3°
b = 13.1420 (2) Å	µ = 0.37 mm^−1
c = 14.6170 (3) Å	T = 123 K
V = 1768.83 (5) Å^3	Block, colourless
Z = 8	0.37 × 0.17 × 0.14 mm

Data collection

Bruker SMART 1K CCD area detector diffractometer	1755 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
ω scans	θmax = 28.0°, θmin = 2.8°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −11→12
Tmin = 0.673, Tmax = 0.854	k = −17→17
21156 measured reflections	l = −19→17
2133 independent reflections

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0542P)^2 + 0.3573P] where P = (Fo^2 + 2Fc^2)/3
2133 reflections	(Δ/σ)max = 0.001
124 parameters	Δρmax = 0.35 e Å^−3
26 restraints	Δρmin = −0.23 e Å^−3

Special details

Experimental. absorption corrections were made using the program SADABS (Sheldrick, 1996).

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	Occ. (<1)
C1	0.55804 (13)	0.55512 (9)	0.64640 (9)	0.0252 (3)
C2	0.64515 (15)	0.46993 (10)	0.66053 (10)	0.0329 (3)
C3	0.75280 (16)	0.45029 (12)	0.59583 (12)	0.0439 (4)
H3	0.814	0.3927	0.6032	0.053*
C4	0.77186 (17)	0.51311 (14)	0.52130 (11)	0.0471 (4)
H4	0.8466	0.4987	0.4784	0.057*
C5	0.68401 (16)	0.59646 (12)	0.50818 (10)	0.0392 (4)
H5	0.6978	0.6387	0.4562	0.047*
C6	0.57488 (14)	0.61907 (10)	0.57098 (9)	0.0273 (3)
C7	0.46278 (13)	0.62695 (10)	0.78809 (9)	0.0253 (3)
H7	0.3771	0.6428	0.8214	0.03*
N1	0.44466 (11)	0.57881 (8)	0.71005 (8)	0.0253 (3)
H1	0.3577 (18)	0.5705 (12)	0.6904 (11)	0.03*
S1	0.61767 (3)	0.66288 (3)	0.83460 (2)	0.02916 (14)
C8	0.6217 (4)	0.4031 (3)	0.7421 (2)	0.0393 (9)	0.891 (2)
H8A	0.6959	0.3497	0.7432	0.059*	0.891 (2)
H8B	0.5252	0.3719	0.7385	0.059*	0.891 (2)
H8C	0.6286	0.444	0.798	0.059*	0.891 (2)
C9	0.4758 (5)	0.7093 (3)	0.5580 (3)	0.0376 (9)	0.891 (2)
H9A	0.5101	0.7502	0.5063	0.056*	0.891 (2)
H9B	0.4759	0.7509	0.6137	0.056*	0.891 (2)
H9C	0.3769	0.6854	0.5457	0.056*	0.891 (2)
Cl1	0.6193 (11)	0.3934 (6)	0.7553 (5)	0.053 (3)	0.109 (2)
Cl2	0.4636 (9)	0.7248 (5)	0.5563 (7)	0.036 (2)	0.109 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0192 (6)	0.0264 (6)	0.0301 (7)	−0.0056 (5)	−0.0032 (5)	−0.0057 (5)
C2	0.0268 (7)	0.0283 (7)	0.0437 (9)	−0.0022 (5)	−0.0100 (6)	−0.0113 (6)
C3	0.0326 (8)	0.0410 (8)	0.0580 (11)	0.0077 (6)	−0.0116 (7)	−0.0280 (8)
C4	0.0348 (8)	0.0667 (11)	0.0398 (9)	−0.0031 (8)	0.0037 (7)	−0.0309 (9)
C5	0.0363 (8)	0.0534 (9)	0.0279 (8)	−0.0109 (7)	0.0050 (6)	−0.0151 (7)
C6	0.0249 (6)	0.0321 (7)	0.0250 (7)	−0.0085 (5)	−0.0014 (5)	−0.0073 (6)
C7	0.0191 (6)	0.0288 (6)	0.0279 (7)	0.0043 (5)	0.0055 (5)	0.0104 (5)
N1	0.0146 (5)	0.0295 (6)	0.0317 (6)	−0.0040 (4)	−0.0016 (4)	0.0077 (5)
S1	0.0217 (2)	0.0388 (2)	0.0270 (2)	0.00552 (13)	−0.00093 (12)	−0.00606 (14)
C8	0.0338 (16)	0.0179 (13)	0.066 (2)	0.0010 (11)	−0.0140 (14)	0.0100 (13)
C9	0.052 (2)	0.0414 (16)	0.0198 (16)	−0.0185 (12)	0.0011 (13)	0.0060 (12)
Cl1	0.066 (5)	0.027 (3)	0.065 (4)	0.003 (3)	−0.020 (3)	0.016 (3)
Cl2	0.040 (3)	0.027 (2)	0.042 (4)	−0.006 (2)	−0.001 (3)	0.012 (2)

Geometric parameters (Å, º)

C1—C2	1.3926 (19)	C6—C9	1.508 (3)
C1—C6	1.3949 (19)	C6—Cl2	1.740 (4)
C1—N1	1.4326 (17)	C7—N1	1.3151 (18)
C2—C3	1.394 (2)	C7—S1	1.6490 (13)
C2—C8	1.497 (3)	C7—H7	0.95
C2—Cl1	1.729 (4)	N1—H1	0.858 (16)
C3—C4	1.378 (3)	C8—H8A	0.98
C3—H3	0.95	C8—H8B	0.98
C4—C5	1.375 (2)	C8—H8C	0.98
C4—H4	0.95	C9—H9A	0.98
C5—C6	1.3931 (19)	C9—H9B	0.98
C5—H5	0.95	C9—H9C	0.98
C2—C1—C6	122.52 (13)	C5—C6—C1	118.19 (13)
C2—C1—N1	119.87 (12)	C5—C6—C9	121.4 (2)
C6—C1—N1	117.60 (11)	C1—C6—C9	120.4 (2)
C1—C2—C3	117.24 (14)	C5—C6—Cl2	120.9 (3)
C1—C2—C8	120.4 (2)	C1—C6—Cl2	120.9 (3)
C3—C2—C8	122.3 (2)	N1—C7—S1	127.23 (10)
C1—C2—Cl1	120.5 (3)	N1—C7—H7	116.4
C3—C2—Cl1	122.3 (3)	S1—C7—H7	116.4
C4—C3—C2	121.06 (15)	C7—N1—C1	125.13 (10)
C4—C3—H3	119.5	C7—N1—H1	118.0 (11)
C2—C3—H3	119.5	C1—N1—H1	115.8 (11)
C5—C4—C3	120.83 (15)	C2—C8—H8A	109.5
C5—C4—H4	119.6	C2—C8—H8B	109.5
C3—C4—H4	119.6	C2—C8—H8C	109.5
C4—C5—C6	120.16 (15)	C6—C9—H9A	109.5
C4—C5—H5	119.9	C6—C9—H9B	109.5
C6—C5—H5	119.9	C6—C9—H9C	109.5
C6—C1—C2—C3	0.37 (13)	C4—C5—C6—C9	−179.4 (2)
N1—C1—C2—C3	179.43 (11)	C4—C5—C6—Cl2	179.4 (4)
C6—C1—C2—C8	−179.4 (2)	C2—C1—C6—C5	−0.44 (17)
N1—C1—C2—C8	−0.3 (2)	N1—C1—C6—C5	−179.51 (11)
C6—C1—C2—Cl1	180.0 (4)	C2—C1—C6—C9	178.9 (2)
N1—C1—C2—Cl1	−1.0 (4)	N1—C1—C6—C9	−0.2 (3)
C1—C2—C3—C4	0.20 (15)	C2—C1—C6—Cl2	−179.9 (4)
C8—C2—C3—C4	179.9 (2)	N1—C1—C6—Cl2	1.0 (4)
Cl1—C2—C3—C4	−179.4 (4)	S1—C7—N1—C1	−5.15 (19)
C2—C3—C4—C5	−0.7 (2)	C2—C1—N1—C7	81.77 (15)
C3—C4—C5—C6	0.6 (2)	C6—C1—N1—C7	−99.13 (15)
C4—C5—C6—C1	−0.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1^i	0.858 (16)	2.548 (17)	3.2730 (11)	142.9 (14)

Symmetry code: (i) x−1/2, y, −z+3/2.

(4) (N-(2,6-diisopropylphenyl)formamide). (N-(2,6-diisopropylphenyl)thioamide) 0.54:0.46

Crystal data

C13H19NO0.54S0.46	F(000) = 464
Mr = 213.32	Dx = 1.119 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 886 reflections
a = 9.022 (1) Å	θ = 2.6–24.7°
b = 9.0030 (9) Å	µ = 0.15 mm^−1
c = 16.0050 (16) Å	T = 173 K
β = 103.170 (5)°	Block, colourless
V = 1265.8 (2) Å^3	0.43 × 0.18 × 0.14 mm
Z = 4

Data collection

Bruker SMART 1K CCD area detector diffractometer	1775 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.095
ω scans	θmax = 28°, θmin = 2.3°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −8→11
Tmin = 0.940, Tmax = 0.980	k = −11→11
15410 measured reflections	l = −21→20
3055 independent reflections

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.200	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0912P)^2 + 0.2341P] where P = (Fo^2 + 2Fc^2)/3
3055 reflections	(Δ/σ)max = 0.005
144 parameters	Δρmax = 0.55 e Å^−3
4 restraints	Δρmin = −0.61 e Å^−3

Special details

Experimental. absorption corrections were made using the program SADABS (Sheldrick, 1996).

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	Occ. (<1)
C1	0.4452 (3)	0.6580 (2)	0.33206 (13)	0.0334 (5)
C2	0.5503 (2)	0.7077 (2)	0.40549 (13)	0.0324 (5)
C3	0.4944 (3)	0.7971 (2)	0.46274 (13)	0.0379 (6)
H3	0.5623	0.8322	0.5132	0.046*
C4	0.3418 (3)	0.8355 (2)	0.44724 (15)	0.0410 (6)
H4	0.3064	0.8972	0.4868	0.049*
C5	0.2408 (3)	0.7847 (2)	0.37475 (15)	0.0402 (6)
H5	0.1364	0.8113	0.3652	0.048*
C6	0.2898 (3)	0.6950 (2)	0.31531 (14)	0.0381 (5)
C7	0.5694 (3)	0.5958 (3)	0.21717 (15)	0.0580 (7)
H7	0.5947	0.5163	0.184	0.07*
C8	0.7169 (3)	0.6614 (3)	0.42630 (14)	0.0386 (5)
H8	0.737	0.6077	0.3753	0.046*
C9	0.1786 (3)	0.6403 (3)	0.23433 (17)	0.0546 (7)
H9	0.2146	0.5403	0.2203	0.066*
C10	0.8247 (3)	0.7948 (3)	0.44432 (19)	0.0565 (7)
H10A	0.9303	0.7598	0.4573	0.085*
H10B	0.8058	0.8505	0.4935	0.085*
H10C	0.807	0.8594	0.3938	0.085*
C11	0.7507 (3)	0.5547 (3)	0.5024 (2)	0.0687 (9)
H11A	0.8583	0.5262	0.5147	0.103*
H11B	0.6871	0.4659	0.4887	0.103*
H11C	0.7284	0.6037	0.5529	0.103*
C12	0.0164 (4)	0.6213 (4)	0.2460 (2)	0.0974 (13)
H12A	0.0171	0.5555	0.2948	0.146*
H12B	−0.0473	0.5778	0.1939	0.146*
H12C	−0.0247	0.7184	0.2567	0.146*
C13	0.1813 (4)	0.7421 (4)	0.15842 (18)	0.0696 (9)
H13A	0.1096	0.705	0.1072	0.104*
H13B	0.2841	0.744	0.148	0.104*
H13C	0.1518	0.8428	0.1713	0.104*
O1	0.6117 (5)	0.7179 (3)	0.2009 (3)	0.0324 (12)*	0.536 (6)
S1	0.6322 (3)	0.7584 (3)	0.19902 (13)	0.0522 (7)	0.464 (6)
N1	0.4957 (2)	0.5608 (2)	0.27287 (12)	0.0440 (5)
H1	0.471 (3)	0.469 (3)	0.2750 (16)	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0420 (13)	0.0245 (10)	0.0340 (11)	−0.0007 (9)	0.0096 (9)	−0.0021 (8)
C2	0.0407 (12)	0.0269 (10)	0.0303 (10)	−0.0033 (9)	0.0098 (9)	0.0013 (8)
C3	0.0512 (14)	0.0373 (12)	0.0275 (11)	−0.0042 (11)	0.0136 (10)	−0.0019 (9)
C4	0.0582 (15)	0.0306 (12)	0.0421 (13)	0.0011 (11)	0.0279 (11)	0.0017 (10)
C5	0.0399 (13)	0.0326 (12)	0.0520 (14)	0.0026 (10)	0.0185 (11)	0.0080 (10)
C6	0.0423 (13)	0.0272 (11)	0.0437 (12)	−0.0040 (10)	0.0073 (10)	0.0026 (9)
C7	0.0557 (16)	0.0728 (19)	0.0419 (13)	0.0153 (15)	0.0037 (12)	−0.0172 (14)
C8	0.0416 (13)	0.0425 (13)	0.0311 (11)	0.0019 (11)	0.0074 (9)	−0.0024 (9)
C9	0.0483 (16)	0.0427 (14)	0.0638 (17)	0.0010 (12)	−0.0063 (12)	−0.0115 (12)
C10	0.0435 (15)	0.0529 (16)	0.0699 (18)	−0.0066 (13)	0.0060 (13)	0.0079 (13)
C11	0.0613 (18)	0.0608 (18)	0.084 (2)	0.0162 (15)	0.0175 (15)	0.0348 (16)
C12	0.068 (2)	0.110 (3)	0.105 (3)	−0.050 (2)	0.001 (2)	−0.006 (2)
C13	0.0585 (18)	0.095 (2)	0.0464 (15)	0.0023 (17)	−0.0063 (13)	−0.0071 (16)
S1	0.0771 (14)	0.0321 (11)	0.0495 (10)	−0.0104 (9)	0.0190 (8)	0.0099 (8)
N1	0.0528 (13)	0.0393 (11)	0.0376 (11)	0.0082 (10)	0.0052 (9)	−0.0142 (9)

Geometric parameters (Å, º)

C1—C2	1.405 (3)	C8—H8	1
C1—C6	1.406 (3)	C9—C12	1.526 (4)
C1—N1	1.438 (3)	C9—C13	1.527 (4)
C2—C3	1.397 (3)	C9—H9	1
C2—C8	1.522 (3)	C10—H10A	0.98
C3—C4	1.386 (3)	C10—H10B	0.98
C3—H3	0.95	C10—H10C	0.98
C4—C5	1.380 (3)	C11—H11A	0.98
C4—H4	0.95	C11—H11B	0.98
C5—C6	1.394 (3)	C11—H11C	0.98
C5—H5	0.95	C12—H12A	0.98
C6—C9	1.528 (3)	C12—H12B	0.98
C7—O1	1.2111 (5)	C12—H12C	0.98
C7—N1	1.267 (3)	C13—H13A	0.98
C7—S1	1.6196 (2)	C13—H13B	0.98
C7—H7	0.95	C13—H13C	0.98
C8—C11	1.527 (3)	N1—H1	0.86 (3)
C8—C10	1.531 (3)
C2—C1—C6	122.55 (19)	C13—C9—C6	110.8 (2)
C2—C1—N1	119.34 (19)	C12—C9—H9	107.3
C6—C1—N1	118.06 (18)	C13—C9—H9	107.3
C3—C2—C1	117.1 (2)	C6—C9—H9	107.3
C3—C2—C8	120.02 (19)	C8—C10—H10A	109.5
C1—C2—C8	122.74 (18)	C8—C10—H10B	109.5
C4—C3—C2	121.2 (2)	H10A—C10—H10B	109.5
C4—C3—H3	119.4	C8—C10—H10C	109.5
C2—C3—H3	119.4	H10A—C10—H10C	109.5
C5—C4—C3	120.4 (2)	H10B—C10—H10C	109.5
C5—C4—H4	119.8	C8—C11—H11A	109.5
C3—C4—H4	119.8	C8—C11—H11B	109.5
C4—C5—C6	121.0 (2)	H11A—C11—H11B	109.5
C4—C5—H5	119.5	C8—C11—H11C	109.5
C6—C5—H5	119.5	H11A—C11—H11C	109.5
C5—C6—C1	117.6 (2)	H11B—C11—H11C	109.5
C5—C6—C9	121.1 (2)	C9—C12—H12A	109.5
C1—C6—C9	121.2 (2)	C9—C12—H12B	109.5
O1—C7—N1	128.2 (3)	H12A—C12—H12B	109.5
O1—C7—S1	2.5 (3)	C9—C12—H12C	109.5
N1—C7—S1	127.7 (2)	H12A—C12—H12C	109.5
O1—C7—H7	115.9	H12B—C12—H12C	109.5
N1—C7—H7	115.9	C9—C13—H13A	109.5
S1—C7—H7	116.3	C9—C13—H13B	109.5
C2—C8—C11	110.8 (2)	H13A—C13—H13B	109.5
C2—C8—C10	112.32 (19)	C9—C13—H13C	109.5
C11—C8—C10	109.9 (2)	H13A—C13—H13C	109.5
C2—C8—H8	107.9	H13B—C13—H13C	109.5
C11—C8—H8	107.9	C7—N1—C1	127.4 (2)
C10—C8—H8	107.9	C7—N1—H1	116.8 (18)
C12—C9—C13	110.7 (3)	C1—N1—H1	115.7 (18)
C12—C9—C6	113.3 (2)
C6—C1—C2—C3	0.0 (3)	N1—C1—C6—C9	−3.1 (3)
N1—C1—C2—C3	−177.52 (19)	C3—C2—C8—C11	68.1 (3)
C6—C1—C2—C8	176.67 (19)	C1—C2—C8—C11	−108.5 (3)
N1—C1—C2—C8	−0.8 (3)	C3—C2—C8—C10	−55.2 (3)
C1—C2—C3—C4	−0.3 (3)	C1—C2—C8—C10	128.2 (2)
C8—C2—C3—C4	−177.1 (2)	C5—C6—C9—C12	−29.6 (4)
C2—C3—C4—C5	0.6 (3)	C1—C6—C9—C12	151.1 (3)
C3—C4—C5—C6	−0.5 (3)	C5—C6—C9—C13	95.5 (3)
C4—C5—C6—C1	0.2 (3)	C1—C6—C9—C13	−83.8 (3)
C4—C5—C6—C9	−179.1 (2)	O1—C7—N1—C1	−0.9 (4)
C2—C1—C6—C5	0.1 (3)	S1—C7—N1—C1	2.2 (3)
N1—C1—C6—C5	177.6 (2)	C2—C1—N1—C7	−77.4 (3)
C2—C1—C6—C9	179.4 (2)	C6—C1—N1—C7	105.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1^i	0.86 (3)	2.19 (3)	3.030 (3)	165 (3)
N1—H1···O1^i	0.86 (3)	2.43 (3)	3.291 (4)	172 (2)

Symmetry code: (i) −x+1, y−1/2, −z+1/2.