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In the solid state, 4-methoxy-
N'-(2,2,2-trichloroethanimidoyl)benzene-1-carboximidamide, C
10H
10Cl
3N
3O, (I),
N'-(2,2,2-trichloroethanimidoyl)benzene-1-carboximidamide, C
9H
8Cl
3N
3, (II), 4-chloro-
N'-(2,2,2-trichloroethanimidoyl)benzene-1-carboximidamide, C
9H
7Cl
4N
3, (III), 4-bromo-
N'-(2,2,2-trichloroethanimidoyl)benzene-1-carboximidamide, C
9H
7BrCl
3N
3, (IV), and 4-trifluoromethyl-
N'-(2,2,2-trichloroethanimidoyl)benzene-1-carboximidamide, C
10H
7Cl
3F
3N
3, (V), display strong intramolecular N-H
N hydrogen bonding across the chelate ring and also intramolecular N-H
Cl contacts. Additional intermolecular hydrogen bonds link the molecules into chains, double chains or sheets in all cases except for compound (V). For compound (II), there are three independent molecules per asymmetric unit.
Supporting information
CCDC references: 842129; 842130; 842131; 842132; 842133
Compounds (I)–(V) were prepared using a modification of a literature procedure
(Peters & Schaefer, 1964) by addition of trichloroacetonitrile to the
corresponding para-substituted benzamidines in acetonitrile. Crystals
suitable for X-ray diffraction were grown by vacuum sublimation in a
three-zone tube furnace, or by slow cooling of acetonitrile solutions [m.p.
for (I) 377–379 K, for (II) 341–342 K, for (III) 384–386 K, for (IV)
371–372 K, and for (V) 369–370 K]. A full hemisphere of data was collected
for all five structures at low temperature (173 K) using molybdenum radiation.
C-bound H atoms were treated as riding, with C—H = 0.98 Å and
Uiso(H) = 1.5Ueq(C) for methyl H, and with C—H =
0.95–0.96 Å and Uiso(H) = 1.2Ueq(C) for all others.
[Please check added text] The three N-bound H-atom positions were refined
using a distance restraint of 0.88 Å and with Uiso(H) =
1.2Ueq(N).
For all compounds, data collection: APEX2 (Bruker, 2006); cell refinement: SAINT-Plus (Bruker, 2006); data reduction: SAINT-Plus (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
(I) 4-methoxy-
N'-(2,2,2-trichloroethanimidoyl)benzene-1-carboximidamide
top
Crystal data top
C10H10Cl3N3O | F(000) = 600 |
Mr = 294.56 | Dx = 1.607 Mg m−3 |
Monoclinic, P21/c | Melting point: 379 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 12.0988 (10) Å | Cell parameters from 5637 reflections |
b = 8.6425 (7) Å | θ = 2.9–27.6° |
c = 12.2023 (10) Å | µ = 0.74 mm−1 |
β = 107.445 (1)° | T = 173 K |
V = 1217.23 (17) Å3 | Plate, colourless |
Z = 4 | 0.21 × 0.19 × 0.07 mm |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 2812 independent reflections |
Radiation source: fine-focus sealed tube, Bruker D8 | 2448 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ϕ and ω scans | θmax = 27.5°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | h = −15→15 |
Tmin = 0.697, Tmax = 0.746 | k = −11→11 |
17246 measured reflections | l = −15→15 |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0268P)2 + 0.5682P] where P = (Fo2 + 2Fc2)/3 |
2812 reflections | (Δ/σ)max = 0.001 |
164 parameters | Δρmax = 0.30 e Å−3 |
3 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
C10H10Cl3N3O | V = 1217.23 (17) Å3 |
Mr = 294.56 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.0988 (10) Å | µ = 0.74 mm−1 |
b = 8.6425 (7) Å | T = 173 K |
c = 12.2023 (10) Å | 0.21 × 0.19 × 0.07 mm |
β = 107.445 (1)° | |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 2812 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | 2448 reflections with I > 2σ(I) |
Tmin = 0.697, Tmax = 0.746 | Rint = 0.026 |
17246 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | 3 restraints |
wR(F2) = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.30 e Å−3 |
2812 reflections | Δρmin = −0.25 e Å−3 |
164 parameters | |
Special details top
Experimental. A crystal coated in Paratone (TM) oil was mounted on the end of a thin glass
capillary and cooled in the gas stream of the diffractometer Kryoflex device. |
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 (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.22219 (3) | 1.12498 (4) | 0.29453 (3) | 0.02805 (10) | |
Cl2 | 0.45878 (3) | 1.21630 (5) | 0.34343 (3) | 0.03239 (10) | |
Cl3 | 0.40231 (4) | 0.89667 (4) | 0.36966 (3) | 0.03220 (10) | |
O1 | −0.16574 (9) | 0.52503 (12) | −0.16730 (9) | 0.0268 (2) | |
N1 | 0.27253 (13) | 0.97377 (17) | −0.07690 (11) | 0.0295 (3) | |
H1 | 0.2362 (15) | 0.973 (2) | −0.1487 (13) | 0.035* | |
H2 | 0.3350 (14) | 1.027 (2) | −0.0493 (16) | 0.035* | |
N2 | 0.25961 (11) | 0.93385 (14) | 0.11013 (10) | 0.0232 (3) | |
N3 | 0.42567 (13) | 1.07952 (18) | 0.11169 (12) | 0.0355 (3) | |
H3 | 0.4757 (15) | 1.138 (2) | 0.1582 (15) | 0.043* | |
C1 | 0.22335 (13) | 0.91356 (16) | −0.00248 (12) | 0.0220 (3) | |
C2 | 0.35160 (13) | 1.02903 (17) | 0.15842 (12) | 0.0228 (3) | |
C3 | 0.35881 (12) | 1.06573 (16) | 0.28524 (12) | 0.0217 (3) | |
C4 | 0.11884 (12) | 0.81590 (16) | −0.04816 (12) | 0.0211 (3) | |
C5 | 0.09763 (12) | 0.73382 (17) | −0.15131 (12) | 0.0229 (3) | |
H5 | 0.1487 | 0.7448 | −0.1967 | 0.027* | |
C6 | 0.00272 (13) | 0.63683 (17) | −0.18750 (12) | 0.0238 (3) | |
H6 | −0.0101 | 0.5797 | −0.2567 | 0.029* | |
C7 | −0.07419 (12) | 0.62242 (16) | −0.12296 (12) | 0.0215 (3) | |
C8 | −0.05565 (13) | 0.70580 (17) | −0.02167 (12) | 0.0246 (3) | |
H8 | −0.1087 | 0.6983 | 0.0219 | 0.029* | |
C9 | 0.04093 (13) | 0.79985 (17) | 0.01500 (12) | 0.0244 (3) | |
H9 | 0.0544 | 0.8550 | 0.0852 | 0.029* | |
C10 | −0.25077 (14) | 0.5113 (2) | −0.10765 (14) | 0.0320 (4) | |
H10A | −0.2133 | 0.4769 | −0.0287 | 0.048* | |
H10B | −0.3096 | 0.4355 | −0.1470 | 0.048* | |
H10C | −0.2876 | 0.6120 | −0.1065 | 0.048* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.02641 (18) | 0.03102 (19) | 0.02742 (19) | 0.00546 (15) | 0.00913 (15) | 0.00012 (15) |
Cl2 | 0.0339 (2) | 0.0366 (2) | 0.02458 (19) | −0.01100 (16) | 0.00560 (16) | −0.00661 (16) |
Cl3 | 0.0414 (2) | 0.0292 (2) | 0.02365 (19) | 0.01073 (16) | 0.00628 (16) | 0.00784 (15) |
O1 | 0.0279 (5) | 0.0322 (6) | 0.0203 (5) | −0.0050 (4) | 0.0071 (4) | −0.0013 (4) |
N1 | 0.0351 (7) | 0.0366 (7) | 0.0168 (6) | −0.0086 (6) | 0.0076 (6) | −0.0009 (6) |
N2 | 0.0273 (6) | 0.0247 (6) | 0.0170 (6) | −0.0024 (5) | 0.0054 (5) | 0.0004 (5) |
N3 | 0.0378 (8) | 0.0443 (8) | 0.0272 (7) | −0.0161 (7) | 0.0140 (6) | −0.0069 (6) |
C1 | 0.0268 (7) | 0.0197 (6) | 0.0198 (7) | 0.0025 (6) | 0.0071 (6) | 0.0012 (5) |
C2 | 0.0279 (7) | 0.0223 (7) | 0.0176 (7) | 0.0004 (6) | 0.0062 (6) | 0.0007 (5) |
C3 | 0.0228 (7) | 0.0218 (7) | 0.0188 (7) | 0.0009 (5) | 0.0038 (6) | 0.0023 (5) |
C4 | 0.0245 (7) | 0.0211 (7) | 0.0167 (7) | 0.0032 (5) | 0.0045 (6) | 0.0016 (5) |
C5 | 0.0253 (7) | 0.0269 (7) | 0.0174 (7) | 0.0026 (6) | 0.0077 (6) | 0.0004 (6) |
C6 | 0.0271 (7) | 0.0273 (7) | 0.0163 (7) | 0.0025 (6) | 0.0053 (6) | −0.0032 (6) |
C7 | 0.0219 (7) | 0.0224 (7) | 0.0181 (7) | 0.0025 (5) | 0.0026 (6) | 0.0035 (5) |
C8 | 0.0287 (7) | 0.0283 (7) | 0.0190 (7) | 0.0019 (6) | 0.0105 (6) | 0.0008 (6) |
C9 | 0.0308 (8) | 0.0258 (7) | 0.0168 (7) | 0.0012 (6) | 0.0076 (6) | −0.0017 (6) |
C10 | 0.0293 (8) | 0.0378 (9) | 0.0310 (8) | −0.0043 (7) | 0.0120 (7) | 0.0030 (7) |
Geometric parameters (Å, º) top
Cl1—C3 | 1.7663 (15) | C4—C9 | 1.392 (2) |
Cl2—C3 | 1.7736 (15) | C4—C5 | 1.400 (2) |
Cl3—C3 | 1.7742 (14) | C5—C6 | 1.383 (2) |
O1—C7 | 1.3671 (17) | C5—H5 | 0.9500 |
O1—C10 | 1.4321 (18) | C6—C7 | 1.393 (2) |
N1—C1 | 1.3318 (19) | C6—H6 | 0.9500 |
N1—H1 | 0.854 (14) | C7—C8 | 1.390 (2) |
N1—H2 | 0.861 (14) | C8—C9 | 1.383 (2) |
N2—C1 | 1.3228 (18) | C8—H8 | 0.9500 |
N2—C2 | 1.3672 (19) | C9—H9 | 0.9500 |
N3—C2 | 1.2747 (19) | C10—H10A | 0.9800 |
N3—H3 | 0.858 (15) | C10—H10B | 0.9800 |
C1—C4 | 1.483 (2) | C10—H10C | 0.9800 |
C2—C3 | 1.5563 (19) | | |
| | | |
C7—O1—C10 | 118.05 (12) | C6—C5—C4 | 120.34 (14) |
C1—N1—H1 | 119.8 (13) | C6—C5—H5 | 119.8 |
C1—N1—H2 | 117.4 (13) | C4—C5—H5 | 119.8 |
H1—N1—H2 | 121.9 (18) | C5—C6—C7 | 120.34 (13) |
C1—N2—C2 | 120.07 (12) | C5—C6—H6 | 119.8 |
C2—N3—H3 | 110.9 (13) | C7—C6—H6 | 119.8 |
N2—C1—N1 | 125.42 (14) | O1—C7—C8 | 124.54 (13) |
N2—C1—C4 | 116.48 (12) | O1—C7—C6 | 115.50 (12) |
N1—C1—C4 | 118.10 (13) | C8—C7—C6 | 119.96 (13) |
N3—C2—N2 | 127.14 (14) | C9—C8—C7 | 119.21 (13) |
N3—C2—C3 | 122.53 (13) | C9—C8—H8 | 120.4 |
N2—C2—C3 | 110.30 (12) | C7—C8—H8 | 120.4 |
C2—C3—Cl1 | 110.38 (10) | C8—C9—C4 | 121.75 (13) |
C2—C3—Cl2 | 112.08 (10) | C8—C9—H9 | 119.1 |
Cl1—C3—Cl2 | 107.49 (8) | C4—C9—H9 | 119.1 |
C2—C3—Cl3 | 109.15 (10) | O1—C10—H10A | 109.5 |
Cl1—C3—Cl3 | 108.78 (8) | O1—C10—H10B | 109.5 |
Cl2—C3—Cl3 | 108.89 (8) | H10A—C10—H10B | 109.5 |
C9—C4—C5 | 118.38 (13) | O1—C10—H10C | 109.5 |
C9—C4—C1 | 119.43 (13) | H10A—C10—H10C | 109.5 |
C5—C4—C1 | 122.15 (13) | H10B—C10—H10C | 109.5 |
| | | |
C2—N2—C1—N1 | 3.2 (2) | N1—C1—C4—C5 | 26.8 (2) |
C2—N2—C1—C4 | −176.48 (13) | C9—C4—C5—C6 | −1.4 (2) |
C1—N2—C2—N3 | −16.0 (2) | C1—C4—C5—C6 | 176.14 (13) |
C1—N2—C2—C3 | 166.24 (12) | C4—C5—C6—C7 | 1.4 (2) |
N3—C2—C3—Cl1 | 133.01 (14) | C10—O1—C7—C8 | 2.1 (2) |
N2—C2—C3—Cl1 | −49.13 (14) | C10—O1—C7—C6 | −177.03 (13) |
N3—C2—C3—Cl2 | 13.23 (19) | C5—C6—C7—O1 | 179.21 (13) |
N2—C2—C3—Cl2 | −168.91 (10) | C5—C6—C7—C8 | 0.0 (2) |
N3—C2—C3—Cl3 | −107.48 (15) | O1—C7—C8—C9 | 179.46 (13) |
N2—C2—C3—Cl3 | 70.38 (13) | C6—C7—C8—C9 | −1.4 (2) |
N2—C1—C4—C9 | 24.02 (19) | C7—C8—C9—C4 | 1.4 (2) |
N1—C1—C4—C9 | −155.71 (14) | C5—C4—C9—C8 | 0.0 (2) |
N2—C1—C4—C5 | −153.50 (14) | C1—C4—C9—C8 | −177.64 (13) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2···N3 | 0.86 (1) | 2.00 (2) | 2.647 (2) | 132 (2) |
N3—H3···Cl2 | 0.86 (2) | 2.43 (2) | 2.9791 (15) | 123 (2) |
N1—H1···O1i | 0.85 (1) | 2.20 (2) | 3.0315 (17) | 166 (2) |
N3—H3···Cl3ii | 0.86 (2) | 2.76 (2) | 3.4077 (15) | 134 (2) |
Symmetry codes: (i) −x, y+1/2, −z−1/2; (ii) −x+1, y+1/2, −z+1/2. |
(II)
N'-(2,2,2-trichloroethanimidoyl)benzene-1-carboximidamide
top
Crystal data top
C9H8Cl3N3 | Z = 6 |
Mr = 264.53 | F(000) = 804 |
Triclinic, P1 | Dx = 1.513 Mg m−3 |
Hall symbol: -P 1 | Melting point: 342 K |
a = 10.2999 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.9423 (3) Å | Cell parameters from 14588 reflections |
c = 15.6902 (4) Å | θ = 1.3–27.7° |
α = 85.5518 (12)° | µ = 0.76 mm−1 |
β = 86.5092 (12)° | T = 173 K |
γ = 81.5436 (11)° | Prism, colourless |
V = 1741.67 (8) Å3 | 0.18 × 0.15 × 0.10 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 7908 independent reflections |
Radiation source: fine-focus sealed tube, Nonius KappaCCD | 4900 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.076 |
ϕ and ω scans | θmax = 27.7°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | h = −13→13 |
Tmin = 0.876, Tmax = 0.928 | k = −14→14 |
14588 measured reflections | l = −20→20 |
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)] = 0.055 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.151 | w = 1/[σ2(Fo2) + (0.0773P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max < 0.001 |
7908 reflections | Δρmax = 0.47 e Å−3 |
434 parameters | Δρmin = −0.49 e Å−3 |
9 restraints | Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0229 (19) |
Crystal data top
C9H8Cl3N3 | γ = 81.5436 (11)° |
Mr = 264.53 | V = 1741.67 (8) Å3 |
Triclinic, P1 | Z = 6 |
a = 10.2999 (3) Å | Mo Kα radiation |
b = 10.9423 (3) Å | µ = 0.76 mm−1 |
c = 15.6902 (4) Å | T = 173 K |
α = 85.5518 (12)° | 0.18 × 0.15 × 0.10 mm |
β = 86.5092 (12)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 7908 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | 4900 reflections with I > 2σ(I) |
Tmin = 0.876, Tmax = 0.928 | Rint = 0.076 |
14588 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | 9 restraints |
wR(F2) = 0.151 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | Δρmax = 0.47 e Å−3 |
7908 reflections | Δρmin = −0.49 e Å−3 |
434 parameters | |
Special details top
Experimental. A crystal coated in Paratone (TM) oil was mounted on the end of a thin glass
capillary and cooled in the gas stream of the diffractometer Oxford Cryostream
device. |
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. The three N—H hydrogen atom positions were refined using a
distance constraint (0.88 Å) with isotropic thermal parameters constrained
to 1.2 × that of the attached nitrogen atom. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1A | 0.60376 (8) | 0.68696 (8) | 0.05980 (5) | 0.0382 (2) | |
Cl3A | 0.85852 (10) | 0.64967 (10) | −0.02951 (6) | 0.0512 (3) | |
Cl2A | 0.74929 (10) | 0.44303 (8) | 0.05492 (6) | 0.0475 (3) | |
N1A | 0.9712 (3) | 0.7141 (3) | 0.26620 (17) | 0.0335 (6) | |
H1A | 1.023 (3) | 0.746 (3) | 0.2982 (19) | 0.040* | |
H2A | 0.962 (3) | 0.6344 (19) | 0.271 (2) | 0.040* | |
N2A | 0.8396 (2) | 0.7473 (2) | 0.14600 (16) | 0.0270 (6) | |
N3A | 0.8634 (3) | 0.5374 (3) | 0.2018 (2) | 0.0457 (8) | |
H3A | 0.844 (4) | 0.467 (2) | 0.186 (2) | 0.055* | |
C1A | 0.9100 (3) | 0.7853 (3) | 0.20468 (18) | 0.0258 (7) | |
C2A | 0.8291 (3) | 0.6245 (3) | 0.1447 (2) | 0.0305 (7) | |
C3A | 0.7639 (3) | 0.6011 (3) | 0.06152 (19) | 0.0304 (7) | |
C4A | 0.9202 (3) | 0.9191 (3) | 0.20026 (19) | 0.0263 (7) | |
C5A | 0.9272 (3) | 0.9789 (3) | 0.2751 (2) | 0.0314 (7) | |
H5A | 0.9248 | 0.9323 | 0.3295 | 0.038* | |
C6A | 0.9389 (3) | 1.1043 (3) | 0.2696 (2) | 0.0402 (9) | |
H6A | 0.9431 | 1.1452 | 0.3211 | 0.048* | |
C7A | 0.9429 (3) | 1.1703 (3) | 0.1912 (2) | 0.0411 (9) | |
H7A | 0.9519 | 1.2567 | 0.1881 | 0.049* | |
C8A | 0.9352 (3) | 1.1110 (3) | 0.1164 (2) | 0.0400 (8) | |
H8A | 0.9383 | 1.1560 | 0.0615 | 0.048* | |
C9A | 0.9233 (3) | 0.9864 (3) | 0.1210 (2) | 0.0298 (7) | |
H9A | 0.9168 | 0.9464 | 0.0694 | 0.036* | |
Cl2B | 0.42045 (11) | 1.45466 (8) | 0.18858 (6) | 0.0554 (3) | |
Cl3B | 0.54312 (11) | 1.33750 (8) | 0.33855 (6) | 0.0543 (3) | |
Cl1B | 0.27927 (9) | 1.30194 (8) | 0.30614 (6) | 0.0453 (3) | |
N1B | 0.6096 (3) | 0.9670 (3) | 0.16516 (16) | 0.0273 (6) | |
H1B | 0.666 (3) | 0.901 (2) | 0.158 (2) | 0.033* | |
H2B | 0.596 (3) | 1.032 (2) | 0.1268 (17) | 0.033* | |
N2B | 0.5067 (2) | 1.1002 (2) | 0.26857 (15) | 0.0233 (5) | |
N3B | 0.5213 (3) | 1.2041 (3) | 0.13037 (17) | 0.0379 (7) | |
H3B | 0.510 (4) | 1.281 (2) | 0.107 (2) | 0.045* | |
C1B | 0.5677 (3) | 0.9918 (3) | 0.24448 (18) | 0.0228 (6) | |
C2B | 0.4927 (3) | 1.2012 (3) | 0.21114 (18) | 0.0251 (6) | |
C3B | 0.4360 (3) | 1.3185 (3) | 0.25786 (19) | 0.0306 (7) | |
C4B | 0.5870 (3) | 0.8898 (3) | 0.31318 (19) | 0.0242 (6) | |
C5B | 0.5848 (3) | 0.7677 (3) | 0.2950 (2) | 0.0294 (7) | |
H5B | 0.5730 | 0.7490 | 0.2374 | 0.035* | |
C6B | 0.5980 (4) | 0.6743 (3) | 0.3600 (2) | 0.0388 (8) | |
H6B | 0.5985 | 0.5898 | 0.3475 | 0.047* | |
C7B | 0.6124 (4) | 0.7022 (3) | 0.4429 (2) | 0.0388 (8) | |
H7B | 0.6198 | 0.6374 | 0.4880 | 0.047* | |
C8B | 0.6152 (3) | 0.8226 (3) | 0.4614 (2) | 0.0353 (8) | |
H8B | 0.6271 | 0.8412 | 0.5190 | 0.042* | |
C9B | 0.6019 (3) | 0.9176 (3) | 0.39690 (19) | 0.0291 (7) | |
H9B | 0.6024 | 1.0019 | 0.4096 | 0.035* | |
Cl2C | 0.14101 (9) | 0.62248 (8) | 0.59828 (5) | 0.0385 (2) | |
Cl3C | 0.15617 (9) | 0.55349 (7) | 0.42581 (5) | 0.0407 (2) | |
Cl1C | −0.06225 (8) | 0.73018 (9) | 0.48515 (6) | 0.0427 (2) | |
N1C | 0.2826 (3) | 0.9864 (2) | 0.36848 (17) | 0.0291 (6) | |
H1C | 0.331 (3) | 1.035 (3) | 0.3381 (18) | 0.035* | |
H2C | 0.281 (3) | 0.974 (3) | 0.4253 (12) | 0.035* | |
N2C | 0.1782 (2) | 0.8084 (2) | 0.37308 (15) | 0.0248 (6) | |
N3C | 0.2278 (3) | 0.8556 (3) | 0.51154 (17) | 0.0384 (7) | |
H3C | 0.221 (4) | 0.823 (3) | 0.5640 (14) | 0.046* | |
C1C | 0.2373 (3) | 0.8974 (3) | 0.33215 (18) | 0.0230 (6) | |
C2C | 0.1797 (3) | 0.7900 (3) | 0.46059 (18) | 0.0254 (7) | |
C3C | 0.1096 (3) | 0.6786 (3) | 0.49120 (19) | 0.0282 (7) | |
C4C | 0.2535 (3) | 0.8944 (3) | 0.23692 (18) | 0.0237 (6) | |
C5C | 0.2589 (3) | 1.0003 (3) | 0.18363 (19) | 0.0275 (7) | |
H5C | 0.2509 | 1.0791 | 0.2080 | 0.033* | |
C6C | 0.2776 (3) | 0.9933 (3) | 0.0957 (2) | 0.0346 (8) | |
H6C | 0.2818 | 1.0667 | 0.0586 | 0.042* | |
C7C | 0.2902 (3) | 0.8789 (3) | 0.0612 (2) | 0.0371 (8) | |
H7C | 0.3025 | 0.8738 | 0.0003 | 0.045* | |
C8C | 0.2842 (3) | 0.7729 (3) | 0.1142 (2) | 0.0347 (8) | |
H8C | 0.2919 | 0.6939 | 0.0902 | 0.042* | |
C9C | 0.2669 (3) | 0.7795 (3) | 0.20168 (19) | 0.0293 (7) | |
H9C | 0.2646 | 0.7056 | 0.2387 | 0.035* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1A | 0.0350 (5) | 0.0441 (5) | 0.0359 (5) | 0.0005 (4) | −0.0128 (3) | −0.0091 (4) |
Cl3A | 0.0554 (6) | 0.0666 (7) | 0.0346 (5) | −0.0196 (5) | 0.0094 (4) | −0.0114 (4) |
Cl2A | 0.0612 (6) | 0.0318 (5) | 0.0534 (6) | −0.0077 (4) | −0.0166 (5) | −0.0153 (4) |
N1A | 0.0406 (17) | 0.0282 (15) | 0.0338 (16) | −0.0091 (13) | −0.0137 (13) | 0.0015 (12) |
N2A | 0.0287 (14) | 0.0246 (13) | 0.0283 (14) | −0.0032 (11) | −0.0068 (11) | −0.0029 (11) |
N3A | 0.069 (2) | 0.0248 (15) | 0.0459 (18) | −0.0077 (15) | −0.0264 (16) | 0.0020 (13) |
C1A | 0.0247 (16) | 0.0270 (16) | 0.0258 (16) | −0.0044 (13) | −0.0023 (13) | 0.0001 (13) |
C2A | 0.0295 (17) | 0.0308 (17) | 0.0314 (17) | 0.0002 (14) | −0.0043 (14) | −0.0086 (14) |
C3A | 0.0337 (18) | 0.0299 (17) | 0.0287 (17) | −0.0046 (14) | −0.0060 (13) | −0.0062 (13) |
C4A | 0.0198 (15) | 0.0292 (16) | 0.0303 (16) | −0.0042 (13) | −0.0030 (12) | −0.0016 (13) |
C5A | 0.0298 (17) | 0.0327 (17) | 0.0318 (17) | −0.0027 (14) | −0.0002 (14) | −0.0075 (14) |
C6A | 0.039 (2) | 0.0340 (19) | 0.048 (2) | −0.0022 (16) | 0.0053 (16) | −0.0175 (16) |
C7A | 0.037 (2) | 0.0255 (17) | 0.060 (2) | −0.0030 (15) | −0.0026 (17) | −0.0050 (16) |
C8A | 0.0327 (19) | 0.0328 (19) | 0.053 (2) | −0.0030 (15) | −0.0047 (16) | 0.0071 (16) |
C9A | 0.0276 (17) | 0.0316 (17) | 0.0303 (17) | −0.0050 (14) | −0.0023 (13) | −0.0014 (14) |
Cl2B | 0.0897 (8) | 0.0239 (4) | 0.0457 (6) | 0.0033 (5) | 0.0094 (5) | 0.0100 (4) |
Cl3B | 0.0752 (7) | 0.0362 (5) | 0.0572 (6) | −0.0127 (5) | −0.0250 (5) | −0.0127 (4) |
Cl1B | 0.0461 (5) | 0.0318 (5) | 0.0553 (6) | −0.0007 (4) | 0.0154 (4) | −0.0095 (4) |
N1B | 0.0279 (14) | 0.0278 (14) | 0.0241 (14) | 0.0038 (12) | −0.0003 (11) | −0.0035 (11) |
N2B | 0.0282 (14) | 0.0204 (13) | 0.0217 (12) | −0.0048 (11) | −0.0024 (10) | 0.0000 (10) |
N3B | 0.0545 (19) | 0.0321 (16) | 0.0236 (15) | 0.0007 (14) | 0.0024 (13) | 0.0039 (12) |
C1B | 0.0216 (15) | 0.0242 (15) | 0.0234 (15) | −0.0065 (13) | −0.0023 (12) | −0.0009 (12) |
C2B | 0.0258 (16) | 0.0243 (15) | 0.0245 (16) | −0.0025 (13) | −0.0017 (12) | 0.0010 (12) |
C3B | 0.0426 (19) | 0.0221 (15) | 0.0269 (16) | −0.0059 (14) | −0.0003 (14) | 0.0017 (13) |
C4B | 0.0217 (15) | 0.0208 (15) | 0.0294 (16) | −0.0007 (12) | −0.0027 (12) | −0.0014 (12) |
C5B | 0.0335 (18) | 0.0275 (16) | 0.0274 (16) | −0.0035 (14) | −0.0011 (13) | −0.0052 (13) |
C6B | 0.052 (2) | 0.0197 (16) | 0.045 (2) | −0.0040 (15) | −0.0018 (17) | −0.0014 (14) |
C7B | 0.048 (2) | 0.0315 (18) | 0.0346 (19) | −0.0011 (16) | −0.0072 (16) | 0.0082 (15) |
C8B | 0.045 (2) | 0.0345 (18) | 0.0269 (17) | −0.0061 (16) | −0.0084 (15) | 0.0020 (14) |
C9B | 0.0349 (18) | 0.0257 (16) | 0.0279 (16) | −0.0067 (14) | −0.0062 (13) | −0.0017 (13) |
Cl2C | 0.0556 (6) | 0.0360 (5) | 0.0256 (4) | −0.0133 (4) | −0.0079 (4) | 0.0044 (3) |
Cl3C | 0.0673 (6) | 0.0234 (4) | 0.0329 (4) | −0.0079 (4) | −0.0094 (4) | −0.0034 (3) |
Cl1C | 0.0319 (5) | 0.0477 (5) | 0.0479 (5) | −0.0127 (4) | −0.0007 (4) | 0.0134 (4) |
N1C | 0.0362 (16) | 0.0314 (15) | 0.0231 (13) | −0.0151 (12) | 0.0031 (12) | −0.0060 (11) |
N2C | 0.0293 (14) | 0.0257 (13) | 0.0212 (13) | −0.0086 (11) | −0.0023 (10) | −0.0029 (10) |
N3C | 0.0555 (19) | 0.0456 (18) | 0.0204 (14) | −0.0267 (15) | 0.0001 (13) | −0.0063 (13) |
C1C | 0.0219 (15) | 0.0251 (15) | 0.0223 (15) | −0.0042 (13) | −0.0010 (12) | −0.0026 (12) |
C2C | 0.0291 (16) | 0.0257 (16) | 0.0222 (15) | −0.0061 (13) | 0.0001 (12) | −0.0027 (12) |
C3C | 0.0344 (18) | 0.0275 (16) | 0.0247 (16) | −0.0096 (14) | −0.0044 (13) | −0.0016 (12) |
C4C | 0.0195 (15) | 0.0275 (16) | 0.0248 (15) | −0.0050 (12) | −0.0024 (12) | −0.0032 (12) |
C5C | 0.0230 (16) | 0.0318 (17) | 0.0279 (16) | −0.0051 (13) | −0.0026 (12) | −0.0011 (13) |
C6C | 0.0286 (17) | 0.046 (2) | 0.0286 (17) | −0.0084 (16) | −0.0043 (14) | 0.0071 (15) |
C7C | 0.0337 (19) | 0.056 (2) | 0.0210 (16) | −0.0023 (17) | 0.0007 (14) | −0.0068 (16) |
C8C | 0.0366 (19) | 0.0384 (19) | 0.0283 (17) | 0.0032 (15) | −0.0055 (14) | −0.0112 (15) |
C9C | 0.0327 (18) | 0.0280 (17) | 0.0267 (16) | −0.0016 (14) | −0.0037 (13) | −0.0022 (13) |
Geometric parameters (Å, º) top
Cl1A—C3A | 1.775 (3) | C4B—C5B | 1.392 (4) |
Cl3A—C3A | 1.771 (3) | C4B—C9B | 1.393 (4) |
Cl2A—C3A | 1.770 (3) | C5B—C6B | 1.385 (5) |
N1A—C1A | 1.322 (4) | C5B—H5B | 0.9600 |
N1A—H1A | 0.878 (18) | C6B—C7B | 1.380 (5) |
N1A—H2A | 0.888 (18) | C6B—H6B | 0.9600 |
N2A—C1A | 1.332 (4) | C7B—C8B | 1.376 (5) |
N2A—C2A | 1.366 (4) | C7B—H7B | 0.9600 |
N3A—C2A | 1.281 (4) | C8B—C9B | 1.391 (4) |
N3A—H3A | 0.883 (18) | C8B—H8B | 0.9600 |
C1A—C4A | 1.479 (4) | C9B—H9B | 0.9600 |
C2A—C3A | 1.559 (4) | Cl2C—C3C | 1.775 (3) |
C4A—C9A | 1.396 (4) | Cl3C—C3C | 1.766 (3) |
C4A—C5A | 1.399 (4) | Cl1C—C3C | 1.783 (3) |
C5A—C6A | 1.391 (5) | N1C—C1C | 1.321 (4) |
C5A—H5A | 0.9600 | N1C—H1C | 0.873 (18) |
C6A—C7A | 1.379 (5) | N1C—H2C | 0.892 (18) |
C6A—H6A | 0.9600 | N2C—C1C | 1.327 (4) |
C7A—C8A | 1.396 (5) | N2C—C2C | 1.373 (4) |
C7A—H7A | 0.9600 | N3C—C2C | 1.281 (4) |
C8A—C9A | 1.383 (4) | N3C—H3C | 0.872 (18) |
C8A—H8A | 0.9600 | C1C—C4C | 1.496 (4) |
C9A—H9A | 0.9600 | C2C—C3C | 1.538 (4) |
Cl2B—C3B | 1.768 (3) | C4C—C5C | 1.381 (4) |
Cl3B—C3B | 1.772 (3) | C4C—C9C | 1.398 (4) |
Cl1B—C3B | 1.769 (3) | C5C—C6C | 1.388 (4) |
N1B—C1B | 1.327 (4) | C5C—H5C | 0.9601 |
N1B—H1B | 0.866 (18) | C6C—C7C | 1.387 (5) |
N1B—H2B | 0.893 (18) | C6C—H6C | 0.9601 |
N2B—C1B | 1.328 (4) | C7C—C8C | 1.381 (5) |
N2B—C2B | 1.367 (4) | C7C—H7C | 0.9600 |
N3B—C2B | 1.283 (4) | C8C—C9C | 1.380 (4) |
N3B—H3B | 0.882 (18) | C8C—H8C | 0.9600 |
C1B—C4B | 1.491 (4) | C9C—H9C | 0.9601 |
C2B—C3B | 1.549 (4) | | |
| | | |
C1A—N1A—H1A | 119 (2) | C5B—C4B—C1B | 120.5 (3) |
C1A—N1A—H2A | 118 (2) | C9B—C4B—C1B | 119.7 (3) |
H1A—N1A—H2A | 123 (3) | C6B—C5B—C4B | 119.9 (3) |
C1A—N2A—C2A | 119.9 (3) | C6B—C5B—H5B | 120.6 |
C2A—N3A—H3A | 109 (3) | C4B—C5B—H5B | 119.6 |
N1A—C1A—N2A | 125.8 (3) | C7B—C6B—C5B | 120.2 (3) |
N1A—C1A—C4A | 117.4 (3) | C7B—C6B—H6B | 119.7 |
N2A—C1A—C4A | 116.8 (3) | C5B—C6B—H6B | 120.1 |
N3A—C2A—N2A | 127.7 (3) | C8B—C7B—C6B | 120.3 (3) |
N3A—C2A—C3A | 122.3 (3) | C8B—C7B—H7B | 119.8 |
N2A—C2A—C3A | 109.9 (3) | C6B—C7B—H7B | 119.9 |
C2A—C3A—Cl2A | 112.3 (2) | C7B—C8B—C9B | 120.3 (3) |
C2A—C3A—Cl3A | 110.0 (2) | C7B—C8B—H8B | 119.9 |
Cl2A—C3A—Cl3A | 108.29 (16) | C9B—C8B—H8B | 119.8 |
C2A—C3A—Cl1A | 109.2 (2) | C8B—C9B—C4B | 119.6 (3) |
Cl2A—C3A—Cl1A | 107.94 (16) | C8B—C9B—H9B | 120.7 |
Cl3A—C3A—Cl1A | 109.06 (18) | C4B—C9B—H9B | 119.8 |
C9A—C4A—C5A | 119.6 (3) | C1C—N1C—H1C | 120 (2) |
C9A—C4A—C1A | 120.0 (3) | C1C—N1C—H2C | 112 (2) |
C5A—C4A—C1A | 120.4 (3) | H1C—N1C—H2C | 125 (3) |
C6A—C5A—C4A | 119.6 (3) | C1C—N2C—C2C | 120.3 (2) |
C6A—C5A—H5A | 121.1 | C2C—N3C—H3C | 110 (2) |
C4A—C5A—H5A | 119.3 | N1C—C1C—N2C | 125.5 (3) |
C7A—C6A—C5A | 120.7 (3) | N1C—C1C—C4C | 118.2 (3) |
C7A—C6A—H6A | 120.0 | N2C—C1C—C4C | 116.3 (2) |
C5A—C6A—H6A | 119.3 | N3C—C2C—N2C | 126.9 (3) |
C6A—C7A—C8A | 119.9 (3) | N3C—C2C—C3C | 123.3 (3) |
C6A—C7A—H7A | 120.0 | N2C—C2C—C3C | 109.8 (2) |
C8A—C7A—H7A | 120.2 | C2C—C3C—Cl3C | 111.5 (2) |
C9A—C8A—C7A | 120.0 (3) | C2C—C3C—Cl2C | 113.4 (2) |
C9A—C8A—H8A | 119.5 | Cl3C—C3C—Cl2C | 107.40 (17) |
C7A—C8A—H8A | 120.5 | C2C—C3C—Cl1C | 106.6 (2) |
C8A—C9A—C4A | 120.3 (3) | Cl3C—C3C—Cl1C | 109.57 (16) |
C8A—C9A—H9A | 119.6 | Cl2C—C3C—Cl1C | 108.35 (17) |
C4A—C9A—H9A | 120.1 | C5C—C4C—C9C | 119.5 (3) |
C1B—N1B—H1B | 118 (2) | C5C—C4C—C1C | 122.3 (3) |
C1B—N1B—H2B | 114 (2) | C9C—C4C—C1C | 118.2 (3) |
H1B—N1B—H2B | 125 (3) | C4C—C5C—C6C | 120.5 (3) |
C1B—N2B—C2B | 120.2 (2) | C4C—C5C—H5C | 119.4 |
C2B—N3B—H3B | 111 (2) | C6C—C5C—H5C | 120.1 |
N1B—C1B—N2B | 125.7 (3) | C7C—C6C—C5C | 119.7 (3) |
N1B—C1B—C4B | 118.1 (3) | C7C—C6C—H6C | 119.7 |
N2B—C1B—C4B | 116.2 (2) | C5C—C6C—H6C | 120.6 |
N3B—C2B—N2B | 127.4 (3) | C8C—C7C—C6C | 120.0 (3) |
N3B—C2B—C3B | 122.7 (3) | C8C—C7C—H7C | 120.1 |
N2B—C2B—C3B | 109.9 (2) | C6C—C7C—H7C | 119.8 |
C2B—C3B—Cl2B | 112.8 (2) | C9C—C8C—C7C | 120.4 (3) |
C2B—C3B—Cl1B | 110.1 (2) | C9C—C8C—H8C | 119.6 |
Cl2B—C3B—Cl1B | 108.29 (18) | C7C—C8C—H8C | 120.0 |
C2B—C3B—Cl3B | 108.8 (2) | C8C—C9C—C4C | 119.9 (3) |
Cl2B—C3B—Cl3B | 107.92 (16) | C8C—C9C—H9C | 120.5 |
Cl1B—C3B—Cl3B | 108.94 (17) | C4C—C9C—H9C | 119.7 |
C5B—C4B—C9B | 119.8 (3) | | |
| | | |
C2A—N2A—C1A—N1A | −1.9 (5) | N2B—C1B—C4B—C5B | 147.1 (3) |
C2A—N2A—C1A—C4A | 178.2 (3) | N1B—C1B—C4B—C9B | 151.1 (3) |
C1A—N2A—C2A—N3A | 11.2 (5) | N2B—C1B—C4B—C9B | −30.3 (4) |
C1A—N2A—C2A—C3A | −169.9 (3) | C9B—C4B—C5B—C6B | −0.3 (5) |
N3A—C2A—C3A—Cl2A | −1.9 (4) | C1B—C4B—C5B—C6B | −177.6 (3) |
N2A—C2A—C3A—Cl2A | 179.2 (2) | C4B—C5B—C6B—C7B | 0.5 (5) |
N3A—C2A—C3A—Cl3A | −122.6 (3) | C5B—C6B—C7B—C8B | −0.8 (5) |
N2A—C2A—C3A—Cl3A | 58.5 (3) | C6B—C7B—C8B—C9B | 0.9 (5) |
N3A—C2A—C3A—Cl1A | 117.8 (3) | C7B—C8B—C9B—C4B | −0.7 (5) |
N2A—C2A—C3A—Cl1A | −61.1 (3) | C5B—C4B—C9B—C8B | 0.3 (5) |
N1A—C1A—C4A—C9A | 146.2 (3) | C1B—C4B—C9B—C8B | 177.7 (3) |
N2A—C1A—C4A—C9A | −33.8 (4) | C2C—N2C—C1C—N1C | −11.3 (5) |
N1A—C1A—C4A—C5A | −33.6 (4) | C2C—N2C—C1C—C4C | 168.3 (3) |
N2A—C1A—C4A—C5A | 146.4 (3) | C1C—N2C—C2C—N3C | 4.1 (5) |
C9A—C4A—C5A—C6A | −0.9 (5) | C1C—N2C—C2C—C3C | −177.7 (3) |
C1A—C4A—C5A—C6A | 178.9 (3) | N3C—C2C—C3C—Cl3C | −138.0 (3) |
C4A—C5A—C6A—C7A | 0.5 (5) | N2C—C2C—C3C—Cl3C | 43.7 (3) |
C5A—C6A—C7A—C8A | −0.1 (5) | N3C—C2C—C3C—Cl2C | −16.7 (4) |
C6A—C7A—C8A—C9A | 0.2 (5) | N2C—C2C—C3C—Cl2C | 165.0 (2) |
C7A—C8A—C9A—C4A | −0.6 (5) | N3C—C2C—C3C—Cl1C | 102.4 (3) |
C5A—C4A—C9A—C8A | 1.0 (5) | N2C—C2C—C3C—Cl1C | −75.8 (3) |
C1A—C4A—C9A—C8A | −178.8 (3) | N1C—C1C—C4C—C5C | −28.6 (4) |
C2B—N2B—C1B—N1B | −5.9 (4) | N2C—C1C—C4C—C5C | 151.8 (3) |
C2B—N2B—C1B—C4B | 175.5 (2) | N1C—C1C—C4C—C9C | 149.7 (3) |
C1B—N2B—C2B—N3B | 7.2 (5) | N2C—C1C—C4C—C9C | −29.9 (4) |
C1B—N2B—C2B—C3B | −172.3 (2) | C9C—C4C—C5C—C6C | 0.0 (4) |
N3B—C2B—C3B—Cl2B | −1.7 (4) | C1C—C4C—C5C—C6C | 178.3 (3) |
N2B—C2B—C3B—Cl2B | 177.8 (2) | C4C—C5C—C6C—C7C | 0.3 (5) |
N3B—C2B—C3B—Cl1B | 119.3 (3) | C5C—C6C—C7C—C8C | 0.0 (5) |
N2B—C2B—C3B—Cl1B | −61.2 (3) | C6C—C7C—C8C—C9C | −0.6 (5) |
N3B—C2B—C3B—Cl3B | −121.4 (3) | C7C—C8C—C9C—C4C | 0.9 (5) |
N2B—C2B—C3B—Cl3B | 58.1 (3) | C5C—C4C—C9C—C8C | −0.6 (5) |
N1B—C1B—C4B—C5B | −31.5 (4) | C1C—C4C—C9C—C8C | −178.9 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H2A···N3A | 0.89 (2) | 1.99 (3) | 2.657 (4) | 130 (3) |
N3A—H3A···Cl2A | 0.88 (2) | 2.38 (3) | 2.969 (3) | 125 (3) |
N1A—H1A···N2Ci | 0.88 (2) | 2.26 (2) | 3.126 (4) | 172 (3) |
N1B—H1B···N2A | 0.87 (2) | 2.28 (2) | 3.136 (4) | 171 (3) |
N3B—H3B···Cl2B | 0.88 (2) | 2.41 (3) | 2.978 (3) | 122 (3) |
N1B—H2B···N3B | 0.89 (2) | 1.94 (3) | 2.646 (4) | 135 (3) |
N3B—H3B···Cl1Aii | 0.88 (2) | 2.91 (3) | 3.383 (3) | 115 (3) |
N1C—H2C···N3C | 0.89 (2) | 1.91 (3) | 2.644 (4) | 138 (3) |
N3C—H3C···Cl2C | 0.87 (2) | 2.47 (3) | 3.023 (3) | 122 (3) |
N1C—H1C···N2B | 0.87 (2) | 2.24 (2) | 3.072 (3) | 160 (3) |
N1C—H1C···Cl1B | 0.87 (2) | 2.90 (3) | 3.511 (3) | 128 (3) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+2, −z. |
(III) 4-chloro-
N'-(2,2,2-trichloroethanimidoyl)benzene-1-carboximidamide
top
Crystal data top
C9H7Cl4N3 | F(000) = 600 |
Mr = 298.98 | Dx = 1.625 Mg m−3 |
Monoclinic, P21/n | Melting point: 386 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 5.762 (2) Å | Cell parameters from 9122 reflections |
b = 22.711 (8) Å | θ = 2.4–27.6° |
c = 9.713 (4) Å | µ = 0.94 mm−1 |
β = 106.031 (4)° | T = 173 K |
V = 1221.7 (8) Å3 | Plate, colourless |
Z = 4 | 0.32 × 0.10 × 0.08 mm |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 2803 independent reflections |
Radiation source: fine-focus sealed tube, Bruker D8 | 2248 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
ϕ and ω scans | θmax = 27.6°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | h = −7→7 |
Tmin = 0.613, Tmax = 0.746 | k = −29→29 |
16666 measured reflections | l = −12→12 |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.122 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.21 | w = 1/[σ2(Fo2) + (0.0382P)2 + 2.1126P] where P = (Fo2 + 2Fc2)/3 |
2803 reflections | (Δ/σ)max < 0.001 |
154 parameters | Δρmax = 0.50 e Å−3 |
3 restraints | Δρmin = −0.35 e Å−3 |
Crystal data top
C9H7Cl4N3 | V = 1221.7 (8) Å3 |
Mr = 298.98 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.762 (2) Å | µ = 0.94 mm−1 |
b = 22.711 (8) Å | T = 173 K |
c = 9.713 (4) Å | 0.32 × 0.10 × 0.08 mm |
β = 106.031 (4)° | |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 2803 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | 2248 reflections with I > 2σ(I) |
Tmin = 0.613, Tmax = 0.746 | Rint = 0.041 |
16666 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 3 restraints |
wR(F2) = 0.122 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.21 | Δρmax = 0.50 e Å−3 |
2803 reflections | Δρmin = −0.35 e Å−3 |
154 parameters | |
Special details top
Experimental. A crystal coated in Paratone (TM) oil was mounted on the end of a thin glass
capillary and cooled in the gas stream of the diffractometer Kryoflex device. |
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. The three N—H hydrogen atom positions were refined using a
distance constraint (0.88 Å) with isotropic thermal parameters constrained
to 1.2 × that of the attached nitrogen atom. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | −0.00475 (17) | 0.38480 (4) | 0.54834 (9) | 0.0350 (2) | |
Cl2 | −0.09542 (18) | 0.46198 (4) | 0.30420 (10) | 0.0411 (2) | |
Cl3 | 0.37047 (16) | 0.40846 (4) | 0.41173 (11) | 0.0407 (2) | |
Cl4 | 0.81260 (16) | 0.05682 (4) | 0.50241 (10) | 0.0352 (2) | |
N1 | −0.1001 (5) | 0.23304 (13) | 0.1498 (3) | 0.0300 (6) | |
H1 | −0.102 (7) | 0.1998 (11) | 0.104 (4) | 0.036* | |
H2 | −0.205 (6) | 0.2618 (13) | 0.128 (4) | 0.036* | |
N2 | 0.1227 (5) | 0.29573 (12) | 0.3323 (3) | 0.0240 (6) | |
N3 | −0.2290 (5) | 0.34175 (14) | 0.1853 (3) | 0.0357 (7) | |
H3 | −0.297 (7) | 0.3767 (11) | 0.176 (4) | 0.043* | |
C1 | 0.0864 (5) | 0.24533 (14) | 0.2625 (3) | 0.0226 (6) | |
C2 | −0.0325 (6) | 0.34201 (14) | 0.2862 (3) | 0.0242 (6) | |
C3 | 0.0567 (6) | 0.39702 (14) | 0.3809 (3) | 0.0250 (7) | |
C4 | 0.2664 (6) | 0.19779 (14) | 0.3160 (3) | 0.0234 (6) | |
C5 | 0.1988 (6) | 0.13896 (14) | 0.3090 (3) | 0.0262 (7) | |
H5 | 0.0356 | 0.1286 | 0.2643 | 0.031* | |
C6 | 0.3645 (6) | 0.09515 (14) | 0.3659 (3) | 0.0270 (7) | |
H6 | 0.3169 | 0.0550 | 0.3616 | 0.032* | |
C7 | 0.6016 (6) | 0.11147 (14) | 0.4294 (3) | 0.0264 (7) | |
C8 | 0.6766 (6) | 0.16943 (14) | 0.4368 (4) | 0.0269 (7) | |
H8 | 0.8405 | 0.1794 | 0.4805 | 0.032* | |
C9 | 0.5075 (6) | 0.21290 (14) | 0.3790 (3) | 0.0249 (7) | |
H9 | 0.5561 | 0.2530 | 0.3825 | 0.030* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0420 (5) | 0.0424 (5) | 0.0212 (4) | 0.0063 (4) | 0.0094 (3) | 0.0002 (3) |
Cl2 | 0.0457 (5) | 0.0287 (4) | 0.0415 (5) | 0.0059 (4) | −0.0003 (4) | 0.0092 (4) |
Cl3 | 0.0262 (4) | 0.0468 (5) | 0.0476 (5) | −0.0059 (4) | 0.0076 (4) | −0.0035 (4) |
Cl4 | 0.0322 (4) | 0.0271 (4) | 0.0426 (5) | 0.0049 (3) | 0.0040 (4) | 0.0001 (3) |
N1 | 0.0322 (15) | 0.0332 (15) | 0.0189 (13) | −0.0013 (12) | −0.0025 (11) | −0.0018 (11) |
N2 | 0.0228 (13) | 0.0310 (14) | 0.0155 (12) | 0.0057 (11) | 0.0007 (10) | 0.0009 (10) |
N3 | 0.0342 (16) | 0.0374 (17) | 0.0267 (15) | 0.0093 (13) | −0.0063 (13) | 0.0015 (13) |
C1 | 0.0200 (14) | 0.0312 (16) | 0.0164 (14) | −0.0002 (12) | 0.0046 (11) | 0.0019 (12) |
C2 | 0.0238 (15) | 0.0318 (17) | 0.0160 (14) | 0.0027 (12) | 0.0039 (12) | 0.0028 (12) |
C3 | 0.0225 (15) | 0.0282 (16) | 0.0227 (15) | 0.0033 (12) | 0.0034 (12) | 0.0042 (12) |
C4 | 0.0248 (15) | 0.0311 (16) | 0.0143 (14) | 0.0022 (12) | 0.0053 (12) | −0.0025 (12) |
C5 | 0.0253 (16) | 0.0321 (17) | 0.0201 (15) | −0.0020 (13) | 0.0045 (13) | −0.0046 (13) |
C6 | 0.0279 (16) | 0.0258 (16) | 0.0285 (16) | −0.0046 (13) | 0.0099 (13) | −0.0048 (13) |
C7 | 0.0287 (16) | 0.0275 (16) | 0.0232 (15) | 0.0048 (13) | 0.0076 (13) | −0.0011 (13) |
C8 | 0.0204 (15) | 0.0314 (17) | 0.0285 (16) | −0.0023 (12) | 0.0061 (13) | −0.0054 (13) |
C9 | 0.0238 (15) | 0.0261 (16) | 0.0239 (16) | −0.0020 (12) | 0.0049 (12) | −0.0022 (12) |
Geometric parameters (Å, º) top
Cl1—C3 | 1.779 (3) | C2—C3 | 1.553 (4) |
Cl2—C3 | 1.772 (3) | C4—C5 | 1.388 (5) |
Cl3—C3 | 1.768 (3) | C4—C9 | 1.397 (4) |
Cl4—C7 | 1.745 (3) | C5—C6 | 1.384 (5) |
N1—C1 | 1.335 (4) | C5—H5 | 0.9500 |
N1—H1 | 0.873 (18) | C6—C7 | 1.386 (4) |
N1—H2 | 0.874 (18) | C6—H6 | 0.9500 |
N2—C1 | 1.317 (4) | C7—C8 | 1.381 (5) |
N2—C2 | 1.373 (4) | C8—C9 | 1.392 (4) |
N3—C2 | 1.276 (4) | C8—H8 | 0.9500 |
N3—H3 | 0.878 (19) | C9—H9 | 0.9500 |
C1—C4 | 1.488 (4) | | |
| | | |
C1—N1—H1 | 119 (3) | C5—C4—C1 | 121.5 (3) |
C1—N1—H2 | 113 (3) | C9—C4—C1 | 119.2 (3) |
H1—N1—H2 | 128 (4) | C6—C5—C4 | 121.3 (3) |
C1—N2—C2 | 120.0 (3) | C6—C5—H5 | 119.4 |
C2—N3—H3 | 110 (3) | C4—C5—H5 | 119.4 |
N2—C1—N1 | 125.6 (3) | C5—C6—C7 | 118.2 (3) |
N2—C1—C4 | 117.0 (3) | C5—C6—H6 | 120.9 |
N1—C1—C4 | 117.4 (3) | C7—C6—H6 | 120.9 |
N3—C2—N2 | 127.4 (3) | C8—C7—C6 | 122.3 (3) |
N3—C2—C3 | 122.5 (3) | C8—C7—Cl4 | 118.9 (3) |
N2—C2—C3 | 110.1 (2) | C6—C7—Cl4 | 118.8 (3) |
C2—C3—Cl3 | 112.0 (2) | C7—C8—C9 | 118.7 (3) |
C2—C3—Cl2 | 112.1 (2) | C7—C8—H8 | 120.6 |
Cl3—C3—Cl2 | 108.23 (18) | C9—C8—H8 | 120.6 |
C2—C3—Cl1 | 107.4 (2) | C8—C9—C4 | 120.2 (3) |
Cl3—C3—Cl1 | 108.70 (17) | C8—C9—H9 | 119.9 |
Cl2—C3—Cl1 | 108.31 (18) | C4—C9—H9 | 119.9 |
C5—C4—C9 | 119.3 (3) | | |
| | | |
C2—N2—C1—N1 | −3.1 (5) | N2—C1—C4—C9 | −32.2 (4) |
C2—N2—C1—C4 | 178.1 (3) | N1—C1—C4—C9 | 148.9 (3) |
C1—N2—C2—N3 | 5.9 (5) | C9—C4—C5—C6 | 1.4 (5) |
C1—N2—C2—C3 | −177.0 (3) | C1—C4—C5—C6 | −176.4 (3) |
N3—C2—C3—Cl3 | −137.6 (3) | C4—C5—C6—C7 | −0.6 (5) |
N2—C2—C3—Cl3 | 45.1 (3) | C5—C6—C7—C8 | −0.3 (5) |
N3—C2—C3—Cl2 | −15.8 (4) | C5—C6—C7—Cl4 | 179.7 (2) |
N2—C2—C3—Cl2 | 167.0 (2) | C6—C7—C8—C9 | 0.3 (5) |
N3—C2—C3—Cl1 | 103.1 (3) | Cl4—C7—C8—C9 | −179.7 (2) |
N2—C2—C3—Cl1 | −74.2 (3) | C7—C8—C9—C4 | 0.5 (5) |
N2—C1—C4—C5 | 145.6 (3) | C5—C4—C9—C8 | −1.4 (5) |
N1—C1—C4—C5 | −33.3 (4) | C1—C4—C9—C8 | 176.5 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2···N3 | 0.87 (2) | 1.92 (3) | 2.628 (4) | 137 (3) |
N3—H3···Cl2 | 0.88 (2) | 2.42 (4) | 2.982 (3) | 122 (3) |
N1—H1···N2i | 0.87 (2) | 2.68 (4) | 3.125 (4) | 113 (3) |
N1—H1···Cl1i | 0.87 (2) | 2.95 (3) | 3.507 (3) | 124 (3) |
N3—H3···Cl4ii | 0.88 (2) | 2.85 (3) | 3.585 (3) | 143 (3) |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x−3/2, −y+1/2, z−1/2. |
(IV) 4-bromo-
N'-(2,2,2-trichloroethanimidoyl)benzene-1-carboximidamide
top
Crystal data top
C9H7BrCl3N3 | F(000) = 672 |
Mr = 343.44 | Dx = 1.811 Mg m−3 |
Monoclinic, P21/n | Melting point: 372 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 5.8124 (17) Å | Cell parameters from 9949 reflections |
b = 23.379 (7) Å | θ = 2.4–27.5° |
c = 9.715 (3) Å | µ = 3.87 mm−1 |
β = 107.407 (3)° | T = 173 K |
V = 1259.7 (6) Å3 | Block, colourless |
Z = 4 | 0.22 × 0.20 × 0.11 mm |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 2898 independent reflections |
Radiation source: fine-focus sealed tube, Bruker D8 | 2563 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.068 |
ϕ and ω scans | θmax = 27.5°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | h = −7→7 |
Tmin = 0.483, Tmax = 0.684 | k = −30→30 |
17762 measured reflections | l = −12→12 |
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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.032P)2 + 0.0355P] where P = (Fo2 + 2Fc2)/3 |
2898 reflections | (Δ/σ)max < 0.001 |
157 parameters | Δρmax = 0.61 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
Crystal data top
C9H7BrCl3N3 | V = 1259.7 (6) Å3 |
Mr = 343.44 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.8124 (17) Å | µ = 3.87 mm−1 |
b = 23.379 (7) Å | T = 173 K |
c = 9.715 (3) Å | 0.22 × 0.20 × 0.11 mm |
β = 107.407 (3)° | |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 2898 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | 2563 reflections with I > 2σ(I) |
Tmin = 0.483, Tmax = 0.684 | Rint = 0.068 |
17762 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.61 e Å−3 |
2898 reflections | Δρmin = −0.36 e Å−3 |
157 parameters | |
Special details top
Experimental. A crystal coated in Paratone (TM) oil was mounted on the end of a thin glass
capillary and cooled in the gas stream of the diffractometer Kryoflex device. |
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. The three N—H hydrogen atom positions were refined using a
distance constraint (0.88 Å) with isotropic thermal parameters constrained
to 1.2 × that of the attached nitrogen atom. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | −0.31061 (3) | 0.055482 (7) | −0.00590 (2) | 0.03134 (8) | |
Cl3 | 0.10682 (9) | 0.40490 (2) | 0.07715 (6) | 0.03762 (13) | |
Cl1 | 0.48116 (9) | 0.38658 (2) | −0.05926 (5) | 0.03232 (12) | |
Cl2 | 0.56396 (10) | 0.46071 (2) | 0.18824 (6) | 0.03954 (13) | |
N1 | 0.6083 (3) | 0.23809 (7) | 0.34129 (17) | 0.0293 (3) | |
H1 | 0.618 (4) | 0.2086 (7) | 0.393 (2) | 0.035* | |
H2 | 0.705 (3) | 0.2673 (8) | 0.372 (2) | 0.035* | |
N2 | 0.3693 (3) | 0.29746 (6) | 0.15879 (15) | 0.0240 (3) | |
N3 | 0.7189 (3) | 0.34433 (7) | 0.30475 (19) | 0.0359 (4) | |
H3 | 0.777 (4) | 0.3780 (7) | 0.313 (3) | 0.043* | |
C1 | 0.4163 (3) | 0.24862 (7) | 0.23064 (18) | 0.0227 (4) | |
C2 | 0.5193 (3) | 0.34356 (7) | 0.20405 (18) | 0.0244 (4) | |
C3 | 0.4206 (3) | 0.39678 (7) | 0.1098 (2) | 0.0250 (4) | |
C4 | 0.2394 (3) | 0.20153 (7) | 0.17975 (18) | 0.0225 (4) | |
C5 | 0.3140 (3) | 0.14443 (7) | 0.19087 (19) | 0.0241 (4) | |
H5 | 0.4786 | 0.1354 | 0.2363 | 0.029* | |
C6 | 0.1504 (3) | 0.10101 (7) | 0.1363 (2) | 0.0252 (4) | |
H6 | 0.2011 | 0.0622 | 0.1437 | 0.030* | |
C7 | −0.0875 (3) | 0.11519 (7) | 0.07086 (19) | 0.0237 (4) | |
C8 | −0.1686 (3) | 0.17124 (7) | 0.0598 (2) | 0.0265 (4) | |
H8 | −0.3338 | 0.1800 | 0.0152 | 0.032* | |
C9 | −0.0020 (3) | 0.21445 (7) | 0.1156 (2) | 0.0257 (4) | |
H9 | −0.0541 | 0.2531 | 0.1097 | 0.031* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.02543 (11) | 0.02462 (11) | 0.04149 (14) | −0.00413 (7) | 0.00622 (9) | 0.00085 (7) |
Cl3 | 0.0244 (2) | 0.0431 (3) | 0.0454 (3) | 0.00339 (19) | 0.0105 (2) | 0.0013 (2) |
Cl1 | 0.0348 (3) | 0.0404 (3) | 0.0232 (2) | −0.00569 (19) | 0.0109 (2) | 0.00028 (19) |
Cl2 | 0.0436 (3) | 0.0277 (2) | 0.0408 (3) | −0.0082 (2) | 0.0027 (2) | −0.0075 (2) |
N1 | 0.0303 (9) | 0.0304 (8) | 0.0212 (8) | −0.0007 (7) | −0.0015 (7) | 0.0015 (6) |
N2 | 0.0228 (7) | 0.0278 (8) | 0.0187 (8) | −0.0055 (6) | 0.0019 (6) | −0.0004 (6) |
N3 | 0.0312 (9) | 0.0346 (9) | 0.0317 (10) | −0.0094 (7) | −0.0060 (7) | 0.0006 (7) |
C1 | 0.0224 (9) | 0.0286 (9) | 0.0173 (9) | −0.0012 (7) | 0.0061 (7) | −0.0029 (7) |
C2 | 0.0240 (9) | 0.0308 (9) | 0.0175 (9) | −0.0034 (7) | 0.0050 (7) | −0.0018 (7) |
C3 | 0.0226 (9) | 0.0289 (9) | 0.0225 (9) | −0.0055 (7) | 0.0051 (7) | −0.0044 (7) |
C4 | 0.0232 (9) | 0.0277 (9) | 0.0179 (9) | −0.0015 (7) | 0.0081 (7) | 0.0006 (7) |
C5 | 0.0212 (8) | 0.0283 (9) | 0.0221 (9) | 0.0021 (7) | 0.0054 (7) | 0.0029 (7) |
C6 | 0.0251 (9) | 0.0230 (8) | 0.0292 (10) | 0.0034 (7) | 0.0108 (8) | 0.0038 (7) |
C7 | 0.0236 (9) | 0.0237 (8) | 0.0251 (10) | −0.0054 (7) | 0.0095 (8) | 0.0007 (7) |
C8 | 0.0193 (8) | 0.0282 (9) | 0.0319 (10) | 0.0009 (7) | 0.0077 (7) | 0.0045 (8) |
C9 | 0.0247 (9) | 0.0226 (8) | 0.0310 (10) | 0.0012 (7) | 0.0101 (8) | 0.0028 (7) |
Geometric parameters (Å, º) top
Br1—C7 | 1.8996 (17) | C2—C3 | 1.550 (2) |
Cl3—C3 | 1.7657 (19) | C4—C9 | 1.387 (2) |
Cl1—C3 | 1.7953 (19) | C4—C5 | 1.398 (2) |
Cl2—C3 | 1.7690 (18) | C5—C6 | 1.383 (2) |
N1—C1 | 1.321 (2) | C5—H5 | 0.9500 |
N1—H1 | 0.846 (15) | C6—C7 | 1.379 (2) |
N1—H2 | 0.876 (15) | C6—H6 | 0.9500 |
N2—C1 | 1.323 (2) | C7—C8 | 1.386 (3) |
N2—C2 | 1.373 (2) | C8—C9 | 1.392 (2) |
N3—C2 | 1.275 (2) | C8—H8 | 0.9500 |
N3—H3 | 0.851 (16) | C9—H9 | 0.9500 |
C1—C4 | 1.487 (2) | | |
| | | |
C1—N1—H1 | 121.7 (15) | C9—C4—C1 | 119.61 (15) |
C1—N1—H2 | 115.4 (15) | C5—C4—C1 | 120.92 (15) |
H1—N1—H2 | 121 (2) | C6—C5—C4 | 120.63 (16) |
C1—N2—C2 | 119.82 (15) | C6—C5—H5 | 119.7 |
C2—N3—H3 | 109.4 (16) | C4—C5—H5 | 119.7 |
N1—C1—N2 | 125.51 (16) | C7—C6—C5 | 118.66 (16) |
N1—C1—C4 | 117.70 (15) | C7—C6—H6 | 120.7 |
N2—C1—C4 | 116.78 (15) | C5—C6—H6 | 120.7 |
N3—C2—N2 | 126.99 (17) | C6—C7—C8 | 122.29 (16) |
N3—C2—C3 | 122.23 (16) | C6—C7—Br1 | 118.50 (13) |
N2—C2—C3 | 110.72 (15) | C8—C7—Br1 | 119.21 (14) |
C2—C3—Cl3 | 111.85 (12) | C7—C8—C9 | 118.37 (17) |
C2—C3—Cl2 | 112.36 (12) | C7—C8—H8 | 120.8 |
Cl3—C3—Cl2 | 108.33 (9) | C9—C8—H8 | 120.8 |
C2—C3—Cl1 | 107.15 (12) | C4—C9—C8 | 120.60 (16) |
Cl3—C3—Cl1 | 108.95 (10) | C4—C9—H9 | 119.7 |
Cl2—C3—Cl1 | 108.09 (9) | C8—C9—H9 | 119.7 |
C9—C4—C5 | 119.43 (16) | | |
| | | |
C2—N2—C1—N1 | −4.3 (3) | N1—C1—C4—C5 | −31.6 (2) |
C2—N2—C1—C4 | 177.01 (14) | N2—C1—C4—C5 | 147.16 (16) |
C1—N2—C2—N3 | 6.3 (3) | C9—C4—C5—C6 | 1.2 (3) |
C1—N2—C2—C3 | −176.51 (15) | C1—C4—C5—C6 | −176.50 (15) |
N3—C2—C3—Cl3 | −138.95 (16) | C4—C5—C6—C7 | −0.1 (3) |
N2—C2—C3—Cl3 | 43.72 (18) | C5—C6—C7—C8 | −0.9 (3) |
N3—C2—C3—Cl2 | −16.9 (2) | C5—C6—C7—Br1 | 179.29 (12) |
N2—C2—C3—Cl2 | 165.81 (11) | C6—C7—C8—C9 | 0.7 (3) |
N3—C2—C3—Cl1 | 101.71 (18) | Br1—C7—C8—C9 | −179.47 (13) |
N2—C2—C3—Cl1 | −75.61 (15) | C5—C4—C9—C8 | −1.4 (3) |
N1—C1—C4—C9 | 150.74 (17) | C1—C4—C9—C8 | 176.35 (15) |
N2—C1—C4—C9 | −30.5 (2) | C7—C8—C9—C4 | 0.4 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2···N3 | 0.88 (2) | 1.93 (2) | 2.616 (2) | 135 (2) |
N3—H3···Cl2 | 0.85 (2) | 2.42 (2) | 2.9809 (19) | 124 (2) |
N1—H1···N2i | 0.85 (2) | 2.56 (2) | 3.116 (2) | 124 (2) |
N3—H3···Br1ii | 0.85 (2) | 2.95 (2) | 3.6523 (18) | 141 (2) |
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) x+3/2, −y+1/2, z+1/2. |
(V) 4-trifluoromethyl-
N'-(2,2,2-trichloroethanimidoyl)benzene-
1-carboximidamide
top
Crystal data top
C10H7Cl3F3N3 | F(000) = 664 |
Mr = 332.54 | Dx = 1.734 Mg m−3 |
Monoclinic, P21/n | Melting point: 370 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 11.2939 (17) Å | Cell parameters from 8858 reflections |
b = 8.3914 (13) Å | θ = 2.5–28.7° |
c = 13.505 (2) Å | µ = 0.74 mm−1 |
β = 95.505 (2)° | T = 173 K |
V = 1274.0 (3) Å3 | Block, colourless |
Z = 4 | 0.25 × 0.25 × 0.12 mm |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 3191 independent reflections |
Radiation source: fine-focus sealed tube, Bruker D8 | 2862 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ϕ and ω scans | θmax = 28.9°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | h = −15→14 |
Tmin = 0.699, Tmax = 0.746 | k = −11→11 |
18460 measured reflections | l = −18→18 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0459P)2 + 1.189P] where P = (Fo2 + 2Fc2)/3 |
3191 reflections | (Δ/σ)max < 0.001 |
181 parameters | Δρmax = 0.90 e Å−3 |
3 restraints | Δρmin = −0.58 e Å−3 |
Crystal data top
C10H7Cl3F3N3 | V = 1274.0 (3) Å3 |
Mr = 332.54 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.2939 (17) Å | µ = 0.74 mm−1 |
b = 8.3914 (13) Å | T = 173 K |
c = 13.505 (2) Å | 0.25 × 0.25 × 0.12 mm |
β = 95.505 (2)° | |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 3191 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | 2862 reflections with I > 2σ(I) |
Tmin = 0.699, Tmax = 0.746 | Rint = 0.018 |
18460 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 3 restraints |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.90 e Å−3 |
3191 reflections | Δρmin = −0.58 e Å−3 |
181 parameters | |
Special details top
Experimental. A crystal coated in Paratone (TM) oil was mounted on the end of a thin glass
capillary and cooled in the gas stream of the diffractometer Kryoflex device. |
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. The three N—H hydrogen atom positions were refined using a
distance constraint (0.88 Å) with isotropic thermal parameters constrained
to 1.2 × that of the attached nitrogen atom. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.07598 (4) | 0.17549 (6) | 0.34650 (4) | 0.03310 (13) | |
Cl2 | 0.05810 (4) | −0.15293 (6) | 0.40281 (4) | 0.03458 (13) | |
Cl3 | 0.24053 (4) | −0.05899 (6) | 0.28148 (3) | 0.03334 (13) | |
N1 | 0.43487 (16) | 0.1229 (2) | 0.61038 (12) | 0.0332 (4) | |
H1 | 0.5042 (17) | 0.132 (3) | 0.6434 (17) | 0.040* | |
H2 | 0.3764 (19) | 0.068 (3) | 0.6300 (19) | 0.040* | |
N2 | 0.33288 (13) | 0.13981 (19) | 0.45102 (11) | 0.0257 (3) | |
N3 | 0.22810 (15) | −0.0136 (2) | 0.56173 (12) | 0.0294 (3) | |
H3 | 0.1668 (18) | −0.077 (3) | 0.5618 (18) | 0.035* | |
C1 | 0.42252 (15) | 0.1734 (2) | 0.51656 (13) | 0.0222 (3) | |
C2 | 0.24428 (15) | 0.0396 (2) | 0.47579 (13) | 0.0233 (3) | |
C3 | 0.15932 (15) | 0.0009 (2) | 0.38128 (13) | 0.0249 (3) | |
C4 | 0.51996 (14) | 0.2725 (2) | 0.48188 (12) | 0.0215 (3) | |
C5 | 0.60362 (16) | 0.3475 (2) | 0.54866 (13) | 0.0249 (3) | |
H5 | 0.5968 | 0.3401 | 0.6181 | 0.030* | |
C6 | 0.69674 (16) | 0.4330 (2) | 0.51476 (14) | 0.0266 (4) | |
H6 | 0.7539 | 0.4836 | 0.5606 | 0.032* | |
C7 | 0.70557 (16) | 0.4440 (2) | 0.41340 (14) | 0.0248 (3) | |
C8 | 0.62103 (17) | 0.3739 (2) | 0.34570 (13) | 0.0263 (4) | |
H8 | 0.6267 | 0.3848 | 0.2763 | 0.032* | |
C9 | 0.52848 (16) | 0.2882 (2) | 0.37967 (13) | 0.0252 (3) | |
H9 | 0.4706 | 0.2399 | 0.3335 | 0.030* | |
C10 | 0.80815 (18) | 0.5304 (2) | 0.37550 (15) | 0.0330 (4) | |
F1 | 0.87562 (15) | 0.4359 (2) | 0.32727 (16) | 0.0705 (5) | |
F2 | 0.77309 (17) | 0.6395 (3) | 0.30794 (18) | 0.0899 (7) | |
F3 | 0.87537 (18) | 0.6042 (3) | 0.44403 (13) | 0.0922 (8) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0291 (2) | 0.0379 (3) | 0.0319 (2) | 0.00576 (18) | 0.00042 (17) | 0.00676 (18) |
Cl2 | 0.0298 (2) | 0.0392 (3) | 0.0342 (2) | −0.01267 (19) | 0.00013 (18) | 0.00240 (19) |
Cl3 | 0.0291 (2) | 0.0469 (3) | 0.0243 (2) | 0.00111 (19) | 0.00397 (17) | −0.00443 (18) |
N1 | 0.0298 (8) | 0.0453 (10) | 0.0236 (8) | −0.0116 (7) | −0.0027 (6) | 0.0075 (7) |
N2 | 0.0233 (7) | 0.0311 (8) | 0.0224 (7) | −0.0041 (6) | 0.0006 (6) | 0.0029 (6) |
N3 | 0.0265 (8) | 0.0363 (9) | 0.0257 (7) | −0.0052 (7) | 0.0033 (6) | 0.0041 (6) |
C1 | 0.0228 (8) | 0.0226 (8) | 0.0214 (8) | 0.0019 (6) | 0.0034 (6) | −0.0001 (6) |
C2 | 0.0208 (8) | 0.0259 (8) | 0.0230 (8) | 0.0005 (6) | 0.0016 (6) | 0.0007 (6) |
C3 | 0.0207 (8) | 0.0297 (9) | 0.0244 (8) | −0.0014 (7) | 0.0027 (6) | 0.0024 (7) |
C4 | 0.0208 (7) | 0.0213 (8) | 0.0224 (8) | 0.0018 (6) | 0.0021 (6) | 0.0003 (6) |
C5 | 0.0269 (8) | 0.0274 (8) | 0.0205 (8) | −0.0005 (7) | 0.0024 (6) | −0.0009 (6) |
C6 | 0.0262 (8) | 0.0268 (9) | 0.0264 (9) | −0.0034 (7) | 0.0011 (7) | −0.0038 (7) |
C7 | 0.0251 (8) | 0.0221 (8) | 0.0281 (8) | −0.0009 (6) | 0.0064 (7) | −0.0015 (6) |
C8 | 0.0295 (9) | 0.0274 (9) | 0.0223 (8) | −0.0007 (7) | 0.0044 (7) | 0.0002 (7) |
C9 | 0.0260 (8) | 0.0270 (8) | 0.0221 (8) | −0.0013 (7) | 0.0004 (6) | −0.0005 (7) |
C10 | 0.0347 (10) | 0.0321 (10) | 0.0340 (10) | −0.0076 (8) | 0.0121 (8) | −0.0048 (8) |
F1 | 0.0537 (9) | 0.0596 (10) | 0.1066 (14) | −0.0099 (8) | 0.0514 (10) | −0.0237 (9) |
F2 | 0.0653 (11) | 0.0827 (14) | 0.1254 (18) | −0.0073 (10) | 0.0275 (11) | 0.0643 (13) |
F3 | 0.0891 (13) | 0.1373 (18) | 0.0550 (10) | −0.0879 (14) | 0.0317 (9) | −0.0372 (11) |
Geometric parameters (Å, º) top
Cl1—C3 | 1.7799 (19) | C4—C9 | 1.399 (2) |
Cl2—C3 | 1.7669 (18) | C5—C6 | 1.387 (3) |
Cl3—C3 | 1.7742 (18) | C5—H5 | 0.9500 |
N1—C1 | 1.331 (2) | C6—C7 | 1.385 (3) |
N1—H1 | 0.867 (16) | C6—H6 | 0.9500 |
N1—H2 | 0.866 (17) | C7—C8 | 1.388 (3) |
N2—C1 | 1.310 (2) | C7—C10 | 1.498 (3) |
N2—C2 | 1.373 (2) | C8—C9 | 1.383 (3) |
N3—C2 | 1.273 (2) | C8—H8 | 0.9500 |
N3—H3 | 0.872 (16) | C9—H9 | 0.9500 |
C1—C4 | 1.490 (2) | C10—F3 | 1.297 (3) |
C2—C3 | 1.556 (2) | C10—F1 | 1.315 (2) |
C4—C5 | 1.393 (2) | C10—F2 | 1.326 (3) |
| | | |
C1—N1—H1 | 117.9 (17) | C6—C5—H5 | 119.7 |
C1—N1—H2 | 116.5 (17) | C4—C5—H5 | 119.7 |
H1—N1—H2 | 125 (2) | C7—C6—C5 | 119.30 (16) |
C1—N2—C2 | 120.08 (15) | C7—C6—H6 | 120.3 |
C2—N3—H3 | 113.4 (17) | C5—C6—H6 | 120.3 |
N2—C1—N1 | 125.35 (17) | C6—C7—C8 | 120.84 (16) |
N2—C1—C4 | 116.99 (15) | C6—C7—C10 | 120.09 (17) |
N1—C1—C4 | 117.63 (15) | C8—C7—C10 | 119.07 (16) |
N3—C2—N2 | 127.51 (16) | C9—C8—C7 | 119.74 (16) |
N3—C2—C3 | 122.93 (16) | C9—C8—H8 | 120.1 |
N2—C2—C3 | 109.54 (14) | C7—C8—H8 | 120.1 |
C2—C3—Cl2 | 112.04 (12) | C8—C9—C4 | 120.13 (16) |
C2—C3—Cl3 | 111.06 (12) | C8—C9—H9 | 119.9 |
Cl2—C3—Cl3 | 107.93 (10) | C4—C9—H9 | 119.9 |
C2—C3—Cl1 | 108.29 (12) | F3—C10—F1 | 108.3 (2) |
Cl2—C3—Cl1 | 108.10 (9) | F3—C10—F2 | 106.1 (2) |
Cl3—C3—Cl1 | 109.36 (9) | F1—C10—F2 | 103.0 (2) |
C5—C4—C9 | 119.32 (16) | F3—C10—C7 | 113.97 (17) |
C5—C4—C1 | 121.63 (15) | F1—C10—C7 | 112.43 (17) |
C9—C4—C1 | 119.04 (15) | F2—C10—C7 | 112.30 (18) |
C6—C5—C4 | 120.62 (16) | | |
| | | |
C2—N2—C1—N1 | −2.9 (3) | C1—C4—C5—C6 | 176.99 (16) |
C2—N2—C1—C4 | 175.25 (15) | C4—C5—C6—C7 | 0.4 (3) |
C1—N2—C2—N3 | 9.7 (3) | C5—C6—C7—C8 | 1.6 (3) |
C1—N2—C2—C3 | −171.99 (16) | C5—C6—C7—C10 | −177.59 (17) |
N3—C2—C3—Cl2 | −11.6 (2) | C6—C7—C8—C9 | −1.8 (3) |
N2—C2—C3—Cl2 | 170.06 (12) | C10—C7—C8—C9 | 177.35 (17) |
N3—C2—C3—Cl3 | −132.36 (17) | C7—C8—C9—C4 | 0.1 (3) |
N2—C2—C3—Cl3 | 49.28 (18) | C5—C4—C9—C8 | 1.7 (3) |
N3—C2—C3—Cl1 | 107.55 (18) | C1—C4—C9—C8 | −177.27 (16) |
N2—C2—C3—Cl1 | −70.81 (16) | C6—C7—C10—F3 | −7.1 (3) |
N2—C1—C4—C5 | 163.99 (17) | C8—C7—C10—F3 | 173.7 (2) |
N1—C1—C4—C5 | −17.7 (3) | C6—C7—C10—F1 | 116.6 (2) |
N2—C1—C4—C9 | −17.0 (2) | C8—C7—C10—F1 | −62.5 (3) |
N1—C1—C4—C9 | 161.27 (17) | C6—C7—C10—F2 | −127.8 (2) |
C9—C4—C5—C6 | −2.0 (3) | C8—C7—C10—F2 | 53.0 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2···N3 | 0.87 (2) | 1.96 (2) | 2.628 (2) | 133 (2) |
N3—H3···Cl2 | 0.87 (2) | 2.45 (2) | 2.9779 (17) | 119 (2) |
Experimental details
| (I) | (II) | (III) | (IV) |
Crystal data |
Chemical formula | C10H10Cl3N3O | C9H8Cl3N3 | C9H7Cl4N3 | C9H7BrCl3N3 |
Mr | 294.56 | 264.53 | 298.98 | 343.44 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 173 | 173 | 173 | 173 |
a, b, c (Å) | 12.0988 (10), 8.6425 (7), 12.2023 (10) | 10.2999 (3), 10.9423 (3), 15.6902 (4) | 5.762 (2), 22.711 (8), 9.713 (4) | 5.8124 (17), 23.379 (7), 9.715 (3) |
α, β, γ (°) | 90, 107.445 (1), 90 | 85.5518 (12), 86.5092 (12), 81.5436 (11) | 90, 106.031 (4), 90 | 90, 107.407 (3), 90 |
V (Å3) | 1217.23 (17) | 1741.67 (8) | 1221.7 (8) | 1259.7 (6) |
Z | 4 | 6 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.74 | 0.76 | 0.94 | 3.87 |
Crystal size (mm) | 0.21 × 0.19 × 0.07 | 0.18 × 0.15 × 0.10 | 0.32 × 0.10 × 0.08 | 0.22 × 0.20 × 0.11 |
|
Data collection |
Diffractometer | Bruker APEXII CCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer | Bruker APEXII CCD area-detector diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2006) | Multi-scan (SADABS; Bruker, 2006) | Multi-scan (SADABS; Bruker, 2006) | Multi-scan (SADABS; Bruker, 2006) |
Tmin, Tmax | 0.697, 0.746 | 0.876, 0.928 | 0.613, 0.746 | 0.483, 0.684 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17246, 2812, 2448 | 14588, 7908, 4900 | 16666, 2803, 2248 | 17762, 2898, 2563 |
Rint | 0.026 | 0.076 | 0.041 | 0.068 |
(sin θ/λ)max (Å−1) | 0.651 | 0.654 | 0.651 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.064, 1.05 | 0.055, 0.151, 0.97 | 0.050, 0.122, 1.21 | 0.024, 0.062, 1.08 |
No. of reflections | 2812 | 7908 | 2803 | 2898 |
No. of parameters | 164 | 434 | 154 | 157 |
No. of restraints | 3 | 9 | 3 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.25 | 0.47, −0.49 | 0.50, −0.35 | 0.61, −0.36 |
| (V) |
Crystal data |
Chemical formula | C10H7Cl3F3N3 |
Mr | 332.54 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 11.2939 (17), 8.3914 (13), 13.505 (2) |
α, β, γ (°) | 90, 95.505 (2), 90 |
V (Å3) | 1274.0 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.74 |
Crystal size (mm) | 0.25 × 0.25 × 0.12 |
|
Data collection |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2006) |
Tmin, Tmax | 0.699, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18460, 3191, 2862 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.680 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.098, 1.06 |
No. of reflections | 3191 |
No. of parameters | 181 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.90, −0.58 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2···N3 | 0.861 (14) | 1.995 (17) | 2.647 (2) | 131.7 (17) |
N3—H3···Cl2 | 0.858 (15) | 2.426 (18) | 2.9791 (15) | 122.7 (16) |
N1—H1···O1i | 0.854 (14) | 2.197 (15) | 3.0315 (17) | 165.6 (17) |
N3—H3···Cl3ii | 0.858 (15) | 2.757 (18) | 3.4077 (15) | 133.8 (16) |
Symmetry codes: (i) −x, y+1/2, −z−1/2; (ii) −x+1, y+1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H2A···N3A | 0.888 (18) | 1.99 (3) | 2.657 (4) | 130 (3) |
N3A—H3A···Cl2A | 0.883 (18) | 2.38 (3) | 2.969 (3) | 125 (3) |
N1A—H1A···N2Ci | 0.878 (18) | 2.255 (19) | 3.126 (4) | 172 (3) |
N1B—H1B···N2A | 0.866 (18) | 2.278 (19) | 3.136 (4) | 171 (3) |
N3B—H3B···Cl2B | 0.882 (18) | 2.41 (3) | 2.978 (3) | 122 (3) |
N1B—H2B···N3B | 0.893 (18) | 1.94 (3) | 2.646 (4) | 135 (3) |
N3B—H3B···Cl1Aii | 0.882 (18) | 2.91 (3) | 3.383 (3) | 115 (3) |
N1C—H2C···N3C | 0.892 (18) | 1.91 (3) | 2.644 (4) | 138 (3) |
N3C—H3C···Cl2C | 0.872 (18) | 2.47 (3) | 3.023 (3) | 122 (3) |
N1C—H1C···N2B | 0.873 (18) | 2.24 (2) | 3.072 (3) | 160 (3) |
N1C—H1C···Cl1B | 0.873 (18) | 2.90 (3) | 3.511 (3) | 128 (3) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+2, −z. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2···N3 | 0.874 (18) | 1.92 (3) | 2.628 (4) | 137 (3) |
N3—H3···Cl2 | 0.878 (19) | 2.42 (4) | 2.982 (3) | 122 (3) |
N1—H1···N2i | 0.873 (18) | 2.68 (4) | 3.125 (4) | 113 (3) |
N1—H1···Cl1i | 0.873 (18) | 2.95 (3) | 3.507 (3) | 124 (3) |
N3—H3···Cl4ii | 0.878 (19) | 2.85 (3) | 3.585 (3) | 143 (3) |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x−3/2, −y+1/2, z−1/2. |
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2···N3 | 0.876 (15) | 1.925 (19) | 2.616 (2) | 135 (2) |
N3—H3···Cl2 | 0.851 (16) | 2.42 (2) | 2.9809 (19) | 124 (2) |
N1—H1···N2i | 0.846 (15) | 2.56 (2) | 3.116 (2) | 124.2 (18) |
N3—H3···Br1ii | 0.851 (16) | 2.95 (2) | 3.6523 (18) | 141 (2) |
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) x+3/2, −y+1/2, z+1/2. |
Hydrogen-bond geometry (Å, º) for (V) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2···N3 | 0.866 (17) | 1.96 (2) | 2.628 (2) | 133 (2) |
N3—H3···Cl2 | 0.872 (16) | 2.45 (2) | 2.9779 (17) | 119 (2) |
Average bond lengths (Å) and angles (°) for compounds (I)–(V), and
comparison with the averages in two biguanides (CSD refcodes BIGUAN01 and
NIWCAY) topBond | Average (I)–(V) | Biguanides | Angle | Average (I)–(V) | Biguanides |
N1—C1 | 1.327 (5) | 1.325 (2) | N1–C1–N2 | 125.6 (2) | 128.6 (2) |
C1—N2 | 1.323 (7) | 1.329 (2) | N1–C1–C4 | 117.8 (4) | |
N2—C2 | 1.370 (3) | 1.382 (2) | C4–C1–N2 | 116.7 (3) | |
C2—N3 | 1.278 (3) | 1.295 (2) | C1–N2–C2 | 120.1 (2) | 118.1 (2) |
C2—C3 | 1.552 (7) | | N2–C2–N3 | 127.3 (3) | 128.1 (2) |
C1—C4 | 1.488 (5) | | N2–C2–C3 | 110.0 (4) | |
| | | N3–C2–C3 | 122.7 (4) | |
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N-Imidoylamidines are trinitrogen analogues of pentadienes containing unsaturated N≐C≐N≐C≐N chains which may have different degrees of substitution at N. If the substituents at C are further N groups, the familiar biguanides are obtained; imidoylamidines have C substituents on the backbone C atoms. Primary N-imidoylamidines have three ionizable H atoms on N with the possibility of several tautomeric structures. Tertiary exemplars retain a single ionizable H atom. Both primary and, more commonly, tertiary imidoylamidines are potent chelating ligands as deprotonated monoanions. Applications for metal complexes of this ligand type include the development of molecular magnets (Zheng et al., 2007) and switches (Atkinson et al., 2002), and π-activation agents for alkynes (Dias et al., 2009), as well as in catalysis (Flores et al., 2009). Both the chemistry of the neutral molecules and the coordination chemistry of the deprotonated anions have recently been comprehensively reviewed (Kopylovich & Pombeiro, 2011). Crystal structures of the neutral primary N-imidoylamidines are virtually non-existent. We recently reported the synthesis and crystal structures of a number of aryl-trifluoromethyl N-imidoylamidines (Boeré et al., 2011). Herein, we report the crystal structures of five new trichloromethyl analogues, (I)–(V), bearing push and pull substituents on the aryl rings.
The molecular structures of (I)–(V) are remarkably similar and a displacement ellipsoid plot of a representative example is shown in Fig. 1. The same atom-numbering scheme is used for all five structures [modified in the case of (II) by suffixes `A', `B' and `C' to identify the three crystallographically independent molecules in the asymetric unit]. Average bond lengths and angles for the N≐C≐N≐C≐N cores have been compiled along with s.u.s and are listed in Table 6.
The average bond lengths show that C1≐N1 and C1≐N2 are of an intermediate length between single and double bonds, as is characteristic of delocalized amidines, and are identical within their s.u.s. The C2═N3 bonds are short and more characteristic of imines, while the N2—C2 bonds are longer and approximate single bonds. By contrast, the two C—N bonds to which the CCl3 group is attached in (Z)-2,2,2-trichloro-N2-cyanoacetamidine differ in length by only 0.008 Å (Baker & Boeré, 2009). The averaged bond lengths are nearly identical, within their s.u.s, to the recently reported trifluoromethyl series (Boeré et al., 2011). Other known structures of primary imidoylamidines include an unusual chloro-imidoylamidinium salt (Privett et al., 1987) and two biguanides (Pinkerton & Schwarzenbach, 1978; Ernst & Cagle, 1977; Zheng et al., 2007) [Cambridge Structural Database ( Allen, 2002) refcodes HDCADPZ, BIGUAN, BIGUAN01 and NIWCAY, respectively]. The molecular structure of the new compounds (I)–(V) is reminiscent of diiminoisoindoline (Zhang, Njus et al., 2004), including the observation of the amino tautomer in the solid state. Furthermore, the hydrogen-bonding pattern in the new compounds is similar to that in diiminoisoindoline and 1-amino-3-phenyliminoisoindoline (Zhang, Uth et al., 2004).
The pentaazadiene cores of (I)–(V) are close to planar and form pseudo six-membered rings through N1—H2···N3 hydrogen bonding (labelled I in Fig. 2), with donor–acceptor N···N distances in the range 2.616 (2)–2.657 (4) Å. The average distance in all seven independent molecules is 2.638 (14) Å. The related trifluoromethyl series displays a very similar N···N distance of 2.658 (22) Å (Boeré et al., 2011). Each example also shows short N3—H3···Cl2 contacts (II in Fig. 2), with an average donor–acceptor distance of 2.984 (18) Å. This weak contact is sufficient to orient atom Cl2 close to coplanar with the pentaazadiene core for all seven independent molecules.
The intermolecular hydrogen bonding is also very noteworthy. Within the crystal structure, molecules of (I) are linked by N1—H1···O1i,iii hydrogen bonds that form a twofold helix along the [010] direction (Fig. 3). More significantly, the three independent molecules of (II) form threefold helices along the [100] direction, defining a non-crystallographic threefold screw axis through N1—H1···N2i,iii contacts (Fig. 4). In both (III) and isostructural (IV), there are twofold helices in the [100] direction (Fig. 5), also through N1—H1···N2i,iii contacts. Only (V) does not display intermolecular hydrogen bonding, presumably a consequence of the rather bulky CF3 group on the aryl ring. In (II), (III) and (IV), the main hydrogen bonds are of the type N1—H1···N2i,iii, thus linking a terminal NH2 group on one molecule with the central (backbone) N atom of a neighbouring molecule (III in Fig. 2). The average donor–acceptor distance for this interaction is 3.115 (25) Å, which is also, within the s.u.s, equal to such bonds in the trifluoromethyl series at 3.088 (90) Å. While complete atom transfer would generate a diimine tautomer, all seven examples here and from the trifluoromethyl series (Boeré et al., 2011) show the single tautomeric form in the solid-state structure, which is clearly shown in Fig. 1. The terminal NH2 group is typically involved in ring-forming (H2) and chain-forming (H1) interactions, while the terminal ═NH group has contacts to atom Cl2 and often [in (I)–(IV)] displays additional intermolecular interactions with other Cl or Br atoms (V in Fig. 2). In molecule C of (II), there is an additional intermolecular hydrogen bond between N1C—H1C and atom Cl1B of a neighbouring CCl3 group (IV in Fig. 2).