A series of (E)-5-(aryl­idene­amino)-1-tert-butyl-1H-pyrrole-3-carbo­nitriles and their reduction products to secondary amines: syntheses and X-ray structural studies

An efficent access to a series of N-(pyrrol-2-yl)amines, namely (E)-1-tert-butyl-5-[(4-chloro­benzyl­idene)amino]-1H-pyrrole-3-carbo­nitrile, C₁₆H₁₆ClN₃, (7a), (E)-1-tert-butyl-5-[(2,4-di­chloro­benzyl­idene)amino]-1H-pyrrole-3-carbo­nitrile, C₁₆H₁₅Cl₂N₃, (7b), (E)-1-tert-butyl-5-[(pyridin-4-yl­methyl­ene)amino]-1H-pyrrole-3-carbo­nitrile, C₁₅H₁₆N₄, (7c), 1-tert-butyl-5-[(4-chloro­benz­yl)amino]-1H-pyrrole-3-carbo­nitrile, C₁₆H₁₈ClN₃, (8a), and 1-tert-butyl-5-[(2,4-di­chloro­benz­yl)amino]-1H-pyrrole-3-carbo­nitrile, C₁₆H₁₇Cl₂N₃, (8b), by a two-step synthesis sequence (solvent-free condensation and reduction) starting from 5-amino-1-tert-butyl-1H-pyrrole-3-carbo­nitrile is described. The syntheses proceed via isolated N-(pyrrol-2-yl)imines, which are also key synthetic inter­mediates of other valuable compounds. The crystal structures of the reduced compounds showed a reduction in the symmetry compared with the corresponding precursors, viz. Pbcm to P from compound (7a) to (8a) and P2₁/c to P from compound (7b) to (8b), probably due to a severe change in the mol­ecular conformations, resulting in the loss of planarity observed in the nonreduced compounds. In all of the crystals, the supra­molecular assembly is controlled mainly by strong (N,C)—H...N hydrogen bonds. However, in the case of (7a)–(7c), C—H...Cl inter­actions are strong enough to help in the three-dimensional architecture, as observed in Hirshfeld surface maps.

Computing details

For all structures, data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

(E)-1-tert-butyl-5-[(4-chlorobenzylidene)amino]-1H-pyrrole-3-carbonitrile (7a)

Crystal data

C16H16ClN3	Dx = 1.271 Mg m^−3
Mr = 285.77	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcm	Cell parameters from 8043 reflections
a = 8.8317 (14) Å	θ = 4.0–28.0°
b = 24.261 (3) Å	µ = 0.25 mm^−1
c = 6.9706 (14) Å	T = 298 K
V = 1493.6 (4) Å^3	Parallelepiped, yellow
Z = 4	0.19 × 0.14 × 0.11 mm
F(000) = 600

Data collection

Agilent SuperNova Dual Source diffractometer with an Atlas detector	1658 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1417 reflections with I > 2σ(I)
Detector resolution: 5.3072 pixels mm^-1	Rint = 0.060
ω scans	θmax = 26.4°, θmin = 2.9°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −11→11
Tmin = 0.828, Tmax = 1.000	k = −30→30
29057 measured reflections	l = −8→8

Refinement

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: mixed
wR(F^2) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0667P)^2 + 0.5084P] where P = (Fo^2 + 2Fc^2)/3
1658 reflections	(Δ/σ)max < 0.001
124 parameters	Δρmax = 0.16 e Å^−3
15 restraints	Δρmin = −0.29 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Cl4	0.86106 (9)	0.04937 (3)	0.750000	0.0877 (4)
C524	0.8268 (3)	0.11940 (10)	0.750000	0.0526 (6)
C525	0.9478 (3)	0.15465 (10)	0.750000	0.0564 (6)
H525	1.046360	0.141182	0.750000	0.068*
C526	0.9201 (3)	0.21091 (10)	0.750000	0.0565 (7)
H526	1.001353	0.235280	0.750000	0.068*
C521	0.7739 (3)	0.23155 (9)	0.750000	0.0417 (5)
C522	0.6541 (3)	0.19449 (10)	0.750000	0.0507 (6)
H522	0.555139	0.207616	0.750000	0.061*
C523	0.6800 (3)	0.13859 (10)	0.750000	0.0585 (7)
H523	0.599257	0.113988	0.750000	0.070*
C52	0.7474 (3)	0.29093 (9)	0.750000	0.0472 (6)
H52	0.830509	0.314479	0.750000	0.057*
N51	0.6172 (2)	0.31146 (8)	0.750000	0.0479 (5)
C5	0.5981 (3)	0.36838 (9)	0.750000	0.0455 (5)
N1	0.4523 (2)	0.39007 (7)	0.750000	0.0472 (5)
C11	0.3066 (3)	0.35837 (9)	0.750000	0.0534 (6)
C12	0.1732 (3)	0.39860 (12)	0.750000	0.0702 (9)
H12B	0.172 (3)	0.4216 (12)	0.624 (4)	0.105*
H12A	0.083 (4)	0.3774 (17)	0.750000	0.105*
C13	0.3003 (2)	0.32337 (7)	0.5675 (3)	0.0663 (6)
H13A	0.309936	0.346819	0.457270	0.100*
H13B	0.205339	0.304180	0.562117	0.100*
H13C	0.381713	0.297150	0.568733	0.100*
C2	0.4636 (3)	0.44565 (9)	0.750000	0.0536 (6)
H2	0.382738	0.470218	0.750000	0.064*
C3	0.6145 (3)	0.45988 (10)	0.750000	0.0519 (6)
C4	0.6996 (3)	0.41106 (10)	0.750000	0.0522 (6)
H4	0.804606	0.408227	0.750000	0.063*
C31	0.6689 (3)	0.51488 (11)	0.750000	0.0616 (7)
N32	0.7127 (4)	0.55906 (10)	0.750000	0.0859 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl4	0.0744 (5)	0.0333 (4)	0.1552 (9)	0.0047 (3)	0.000	0.000
C524	0.0525 (12)	0.0331 (11)	0.0721 (15)	0.0018 (9)	0.000	0.000
C525	0.0426 (12)	0.0408 (12)	0.0856 (17)	0.0061 (9)	0.000	0.000
C526	0.0409 (12)	0.0392 (12)	0.0893 (19)	−0.0015 (10)	0.000	0.000
C521	0.0446 (12)	0.0345 (11)	0.0462 (11)	0.0005 (9)	0.000	0.000
C522	0.0388 (11)	0.0413 (13)	0.0720 (16)	0.0023 (9)	0.000	0.000
C523	0.0472 (12)	0.0409 (13)	0.0873 (18)	−0.0058 (10)	0.000	0.000
C52	0.0447 (12)	0.0359 (11)	0.0610 (14)	−0.0004 (9)	0.000	0.000
N51	0.0469 (11)	0.0319 (9)	0.0649 (12)	0.0035 (8)	0.000	0.000
C5	0.0448 (12)	0.0327 (11)	0.0590 (13)	0.0017 (9)	0.000	0.000
N1	0.0419 (10)	0.0272 (9)	0.0726 (13)	−0.0002 (7)	0.000	0.000
C11	0.0412 (12)	0.0316 (11)	0.0874 (18)	−0.0019 (9)	0.000	0.000
C12	0.0434 (13)	0.0432 (14)	0.124 (3)	0.0012 (11)	0.000	0.000
C13	0.0548 (10)	0.0458 (10)	0.0983 (16)	−0.0041 (7)	−0.0129 (10)	−0.0109 (10)
C2	0.0512 (13)	0.0289 (11)	0.0808 (17)	0.0007 (9)	0.000	0.000
C3	0.0524 (13)	0.0332 (11)	0.0701 (15)	−0.0052 (10)	0.000	0.000
C4	0.0438 (12)	0.0404 (12)	0.0723 (16)	−0.0028 (9)	0.000	0.000
C31	0.0607 (15)	0.0399 (14)	0.0842 (19)	−0.0078 (11)	0.000	0.000
N32	0.0908 (19)	0.0425 (13)	0.124 (2)	−0.0189 (13)	0.000	0.000

Geometric parameters (Å, º)

Cl4—C524	1.726 (2)	N1—C2	1.352 (3)
C524—C525	1.368 (4)	N1—C11	1.499 (3)
C524—C523	1.378 (4)	C11—C12	1.530 (4)
C525—C526	1.387 (3)	C11—C13	1.530 (2)
C525—H525	0.9300	C11—C13^i	1.530 (2)
C526—C521	1.384 (3)	C12—H12B	1.04 (3)
C526—H526	0.9300	C12—H12A	0.95 (4)
C521—C522	1.389 (3)	C13—H13A	0.9600
C521—C52	1.459 (3)	C13—H13B	0.9600
C522—C523	1.375 (3)	C13—H13C	0.9600
C522—H522	0.9300	C2—C3	1.377 (4)
C523—H523	0.9300	C2—H2	0.9300
C52—N51	1.254 (3)	C3—C4	1.403 (3)
C52—H52	0.9300	C3—C31	1.418 (3)
N51—C5	1.391 (3)	C4—H4	0.9300
C5—C4	1.369 (3)	C31—N32	1.140 (3)
C5—N1	1.391 (3)
C525—C524—C523	121.6 (2)	C5—N1—C11	126.92 (18)
C525—C524—Cl4	118.60 (19)	N1—C11—C12	109.50 (19)
C523—C524—Cl4	119.84 (19)	N1—C11—C13	108.40 (13)
C524—C525—C526	118.5 (2)	C12—C11—C13	109.04 (13)
C524—C525—H525	120.7	N1—C11—C13^i	108.40 (13)
C526—C525—H525	120.7	C12—C11—C13^i	109.04 (13)
C521—C526—C525	121.4 (2)	C13—C11—C13^i	112.4 (2)
C521—C526—H526	119.3	C11—C12—H12B	110.5 (15)
C525—C526—H526	119.3	C11—C12—H12A	107 (2)
C526—C521—C522	118.4 (2)	H12B—C12—H12A	106.6 (18)
C526—C521—C52	120.4 (2)	C11—C13—H13A	109.5
C522—C521—C52	121.1 (2)	C11—C13—H13B	109.5
C523—C522—C521	120.8 (2)	H13A—C13—H13B	109.5
C523—C522—H522	119.6	C11—C13—H13C	109.5
C521—C522—H522	119.6	H13A—C13—H13C	109.5
C522—C523—C524	119.3 (2)	H13B—C13—H13C	109.5
C522—C523—H523	120.3	N1—C2—C3	108.7 (2)
C524—C523—H523	120.3	N1—C2—H2	125.6
N51—C52—C521	122.7 (2)	C3—C2—H2	125.6
N51—C52—H52	118.7	C2—C3—C4	107.9 (2)
C521—C52—H52	118.7	C2—C3—C31	124.3 (2)
C52—N51—C5	120.4 (2)	C4—C3—C31	127.8 (2)
C4—C5—N51	132.2 (2)	C5—C4—C3	106.7 (2)
C4—C5—N1	108.65 (19)	C5—C4—H4	126.6
N51—C5—N1	119.17 (19)	C3—C4—H4	126.6
C2—N1—C5	108.00 (18)	N32—C31—C3	179.9 (3)
C2—N1—C11	125.08 (19)
C523—C524—C525—C526	0.0	C4—C5—N1—C11	180.0
Cl4—C524—C525—C526	180.0	N51—C5—N1—C11	0.0
C524—C525—C526—C521	0.0	C2—N1—C11—C12	0.0
C525—C526—C521—C522	0.0	C5—N1—C11—C12	180.0
C525—C526—C521—C52	180.0	C2—N1—C11—C13	118.85 (13)
C526—C521—C522—C523	0.0	C5—N1—C11—C13	−61.15 (13)
C52—C521—C522—C523	180.0	C2—N1—C11—C13^i	−118.85 (13)
C521—C522—C523—C524	0.0	C5—N1—C11—C13^i	61.15 (13)
C525—C524—C523—C522	0.0	C5—N1—C2—C3	0.0
Cl4—C524—C523—C522	180.0	C11—N1—C2—C3	180.0
C526—C521—C52—N51	180.0	N1—C2—C3—C4	0.0
C522—C521—C52—N51	0.0	N1—C2—C3—C31	180.0
C521—C52—N51—C5	180.0	N51—C5—C4—C3	180.0
C52—N51—C5—C4	0.0	N1—C5—C4—C3	0.0
C52—N51—C5—N1	180.0	C2—C3—C4—C5	0.0
C4—C5—N1—C2	0.0	C31—C3—C4—C5	180.0
N51—C5—N1—C2	180.0

Symmetry code: (i) x, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13C···N51	0.96	2.46	3.088 (3)	123
C13—H13A···N32^ii	0.96	2.71	3.612 (3)	157
C2—H2···Cl4^iii	0.93	2.89	3.815 (3)	178

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

(E)-1-tert-Butyl-5-[(2,4-dichlorobenzylidene)amino]-1H-pyrrole-3-carbonitrile (7b)

Crystal data

C16H15Cl2N3	F(000) = 664
Mr = 320.21	Dx = 1.345 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.5428 (7) Å	Cell parameters from 4572 reflections
b = 7.9586 (11) Å	θ = 4.2–27.4°
c = 30.415 (5) Å	µ = 0.41 mm^−1
β = 92.987 (13)°	T = 298 K
V = 1581.6 (4) Å^3	Parallelepiped, yellow
Z = 4	0.29 × 0.15 × 0.11 mm

Data collection

Agilent SuperNova Dual Source diffractometer with an Atlas detector	3206 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2577 reflections with I > 2σ(I)
Detector resolution: 5.3072 pixels mm^-1	Rint = 0.063
ω scans	θmax = 26.4°, θmin = 2.9°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −8→8
Tmin = 0.425, Tmax = 1.000	k = −9→9
16620 measured reflections	l = −37→36

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.056	H-atom parameters constrained
wR(F^2) = 0.152	w = 1/[σ^2(Fo^2) + (0.0692P)^2 + 0.5679P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
3206 reflections	Δρmax = 0.30 e Å^−3
194 parameters	Δρmin = −0.27 e Å^−3
0 restraints	Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: iterative	Extinction coefficient: 0.012 (2)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Cl4	0.03393 (12)	0.27165 (12)	0.50311 (3)	0.1005 (3)
C524	0.2456 (4)	0.2442 (4)	0.47138 (9)	0.0666 (7)
C525	0.3505 (4)	0.3820 (4)	0.45781 (9)	0.0727 (7)
H525	0.309572	0.489756	0.465247	0.087*
C526	0.5187 (4)	0.3577 (3)	0.43283 (9)	0.0665 (7)
H526	0.590837	0.450933	0.423662	0.080*
C521	0.5831 (3)	0.1988 (3)	0.42101 (7)	0.0510 (5)
C522	0.4701 (3)	0.0640 (3)	0.43527 (7)	0.0553 (5)
C523	0.3015 (3)	0.0851 (4)	0.46058 (8)	0.0654 (7)
H523	0.228285	−0.007213	0.469952	0.079*
Cl2	0.53068 (11)	−0.13911 (9)	0.42043 (3)	0.0821 (3)
C52	0.7592 (3)	0.1784 (3)	0.39353 (7)	0.0523 (5)
H52	0.805700	0.071026	0.387308	0.063*
N51	0.8487 (3)	0.3046 (2)	0.37821 (6)	0.0523 (5)
C5	1.0160 (3)	0.2813 (3)	0.35257 (7)	0.0467 (5)
N1	1.0828 (2)	0.4132 (2)	0.32711 (6)	0.0477 (4)
C2	1.2493 (3)	0.3597 (3)	0.30603 (7)	0.0513 (5)
H2	1.322469	0.423055	0.286539	0.062*
C3	1.2912 (3)	0.1975 (3)	0.31820 (7)	0.0498 (5)
C4	1.1429 (3)	0.1476 (3)	0.34734 (7)	0.0509 (5)
H4	1.133051	0.042866	0.360606	0.061*
C31	1.4582 (3)	0.0989 (3)	0.30407 (8)	0.0578 (6)
N32	1.5904 (3)	0.0178 (3)	0.29370 (8)	0.0779 (7)
C11	0.9860 (3)	0.5830 (3)	0.32291 (8)	0.0561 (6)
C12	1.0988 (5)	0.6875 (3)	0.28982 (11)	0.0811 (8)
H12A	1.087322	0.634141	0.261486	0.122*
H12B	1.240566	0.696318	0.299372	0.122*
H12C	1.039524	0.797714	0.287768	0.122*
C13	0.7630 (4)	0.5615 (4)	0.30588 (10)	0.0774 (8)
H13A	0.704093	0.669864	0.299540	0.116*
H13B	0.687146	0.506433	0.327891	0.116*
H13C	0.758162	0.494840	0.279548	0.116*
C14	1.0010 (5)	0.6677 (3)	0.36761 (10)	0.0770 (8)
H14A	1.142340	0.684605	0.376579	0.115*
H14B	0.937733	0.597860	0.388756	0.115*
H14C	0.932350	0.774287	0.365803	0.115*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl4	0.0738 (5)	0.1201 (7)	0.1128 (7)	0.0060 (4)	0.0553 (5)	0.0066 (5)
C524	0.0513 (13)	0.0881 (18)	0.0623 (14)	−0.0009 (12)	0.0213 (11)	0.0019 (13)
C525	0.0668 (15)	0.0722 (17)	0.0819 (18)	0.0025 (13)	0.0299 (13)	−0.0070 (14)
C526	0.0613 (14)	0.0606 (15)	0.0802 (17)	−0.0061 (11)	0.0281 (12)	−0.0025 (12)
C521	0.0451 (11)	0.0582 (13)	0.0507 (11)	−0.0051 (9)	0.0117 (9)	0.0024 (10)
C522	0.0524 (11)	0.0607 (13)	0.0536 (12)	−0.0034 (10)	0.0118 (9)	0.0085 (10)
C523	0.0534 (13)	0.0768 (17)	0.0677 (15)	−0.0085 (12)	0.0187 (11)	0.0151 (13)
Cl2	0.0864 (5)	0.0578 (4)	0.1053 (6)	−0.0051 (3)	0.0349 (4)	0.0081 (3)
C52	0.0496 (11)	0.0518 (12)	0.0569 (12)	−0.0021 (9)	0.0157 (9)	0.0002 (10)
N51	0.0471 (9)	0.0541 (10)	0.0571 (10)	−0.0024 (8)	0.0179 (8)	−0.0007 (8)
C5	0.0422 (10)	0.0493 (11)	0.0496 (11)	−0.0045 (8)	0.0111 (8)	−0.0002 (9)
N1	0.0445 (9)	0.0458 (9)	0.0538 (10)	−0.0027 (7)	0.0137 (7)	0.0011 (8)
C2	0.0450 (11)	0.0567 (13)	0.0539 (12)	−0.0049 (9)	0.0167 (9)	0.0001 (10)
C3	0.0440 (10)	0.0549 (12)	0.0513 (11)	0.0004 (9)	0.0117 (9)	−0.0059 (9)
C4	0.0517 (11)	0.0479 (11)	0.0543 (12)	−0.0020 (9)	0.0134 (9)	0.0005 (9)
C31	0.0546 (12)	0.0633 (14)	0.0567 (13)	0.0033 (11)	0.0142 (10)	−0.0041 (11)
N32	0.0713 (13)	0.0855 (16)	0.0790 (14)	0.0203 (12)	0.0255 (11)	−0.0075 (12)
C11	0.0529 (12)	0.0465 (11)	0.0703 (14)	0.0005 (9)	0.0178 (10)	0.0039 (10)
C12	0.0856 (19)	0.0593 (15)	0.102 (2)	0.0056 (13)	0.0365 (16)	0.0230 (15)
C13	0.0582 (14)	0.0753 (17)	0.099 (2)	0.0083 (13)	0.0018 (13)	0.0176 (15)
C14	0.0852 (18)	0.0540 (14)	0.094 (2)	−0.0080 (13)	0.0267 (15)	−0.0155 (13)

Geometric parameters (Å, º)

Cl4—C524	1.743 (2)	C2—C3	1.367 (3)
C524—C523	1.363 (4)	C2—H2	0.9300
C524—C525	1.369 (4)	C3—C4	1.405 (3)
C525—C526	1.383 (3)	C3—C31	1.429 (3)
C525—H525	0.9300	C4—H4	0.9300
C526—C521	1.386 (3)	C31—N32	1.137 (3)
C526—H526	0.9300	C11—C14	1.516 (4)
C521—C522	1.386 (3)	C11—C12	1.525 (3)
C521—C52	1.467 (3)	C11—C13	1.532 (3)
C522—C523	1.388 (3)	C12—H12A	0.9600
C522—Cl2	1.730 (3)	C12—H12B	0.9600
C523—H523	0.9300	C12—H12C	0.9600
C52—N51	1.263 (3)	C13—H13A	0.9600
C52—H52	0.9300	C13—H13B	0.9600
N51—C5	1.389 (3)	C13—H13C	0.9600
C5—C4	1.364 (3)	C14—H14A	0.9600
C5—N1	1.389 (3)	C14—H14B	0.9600
N1—C2	1.361 (3)	C14—H14C	0.9600
N1—C11	1.495 (3)
C523—C524—C525	121.8 (2)	C2—C3—C4	107.56 (19)
C523—C524—Cl4	118.7 (2)	C2—C3—C31	125.7 (2)
C525—C524—Cl4	119.5 (2)	C4—C3—C31	126.8 (2)
C524—C525—C526	118.7 (2)	C5—C4—C3	107.35 (19)
C524—C525—H525	120.7	C5—C4—H4	126.3
C526—C525—H525	120.7	C3—C4—H4	126.3
C525—C526—C521	122.1 (2)	N32—C31—C3	178.3 (3)
C525—C526—H526	118.9	N1—C11—C14	108.5 (2)
C521—C526—H526	118.9	N1—C11—C12	109.38 (18)
C526—C521—C522	116.8 (2)	C14—C11—C12	109.8 (2)
C526—C521—C52	120.5 (2)	N1—C11—C13	108.65 (19)
C522—C521—C52	122.7 (2)	C14—C11—C13	111.6 (2)
C521—C522—C523	122.2 (2)	C12—C11—C13	108.8 (2)
C521—C522—Cl2	120.57 (17)	C11—C12—H12A	109.5
C523—C522—Cl2	117.24 (19)	C11—C12—H12B	109.5
C524—C523—C522	118.5 (2)	H12A—C12—H12B	109.5
C524—C523—H523	120.7	C11—C12—H12C	109.5
C522—C523—H523	120.7	H12A—C12—H12C	109.5
N51—C52—C521	121.0 (2)	H12B—C12—H12C	109.5
N51—C52—H52	119.5	C11—C13—H13A	109.5
C521—C52—H52	119.5	C11—C13—H13B	109.5
C52—N51—C5	119.67 (19)	H13A—C13—H13B	109.5
C4—C5—N51	132.22 (19)	C11—C13—H13C	109.5
C4—C5—N1	108.26 (17)	H13A—C13—H13C	109.5
N51—C5—N1	119.50 (18)	H13B—C13—H13C	109.5
C2—N1—C5	108.00 (17)	C11—C14—H14A	109.5
C2—N1—C11	126.06 (17)	C11—C14—H14B	109.5
C5—N1—C11	125.93 (16)	H14A—C14—H14B	109.5
N1—C2—C3	108.82 (18)	C11—C14—H14C	109.5
N1—C2—H2	125.6	H14A—C14—H14C	109.5
C3—C2—H2	125.6	H14B—C14—H14C	109.5
C523—C524—C525—C526	−0.6 (4)	C4—C5—N1—C2	0.6 (2)
Cl4—C524—C525—C526	179.7 (2)	N51—C5—N1—C2	178.83 (18)
C524—C525—C526—C521	0.3 (4)	C4—C5—N1—C11	179.39 (19)
C525—C526—C521—C522	0.3 (4)	N51—C5—N1—C11	−2.3 (3)
C525—C526—C521—C52	178.5 (2)	C5—N1—C2—C3	−1.0 (2)
C526—C521—C522—C523	−0.7 (3)	C11—N1—C2—C3	−179.8 (2)
C52—C521—C522—C523	−178.8 (2)	N1—C2—C3—C4	1.1 (2)
C526—C521—C522—Cl2	177.28 (19)	N1—C2—C3—C31	−178.1 (2)
C52—C521—C522—Cl2	−0.9 (3)	N51—C5—C4—C3	−177.9 (2)
C525—C524—C523—C522	0.3 (4)	N1—C5—C4—C3	0.1 (2)
Cl4—C524—C523—C522	179.93 (18)	C2—C3—C4—C5	−0.7 (2)
C521—C522—C523—C524	0.4 (4)	C31—C3—C4—C5	178.4 (2)
Cl2—C522—C523—C524	−177.6 (2)	C2—N1—C11—C14	−117.9 (2)
C526—C521—C52—N51	−3.8 (3)	C5—N1—C11—C14	63.5 (3)
C522—C521—C52—N51	174.3 (2)	C2—N1—C11—C12	1.9 (3)
C521—C52—N51—C5	179.55 (19)	C5—N1—C11—C12	−176.8 (2)
C52—N51—C5—C4	−17.9 (4)	C2—N1—C11—C13	120.5 (2)
C52—N51—C5—N1	164.3 (2)	C5—N1—C11—C13	−58.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13B···N51	0.96	2.42	3.034 (3)	121
C14—H14B···N51	0.96	2.42	3.079 (3)	125
C52—H52···Cl2	0.93	2.69	3.069 (2)	105
C523—H523···Cl4^i	0.93	2.86	3.788 (3)	174
C2—H2···N32^ii	0.93	2.64	3.495 (3)	152

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

(E)-1-tert-Butyl-5-[(pyridin-4-ylmethylene)amino]-1H-pyrrole-3-carbonitrile (7c)

Crystal data

C15H16N4	Z = 2
Mr = 252.32	F(000) = 268
Triclinic, P1	Dx = 1.217 Mg m^−3
a = 8.1494 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.0629 (10) Å	Cell parameters from 6196 reflections
c = 9.4859 (9) Å	θ = 3.5–26.3°
α = 92.465 (8)°	µ = 0.08 mm^−1
β = 97.113 (8)°	T = 298 K
γ = 97.136 (9)°	Parallelepiped, yellow
V = 688.61 (12) Å^3	0.31 × 0.28 × 0.19 mm

Data collection

Agilent SuperNova Dual Source diffractometer with an Atlas detector	2807 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2419 reflections with I > 2σ(I)
Detector resolution: 5.3072 pixels mm^-1	Rint = 0.045
ω scans	θmax = 26.4°, θmin = 3.0°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −9→10
Tmin = 0.831, Tmax = 1.000	k = −11→11
14493 measured reflections	l = −11→11

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.151	w = 1/[σ^2(Fo^2) + (0.0646P)^2 + 0.2783P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
2807 reflections	Δρmax = 0.23 e Å^−3
176 parameters	Δρmin = −0.18 e Å^−3
0 restraints	Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: iterative	Extinction coefficient: 0.049 (7)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
N1	0.61053 (16)	0.72071 (15)	0.16935 (14)	0.0405 (4)
C5	0.7818 (2)	0.75187 (19)	0.20946 (17)	0.0415 (4)
N51	0.84879 (17)	0.72275 (16)	0.34611 (15)	0.0441 (4)
C52	0.9862 (2)	0.7983 (2)	0.39940 (18)	0.0441 (4)
H52	1.039742	0.867236	0.344820	0.053*
C521	1.0622 (2)	0.77937 (19)	0.54474 (17)	0.0407 (4)
C522	1.0027 (2)	0.6685 (2)	0.6283 (2)	0.0539 (5)
H522	0.912991	0.597861	0.592067	0.065*
C523	1.0780 (3)	0.6642 (3)	0.7656 (2)	0.0638 (6)
H523	1.037087	0.588644	0.820113	0.077*
N524	1.2068 (2)	0.7622 (2)	0.82561 (17)	0.0614 (5)
C525	1.2629 (2)	0.8670 (2)	0.7440 (2)	0.0543 (5)
H525	1.352426	0.936378	0.783235	0.065*
C526	1.1973 (2)	0.8801 (2)	0.60481 (19)	0.0471 (4)
H526	1.242843	0.955235	0.552054	0.057*
C4	0.8526 (2)	0.8119 (2)	0.09749 (18)	0.0477 (4)
H4	0.965593	0.841379	0.094746	0.057*
C3	0.7221 (2)	0.8203 (2)	−0.01232 (17)	0.0448 (4)
C2	0.5754 (2)	0.76432 (19)	0.03553 (17)	0.0430 (4)
H2	0.469588	0.757594	−0.015734	0.052*
C31	0.7340 (2)	0.8783 (2)	−0.14841 (19)	0.0518 (5)
N32	0.7428 (3)	0.9256 (2)	−0.25738 (19)	0.0730 (6)
C11	0.4845 (2)	0.6527 (2)	0.25875 (18)	0.0449 (4)
C14	0.4869 (3)	0.7555 (2)	0.3906 (2)	0.0573 (5)
H14A	0.403992	0.714575	0.446723	0.086*
H14B	0.463250	0.851904	0.362193	0.086*
H14C	0.594983	0.764949	0.445949	0.086*
C12	0.3125 (3)	0.6369 (3)	0.1725 (2)	0.0740 (7)
H12A	0.230620	0.595492	0.229443	0.111*
H12B	0.310401	0.572099	0.089351	0.111*
H12C	0.287761	0.733002	0.144313	0.111*
C13	0.5274 (3)	0.4994 (2)	0.2981 (2)	0.0575 (5)
H13A	0.442234	0.451203	0.348188	0.086*
H13B	0.632707	0.510129	0.357858	0.086*
H13C	0.534114	0.440257	0.213104	0.086*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0352 (7)	0.0496 (8)	0.0336 (7)	−0.0013 (6)	−0.0019 (5)	0.0073 (6)
C5	0.0366 (9)	0.0482 (9)	0.0371 (8)	0.0007 (7)	−0.0020 (6)	0.0057 (7)
N51	0.0369 (8)	0.0544 (8)	0.0383 (7)	0.0034 (6)	−0.0039 (6)	0.0062 (6)
C52	0.0381 (9)	0.0531 (10)	0.0392 (9)	0.0023 (7)	−0.0004 (7)	0.0062 (7)
C521	0.0319 (8)	0.0492 (9)	0.0401 (9)	0.0069 (7)	−0.0012 (7)	0.0028 (7)
C522	0.0419 (10)	0.0627 (11)	0.0511 (10)	−0.0054 (8)	−0.0078 (8)	0.0119 (9)
C523	0.0575 (12)	0.0761 (14)	0.0518 (11)	−0.0049 (10)	−0.0086 (9)	0.0212 (10)
N524	0.0572 (10)	0.0738 (11)	0.0473 (9)	0.0049 (8)	−0.0137 (7)	0.0078 (8)
C525	0.0475 (11)	0.0562 (11)	0.0525 (11)	0.0008 (8)	−0.0121 (8)	−0.0027 (8)
C526	0.0417 (9)	0.0491 (9)	0.0474 (10)	0.0016 (7)	−0.0022 (7)	0.0025 (7)
C4	0.0363 (9)	0.0618 (11)	0.0426 (9)	−0.0010 (7)	0.0017 (7)	0.0080 (8)
C3	0.0438 (9)	0.0538 (10)	0.0346 (8)	−0.0004 (7)	0.0015 (7)	0.0058 (7)
C2	0.0400 (9)	0.0513 (9)	0.0344 (8)	−0.0002 (7)	−0.0039 (7)	0.0058 (7)
C31	0.0475 (10)	0.0624 (11)	0.0434 (10)	−0.0022 (8)	0.0044 (8)	0.0117 (8)
N32	0.0728 (13)	0.0933 (14)	0.0525 (10)	0.0008 (10)	0.0091 (9)	0.0281 (10)
C11	0.0377 (9)	0.0543 (10)	0.0404 (9)	−0.0037 (7)	0.0028 (7)	0.0109 (7)
C14	0.0607 (12)	0.0613 (12)	0.0537 (11)	0.0094 (9)	0.0182 (9)	0.0100 (9)
C12	0.0398 (11)	0.1106 (19)	0.0653 (13)	−0.0148 (11)	−0.0024 (9)	0.0319 (13)
C13	0.0664 (13)	0.0492 (10)	0.0535 (11)	−0.0056 (9)	0.0057 (9)	0.0083 (8)

Geometric parameters (Å, º)

N1—C2	1.353 (2)	C4—C3	1.405 (2)
N1—C5	1.391 (2)	C4—H4	0.9300
N1—C11	1.502 (2)	C3—C2	1.377 (2)
C5—C4	1.371 (2)	C3—C31	1.424 (2)
C5—N51	1.392 (2)	C2—H2	0.9300
N51—C52	1.272 (2)	C31—N32	1.143 (2)
C52—C521	1.466 (2)	C11—C12	1.520 (3)
C52—H52	0.9300	C11—C14	1.524 (3)
C521—C522	1.385 (3)	C11—C13	1.525 (3)
C521—C526	1.385 (2)	C14—H14A	0.9600
C522—C523	1.373 (3)	C14—H14B	0.9600
C522—H522	0.9300	C14—H14C	0.9600
C523—N524	1.338 (3)	C12—H12A	0.9600
C523—H523	0.9300	C12—H12B	0.9600
N524—C525	1.324 (3)	C12—H12C	0.9600
C525—C526	1.378 (3)	C13—H13A	0.9600
C525—H525	0.9300	C13—H13B	0.9600
C526—H526	0.9300	C13—H13C	0.9600
C2—N1—C5	108.18 (14)	C2—C3—C31	124.78 (16)
C2—N1—C11	125.40 (14)	C4—C3—C31	127.59 (17)
C5—N1—C11	126.41 (13)	N1—C2—C3	108.83 (15)
C4—C5—N1	108.36 (14)	N1—C2—H2	125.6
C4—C5—N51	132.38 (15)	C3—C2—H2	125.6
N1—C5—N51	119.25 (14)	N32—C31—C3	179.5 (2)
C52—N51—C5	117.94 (15)	N1—C11—C12	108.79 (14)
N51—C52—C521	121.62 (16)	N1—C11—C14	108.93 (14)
N51—C52—H52	119.2	C12—C11—C14	109.19 (18)
C521—C52—H52	119.2	N1—C11—C13	108.73 (15)
C522—C521—C526	117.55 (16)	C12—C11—C13	109.60 (17)
C522—C521—C52	123.47 (16)	C14—C11—C13	111.55 (15)
C526—C521—C52	118.93 (16)	C11—C14—H14A	109.5
C523—C522—C521	119.04 (18)	C11—C14—H14B	109.5
C523—C522—H522	120.5	H14A—C14—H14B	109.5
C521—C522—H522	120.5	C11—C14—H14C	109.5
N524—C523—C522	124.00 (19)	H14A—C14—H14C	109.5
N524—C523—H523	118.0	H14B—C14—H14C	109.5
C522—C523—H523	118.0	C11—C12—H12A	109.5
C525—N524—C523	116.20 (16)	C11—C12—H12B	109.5
N524—C525—C526	124.30 (17)	H12A—C12—H12B	109.5
N524—C525—H525	117.8	C11—C12—H12C	109.5
C526—C525—H525	117.8	H12A—C12—H12C	109.5
C525—C526—C521	118.88 (17)	H12B—C12—H12C	109.5
C525—C526—H526	120.6	C11—C13—H13A	109.5
C521—C526—H526	120.6	C11—C13—H13B	109.5
C5—C4—C3	106.99 (15)	H13A—C13—H13B	109.5
C5—C4—H4	126.5	C11—C13—H13C	109.5
C3—C4—H4	126.5	H13A—C13—H13C	109.5
C2—C3—C4	107.62 (15)	H13B—C13—H13C	109.5
C2—N1—C5—C4	−1.5 (2)	C52—C521—C526—C525	176.50 (16)
C11—N1—C5—C4	179.40 (16)	N1—C5—C4—C3	1.1 (2)
C2—N1—C5—N51	177.32 (15)	N51—C5—C4—C3	−177.47 (18)
C11—N1—C5—N51	−1.8 (3)	C5—C4—C3—C2	−0.3 (2)
C4—C5—N51—C52	24.2 (3)	C5—C4—C3—C31	178.36 (18)
N1—C5—N51—C52	−154.26 (17)	C5—N1—C2—C3	1.3 (2)
C5—N51—C52—C521	177.45 (15)	C11—N1—C2—C3	−179.61 (15)
N51—C52—C521—C522	7.6 (3)	C4—C3—C2—N1	−0.6 (2)
N51—C52—C521—C526	−170.00 (17)	C31—C3—C2—N1	−179.32 (17)
C526—C521—C522—C523	0.6 (3)	C2—N1—C11—C12	1.7 (3)
C52—C521—C522—C523	−177.03 (19)	C5—N1—C11—C12	−179.35 (19)
C521—C522—C523—N524	0.4 (4)	C2—N1—C11—C14	−117.26 (18)
C522—C523—N524—C525	−0.8 (4)	C5—N1—C11—C14	61.7 (2)
C523—N524—C525—C526	0.1 (3)	C2—N1—C11—C13	120.98 (18)
N524—C525—C526—C521	0.9 (3)	C5—N1—C11—C13	−60.0 (2)
C522—C521—C526—C525	−1.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14C···N51	0.96	2.44	3.079 (3)	123
C13—H13B···N51	0.96	2.46	3.078 (2)	122
C2—H2···N524^i	0.93	2.47	3.390 (2)	172
C52—H52···N32^ii	0.93	2.65	3.551 (3)	163
C525—H525···Cg1^iii	0.93	2.93	3.486 (2)	120

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

1-tert-Butyl-5-[(4-chlorobenzyl)amino]-1H-pyrrole-3-carbonitrile (8a)

Crystal data

C16H18ClN3	F(000) = 608
Mr = 287.78	Dx = 1.231 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.2422 (10) Å	Cell parameters from 8656 reflections
b = 9.2361 (10) Å	θ = 4.1–27.1°
c = 20.623 (2) Å	µ = 0.24 mm^−1
β = 98.521 (11)°	T = 298 K
V = 1552.6 (3) Å^3	Parallelepiped, yellow
Z = 4	0.30 × 0.17 × 0.13 mm

Data collection

Agilent SuperNova Dual Source diffractometer with an Atlas detector	4416 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2938 reflections with I > 2σ(I)
Detector resolution: 5.3072 pixels mm^-1	Rint = 0.053
ω scans	θmax = 30.6°, θmin = 3.0°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −11→11
Tmin = 0.663, Tmax = 1.000	k = −13→12
36135 measured reflections	l = −28→28

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.067	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.198	w = 1/[σ^2(Fo^2) + (0.0678P)^2 + 0.6772P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max < 0.001
4416 reflections	Δρmax = 0.43 e Å^−3
188 parameters	Δρmin = −0.36 e Å^−3
15 restraints	Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: iterative	Extinction coefficient: 0.012 (2)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Cl4	1.15686 (10)	−0.31760 (11)	0.50375 (5)	0.1107 (4)
H51	0.640 (5)	0.064 (4)	0.644 (2)	0.133*
C524	0.9855 (3)	−0.2574 (3)	0.53619 (13)	0.0684 (5)
C525	0.9558 (3)	−0.3102 (3)	0.59510 (14)	0.0720 (5)
H525	1.026427	−0.377368	0.617961	0.086*
C526	0.8191 (3)	−0.2623 (3)	0.62024 (13)	0.0674 (6)
H526	0.798278	−0.297728	0.660405	0.081*
C521	0.7129 (2)	−0.1630 (2)	0.58688 (10)	0.0497 (5)
C52	0.5601 (3)	−0.1174 (2)	0.61352 (12)	0.0565 (5)
H52A	0.464500	−0.152522	0.584675	0.068*
H52B	0.559862	−0.161050	0.656291	0.068*
N51	0.5496 (2)	0.03900 (19)	0.61932 (9)	0.0518 (4)
C5	0.4117 (2)	0.0863 (2)	0.64573 (9)	0.0448 (4)
N1	0.3873 (2)	0.23093 (17)	0.66020 (8)	0.0459 (4)
C11	0.4908 (3)	0.3581 (2)	0.64722 (10)	0.0501 (5)
C12	0.4250 (3)	0.4941 (3)	0.67646 (15)	0.0735 (7)
H12A	0.494831	0.574754	0.670576	0.110*
H12B	0.422788	0.479470	0.722403	0.110*
H12C	0.315898	0.513630	0.654760	0.110*
C14	0.4828 (3)	0.3756 (3)	0.57346 (13)	0.0715 (7)
H14A	0.518452	0.287662	0.555134	0.107*
H14B	0.552876	0.453841	0.564541	0.107*
H14C	0.371954	0.396275	0.554169	0.107*
C13	0.6682 (3)	0.3361 (3)	0.67952 (15)	0.0705 (7)
H13A	0.723910	0.274796	0.652354	0.106*
H13B	0.669556	0.291631	0.721660	0.106*
H13C	0.722679	0.428175	0.684832	0.106*
C2	0.2414 (3)	0.2406 (2)	0.68459 (10)	0.0519 (5)
H2	0.196252	0.324937	0.698869	0.062*
C3	0.1740 (2)	0.1057 (2)	0.68435 (10)	0.0498 (5)
C4	0.2815 (2)	0.0071 (2)	0.65935 (10)	0.0492 (5)
H4	0.266113	−0.092036	0.653439	0.059*
C31	0.0258 (3)	0.0692 (3)	0.70868 (11)	0.0560 (5)
N32	−0.0910 (3)	0.0381 (3)	0.72869 (12)	0.0760 (6)
C522	0.7481 (3)	−0.1102 (3)	0.52805 (11)	0.0632 (6)
H522	0.678976	−0.041770	0.505313	0.076*
C523	0.8841 (3)	−0.1573 (3)	0.50226 (13)	0.0675 (5)
H523	0.906526	−0.121350	0.462399	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl4	0.0763 (5)	0.1201 (7)	0.1472 (8)	0.0265 (5)	0.0541 (5)	−0.0121 (6)
C524	0.0576 (9)	0.0735 (11)	0.0769 (10)	0.0129 (8)	0.0194 (8)	−0.0049 (8)
C525	0.0607 (10)	0.0748 (12)	0.0825 (11)	0.0164 (9)	0.0171 (9)	0.0029 (9)
C526	0.0637 (14)	0.0653 (14)	0.0759 (15)	0.0128 (11)	0.0198 (12)	0.0128 (12)
C521	0.0470 (10)	0.0447 (10)	0.0586 (11)	0.0027 (8)	0.0115 (8)	−0.0073 (8)
C52	0.0544 (12)	0.0453 (11)	0.0736 (14)	0.0025 (9)	0.0216 (10)	−0.0039 (10)
N51	0.0477 (9)	0.0437 (9)	0.0683 (11)	0.0049 (7)	0.0223 (8)	−0.0017 (8)
C5	0.0437 (9)	0.0447 (10)	0.0481 (9)	0.0047 (8)	0.0131 (8)	0.0030 (8)
N1	0.0450 (8)	0.0436 (8)	0.0523 (9)	0.0037 (7)	0.0174 (7)	0.0022 (7)
C11	0.0497 (11)	0.0419 (10)	0.0616 (11)	−0.0002 (8)	0.0175 (9)	0.0012 (8)
C12	0.0739 (16)	0.0449 (12)	0.108 (2)	0.0025 (11)	0.0345 (14)	−0.0033 (12)
C14	0.0778 (17)	0.0702 (16)	0.0704 (15)	−0.0061 (13)	0.0240 (13)	0.0134 (12)
C13	0.0583 (13)	0.0546 (13)	0.0962 (18)	−0.0027 (11)	0.0032 (12)	−0.0106 (13)
C2	0.0483 (11)	0.0538 (11)	0.0571 (11)	0.0081 (9)	0.0195 (9)	0.0039 (9)
C3	0.0430 (10)	0.0560 (11)	0.0525 (10)	0.0034 (8)	0.0138 (8)	0.0054 (9)
C4	0.0468 (10)	0.0466 (10)	0.0561 (11)	−0.0002 (8)	0.0137 (8)	0.0031 (8)
C31	0.0468 (11)	0.0601 (13)	0.0636 (12)	0.0040 (9)	0.0164 (9)	0.0062 (10)
N32	0.0559 (11)	0.0793 (15)	0.0994 (16)	−0.0018 (10)	0.0327 (11)	0.0079 (12)
C522	0.0577 (13)	0.0749 (15)	0.0575 (12)	0.0174 (11)	0.0098 (10)	0.0035 (11)
C523	0.0596 (10)	0.0761 (12)	0.0699 (11)	0.0108 (9)	0.0193 (8)	−0.0036 (8)

Geometric parameters (Å, º)

Cl4—C524	1.741 (2)	C11—C13	1.528 (3)
C524—C525	1.365 (4)	C12—H12A	0.9600
C524—C523	1.368 (4)	C12—H12B	0.9600
C525—C526	1.380 (3)	C12—H12C	0.9600
C525—H525	0.9300	C14—H14A	0.9600
C526—C521	1.380 (3)	C14—H14B	0.9600
C526—H526	0.9300	C14—H14C	0.9600
C521—C522	1.377 (3)	C13—H13A	0.9600
C521—C52	1.507 (3)	C13—H13B	0.9600
C52—N51	1.453 (3)	C13—H13C	0.9600
C52—H52A	0.9700	C2—C3	1.364 (3)
C52—H52B	0.9700	C2—H2	0.9300
N51—C5	1.401 (2)	C3—C4	1.420 (3)
N51—H51	0.87 (4)	C3—C31	1.427 (3)
C5—C4	1.361 (3)	C4—H4	0.9300
C5—N1	1.390 (2)	C31—N32	1.139 (3)
N1—C2	1.373 (2)	C522—C523	1.381 (3)
N1—C11	1.499 (3)	C522—H522	0.9300
C11—C14	1.521 (3)	C523—H523	0.9300
C11—C12	1.528 (3)
C525—C524—C523	121.3 (2)	C11—C12—H12B	109.5
C525—C524—Cl4	119.4 (2)	H12A—C12—H12B	109.5
C523—C524—Cl4	119.2 (2)	C11—C12—H12C	109.5
C524—C525—C526	119.0 (2)	H12A—C12—H12C	109.5
C524—C525—H525	120.5	H12B—C12—H12C	109.5
C526—C525—H525	120.5	C11—C14—H14A	109.5
C521—C526—C525	121.2 (2)	C11—C14—H14B	109.5
C521—C526—H526	119.4	H14A—C14—H14B	109.5
C525—C526—H526	119.4	C11—C14—H14C	109.5
C522—C521—C526	118.3 (2)	H14A—C14—H14C	109.5
C522—C521—C52	121.3 (2)	H14B—C14—H14C	109.5
C526—C521—C52	120.4 (2)	C11—C13—H13A	109.5
N51—C52—C521	111.75 (17)	C11—C13—H13B	109.5
N51—C52—H52A	109.3	H13A—C13—H13B	109.5
C521—C52—H52A	109.3	C11—C13—H13C	109.5
N51—C52—H52B	109.3	H13A—C13—H13C	109.5
C521—C52—H52B	109.3	H13B—C13—H13C	109.5
H52A—C52—H52B	107.9	C3—C2—N1	108.54 (18)
C5—N51—C52	113.79 (17)	C3—C2—H2	125.7
C5—N51—H51	111 (3)	N1—C2—H2	125.7
C52—N51—H51	105 (3)	C2—C3—C4	108.11 (18)
C4—C5—N1	109.20 (17)	C2—C3—C31	125.7 (2)
C4—C5—N51	128.49 (19)	C4—C3—C31	126.1 (2)
N1—C5—N51	122.28 (17)	C5—C4—C3	106.49 (19)
C2—N1—C5	107.64 (16)	C5—C4—H4	126.8
C2—N1—C11	124.53 (17)	C3—C4—H4	126.8
C5—N1—C11	127.65 (16)	N32—C31—C3	178.8 (3)
N1—C11—C14	108.68 (18)	C521—C522—C523	121.1 (2)
N1—C11—C12	109.21 (17)	C521—C522—H522	119.4
C14—C11—C12	110.0 (2)	C523—C522—H522	119.4
N1—C11—C13	110.57 (17)	C524—C523—C522	119.0 (2)
C14—C11—C13	110.3 (2)	C524—C523—H523	120.5
C12—C11—C13	108.1 (2)	C522—C523—H523	120.5
C11—C12—H12A	109.5
C523—C524—C525—C526	0.8 (5)	C5—N1—C11—C12	−175.4 (2)
Cl4—C524—C525—C526	−179.7 (2)	C2—N1—C11—C13	128.8 (2)
C524—C525—C526—C521	0.1 (4)	C5—N1—C11—C13	−56.6 (3)
C525—C526—C521—C522	−1.1 (4)	C5—N1—C2—C3	−1.1 (2)
C525—C526—C521—C52	177.0 (2)	C11—N1—C2—C3	174.42 (18)
C522—C521—C52—N51	−55.6 (3)	N1—C2—C3—C4	0.4 (2)
C526—C521—C52—N51	126.3 (2)	N1—C2—C3—C31	177.03 (19)
C521—C52—N51—C5	−178.24 (18)	N1—C5—C4—C3	−1.1 (2)
C52—N51—C5—C4	−7.8 (3)	N51—C5—C4—C3	−179.1 (2)
C52—N51—C5—N1	174.49 (19)	C2—C3—C4—C5	0.4 (2)
C4—C5—N1—C2	1.4 (2)	C31—C3—C4—C5	−176.2 (2)
N51—C5—N1—C2	179.51 (18)	C526—C521—C522—C523	1.2 (4)
C4—C5—N1—C11	−173.94 (18)	C52—C521—C522—C523	−176.9 (2)
N51—C5—N1—C11	4.2 (3)	C525—C524—C523—C522	−0.7 (4)
C2—N1—C11—C14	−110.0 (2)	Cl4—C524—C523—C522	179.8 (2)
C5—N1—C11—C14	64.6 (3)	C521—C522—C523—C524	−0.3 (4)
C2—N1—C11—C12	10.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···N51	0.96	2.64	3.109 (3)	110
C14—H14A···N51	0.96	2.64	3.272 (3)	123
N51—H51···N32^i	0.87 (4)	2.62 (4)	3.447 (3)	159 (3)
C2—H2···N32^ii	0.93	2.69	3.598 (3)	165

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

1-tert-Butyl-5-[(2,4-dichlorobenzyl)amino]-1H-pyrrole-3-carbonitrile (8b)

Crystal data

C16H17Cl2N3	Z = 2
Mr = 322.22	F(000) = 336
Triclinic, P1	Dx = 1.319 Mg m^−3
a = 8.9700 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.3244 (12) Å	Cell parameters from 3822 reflections
c = 10.4645 (14) Å	θ = 4.1–26.4°
α = 105.057 (12)°	µ = 0.40 mm^−1
β = 103.589 (12)°	T = 298 K
γ = 95.078 (11)°	Parallelepiped, yellow
V = 811.05 (19) Å^3	0.25 × 0.11 × 0.10 mm

Data collection

Agilent SuperNova Dual Source diffractometer with an Atlas detector	3302 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2520 reflections with I > 2σ(I)
Detector resolution: 5.3072 pixels mm^-1	Rint = 0.038
ω scans	θmax = 26.4°, θmin = 3.0°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −11→11
Tmin = 0.786, Tmax = 1.000	k = −11→10
10849 measured reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: mixed
wR(F^2) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0519P)^2 + 0.4113P] where P = (Fo^2 + 2Fc^2)/3
3302 reflections	(Δ/σ)max < 0.001
196 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Cl4	0.69422 (8)	0.49248 (9)	0.18116 (8)	0.0732 (3)
H1	0.113 (4)	0.109 (4)	0.291 (4)	0.088*
C524	0.5471 (3)	0.4365 (3)	0.2490 (2)	0.0456 (5)
C523	0.4050 (3)	0.4818 (2)	0.2140 (2)	0.0469 (5)
H523	0.387257	0.542512	0.155904	0.056*
C522	0.2892 (3)	0.4344 (3)	0.2681 (2)	0.0472 (5)
Cl2	0.10932 (8)	0.48852 (9)	0.22039 (9)	0.0783 (3)
C521	0.3137 (3)	0.3468 (3)	0.3583 (2)	0.0463 (5)
C526	0.4590 (3)	0.3047 (3)	0.3891 (2)	0.0508 (6)
H526	0.478101	0.244638	0.447741	0.061*
C525	0.5766 (3)	0.3487 (3)	0.3359 (2)	0.0500 (6)
H525	0.673469	0.319480	0.358552	0.060*
C52	0.1907 (3)	0.3006 (3)	0.4227 (2)	0.0561 (6)
H52A	0.239053	0.269501	0.502065	0.067*
H52B	0.140667	0.386169	0.453855	0.067*
N51	0.0744 (2)	0.1780 (2)	0.32601 (19)	0.0463 (5)
C5	−0.0481 (2)	0.1339 (2)	0.3766 (2)	0.0401 (5)
N1	−0.17814 (19)	0.0318 (2)	0.29286 (17)	0.0390 (4)
C2	−0.2757 (2)	0.0127 (3)	0.3715 (2)	0.0418 (5)
H2	−0.370514	−0.051319	0.341052	0.050*
C3	−0.2108 (2)	0.1035 (3)	0.5026 (2)	0.0425 (5)
C4	−0.0658 (2)	0.1806 (3)	0.5062 (2)	0.0435 (5)
H4	0.003722	0.249602	0.582086	0.052*
C31	−0.2807 (3)	0.1135 (3)	0.6128 (2)	0.0492 (6)
N32	−0.3377 (3)	0.1186 (3)	0.7001 (2)	0.0722 (7)
C11	−0.2132 (3)	−0.0412 (3)	0.1416 (2)	0.0460 (5)
C12	−0.3764 (3)	−0.1323 (3)	0.0908 (3)	0.0606 (7)
H12A	−0.401479	−0.176172	−0.006929	0.091*
H12B	−0.449857	−0.067449	0.112727	0.091*
H12C	−0.380665	−0.210604	0.134553	0.091*
C13	−0.2088 (3)	0.0820 (4)	0.0700 (3)	0.0690 (8)
H13A	−0.233937	0.036828	−0.027521	0.103*
H13B	−0.106670	0.140416	0.101246	0.103*
H13C	−0.283064	0.146062	0.091343	0.103*
C14	−0.0968 (3)	−0.1470 (3)	0.1142 (3)	0.0679 (8)
H14A	−0.121486	−0.197649	0.017687	0.102*
H14B	−0.101679	−0.219814	0.163876	0.102*
H14C	0.006008	−0.090129	0.143956	0.102*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl4	0.0587 (4)	0.0854 (5)	0.0907 (6)	0.0034 (3)	0.0395 (4)	0.0366 (4)
C524	0.0406 (12)	0.0457 (13)	0.0485 (13)	−0.0019 (9)	0.0163 (10)	0.0093 (10)
C523	0.0495 (13)	0.0408 (12)	0.0503 (13)	0.0045 (10)	0.0135 (10)	0.0139 (10)
C522	0.0372 (11)	0.0434 (12)	0.0525 (13)	0.0051 (9)	0.0103 (10)	0.0016 (10)
Cl2	0.0462 (4)	0.0761 (5)	0.1094 (6)	0.0206 (3)	0.0172 (4)	0.0210 (4)
C521	0.0419 (12)	0.0474 (13)	0.0407 (12)	−0.0072 (10)	0.0125 (9)	0.0011 (10)
C526	0.0469 (13)	0.0535 (14)	0.0499 (14)	−0.0034 (10)	0.0083 (10)	0.0193 (11)
C525	0.0365 (11)	0.0527 (14)	0.0584 (15)	0.0028 (10)	0.0092 (10)	0.0166 (12)
C52	0.0467 (13)	0.0644 (16)	0.0460 (13)	−0.0132 (11)	0.0168 (11)	0.0004 (12)
N51	0.0378 (10)	0.0546 (12)	0.0401 (10)	−0.0059 (8)	0.0148 (8)	0.0033 (9)
C5	0.0335 (10)	0.0472 (12)	0.0384 (11)	0.0016 (9)	0.0100 (8)	0.0119 (9)
N1	0.0330 (9)	0.0475 (10)	0.0355 (9)	0.0020 (7)	0.0100 (7)	0.0109 (8)
C2	0.0324 (10)	0.0516 (13)	0.0451 (12)	0.0035 (9)	0.0127 (9)	0.0190 (10)
C3	0.0375 (11)	0.0555 (13)	0.0411 (12)	0.0088 (9)	0.0149 (9)	0.0207 (10)
C4	0.0374 (11)	0.0549 (13)	0.0353 (11)	0.0016 (9)	0.0099 (9)	0.0101 (10)
C31	0.0390 (12)	0.0649 (15)	0.0453 (13)	0.0037 (10)	0.0133 (10)	0.0183 (11)
N32	0.0591 (14)	0.1044 (19)	0.0547 (13)	−0.0047 (13)	0.0272 (11)	0.0209 (13)
C11	0.0404 (11)	0.0579 (14)	0.0336 (11)	0.0007 (10)	0.0079 (9)	0.0072 (10)
C12	0.0469 (14)	0.0711 (17)	0.0483 (14)	−0.0064 (12)	0.0031 (11)	0.0049 (13)
C13	0.0688 (17)	0.090 (2)	0.0438 (14)	−0.0053 (15)	0.0045 (12)	0.0284 (14)
C14	0.0534 (15)	0.0785 (19)	0.0581 (16)	0.0107 (13)	0.0166 (12)	−0.0055 (14)

Geometric parameters (Å, º)

Cl4—C524	1.740 (2)	N1—C11	1.496 (3)
C524—C525	1.371 (3)	C2—C3	1.368 (3)
C524—C523	1.376 (3)	C2—H2	0.9300
C523—C522	1.386 (3)	C3—C4	1.417 (3)
C523—H523	0.9300	C3—C31	1.424 (3)
C522—C521	1.393 (3)	C4—H4	0.9300
C522—Cl2	1.733 (2)	C31—N32	1.140 (3)
C521—C526	1.384 (3)	C11—C14	1.523 (4)
C521—C52	1.508 (3)	C11—C12	1.526 (3)
C526—C525	1.382 (3)	C11—C13	1.527 (4)
C526—H526	0.9300	C12—H12A	0.9600
C525—H525	0.9300	C12—H12B	0.9600
C52—N51	1.453 (3)	C12—H12C	0.9600
C52—H52A	0.9700	C13—H13A	0.9600
C52—H52B	0.9700	C13—H13B	0.9600
N51—C5	1.401 (3)	C13—H13C	0.9600
N51—H1	0.80 (3)	C14—H14A	0.9600
C5—C4	1.363 (3)	C14—H14B	0.9600
C5—N1	1.388 (3)	C14—H14C	0.9600
N1—C2	1.364 (3)
C525—C524—C523	122.0 (2)	N1—C2—H2	125.7
C525—C524—Cl4	118.90 (18)	C3—C2—H2	125.7
C523—C524—Cl4	119.08 (18)	C2—C3—C4	107.84 (19)
C524—C523—C522	118.0 (2)	C2—C3—C31	124.3 (2)
C524—C523—H523	121.0	C4—C3—C31	127.9 (2)
C522—C523—H523	121.0	C5—C4—C3	106.64 (19)
C523—C522—C521	122.2 (2)	C5—C4—H4	126.7
C523—C522—Cl2	117.64 (19)	C3—C4—H4	126.7
C521—C522—Cl2	120.13 (18)	N32—C31—C3	178.7 (3)
C526—C521—C522	117.0 (2)	N1—C11—C14	108.99 (18)
C526—C521—C52	120.4 (2)	N1—C11—C12	108.95 (18)
C522—C521—C52	122.6 (2)	C14—C11—C12	108.9 (2)
C525—C526—C521	122.3 (2)	N1—C11—C13	108.52 (19)
C525—C526—H526	118.9	C14—C11—C13	112.8 (2)
C521—C526—H526	118.9	C12—C11—C13	108.6 (2)
C524—C525—C526	118.5 (2)	C11—C12—H12A	109.5
C524—C525—H525	120.8	C11—C12—H12B	109.5
C526—C525—H525	120.8	H12A—C12—H12B	109.5
N51—C52—C521	111.43 (18)	C11—C12—H12C	109.5
N51—C52—H52A	109.3	H12A—C12—H12C	109.5
C521—C52—H52A	109.3	H12B—C12—H12C	109.5
N51—C52—H52B	109.3	C11—C13—H13A	109.5
C521—C52—H52B	109.3	C11—C13—H13B	109.5
H52A—C52—H52B	108.0	H13A—C13—H13B	109.5
C5—N51—C52	114.63 (18)	C11—C13—H13C	109.5
C5—N51—H1	114 (2)	H13A—C13—H13C	109.5
C52—N51—H1	112 (3)	H13B—C13—H13C	109.5
C4—C5—N1	108.88 (18)	C11—C14—H14A	109.5
C4—C5—N51	129.11 (19)	C11—C14—H14B	109.5
N1—C5—N51	121.99 (18)	H14A—C14—H14B	109.5
C2—N1—C5	108.01 (17)	C11—C14—H14C	109.5
C2—N1—C11	124.53 (17)	H14A—C14—H14C	109.5
C5—N1—C11	127.40 (17)	H14B—C14—H14C	109.5
N1—C2—C3	108.60 (18)
C525—C524—C523—C522	−0.9 (3)	C4—C5—N1—C2	−1.2 (2)
Cl4—C524—C523—C522	179.27 (17)	N51—C5—N1—C2	−179.8 (2)
C524—C523—C522—C521	1.8 (3)	C4—C5—N1—C11	176.0 (2)
C524—C523—C522—Cl2	−178.56 (17)	N51—C5—N1—C11	−2.6 (3)
C523—C522—C521—C526	−1.9 (3)	C5—N1—C2—C3	1.3 (2)
Cl2—C522—C521—C526	178.43 (17)	C11—N1—C2—C3	−176.03 (19)
C523—C522—C521—C52	177.1 (2)	N1—C2—C3—C4	−0.9 (3)
Cl2—C522—C521—C52	−2.5 (3)	N1—C2—C3—C31	179.7 (2)
C522—C521—C526—C525	1.2 (3)	N1—C5—C4—C3	0.6 (3)
C52—C521—C526—C525	−177.9 (2)	N51—C5—C4—C3	179.1 (2)
C523—C524—C525—C526	0.2 (4)	C2—C3—C4—C5	0.2 (3)
Cl4—C524—C525—C526	−179.94 (18)	C31—C3—C4—C5	179.5 (2)
C521—C526—C525—C524	−0.4 (4)	C2—N1—C11—C14	−116.1 (2)
C526—C521—C52—N51	−103.9 (3)	C5—N1—C11—C14	67.1 (3)
C522—C521—C52—N51	77.2 (3)	C2—N1—C11—C12	2.6 (3)
C521—C52—N51—C5	−177.0 (2)	C5—N1—C11—C12	−174.1 (2)
C52—N51—C5—C4	−6.5 (4)	C2—N1—C11—C13	120.7 (2)
C52—N51—C5—N1	171.9 (2)	C5—N1—C11—C13	−56.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13B···N51	0.96	2.44	3.096 (3)	125
C14—H14C···N51	0.96	2.64	3.247 (3)	122
C2—H2···N32^i	0.93	2.54	3.411 (3)	155
C525—H525···Cg1^ii	0.93	2.81	3.630 (3)	148

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