3-tert-Butyl-1-(3-nitro-phen-yl)-1H-pyrazol-5-amine.

In the title compound, C(13)H(16)N(4)O(2), the pyrazole ring forms a dihedral angle of 50.61 (6)° with the 3-nitro-phenyl ring. The plane of the nitro group is twisted by 6.8 (7)° out of the plane of the phenyl ring. In the crystal, the mol-ecules are linked by N-H⋯N and N-H⋯O hydrogen bonds, forming sheets in the bc plane. In addition, a weak C-H⋯N inter-action is observed.

Related literature

For background to pyrazole-based ligands, see; Ahmed et al. (2005 ▶); Abonia et al. (2002 ▶, 2004 ▶, 2010 ▶); Guerrero et al. (2009 ▶); Quiroga et al. (2008 ▶); Schutznerová, et al. (2012 ▶). For structure of an isomer of the title compound, see: Low et al. (2004 ▶).

Experimental

Crystal data

C13H16N4O2

M = 260.30

Monoclinic,

a = 11.9421 (14) Å

b = 9.6419 (11) Å

c = 11.7694 (13) Å

β = 93.504 (2)°

V = 1352.6 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 298 K

0.46 × 0.36 × 0.32 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

14529 measured reflections

2486 independent reflections

2036 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.115

S = 1.05

2486 reflections

181 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.17 e Å−3

Δρmin = −0.17 e Å−3

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812042791/bt6847sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812042791/bt6847Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C13H16N4O2	F(000) = 552
Mr = 260.30	Dx = 1.278 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7587 reflections
a = 11.9421 (14) Å	θ = 2.7–25.3°
b = 9.6419 (11) Å	µ = 0.09 mm−1
c = 11.7694 (13) Å	T = 298 K
β = 93.504 (2)°	Prism, orange
V = 1352.6 (3) Å3	0.46 × 0.36 × 0.32 mm
Z = 4

Bruker SMART APEX CCD area-detector diffractometer	2036 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.044
Graphite monochromator	θmax = 25.4°, θmin = 2.7°
Detector resolution: 0.83 pixels mm-1	h = −14→14
ω scans	k = −11→11
14529 measured reflections	l = −14→14
2486 independent reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0644P)2 + 0.1233P] where P = (Fo2 + 2Fc2)/3
2486 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.17 e Å−3
2 restraints	Δρmin = −0.17 e Å−3

Geometry. All e.s.d.'s (except the those 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.

	x	y	z	Uiso*/Ueq
O1	0.61664 (14)	−0.30475 (15)	0.45577 (16)	0.1090 (6)
O2	0.76468 (15)	−0.18160 (16)	0.45837 (14)	0.1006 (5)
N1	0.71780 (9)	0.17992 (11)	0.75434 (9)	0.0403 (3)
N2	0.78018 (9)	0.26705 (11)	0.68907 (9)	0.0426 (3)
N3	0.67228 (15)	−0.20551 (15)	0.48900 (13)	0.0686 (4)
N4	0.68987 (11)	0.12825 (14)	0.94996 (10)	0.0516 (3)
H4A	0.7163 (13)	0.1491 (17)	1.0213 (9)	0.062*
H4B	0.6699 (13)	0.0411 (11)	0.9321 (14)	0.062*
C3	0.84041 (11)	0.34268 (13)	0.76494 (11)	0.0401 (3)
C4	0.81984 (11)	0.30418 (14)	0.87650 (11)	0.0433 (3)
H4	0.8523	0.3421	0.9433	0.052*
C5	0.74255 (11)	0.19985 (13)	0.86760 (11)	0.0400 (3)
C6	0.91855 (12)	0.45492 (15)	0.72699 (13)	0.0488 (4)
C7	0.99208 (17)	0.3989 (2)	0.63582 (17)	0.0768 (6)
H7A	1.0374	0.3241	0.6669	0.115*
H7B	1.0398	0.4716	0.6110	0.115*
H7C	0.9453	0.3657	0.5723	0.115*
C8	0.85048 (16)	0.57837 (16)	0.67990 (16)	0.0698 (5)
H8A	0.8051	0.5500	0.6138	0.105*
H8B	0.9005	0.6509	0.6594	0.105*
H8C	0.8030	0.6119	0.7368	0.105*
C9	0.99367 (15)	0.50386 (18)	0.82913 (16)	0.0657 (5)
H9A	0.9483	0.5454	0.8845	0.098*
H9B	1.0464	0.5709	0.8044	0.098*
H9C	1.0334	0.4260	0.8626	0.098*
C11	0.64947 (11)	0.07495 (13)	0.70143 (11)	0.0413 (3)
C12	0.69297 (12)	−0.00946 (14)	0.62034 (12)	0.0458 (4)
H12	0.7658	0.0027	0.5985	0.055*
C13	0.62517 (13)	−0.11245 (14)	0.57271 (12)	0.0490 (4)
C14	0.51684 (14)	−0.13283 (15)	0.60126 (14)	0.0555 (4)
H14	0.4727	−0.2023	0.5668	0.067*
C15	0.47534 (14)	−0.04795 (17)	0.68205 (15)	0.0598 (4)
H15	0.4022	−0.0603	0.7032	0.072*
C16	0.54076 (12)	0.05548 (16)	0.73219 (13)	0.0535 (4)
H16	0.5117	0.1124	0.7869	0.064*

	U11	U22	U33	U12	U13	U23
O1	0.1062 (12)	0.0705 (9)	0.1473 (15)	−0.0008 (8)	−0.0181 (10)	−0.0588 (10)
O2	0.1094 (13)	0.0912 (11)	0.1050 (12)	−0.0042 (9)	0.0366 (10)	−0.0347 (9)
N1	0.0438 (6)	0.0374 (6)	0.0390 (6)	−0.0066 (5)	−0.0035 (5)	0.0012 (5)
N2	0.0464 (7)	0.0400 (6)	0.0408 (6)	−0.0063 (5)	−0.0029 (5)	0.0030 (5)
N3	0.0837 (11)	0.0507 (8)	0.0697 (9)	0.0057 (8)	−0.0079 (8)	−0.0137 (7)
N4	0.0619 (8)	0.0505 (7)	0.0418 (7)	−0.0070 (6)	−0.0016 (6)	0.0068 (6)
C3	0.0411 (7)	0.0346 (7)	0.0435 (7)	0.0009 (6)	−0.0056 (6)	0.0008 (6)
C4	0.0487 (8)	0.0402 (7)	0.0398 (7)	−0.0025 (6)	−0.0089 (6)	−0.0019 (6)
C5	0.0429 (7)	0.0370 (7)	0.0393 (7)	0.0041 (6)	−0.0037 (6)	0.0025 (5)
C6	0.0518 (8)	0.0404 (7)	0.0530 (8)	−0.0076 (6)	−0.0062 (7)	0.0043 (6)
C7	0.0860 (13)	0.0648 (11)	0.0827 (13)	−0.0206 (10)	0.0292 (11)	0.0050 (10)
C8	0.0834 (12)	0.0428 (9)	0.0797 (12)	−0.0123 (8)	−0.0248 (10)	0.0123 (8)
C9	0.0610 (10)	0.0575 (10)	0.0756 (11)	−0.0208 (8)	−0.0191 (9)	0.0098 (8)
C11	0.0442 (8)	0.0361 (7)	0.0426 (7)	−0.0044 (6)	−0.0060 (6)	0.0030 (6)
C12	0.0460 (8)	0.0427 (8)	0.0478 (8)	−0.0014 (6)	−0.0044 (6)	0.0011 (6)
C13	0.0606 (9)	0.0365 (7)	0.0484 (8)	0.0008 (7)	−0.0084 (7)	−0.0012 (6)
C14	0.0612 (10)	0.0420 (8)	0.0611 (9)	−0.0129 (7)	−0.0132 (8)	0.0031 (7)
C15	0.0495 (9)	0.0606 (10)	0.0690 (10)	−0.0154 (8)	−0.0001 (8)	−0.0018 (8)
C16	0.0494 (9)	0.0525 (9)	0.0585 (9)	−0.0054 (7)	0.0020 (7)	−0.0050 (7)

O1—N3	1.2159 (19)	C7—H7B	0.9600
O2—N3	1.204 (2)	C7—H7C	0.9600
N1—C5	1.3613 (17)	C8—H8A	0.9600
N1—N2	1.3858 (15)	C8—H8B	0.9600
N1—C11	1.4198 (16)	C8—H8C	0.9600
N2—C3	1.3297 (17)	C9—H9A	0.9600
N3—C13	1.470 (2)	C9—H9B	0.9600
N4—C5	1.3735 (18)	C9—H9C	0.9600
N4—H4A	0.901 (9)	C11—C12	1.380 (2)
N4—H4B	0.895 (9)	C11—C16	1.382 (2)
C3—C4	1.4005 (19)	C12—C13	1.378 (2)
C3—C6	1.5140 (19)	C12—H12	0.9300
C4—C5	1.3650 (19)	C13—C14	1.370 (2)
C4—H4	0.9300	C14—C15	1.370 (2)
C6—C8	1.526 (2)	C14—H14	0.9300
C6—C7	1.526 (2)	C15—C16	1.377 (2)
C6—C9	1.530 (2)	C15—H15	0.9300
C7—H7A	0.9600	C16—H16	0.9300
C5—N1—N2	111.43 (10)	C6—C8—H8A	109.5
C5—N1—C11	127.92 (11)	C6—C8—H8B	109.5
N2—N1—C11	120.20 (10)	H8A—C8—H8B	109.5
C3—N2—N1	104.32 (10)	C6—C8—H8C	109.5
O2—N3—O1	123.17 (17)	H8A—C8—H8C	109.5
O2—N3—C13	118.64 (15)	H8B—C8—H8C	109.5
O1—N3—C13	118.17 (17)	C6—C9—H9A	109.5
C5—N4—H4A	113.3 (11)	C6—C9—H9B	109.5
C5—N4—H4B	115.7 (11)	H9A—C9—H9B	109.5
H4A—N4—H4B	120.1 (16)	C6—C9—H9C	109.5
N2—C3—C4	111.44 (12)	H9A—C9—H9C	109.5
N2—C3—C6	120.78 (12)	H9B—C9—H9C	109.5
C4—C3—C6	127.78 (12)	C12—C11—C16	120.04 (13)
C5—C4—C3	106.26 (12)	C12—C11—N1	119.55 (12)
C5—C4—H4	126.9	C16—C11—N1	120.40 (13)
C3—C4—H4	126.9	C13—C12—C11	118.00 (13)
N1—C5—C4	106.53 (11)	C13—C12—H12	121.0
N1—C5—N4	122.60 (12)	C11—C12—H12	121.0
C4—C5—N4	130.77 (13)	C14—C13—C12	122.92 (14)
C3—C6—C8	109.90 (12)	C14—C13—N3	118.85 (14)
C3—C6—C7	110.23 (12)	C12—C13—N3	118.23 (14)
C8—C6—C7	109.71 (14)	C15—C14—C13	118.12 (14)
C3—C6—C9	109.33 (12)	C15—C14—H14	120.9
C8—C6—C9	108.57 (13)	C13—C14—H14	120.9
C7—C6—C9	109.07 (14)	C14—C15—C16	120.67 (15)
C6—C7—H7A	109.5	C14—C15—H15	119.7
C6—C7—H7B	109.5	C16—C15—H15	119.7
H7A—C7—H7B	109.5	C15—C16—C11	120.24 (14)
C6—C7—H7C	109.5	C15—C16—H16	119.9
H7A—C7—H7C	109.5	C11—C16—H16	119.9
H7B—C7—H7C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N2i	0.90 (1)	2.23 (1)	3.1195 (17)	172 (2)
N4—H4B···O1ii	0.90 (1)	2.39 (1)	3.241 (2)	160 (2)
C14—H14···N4iii	0.93	2.54	3.403 (2)	155

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯N2i	0.90 (1)	2.23 (1)	3.1195 (17)	172 (2)
N4—H4B⋯O1ii	0.90 (1)	2.39 (1)	3.241 (2)	160 (2)
C14—H14⋯N4iii	0.93	2.54	3.403 (2)	155

Symmetry codes: (i) ; (ii) ; (iii) .