trans-4-(2-Amino-5-bromo-6-methyl-pyrimidin-4-ylamino)-1-methyl-cyclo-hexa-nol.

The title compound, C(12)H(19)BrN(4)O, represents the minor component of the two products obtained in a series of transformations involving the Grignard reaction of tert-butoxy-carbonyl-protected 4-amino-cyclo-hexa-none with MeMgBr, and subsequent inter-action of the obtained amino-substituted cyclo-hexa-nol with 4-chloro-6-methyl-pyrimidin-2-amine followed by bromination with N-bromo-succinimide. The X-ray structure showed that this product represents a trans isomer with respect to the amino and hydr-oxy substituents in the cyclo-hexyl ring; the dihedral angle between the amino-pyrimidine plane and the (noncrystallographic) mirror plane of the substituted cyclo-hexyl fragment is 33.6 (3)°. Only two of the four potentially 'active' H atoms participate in inter-molecular N-H⋯O and O-H⋯N hydrogen bonds, linking the mol-ecules into layers parallel to the (10) plane.

Related literature

For the structure of a similar N-pyrimidine derivative of amino­cyclo­hexane, see Melguizo et al. (2003 ▶).

Experimental

Crystal data

C12H19BrN4O

M = 315.22

Monoclinic,

a = 9.9514 (18) Å

b = 7.1879 (11) Å

c = 19.566 (4) Å

β = 91.053 (3)°

V = 1399.3 (4) Å3

Z = 4

Mo Kα radiation

μ = 2.93 mm−1

T = 198 K

0.10 × 0.10 × 0.08 mm

Data collection

Siemens P4 with APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.758, T max = 0.799

8853 measured reflections

3251 independent reflections

2500 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.114

S = 1.05

3251 reflections

166 parameters

H-atom parameters constrained

Δρmax = 0.83 e Å−3

Δρmin = −0.77 e Å−3

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-32 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809035533/bg2293sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809035533/bg2293Isup2.hkl

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

C12H19BrN4O	F(000) = 648
Mr = 315.22	Dx = 1.496 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2554 reflections
a = 9.9514 (18) Å	θ = 2.3–26.0°
b = 7.1879 (11) Å	µ = 2.93 mm−1
c = 19.566 (4) Å	T = 198 K
β = 91.053 (3)°	Prism, colorless
V = 1399.3 (4) Å3	0.10 × 0.10 × 0.08 mm
Z = 4

Siemens P4 with APEX CCD area-detector diffractometer	3251 independent reflections
Radiation source: fine-focus sealed tube	2500 reflections with I > 2σ(I)
graphite	Rint = 0.030
φ and ω scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −13→13
Tmin = 0.758, Tmax = 0.799	k = −9→3
8853 measured reflections	l = −25→25

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0567P)2 + 0.5508P] where P = (Fo2 + 2Fc2)/3
3251 reflections	(Δ/σ)max < 0.001
166 parameters	Δρmax = 0.83 e Å−3
0 restraints	Δρmin = −0.77 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.5559 (2)	0.1796 (4)	0.70305 (12)	0.0340 (5)
C2	0.4564 (2)	0.4484 (3)	0.74028 (12)	0.0345 (5)
C3	0.3689 (2)	0.4380 (4)	0.68582 (12)	0.0343 (5)
C4	0.3783 (2)	0.2877 (3)	0.64026 (11)	0.0308 (5)
C5	0.4551 (4)	0.6010 (4)	0.79203 (16)	0.0553 (8)
H5A	0.5224	0.5753	0.8280	0.083*
H5B	0.3659	0.6084	0.8123	0.083*
H5C	0.4760	0.7195	0.7698	0.083*
C6	0.3088 (3)	0.1409 (3)	0.53025 (12)	0.0360 (5)
H6	0.3451	0.0203	0.5480	0.043*
C7	0.4063 (2)	0.2217 (4)	0.47943 (12)	0.0371 (6)
H7A	0.4223	0.1297	0.4428	0.045*
H7B	0.4934	0.2472	0.5029	0.045*
C8	0.3519 (3)	0.4009 (4)	0.44790 (13)	0.0387 (6)
H8A	0.4163	0.4467	0.4138	0.046*
H8B	0.3452	0.4964	0.4841	0.046*
C9	0.2144 (3)	0.3769 (3)	0.41323 (12)	0.0337 (5)
C10	0.1169 (2)	0.2822 (4)	0.46142 (13)	0.0359 (5)
H10A	0.0340	0.2493	0.4354	0.043*
H10B	0.0919	0.3715	0.4976	0.043*
C11	0.1739 (3)	0.1065 (3)	0.49515 (14)	0.0400 (6)
H11A	0.1095	0.0603	0.5292	0.048*
H11B	0.1842	0.0088	0.4600	0.048*
C12	0.1583 (3)	0.5624 (4)	0.38954 (16)	0.0529 (7)
H12A	0.2230	0.6233	0.3597	0.079*
H12B	0.1421	0.6415	0.4293	0.079*
H12C	0.0737	0.5423	0.3643	0.079*
N1	0.5510 (2)	0.3157 (3)	0.75037 (10)	0.0354 (5)
N2	0.4744 (2)	0.1602 (3)	0.64825 (10)	0.0334 (4)
N3	0.6521 (2)	0.0517 (4)	0.71160 (12)	0.0510 (6)
H3A	0.6596	−0.0397	0.6820	0.061*
H3B	0.7081	0.0588	0.7469	0.061*
N4	0.2904 (2)	0.2682 (3)	0.58727 (10)	0.0355 (5)
H4	0.2173	0.3370	0.5872	0.043*
O1	0.23817 (18)	0.2603 (3)	0.35549 (9)	0.0420 (4)
H1	0.1654	0.2413	0.3342	0.063*
Br1	0.23506 (4)	0.62118 (5)	0.671478 (18)	0.06510 (16)

	U11	U22	U33	U12	U13	U23
C1	0.0334 (12)	0.0391 (13)	0.0292 (12)	0.0023 (10)	−0.0052 (10)	−0.0036 (10)
C2	0.0362 (13)	0.0361 (12)	0.0311 (12)	−0.0024 (10)	0.0010 (10)	−0.0052 (10)
C3	0.0341 (13)	0.0357 (12)	0.0330 (12)	0.0048 (10)	−0.0012 (10)	−0.0026 (10)
C4	0.0305 (12)	0.0357 (13)	0.0261 (11)	−0.0010 (9)	−0.0015 (9)	0.0012 (9)
C5	0.0625 (19)	0.0506 (17)	0.0523 (18)	0.0074 (14)	−0.0080 (15)	−0.0204 (14)
C6	0.0397 (14)	0.0341 (13)	0.0336 (13)	0.0029 (10)	−0.0131 (10)	−0.0028 (10)
C7	0.0305 (12)	0.0488 (15)	0.0318 (12)	0.0033 (10)	−0.0085 (10)	−0.0130 (11)
C8	0.0392 (14)	0.0455 (14)	0.0315 (12)	−0.0098 (11)	0.0002 (10)	−0.0048 (11)
C9	0.0378 (13)	0.0344 (12)	0.0289 (12)	0.0038 (10)	−0.0043 (10)	−0.0023 (10)
C10	0.0308 (12)	0.0419 (14)	0.0346 (12)	0.0000 (10)	−0.0085 (10)	0.0023 (11)
C11	0.0418 (14)	0.0376 (14)	0.0402 (14)	−0.0080 (11)	−0.0122 (11)	0.0056 (11)
C12	0.070 (2)	0.0410 (15)	0.0473 (17)	0.0115 (14)	0.0002 (15)	0.0079 (13)
N1	0.0342 (11)	0.0412 (11)	0.0306 (10)	0.0010 (9)	−0.0056 (8)	−0.0077 (9)
N2	0.0359 (11)	0.0374 (11)	0.0267 (10)	0.0035 (8)	−0.0071 (8)	−0.0059 (8)
N3	0.0541 (14)	0.0575 (14)	0.0405 (12)	0.0239 (12)	−0.0226 (11)	−0.0177 (11)
N4	0.0321 (10)	0.0446 (12)	0.0297 (10)	0.0073 (9)	−0.0075 (8)	−0.0030 (9)
O1	0.0410 (10)	0.0525 (11)	0.0319 (9)	0.0119 (8)	−0.0100 (7)	−0.0119 (8)
Br1	0.0679 (3)	0.0608 (2)	0.0659 (3)	0.03307 (16)	−0.01891 (17)	−0.01908 (15)

C1—N3	1.335 (3)	C7—H7B	0.9900
C1—N2	1.340 (3)	C8—C9	1.526 (3)
C1—N1	1.349 (3)	C8—H8A	0.9900
C2—N1	1.352 (3)	C8—H8B	0.9900
C2—C3	1.366 (3)	C9—O1	1.430 (3)
C2—C5	1.493 (4)	C9—C12	1.514 (4)
C3—C4	1.405 (3)	C9—C10	1.525 (3)
C3—Br1	1.891 (2)	C10—C11	1.529 (3)
C4—N2	1.331 (3)	C10—H10A	0.9900
C4—N4	1.351 (3)	C10—H10B	0.9900
C5—H5A	0.9800	C11—H11A	0.9900
C5—H5B	0.9800	C11—H11B	0.9900
C5—H5C	0.9800	C12—H12A	0.9800
C6—N4	1.457 (3)	C12—H12B	0.9800
C6—C11	1.517 (3)	C12—H12C	0.9800
C6—C7	1.518 (4)	N3—H3A	0.8800
C6—H6	1.0000	N3—H3B	0.8800
C7—C8	1.523 (4)	N4—H4	0.8800
C7—H7A	0.9900	O1—H1	0.8400
N3—C1—N2	116.8 (2)	H8A—C8—H8B	107.8
N3—C1—N1	116.6 (2)	O1—C9—C12	109.9 (2)
N2—C1—N1	126.6 (2)	O1—C9—C10	110.1 (2)
N1—C2—C3	120.5 (2)	C12—C9—C10	110.3 (2)
N1—C2—C5	115.7 (2)	O1—C9—C8	104.89 (19)
C3—C2—C5	123.8 (2)	C12—C9—C8	111.0 (2)
C2—C3—C4	119.2 (2)	C10—C9—C8	110.5 (2)
C2—C3—Br1	121.01 (19)	C9—C10—C11	113.6 (2)
C4—C3—Br1	119.76 (17)	C9—C10—H10A	108.8
N2—C4—N4	118.2 (2)	C11—C10—H10A	108.8
N2—C4—C3	120.7 (2)	C9—C10—H10B	108.8
N4—C4—C3	121.1 (2)	C11—C10—H10B	108.8
C2—C5—H5A	109.5	H10A—C10—H10B	107.7
C2—C5—H5B	109.5	C6—C11—C10	112.2 (2)
H5A—C5—H5B	109.5	C6—C11—H11A	109.2
C2—C5—H5C	109.5	C10—C11—H11A	109.2
H5A—C5—H5C	109.5	C6—C11—H11B	109.2
H5B—C5—H5C	109.5	C10—C11—H11B	109.2
N4—C6—C11	109.1 (2)	H11A—C11—H11B	107.9
N4—C6—C7	110.6 (2)	C9—C12—H12A	109.5
C11—C6—C7	109.7 (2)	C9—C12—H12B	109.5
N4—C6—H6	109.1	H12A—C12—H12B	109.5
C11—C6—H6	109.1	C9—C12—H12C	109.5
C7—C6—H6	109.1	H12A—C12—H12C	109.5
C6—C7—C8	111.2 (2)	H12B—C12—H12C	109.5
C6—C7—H7A	109.4	C1—N1—C2	116.5 (2)
C8—C7—H7A	109.4	C4—N2—C1	116.4 (2)
C6—C7—H7B	109.4	C1—N3—H3A	120.0
C8—C7—H7B	109.4	C1—N3—H3B	120.0
H7A—C7—H7B	108.0	H3A—N3—H3B	120.0
C7—C8—C9	113.2 (2)	C4—N4—C6	124.3 (2)
C7—C8—H8A	108.9	C4—N4—H4	117.8
C9—C8—H8A	108.9	C6—N4—H4	117.8
C7—C8—H8B	108.9	C9—O1—H1	109.5
C9—C8—H8B	108.9

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1i	0.88	2.03	2.828 (3)	151
O1—H1···N1ii	0.84	2.02	2.803 (3)	155

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1i	0.88	2.03	2.828 (3)	151
O1—H1⋯N1ii	0.84	2.02	2.803 (3)	155

Symmetry codes: (i) ; (ii) .