7-Amino-1-(3-bromo­phen­yl)-3-cyano­pyrazolo[4,3-d]pyrimidine

In the title compound, C₁₂H₇BrN₆, the dihedral angle between the bromo­phenyl ring and planar pyrazolopyrimidine skeleton is 46.9 (8)°. The crystal packing is stabilized by N—H...N, C—H...N, N—H...Br and C—H...Br inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.033
• wR factor = 0.087
• Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found





Alert level C
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C3     -   C4     ...       1.43 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6'    ..  N4      ..       2.67 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5     ..  BR      ..       2.96 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

Author Response: 2 authors are involved in the synthesis, 1 in the spectroscopic characterization, 1 in the X ray data collections and 2 in the structure resolution.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

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Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

7-Amino-1-(3-bromophenyl)-3-cyanopyrazolo[4,3-d]pyrimidine

Crystal data

C12H7BrN6	F(000) = 624
Mr = 315.15	Dx = 1.756 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8516 reflections
a = 7.7153 (3) Å	θ = 2.9–26.0°
b = 7.6270 (4) Å	µ = 3.44 mm^−1
c = 20.3497 (7) Å	T = 200 K
β = 95.560 (2)°	Prism, orange
V = 1191.84 (9) Å^3	0.18 × 0.16 × 0.1 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	2000 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromator	Rint = 0.062
φ scans and ω scans winth κ offsets	θmax = 26.1°, θmin = 2.9°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −9→9
Tmin = 0.548, Tmax = 0.709	k = −8→9
7624 measured reflections	l = −25→25
2361 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.033	w = 1/[σ^2(Fo^2) + (0.0505P)^2 + 0.2909P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.087	(Δ/σ)max = 0.026
S = 1.05	Δρmax = 0.76 e Å^−3
2361 reflections	Δρmin = −0.98 e Å^−3
173 parameters

Special details

Experimental. (II) δ (CDCl3) 1.44 (3H, t J 7.0?Hz, OCH2CH3), 4.47 (2H, q J 7.0?Hz, OCH2CH3), 7.45 (1H, t J 8.0 Hz, H-5') 7.65–7.71 (2H, m, H-4' and H-6'), 7.88–7.93 (1H, m, H-2'), 8.22 (1H, s, H—C=N).

(IIIa) λmax (EtOH, ε) 218 (14815) 311 (8653) nm; νmax (Nujol) 3459, 3294, 3066, 2235, 1646, 1587, 1571, 1557, 1481, 1463, 1383, 1278, 1202, 1135, 1072, 1006, 892, 797, 698?cm-1; δ (acetone-d6) 6.75 (2H, very br s, NH2), 7.69 (1H, t J 7.8 Hz, H-5'), 7.70–7.89 (2H, m, H-4'and H-6'), 8.03 (1H, t J 1.8 Hz, H-2'), 8.47 (1H, s, H-5). 13 C (acetone-d6+DMSO-d6) 157.2 (C7), 155.1 (C5), 151.6 (C3), 146.2 (C3a), 140.2 (C1'), 133.4, 132.0, 129.1, 125.1, 122.8 (C3'), 120.4 (C7a), 112.4 (CN). Found: (M++1) 315.0007. Expected for C12H8N6 79Br: 314.9994.

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.

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

	x	y	z	Uiso*/Ueq
N6	0.1980 (3)	0.4330 (3)	−0.03637 (11)	0.0297 (5)
C1'	0.4865 (3)	0.1784 (4)	0.14990 (12)	0.0263 (5)
N1	0.5115 (3)	0.1960 (3)	0.08155 (11)	0.0273 (5)
C9	0.5060 (4)	0.2681 (3)	−0.02436 (13)	0.0258 (5)
C7	0.2458 (3)	0.3602 (3)	0.02250 (13)	0.0277 (5)
N4	0.4545 (3)	0.3379 (3)	−0.08434 (11)	0.0295 (5)
C2'	0.5206 (3)	0.0169 (3)	0.17933 (13)	0.0284 (6)
H2'	0.5539	−0.0802	0.1541	0.034*
C3	0.6578 (3)	0.1714 (3)	−0.00269 (13)	0.0276 (5)
N2	0.6607 (3)	0.1295 (3)	0.06115 (11)	0.0292 (5)
C4	0.7940 (4)	0.1219 (4)	−0.04168 (14)	0.0338 (6)
N7	0.1352 (3)	0.3695 (3)	0.06892 (11)	0.0347 (5)
H7A	0.0342	0.4224	0.0604	0.042*
H7B	0.1634	0.3227	0.108	0.042*
C8	0.4134 (4)	0.2793 (3)	0.03087 (13)	0.0257 (5)
C5	0.3032 (4)	0.4181 (3)	−0.08522 (13)	0.0302 (6)
H5	0.2627	0.4729	−0.1258	0.036*
Br	0.55734 (4)	−0.22152 (4)	0.285832 (13)	0.03521 (14)
C5'	0.4216 (4)	0.2997 (3)	0.25268 (14)	0.0308 (6)
H5'	0.3876	0.3964	0.2779	0.037*
C6'	0.4381 (3)	0.3218 (4)	0.18626 (14)	0.0282 (5)
H6'	0.4168	0.4327	0.1658	0.034*
C3'	0.5055 (3)	−0.0002 (4)	0.24571 (13)	0.0277 (5)
C4'	0.4538 (4)	0.1390 (4)	0.28326 (13)	0.0305 (6)
H4'	0.4408	0.1244	0.3289	0.037*
N3	0.8941 (4)	0.0828 (4)	−0.07707 (14)	0.0516 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N6	0.0313 (12)	0.0285 (11)	0.0291 (12)	0.0014 (9)	0.0018 (9)	0.0006 (9)
C1'	0.0278 (12)	0.0310 (13)	0.0199 (12)	0.0009 (11)	0.0014 (10)	0.0007 (10)
N1	0.0302 (11)	0.0260 (11)	0.0264 (11)	0.0055 (9)	0.0060 (9)	−0.0001 (9)
C9	0.0316 (14)	0.0218 (12)	0.0242 (13)	−0.0025 (10)	0.0044 (11)	−0.0025 (9)
C7	0.0320 (13)	0.0224 (13)	0.0289 (13)	0.0005 (10)	0.0034 (11)	−0.0014 (10)
N4	0.0373 (12)	0.0267 (11)	0.0245 (11)	−0.0020 (10)	0.0027 (9)	−0.0005 (9)
C2'	0.0333 (14)	0.0250 (13)	0.0268 (13)	0.0032 (11)	0.0020 (11)	−0.0020 (10)
C3	0.0337 (14)	0.0233 (12)	0.0264 (13)	0.0011 (11)	0.0063 (11)	−0.0031 (10)
N2	0.0314 (12)	0.0276 (12)	0.0294 (11)	0.0021 (9)	0.0071 (9)	−0.0001 (9)
C4	0.0372 (15)	0.0338 (15)	0.0309 (14)	0.0030 (12)	0.0055 (12)	0.0023 (11)
N7	0.0336 (12)	0.0428 (14)	0.0284 (12)	0.0109 (11)	0.0059 (10)	0.0063 (10)
C8	0.0328 (14)	0.0203 (12)	0.0238 (13)	−0.0011 (10)	0.0016 (11)	0.0003 (9)
C5	0.0367 (14)	0.0279 (14)	0.0254 (13)	−0.0008 (11)	0.0002 (11)	0.0034 (10)
Br	0.0453 (2)	0.0283 (2)	0.03189 (19)	0.00302 (12)	0.00313 (13)	0.00509 (10)
C5'	0.0354 (14)	0.0281 (14)	0.0291 (14)	0.0037 (11)	0.0045 (11)	−0.0050 (11)
C6'	0.0308 (13)	0.0237 (12)	0.0302 (14)	0.0035 (10)	0.0036 (11)	0.0020 (11)
C3'	0.0287 (13)	0.0263 (13)	0.0278 (13)	−0.0024 (10)	0.0006 (10)	−0.0008 (10)
C4'	0.0344 (14)	0.0331 (15)	0.0242 (13)	0.0001 (11)	0.0042 (11)	0.0018 (10)
N3	0.0478 (16)	0.0629 (19)	0.0471 (16)	0.0126 (14)	0.0197 (13)	0.0038 (14)

Geometric parameters (Å, º)

N6—C7	1.339 (3)	C2'—H2'	0.95
N6—C5	1.348 (3)	C3—N2	1.336 (3)
C1'—C2'	1.384 (4)	C3—C4	1.427 (4)
C1'—C6'	1.392 (4)	C4—N3	1.145 (4)
C1'—N1	1.429 (3)	N7—H7A	0.88
N1—N2	1.359 (3)	N7—H7B	0.88
N1—C8	1.374 (3)	C5—H5	0.95
C9—N4	1.355 (3)	Br—C3'	1.901 (3)
C9—C8	1.392 (4)	C5'—C6'	1.380 (4)
C9—C3	1.418 (4)	C5'—C4'	1.386 (4)
C7—N7	1.335 (3)	C5'—H5'	0.95
C7—C8	1.428 (4)	C6'—H6'	0.95
N4—C5	1.317 (4)	C3'—C4'	1.389 (4)
C2'—C3'	1.373 (4)	C4'—H4'	0.95
C7—N6—C5	119.4 (2)	C7—N7—H7A	120
C2'—C1'—C6'	121.3 (2)	C7—N7—H7B	120
C2'—C1'—N1	117.8 (2)	H7A—N7—H7B	120
C6'—C1'—N1	120.8 (2)	N1—C8—C9	106.8 (2)
N2—N1—C8	111.4 (2)	N1—C8—C7	135.7 (2)
N2—N1—C1'	117.4 (2)	C9—C8—C7	117.4 (2)
C8—N1—C1'	131.1 (2)	N4—C5—N6	128.7 (2)
N4—C9—C8	125.1 (2)	N4—C5—H5	115.6
N4—C9—C3	130.2 (2)	N6—C5—H5	115.6
C8—C9—C3	104.7 (2)	C6'—C5'—C4'	121.2 (2)
N7—C7—N6	118.1 (2)	C6'—C5'—H5'	119.4
N7—C7—C8	124.9 (2)	C4'—C5'—H5'	119.4
N6—C7—C8	117.0 (2)	C5'—C6'—C1'	118.7 (2)
C5—N4—C9	112.1 (2)	C5'—C6'—H6'	120.7
C3'—C2'—C1'	118.6 (2)	C1'—C6'—H6'	120.7
C3'—C2'—H2'	120.7	C2'—C3'—C4'	121.7 (2)
C1'—C2'—H2'	120.7	C2'—C3'—Br	118.2 (2)
N2—C3—C9	111.2 (2)	C4'—C3'—Br	120.1 (2)
N2—C3—C4	122.3 (2)	C5'—C4'—C3'	118.5 (2)
C9—C3—C4	126.5 (2)	C5'—C4'—H4'	120.7
C3—N2—N1	105.8 (2)	C3'—C4'—H4'	120.7
N3—C4—C3	174.8 (3)
C2'—C1'—N1—N2	−45.9 (3)	N2—N1—C8—C7	175.1 (3)
C6'—C1'—N1—N2	130.9 (3)	C1'—N1—C8—C7	−8.8 (5)
C2'—C1'—N1—C8	138.2 (3)	N4—C9—C8—N1	−178.5 (2)
C6'—C1'—N1—C8	−45.0 (4)	C3—C9—C8—N1	1.4 (3)
C5—N6—C7—N7	−176.7 (2)	N4—C9—C8—C7	4.5 (4)
C5—N6—C7—C8	3.8 (4)	C3—C9—C8—C7	−175.6 (2)
C8—C9—N4—C5	−0.6 (4)	N7—C7—C8—N1	−1.2 (5)
C3—C9—N4—C5	179.5 (3)	N6—C7—C8—N1	178.2 (3)
C6'—C1'—C2'—C3'	0.2 (4)	N7—C7—C8—C9	174.7 (3)
N1—C1'—C2'—C3'	176.9 (2)	N6—C7—C8—C9	−5.9 (3)
N4—C9—C3—N2	178.7 (3)	C9—N4—C5—N6	−2.0 (4)
C8—C9—C3—N2	−1.2 (3)	C7—N6—C5—N4	0.3 (4)
N4—C9—C3—C4	−1.3 (5)	C4'—C5'—C6'—C1'	0.6 (4)
C8—C9—C3—C4	178.8 (3)	C2'—C1'—C6'—C5'	−1.1 (4)
C9—C3—N2—N1	0.6 (3)	N1—C1'—C6'—C5'	−177.7 (2)
C4—C3—N2—N1	−179.5 (2)	C1'—C2'—C3'—C4'	1.3 (4)
C8—N1—N2—C3	0.3 (3)	C1'—C2'—C3'—Br	−178.8 (2)
C1'—N1—N2—C3	−176.4 (2)	C6'—C5'—C4'—C3'	0.8 (4)
N2—N1—C8—C9	−1.1 (3)	C2'—C3'—C4'—C5'	−1.7 (4)
C1'—N1—C8—C9	175.0 (2)	Br—C3'—C4'—C5'	178.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7A···N6^i	0.88	2.12	2.998 (3)	175
C2′—H2′···N4^ii	0.95	2.42	3.342 (3)	163
C6′—H6′···N4^iii	0.95	2.67	3.472 (3)	143
N7—H7B···Br^iv	0.88	2.9	3.504 (2)	128
C5—H5···Br^v	0.95	2.96	3.857 (3)	157

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