7-Benzyl­oxymethyl-9-bromo-6-chloro-9-deaza­purine

Gainsford, G.J.; Mason, J.M.; Gulab, S.A.

doi:10.1107/S1600536809050879

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o138

doi:10.1107/S1600536809050879

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7-Benzyloxymethyl-9-bromo-6-chloro-9-deazapurine

Graeme J. Gainsford,^a ^* Jennifer M. Mason ^a and Shivali A. Gulab ^a

^aIndustrial Research Limited, PO Box 31-310, Lower Hutt, New Zealand
^*Correspondence e-mail: g.gainsford@irl.cri.nz

(Received 18 November 2009; accepted 25 November 2009; online 16 December 2009)

The title compound, C₁₄H₁₁BrClN₃O, crystallizes with two independent molecules in the asymmetric unit. In the crystal, the molecules are linked by C—N⋯Br halogen bonds, as well as weak methylene C—H⋯π, phenyl C—H⋯π, C—H⋯Br and phenyl C—H⋯O(ether) interactions.

Related literature

For synthetic details, see Clinch et al. (2010 ). For Br⋯N halogen bonding, see: Kubicki (2004 ); Metrangolo et al. (2008 ). For a related structure, see: Sakore & Sobell (1969 ).

Experimental

Crystal data

C₁₄H₁₁BrClN₃O
M_r = 352.62
Triclinic, $[P \overline 1]$
a = 7.8999 (2) Å
b = 11.5023 (4) Å
c = 15.5571 (5) Å
α = 86.111 (2)°
β = 84.564 (2)°
γ = 89.037 (2)°
V = 1403.95 (8) Å³
Z = 4
Mo Kα radiation
μ = 3.12 mm⁻¹
T = 118 K
0.41 × 0.21 × 0.02 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (Blessing, 1995 ) T_min = 0.606, T_max = 0.747
40101 measured reflections
9403 independent reflections
6435 reflections with I > 2σ(I)
R_int = 0.060

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.081
S = 1.01
9403 reflections
361 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Selected torsion angles (°)

C5—N7—C8—C9	0.3 (3)
N7—C10—O11—C12	−68.2 (3)
C10—O11—C12—C13	−172.6 (2)
C5′—N7′—C8′—C9′	0.1 (3)
N7′—C10′—O11′—C12′	−77.3 (2)
C10′—O11′—C12′—C13′	−161.5 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯Br9ⁱ	0.95	2.90	3.805 (3)	159
C8—H8⋯N1ⁱⁱ	0.95	2.46	3.394 (3)	166
C8′—H8′⋯N1′ⁱⁱ	0.95	2.48	3.410 (3)	166
C10′—H10C⋯Br9ⁱⁱⁱ	0.99	2.78	3.700 (2)	156
C15—H15⋯O11′^iv	0.95	2.60	3.497 (4)	158
C10—H10A⋯Cg1^v	0.99	2.60	3.466 (3)	146
C14—H14⋯Cg2^iv	0.95	2.87	3.794 (3)	165
Symmetry codes: (i) x+1, y, z; (ii) x-1, y, z; (iii) -x+1, -y, -z+1; (iv) x-1, y, z+1; (v) -x+1, -y+1, -z+1. Cg1 and Cg2 are the centroids of the N7′,C4′,C5′,C8′,C9′ and C13′–C18′ rings, respectively.

Table 3
C—N⋯Br interactions (Å, °)

C—N⋯Br	C—N	N⋯Br	C⋯Br	C—N⋯Br
C2—N3⋯Br9′^vi	1.320 (3)	2.964 (2)	3.457 (3)	100.45 (17)
C2′—N3′⋯Br^vii	1.324 (3)	3.043 (2)	3.565 (3)	102.17 (14)
Symmetry codes: (vi) x, y-1, z; (vii) 1+x, 1+y, z.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT and SADABS (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97 and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809050879/wn2368sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809050879/wn2368Isup2.hkl

checkCIF report

Comment top

The title compound was prepared for incorporation into potential transition state analogue inhibitors of human methylthioadenosine phosphorylase and bacterial methylthioadenosine/S-adenosylhomocysteine nucleosidase (Clinch et al., 2010).

The asymmetric unit of the title compound contains two independent 7-benzyloxymethyl-9-bromo-6-chloro-9-deazapurine molecules (Fig. 1, Table 1) which are nearly identical. The molecular labels are related by the addition of a prime (e.g. molecule 1, Br9 and molecule 2, Br9'). The overlay figure (Fig. 2) illustrates the rmsd fit of 0.077 Å, with maximum deviation at the Cl6 (C16') atom sites of 0.274 Å. The five-membered rings (i.e. C4,C5,C8,C9,N7) are planar (maximum deviations 0.004 (2), 0.001 (2) Å), as are the fused six-membered rings (C4,C5,C6,N1,C2,N3) with maximum deviations 0.017 (2), 0.010 (2) Å; the angles between these two planes are 2.62 (13) and 1.00 (12)°, respectively. The dihedral angles between the mean planes through the deazapurine ring systems and the phenyl rings are 52.76 (12) and 58.02 (11)°.

Torsion angles (Table 1) are similar to those observed earlier in 9-ethyl-8-bromohypoxanthine (Sakore & Sobell, 1969).

Lattice binding is provided principally by Br···N halogen bonding (Metrangolo et al., 2008; Kubicki, 2004) between the two independent molecules, forming layers parallel to the (0,1,2) plane (Table 3; Fig. 3). Inter-layer links are provided by weak methylene C–H···π, phenyl C–H···π, C–H···Br, and phenyl C–H···O(ether) interactions (Table 2). In Table 2, Cg1 and Cg2 are the centroids of N7',C4',C5',C8',C9' and C13'–C18', respectively.

Related literature top

For synthetic details, see Clinch et al. (2010). For Br···N halogen bonding, see: Kubicki (2004); Metrangolo et al. (2008). For a related structure, see: Sakore & Sobell (1969). Cg1 and Cg2 are the centroids of the N7',C4',C5',C8',C9' and C13'–C18' rings, respectively.

Experimental top

Synthetic details are given in Clinch et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT and SADABS (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Asymmetric unit of the title compound (Farrugia, 1997).
	Fig. 2. Overlap view of the two molecules (Mercury 2.3, Macrae et al. (2008)). Single coloured (purple) molecule is primed molecule 2.
	Fig. 3. A packing view (Mercury 2.3, Macrae et al. (2008)) of the unit cell, highlighting the layers formed by Br···N bonding in the crystal structure (Table 3). Some of the other weak interactions (Table 2) are shown, with contact atoms in ball mode; only H atoms involved in short contacts are included. Symmetry codes: (i) x, 1 + y,z (ii) x - 1,y,z (iii) 1 - x,1 - y,1 - z (iv) x - 1,1 + y,z.

5-Benzyloxymethyl-7-bromo-4-chloro-5H-pyrrolo[3,2-d]pyrimidine top

Crystal data top

C₁₄H₁₁BrClN₃O	Z = 4
M_r = 352.62	F(000) = 704
Triclinic, P1	D_x = 1.668 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8999 (2) Å	Cell parameters from 7237 reflections
b = 11.5023 (4) Å	θ = 2.3–28.2°
c = 15.5571 (5) Å	µ = 3.12 mm⁻¹
α = 86.111 (2)°	T = 118 K
β = 84.564 (2)°	Plate, colourless
γ = 89.037 (2)°	0.41 × 0.21 × 0.02 mm
V = 1403.95 (8) Å³

Data collection top

Bruker APEXII CCD diffractometer	9403 independent reflections
Radiation source: fine-focus sealed tube	6435 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
Detector resolution: 8.333 pixels mm^-1	θ_max = 32.0°, θ_min = 2.8°
ϕ and ω scans	h = −11→11
Absorption correction: multi-scan (Blessing, 1995)	k = −17→17
T_min = 0.606, T_max = 0.747	l = −23→23
40101 measured reflections

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0269P)² + 0.5143P] where P = (F_o² + 2F_c²)/3
9403 reflections	(Δ/σ)_max = 0.002
361 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

C₁₄H₁₁BrClN₃O	γ = 89.037 (2)°
M_r = 352.62	V = 1403.95 (8) Å³
Triclinic, P1	Z = 4
a = 7.8999 (2) Å	Mo Kα radiation
b = 11.5023 (4) Å	µ = 3.12 mm⁻¹
c = 15.5571 (5) Å	T = 118 K
α = 86.111 (2)°	0.41 × 0.21 × 0.02 mm
β = 84.564 (2)°

Data collection top

Bruker APEXII CCD diffractometer	9403 independent reflections
Absorption correction: multi-scan (Blessing, 1995)	6435 reflections with I > 2σ(I)
T_min = 0.606, T_max = 0.747	R_int = 0.060
40101 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.081	H-atom parameters constrained
S = 1.01	Δρ_max = 0.54 e Å⁻³
9403 reflections	Δρ_min = −0.45 e Å⁻³
361 parameters

Special details top

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	U_iso*/U_eq
Br9	0.07829 (3)	−0.13291 (2)	0.558649 (16)	0.02240 (6)
Cl6	0.55993 (8)	0.24034 (6)	0.75030 (4)	0.03239 (15)
N1	0.6523 (2)	0.0585 (2)	0.66667 (15)	0.0294 (5)
C2	0.6243 (3)	−0.0336 (3)	0.62176 (19)	0.0337 (7)
H2	0.7222	−0.0760	0.6010	0.040*
N3	0.4768 (2)	−0.07252 (19)	0.60296 (14)	0.0271 (5)
C4	0.3419 (3)	−0.0102 (2)	0.63424 (15)	0.0204 (5)
C5	0.3551 (3)	0.0859 (2)	0.68449 (15)	0.0194 (5)
C6	0.5190 (3)	0.1184 (2)	0.69711 (16)	0.0226 (5)
N7	0.1938 (2)	0.12957 (17)	0.70536 (13)	0.0200 (4)
C8	0.0815 (3)	0.0629 (2)	0.66795 (15)	0.0207 (5)
H8	−0.0383	0.0745	0.6720	0.025*
C9	0.1670 (3)	−0.0223 (2)	0.62432 (15)	0.0187 (5)
C10	0.1459 (3)	0.2263 (2)	0.75875 (16)	0.0244 (5)
H10A	0.2034	0.2975	0.7321	0.029*
H10B	0.0218	0.2400	0.7592	0.029*
O11	0.1867 (2)	0.20846 (15)	0.84366 (11)	0.0265 (4)
C12	0.0892 (4)	0.1195 (3)	0.89288 (19)	0.0465 (8)
H12A	0.1187	0.0426	0.8702	0.056*
H12B	−0.0336	0.1344	0.8888	0.056*
C13	0.1286 (4)	0.1199 (3)	0.98518 (18)	0.0343 (6)
C14	0.0310 (4)	0.1865 (2)	1.0417 (2)	0.0362 (7)
H14	−0.0592	0.2333	1.0215	0.043*
C15	0.0629 (4)	0.1861 (3)	1.12723 (19)	0.0377 (7)
H15	−0.0061	0.2318	1.1656	0.045*
C16	0.1938 (4)	0.1200 (3)	1.1573 (2)	0.0395 (7)
H16	0.2158	0.1200	1.2163	0.047*
C17	0.2929 (4)	0.0539 (3)	1.1013 (2)	0.0446 (8)
H17	0.3841	0.0082	1.1215	0.054*
C18	0.2602 (4)	0.0536 (3)	1.0156 (2)	0.0410 (7)
H18	0.3289	0.0073	0.9773	0.049*
Br9'	0.59248 (3)	0.72770 (2)	0.500913 (16)	0.02152 (6)
Cl6'	1.15241 (7)	0.36355 (6)	0.28870 (4)	0.02845 (14)
N1'	1.2108 (2)	0.54047 (18)	0.37585 (13)	0.0228 (4)
C2'	1.1644 (3)	0.6305 (2)	0.42386 (17)	0.0257 (5)
H2'	1.2547	0.6744	0.4411	0.031*
N3'	1.0089 (2)	0.66584 (18)	0.45013 (13)	0.0223 (4)
C4'	0.8857 (3)	0.6018 (2)	0.42261 (15)	0.0182 (5)
C5'	0.9182 (3)	0.5069 (2)	0.37055 (14)	0.0175 (4)
C6'	1.0881 (3)	0.4791 (2)	0.34985 (15)	0.0197 (5)
N7'	0.7642 (2)	0.46355 (17)	0.35311 (12)	0.0190 (4)
C8'	0.6378 (3)	0.5300 (2)	0.39368 (15)	0.0199 (5)
H8'	0.5194	0.5186	0.3921	0.024*
C9'	0.7066 (3)	0.6140 (2)	0.43611 (15)	0.0190 (5)
C10'	0.7317 (3)	0.3645 (2)	0.30284 (16)	0.0225 (5)
H10C	0.8014	0.2971	0.3222	0.027*
H10D	0.6107	0.3427	0.3150	0.027*
O11'	0.76778 (19)	0.38677 (15)	0.21388 (11)	0.0250 (4)
C12'	0.6421 (3)	0.4559 (3)	0.17201 (17)	0.0320 (6)
H12C	0.6546	0.5392	0.1820	0.038*
H12D	0.5264	0.4312	0.1953	0.038*
C13'	0.6698 (3)	0.4377 (2)	0.07720 (17)	0.0271 (6)
C14'	0.5969 (3)	0.3438 (3)	0.04404 (19)	0.0361 (7)
H14'	0.5247	0.2928	0.0810	0.043*
C15'	0.6289 (4)	0.3240 (3)	−0.04277 (19)	0.0408 (7)
H15'	0.5790	0.2592	−0.0652	0.049*
C16'	0.7331 (3)	0.3979 (3)	−0.09698 (19)	0.0371 (7)
H16'	0.7555	0.3842	−0.1565	0.045*
C17'	0.8045 (4)	0.4920 (3)	−0.06387 (19)	0.0397 (7)
H17'	0.8758	0.5434	−0.1008	0.048*
C18'	0.7726 (3)	0.5115 (3)	0.02262 (18)	0.0357 (7)
H18'	0.8221	0.5766	0.0448	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br9	0.01902 (11)	0.02210 (13)	0.02763 (14)	−0.00162 (8)	−0.00850 (9)	−0.00370 (10)
Cl6	0.0302 (3)	0.0355 (4)	0.0336 (4)	−0.0109 (3)	−0.0062 (3)	−0.0109 (3)
N1	0.0160 (9)	0.0408 (14)	0.0332 (13)	−0.0029 (8)	−0.0051 (8)	−0.0111 (11)
C2	0.0144 (11)	0.0463 (18)	0.0423 (18)	0.0040 (10)	−0.0035 (10)	−0.0164 (14)
N3	0.0163 (9)	0.0343 (13)	0.0323 (13)	0.0021 (8)	−0.0042 (8)	−0.0107 (10)
C4	0.0173 (10)	0.0242 (13)	0.0198 (13)	−0.0013 (8)	−0.0034 (8)	0.0004 (10)
C5	0.0167 (10)	0.0251 (13)	0.0166 (12)	−0.0010 (8)	−0.0030 (8)	−0.0005 (10)
C6	0.0216 (11)	0.0289 (14)	0.0182 (12)	−0.0054 (9)	−0.0058 (9)	−0.0025 (10)
N7	0.0170 (9)	0.0223 (11)	0.0213 (11)	0.0000 (7)	−0.0034 (7)	−0.0049 (8)
C8	0.0149 (10)	0.0263 (13)	0.0214 (13)	−0.0008 (8)	−0.0044 (8)	−0.0019 (10)
C9	0.0174 (10)	0.0204 (12)	0.0191 (12)	−0.0024 (8)	−0.0052 (8)	−0.0022 (9)
C10	0.0272 (12)	0.0232 (13)	0.0230 (14)	0.0031 (9)	−0.0011 (9)	−0.0045 (11)
O11	0.0326 (9)	0.0286 (10)	0.0185 (9)	−0.0086 (7)	−0.0009 (7)	−0.0031 (8)
C12	0.062 (2)	0.051 (2)	0.0268 (17)	−0.0310 (16)	−0.0012 (14)	0.0029 (14)
C13	0.0421 (15)	0.0349 (16)	0.0258 (15)	−0.0169 (12)	−0.0013 (11)	0.0004 (12)
C14	0.0421 (16)	0.0290 (16)	0.0390 (18)	−0.0022 (12)	−0.0110 (13)	−0.0023 (13)
C15	0.0475 (17)	0.0343 (17)	0.0324 (17)	−0.0003 (13)	−0.0042 (13)	−0.0100 (13)
C16	0.0494 (17)	0.0420 (18)	0.0281 (16)	−0.0092 (14)	−0.0097 (13)	0.0007 (14)
C17	0.0379 (16)	0.049 (2)	0.047 (2)	−0.0003 (14)	−0.0113 (14)	0.0032 (16)
C18	0.0364 (15)	0.0460 (19)	0.0393 (19)	−0.0044 (13)	0.0072 (13)	−0.0086 (15)
Br9'	0.01786 (10)	0.02498 (14)	0.02185 (13)	0.00062 (8)	−0.00097 (8)	−0.00401 (10)
Cl6'	0.0234 (3)	0.0316 (3)	0.0305 (4)	0.0022 (2)	0.0014 (2)	−0.0094 (3)
N1'	0.0177 (9)	0.0271 (12)	0.0235 (12)	−0.0024 (8)	−0.0023 (7)	−0.0005 (9)
C2'	0.0148 (10)	0.0315 (14)	0.0315 (15)	−0.0057 (9)	−0.0052 (9)	−0.0012 (11)
N3'	0.0187 (9)	0.0254 (11)	0.0235 (11)	−0.0034 (8)	−0.0044 (8)	−0.0029 (9)
C4'	0.0177 (10)	0.0192 (12)	0.0178 (12)	−0.0013 (8)	−0.0034 (8)	0.0009 (9)
C5'	0.0166 (9)	0.0222 (12)	0.0142 (11)	−0.0025 (8)	−0.0035 (8)	−0.0017 (9)
C6'	0.0199 (10)	0.0236 (12)	0.0151 (12)	0.0011 (9)	0.0007 (8)	0.0001 (10)
N7'	0.0151 (8)	0.0243 (11)	0.0187 (11)	−0.0031 (7)	−0.0040 (7)	−0.0045 (8)
C8'	0.0122 (9)	0.0282 (13)	0.0189 (12)	−0.0001 (8)	−0.0013 (8)	0.0021 (10)
C9'	0.0188 (10)	0.0224 (12)	0.0158 (12)	−0.0008 (8)	−0.0014 (8)	−0.0007 (9)
C10'	0.0236 (11)	0.0229 (13)	0.0219 (13)	−0.0037 (9)	−0.0056 (9)	−0.0037 (10)
O11'	0.0226 (8)	0.0349 (10)	0.0187 (9)	0.0060 (7)	−0.0058 (6)	−0.0064 (8)
C12'	0.0312 (13)	0.0412 (17)	0.0249 (15)	0.0107 (11)	−0.0078 (10)	−0.0060 (12)
C13'	0.0260 (12)	0.0348 (15)	0.0219 (14)	0.0063 (10)	−0.0079 (10)	−0.0055 (11)
C14'	0.0411 (15)	0.0394 (17)	0.0282 (16)	−0.0068 (12)	−0.0063 (12)	0.0005 (13)
C15'	0.0510 (17)	0.0438 (19)	0.0299 (17)	−0.0083 (14)	−0.0098 (13)	−0.0089 (14)
C16'	0.0405 (15)	0.0497 (19)	0.0226 (15)	0.0026 (13)	−0.0079 (11)	−0.0064 (13)
C17'	0.0404 (16)	0.052 (2)	0.0272 (16)	−0.0108 (13)	−0.0059 (12)	0.0008 (14)
C18'	0.0412 (15)	0.0386 (17)	0.0294 (16)	−0.0075 (12)	−0.0114 (12)	−0.0052 (13)

Geometric parameters (Å, º) top

Br9—C9	1.870 (2)	Br9'—C9'	1.873 (2)
Cl6—C6	1.726 (2)	Cl6'—C6'	1.728 (2)
N1—C6	1.316 (3)	N1'—C6'	1.318 (3)
N1—C2	1.341 (3)	N1'—C2'	1.344 (3)
C2—N3	1.320 (3)	C2'—N3'	1.324 (3)
C2—H2	0.9500	C2'—H2'	0.9500
N3—C4	1.345 (3)	N3'—C4'	1.348 (3)
C4—C5	1.407 (3)	C4'—C5'	1.409 (3)
C4—C9	1.415 (3)	C4'—C9'	1.417 (3)
C5—N7	1.380 (3)	C5'—N7'	1.379 (3)
C5—C6	1.390 (3)	C5'—C6'	1.388 (3)
N7—C8	1.377 (3)	N7'—C8'	1.379 (3)
N7—C10	1.457 (3)	N7'—C10'	1.465 (3)
C8—C9	1.363 (3)	C8'—C9'	1.355 (3)
C8—H8	0.9500	C8'—H8'	0.9500
C10—O11	1.390 (3)	C10'—O11'	1.394 (3)
C10—H10A	0.9900	C10'—H10C	0.9900
C10—H10B	0.9900	C10'—H10D	0.9900
O11—C12	1.427 (3)	O11'—C12'	1.438 (3)
C12—C13	1.498 (4)	C12'—C13'	1.499 (4)
C12—H12A	0.9900	C12'—H12C	0.9900
C12—H12B	0.9900	C12'—H12D	0.9900
C13—C14	1.378 (4)	C13'—C18'	1.377 (4)
C13—C18	1.380 (4)	C13'—C14'	1.385 (4)
C14—C15	1.377 (4)	C14'—C15'	1.384 (4)
C14—H14	0.9500	C14'—H14'	0.9500
C15—C16	1.372 (4)	C15'—C16'	1.381 (4)
C15—H15	0.9500	C15'—H15'	0.9500
C16—C17	1.376 (4)	C16'—C17'	1.380 (4)
C16—H16	0.9500	C16'—H16'	0.9500
C17—C18	1.382 (4)	C17'—C18'	1.378 (4)
C17—H17	0.9500	C17'—H17'	0.9500
C18—H18	0.9500	C18'—H18'	0.9500

C6—N1—C2	117.6 (2)	C6'—N1'—C2'	117.19 (19)
N3—C2—N1	127.8 (2)	N3'—C2'—N1'	128.2 (2)
N3—C2—H2	116.1	N3'—C2'—H2'	115.9
N1—C2—H2	116.1	N1'—C2'—H2'	115.9
C2—N3—C4	113.9 (2)	C2'—N3'—C4'	113.4 (2)
N3—C4—C5	123.5 (2)	N3'—C4'—C5'	123.7 (2)
N3—C4—C9	130.0 (2)	N3'—C4'—C9'	129.7 (2)
C5—C4—C9	106.56 (19)	C5'—C4'—C9'	106.58 (19)
N7—C5—C6	135.4 (2)	N7'—C5'—C6'	135.8 (2)
N7—C5—C4	108.42 (18)	N7'—C5'—C4'	108.19 (18)
C6—C5—C4	116.1 (2)	C6'—C5'—C4'	116.05 (19)
N1—C6—C5	121.1 (2)	N1'—C6'—C5'	121.4 (2)
N1—C6—Cl6	116.47 (17)	N1'—C6'—Cl6'	115.92 (17)
C5—C6—Cl6	122.42 (19)	C5'—C6'—Cl6'	122.65 (18)
C8—N7—C5	107.50 (19)	C8'—N7'—C5'	107.52 (19)
C8—N7—C10	124.96 (19)	C8'—N7'—C10'	123.80 (18)
C5—N7—C10	127.53 (19)	C5'—N7'—C10'	128.67 (19)
C9—C8—N7	110.16 (19)	C9'—C8'—N7'	110.33 (19)
C9—C8—H8	124.9	C9'—C8'—H8'	124.8
N7—C8—H8	124.9	N7'—C8'—H8'	124.8
C8—C9—C4	107.4 (2)	C8'—C9'—C4'	107.4 (2)
C8—C9—Br9	128.03 (17)	C8'—C9'—Br9'	127.83 (17)
C4—C9—Br9	124.56 (18)	C4'—C9'—Br9'	124.78 (17)
O11—C10—N7	113.9 (2)	O11'—C10'—N7'	113.58 (19)
O11—C10—H10A	108.8	O11'—C10'—H10C	108.9
N7—C10—H10A	108.8	N7'—C10'—H10C	108.9
O11—C10—H10B	108.8	O11'—C10'—H10D	108.9
N7—C10—H10B	108.8	N7'—C10'—H10D	108.9
H10A—C10—H10B	107.7	H10C—C10'—H10D	107.7
C10—O11—C12	113.6 (2)	C10'—O11'—C12'	115.05 (18)
O11—C12—C13	108.2 (2)	O11'—C12'—C13'	107.2 (2)
O11—C12—H12A	110.1	O11'—C12'—H12C	110.3
C13—C12—H12A	110.1	C13'—C12'—H12C	110.3
O11—C12—H12B	110.1	O11'—C12'—H12D	110.3
C13—C12—H12B	110.1	C13'—C12'—H12D	110.3
H12A—C12—H12B	108.4	H12C—C12'—H12D	108.5
C14—C13—C18	118.8 (3)	C18'—C13'—C14'	119.2 (3)
C14—C13—C12	119.8 (3)	C18'—C13'—C12'	120.5 (2)
C18—C13—C12	121.4 (3)	C14'—C13'—C12'	120.2 (3)
C15—C14—C13	120.7 (3)	C15'—C14'—C13'	120.2 (3)
C15—C14—H14	119.7	C15'—C14'—H14'	119.9
C13—C14—H14	119.7	C13'—C14'—H14'	119.9
C16—C15—C14	120.4 (3)	C16'—C15'—C14'	120.3 (3)
C16—C15—H15	119.8	C16'—C15'—H15'	119.9
C14—C15—H15	119.8	C14'—C15'—H15'	119.9
C15—C16—C17	119.3 (3)	C17'—C16'—C15'	119.4 (3)
C15—C16—H16	120.3	C17'—C16'—H16'	120.3
C17—C16—H16	120.3	C15'—C16'—H16'	120.3
C16—C17—C18	120.3 (3)	C18'—C17'—C16'	120.2 (3)
C16—C17—H17	119.9	C18'—C17'—H17'	119.9
C18—C17—H17	119.9	C16'—C17'—H17'	119.9
C13—C18—C17	120.5 (3)	C13'—C18'—C17'	120.7 (3)
C13—C18—H18	119.8	C13'—C18'—H18'	119.7
C17—C18—H18	119.8	C17'—C18'—H18'	119.7

C6—N1—C2—N3	0.7 (5)	C6'—N1'—C2'—N3'	1.0 (4)
N1—C2—N3—C4	−0.4 (4)	N1'—C2'—N3'—C4'	−1.0 (4)
C2—N3—C4—C5	−1.7 (4)	C2'—N3'—C4'—C5'	−0.4 (3)
C2—N3—C4—C9	177.1 (3)	C2'—N3'—C4'—C9'	−178.8 (2)
N3—C4—C5—N7	179.8 (2)	N3'—C4'—C5'—N7'	−178.6 (2)
C9—C4—C5—N7	0.8 (3)	C9'—C4'—C5'—N7'	0.1 (3)
N3—C4—C5—C6	3.3 (4)	N3'—C4'—C5'—C6'	1.7 (3)
C9—C4—C5—C6	−175.7 (2)	C9'—C4'—C5'—C6'	−179.6 (2)
C2—N1—C6—C5	1.2 (4)	C2'—N1'—C6'—C5'	0.5 (3)
C2—N1—C6—Cl6	−177.1 (2)	C2'—N1'—C6'—Cl6'	−179.70 (19)
N7—C5—C6—N1	−178.2 (3)	N7'—C5'—C6'—N1'	178.7 (2)
C4—C5—C6—N1	−3.0 (4)	C4'—C5'—C6'—N1'	−1.7 (3)
N7—C5—C6—Cl6	0.0 (4)	N7'—C5'—C6'—Cl6'	−1.0 (4)
C4—C5—C6—Cl6	175.20 (18)	C4'—C5'—C6'—Cl6'	178.51 (17)
C6—C5—N7—C8	174.8 (3)	C6'—C5'—N7'—C8'	179.5 (3)
C4—C5—N7—C8	−0.7 (3)	C4'—C5'—N7'—C8'	−0.1 (3)
C6—C5—N7—C10	−6.7 (4)	C6'—C5'—N7'—C10'	0.6 (4)
C4—C5—N7—C10	177.9 (2)	C4'—C5'—N7'—C10'	−179.0 (2)
C5—N7—C8—C9	0.3 (3)	C5'—N7'—C8'—C9'	0.1 (3)
C10—N7—C8—C9	−178.3 (2)	C10'—N7'—C8'—C9'	179.0 (2)
N7—C8—C9—C4	0.2 (3)	N7'—C8'—C9'—C4'	0.0 (3)
N7—C8—C9—Br9	−177.46 (17)	N7'—C8'—C9'—Br9'	179.70 (17)
N3—C4—C9—C8	−179.5 (3)	N3'—C4'—C9'—C8'	178.6 (2)
C5—C4—C9—C8	−0.6 (3)	C5'—C4'—C9'—C8'	−0.1 (3)
N3—C4—C9—Br9	−1.8 (4)	N3'—C4'—C9'—Br9'	−1.1 (4)
C5—C4—C9—Br9	177.16 (17)	C5'—C4'—C9'—Br9'	−179.77 (17)
C8—N7—C10—O11	116.7 (2)	C8'—N7'—C10'—O11'	107.8 (2)
C5—N7—C10—O11	−61.7 (3)	C5'—N7'—C10'—O11'	−73.4 (3)
N7—C10—O11—C12	−68.2 (3)	N7'—C10'—O11'—C12'	−77.3 (2)
C10—O11—C12—C13	−172.6 (2)	C10'—O11'—C12'—C13'	−161.5 (2)
O11—C12—C13—C14	91.4 (3)	O11'—C12'—C13'—C18'	−92.3 (3)
O11—C12—C13—C18	−89.4 (3)	O11'—C12'—C13'—C14'	85.3 (3)
C18—C13—C14—C15	−0.7 (4)	C18'—C13'—C14'—C15'	0.7 (4)
C12—C13—C14—C15	178.6 (3)	C12'—C13'—C14'—C15'	−177.0 (3)
C13—C14—C15—C16	0.7 (4)	C13'—C14'—C15'—C16'	−0.3 (5)
C14—C15—C16—C17	−0.2 (5)	C14'—C15'—C16'—C17'	−0.2 (5)
C15—C16—C17—C18	−0.3 (5)	C15'—C16'—C17'—C18'	0.3 (4)
C14—C13—C18—C17	0.2 (4)	C14'—C13'—C18'—C17'	−0.6 (4)
C12—C13—C18—C17	−179.0 (3)	C12'—C13'—C18'—C17'	177.0 (3)
C16—C17—C18—C13	0.3 (5)	C16'—C17'—C18'—C13'	0.1 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Br9ⁱ	0.95	2.90	3.805 (3)	159
C8—H8···N1ⁱⁱ	0.95	2.46	3.394 (3)	166
C8′—H8′···N1′ⁱⁱ	0.95	2.48	3.410 (3)	166
C10′—H10C···Br9ⁱⁱⁱ	0.99	2.78	3.700 (2)	156
C15—H15···O11′^iv	0.95	2.60	3.497 (4)	158
C10—H10A···Cg1^v	0.99	2.60	3.466 (3)	146
C14—H14···Cg2^iv	0.95	2.87	3.794 (3)	165

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁BrClN₃O
M_r	352.62
Crystal system, space group	Triclinic, P1
Temperature (K)	118
a, b, c (Å)	7.8999 (2), 11.5023 (4), 15.5571 (5)
α, β, γ (°)	86.111 (2), 84.564 (2), 89.037 (2)
V (Å³)	1403.95 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.12
Crystal size (mm)	0.41 × 0.21 × 0.02

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (Blessing, 1995)
T_min, T_max	0.606, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	40101, 9403, 6435
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.746

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.081, 1.01
No. of reflections	9403
No. of parameters	361
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.45

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SAINT and SADABS (Bruker, 2005), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected torsion angles (º) top

C5—N7—C8—C9	0.3 (3)	C5'—N7'—C8'—C9'	0.1 (3)
N7—C10—O11—C12	−68.2 (3)	N7'—C10'—O11'—C12'	−77.3 (2)
C10—O11—C12—C13	−172.6 (2)	C10'—O11'—C12'—C13'	−161.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Br9ⁱ	0.95	2.90	3.805 (3)	159
C8—H8···N1ⁱⁱ	0.95	2.46	3.394 (3)	166
C8'—H8'···N1'ⁱⁱ	0.95	2.48	3.410 (3)	166
C10'—H10C···Br9ⁱⁱⁱ	0.99	2.78	3.700 (2)	156
C15—H15···O11'^iv	0.95	2.60	3.497 (4)	158
C10—H10A···Cg1^v	0.99	2.60	3.466 (3)	146
C14—H14···Cg2^iv	0.95	2.87	3.794 (3)	165

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

C—N···Br interactions (Å, °) top

C—N···Br	C—N	N···Br	C···Br	C—N···Br
C2—N3···Br9'^vi	1.320 (3)	2.964 (2)	3.457 (3)	100.45 (17)
C2'—N3'···Br^vii	1.324 (3)	3.043 (2)	3.565 (3)	102.17 (14)

Symmetry codes: (vi) x, y-1, z; (vii) 1+x, 1+y, z.

Acknowledgements

This work was supported by a New Zealand Foundation for Research Science and Technology contract [number C08X0701]. We thank Dr C. Fitchett of the University of Canterbury, New Zealand, for his assistance.

References

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